WO1990008798A1 - Latex/sol or gel systems - Google Patents

Latex/sol or gel systems Download PDF

Info

Publication number
WO1990008798A1
WO1990008798A1 PCT/US1990/000568 US9000568W WO9008798A1 WO 1990008798 A1 WO1990008798 A1 WO 1990008798A1 US 9000568 W US9000568 W US 9000568W WO 9008798 A1 WO9008798 A1 WO 9008798A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
salt
surface coating
sol
polymer
Prior art date
Application number
PCT/US1990/000568
Other languages
French (fr)
Inventor
Charles L. Kissel
Original Assignee
Union Oil Company Of California
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/305,451 external-priority patent/US5004562A/en
Priority claimed from US07/345,029 external-priority patent/US5004563A/en
Priority claimed from US07/373,401 external-priority patent/US5041486A/en
Priority claimed from US07/387,933 external-priority patent/US5041487A/en
Priority claimed from US07/412,839 external-priority patent/US5028489A/en
Application filed by Union Oil Company Of California filed Critical Union Oil Company Of California
Publication of WO1990008798A1 publication Critical patent/WO1990008798A1/en

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122Ionic conductors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/205Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
    • C09D5/024Emulsion paints including aerosols characterised by the additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0063Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf
    • D06N7/0071Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing
    • D06N7/0073Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing the back coating or pre-coat being applied as an aqueous dispersion or latex
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00Condition, form or state of the materials
    • D06N2205/04Foam
    • D06N2205/045Froth
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/04Properties of the materials having electrical or magnetic properties
    • D06N2209/046Anti-static
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00Properties of the materials
    • D06N2209/08Properties of the materials having optical properties
    • D06N2209/0838Bright, glossy, shiny surface

Definitions

  • the invention relates to polymer composi ⁇ tions, sol or gel compositions, electrically conduc ⁇ tive compositions containing a latex polymer, and the preparations thereof.
  • This invention relates to the field of textile materials, to antistatic materials, to a composition useful for providing antistatic properties to tex ⁇ tiles, and to methods for manufacturing and using such materials.
  • the present invention relates to sol or gel compositions capable of enhancing the gloss of paints and particularly semi-gloss latex paints.
  • the present invention relates to sol or gel compositions capable of enhancing the tannin blocking property of surface coatings and paints, and particu ⁇ larly latex paints applied to outdoor wood surfaces.
  • the present invention relates to sol or gel compositions capable of enhancing the corrosion-pro ⁇ tection properties of surface coating compositions and paints and particularly latex paints.
  • compositions containing polymers are usually pursued in several ways.
  • One approach con ⁇ sists of modifying the intrinsic bulk properties of polymers by processing, especially by pyrolysis. In this approach, acceptable electrical properties are developed by altering the chemical composition or structure of the initial material.
  • a second approach is to attain the desired conductivity by incorporating macroscopic pieces of conducting material (metal flakes, carbon-black particulates, or carbon fibers, for example) in host polymers to form conducting composites. It is the traditional approach in the preparation of conducting polymers and is used today in the fabrication of nearly all commercial products based on conductive polymers.
  • conjugated polymers i.e., polymers which already have at least some electrical conductance
  • molecular doping it consists of diffusing isolated molecular dopants (AsF 5 or I 2 , for example) into conjugated polymers.
  • Latex polymers capable of being stabilized in aqueous media are called latex polymers and a latex ordinarily contains at least one latex polymer and at least one surfactant dispersed in water.
  • latex polymers are not conjugated, e.g. , latex poly ⁇ mers are considered insulators.
  • materials responsi ⁇ ble for such conductance must be compatibly combined with the latex.
  • Compositions containing latex poly ⁇ mers coagulate when admixed with aqueous solutions of salts.
  • an aqueous solution of cupric acetate added to a latex composition containing sty- rene butadiene rubber will cause coagulation of the styrene butadiene rubber within a short time after contac .
  • ⁇ sols which contain materials such as colloidal antimo- ny oxide in an attempt to find materials which may be added compatibly to a latex composition (i.e., added without coagulation) .
  • a colloidal antimo ⁇ ny oxide hydrosol was mixed in equal amounts with polyvinylidene chloride (PVDC) to improve the clarity of PVDC films.
  • PVDC polyvinylidene chloride
  • the search continues for methods to compati ⁇ bly mix salts with latex polymers.
  • the resultant admixture of latex and salt provides for a number of useful compositions such as electrically conductive compositions containing latex polymers.
  • the field of textile materials involves all man ⁇ ufactured forms of fiber assemblies including wovens, nonwovens, knitted articles, threads, yarns, ropes, etc. which are employed, in one form or another, in almost every aspect of commercial and household use, either alone or as components of composite articles.
  • the accumulation of static electricity as a result of the utilization of fabric assemblies is a phenomenon which has commanded the attention of the textile industry, particularly the carpet industry.
  • Static is a cause of annoyance (e.g., items of apparel cling to the body and are attracted to other garments; fine particles of lint and dust are attracted to upholstery fabrics, increasing the frequency of re ⁇ quiring cleaning; one experiences a jolt or shock upon touching a metal doorknob after walking across a carpet).
  • static is the cause of danger (e.g., a discharge of static electricity can result in sparks capable of igniting flammable mixtures such as ether/air, which are commonly found in hospitals, especially in operating rooms) .
  • Static discharge can also harm sensitive electrical equipment such as com puters and scientific equipment. Representative places where carpets are used having these require ⁇ ments are in hospitals, computer rooms, ballrooms, restaurants and theaters. All of these effects of static are accentuated in atmospheres of low relative humidity.
  • a third group of structures, textile fiber substrates whose surfaces have been coated with finely divided particles of electrically conductive material by vapor deposition, electrodeposition, or by the application of adhesive compositions, are in some cases less costly than metal or carbonized fibers and/or metallic laminate filaments, depending upon the nature of the electrically conductive material em ⁇ ployed.
  • these are difficult to fabricate because large chambers are required to enclose the material to be subjected to electro- or vapordeposi- tion.
  • Such coatings are often found lacking in cohe ⁇ sion and adhesion and are frequently too thick to be practicable in some applications — especially when the nature of the electrically conductive particulate matter is such that a high concentration thereof is required for satisfactory conductivity.
  • Economy is achieved, therefore, only through sacrifices in dura ⁇ bility or conductivity of the fiber.
  • Meth ⁇ ods for preparing blends of extrudates involve either (a) total incorporation of particles in the fiber or substrate (as to be obtained by the spinning of a solution or a melt containing them) , or (b) surface incorporation of particles, achieved by the use of (1) an adhesive — e.g., to produce a true coating — or (2) impregnation of the particles into a fiber surface which has been softened or made tacky by means of a liquid softening agent and/or heat.
  • the total incor ⁇ poration of particles in the fiber or substrate and the use of an adhesive to bind the particles in the fiber or substrate as a true coating are inadequate and undesirable, because of (1) loss of properties such as conductivity as a result of disruption of the structural integrity of the fiber and (2) a low degree of durability.
  • Some materials can be dissolved into an adhesive mixture to provide antistatic performance. These materials include quaternary ammonium salts and some inorganic salts. However, only a few materials are available because they are usually not compatible with polymeric, (e.g. latex) adhesives, and those that are are difficult to incorporate into a wide variety of formulations.
  • compositions containing polymers particularly latex
  • extremely small quanti ⁇ ties of catalysts, activators, etc. are added during synthesis.
  • a resulting latex such as styrene butadiene rubber (SBR) contains up to about 1 weight percent of such materials, and acrylic or vinyl acryl ⁇ ic latexes contain about 0.1 weight percent.
  • anionic surfactants of up to 1 weight percent are used to stabilize latex emulsions. These materials are not antistatic.
  • salt materials In order to produce acceptable electrical conductivity in a latex, salt materials must be com ⁇ patibly combined with the latex in a sufficient con ⁇ centration to provide ade»quate antistatic properties to textile materials to which the latex is applied.
  • Surface coating compositions typically include such materials as paints, lacquers and var- nishes. Paints contain pigmented materials whereas lacquers or varnishes are generally clear or transpar ⁇ ent. The purposes of surface coatings are aesthetic and/or protective. A coating can enhance the appear ⁇ ance of a substrate in terms of color and gloss as well as give protection against such problems as weathering or corrosion.
  • paints can be divided into three basic categories, namely, (1) flat paints having a specular gloss of less than about 15 percent reflectance, (2) semi-gloss paints having a specular gloss of about 35 to about 50 percent reflectance, and (3) high-gloss paints having a specular gloss greater than about 70 percent reflectance based upon light having about a 60° angle of incidence.
  • Oil-base paints can easily be formulated into these three categories of paints.
  • waterborne paints particularly water-dispersible (latex) paints having a high specular gloss.
  • dyes and pigments can contribute to color. Dyes usually have good solubility in paint compositions; however, the durability of such paints is lacking. In contrast to dye-containing paints, pigments in paint formulations exhibit better durability, but such pig ented paints have relatively poor solubility of the pigments.
  • Wood is widely used in buildings for such items as roof trusses, timber frames, joists, doors, window frames, cladding and fencing.
  • wood is vulnerable to a variety of degrading influences, often caused by weathering, which include light, moisture and biological attack.
  • a phenomenon of the weathering of wood is the generation of tannins which migrate in the wood. Tannins in wood are essentially derivatives of tannic acid (also called gallotannic phenolics) . Tannins, and their migration in wood, can cause visi ⁇ bility of wood grains through inferior wood surface coatings or can cause discoloration of the coating.
  • the invention relates to a substantially nonaqueous composition containing a latex polymer and a salt.
  • the salt is dispersed in the latex polymer in the form of anions and cations and/or colloidal salt particulates.
  • the resultant latex polymer/salt compo ⁇ sition is usually prepared by admixing a composition containing a starting latex polymer with a sol or gel containing a salt.
  • a novel process is used to prepare a nonaqueous sol or gel wherein at least one nonaqueous solvent, at least one stabilizer, and at least one salt are admixed and then heated to a temperature sufficient to produce a sol or gel containing the salt.
  • An acidic component is also usually added to the admixture prior to heating.
  • the nonaqueous solvent is usually a form of polyhydroxyl ether or polyhydroxyl alcohol
  • the stabilizer is usually a chelator, such as a hydroxycarboxylic acid, or a nonionic surfactant
  • the admixture is usually heated to a temperature less than 100° C. to form a product sol or gel composition.
  • such a product sol or gel may be admixed with a composition containing a latex polymer to produce a stable, nonco- agulated product admixture composition containing a latex polymer and a salt.
  • a novel sol or gel composition contains at " least one solvent, at least one salt, and a stabilizer comprising a nonionic surfactant.
  • a typical nonionic surfactant has the formula
  • each of R and R x is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide and x and y are nonnegative integers, but not simultaneously zero.
  • the invention relates to a novel intermediate composition useful in the preparation of a sol or gel.
  • the composition includes a mixture of at least one solvent, at least one salt, and a stabilizer comprising a nonionic surfactant.
  • the solvent is nonaqueous, and the pH is less than 7.0 and is capable of being heated to form a sol or gel.
  • the sol or gel compositions of the invention may be admixed with a composition containing a polymer to produce a product admixture containing the sol or gel and the polymer.
  • the product admixture is dried to produce a product composition containing the salt from the sol or gel and the polymer.
  • the salt is dispersed in the polymer in a form compatible to the particular polymer.
  • a stable, noncoagulated product admixture composition is prepared by admixing an above-mentioned sol or gel composition with a composition containing a latex polymer.
  • the stable, noncoagulated product admixture containing the latex polymer and sol or gel is dried to produce a resultant latex polymer/salt composition which is highly useful as a latex polymer composition having electrically conductive properties.
  • the invention relates to a textile composition having antistatic properties.
  • the textile composition contains a textile treated with a sol or gel composi ⁇ tion containing a salt so that the salt is dispersed on the surface of or among the fibers comprising the textile.
  • the sol or gel composition may be admixed with a polymer, such as a latex polymer, to produce a product admixture composition which can be employed to treat a textile.
  • the product admixture composition is combined with a filler material to produce a compounded polymer/salt product composition which may then be utilized to treat a starting textile material such as carpet to produce a textile composi ⁇ tion of the invention.
  • the textile product composi ⁇ tion of the invention usually has an electrical con ⁇ ductivity in the range effective for controlling static electricity, i.e., from about 10 ⁇ 8 to about 10 Seimens/cm.
  • the present invention also involves a method for enhancing the gloss property of a surface coating composition, including a paint composition.
  • a sol or gel composition containing a salt is added to a poly ⁇ mer composition, or to a surface coating or paint composition containing a polymer, or to a surface coating precursor composition containing a polymer, to produce a product surface coating or paint composition having an enhanced gloss property.
  • the salt in the sol or gel composition is contained in sufficient amount to increase the specular gloss, usually by at least about 2 percent reflectance, based upon light having about 60° angle of incidence.
  • the invention also involves a surface coat ⁇ ing composition comprising a polymer binder and a salt homogeneously distributed in the composition.
  • the surface coating composition particularly a waterborne surface coating composition, comprises a sol or gel composition containing a gloss-enhancing amount of salt, at least one water-soluble or water-dispersible polymer binder, and usually a paste stock containing such ingredients as pigments, coalescing aids, thick ⁇ ening aids, dispersing aids, defoamers, biocides, and fillers.
  • the surface coating compositions of the invention prepared from the sol or gel composition and polymer are applied to several substrates.
  • the re ⁇ sultant dried surface coating compositions and the coated substrates formed therefrom provide composi ⁇ tions having enhanced gloss properties compared to compositions not prepared with sol or gel composi ⁇ tions.
  • Such compositions and coated substrates of the invention retain adequate scrub and wet adhesion properties while gloss is enhanced.
  • the present invention also involves a method for enhancing the tannin blocking property of a sur ⁇ face coating composition, including a paint composi ⁇ tion.
  • a sol or gel composition containing a salt is added to a polymer composition, or to a surface coat ⁇ ing or paint composition containing a polymer, or to a surface coating precursor composition containing a polymer, to produce a product surface coating or paint composition having an enhanced tannin blocking proper ⁇ ty.
  • the salt in the sol or gel composition is con ⁇ tained in sufficient amount to increase the tannin blocking property of the surface coating composition prepared therefrom.
  • the particular salt utilized and the particular amount of sol or gel composition and salt utilized depends upon the par ⁇ ticular polymer utilized and the particular substrate that is coated.
  • the invention also involves a surface coat ⁇ ing composition
  • a surface coat ⁇ ing composition comprising a polymer binder and a salt homogeneously distributed in the composition in suffi ⁇ cient concentration to block the effects of tannins contained in a wood-containing substrate, i.e., to prolong the visibility of wood grains of the substrate through the coating and/or discoloration of the coat ⁇ ing.
  • the surface coating composition particularly a waterborne surface coating composition, comprises a sol or gel composition containing a tannin block- enhancing amount of salt, at least one water-soluble or water-dispersible polymer binder, and usually a paste stock containing such ingredients as pigments, coa ⁇ lescing aids, thickening aids, dispersing aids, de ⁇ foamers, biocides, and fillers.
  • the surface coating compositions of the invention prepared from the sol or gel composition and polymer are applied to wood-containing substrates.
  • the resultant dried surface coating compositions and the coated substrates formed therefrom provide compo ⁇ sitions having enhanced tannin-blocking properties compared to compositions not prepared with the de ⁇ scribed sol or gel compositions.
  • One of the advan ⁇ tages of the compositions described herein as useful for coating wood-containing substrates is that a single coat of such compositions provides tannin blocking properties which are as effective as a con ⁇ ventional two-coat application.
  • the present invention further involves a method for preventing the corrosion of free metal- containing substrates.
  • the method includes enhancing the corrosion protection property of a surface coating composition, including a paint composition, which is applied to such substrates.
  • a sol or gel composition containing a salt is added to a polymer-containing composition, preferably to a surface coating or paint composition containing a polymer, to produce a product surface coating composition having an enhanced corro ⁇ sion protection property.
  • the salt in the sol or gel composition is contained in sufficient amount to prevent corrosion on a free metal-containing substrate when the surface coating composition containing the salt is coated and dried on the substrate.
  • the invention also involves a surface coat ⁇ ing composition
  • a surface coat ⁇ ing composition comprising a polymer binder and a salt homogeneously distributed in the composition in suffi ⁇ cient concentration to inhibit the effects of corro ⁇ sion on a free metal-containing substrate.
  • the pro ⁇ tective surface coating composition particularly a waterborne surface coating composition, comprises a sol or gel composition containing a corrosion protec ⁇ tion-enhancing amount of salt, at least one water- soluble or water-dispersible polymer binder, and usually a paste stock containing such ingredients as pigments, coalescing aids, thickening aids, dispersing aids, defoamers, biocides, and fillers.
  • the protective surface coating compositions of the invention prepared from the sol or gel composi ⁇ tion and polymer may be applied to several different free metal-containing substrates.
  • the resultant dried surface coating compositions and the coated free metal-containing substrates formed therefrom provide compositions having substantially enhanced corrosion protection properties compared to compositions not prepared with the described sol or gel compositions.
  • Such compositions and less corrosion-prone coated free metal-containing substrates produced therefrom also retain adequate scrub and wet adhesion properties while gloss is enhanced.
  • a sol or gel is prepared for addition to a composition containing a polymer, preferably a latex polymer.
  • the sol or gel composition is prepared by admixing, in any order, at least one solvent, at least one stabilizer, and at least one salt.
  • an acidic component may also be added to the admixture.
  • the sol or gel compositions are typically acidic in nature, i.e., have a pH less than about 7.0, and contain a salt, a nona-queous solvent, a stabilizer and, optionally, an acidic component.
  • Typical solvents utilized in the preparation of the sol or gel include nona-queous solvents such as organic solvents, such as ether, ester, alcohol or combinations thereof, and particularly polyols, such as for example a polyhydroxyl ether or a polyhydroxyl alcohol.
  • nonaqueous sols or gels containing organic solvents and essentially no water are typically re ⁇ ferred to as organosols or organogels.
  • More particu ⁇ lar examples of useful solvents for preparing organo ⁇ sols or organogels include ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyoxyethlene-polypropylene) glycol and blocked (polyoxyethlene-polyoxypropylene) glycol.
  • ethylene glycol, glycerine, pentanediol polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyoxyethlene-polypropylene) glycol and blocked (polyoxyethlene-polyoxypropylene) glycol.
  • at least one stabilizer is added to the admix ⁇ ture.
  • the stabilizer is usually a chelator and/or a nonionic surfactant.
  • nonionic surfactant stabilizers ordinarily contain ethylene oxide (EO) and/or propylene oxide (PO) .
  • the nonionic surfactant stabilizers may also include mixed EO-PO or blocked EO-PO arrays.
  • EO ethylene oxide
  • PO propylene oxide
  • One example of a nonionic surfactant has the formula
  • R-(EO) ⁇ (PO) y -R 1 wherein each of R and R 1 is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals, and x and y are nonnegative integers, but not simulta ⁇ neously zero.
  • Another nonionic stabilizer is a glyc ⁇ erine derived nonionic surfactant having the formula (EO) ⁇ (PO) y -R glycerine (EO) a (PO) ⁇ -R 1 (EO) m (PO) n -R 1:L wherein each of R, R 1 and R 11 is independently select ⁇ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla- ryl, dialkylaryl aliphatic ester and aryl ester radi ⁇ cals, and x, y, a, b, m and n are nonnegative inte ⁇ gers, but not simultaneously zero.
  • nonionic surfactants are alkylpolyglycol ethers such as ethoxylation products of lauryl, oleyl, and stearyl alcohols or mixtures of such alcohols as coconut fatty alcohols; alkylphenol polyglycol ethers such as et ⁇ hoxylation products of octyl- or nonylphenol, diiso- propylphenol, triisopropylphenol, di- or tritertiary- butyl phenol, etc.
  • Preferred nonionic surfactants include mono- or di-alkyl oxyalkylated phenolics.
  • a highly preferred nonionic surfactant useful herein contains about 1 to about 100 percent by weight of ethylene oxide, in combination with 0 to about 99 percent by weight of propylene oxide and has a molecu ⁇ lar weight from about 62 to about 5,000.
  • surfactants include 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco- hoi, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol RO octyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate or monocetylate, monomystralate or monos- tearate.
  • any salt is useful in the sol or gel compo ⁇ sitions; however, salts which provide an acidic sol or gel composition are preferred in the invention. Both organic and inorganic salts may be utilized.
  • the salt speciesa in the sol or gel must be capable of (1) existing as colloidal salt particulates, (2) existing in ion species or (3) forming ions when dispersed in a composition containing a polymer, particularly a latex polymer.
  • the salt contains cations or anions capable of being dispersed in the admixture of solvent and stabilizer, and fur ⁇ ther being capable of being dispersed in the polymer composition contained in the stable product admixture composition of salt-containing sol or gel and polymer.
  • the anions or cations of the salt are usually metallic cations or metallic-containing anions, monomeric nonmetallic cations or monomeric nonmetallic anions, or polymeric nonmetallic cations or polymeric nonme ⁇ tallic anions. Any metal or nonmetal may be contained in the cations or anions.
  • Useful metallic cations of the salt include the cations of antimony, yttrium, cadmium, silver, calcium, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseo ⁇ dymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, strontium, ytterbium, titanium, tantalum, tungsten and mercury.
  • Examples of useful monomeric nonmetallic cations of the salt include ammonium, boron and silicon-containing cations.
  • Useful monomeric nonmetallic anions of the salt in ⁇ clude those containing nitrates, acetates, halides, borates, chromates, molybdates, silymolybdates, for ⁇ mates, citrates, benzoates, tartrates, phosphates, plumbates, silicates, nitrites, carbonates, oxides and alkoxides.
  • Examples of a number of metallic-contain ⁇ ing anions useful herein include those containing the elements arsenic, chromium, manganese, tin, aluminum, titanium, zirconium, vanadium or molybdenum.
  • Salts useful herein containing nonmetallic anions typically contain an element such as fluorine, oxygen, nitrogen, carbon, tellurium, selenium, phosphorus, sulfur, chlorine, bromine and iodine. Furthermore, the salts may provide polymeric cations such as monoolefinic quaternary ammonium cations, diolefinic quaternary ammonium cations, triolefinic quaternary ammonium cations and tetraolefinic quaternary ammonium cations.
  • the salts may contain polymeric anions such as alkyl, aryl, ether, or alkylaryl sulfonates, sulfates, phosphates, carboxylates and polycarboxylates, partic ⁇ ularly the salts producing an acidic sol or gel compo ⁇ sition.
  • polymeric anions such as alkyl, aryl, ether, or alkylaryl sulfonates, sulfates, phosphates, carboxylates and polycarboxylates, partic ⁇ ularly the salts producing an acidic sol or gel compo ⁇ sition.
  • sols or gel composition of the invention may be highly dependent on the particular polymer in which it is combined in a stable product admixture composition
  • some particularly useful salts contained in sols or gels which are utilized to prepare surface coating compositions include the acetates, chromates, cit ⁇ rates, molybdates, nitrates, phosphates, bromates, halides and silicates of the herein disclosed cations.
  • highly preferred salts for improving gloss in a surface coating composition may contain a rare earth metallic cation, such as lanthanum, exam ⁇ ples include lanthanum, acetate, lanthanum chloride, lanthanum nitrate and lanthanum oxide or a silicon- containing salt such as silicon acetate.
  • salts which contain aluminum metallic cations are preferred, such as aluminum acetate, aluminum chloride, aluminum nitrate and aluminum isoperoxide.
  • highly preferred salts contain at least one divalent cation such as a zinc cation, and partic ⁇ ularly, in combination with chromates, molybdates, phosphates and silicates.
  • divalent cations for corrosion protection purposes include barium, cadmium, calcium, copper, magnesium, mercury and strontium.
  • an acidic component is sometimes added to the admix ⁇ ture of solvent, stabilizer and salt.
  • the acid component is usually a protic acid, such as concentrated nitric acid, concentrated hydrochloric acid or concentrated sulfuric acid; however, a Lewis acid may also be utilized.
  • An acidic component may be added to the admixture of solvent, stabilizer and salt either before, during or after the admixture is heated to a temperature sufficient to form a sol or gel.
  • the admixture of solvent, stabilizer and salt, and optionally an acidic component is ordinarily prepared at room temperature and the temperature raised usually to less than 100° C. to produce a sol or gel containing the desired salt.
  • the temperature to which the admixture is heated is usually dependent upon the particular salt or salts contained in the admixture; however, a significant number of admixtures containing a salt, particularly an inorganic salt, are heated to a temperature in the range from about 30° C. to about 90° C. and more preferably in the range from about 35° C. to about 85° C.
  • the ingredients are admixed at room temperature and slowly heated to a temperature in the range from about 35° C. to about 85° C. for a period sufficient to produce a transparent product, ordinarily from about 0.5 to about 15 hours and having the color of the characteristic anion or cation of the particular salt in the admixture.
  • the transparent product is a sol or gel composition con ⁇ taining the cations and anions and/or colloidal salt particulates of the particular salt of the admixture. Often the transparent product becomes cloudy or opaque when the admixture is cooled to room temperature. If the transparent product becomes opaque or cloudy, additional sufficient portions of the acidic component may be added to the opaque product to produce a sol or gel composition having substantially the same degree of transparency and clarity as observed at the elevat ⁇ ed temperature necessary to initially form the sol or gel.
  • the pH of the admixture is generally less than 7.0 and usually less than 4.0. It is preferred that the pH of the admixture of the sol or gel composition be less than about 3.0, partic ⁇ ularly when the acidic component is added to the admixture, and it is highly preferred that the pH be less than about 1.0. Also, as will be seen hereinaf ⁇ ter in the examples, many instances exist where the pH of the sol or gel composition is less than about 0.1. The pH of the sol or gel composition can readily be determined with a conventional pH meter such as Orion Model No. 701.
  • a novel sol or gel composition is prepared by heating a mixture of at least one solvent with at least one salt and a stabilizer containing a nonionic surfactant.
  • An acidic component may optionally be added to the admix ⁇ ture either before or after heating the admixture to a temperature sufficient to form a sol or gel composi ⁇ tion; typically such a temperature is in the range from about 30° to about 95° C.
  • the solvent is typi ⁇ cally a nonaqueous solvent, commonly an organic sol ⁇ vent, which, in admixture with the nonionic surfactant and the salt, comprises an organosol or organogel when the temperature of the admixture has been increased sufficiently to form the sol or gel composition.
  • the sol or gel composition described herein may be combined with a composition containing a poly- er to produce a product admixture containing the components of the sol or gel composition and the polymer.
  • Polymers contemplated for use herein include natural polymers such as polymerized oils (for in ⁇ stance vegetable oils found in varnishes) , cellulose- derived materials (for instance, nitrocellulose found in lacquers) , and various resins (for instance, those found in oil-based paints, lacquers or varnishes) , and the like; also synthetic polymers such as thermal plastic and thermal setting polymers as well as semi- synthetic polymers.
  • a stable, noncoagu ⁇ lated product admixture composition containing a latex polymer and a salt is prepared by admixing the sol or gel composition described herein with a composition containing a latex polymer.
  • a latex polymer is preferably employed as the polymer to which the sol or gel composition is admixed.
  • a stable, noncoagulated product admixture compo ⁇ sition containing a latex polymer and a salt is pre ⁇ pared by admixing a sol or gel composition described herein by charge addition, delay addition or post blending with a composition containing a latex polymer or at least one monomer composition containing at least one monomer unit of the latex polymer.
  • the compatibility of the salt-containing sols or gels disclosed herein with the water-dispersible polymers is critical.
  • the resulting stability of a latex after addition of significant amounts of salt from the salt-containing sol or gel i.e. greater than 0.001, and preferably greater than 0.01 weight percent of salt in latex renders a latex polymer the most highly preferred polymer for the invention disclosed herein.
  • Exemplary polymers include, but are not limited to, resins, vinyl acrylic polymers, acrylic polymers, vinyl chlo ⁇ ride acrylic polymers, vinylidene chloride polymers, stryene-butadiene copolymers, stryene-acrylate copoly ⁇ mers and vinyl acetate-ethylene copolymers.
  • any polymer capable of being dispersed, emul ⁇ sified or suspended in a latex is considered a latex polymer.
  • the latex polymer utilized herein is not conjugated.
  • Preferred latex polymers of the invention as more specifically disclosed include (1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms, preferably containing at least 10 weight percent of the conjugat ⁇ ed diene monomers, and usually in combination with one or more alkenyl substituted monoaromatic monomers, typically in the range from about 1 to about 70 weight percent of the latex polymer, (2) olefin-ester inter- polymers containing a onoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid, preferably containing at least 10 weight percent of the polymer, (3) olefini- cally unsaturated carboxylic acid ester polymers containing polymerized, olefinically unsaturated monomers containing polymerized olefinically unsatu ⁇ rated carboxylic acid ester monomers, preferably containing at least 10 weight percent of the latex polymer
  • a feature of the invention is that the salt contained in the sol or gel composition or in the stable product admixture composition is in a concen ⁇ tration which is greater than the lowest concentration of the same salt which otherwise effects destabiliza- tion of essentially the same product admixture compo ⁇ sition but essentially free of the salt from the sol or gel composition.
  • the pH of the stable product admixture composition is less than 7.0, usually less than about 4.0, and preferably less than about 3.0.
  • compositions containing starting latex polymers can be prepared as aqueous dispersions, emulsions, suspensions, and the like by procedures known in the art to be suitable for preparation of the aforementioned 5 classes of starting latex polymers.
  • aqueous starting latex polymer disper ⁇ sions can be prepared by gradually adding each monomer simultaneously to an aqueous reaction medium at a rate proportionate to the respective percentage of each monomer in a finished polymer and initiating and continuing polymerization by providing in the aqueous reaction medium a suitable polymerization catalyst.
  • catalysts are free radical initi ⁇ ators and redox systems such as hydrogen peroxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide, lauryl peroxide, di-tertiarybutyl peroxide, bisazodiisobutyronitrile, either alone or together with one or more reducing components such as sodium bisulfite, sodium metabisulfite, glucose, ascorbic acid, erythorbic acid, etc.
  • the reaction is continued with agitation at a temperature sufficient to maintain an adequate reaction rate until all added monomers are consumed.
  • Monomer addition is usually continued until the latex (dispersion) reaches a polymer concentration of about 10 to about 70 weight percent, and usually about 40 to 70 weight percent.
  • Protective colloids may be added to an aqueous polymer dispersion either during or after the reaction period.
  • Illustrative protective colloids include gum arabic, starch, alginates, and modified natural substances such as methyl-, ethyl-, hydroxyal- kyl-, and carboxy ethyl cellulose, and synthetic substances such as polyvinyl alcohol, polyvinyl pyrro- lidone, and mixtures of two or more of such sub- stances.
  • Fillers and/or extenders, such as dispersible clays and colorants, including pigments and dyes can also be added to the aqueous dispersions either during or after polymerization.
  • compositions containing a starting latex polymer are ordinari ⁇ ly greater than about 0.1 weight percent of the compo ⁇ sition.
  • concentrations are greater than 1 weight percent and preferably greater than 5 weight percent, most preferably greater than 35 weight per ⁇ cent, but most commonly in the range from about 40 to 70 percent for those latexes resulting from emulsion polymerization.
  • the dispersed polymer particles in the composition containing the latex polymer can be of any size suitable for the intended use, although particle sizes of usually at least about 120 nanome ⁇ ters are presently preferred since latex viscosity increases as particle size is reduced substantially below that level.
  • the described latexes will have polymer particle sizes within the range from about 120 to about 300 nanometers as determined on the N-4 "Nanosizer" available from Colter Electronics, Inc., of Hialeah, Florida.
  • the stable, noncoagulated product admixture composition produced by the admixing of the sol or gel composition with the composition containing at least one latex polymer is usually dried by suitable methods known in the art to produce a dried, substantially nonaqueous resultant latex polymer/salt composition.
  • the product admixture composition is usually air dried or oven dried at a temperature less than about 100° C
  • the dried (nonaqueous) resultant latex polymer/salt composition ordinarily contains less water than contained in the aqueous dispersion of the starting latex polymer, and preferably contains sub ⁇ stantially no water, e. g. , less than 1 weight percent water in the resultant latex polymer/salt composition.
  • the resultant latex polymer/salt composition usually contains the same starting latex polymer; however, it is within the scope of the present invention that the starting latex polymer can be converted to a different latex polymer after admixture of the sol or gel with the starting latex polymer. At least one cation and/or at least one anion of the salt is dis ⁇ persed in the dried resultant latex polymer/salt composition.
  • the invention is not bound by any theory, it is believed that at least some of the particulates derived from the starting salt contained in the sol or gel exists as anions or cations of the salt or as colloidal salt particulates dispersed in the resultant latex polymer/salt composition.
  • the derived ions or particulates are homogeneously dis ⁇ tributed in the salt/polymer composition comprising the stable product admixture composition of the inven ⁇ tion.
  • the concentration of the salt in any of the compositions described herein is dependent upon the use of the particular composition. Ordinari ⁇ ly, a concentration of greater than about 0.001 weight percent of salt and typically greater than 0.1 weight percent of salt in the sol or gel composition is sufficient for most uses, although the dried product composition, such as the salt/ latex polymer composi ⁇ tion, may contain a considerably lower concentration of salt, such as greater than typical detectable limits, i.e., greater than about 10 ⁇ 7 weight percent, and preferably greater than 10 ⁇ 4 weight percent.
  • the aqueous stable product admixture composition or the dried salt/polymer compo ⁇ sition has a salt concentration greater than about 0.001 weight percent, typically more than about 0.01 weight percent and ordinarily greater than about 0.1 weight percent of salt in the polymer-containing composition.
  • the dried salt/polymer composition of the invention typically has a salt concentration from about 1 to about 30 weight percent, and preferably about 5 to about 30 weight percent.
  • the particular salt utilized in an embodiment of the invention wherein the stable product admixture composition is a surface coating composition, depends upon the particular polymer utilized and the particular substrate that is coated. Although the amount of salt contributed from the sol or gel and the amount of polymer are determined by the particular coating use, typically the concentration of salt homogeneously distributed in the stable product admixture composition (e.g., surface coating composi ⁇ tion) is about 0.02 and about 1 weight percent. Typ ⁇ ically the concentration of sol or gel composition in the stable product admixture composition (e.g., sur ⁇ face coating composition) which is necessary to achieve such salt concentrations is usually about 0.1 to about 5 weight percent.
  • the concen ⁇ tration of salt in the sol or gel composition is usually about 1 to about 50, preferably about 10 to about 20 weight percent.
  • the concentration of the sol or gel in the stable product admixture composition is usually about 0.5 to about 25 weight percent, and the concentration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.1 to about 5 weight percent.
  • the invention encompasses surface coating compositions which have a continuous and discontinuous phase, including paints, lacquers and varnishes.
  • the surface coating composition contains a salt derived from a salt-containing sol or gel composition admixed with a composition containing a polymer.
  • the inven- tion is particularly directed to a waterborne surface coating composition wherein the continuous water phase contains a binder comprising a water-soluble polymer, and, more particularly, to waterborne surface coating compositions wherein the discontinuous phase comprises a water-dispersible polymer binder, such as a latex.
  • the discontinuous phase of the surface coating compo ⁇ sitions of the invention also contains salt components of the sol or gel compositions described herein and typically a paste stock usually containing one or more of the following components: a pigment, an extender pigment, a coalescing aid, a thickening aid, a dis ⁇ persing aid, a protective colloid, a defoamer, a biocide, an amine solubilizer, a flow additive, a drier, a cosolvent and a filler material.
  • a paste stock usually containing one or more of the following components: a pigment, an extender pigment, a coalescing aid, a thickening aid, a dis ⁇ persing aid, a protective colloid, a defoamer, a biocide, an amine solubilizer, a flow additive, a drier, a cosolvent and a filler material.
  • the water- borne coating compositions of the invention contain water, the sol or gel compositions described herein, usually a paste stock and either water-soluble poly ⁇ mers such as water-soluble resins, alkyds, polyureth- anes, unsaturated polyesters, and the like, or water- dispersible polymers such as latex polymers.
  • water-soluble poly ⁇ mers such as water-soluble resins, alkyds, polyureth- anes, unsaturated polyesters, and the like
  • water- dispersible polymers such as latex polymers.
  • the invention is not bound by any theory, it is believed that at least some of the particulates derived from the starting salt contained in the sol or gel exists as anions or cations of the salt or as colloidal salt particulates, the derived particulates being homogeneously distributed in the resultant polymer/salt composition comprising the surface coating composition of the invention.
  • colloidal salt particulates ordinarily have a diameter less than about 40 nanometers, usually less than about 20 nanometers, and often less than about 10 nanome ⁇ ters.
  • the salt components introduced into the surface coating compositions of the invention by means of the sol or gel compositions are continu ⁇ ously and permanently distributed throughout the sur face coating composition, or a precursor thereof, so as to be homogeneously distributed in the product composition.
  • homogeneously distributed refers to those arrangements and distribu ⁇ tions of salt components (whether cations, anions or colloidal salt particulates) derived from the sol or gel composition being closer to the homogeneity and permanence existing in a true solution (wherein a salt is completely dissolved in water and permanently maintained in such a phase) than that in conventional surface coating compositions containing ground dis ⁇ persed salt pigments.
  • the finely ground conventional dispersed paint pigment or other additive comprising a salt is considered herein to be heterogeneously dis ⁇ tributed in a surface coating composition.
  • the homogeneity of the salt components of the compositions of the invention is better than that for the ground pigment salts, and the like, of conventional surface coating compositions.
  • the distribution and arrange ⁇ ment of butterfat particles in homogenized milk, when viewed through a magnifying glass, is considered homogeneous.
  • any polymer binder compatible with the salt components of the sol or gel compositions described herein may be utilized in a surface coating composition of the invention, water-dispersible poly ⁇ mers are preferred.
  • a typical polymerization process yields an emulsion comprising a latex polymer and water.
  • the emulsion can further comprise a surfactant, a chain transfer agent, catalysts, and activators.
  • the emulsion in combination with the salt- containing sol or gel compositions described herein can be used to replace at least a portion of the polymer binder used in a waterborne surface coating composition, such as a water-base paint composition containing a latex poly ⁇ mer.
  • a typical surface coating or paint composition comprises an emulsion containing a polymer binder, salt (from a sol or gel) which is homogeneously dis ⁇ tributed therein, at least one pigment, a coalescing aid, a thickening aid, a dispersing aid, a defoamer, a biocide, and a filler.
  • Coalescing aids, thickening aids, dispersing aids, defoamers, biocides and fillers suitable for use in surface coating paint compositions are well known to those skilled in the art.
  • Exemplary polymer binders include, but are not limited to, resins, vinyl acrylic polymers, acrylic polymers, vinyl chloride acrylic polymers, vinylidene chloride polymers, styrene-butadiene copolymers, styrene-acry- late copolymers, and vinyl acetate-ethylene copoly- mers.
  • Preferred polymers include vinylidene chloride polymers, vinylacrylic polymers and styrene-acrylate copolymers.
  • the product admixture composition of the invention can be replaced by the product admixture composition of the invention.
  • the product admixture composition replaces about 1 to about 30 weight percent of the polymer binder's solid content.
  • the product admixture composition replaces about 5 to about 25, and more preferably from about 10 to about 20 weight percent of the solid content of the polymer binder is replaced by the product admixture composition.
  • Parint compositions suitable for use in conjunction with the product admixture composition typically have a pigment volume concentration (pvc) of less than about 25 volume by volume percent (v/v%) .
  • the paint composition has a pvc of about 15 to about 25 v/v%.
  • the surface coating composition of the invention can contain a surface coating paste stock.
  • the paste stock particularly a paste stock suitable in combination with a water- dispersible polymer, usually contains at least one pigment and usually at least one of the aforementioned additives such as a coalescing aid, a thickening aid, a defoamer, a biocide and/or a filler material or ex ⁇ tender.
  • a waterborne coat ⁇ ing composition containing a water-dispersible polymer binder and water usually contains a surface coating paste stock containing at least one pigment or dye and usually at least one additive such as a pigment dis- persant, an amine solubilizer, a flow additive, a drier, and/or a cosolvent.
  • Conventional ground pig ⁇ ments useful herein include titanium dioxide; copper carbonate; manganese dioxide; lead, zinc and boron chromates; cadmium sulphide; iron oxides; Prussian blue; cobalt blue; ultramarine; chromium oxide; cadmi ⁇ um selenide; red lead; chrome lead; zinc oxide; anti ⁇ mony oxide and lead or calcium carbonate.
  • the salt components derived from the sol or gel composition described herein can also comprise all or a part of the pigment or dye contained in the surface coating composition.
  • Several salts contained in the sol or gel compositions provide either color or colorless compositions, and can also be employed to control opacity of the surface coating compositions described herein.
  • the salts derived from the sol or gel which contribute to a paint formulation to produce or effect color or colorless paint compositions provide a paint formulator with materials which provide more durabili ⁇ ty to the paint then dyes and more solubility in the paint than pigments.
  • aluminum acetate sol is yellow
  • aluminum nitrate sol is colorless
  • cupric acetate is blue
  • cobalt acetate is red
  • neody- mium chloride is yellow-green
  • ferric citrate is brown
  • salts also provide antioxidation or antiyellowing of surface coating compositions described herein.
  • the salt contained in the sol or gel pro ⁇ vides an enhancement to the gloss, tannin blocking and corrosion protection properties of the composition.
  • Such enhancement is particularly effective for the gloss enhancement, tannin blocking and corrosion protection properties of a paint composition contain ⁇ ing a latex.
  • the salt contained in the sol or gel provides an enhancement to the tannin blocking property of the composition.
  • Such enhancement is particularly effective for the blocking effects of tannins produced from weathering influences on wood-containing substrates which are coated by the surface coating compositions described herein.
  • wood-containing substrates such as redwood and cedar lumber, are coated with the surface coating compositions described herein.
  • the salt contained in the sol or gel provides an enhancement to the gloss property of the composition.
  • Such enhancement is particularly effective for the gloss property of a semi-gloss or high-gloss paint composition.
  • a sol or gel containing a salt is admixed with a polymer such as a resin.
  • the product admixture composition is blended with a surface coating paste stock to produce a water-soluble surface coating composition.
  • the salt-containing sol or gel is admixed with a latex polymer, water and a surface coating paste stock to produce a water-dispersible surface coating composition.
  • the product coating compositions. have enhanced gloss properties and such salt addition does not substantially reduce the scrub or wet adhesion properties of the compositions.
  • the surface coating paint composition can be applied to at least a portion of a surface of a sub ⁇ strate.
  • the surface coating or paint When applied to a substrate having a white glossy surface, the surface coating or paint, upon drying, forms a composition that typically has a specular gloss of at least about 35 percent reflect ⁇ ance, and preferably at least about 70 percent re ⁇ flectance, when measured at an angle of incidence of about 60°.
  • a commercially available substrate having a white, glossy surface is Form WB grade plain white charts available from Leneta Company of Ho-Ho-Kus, New Jersey.
  • sufficient salt i.e., a gloss-enhancing amount of salt
  • sufficient sol or gel containing salt is admixed with a composition containing a polymer and/or a paste stock in an amount to increase the specular gloss by at least about 2 percent reflectance, based upon light having about a 60° angle of incidence, as compared to the same surface coating composition without contain ⁇ ing the salt from the sol or gel composition.
  • specular gloss is directly proportional to the percent reflectance at a given angle of incidence, it is preferred that the percent reflectance obtained by the composition be at least about 35, and more preferably at least about 45 for semi-gloss paints.
  • the percent reflectance for high-gloss paints should be at least about 70, and preferably at least about 75.
  • the sol or gel composition or product admixture composition of the instant invention is capable of enhancing the specular gloss of a paint.
  • a gloss-enhancing amount of the salt is homogeneously distributed in the surface coating composition of the invention or it& precursor by means involving admixing a sol or gel composition containing sufficient salt with a composition containing a poly ⁇ mer and ordinarily also with a surface coating paste stock.
  • concentration of salt homoge ⁇ neously distributed in the surface coating composition is about 0.05 and about 5 weight percent.
  • concentration of sol or gel composition in the surface coating composition which is necessary to achieve such salt concentrations is usually about 0.1 to about 2 weight percent.
  • the concen ⁇ tration of salt in the sol or gel composition is usually about 2 to about 50, preferably about 10 to about 20 weight percent.
  • the concentration of the sol or gel in the product admixture composition is usually about 2 to about 20 weight percent, and the concentration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.5 to about 25 weight percent.
  • the surface coating compositions of the invention are applied to the surface of a solid sub ⁇ strate such as wood, metal, ceramic, plastic, glass, paper, cement, combinations thereof, and the like, or applied to such substrates over a previously coated surface.
  • the applied surface coating composition of the invention is dried by suitable methods known in the art to produce a dried, resultant coating composi ⁇ tion containing a coalesced polymer and salt compo ⁇ nents derived from the sol or gel composition.
  • the resulting coated substrate comprising any solid substrate and the dried resultant surface coating composition of the invention has a dried resultant surface coating having an enhanced gloss property compared to a comparable coating composition not prepared with the sol or gel composition described herein.
  • Either a coated substrate comprising any solid substrate and the dried resultant surface coat ⁇ ing composition or the surface coating composition may contain a controlled quantity of sol or gel composi ⁇ tion and/or salt contained therein so as to have controlled opacity and/or color and other visual effects.
  • the resulting coated substrates produced by the combination of the dried resultant coating compo ⁇ sition and the solid substrate upon which the surface coating composition of the invention is at least partially applied also depend upon the reaction be ⁇ tween the coating composition of the invention and the particular substrate that is coated.
  • the dried re ⁇ sultant coating composition of the invention in a coated substrate comprising a wood-containing sub ⁇ strate contains tannin blocking properties effective for reducing the weathering of the wood.
  • the dried resultant surface coating composition of the invention contained as a portion of a coated substrate compris ⁇ ing a corrosion-prone substrate (i.e., a metal-con- taining or plastic-containing substrate) has a corro ⁇ sion-reducing or corrosion-inhibiting property.
  • a sol or gel containing a salt is admixed with a polymer such as a resin.
  • the product admixture composition is blended with a surface coating paste stock to produce a water-soluble surface coating composition.
  • the salt-containing sol or gel is admixed with a latex polymer, water and a surface coating paste stock to produce a water-dispersible surface coating composition.
  • the product coating compositions have enhanced tannin blocking properties and also such salt addition does not substantially reduce the scrub or wet adhesion properties of the compositions.
  • the surface coating paint composition can be applied to at least a portion of a surface of a wood- containing substrate.
  • the surface coating or paint upon drying, forms a dried (nonaqueous) resultant coating composition that typically has a better tannin-blocking property than the same coating composition not containing the salt derived from the sol or gel composition described herein.
  • sufficient salt i.e., a tannin blocking-enhancing amount of ⁇ salt
  • sufficient sol or gel-containing salt is ad ⁇ mixed with a composition containing a polymer and/or a paste stock in an amount to increase the tannin block ⁇ ing property of a surface coating composition of the invention compared to the same surface coating compo ⁇ sition not containing the salt from the sol or gel composition.
  • the dried sol or gel composition or (2) the dried product admixture composition or (3) the dried surface coating compositions described herein of the instant invention are capable of reducing the effects of tannins.
  • a tannin blocking-enhancing amount of the salt is homogeneously distributed in the surface coating composition of the invention or its precursor by a method involving admixing a sol or gel composi ⁇ tion containing sufficient salt with a composition containing a polymer and ordinarily also with a sur ⁇ face coating paste stock.
  • the concentra ⁇ tion of salt homogeneously distributed in the surface coating composition is about 0.02 and about 1 weight percent.
  • concentration of sol or gel composition in the surface coating composition which is necessary to achieve such salt concentrations is usually about 0.1 to about 5 weight percent. Further ⁇ more, the concentration of salt in the sol or gel composition is usually about 1 to about 50, preferably about 10 to about 20 weight percent.
  • the concentration of the sol or gel in the product admixture composition is usually about 0.5 to about 25 weight percent, and the concen ⁇ tration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.1 to about 5 weight percent.
  • sol or gel compositions or product admixture compositions or surface coating compositions described herein include wood pretreat- ments, primers, stains and paints.
  • wood pretreatments may be water repellants
  • primers can include shellac, alkyd primer paint and acrylic latex primer paint
  • stains may be transparent oil based, semitransparent oil-based, transparent latex, semi- transparent latex, solid color oil or latex
  • paints can be oil-based or latex, indoor or outdoor and the like.
  • the preferred compositions contain latex.
  • the sol or gel compositions, the product admixture compositions or the surface coating composi ⁇ tions of the invention are applied either to the surface of an uncoated wood substrate, or applied to such substrates over a previously coated surface.
  • the applied surface coating composition of the invention is dried by suitable methods known in the art to produce a dried, resultant coating composition con ⁇ taining a coalesced polymer and salt components de ⁇ rived from the sol or gel composition.
  • the resulting coated substrate comprising the wood substrate and the dried resultant surface coating composition of the invention has a dried resultant surface coating having an enhanced tannin blocking property compared to a comparable coating composition not prepared with the sol or gel composi ⁇ tion described herein.
  • a coated substrate comprising a wood-containing substrate and the dried resultant surface coating composition or the surface coating composition may, in addition to the tannin blocking properties, contain a controlled quantity of sol or gel composition and/or salt contained therein, so as to have controlled opacity and/or color and other visual effects.
  • the resulting coated substrates produced by the combination of the dried resultant coating compo ⁇ sition and the wood substrate upon which the surface coating composition of the invention is at least partially applied also depend upon the reaction be ⁇ tween the coating composition of the invention and the particular wood substrate that is coated.
  • an accelerated weathering evaluation of the tannin block property of the compositions described herein is determined by applying a single coating of the evaluation composition on a wood-containing sub ⁇ strate, such as redwood, cedar and the like, drying the coating for at least one half hour, and exposing the substrate to 4 hour intervals of light (using UVB- 313 lamps at 45° C.) and moist darkness for at least one week.
  • a typical evaluation of tannin block properties involves the placement of coated wood- containing substrates in a QUV Weatherometer (Q-Panel Company, Cleveland, Ohio) for one week and visual observation of the wood grains and the discoloration of the coating.
  • the salt-contain ⁇ ing sol or gel is admixed with a latex polymer, water and a surface coating paste stock to produce a water- dispersible surface coating composition.
  • the product coating compositions have enhanced corrosion protec ⁇ tion properties and such salt addition does not sub ⁇ stantially reduce the scrub or wet adhesion properties of the compositions.
  • the surface coating or paint composition can be applied to at least a portion of a surface of a free metal-containing or substrate.
  • a free metal- containing substrate contains at least a portion of a free metal or alloys contain ⁇ ing mixtures of free metals.
  • Typical free metal- containing substrates comprise, for instance, iron, mild steel, cast iron, wrought iron, galvanized steel, stainless steel, aluminum, copper, brass, alloys thereof, and other corrodible free metals.
  • the dried sol or gel composition or (2) the dried product admixture composition or (3) the dried surface coating compositions of the invention described herein are capable of reducing or inhibiting the effects of corrosion.
  • the free metal-containing substrate coated (and dried) with the compositions containing the salt-containing sol or gel compositions of the invention exhibit either (1) a substantially greater time interval before corrosion effects are indicated on the free metal-containing substrate or (2) less surface area indicating the effects of corrosion over a given period of time in a given environment.
  • the product admixture composition, surface coating or paint When applied to a mild steel substrate (the mild steel containing less than 1 weight percent of carbon) , the product admixture composition, surface coating or paint, upon drying, forms a dried composition that typically prevents the formation of rust on the mild steel substrate for at least one week under accelerated weathering conditions.
  • sufficient salt i.e., a corrosion protection-enhancing amount of salt
  • sufficient sol or gel containing salt is ad ⁇ mixed with a composition containing a polymer (and/or a paste stock) in an amount which prevents the forma ⁇ tion of rust under accelerated weathering conditions for at least 4 days on a mild steel "Q" panel sub ⁇ strate.
  • "Q" panels contain uncoated mild steel.
  • the product admixture composition, surface coating compo ⁇ sition or paint composition is applied to the "Q" pan ⁇ el, dried for one week and subjected to accelerated weathering conditions which are either "salt fog" conditions or QUV Weatherometer conditions for at least 4 days.
  • free metal-containing substrates coated with the dried compositions of the invention exhibit corrosion ef ⁇ fects (such as rusting) on less than 0.2 percent of the surface area, and usually on less than 0.1 percent of the surface area, after at least 4 days under either the "salt fog" or Weatherometer conditions.
  • the surface coating compositions described herein exhibit suitable or improved properties with respect to abrasion, impact, adhesion, flexibility, moisture vapor trans ⁇ mission, pendulum hardness and dry temperature resist ⁇ ance.
  • An amount of the salt which enhances the corrosion prevention property of the surface coating composition is homogeneously distributed in the sur ⁇ face coating composition of the invention or its precursor by a method involving admixing a sol or gel composition containing sufficient salt with a composi ⁇ tion containing a polymer.
  • the particular salt utilized, the particular amount of sol or gel composition and salt amount utilized depends upon the particular polymer utilized and the particular sub ⁇ strate that is coated.
  • the concentration of salt homogeneously distributed in the surface coating com ⁇ position is about 0.02 and about 1 weight percent.
  • the concentration of sol or gel composition in the surface coating composition which is necessary to achieve such salt concentrations is usually about 0.1 to about 5 weight percent.
  • the concentration of salt in the sol or gel composition is usually about 1 to about 50, preferably about 10 to about 20 weight percent.
  • the concentration of the sol or gel in the product admixture composition is usually about 0.5 to about 25 weight percent, and the concentration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.1 to about 5 weight percent.
  • sol or gel compositions, the product admixture compositions or the surface coating composi ⁇ tions of the invention are applied either to the surface of an uncoated solid metal-containing sub ⁇ strate, or applied to such substrates over a previous ⁇ ly coated surface.
  • Such applied compositions of the invention are dried or cured by suitable methods known in the art (generally exposure to air) to produce a dried, resultant protective coating composition con ⁇ taining a coalesced polymer and salt components de ⁇ rived from the sol or gel composition.
  • the resulting coated substrate containing both a solid free metal-containing substrate and the dried resultant protective surface coating composition of the invention has a dried resultant surface coating having an enhanced corrosion prevention property compared to that of a similar coating composition not prepared with the sol or gel composition described herein.
  • the surface coating compositions of the invention may, in addition to the corrosion protection properties, contain a controlled quantity of sol or gel composition and/or salt contained therein, so as to have desired opacity and/or color and other visual effects.
  • the resulting coated substrates produced by the combination of the dried resultant coating compo ⁇ sition and the solid substrate upon which the surface coating composition of the invention is at least partially applied may also depend upon the reaction between the salt contained in the sol or gel composi- tion in the coating compositions of the invention and the particular substrate that is coated.
  • the dried resultant protective surface coating paint or product admixture composition of the present invention con ⁇ tained as a portion of a coated substrate comprising a corrosion-prone substrate (i.e., a free metal-contain ⁇ ing substrate) , has a corrosion-reducing or corrosion- inhibiting property.
  • Mechanisms for corrosion protec ⁇ tion may vary, depending upon which salts, polymers and substrates are involved.
  • inhibitive salt pigments utilizing a sacrificial cathodic mecha ⁇ nism may be utilized in the sol or gel compositions.
  • Some forms of barrier salts may be provided by the sol or gel compositions.
  • Latex and oil-based polymer compositions may vary the permeability of the applied coating composition in combination with the particular salt utilized.
  • iron-containing and non-iron- containing substrates may typically be protected from corrosion by different mechanisms.
  • the present invention encompasses salts, introduced into the product admixture, surface coating or paint compositions described herein, which utilize whatever suitable mechanism which reduces the corro ⁇ sion of a free metal-containing substrate as compared to the same respective polymer containing compositions except not containing the salts derived from the sol or gel compositions.
  • the salt-containing sol or gel compositions, the stable product admixture composition or the sur ⁇ face coating compositons described herein can be utilized in an aqueous form or in a dried form and employed as a catalyst, or be applied to a substrate to provide catalytic properties to a resultant cata ⁇ lytic composition.
  • a substrate contacted with such salt-containing compositions is typically a solid substrate such as wood, paper, porous refracory oxides, free and alloyed metal, ceramic, plastic, glass, cement, combinations thereof, and the like. »
  • the resultant catalytic composition is useful to promote any process for which the salt components are known to be effective.
  • a resultant salt- containing catalytic composition containing ceramic or porous refractory oxides such as zeolites or aluminas is employed to promote hydrocarbon conversion reaction during upgrading of hydrocarbon-containing feedstocks.
  • Resultant salt-containing catalytic compositions containing cellulose (paper) substrates can be uti ⁇ lized in automobile filters, etc.-
  • the presence of the salt dispersed in the resultant latex polymer/salt composition provides an improved electrical (alternating or direct) conductive or semiconductive property compared to the starting polymer without the added salt.
  • the resultant latex polymer/salt compositions exhibit conductive proper ⁇ ties greater than about 10 ""7 Seimens/cm.
  • the result ⁇ ant latex polymer/salt composition is ordinarily capable of conducting at least 0.5 microamperes of alternating electrical current when 5,000 volts (AC) of electricity are applied between brass electrodes that are one inch apart.
  • One electrical testing apparatus suitable for conducting this test is avail ⁇ able from Biddle Instruments (Model No. 22005) of Philadelphia, Pennsyvlania.
  • Such electrical conduc ⁇ tive properties are applied, as for example, when the product admixture composition is coated and dried on a textile material such as carpet backing fibers to provide antistatic properties to the carpeting.
  • a starting textile material useful in the present invention includes assemblies of natural or synthetic fibers, filaments, yarns, and the like, as for example, wovens,- nonwovens, knitted textiles, threads, ropes, yarns, etc., which are employed, in one form or another, either alone or as components of composite articles.
  • reference to fibers includes filaments and yarns.
  • the fibers may be obtained from animals (for example, wool, hair, silk, fur and the like) , from vegetable matter (as for example, cotton, flax, hemp, straw and the like) , from minerals or metals (for example, asbestos, aluminum, gold, etc.), or from commercial synthesis (for exam ⁇ ple, polymers such as rayon, nylon, polyester acryl ⁇ ics, polyurethanes, glass fiber, etc.), either wholly crystalline like asbestos and metal wires, wholly amorphous like glass, or in the case of the preferred group of fibers, e.g., polymer compositions, partly crystalline and partly amorphous.
  • textile materials treated in accordance with the present invention include nonwovens such as hospital sheets, gowns, masks, diapers, roofing materials, napkins, tile backings (for ungrouted tile prior to installa ⁇ tion) , drapery materials, clothing materials (includ ⁇ ing apparel interlinings and interfacings) , carpet materials, consumer and industrial wipes, towels, carpet and rug backings, components of automobile tops, roadbed underlay ents, insulation, siding, interior wall and ceiling finishes, quilts, mattress pads, mattress covers, sleeping bags, furniture under ⁇ layments (padding) , air filters, carpet underlayments (e.g., carpet pads), padding and packaging for stored and shipped materials, floor care pads, crib kick pads, house robes, furniture and toss pillows, kitchen and industrial scrub pads, and others too numerous to mention.
  • nonwovens such as hospital sheets, gowns, masks, diapers, roofing materials, napkins, tile backings (for ungrouted tile prior to installa ⁇ tion) , drapery materials, clothing materials (in
  • Such starting textile materials provide the fiber substrate which is suffused by the herein de ⁇ scribed sol or gel composition or product admixture composition containing a sol or gel and a polymer.
  • the word "suffuse” is used to describe the mechanism by which the components of the sol or gel composition or components of the admixture product composition are contacted and held to the fibers of the textile mate ⁇ rial.
  • the invention embraces whatever mechanism, including adsorption, absorption, diffusion, deposi ⁇ tion, chemical reaction, etc. , or some combination of such mechanisms, by which the components of the sol or gel composition or admixture product composition are retained by the fibers of the textile material.
  • the contacting methods include, but are not limited to, total incorporation, including solution, emulsifica- tion, dispersion and chemical reaction; surface incor ⁇ poration, including coating, deposition and impregna ⁇ tion; and combinations thereof.
  • water is usually removed from the treated composition by any drying method which is ordinarily employed for drying the particular textile material.
  • the product admixture compositions may be mixed with a filler to produce a compounded polymer/ salt product composition which may be combined with a starting textile material to produce a textile composition containing a latex polymer, a salt (in a salt-containing sol or gel) and a filler material.
  • a starting textile material such as carpet backing surfaces.
  • a textile composition containing a latex polymer, a salt (in a salt-containing sol or gel) and a filler material.
  • Such compositions are typically applied to carpet backing surfaces.
  • either the front or back surface of a textile material may be contacted with the sol or gel composition described herein to produce a textile composition containing components of the sol or gel.
  • the filler material is optional; e.g., the filler is employed to replace at least a portion of the sol or gel composition or product admixture compo ⁇ sition primarily to reduce the expense of the prepara ⁇ tion method and finished product.
  • the sol or gel composition described herein or the product admixture composition containing the sol or gel components and the polymer described herein are mixed with a filler material, and option ⁇ ally one or more emulsified compatible plasticizers, and further optionally a frothing agent.
  • the amount of salt contained in the sol or gel composition is dependent upon the amount of salt needed to be added to a starting textile material to provide an electrical conductivity to a textile compo ⁇ sition that is greater than the electrical conductivi ⁇ ty of the textile composition without the added salt.
  • the textile composition of the invention contains sufficient salt suffused therein to provide at least 5 percent, preferably at least 10 percent, and most preferably at least 25 percent greater elec ⁇ trical conductivity than the textile composition without the added salt.
  • the textile composition of the invention ordinarily contains added salt in an amount greater than 0.1 weight percent, usually greater than 0.3 weight percent and preferably greater than 0.5 weight percent.
  • the amount of salt contained in the product admixture composition of sol or gel and poly ⁇ mer is dependent upon the particular composition of polymer and the particular salt comprising the product admixture, ordinarily the salt contained in the sol or gel composition -which is added to the composition containing the polymer comprises sufficient additional salt to provide an antistatic property to the treated textile composition of the invention.
  • the term "added salt” or “additional salt”, as used herein, refers to any amount of salt added to the composition containing a polymer or to the starting textile material which converts such compositions or materials (1) from having no antistatic property to having antistatic property (2) or from having low antistatic property to having increased antistatic property.
  • the weight percent of sufficient added salt in the product admixture composition is usually greater than 0.05, preferably greater than 0.1, and most preferably greater than 0.5.
  • Such product admixture compositions when applied to starting textile materi ⁇ als provide effective antistatic properties to the textile composition of the invention, i.e., the tex ⁇ tile composition usually has an electrical conductivi ⁇ ty greater than 10 ⁇ 10 Seimens/c , preferably in the range from about 10 ⁇ 8 Seimens/cm to about 10 Seimens/cm, and most preferably from about 0.1 Sei ⁇ mens/cm to about 10 Seimens/cm.
  • Suitable compatible plasticizers if uti ⁇ lized, depend upon the polymer combined with the sol or gel composition, and in an amount required to obtain a desired flexibility, lowered glass transition temperature (Tg) or softness.
  • Fillers are added to the sol or gel composition or, in the alter ⁇ native, to the product admixture containing the compo ⁇ nents of the sol or gel and a polymer, in an amount of at least about ' 50 parts by weight per hundred parts by weight (dry) of the polymer.
  • the filler is added in an amount from about 100 to about 500, pref- erably from about 200 to about 400, parts by weight per hundred parts by weight (dry) of the polymer.
  • Examples of useful fillers are calcium carbonate (particularly from a source such as limestone) , ba- rytes, diatomaceous earth, aluminum trihydrates, hydrated aluminum silicates (clays) , particularly from a source such as mica or talc, and the like and mix ⁇ tures thereof.
  • Calcium carbonate is highly preferred.
  • An unusual feature of the invention is the compatibility of the product admixture composition (containing a sol or gel composition and a polymer, preferably a latex polymer) with a filler material.
  • the filler material has a pH greater than about 4.0, preferably greater than about 7.0 and typically in the range from about 8.0 to about 11.0.
  • the sol or gel composition or the product admixture composi ⁇ tions containing the sol or gel admixture with the polymer are acidic and have a pH less than 7.0 and typically less than 4.0
  • the compounded polymer/salt product composition obtained from mixing the sol or gel or product admixture compositions with the filler material itself is stable and noncoagulated, having well dispersed components (such as salt) therein, i.e. no coagulation or precipitation of the admixed compo ⁇ nent is observed.
  • the compounded polymer/salt product composition containing the filler material usually has a pH in the range from about 7.0 to about 9.0 and is capable of being readily suffused with a starting textile material to produce the textile composition of the invention.
  • a frothing agent may be used in a minor amount by weight (dry) sufficient to froth a polymer composition, i.e., the product admixture composition comprising a latex polymer and sol or gel containing a salt.
  • the frothing agent is usually used to form a froth or foam of the composition containing the latex polymer, filler and optionally the emulsi ⁇ fied plasticizer.
  • Frothing agents well known in the art may be utilized in the invention.
  • a suitable frothing agent comprises urea, the sodium salt of condensed naphthalene, sulfonic acid, mixed C 8 -C 18 fatty alcohols, ammonium or sodium lauryl sulfate and water.
  • the frothing of a polymer-containing (i.e., latex) mixture or composition can be conducted in an Oakes, Firestone or other type foamer using air or an inert gas such as nitrogen to the desired froth densi ⁇ ty. Also, mixtures of frothing agents can be used. Other compounding ingredients may be added to the product admixture composition such as thicken ⁇ ers, pigment colors, coalescence aids, additional surfactants, defoamers for use during blending and the like.
  • the sols or gels described herein can be applied to the back or front of any textile material, particularly to aid in securing base yarns of the textile and may also be applied to a secondary back ⁇ ing.
  • the sols or gels, product admixtures or compounded polymer/salt product compositions may be applied to piled or tufted carpet material.
  • a com ⁇ pounded polymer/salt product composition can be ap ⁇ plied to a textile material, preferably a carpet, by means typical for the particular textile material and then dried (such as air or oven dried) to produce a dried compounded polymer/salt product composition which provides the textile material with antistatic properties.
  • Such a dried compounded polymer/salt product composition contains a greater amount, prefer ⁇ ably at least 10 percent greater, and most preferably at least 25 percent greater amount of salt than is contained in a composition not prepared by introducing the salt into the composition by addition of a salt- •* containing sol or gel composition.
  • the textile composition of the invention containing a textile material suffused with at least one salt, ordinarily has an electrical conductivity greater than 10 ⁇ 10 Seimens/cm, and usually greater than 10 ⁇ 8 Seimens/cm.
  • Favorable antistatic properties are imparted to the textile composition of the inven ⁇ tion when the electrical conductivity of the textile composition is in the range from about 10 ⁇ 8 Seimens/cm to about 10 Seimens/cm, and preferably from about 0.1 to about 10 Seimens/cm.
  • a sol containing cupric acetate is prepared as follows: to a 1 liter container is added 246 grams of ethylene glycol solvent, 166 grams of citric acid (monohydrate) stabilizer, 50 grams of cupric acetate (dihydrate) and 21.4 grams of concentrated nitric acid. From room temperature (about 25°C), the mix ⁇ ture is slowly heated to 65°C. and held at 65°C. for 10 hours. A clear, transparent product sol is formed having a blue color. The transparent blue-colored sol contains cupric cations, acetate anions and colloidal size cupric acetate salt particles dispersed in the liquid medium. Such a product is cooled to room temperature and the transparent product becomes opaque.
  • the transparent product is a stable sol having a pH of 0.1 and a viscosity of 290 cps.
  • EXAMPLE 2 Stable citric acid/ethylene glycol/nitric acid sols containing various salts are prepared in the same manner as in Example 1, except various salts require different temperatures sufficient to form the sol. These temperatures and the characteristics of the resulting sols are shown in Table A.
  • EXAMPLE 3 A sol is prepared in the same manner as in Example 1, except the 166 grams of citric acid monohy- drate stabilizer is replaced with 166 grams of a nonionic surfactant stabilizer which is a polyethoxy- lated nonylphenol surfactant having 9 moles of ethyl ⁇ ene oxide per mole. Also, no nitric acid is added to the cooled admixture. The resulting sol is transpar- ent and has a green color, a pH of 2.8 and a viscosity of 155 cps.
  • EXAMPLE 5 Sols containing cupric acetate prepared in the same manner as in Examples 1 and 3, except the stabilizer is replaced in each sol with an individual ⁇ ly different nonionic surfactant. Characteristics of the sols including product viscosity, pH, surfactant Hydrophilic-Lipophlic Balance (HLB) , and the sol forming temperature are summarized in Table C.
  • HLB Hydrophilic-Lipophlic Balance
  • Polyoxethylene glycol 1500 85 2.9 165
  • Tetronic 304 Tetronic 704 Tetronic 904 Tetronic 1102 Tetronic 1504
  • Pluronic and Tetronic nonionic surfactants contain mix ⁇ tures of polyols as determined by basic grid figures 2 and 6, pp. 2 and 4, respectively, disclosed in "Pluronic Tetronic Surfactants," copyright BASF (1987).
  • EXAMPLE 6 Sols containing cupric acetate are prepared in the same manner as in Example 5, except each sol contains a mixture of nonionic surfactants as the stabilizer. The sols exhibit the following character ⁇ istics as shown in Table D.
  • Igepal CO530 6 mol EO nonylphenol
  • Igepal CO890 40 mol EO nonylphenol
  • Example 2 the same manner as in Example 1, except the polyol solvents in Table E are substituted for the ethylene glycol solvent.
  • the temperature required to form the sol, pH of the sol and viscosity of the sol are summa ⁇ rized in Table E.
  • a cupric acetate salt is admixed with a commercially available latex polymer composition (designated as as "76 RES 4400" available from Union Chemicals Division of Unocal Corp., i.e., "UCD") containing a styrene butadiene rubber (SBR) , to pro- prise a noncoagulated product admixture composition containing the stable, latex polymer together with the cupric acetate salt uniformly dispersed in the product admixture.
  • the cupric acetate salt is added to the composition containing the latex polymer by addition of the sol prepared in Example 1 containing the cupric acetate salt.
  • cupric acetate- containing sol One part by weight of the cupric acetate- containing sol is admixed with 29 parts by weight of the composition containing the latex polymer to pro ⁇ consider a stable, noncoagulated product admixture compo ⁇ sition containing cupric acetate salt, including cupric cations, uniformly dispersed in the latex polymer.
  • the stable product admixture indicates the sol and latex polymer are compatible, the resulting latex polymer product admixture being blue in color and no coagulation of the latex polymer composition being observed for at least one month following admix ⁇ ing.
  • EXAMPLE 9 Several compositions containing .latex poly ⁇ mers other than that in Example 8 are admixed in separate tests with the sol of Example 1.
  • the follow- ing commercially available UCD compositions containing latex polymer derived by emulsion polymerization are all compatible (i.e., form stable, noncoagulated % product admixtures) with the cupric acetate sol when admixed in the same manner as in Example 8: (76 RES 3103) polyvinylacetate, (76 RES 1019) styrene/acry- late, (76 RES 9608) acrylic, (76 RES 701) polyvinyli- dene chloride and (76 RES 661) vinyl acrylics.
  • Citric acid/ethylene glycol/nitric acid sols from Examples 1 and 2 are compatibly combined with 76 RES 4400 in the same manner as in Example 8.
  • the product admixture is prepared in a 3.5 inch Petri dish and air dried at room temperature for 1 week.
  • the dried resultant latex polymer/salt films contain ⁇ ing the various salts (and/or cations and/or anions) have the electrical conductivity properties summarized in Table F.
  • the Biddle Model No. 22005 Electric Testing Equipment is used to test the dried resultant latex polymer/salt films.
  • the Biddle Testing Equip ⁇ ment contains brass strips which are placed one inch * apart and voltage is applied while determining current
  • Aluminum Acetate 2700 Aluminum Nitrate 1000 Ammonium Acetate 950 Ammonium Molybdate 1700 Ammonium Molybdocobaltate 1700 Ammonium Nitrate 1500 Antimony Acetate 2000 Antimony Ethyleneglycoxide 2300
  • EXAMPLE 11 Some cupric acetate/ethylene glycol/nitric acid sols from Examples 5 and 6 using different non ⁇ ionic surfactants as stabilizers of the sol are com ⁇ patibly admixed with 76 RES 4400 SBR latex and dried in the same manner as in Example 10. The dried re ⁇ sultant latex polymer/salt compositions are tested as in Example 10 and the observed current flow data summarized in Table G.
  • Polyoxyethylene glycol 400 Polyoxyethylene glycol 600 Polyoxyethylene glycol 1000 Polyoxyethylene glycol 1500
  • EXAMPLE 12 Sols prepared in Example 4 are admixed with 76 RES 4400 SBR latex, dried, and the resultant latex polymer/salt compositions tested for electrical con ⁇ ductivity in the same manner as in Example 10. The dried sol/latex products are tested as in Example 10 and the observed current flow data summarized in Table H.
  • EXAMPLE 14 A sol containing neodymium nitrate is prepared as follows: to a 1 liter container is added 492 grams of ethylene glycol solvent, 332 grams of 9 mol EO nonyl ⁇ phenol surfactant stabilizer (i.e., a nonionic sur ⁇ factant which is a polyethoxylated nonylphenol sur ⁇ factant having 9 moles of ethylene oxide per mole) and 100 grams of neodymium nitrate (pentahydrate) . From room temperature (about 25°C), the mixture is slowly heated to 40°C. and held at 40°C. for 4 hours. A clear, transparent product sol is formed having a violet color.
  • 9 EO nonyl ⁇ phenol surfactant stabilizer i.e., a nonionic sur ⁇ factant which is a polyethoxylated nonylphenol sur ⁇ factant having 9 moles of ethylene oxide per mole
  • neodymium nitrate penentahydrate
  • the transparent violet colored sol contains neodymium cations (Nd 3+ ) , nitrate anions and colloidal size neodymium nitrate salt particles dis ⁇ persed in the liquid medium. Such a product is then cooled to room temperature.
  • the transparent product is a stable sol having a pH of 2.73 and a viscosity of 98
  • a neodymium nitrate salt is admixed with 76 RES 4400 to produce a noncoagulated product admixture composition containing the stable, latex polymer together with the neodymium nitrate salt uniformly dispersed in the product admixture.
  • the neodymium nitrate salt is added to the composition containing the latex polymer by addition of the sol prepared in Example 1 containing the neodymium nitrate salt.
  • One part by weight (30 grams) of the neodymium nitrate containing sol is admixed with 9 parts by weight (270 grams) of the composition containing the latex polymer to produce a stable, noncoagulated product admixture composition containing neodymium nitrate salt, including neodymium (Nd 3+ ) cations, uniformly dispersed in the latex polymer.
  • the stable product admixture indicates the sol and latex polymer are compatible, with the resultant latex polymer product admixture being not coagulated. No coagula ⁇ tion of the latex polymer composition is observed for at least four months following admixing.
  • the resultant latex polymer product admixture is then compounded with a filler material containing calcium carbonate (CaC0 3 ) to produce a compounded latex/salt product.
  • the compounding is done by blend ⁇ ing 31 grams of the resultant latex polymer/salt product admixture with 67 grams Franklin limestone filler material, 0.16 grams sodium vinyl sulfonate frothing agent, and 2.1 grams water.
  • the blend is then thickened to 6000 cps. by the addition of 35 grams of a polyacrylic acid/polyacrylamide product thickener (i.e., Jarco 1111). Thirty grams of this compounded latex/salt product is poured into a 3 inch Petri dish and air dried.
  • EXAMPLE 16 Several sols prepared according to the pro ⁇ cedure in Example 14 are compatibly combined with 76 RES 4400 in the same manner as in Example 15. Each product admixture is prepared in a 3.5 inch Petri dish and air dried at room temperature for 1 week.
  • the dried resultant latex polymer/salt films containing the various salts (and/or cations cations and/or anions) have the electrical conductivity properties summarized in Table K.
  • the Biddle Model No. 22005 Electric Testing Equipment is used to test the dried resultant latex polymer/salt films.
  • the Biddle Test ⁇ ing Equipment contains brass strips which are placed one inch apart and voltage is applied while determin ⁇ ing current flow. The observed alternating electrical current flow (microamperes) at the indicated applied voltage (kilovolts, KV) as summarized in Table K for several compounded dried resultant latex polymer/salt films is as follows:
  • Example 15 In a procedure similar to that in Example 15 a 1-liter reactor is charged with 246 grams ethylene glycol, 166 grams citric acid (monohydrate) , 50 grams neodymium nitrate (pentahydrate) , and 21 grams nitric acid. The mixture is heated at 40° C. for 6 hours. The transparent product when cooled to room tempera ⁇ ture has a pH of 0.1 and a Brookfield viscosity of 193 cps.
  • Dysprosium nitrate and ammonium nitrate are used to prepare citric acid sols in the same manner.
  • the dysprosium sol has a pH of *0.1 and a Brookfield viscosity of 326 cps.
  • the ammonium sol has a pH of 0.1 and a Brookfield viscosity of 396 cps.
  • EXAMPLE 18 Sols from Example 17 using citric acid as a stabilizer of the sol are compatibly admixed with 76 RES 4400 SBR latex and dried in the same manner as in Example 15. The dried resultant latex polymer/salt compositions are tested as in Example 16 and the observed current flow data summarized in Table L.
  • Example 14 Using the method of Examples 15 and 16, the weight percent of neodymium nitrate/nonionic sol of Example 14 is varied in the 76 RES 4400 SBR latex of Example 15 and evaluated by the Biddle testing method of Example 16.
  • the amount of compounded latex/salt product composi ⁇ tion used is 80 grams, which is applied to the carpet backing using a #40 drawdown rod.
  • the textile composition (i.e., dried carpet) is evaluated using the Biddle testing equipment in a similar manner as in Example 16. Measurements are made in three directions: (1) the cross direction, (2) the machine direction, and (3) on a diagonal line using a 36 inch spacing between the brass electrodes. The values for 5 KV applied voltage are: cross, 3100 microamps; machine, 500 microamps; diagonal, 3200 microamps.
  • a sample of carpet treated similarly but without the neodymium sol component shows the follow ⁇ ing current flows at 5 KV applied voltage: ⁇ cross, 4 microamps; machine, 11 microamps; diagonal, 4 mi ⁇ croamps.
  • EXAMPLE 21 A 1-liter kettle is charged with 50g lanthanum nitrate, 246g ethylene glycol, 166g citric acid, and 15ml (21.4g) concentrated nitric acid. The mixture is heated at 50° C. for 6 hours, and then cooled to room temperature. The clear, straw colored sol had a pH ⁇ 0.1 and a Brookfield viscosity 226 cps. The sol ' contains about 10 weight percent of the lan ⁇ thanum nitrate salt. Various other sols are prepared in the same manner. These sols are blended with vinyl acrylic latex (76 RES 3077, available from UCD, Schau - burg, Illinois).
  • sol/latex product admixture is then made into formulated paint useful for semi-gloss architec ⁇ tural coatings applications.
  • the following materials are blended at 400 rpm using a 4-inch Cowels blade: 1845g water, 610g 1,3-propylene glycol, 31g Natrasol 250HR, 8.9 colloid 681-F, 70.9g Tanol 731, 26.6g Igepal CO630, 8.9g phenylmercuric acetate, and 2215 Tronox CR800.
  • the blend is then ground at 1800 rpm for 2 hours to achieve a grind gauge value of 7NS.
  • the material is cooled to room temperature and the following ingredi ⁇ ents are added at 400 rpm: 117g Texanol, 17.7 col ⁇ loid, 681-F, and 886g water.
  • the resulting material is a paste stock for paint.
  • the formulated paint is prepared using 124.3g paste stock, 75.3g sol/latex, and 0.38g Triton GR-5. These ingredients are blended at 400 rpm for 20 minutes.
  • Plain white Leneta Charts Form WB (Leneta Company, Ho-Ho-Kus, New Jersey) is coated with com ⁇ pounded paints from Example 21 using a 6 mil drawdown bar (Gardner, Bethesda, Maryland) .
  • the panels are air dried under controlled conditions for 1 week under conditions including 50% humidity and 73° F.
  • the gloss readings in the following Table N are made using a 60° Glossgard II meter (Gardner, Bethesda, Maryland) .
  • Black scrub test panels (Leneta, Ho-Ho-Kus, New Jersey) Form P-121-10N are coated with compounded paints from Example 21 using a 6 mil drawdown bar (Gardner, Bethesda, Maryland) . The panels are dried l week at 73° F. and 50% humidity. The scrub performance is determined in accordance with the procedure of ASTM D2486-79 using a straight line washability and abra ⁇ sion machine (Model MA1492, Gardner, Bethesda, Mary ⁇ land) and standard scrub medium SC-2, abrasive type (Leneta, Ho-Ho-Kus, New Jersey) .
  • Plain white Leneta Charts Form WB (Leneta Company, Ho-Ho-Kus, New Jersey) are coated with black enamel paint (such as interior/exterior 54-309 from Pittsburgh Paints, Pittsburgh, Pennsylvania) prepared from sols in the same manner as in Examples 21 and 22 while using a 10 mil drawdown bar (Gardner, Bethesda, Maryland) , and dried for 1 week at 73° F. and 50% humidity.
  • the wet adhesion performance is determined using the wet pick and peel procedure of ASTM D3359- 83.
  • Example 21 The compounded paint of Example 21 (contain ⁇ ing 10 weight percent sol in latex which is 3.35 weight percent lanthanum nitrate in the sol/latex) along with other lanthanum nitrate sols containing different amounts of lanthanum nitrate at the same and other sol/latex weight ratios are evaluated for scrub, gloss and wet adhesion as described in Examples 22, 23 and 24.
  • Example 21 The method of Example 21 is used to prepare sols from commercial quality lanthanum nitrate (ob ⁇ tained from Molycorp, Washington, Pennsylvania) .
  • the sols are used to prepare paints as in Example 21, and then tested as described in Examples 22, 23 and 24.
  • EXAMPLE 27 A 2 liter resin kettle is charged with 492g ethylene glycol, lOOg aluminum acetate, 333g citric acid, and 30ml concentrated nitric acid. The mixture is heated to 70° C. for 4 hours. The material is then cooled to room temperature. The resulting straw colored sol has a pH of ⁇ 0.1 and a Brookfield viscosi ⁇ ty of 450 cps.
  • the sol is blended into a commercial sty- rene-vinyl acrylic latex (commercially available as 76 RES 6510 from UCD, herein "Unocal”).
  • the sol to latex weight ratio is 1:10, obtained by using 36.0g sol and 324.Og latex.
  • the product paint is obtained by blending 360.Og of the sol/latex product admixture composition into 1225.8g of the paint paste stock.
  • the resulting formulation had a viscosity of 95KU, a density of 11.81 lbs/gal and a total solids of 58.1% by weight.
  • EXAMPLE 28 The rough finished side of redwood clap board is painted by brush with the paint obtained in Example 27. An additional section of board is painted with a paint formulation like that in Example 1, except without the sol, and 360.Og of Unocal 76 RES 6510 styrene-vinyl acrylic latex is used. Single coats of paint are compared subjectively and visually upon drying for 30 minutes. The paint prepared from the aluminum acetate sol and latex hid the redwood grain better than the comparable paint without the sol.
  • EXAMPLE 29 Several sols containing salts and ethylene glycol solvent are evaluated as tannin block agents.
  • Four latexes are used: a styrene-vinyl acrylic latex (Unocal 76 RES 6510), a polyvinylacetate, i.e., PVA latex (Unocal 76 RES 60011) , a polyvinylacetate, i.e.
  • PVA latex (Unocal 76 RES 6004) and a styrene butadiene rubber, i.e. SBR latex (Unocal 76 RES 4076).
  • Product admixture compositions containing sol and latex in a 1:10 weight ratio, respectively, are prepared and added to the paint paste stock of Example 27 to pro ⁇ cute product paints as set forth in Example 27.
  • the sols containing a citric acid stabilizer are prepared in the same manner as in Example 27 and the sols containing nonionic surfactant stabilizers (Igepal C0610, CO620, C0630 - phenoxypolyoxyethylenes) are also prepared in the same manner as in Example 27, except no nitric acid is added.
  • the product paints are evaluated in the same manner as in Example 28.
  • the paint compositions of Table S indicate that several sols in combination with various kinds of latexes give good tannin block performance as freshly painted coatings on redwood board.
  • All product paints are evaluated for per ⁇ formance under accelerated weathering conditions. Redwood panels are placed in a QUV Weatherometer for 1 week using 4 hour cycles of light (using UVB-313 lamps, 45° C.) and moist darkness. The panels are again evaluated for tannin block performance. Al ⁇ though all the product paint compositions exhibit suitable tannin blocking performance, substantially better performance without discoloration of the coat ⁇ ing is observed in all four latex paints containing the aluminum acetate-containing sol prepared with a citric acid stabilizer.
  • EXAMPLE 30 Several aluminum salts are utilized to prepare sols containing ethylene glycol solvent using the method of Examples 27 and 29. Using the method of Example 27, paints are prepared with various aluminum- containing salts in respective sols and combined with the latexes of Example 39 and the paint paste stock of Example 27. The product paint compositions are tested as in Examples 28 and 29 and the evaluations summa ⁇ rized in Table T.
  • EXAMPLE 32 A citric acid stabilized sol is prepared using 20 weight of aluminum acetate. The sol is blended with latexes utilized in Example 30 at 5%, 10% and 15 weight percent (based on the latex) , which are then utilized with the paint paste stock of Example 27 to prepare three product paint compositions, which are evaluated under weathering QUV conditions.
  • Example 34 The method of Example 27 is used to prepare a tetrapropylammonium bromide-containing sol. Forty nine and nine-tenths grams (49.9g) tetrapropylammonium bromide, 246g ethylene glycol, 166.4g citric acid, and no nitric acid are combined. The admixture is heated at 40° C. for 1 hour. The product sol has a pH ⁇ 0.1 and a viscosity of 344 cps.
  • a paint paste is prepared using 397.4g water, 8g Natrosol Plus, 5.5g Colloid 226/35, 2.0g Igepal CO630, 3.0g Colloid 640, 2.0g AMP-95, 1.5g potassium tripolyphosphate, 125g Tronox CR822, 150g Minex 4, lOOg ASP-NC2, 20g ethylene glycol, 1.5g Nuosept 95, 10.g Texanol, 3g Colloid 643, and 6g Polyphase AFl.
  • a sol/latex product admixture composition prepared from 30g of the above-prepared sol and 270g of a PVA latex, (Unocal 76 RES 3077) , are blended with equal quanti ⁇ ties of the above-prepared paint paste, but in one paint the aluminum acetate sol of Example 27 is re ⁇ placed by tetrapropylammonium bromide sol and no sol is admixed with the latex in the other.
  • the product paint compositions are applied to coat redwood.
  • the tannin blocking property of the paints are observed in Table X.
  • the tetrapropylammonium bromide sol-containing paint exhibits better tannin blocking properties than the aluminum acetate sol-containing paint when a PVA latex (Unocal 76 RES 3077) is employed in the paint formulation of Example 27.
  • PVA latex Unocal 76 RES 3077
  • Such results indicate the tannin blocking property of a paint or surface coating composition is dependent on the particular latex and/or the particular paint paste utilized with a given sol or gel composition.
  • EXAMPLE 35 A 2-liter resin kettle is charged with 491.3g 1,5-pentanediol, 99.82g zinc acetate, 332.7g citric acid and 30 ml concentrated nitric acid. The mixture is heated to 65° C. for 6 hours. The material is cooled to room temperature. The resulting material is a sol having a pH of ⁇ 0.1.
  • EXAMPLE 36 A 1-liter resin kettle is charged with 246g ethylene glycol, 50g zinc acetate, and 166g of a nonionic surfactant Igepal CO630 polyoxyethylene nonylphenol. The mixture is heated to 40° C. for 6 hours. Upon cooling to room temperature, the result ⁇ ing material is a sol having a pH of 2.12 and a vis ⁇ cosity of 175 cps (Brookfield) .
  • Sols containing magnesium, manganese, mer- curous, strontium and uranyl nitrates are prepared in the same manner as the above-mentioned sol containing zinc acetate, ethylene glycol and the nonionic sur ⁇ factant.
  • the pH and viscosity properties of the sols are summarized in Table Y as follows:
  • the sols of Examples 35 and 36 are each admixed with a latex.
  • Each sol is separately mixed with a styrene-acrylate or and a polyvinylidene chlo ⁇ ride (commercially available as 76 RES 1018 and 76 RES 5517, respectively, from UCD.
  • the sol to latex weight ratio is 1:9, obtained by using 36.Og sol and 324g latex.
  • the sols are drawn down on steel Q panels using a 10 mil drawdown bar. The panels are dried for 1 week. The panels are then subjected to a salt fog (3%NaCl) at 80° C. for 100 hours in a Model No.
  • EXAMPLE 38 A 1-liter resin kettle is charged with 246g ethylene glycol, 50g sodium molybdate, 166g citric acid, and 15 ml concentrated citric acid. The mixture is heated at 45° C. for 3 hours. The product is cooled to room temperature to produce a sol. The sol has a pH of 0.1 and a viscosity of 216 cps (Brook ⁇ field) .
  • Sols containing sodium chromate and sodium phosphate (monobasic) are similarly prepared.
  • the pH and viscosity properties of the sols are shown in Table AA.
  • the sols of Example 38 are separately ad ⁇ mixed with Unocal latexes containing polyvinyl acry ⁇ late (i.e., Unocal 76 RES 3077 and 76 RES 3083).
  • Unocal 76 RES 3077 and 76 RES 3083 The sol and latex product admixture compositions are drawn down on steel Q panels using a 10ml drawdown bar. The panels are air dried for 1 week. The panels are then subjected to QUV Weatherometer conditions for 1 week with alternating 4 hour intervals of light and dark ⁇ ness, and overlapping alternating 4 hour rain Simula- tions (using tap water) . Corrosion evaluations on uncoated panels, panels coated with latex containing no sol, and panels coated with product admixture compositions containing sol and latex are summarized in Table BB.
  • Table BB The results in Table BB indicate that the sol/latex coated panels can reduce corrosion by at least about 10 times and often at least about 100 times that of panels coated with the same latex but containing the salt from the sol.

Abstract

An electrically conductive polymer composition containing a nonconjugated polymer and a salt is prepared by admixing a sol or gel composition containing the salt with a polymer. A novel sol or gel composition containing a nonionic surfactant stabilizer is useful for preparing the electrically conductive composition. An intermediate mixture of salt, stabilizer and solvent are heated to prepare a sol or gel which is typically admixed with a latex to produce a product admixture containing the salt and a latex polymer. The product admixture is dried to produce a resultant salt latex polymer composition having electrically conductive properties useful, as for example, as an antistatic textile (carpet) coating. Gloss, tannin block and corrosion-inhibiting properties in surface coating compositions are increased by admixing the salt-containing sol or gel with a polymer and a surface coating past stock.

Description

LATEX/SOL OR GEL SYSTEMS
BACKGROUND OF THE INVENTION The invention relates to polymer composi¬ tions, sol or gel compositions, electrically conduc¬ tive compositions containing a latex polymer, and the preparations thereof.
This invention relates to the field of textile materials, to antistatic materials, to a composition useful for providing antistatic properties to tex¬ tiles, and to methods for manufacturing and using such materials.
The present invention relates to sol or gel compositions capable of enhancing the gloss of paints and particularly semi-gloss latex paints.
The present invention relates to sol or gel compositions capable of enhancing the tannin blocking property of surface coatings and paints, and particu¬ larly latex paints applied to outdoor wood surfaces. The present invention relates to sol or gel compositions capable of enhancing the corrosion-pro¬ tection properties of surface coating compositions and paints and particularly latex paints.
The achievement of tailored electrical properties of compositions containing polymers is usually pursued in several ways. One approach con¬ sists of modifying the intrinsic bulk properties of polymers by processing, especially by pyrolysis. In this approach, acceptable electrical properties are developed by altering the chemical composition or structure of the initial material. A second approach is to attain the desired conductivity by incorporating macroscopic pieces of conducting material (metal flakes, carbon-black particulates, or carbon fibers, for example) in host polymers to form conducting composites. It is the traditional approach in the preparation of conducting polymers and is used today in the fabrication of nearly all commercial products based on conductive polymers. Another approach fo¬ cuses on increasing the electrical conductance of conjugated polymers (i.e., polymers which already have at least some electrical conductance) at the molecular level by controlled incorporation of molecular dopants that may or may not form charge-transfer complexes with » the host conjugated polymer. It is called molecular doping because it consists of diffusing isolated molecular dopants (AsF5 or I2, for example) into conjugated polymers.
Polymers capable of being stabilized in aqueous media are called latex polymers and a latex ordinarily contains at least one latex polymer and at least one surfactant dispersed in water. Presently, latex polymers are not conjugated, e.g. , latex poly¬ mers are considered insulators. In order to produce acceptable electrical conductance properties in compo¬ sitions containing latex polymers, materials responsi¬ ble for such conductance must be compatibly combined with the latex. Compositions containing latex poly¬ mers coagulate when admixed with aqueous solutions of salts. For instance, an aqueous solution of cupric acetate added to a latex composition containing sty- rene butadiene rubber will cause coagulation of the styrene butadiene rubber within a short time after contac .
«
*■ However, investigators have prepared hydro-
\ sols which contain materials such as colloidal antimo- ny oxide in an attempt to find materials which may be added compatibly to a latex composition (i.e., added without coagulation) . For example, in U.S. Patent No. 3,960,989 issued to Petrow et al. , a colloidal antimo¬ ny oxide (hydrosol) was mixed in equal amounts with polyvinylidene chloride (PVDC) to improve the clarity of PVDC films.
The search continues for methods to compati¬ bly mix salts with latex polymers. The resultant admixture of latex and salt provides for a number of useful compositions such as electrically conductive compositions containing latex polymers.
The field of textile materials involves all man¬ ufactured forms of fiber assemblies including wovens, nonwovens, knitted articles, threads, yarns, ropes, etc. which are employed, in one form or another, in almost every aspect of commercial and household use, either alone or as components of composite articles. For sometime, the accumulation of static electricity as a result of the utilization of fabric assemblies is a phenomenon which has commanded the attention of the textile industry, particularly the carpet industry. Static is a cause of annoyance (e.g., items of apparel cling to the body and are attracted to other garments; fine particles of lint and dust are attracted to upholstery fabrics, increasing the frequency of re¬ quiring cleaning; one experiences a jolt or shock upon touching a metal doorknob after walking across a carpet). Also static is the cause of danger (e.g., a discharge of static electricity can result in sparks capable of igniting flammable mixtures such as ether/air, which are commonly found in hospitals, especially in operating rooms) . Static discharge can also harm sensitive electrical equipment such as com puters and scientific equipment. Representative places where carpets are used having these require¬ ments are in hospitals, computer rooms, ballrooms, restaurants and theaters. All of these effects of static are accentuated in atmospheres of low relative humidity.
Of the many proposals for preventing the unde¬ sirable buildup of static electricity, the most satis factory, with respect to their efficiency and perma¬ nence, appear to be those which involve fibers pos¬ sessing electrical conductivity (e.g., metal fibers, fibers coated with electrically conductive material, or metallic laminate filaments) in combination with common, natural and synthetic fibers to produce a woven, nonwoven, knitted, netted, tufted or otherwise fabricated structure, which readily dissipates the static charges as they are generated.
Several fiber structures have been employed to alleviate the static problem. The manufacture of metallic or carbonized fibers of fine denier, espe¬ cially in the form of mono ilaments, is a difficult and costly operation; and since such fibers are quite dissimilar in character from ordinary textile fibers, problems arise in connection with blending and proc¬ essing as well in the handling of the products ob¬ tained. Another structure, a metallic laminate fila¬ ment, does not present blending and processing prob¬ lems because of the close similarity to ordinary textile fibers, and the handling of the products obtained is consequently not objectionable. However, the cost of such filaments is high when compared with the natural or synthetic fibers with which they are blended. A third group of structures, textile fiber substrates whose surfaces have been coated with finely divided particles of electrically conductive material by vapor deposition, electrodeposition, or by the application of adhesive compositions, are in some cases less costly than metal or carbonized fibers and/or metallic laminate filaments, depending upon the nature of the electrically conductive material em¬ ployed. However, these are difficult to fabricate because large chambers are required to enclose the material to be subjected to electro- or vapordeposi- tion. Such coatings are often found lacking in cohe¬ sion and adhesion and are frequently too thick to be practicable in some applications — especially when the nature of the electrically conductive particulate matter is such that a high concentration thereof is required for satisfactory conductivity. Economy is achieved, therefore, only through sacrifices in dura¬ bility or conductivity of the fiber.
Also, extrusion of blends of powdered synthetic polymers and finely divided electrically conductive material (e.g. , carbon black, and metallic powders or flakes) into either fibers or fibrous coated sub¬ strates having the same or a different polymeric composition, is well known. Unfortunately, blends requiring a high concentration of the electrically conductive material are often not readily extruded, if at all, in any fibers. Also, coated fibrous sub¬ strates, are lacking in cohesion and adhesion. Meth¬ ods for preparing blends of extrudates involve either (a) total incorporation of particles in the fiber or substrate (as to be obtained by the spinning of a solution or a melt containing them) , or (b) surface incorporation of particles, achieved by the use of (1) an adhesive — e.g., to produce a true coating — or (2) impregnation of the particles into a fiber surface which has been softened or made tacky by means of a liquid softening agent and/or heat. The total incor¬ poration of particles in the fiber or substrate and the use of an adhesive to bind the particles in the fiber or substrate as a true coating are inadequate and undesirable, because of (1) loss of properties such as conductivity as a result of disruption of the structural integrity of the fiber and (2) a low degree of durability.
Some materials can be dissolved into an adhesive mixture to provide antistatic performance. These materials include quaternary ammonium salts and some inorganic salts. However, only a few materials are available because they are usually not compatible with polymeric, (e.g. latex) adhesives, and those that are are difficult to incorporate into a wide variety of formulations.
In the preparation of compositions containing polymers, particularly latex, extremely small quanti¬ ties of catalysts, activators, etc. are added during synthesis. Usually a resulting latex such as styrene butadiene rubber (SBR) contains up to about 1 weight percent of such materials, and acrylic or vinyl acryl¬ ic latexes contain about 0.1 weight percent. Also, anionic surfactants of up to 1 weight percent are used to stabilize latex emulsions. These materials are not antistatic. In order to produce acceptable electrical conductivity in a latex, salt materials must be com¬ patibly combined with the latex in a sufficient con¬ centration to provide ade»quate antistatic properties to textile materials to which the latex is applied. However, heretofore salts other than those used as described above which are added to a latex in concen¬ trations sufficient to give antistatic performance tend to cause coagulation of the latex. The search continues for polymer compositions containing suffi¬ cient, compatible, flexible and inexpensive salt materials to be effective for providing antistatic properties when applied to textile materials.
Surface coating compositions typically include such materials as paints, lacquers and var- nishes. Paints contain pigmented materials whereas lacquers or varnishes are generally clear or transpar¬ ent. The purposes of surface coatings are aesthetic and/or protective. A coating can enhance the appear¬ ance of a substrate in terms of color and gloss as well as give protection against such problems as weathering or corrosion.
In.terms of appearance, particularly gloss properties, paints can be divided into three basic categories, namely, (1) flat paints having a specular gloss of less than about 15 percent reflectance, (2) semi-gloss paints having a specular gloss of about 35 to about 50 percent reflectance, and (3) high-gloss paints having a specular gloss greater than about 70 percent reflectance based upon light having about a 60° angle of incidence. Oil-base paints can easily be formulated into these three categories of paints. However, it is difficult to formulate waterborne paints, particularly water-dispersible (latex) paints having a high specular gloss. With respect to color, both dyes and pigments can contribute to color. Dyes usually have good solubility in paint compositions; however, the durability of such paints is lacking. In contrast to dye-containing paints, pigments in paint formulations exhibit better durability, but such pig ented paints have relatively poor solubility of the pigments.
Wood is widely used in buildings for such items as roof trusses, timber frames, joists, doors, window frames, cladding and fencing. However, wood is vulnerable to a variety of degrading influences, often caused by weathering, which include light, moisture and biological attack. A phenomenon of the weathering of wood is the generation of tannins which migrate in the wood. Tannins in wood are essentially derivatives of tannic acid (also called gallotannic phenolics) . Tannins, and their migration in wood, can cause visi¬ bility of wood grains through inferior wood surface coatings or can cause discoloration of the coating.
In order to block the effects of tannins, a primer surface coating is usually applied to wood, allowed to dry, and then an overcoat is applied. However, the search continues for better overcoats and for surface coating compositions which require only a single coating application and yet effectively block the effects of tannins in wood substrates. To this end, more effective components of coating compositions which serve as tannin blocking agents are presently being sought.
In terms of corrosion protection, particu¬ larly corrosion protective properties relating to free metal-containing substrates, alternative and improved surface coatings or paints are still being sought. Free metal-containing substrates, particularly iron- containing substrates such as mild steel, cast iron, wrought iron, and the like, and others such as galvan¬ ized steel, aluminum, copper, brass, alloys thereof, etc. , are vulnerable to exposure damage (i.e. , corro¬ sion) without some form of protection. Corrosion includes dry (oxidative) corrosion and stress corro¬ sion. Surface coating defects related to corrosion include rusting, blistering, delamination, undercut¬ ting, under-rusting and film form corrosion. Some of the factors which influence the extent to which a surface coating composition or paint will protect metal-containing substrates from corrosion include permeability to water and oxygen, ion migration through the coating film, electrical resistance of the coating, adhesive performance under wet conditions, alkali resistance, the presence of materials which act to inhibit corrosion and the absence of materials which promote corrosion. Such factors have been considered during formulation of oil-base surface coatings and paints. However, it is difficult to formulate waterborne paints, particularly water-dis¬ persible (latex) paints having a high corrosion pro¬ tection property. The inability to readily formulate corrosion-protective, tannin blocking, and semi-gloss and high gloss latex paints is a significant drawback since oil-base paints are being phased out due to en vironmental restrictions limiting the volatile organic compounds (VOC) content of paints.
SUMMARY OF THE INVENTION The invention relates to a substantially nonaqueous composition containing a latex polymer and a salt. The salt is dispersed in the latex polymer in the form of anions and cations and/or colloidal salt particulates. The resultant latex polymer/salt compo¬ sition is usually prepared by admixing a composition containing a starting latex polymer with a sol or gel containing a salt.
In one embodiment of the invention, a novel process is used to prepare a nonaqueous sol or gel wherein at least one nonaqueous solvent, at least one stabilizer, and at least one salt are admixed and then heated to a temperature sufficient to produce a sol or gel containing the salt. An acidic component is also usually added to the admixture prior to heating. The nonaqueous solvent is usually a form of polyhydroxyl ether or polyhydroxyl alcohol, the stabilizer is usually a chelator, such as a hydroxycarboxylic acid, or a nonionic surfactant, and the admixture is usually heated to a temperature less than 100° C. to form a product sol or gel composition. After cooling with optional addition of more acid component, such a product sol or gel may be admixed with a composition containing a latex polymer to produce a stable, nonco- agulated product admixture composition containing a latex polymer and a salt.
In another embodiment, a novel sol or gel composition contains at" least one solvent, at least one salt, and a stabilizer comprising a nonionic surfactant. A typical nonionic surfactant has the formula
R- (E0) χ (P0) y-R1
wherein each of R and Rx is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide and x and y are nonnegative integers, but not simultaneously zero.
In still another embodiment, the invention relates to a novel intermediate composition useful in the preparation of a sol or gel. The composition includes a mixture of at least one solvent, at least one salt, and a stabilizer comprising a nonionic surfactant. Ordinarily the solvent is nonaqueous, and the pH is less than 7.0 and is capable of being heated to form a sol or gel.
The sol or gel compositions of the invention may be admixed with a composition containing a polymer to produce a product admixture containing the sol or gel and the polymer. The product admixture is dried to produce a product composition containing the salt from the sol or gel and the polymer. The salt is dispersed in the polymer in a form compatible to the particular polymer.
In a preferred embodiment of the invention, a stable, noncoagulated product admixture composition is prepared by admixing an above-mentioned sol or gel composition with a composition containing a latex polymer. The stable, noncoagulated product admixture containing the latex polymer and sol or gel is dried to produce a resultant latex polymer/salt composition which is highly useful as a latex polymer composition having electrically conductive properties.
The invention relates to a textile composition having antistatic properties. The textile composition contains a textile treated with a sol or gel composi¬ tion containing a salt so that the salt is dispersed on the surface of or among the fibers comprising the textile. The sol or gel composition may be admixed with a polymer, such as a latex polymer, to produce a product admixture composition which can be employed to treat a textile. Ordinarily, the product admixture composition is combined with a filler material to produce a compounded polymer/salt product composition which may then be utilized to treat a starting textile material such as carpet to produce a textile composi¬ tion of the invention. The textile product composi¬ tion of the invention usually has an electrical con¬ ductivity in the range effective for controlling static electricity, i.e., from about 10~8 to about 10 Seimens/cm.
The present invention also involves a method for enhancing the gloss property of a surface coating composition, including a paint composition. A sol or gel composition containing a salt is added to a poly¬ mer composition, or to a surface coating or paint composition containing a polymer, or to a surface coating precursor composition containing a polymer, to produce a product surface coating or paint composition having an enhanced gloss property. The salt in the sol or gel composition is contained in sufficient amount to increase the specular gloss, usually by at least about 2 percent reflectance, based upon light having about 60° angle of incidence.
The invention also involves a surface coat¬ ing composition comprising a polymer binder and a salt homogeneously distributed in the composition. The surface coating composition, particularly a waterborne surface coating composition, comprises a sol or gel composition containing a gloss-enhancing amount of salt, at least one water-soluble or water-dispersible polymer binder, and usually a paste stock containing such ingredients as pigments, coalescing aids, thick¬ ening aids, dispersing aids, defoamers, biocides, and fillers.
The surface coating compositions of the invention prepared from the sol or gel composition and polymer are applied to several substrates. The re¬ sultant dried surface coating compositions and the coated substrates formed therefrom provide composi¬ tions having enhanced gloss properties compared to compositions not prepared with sol or gel composi¬ tions. Such compositions and coated substrates of the invention retain adequate scrub and wet adhesion properties while gloss is enhanced.
The present invention also involves a method for enhancing the tannin blocking property of a sur¬ face coating composition, including a paint composi¬ tion. A sol or gel composition containing a salt is added to a polymer composition, or to a surface coat¬ ing or paint composition containing a polymer, or to a surface coating precursor composition containing a polymer, to produce a product surface coating or paint composition having an enhanced tannin blocking proper¬ ty. The salt in the sol or gel composition is con¬ tained in sufficient amount to increase the tannin blocking property of the surface coating composition prepared therefrom. In general, the particular salt utilized and the particular amount of sol or gel composition and salt utilized, depends upon the par¬ ticular polymer utilized and the particular substrate that is coated.
The invention also involves a surface coat¬ ing composition comprising a polymer binder and a salt homogeneously distributed in the composition in suffi¬ cient concentration to block the effects of tannins contained in a wood-containing substrate, i.e., to prolong the visibility of wood grains of the substrate through the coating and/or discoloration of the coat¬ ing. The surface coating composition, particularly a waterborne surface coating composition, comprises a sol or gel composition containing a tannin block- enhancing amount of salt, at least one water-soluble or water-dispersible polymer binder, and usually a paste stock containing such ingredients as pigments, coa¬ lescing aids, thickening aids, dispersing aids, de¬ foamers, biocides, and fillers.
The surface coating compositions of the invention prepared from the sol or gel composition and polymer are applied to wood-containing substrates. The resultant dried surface coating compositions and the coated substrates formed therefrom provide compo¬ sitions having enhanced tannin-blocking properties compared to compositions not prepared with the de¬ scribed sol or gel compositions. One of the advan¬ tages of the compositions described herein as useful for coating wood-containing substrates is that a single coat of such compositions provides tannin blocking properties which are as effective as a con¬ ventional two-coat application.
The present invention further involves a method for preventing the corrosion of free metal- containing substrates. The method includes enhancing the corrosion protection property of a surface coating composition, including a paint composition, which is applied to such substrates. A sol or gel composition containing a salt is added to a polymer-containing composition, preferably to a surface coating or paint composition containing a polymer, to produce a product surface coating composition having an enhanced corro¬ sion protection property. The salt in the sol or gel composition is contained in sufficient amount to prevent corrosion on a free metal-containing substrate when the surface coating composition containing the salt is coated and dried on the substrate.
The invention also involves a surface coat¬ ing composition comprising a polymer binder and a salt homogeneously distributed in the composition in suffi¬ cient concentration to inhibit the effects of corro¬ sion on a free metal-containing substrate. The pro¬ tective surface coating composition, particularly a waterborne surface coating composition, comprises a sol or gel composition containing a corrosion protec¬ tion-enhancing amount of salt, at least one water- soluble or water-dispersible polymer binder, and usually a paste stock containing such ingredients as pigments, coalescing aids, thickening aids, dispersing aids, defoamers, biocides, and fillers. The protective surface coating compositions of the invention prepared from the sol or gel composi¬ tion and polymer may be applied to several different free metal-containing substrates. The resultant dried surface coating compositions and the coated free metal-containing substrates formed therefrom provide compositions having substantially enhanced corrosion protection properties compared to compositions not prepared with the described sol or gel compositions. Such compositions and less corrosion-prone coated free metal-containing substrates produced therefrom also retain adequate scrub and wet adhesion properties while gloss is enhanced.
Other applications of the resultant latex polymer/salt compositions include their use as bioci- dal polymers, polymer coatings for anodic and cathodic protection, microwave food coatings, gloss enhanced polymers, laminated coatings as barriers to stain migration in textiles and floor coverings, sorbents containing flame retardant sols, polymers useful as delay cross linkers in reservoir plugging, polymers for thermal heating elements, catalytic agents, and antistatic adhesive tapes. DETAILED DESCRIPTION OF THE INVENTION A sol or gel is prepared for addition to a composition containing a polymer, preferably a latex polymer. The sol or gel composition is prepared by admixing, in any order, at least one solvent, at least one stabilizer, and at least one salt. In an alterna¬ tive embodiment, an acidic component may also be added to the admixture. The sol or gel compositions are typically acidic in nature, i.e., have a pH less than about 7.0, and contain a salt, a nona-queous solvent, a stabilizer and, optionally, an acidic component.
Typical solvents utilized in the preparation of the sol or gel include nona-queous solvents such as organic solvents, such as ether, ester, alcohol or combinations thereof, and particularly polyols, such as for example a polyhydroxyl ether or a polyhydroxyl alcohol. Nonaqueous sols or gels containing organic solvents and essentially no water are typically re¬ ferred to as organosols or organogels. More particu¬ lar examples of useful solvents for preparing organo¬ sols or organogels include ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyoxyethlene-polypropylene) glycol and blocked (polyoxyethlene-polyoxypropylene) glycol. In the preparation of the sol or gel compo¬ sition, at least one stabilizer is added to the admix¬ ture. The stabilizer is usually a chelator and/or a nonionic surfactant. Examples of common chelators useful in the invention are hydroxycarboxylic acids such as citric acid, tartaric acid, mesotartaric acid, glycolic acid, A-hydroxybutyric acid, mandelic acid, glyceric acid, malic acid, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, acontic acid and lactic acid, with citric acid being the most highly preferred. The nonionic surfactant stabilizers ordinarily contain ethylene oxide (EO) and/or propylene oxide (PO) . The nonionic surfactant stabilizers may also include mixed EO-PO or blocked EO-PO arrays. One example of a nonionic surfactant has the formula
R-(EO)χ(PO)y-R1 wherein each of R and R1 is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals, and x and y are nonnegative integers, but not simulta¬ neously zero. Another nonionic stabilizer is a glyc¬ erine derived nonionic surfactant having the formula (EO)χ(PO)y-R glycerine (EO)a(PO)^-R1 (EO)m(PO)n-R1:L wherein each of R, R1 and R11 is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla- ryl, dialkylaryl aliphatic ester and aryl ester radi¬ cals, and x, y, a, b, m and n are nonnegative inte¬ gers, but not simultaneously zero. Illustrative of nonionic surfactants are alkylpolyglycol ethers such as ethoxylation products of lauryl, oleyl, and stearyl alcohols or mixtures of such alcohols as coconut fatty alcohols; alkylphenol polyglycol ethers such as et¬ hoxylation products of octyl- or nonylphenol, diiso- propylphenol, triisopropylphenol, di- or tritertiary- butyl phenol, etc. Preferred nonionic surfactants include mono- or di-alkyl oxyalkylated phenolics. A highly preferred nonionic surfactant useful herein contains about 1 to about 100 percent by weight of ethylene oxide, in combination with 0 to about 99 percent by weight of propylene oxide and has a molecu¬ lar weight from about 62 to about 5,000. Examples of such surfactants include 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco- hoi, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol RO octyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate or monocetylate, monomystralate or monos- tearate. Numerous other examples of suitable nonionic surfactants are disclosed in U.S. Pat. Nos. 2,600,831, 2,271,622, 2271,623, 2,275,727, 2,787,604, 2,816,920, and 2,739,891, the disclosures of which are incorpo¬ rated herein by reference in their entireties.
Any salt is useful in the sol or gel compo¬ sitions; however, salts which provide an acidic sol or gel composition are preferred in the invention. Both organic and inorganic salts may be utilized. The salt speciesa in the sol or gel must be capable of (1) existing as colloidal salt particulates, (2) existing in ion species or (3) forming ions when dispersed in a composition containing a polymer, particularly a latex polymer. In the formation of a sol or gel, the salt contains cations or anions capable of being dispersed in the admixture of solvent and stabilizer, and fur¬ ther being capable of being dispersed in the polymer composition contained in the stable product admixture composition of salt-containing sol or gel and polymer. The anions or cations of the salt are usually metallic cations or metallic-containing anions, monomeric nonmetallic cations or monomeric nonmetallic anions, or polymeric nonmetallic cations or polymeric nonme¬ tallic anions. Any metal or nonmetal may be contained in the cations or anions. Useful metallic cations of the salt include the cations of antimony, yttrium, cadmium, silver, calcium, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseo¬ dymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, strontium, ytterbium, titanium, tantalum, tungsten and mercury. Examples of useful monomeric nonmetallic cations of the salt include ammonium, boron and silicon-containing cations. Useful monomeric nonmetallic anions of the salt in¬ clude those containing nitrates, acetates, halides, borates, chromates, molybdates, silymolybdates, for¬ mates, citrates, benzoates, tartrates, phosphates, plumbates, silicates, nitrites, carbonates, oxides and alkoxides. Examples of a number of metallic-contain¬ ing anions useful herein include those containing the elements arsenic, chromium, manganese, tin, aluminum, titanium, zirconium, vanadium or molybdenum. Salts useful herein containing nonmetallic anions typically contain an element such as fluorine, oxygen, nitrogen, carbon, tellurium, selenium, phosphorus, sulfur, chlorine, bromine and iodine. Furthermore, the salts may provide polymeric cations such as monoolefinic quaternary ammonium cations, diolefinic quaternary ammonium cations, triolefinic quaternary ammonium cations and tetraolefinic quaternary ammonium cations. Also the salts may contain polymeric anions such as alkyl, aryl, ether, or alkylaryl sulfonates, sulfates, phosphates, carboxylates and polycarboxylates, partic¬ ularly the salts producing an acidic sol or gel compo¬ sition.
Although the particular salt contained in the sol or gel composition of the invention may be highly dependent on the particular polymer in which it is combined in a stable product admixture composition, some particularly useful salts contained in sols or gels which are utilized to prepare surface coating compositions include the acetates, chromates, cit¬ rates, molybdates, nitrates, phosphates, bromates, halides and silicates of the herein disclosed cations. For instance, highly preferred salts for improving gloss in a surface coating composition may contain a rare earth metallic cation, such as lanthanum, exam¬ ples include lanthanum, acetate, lanthanum chloride, lanthanum nitrate and lanthanum oxide or a silicon- containing salt such as silicon acetate. In the case of a surface coating composition having useful proper¬ ties for tannin blocking on wood substrates, salts which contain aluminum metallic cations are preferred, such as aluminum acetate, aluminum chloride, aluminum nitrate and aluminum isoperoxide. In the case of a surface coating composition requiring corrosion pro¬ tective salts, highly preferred salts contain at least one divalent cation such as a zinc cation, and partic¬ ularly, in combination with chromates, molybdates, phosphates and silicates. Other highly preferred divalent cations for corrosion protection purposes include barium, cadmium, calcium, copper, magnesium, mercury and strontium.
In the process of preparing the sol or gel, an acidic component is sometimes added to the admix¬ ture of solvent, stabilizer and salt. Usually the acid component is added to provide for a transparent product. The acidic component is usually a protic acid, such as concentrated nitric acid, concentrated hydrochloric acid or concentrated sulfuric acid; however, a Lewis acid may also be utilized. An acidic component may be added to the admixture of solvent, stabilizer and salt either before, during or after the admixture is heated to a temperature sufficient to form a sol or gel.
The admixture of solvent, stabilizer and salt, and optionally an acidic component is ordinarily prepared at room temperature and the temperature raised usually to less than 100° C. to produce a sol or gel containing the desired salt. The temperature to which the admixture is heated is usually dependent upon the particular salt or salts contained in the admixture; however, a significant number of admixtures containing a salt, particularly an inorganic salt, are heated to a temperature in the range from about 30° C. to about 90° C. and more preferably in the range from about 35° C. to about 85° C. In one embodiment for preparing the sol or gel containing a solvent, stabi¬ lizer, salt and acidic component, the ingredients are admixed at room temperature and slowly heated to a temperature in the range from about 35° C. to about 85° C. for a period sufficient to produce a transparent product, ordinarily from about 0.5 to about 15 hours and having the color of the characteristic anion or cation of the particular salt in the admixture. The transparent product is a sol or gel composition con¬ taining the cations and anions and/or colloidal salt particulates of the particular salt of the admixture. Often the transparent product becomes cloudy or opaque when the admixture is cooled to room temperature. If the transparent product becomes opaque or cloudy, additional sufficient portions of the acidic component may be added to the opaque product to produce a sol or gel composition having substantially the same degree of transparency and clarity as observed at the elevat¬ ed temperature necessary to initially form the sol or gel.
Whether or not the acidic component is added to the admixture of solvent, stabilizer and salt, the pH of the admixture, either before or after heating, is generally less than 7.0 and usually less than 4.0. It is preferred that the pH of the admixture of the sol or gel composition be less than about 3.0, partic¬ ularly when the acidic component is added to the admixture, and it is highly preferred that the pH be less than about 1.0. Also, as will be seen hereinaf¬ ter in the examples, many instances exist where the pH of the sol or gel composition is less than about 0.1. The pH of the sol or gel composition can readily be determined with a conventional pH meter such as Orion Model No. 701.
In another embodiment of the invention, a novel sol or gel composition is prepared by heating a mixture of at least one solvent with at least one salt and a stabilizer containing a nonionic surfactant. An acidic component may optionally be added to the admix¬ ture either before or after heating the admixture to a temperature sufficient to form a sol or gel composi¬ tion; typically such a temperature is in the range from about 30° to about 95° C. The solvent is typi¬ cally a nonaqueous solvent, commonly an organic sol¬ vent, which, in admixture with the nonionic surfactant and the salt, comprises an organosol or organogel when the temperature of the admixture has been increased sufficiently to form the sol or gel composition.
The sol or gel composition described herein may be combined with a composition containing a poly- er to produce a product admixture containing the components of the sol or gel composition and the polymer.
Polymers contemplated for use herein include natural polymers such as polymerized oils (for in¬ stance vegetable oils found in varnishes) , cellulose- derived materials (for instance, nitrocellulose found in lacquers) , and various resins (for instance, those found in oil-based paints, lacquers or varnishes) , and the like; also synthetic polymers such as thermal plastic and thermal setting polymers as well as semi- synthetic polymers. Preferably, a stable, noncoagu¬ lated product admixture composition containing a latex polymer and a salt is prepared by admixing the sol or gel composition described herein with a composition containing a latex polymer. Although the above described sol or gel composition may be admixed with a composition containing any polymer, a latex polymer is preferably employed as the polymer to which the sol or gel composition is admixed. In a preferred embodi¬ ment, a stable, noncoagulated product admixture compo¬ sition containing a latex polymer and a salt is pre¬ pared by admixing a sol or gel composition described herein by charge addition, delay addition or post blending with a composition containing a latex polymer or at least one monomer composition containing at least one monomer unit of the latex polymer.
Due to the coagulation and instability problems associated with the water-dispersible poly¬ mers (particularly latex) with the addition of salts in significant concentrations (such as greater than 0.001 weight percent or more), the compatibility of the salt-containing sols or gels disclosed herein with the water-dispersible polymers is critical. The resulting stability of a latex after addition of significant amounts of salt from the salt-containing sol or gel (i.e. greater than 0.001, and preferably greater than 0.01 weight percent of salt in latex) renders a latex polymer the most highly preferred polymer for the invention disclosed herein. Exemplary polymers include, but are not limited to, resins, vinyl acrylic polymers, acrylic polymers, vinyl chlo¬ ride acrylic polymers, vinylidene chloride polymers, stryene-butadiene copolymers, stryene-acrylate copoly¬ mers and vinyl acetate-ethylene copolymers. As used herein, any polymer capable of being dispersed, emul¬ sified or suspended in a latex is considered a latex polymer. The latex polymer utilized herein is not conjugated. Preferred latex polymers of the invention as more specifically disclosed include (1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms, preferably containing at least 10 weight percent of the conjugat¬ ed diene monomers, and usually in combination with one or more alkenyl substituted monoaromatic monomers, typically in the range from about 1 to about 70 weight percent of the latex polymer, (2) olefin-ester inter- polymers containing a onoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid, preferably containing at least 10 weight percent of the polymer, (3) olefini- cally unsaturated carboxylic acid ester polymers containing polymerized, olefinically unsaturated monomers containing polymerized olefinically unsatu¬ rated carboxylic acid ester monomers, preferably containing at least 10 weight percent of the latex polymer, (4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units, preferably in the amount of at least 10 weight percent of the latex polymer, (5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and (6) combinations thereof.
A feature of the invention is that the salt contained in the sol or gel composition or in the stable product admixture composition is in a concen¬ tration which is greater than the lowest concentration of the same salt which otherwise effects destabiliza- tion of essentially the same product admixture compo¬ sition but essentially free of the salt from the sol or gel composition. The pH of the stable product admixture composition is less than 7.0, usually less than about 4.0, and preferably less than about 3.0.
The compositions containing starting latex polymers can be prepared as aqueous dispersions, emulsions, suspensions, and the like by procedures known in the art to be suitable for preparation of the aforementioned 5 classes of starting latex polymers. For instance, aqueous starting latex polymer disper¬ sions can be prepared by gradually adding each monomer simultaneously to an aqueous reaction medium at a rate proportionate to the respective percentage of each monomer in a finished polymer and initiating and continuing polymerization by providing in the aqueous reaction medium a suitable polymerization catalyst. Illustrative of such catalysts are free radical initi¬ ators and redox systems such as hydrogen peroxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide, lauryl peroxide, di-tertiarybutyl peroxide, bisazodiisobutyronitrile, either alone or together with one or more reducing components such as sodium bisulfite, sodium metabisulfite, glucose, ascorbic acid, erythorbic acid, etc. The reaction is continued with agitation at a temperature sufficient to maintain an adequate reaction rate until all added monomers are consumed. Monomer addition is usually continued until the latex (dispersion) reaches a polymer concentration of about 10 to about 70 weight percent, and usually about 40 to 70 weight percent.
Protective colloids may be added to an aqueous polymer dispersion either during or after the reaction period. Illustrative protective colloids include gum arabic, starch, alginates, and modified natural substances such as methyl-, ethyl-, hydroxyal- kyl-, and carboxy ethyl cellulose, and synthetic substances such as polyvinyl alcohol, polyvinyl pyrro- lidone, and mixtures of two or more of such sub- stances. Fillers and/or extenders, such as dispersible clays and colorants, including pigments and dyes, can also be added to the aqueous dispersions either during or after polymerization.
Polymer concentrations in compositions containing a starting latex polymer, particularly those with dispersions in aqueous media, are ordinari¬ ly greater than about 0.1 weight percent of the compo¬ sition. Usually the concentrations are greater than 1 weight percent and preferably greater than 5 weight percent, most preferably greater than 35 weight per¬ cent, but most commonly in the range from about 40 to 70 percent for those latexes resulting from emulsion polymerization. The dispersed polymer particles in the composition containing the latex polymer can be of any size suitable for the intended use, although particle sizes of usually at least about 120 nanome¬ ters are presently preferred since latex viscosity increases as particle size is reduced substantially below that level. Most often, the described latexes will have polymer particle sizes within the range from about 120 to about 300 nanometers as determined on the N-4 "Nanosizer" available from Colter Electronics, Inc., of Hialeah, Florida.
The stable, noncoagulated product admixture composition produced by the admixing of the sol or gel composition with the composition containing at least one latex polymer is usually dried by suitable methods known in the art to produce a dried, substantially nonaqueous resultant latex polymer/salt composition. For instance, when the composition containing at least one starting latex polymer is an a-queous dispersion, the product admixture composition is usually air dried or oven dried at a temperature less than about 100° C
The dried (nonaqueous) resultant latex polymer/salt composition ordinarily contains less water than contained in the aqueous dispersion of the starting latex polymer, and preferably contains sub¬ stantially no water, e. g. , less than 1 weight percent water in the resultant latex polymer/salt composition. The resultant latex polymer/salt composition usually contains the same starting latex polymer; however, it is within the scope of the present invention that the starting latex polymer can be converted to a different latex polymer after admixture of the sol or gel with the starting latex polymer. At least one cation and/or at least one anion of the salt is dis¬ persed in the dried resultant latex polymer/salt composition. Although the invention is not bound by any theory, it is believed that at least some of the particulates derived from the starting salt contained in the sol or gel exists as anions or cations of the salt or as colloidal salt particulates dispersed in the resultant latex polymer/salt composition. The derived ions or particulates are homogeneously dis¬ tributed in the salt/polymer composition comprising the stable product admixture composition of the inven¬ tion.
In general, the concentration of the salt in any of the compositions described herein is dependent upon the use of the particular composition. Ordinari¬ ly, a concentration of greater than about 0.001 weight percent of salt and typically greater than 0.1 weight percent of salt in the sol or gel composition is sufficient for most uses, although the dried product composition, such as the salt/ latex polymer composi¬ tion, may contain a considerably lower concentration of salt, such as greater than typical detectable limits, i.e., greater than about 10~7 weight percent, and preferably greater than 10~4 weight percent. However, usually either the aqueous stable product admixture composition or the dried salt/polymer compo¬ sition has a salt concentration greater than about 0.001 weight percent, typically more than about 0.01 weight percent and ordinarily greater than about 0.1 weight percent of salt in the polymer-containing composition. The dried salt/polymer composition of the invention typically has a salt concentration from about 1 to about 30 weight percent, and preferably about 5 to about 30 weight percent.
In an embodiment of the invention wherein the stable product admixture composition is a surface coating composition, the particular salt utilized, the particular amount of sol or gel composition and salt amount utilized, depends upon the particular polymer utilized and the particular substrate that is coated. Although the amount of salt contributed from the sol or gel and the amount of polymer are determined by the particular coating use, typically the concentration of salt homogeneously distributed in the stable product admixture composition (e.g., surface coating composi¬ tion) is about 0.02 and about 1 weight percent. Typ¬ ically the concentration of sol or gel composition in the stable product admixture composition (e.g., sur¬ face coating composition) which is necessary to achieve such salt concentrations is usually about 0.1 to about 5 weight percent. Furthermore, the concen¬ tration of salt in the sol or gel composition is usually about 1 to about 50, preferably about 10 to about 20 weight percent. Moreover, when the sol or gel composition is first admixed by charge addition, delay addition or post blending with the hereinbefore disclosed monomer or polymer composition to produce a stable product admixture composition prior to blending with a surface coating paste stock, the concentration of the sol or gel in the stable product admixture composition is usually about 0.5 to about 25 weight percent, and the concentration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.1 to about 5 weight percent.
The invention encompasses surface coating compositions which have a continuous and discontinuous phase, including paints, lacquers and varnishes. The surface coating composition contains a salt derived from a salt-containing sol or gel composition admixed with a composition containing a polymer. The inven- tion is particularly directed to a waterborne surface coating composition wherein the continuous water phase contains a binder comprising a water-soluble polymer, and, more particularly, to waterborne surface coating compositions wherein the discontinuous phase comprises a water-dispersible polymer binder, such as a latex. The discontinuous phase of the surface coating compo¬ sitions of the invention also contains salt components of the sol or gel compositions described herein and typically a paste stock usually containing one or more of the following components: a pigment, an extender pigment, a coalescing aid, a thickening aid, a dis¬ persing aid, a protective colloid, a defoamer, a biocide, an amine solubilizer, a flow additive, a drier, a cosolvent and a filler material. The water- borne coating compositions of the invention contain water, the sol or gel compositions described herein, usually a paste stock and either water-soluble poly¬ mers such as water-soluble resins, alkyds, polyureth- anes, unsaturated polyesters, and the like, or water- dispersible polymers such as latex polymers.
Although the invention is not bound by any theory, it is believed that at least some of the particulates derived from the starting salt contained in the sol or gel exists as anions or cations of the salt or as colloidal salt particulates, the derived particulates being homogeneously distributed in the resultant polymer/salt composition comprising the surface coating composition of the invention. Such colloidal salt particulates ordinarily have a diameter less than about 40 nanometers, usually less than about 20 nanometers, and often less than about 10 nanome¬ ters. In contrast to conventional surface coating compositions containing dispersed salts from a paste stock (including ground pigments comprising salts, i.e., salt pigments), which are ordinarily capable of settling over time, the salt components introduced into the surface coating compositions of the invention by means of the sol or gel compositions are continu¬ ously and permanently distributed throughout the sur face coating composition, or a precursor thereof, so as to be homogeneously distributed in the product composition. The term "homogeneously distributed" as used herein refers to those arrangements and distribu¬ tions of salt components (whether cations, anions or colloidal salt particulates) derived from the sol or gel composition being closer to the homogeneity and permanence existing in a true solution (wherein a salt is completely dissolved in water and permanently maintained in such a phase) than that in conventional surface coating compositions containing ground dis¬ persed salt pigments. The finely ground conventional dispersed paint pigment or other additive comprising a salt is considered herein to be heterogeneously dis¬ tributed in a surface coating composition. When viewing the distribution of salt components in surface coating compositions with visibility aids weaker than the ultra microscope, the homogeneity of the salt components of the compositions of the invention is better than that for the ground pigment salts, and the like, of conventional surface coating compositions. In the present context, the distribution and arrange¬ ment of butterfat particles in homogenized milk, when viewed through a magnifying glass, is considered homogeneous.
Although any polymer binder compatible with the salt components of the sol or gel compositions described herein may be utilized in a surface coating composition of the invention, water-dispersible poly¬ mers are preferred. In a preferred embodiment, a typical polymerization process yields an emulsion comprising a latex polymer and water. However, the emulsion can further comprise a surfactant, a chain transfer agent, catalysts, and activators.
The emulsion in combination with the salt- containing sol or gel compositions described herein (i.e., product admixture composition) can be used to replace at least a portion of the polymer binder used in a waterborne surface coating composition, such as a water-base paint composition containing a latex poly¬ mer. A typical surface coating or paint composition comprises an emulsion containing a polymer binder, salt (from a sol or gel) which is homogeneously dis¬ tributed therein, at least one pigment, a coalescing aid, a thickening aid, a dispersing aid, a defoamer, a biocide, and a filler. Coalescing aids, thickening aids, dispersing aids, defoamers, biocides and fillers suitable for use in surface coating paint compositions are well known to those skilled in the art. Exemplary polymer binders include, but are not limited to, resins, vinyl acrylic polymers, acrylic polymers, vinyl chloride acrylic polymers, vinylidene chloride polymers, styrene-butadiene copolymers, styrene-acry- late copolymers, and vinyl acetate-ethylene copoly- mers. Preferred polymers include vinylidene chloride polymers, vinylacrylic polymers and styrene-acrylate copolymers. Generally, up to about 30 weight percent of the solid content of the polymer binder can be replaced by the product admixture composition of the invention. Usually, the product admixture composition replaces about 1 to about 30 weight percent of the polymer binder's solid content. Preferably, from about 5 to about 25, and more preferably from about 10 to about 20 weight percent of the solid content of the polymer binder is replaced by the product admixture composition. Parint compositions suitable for use in conjunction with the product admixture composition typically have a pigment volume concentration (pvc) of less than about 25 volume by volume percent (v/v%) . Preferably, the paint composition has a pvc of about 15 to about 25 v/v%.
In addition to a polymer binder and a sol or gel composition containing a salt, the surface coating composition of the invention can contain a surface coating paste stock. The paste stock, particularly a paste stock suitable in combination with a water- dispersible polymer, usually contains at least one pigment and usually at least one of the aforementioned additives such as a coalescing aid, a thickening aid, a defoamer, a biocide and/or a filler material or ex¬ tender. In the present invention, a waterborne coat¬ ing composition containing a water-dispersible polymer binder and water usually contains a surface coating paste stock containing at least one pigment or dye and usually at least one additive such as a pigment dis- persant, an amine solubilizer, a flow additive, a drier, and/or a cosolvent. Conventional ground pig¬ ments useful herein include titanium dioxide; copper carbonate; manganese dioxide; lead, zinc and boron chromates; cadmium sulphide; iron oxides; Prussian blue; cobalt blue; ultramarine; chromium oxide; cadmi¬ um selenide; red lead; chrome lead; zinc oxide; anti¬ mony oxide and lead or calcium carbonate. The salt components derived from the sol or gel composition described herein can also comprise all or a part of the pigment or dye contained in the surface coating composition. Several salts contained in the sol or gel compositions provide either color or colorless compositions, and can also be employed to control opacity of the surface coating compositions described herein. The salts derived from the sol or gel which contribute to a paint formulation to produce or effect color or colorless paint compositions provide a paint formulator with materials which provide more durabili¬ ty to the paint then dyes and more solubility in the paint than pigments. For instance, aluminum acetate sol is yellow, aluminum nitrate sol is colorless, cupric acetate is blue, cobalt acetate is red, neody- mium chloride is yellow-green, ferric citrate is brown, etc. Several salts also provide antioxidation or antiyellowing of surface coating compositions described herein.
The salt contained in the sol or gel pro¬ vides an enhancement to the gloss, tannin blocking and corrosion protection properties of the composition. Such enhancement is particularly effective for the gloss enhancement, tannin blocking and corrosion protection properties of a paint composition contain¬ ing a latex.
Aside from providing color or lack thereof to a surface coating composition, the salt contained in the sol or gel provides an enhancement to the tannin blocking property of the composition. Such enhancement is particularly effective for the blocking effects of tannins produced from weathering influences on wood-containing substrates which are coated by the surface coating compositions described herein. For example, wood-containing substrates, such as redwood and cedar lumber, are coated with the surface coating compositions described herein.
Aside from providing color or lack thereof to a surface coating composition, the salt contained in the sol or gel provides an enhancement to the gloss property of the composition. Such enhancement is particularly effective for the gloss property of a semi-gloss or high-gloss paint composition.
In one embodiment of the invention, a sol or gel containing a salt is admixed with a polymer such as a resin. The product admixture composition is blended with a surface coating paste stock to produce a water-soluble surface coating composition. In a preferred embodiment, the salt-containing sol or gel is admixed with a latex polymer, water and a surface coating paste stock to produce a water-dispersible surface coating composition. The product coating compositions. have enhanced gloss properties and such salt addition does not substantially reduce the scrub or wet adhesion properties of the compositions. The surface coating paint composition can be applied to at least a portion of a surface of a sub¬ strate. When applied to a substrate having a white glossy surface, the surface coating or paint, upon drying, forms a composition that typically has a specular gloss of at least about 35 percent reflect¬ ance, and preferably at least about 70 percent re¬ flectance, when measured at an angle of incidence of about 60°. A commercially available substrate having a white, glossy surface is Form WB grade plain white charts available from Leneta Company of Ho-Ho-Kus, New Jersey. In the method of the invention, sufficient salt (i.e., a gloss-enhancing amount of salt) is incorporated into the sol or gel composition and/or sufficient sol or gel containing salt is admixed with a composition containing a polymer and/or a paste stock in an amount to increase the specular gloss by at least about 2 percent reflectance, based upon light having about a 60° angle of incidence, as compared to the same surface coating composition without contain¬ ing the salt from the sol or gel composition. Since specular gloss is directly proportional to the percent reflectance at a given angle of incidence, it is preferred that the percent reflectance obtained by the composition be at least about 35, and more preferably at least about 45 for semi-gloss paints. The percent reflectance for high-gloss paints should be at least about 70, and preferably at least about 75. Accord¬ ingly, the sol or gel composition or product admixture composition of the instant invention is capable of enhancing the specular gloss of a paint.
A gloss-enhancing amount of the salt is homogeneously distributed in the surface coating composition of the invention or it& precursor by means involving admixing a sol or gel composition containing sufficient salt with a composition containing a poly¬ mer and ordinarily also with a surface coating paste stock. In general, the concentration of salt homoge¬ neously distributed in the surface coating composition is about 0.05 and about 5 weight percent. Typically the concentration of sol or gel composition in the surface coating composition which is necessary to achieve such salt concentrations is usually about 0.1 to about 2 weight percent. Furthermore, the concen¬ tration of salt in the sol or gel composition is usually about 2 to about 50, preferably about 10 to about 20 weight percent. Moreover, when the sol or gel composition is first admixed with a composition containing a polymer to produce a product admixture composition prior to blending with a surface coat ing paste stock, the concentration of the sol or gel in the product admixture composition is usually about 2 to about 20 weight percent, and the concentration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.5 to about 25 weight percent.
The surface coating compositions of the invention are applied to the surface of a solid sub¬ strate such as wood, metal, ceramic, plastic, glass, paper, cement, combinations thereof, and the like, or applied to such substrates over a previously coated surface. The applied surface coating composition of the invention is dried by suitable methods known in the art to produce a dried, resultant coating composi¬ tion containing a coalesced polymer and salt compo¬ nents derived from the sol or gel composition.
The resulting coated substrate comprising any solid substrate and the dried resultant surface coating composition of the invention has a dried resultant surface coating having an enhanced gloss property compared to a comparable coating composition not prepared with the sol or gel composition described herein. Either a coated substrate comprising any solid substrate and the dried resultant surface coat¬ ing composition or the surface coating composition may contain a controlled quantity of sol or gel composi¬ tion and/or salt contained therein so as to have controlled opacity and/or color and other visual effects.
The resulting coated substrates produced by the combination of the dried resultant coating compo¬ sition and the solid substrate upon which the surface coating composition of the invention is at least partially applied also depend upon the reaction be¬ tween the coating composition of the invention and the particular substrate that is coated. The dried re¬ sultant coating composition of the invention in a coated substrate comprising a wood-containing sub¬ strate contains tannin blocking properties effective for reducing the weathering of the wood. The dried resultant surface coating composition of the invention contained as a portion of a coated substrate compris¬ ing a corrosion-prone substrate (i.e., a metal-con- taining or plastic-containing substrate) has a corro¬ sion-reducing or corrosion-inhibiting property.
In another embodiment of the invention, a sol or gel containing a salt is admixed with a polymer such as a resin. The product admixture composition is blended with a surface coating paste stock to produce a water-soluble surface coating composition. In a preferred embodiment, the salt-containing sol or gel is admixed with a latex polymer, water and a surface coating paste stock to produce a water-dispersible surface coating composition. The product coating compositions have enhanced tannin blocking properties and also such salt addition does not substantially reduce the scrub or wet adhesion properties of the compositions.
The surface coating paint composition can be applied to at least a portion of a surface of a wood- containing substrate. When applied to the substrate, the surface coating or paint, upon drying, forms a dried (nonaqueous) resultant coating composition that typically has a better tannin-blocking property than the same coating composition not containing the salt derived from the sol or gel composition described herein. In the method of the invention, sufficient salt (i.e., a tannin blocking-enhancing amount of salt) is incorporated into the sol or gel composition and/or sufficient sol or gel-containing salt is ad¬ mixed with a composition containing a polymer and/or a paste stock in an amount to increase the tannin block¬ ing property of a surface coating composition of the invention compared to the same surface coating compo¬ sition not containing the salt from the sol or gel composition. When applied on wood-containing sub¬ strates, (1) the dried sol or gel composition or (2) the dried product admixture composition or (3) the dried surface coating compositions described herein of the instant invention are capable of reducing the effects of tannins.
A tannin blocking-enhancing amount of the salt is homogeneously distributed in the surface coating composition of the invention or its precursor by a method involving admixing a sol or gel composi¬ tion containing sufficient salt with a composition containing a polymer and ordinarily also with a sur¬ face coating paste stock. In general, the concentra¬ tion of salt homogeneously distributed in the surface coating composition is about 0.02 and about 1 weight percent. Typically the concentration of sol or gel composition in the surface coating composition which is necessary to achieve such salt concentrations is usually about 0.1 to about 5 weight percent. Further¬ more, the concentration of salt in the sol or gel composition is usually about 1 to about 50, preferably about 10 to about 20 weight percent. Moreover, when the sol or gel composition is first admixed with a composition containing a polymer to produce a product admixture composition prior to blending with a surface coating paste stock, the concentration of the sol or gel in the product admixture composition is usually about 0.5 to about 25 weight percent, and the concen¬ tration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.1 to about 5 weight percent.
Examples of sol or gel compositions or product admixture compositions or surface coating compositions described herein include wood pretreat- ments, primers, stains and paints. For instance, wood pretreatments may be water repellants; primers can include shellac, alkyd primer paint and acrylic latex primer paint; stains may be transparent oil based, semitransparent oil-based, transparent latex, semi- transparent latex, solid color oil or latex; and paints can be oil-based or latex, indoor or outdoor and the like. The preferred compositions contain latex.
The sol or gel compositions, the product admixture compositions or the surface coating composi¬ tions of the invention are applied either to the surface of an uncoated wood substrate, or applied to such substrates over a previously coated surface. The applied surface coating composition of the invention is dried by suitable methods known in the art to produce a dried, resultant coating composition con¬ taining a coalesced polymer and salt components de¬ rived from the sol or gel composition.
The resulting coated substrate comprising the wood substrate and the dried resultant surface coating composition of the invention has a dried resultant surface coating having an enhanced tannin blocking property compared to a comparable coating composition not prepared with the sol or gel composi¬ tion described herein. Either a coated substrate comprising a wood-containing substrate and the dried resultant surface coating composition or the surface coating composition may, in addition to the tannin blocking properties, contain a controlled quantity of sol or gel composition and/or salt contained therein, so as to have controlled opacity and/or color and other visual effects.
The resulting coated substrates produced by the combination of the dried resultant coating compo¬ sition and the wood substrate upon which the surface coating composition of the invention is at least partially applied also depend upon the reaction be¬ tween the coating composition of the invention and the particular wood substrate that is coated.
The tannin blocking property of the composi¬ tions described herein, e.g., the sol or gel composi¬ tions, the product admixture compositions, the product admixture compositions containing the sol or gel compositions in combination with a composition con¬ taining a polymer such as latex or water-soluble resins, the combinations of sol or gel compositions with compositions containing a polymer and with sur¬ face coating paste stocks, the dried resultant compo¬ sitions of the aforementioned compositions and combi- nations, and the coated wood-containing substrates of the aforementioned composition, refers to the capabil¬ ity of the composition to inhibit or prolong the visibility of wood grains of a wood-containing sub¬ strate through the composition and/ or inhibit or prolong discoloration of the coating. For purposes herein an accelerated weathering evaluation of the tannin block property of the compositions described herein is determined by applying a single coating of the evaluation composition on a wood-containing sub¬ strate, such as redwood, cedar and the like, drying the coating for at least one half hour, and exposing the substrate to 4 hour intervals of light (using UVB- 313 lamps at 45° C.) and moist darkness for at least one week. A typical evaluation of tannin block properties involves the placement of coated wood- containing substrates in a QUV Weatherometer (Q-Panel Company, Cleveland, Ohio) for one week and visual observation of the wood grains and the discoloration of the coating.
In a preferred embodiment, the salt-contain¬ ing sol or gel is admixed with a latex polymer, water and a surface coating paste stock to produce a water- dispersible surface coating composition. The product coating compositions have enhanced corrosion protec¬ tion properties and such salt addition does not sub¬ stantially reduce the scrub or wet adhesion properties of the compositions.
The surface coating or paint composition can be applied to at least a portion of a surface of a free metal-containing or substrate. A free metal- containing substrate, as referred to herein, contains at least a portion of a free metal or alloys contain¬ ing mixtures of free metals. Typical free metal- containing substrates comprise, for instance, iron, mild steel, cast iron, wrought iron, galvanized steel, stainless steel, aluminum, copper, brass, alloys thereof, and other corrodible free metals.
When applied on free metal-containing sub¬ strates, (1) the dried sol or gel composition or (2) the dried product admixture composition or (3) the dried surface coating compositions of the invention described herein are capable of reducing or inhibiting the effects of corrosion. As compared to free metal- containing substrates coated (and dried) with the same surface coating or paint admixture composition but not containing the salt from the sol or gel composition, the free metal-containing substrate coated (and dried) with the compositions containing the salt-containing sol or gel compositions of the invention exhibit either (1) a substantially greater time interval before corrosion effects are indicated on the free metal-containing substrate or (2) less surface area indicating the effects of corrosion over a given period of time in a given environment. When applied to a mild steel substrate (the mild steel containing less than 1 weight percent of carbon) , the product admixture composition, surface coating or paint, upon drying, forms a dried composition that typically prevents the formation of rust on the mild steel substrate for at least one week under accelerated weathering conditions.
In the method of the invention, sufficient salt (i.e., a corrosion protection-enhancing amount of salt) is incorporated into the sol or gel composition and/or sufficient sol or gel containing salt is ad¬ mixed with a composition containing a polymer (and/or a paste stock) in an amount which prevents the forma¬ tion of rust under accelerated weathering conditions for at least 4 days on a mild steel "Q" panel sub¬ strate. "Q" panels contain uncoated mild steel. The product admixture composition, surface coating compo¬ sition or paint composition is applied to the "Q" pan¬ el, dried for one week and subjected to accelerated weathering conditions which are either "salt fog" conditions or QUV Weatherometer conditions for at least 4 days. (QUV Weatherometer conditions are alternating 4 hour intervals of daylight and night (no light) for 1 week with alternating 4 hour rain simula¬ tions overlapping the daylight and night intervals. "Salt fog" conditions subjected on the "Q" panels are a water vapor atmosphere containing 3 vol. % chloride (NaCl) at a temperature of 80° C. for 100 hours using a Model No. 411-1ACD cabinet using an ASTM B-117 test.) As compared to panels coated with essentially the same composition but not containing the sol or gel composition containing a salt yet exhibiting corrosion effects on at least 0.25 percent of the surface area, free metal-containing substrates coated with the dried compositions of the invention exhibit corrosion ef¬ fects (such as rusting) on less than 0.2 percent of the surface area, and usually on less than 0.1 percent of the surface area, after at least 4 days under either the "salt fog" or Weatherometer conditions. Under ordinary performance conditions, the surface coating compositions described herein exhibit suitable or improved properties with respect to abrasion, impact, adhesion, flexibility, moisture vapor trans¬ mission, pendulum hardness and dry temperature resist¬ ance.
An amount of the salt which enhances the corrosion prevention property of the surface coating composition is homogeneously distributed in the sur¬ face coating composition of the invention or its precursor by a method involving admixing a sol or gel composition containing sufficient salt with a composi¬ tion containing a polymer. In general, the particular salt utilized, the particular amount of sol or gel composition and salt amount utilized, depends upon the particular polymer utilized and the particular sub¬ strate that is coated. Although the amount of salt contributed from the sol or gel and the amount of polymer are determined by the particular corrosion prevention use, typically the concentration of salt homogeneously distributed in the surface coating com¬ position is about 0.02 and about 1 weight percent. Typically the concentration of sol or gel composition in the surface coating composition which is necessary to achieve such salt concentrations is usually about 0.1 to about 5 weight percent. Furthermore, the concentration of salt in the sol or gel composition is usually about 1 to about 50, preferably about 10 to about 20 weight percent. Moreover, when the sol or gel composition is first admixed with a composition containing a polymer to produce a product admixture composition prior to blending with a surface coating paste stock, the concentration of the sol or gel in the product admixture composition is usually about 0.5 to about 25 weight percent, and the concentration of the salt (from the sol or gel composition) in the product admixture composition is ordinarily about 0.1 to about 5 weight percent.
The sol or gel compositions, the product admixture compositions or the surface coating composi¬ tions of the invention are applied either to the surface of an uncoated solid metal-containing sub¬ strate, or applied to such substrates over a previous¬ ly coated surface. Such applied compositions of the invention are dried or cured by suitable methods known in the art (generally exposure to air) to produce a dried, resultant protective coating composition con¬ taining a coalesced polymer and salt components de¬ rived from the sol or gel composition.
The resulting coated substrate containing both a solid free metal-containing substrate and the dried resultant protective surface coating composition of the invention has a dried resultant surface coating having an enhanced corrosion prevention property compared to that of a similar coating composition not prepared with the sol or gel composition described herein. The surface coating compositions of the invention may, in addition to the corrosion protection properties, contain a controlled quantity of sol or gel composition and/or salt contained therein, so as to have desired opacity and/or color and other visual effects.
The resulting coated substrates produced by the combination of the dried resultant coating compo¬ sition and the solid substrate upon which the surface coating composition of the invention is at least partially applied may also depend upon the reaction between the salt contained in the sol or gel composi- tion in the coating compositions of the invention and the particular substrate that is coated. The dried resultant protective surface coating paint or product admixture composition of the present invention, con¬ tained as a portion of a coated substrate comprising a corrosion-prone substrate (i.e., a free metal-contain¬ ing substrate) , has a corrosion-reducing or corrosion- inhibiting property. Mechanisms for corrosion protec¬ tion may vary, depending upon which salts, polymers and substrates are involved. For instance, inhibitive salt pigments utilizing a sacrificial cathodic mecha¬ nism may be utilized in the sol or gel compositions. Some forms of barrier salts may be provided by the sol or gel compositions. Latex and oil-based polymer compositions may vary the permeability of the applied coating composition in combination with the particular salt utilized. Also, iron-containing and non-iron- containing substrates may typically be protected from corrosion by different mechanisms.
The present invention encompasses salts, introduced into the product admixture, surface coating or paint compositions described herein, which utilize whatever suitable mechanism which reduces the corro¬ sion of a free metal-containing substrate as compared to the same respective polymer containing compositions except not containing the salts derived from the sol or gel compositions.
The salt-containing sol or gel compositions, the stable product admixture composition or the sur¬ face coating compositons described herein can be utilized in an aqueous form or in a dried form and employed as a catalyst, or be applied to a substrate to provide catalytic properties to a resultant cata¬ lytic composition. A substrate contacted with such salt-containing compositions is typically a solid substrate such as wood, paper, porous refracory oxides, free and alloyed metal, ceramic, plastic, glass, cement, combinations thereof, and the like. » The resultant catalytic composition is useful to promote any process for which the salt components are known to be effective. For example, a resultant salt- containing catalytic composition containing ceramic or porous refractory oxides such as zeolites or aluminas is employed to promote hydrocarbon conversion reaction during upgrading of hydrocarbon-containing feedstocks. Resultant salt-containing catalytic compositions containing cellulose (paper) substrates can be uti¬ lized in automobile filters, etc.-
The presence of the salt dispersed in the resultant latex polymer/salt composition provides an improved electrical (alternating or direct) conductive or semiconductive property compared to the starting polymer without the added salt. The resultant latex polymer/salt compositions exhibit conductive proper¬ ties greater than about 10""7 Seimens/cm. The result¬ ant latex polymer/salt composition is ordinarily capable of conducting at least 0.5 microamperes of alternating electrical current when 5,000 volts (AC) of electricity are applied between brass electrodes that are one inch apart. One electrical testing apparatus suitable for conducting this test is avail¬ able from Biddle Instruments (Model No. 22005) of Philadelphia, Pennsyvlania. Such electrical conduc¬ tive properties are applied, as for example, when the product admixture composition is coated and dried on a textile material such as carpet backing fibers to provide antistatic properties to the carpeting.
A starting textile material useful in the present invention includes assemblies of natural or synthetic fibers, filaments, yarns, and the like, as for example, wovens,- nonwovens, knitted textiles, threads, ropes, yarns, etc., which are employed, in one form or another, either alone or as components of composite articles. As used herein, reference to fibers includes filaments and yarns. The fibers may be obtained from animals (for example, wool, hair, silk, fur and the like) , from vegetable matter (as for example, cotton, flax, hemp, straw and the like) , from minerals or metals (for example, asbestos, aluminum, gold, etc.), or from commercial synthesis (for exam¬ ple, polymers such as rayon, nylon, polyester acryl¬ ics, polyurethanes, glass fiber, etc.), either wholly crystalline like asbestos and metal wires, wholly amorphous like glass, or in the case of the preferred group of fibers, e.g., polymer compositions, partly crystalline and partly amorphous. Examples of textile materials treated in accordance with the present invention include nonwovens such as hospital sheets, gowns, masks, diapers, roofing materials, napkins, tile backings (for ungrouted tile prior to installa¬ tion) , drapery materials, clothing materials (includ¬ ing apparel interlinings and interfacings) , carpet materials, consumer and industrial wipes, towels, carpet and rug backings, components of automobile tops, roadbed underlay ents, insulation, siding, interior wall and ceiling finishes, quilts, mattress pads, mattress covers, sleeping bags, furniture under¬ layments (padding) , air filters, carpet underlayments (e.g., carpet pads), padding and packaging for stored and shipped materials, floor care pads, crib kick pads, house robes, furniture and toss pillows, kitchen and industrial scrub pads, and others too numerous to mention.
Such starting textile materials provide the fiber substrate which is suffused by the herein de¬ scribed sol or gel composition or product admixture composition containing a sol or gel and a polymer. Throughout this specification and the appended claims, the word "suffuse" is used to describe the mechanism by which the components of the sol or gel composition or components of the admixture product composition are contacted and held to the fibers of the textile mate¬ rial. The invention embraces whatever mechanism, including adsorption, absorption, diffusion, deposi¬ tion, chemical reaction, etc. , or some combination of such mechanisms, by which the components of the sol or gel composition or admixture product composition are retained by the fibers of the textile material. The contacting methods include, but are not limited to, total incorporation, including solution, emulsifica- tion, dispersion and chemical reaction; surface incor¬ poration, including coating, deposition and impregna¬ tion; and combinations thereof. After contact of the textile material with the sol or gel composition or the product admixture composition (sol or gel and polymer) , water is usually removed from the treated composition by any drying method which is ordinarily employed for drying the particular textile material.
The product admixture compositions (polymer/sol or gel) may be mixed with a filler to produce a compounded polymer/ salt product composition which may be combined with a starting textile material to produce a textile composition containing a latex polymer, a salt (in a salt-containing sol or gel) and a filler material. Such compositions are typically applied to carpet backing surfaces. Alternatively, either the front or back surface of a textile material may be contacted with the sol or gel composition described herein to produce a textile composition containing components of the sol or gel. In either embodiment, the filler material is optional; e.g., the filler is employed to replace at least a portion of the sol or gel composition or product admixture compo¬ sition primarily to reduce the expense of the prepara¬ tion method and finished product. In a method for preparing a compounded polymer/salt product composi¬ tion, particularly useful for suffusing a carpet backing surface, the sol or gel composition described herein or the product admixture composition containing the sol or gel components and the polymer described herein, are mixed with a filler material, and option¬ ally one or more emulsified compatible plasticizers, and further optionally a frothing agent.
The amount of salt contained in the sol or gel composition is dependent upon the amount of salt needed to be added to a starting textile material to provide an electrical conductivity to a textile compo¬ sition that is greater than the electrical conductivi¬ ty of the textile composition without the added salt. Ordinarily the textile composition of the invention contains sufficient salt suffused therein to provide at least 5 percent, preferably at least 10 percent, and most preferably at least 25 percent greater elec¬ trical conductivity than the textile composition without the added salt. The textile composition of the invention ordinarily contains added salt in an amount greater than 0.1 weight percent, usually greater than 0.3 weight percent and preferably greater than 0.5 weight percent.
Although the amount of salt contained in the product admixture composition of sol or gel and poly¬ mer is dependent upon the particular composition of polymer and the particular salt comprising the product admixture, ordinarily the salt contained in the sol or gel composition -which is added to the composition containing the polymer comprises sufficient additional salt to provide an antistatic property to the treated textile composition of the invention. The term "added salt" or "additional salt", as used herein, refers to any amount of salt added to the composition containing a polymer or to the starting textile material which converts such compositions or materials (1) from having no antistatic property to having antistatic property (2) or from having low antistatic property to having increased antistatic property. Particularly, when compositions containing latex polymers are in¬ volved, the weight percent of sufficient added salt in the product admixture composition is usually greater than 0.05, preferably greater than 0.1, and most preferably greater than 0.5. Such product admixture compositions when applied to starting textile materi¬ als provide effective antistatic properties to the textile composition of the invention, i.e., the tex¬ tile composition usually has an electrical conductivi¬ ty greater than 10~10 Seimens/c , preferably in the range from about 10~8 Seimens/cm to about 10 Seimens/cm, and most preferably from about 0.1 Sei¬ mens/cm to about 10 Seimens/cm.
Suitable compatible plasticizers, if uti¬ lized, depend upon the polymer combined with the sol or gel composition, and in an amount required to obtain a desired flexibility, lowered glass transition temperature (Tg) or softness.
Fillers, particularly inorganic fillers, are added to the sol or gel composition or, in the alter¬ native, to the product admixture containing the compo¬ nents of the sol or gel and a polymer, in an amount of at least about' 50 parts by weight per hundred parts by weight (dry) of the polymer. Usually the filler is added in an amount from about 100 to about 500, pref- erably from about 200 to about 400, parts by weight per hundred parts by weight (dry) of the polymer.
Examples of useful fillers are calcium carbonate (particularly from a source such as limestone) , ba- rytes, diatomaceous earth, aluminum trihydrates, hydrated aluminum silicates (clays) , particularly from a source such as mica or talc, and the like and mix¬ tures thereof. Calcium carbonate is highly preferred.
An unusual feature of the invention is the compatibility of the product admixture composition (containing a sol or gel composition and a polymer, preferably a latex polymer) with a filler material. The filler material has a pH greater than about 4.0, preferably greater than about 7.0 and typically in the range from about 8.0 to about 11.0. Although the sol or gel composition or the product admixture composi¬ tions containing the sol or gel admixture with the polymer are acidic and have a pH less than 7.0 and typically less than 4.0, the compounded polymer/salt product composition obtained from mixing the sol or gel or product admixture compositions with the filler material itself is stable and noncoagulated, having well dispersed components (such as salt) therein, i.e. no coagulation or precipitation of the admixed compo¬ nent is observed. The compounded polymer/salt product composition containing the filler material usually has a pH in the range from about 7.0 to about 9.0 and is capable of being readily suffused with a starting textile material to produce the textile composition of the invention.
Also, a frothing agent may be used in a minor amount by weight (dry) sufficient to froth a polymer composition, i.e., the product admixture composition comprising a latex polymer and sol or gel containing a salt. The frothing agent is usually used to form a froth or foam of the composition containing the latex polymer, filler and optionally the emulsi¬ fied plasticizer. Frothing agents well known in the art may be utilized in the invention. A suitable frothing agent comprises urea, the sodium salt of condensed naphthalene, sulfonic acid, mixed C8-C18 fatty alcohols, ammonium or sodium lauryl sulfate and water. The frothing of a polymer-containing (i.e., latex) mixture or composition can be conducted in an Oakes, Firestone or other type foamer using air or an inert gas such as nitrogen to the desired froth densi¬ ty. Also, mixtures of frothing agents can be used. Other compounding ingredients may be added to the product admixture composition such as thicken¬ ers, pigment colors, coalescence aids, additional surfactants, defoamers for use during blending and the like.
The sols or gels described herein can be applied to the back or front of any textile material, particularly to aid in securing base yarns of the textile and may also be applied to a secondary back¬ ing. Preferably, the sols or gels, product admixtures or compounded polymer/salt product compositions may be applied to piled or tufted carpet material. A com¬ pounded polymer/salt product composition can be ap¬ plied to a textile material, preferably a carpet, by means typical for the particular textile material and then dried (such as air or oven dried) to produce a dried compounded polymer/salt product composition which provides the textile material with antistatic properties. Such a dried compounded polymer/salt product composition contains a greater amount, prefer¬ ably at least 10 percent greater, and most preferably at least 25 percent greater amount of salt than is contained in a composition not prepared by introducing the salt into the composition by addition of a salt- •* containing sol or gel composition.
* The textile composition of the invention, containing a textile material suffused with at least one salt, ordinarily has an electrical conductivity greater than 10~10 Seimens/cm, and usually greater than 10~8 Seimens/cm. Favorable antistatic properties are imparted to the textile composition of the inven¬ tion when the electrical conductivity of the textile composition is in the range from about 10~8 Seimens/cm to about 10 Seimens/cm, and preferably from about 0.1 to about 10 Seimens/cm.
Other applications for the resultant latex polymer/salt compositions include biocidal polymers, polymers have discoloration retardant properties, polymers useful as delay cross linkers in reservoir plugging, polymer coatings for anodic and cathodic protection, polymers for thermal heating elements, antistatic adhesive tapes, catalytic agents, gloss * enhanced polymers, as well as other uses such as
-ϋ laminated coatings as barriers to stain migration in textiles and floor coverings, sorbents containing flame retardant sols, and microwave food coatings.
The invention is further illustrated by the following examples which are illustrative of specific modes of practicing the invention and are not intended as limiting the scope of the invention defined by the appended claims.
EXAMPLE 1 A sol containing cupric acetate is prepared as follows: to a 1 liter container is added 246 grams of ethylene glycol solvent, 166 grams of citric acid (monohydrate) stabilizer, 50 grams of cupric acetate (dihydrate) and 21.4 grams of concentrated nitric acid. From room temperature (about 25°C), the mix¬ ture is slowly heated to 65°C. and held at 65°C. for 10 hours. A clear, transparent product sol is formed having a blue color. The transparent blue-colored sol contains cupric cations, acetate anions and colloidal size cupric acetate salt particles dispersed in the liquid medium. Such a product is cooled to room temperature and the transparent product becomes opaque. An additional 10.7 grams of nitric acid is added to the opaque product which results in the same degree of transparency and clarity as observed at 65°C. The transparent product is a stable sol having a pH of 0.1 and a viscosity of 290 cps.
EXAMPLE 2 Stable citric acid/ethylene glycol/nitric acid sols containing various salts are prepared in the same manner as in Example 1, except various salts require different temperatures sufficient to form the sol. These temperatures and the characteristics of the resulting sols are shown in Table A.
TABLE A
Figure imgf000083_0001
Cobalt Acetate 65 red <0.1 215 Cobalt
Silylmolybdate Cupric Acetate Dysprosium Chloride Dysprosium Nitrate Ferric Citrate Lanthanum Acetate Lanthanum Chloride Lanthanum Nitrate Lanthanum Oxide Lead Acetate Lithium Acetate Magnesium Acetate Mercuric Acetate Neodymium Chloride Neodymium Nitrate Nickel Acetate Nickel
Phosphormolybdate Nickel
Silylmolybdate Nickel
Tetrafluoroborate Potassium Acetate Potassium Phosphate
Monobasic Praseodymium
Acetate Silicon Acetate Silver Acetate Sodium Acetate Sodium Chrornate Sodium Molybdate Sodium Vanadate
Figure imgf000084_0001
TABLE A (continued)
Figure imgf000085_0001
EXAMPLE 3 A sol is prepared in the same manner as in Example 1, except the 166 grams of citric acid monohy- drate stabilizer is replaced with 166 grams of a nonionic surfactant stabilizer which is a polyethoxy- lated nonylphenol surfactant having 9 moles of ethyl¬ ene oxide per mole. Also, no nitric acid is added to the cooled admixture. The resulting sol is transpar- ent and has a green color, a pH of 2.8 and a viscosity of 155 cps.
EXAMPLE 4 Cupric acetate salt is replaced by other metallic salts in the same method of preparation as in Example 3 (i.e., addition of the nonionic surfactant stabilizer) to produce sols having the color, pH, and viscosity characteristics summarized in Table B below:
TABLE B
Metallic Salt
Aluminum Acetate Ammonium Acetate Ammonium Nitrate Barium Acetate Calcium Nitrate Cerous Nitrate Cobalt Acetate Cupric Acetate Dysprosium Nitrate Ferric Nitrate Gadolinium Nitrate Lanthanum Nitrate Magnesium Nitrate Manganous Acetate Mercurous Acetate Neodymium Nitrate Nickel Nitrate Praseodymium
Nitrate Strontium Nitrate
Figure imgf000086_0001
Table B Continued
40 40 40 40
Figure imgf000087_0001
40
EXAMPLE 5 Sols containing cupric acetate prepared in the same manner as in Examples 1 and 3, except the stabilizer is replaced in each sol with an individual¬ ly different nonionic surfactant. Characteristics of the sols including product viscosity, pH, surfactant Hydrophilic-Lipophlic Balance (HLB) , and the sol forming temperature are summarized in Table C.
Figure imgf000088_0001
TABLE C (continued)
Polyoxethylene glycol 1500 85 2.9 165
Figure imgf000089_0001
Polypropylene glycol 425 85 1.4 152
80 mol EO sorbitan monolaurate 20 mol EO sorbitan monopalaurate 20 mol EO sorbitan monodeate 20 mol EO sorbitan monolaurate
Tetronic 304 * Tetronic 704 Tetronic 904 Tetronic 1102 Tetronic 1504
Figure imgf000089_0002
* Pluronic and Tetronic nonionic surfactants contain mix¬ tures of polyols as determined by basic grid figures 2 and 6, pp. 2 and 4, respectively, disclosed in "Pluronic Tetronic Surfactants," copyright BASF (1987). EXAMPLE 6 Sols containing cupric acetate are prepared in the same manner as in Example 5, except each sol contains a mixture of nonionic surfactants as the stabilizer. The sols exhibit the following character¬ istics as shown in Table D.
TABLE D
Sol Nonionic Forming Product Product
Surfactant Blend HLB Temp. °C. pH Viscosity
10 wt. % Pluronic
L31* + 90 Wt. % L35** 17.1 85 2.9 173
90 wt. % Pluronic
L35** + 10 wt. % F38*** 19.7 85 2.7 188
50 wt. % Igepal
C0530 + 50 Wt. %
Igepal C0890 14.3 85 2.9 201
Igepal CO530 = 6 mol EO nonylphenol
Igepal CO890 = 40 mol EO nonylphenol
Pluronic *L31 = 10% EO + 90% PO polyglycol MW = 950
**L35 = 50% EO + 50% PO polyglycol MW = 950
***F38 = 80% EO + 20% PO polyglycol MW = 950
EXAMPLE 7 Sols containing cupric and zinc acetates/citric acid/nitric acid are prepared in 89
the same manner as in Example 1, except the polyol solvents in Table E are substituted for the ethylene glycol solvent. The temperature required to form the sol, pH of the sol and viscosity of the sol are summa¬ rized in Table E.
Figure imgf000091_0001
EXAMPLE 8 A cupric acetate salt is admixed with a commercially available latex polymer composition (designated as as "76 RES 4400" available from Union Chemicals Division of Unocal Corp., i.e., "UCD") containing a styrene butadiene rubber (SBR) , to pro- duce a noncoagulated product admixture composition containing the stable, latex polymer together with the cupric acetate salt uniformly dispersed in the product admixture. The cupric acetate salt is added to the composition containing the latex polymer by addition of the sol prepared in Example 1 containing the cupric acetate salt.
One part by weight of the cupric acetate- containing sol is admixed with 29 parts by weight of the composition containing the latex polymer to pro¬ duce a stable, noncoagulated product admixture compo¬ sition containing cupric acetate salt, including cupric cations, uniformly dispersed in the latex polymer. The stable product admixture indicates the sol and latex polymer are compatible, the resulting latex polymer product admixture being blue in color and no coagulation of the latex polymer composition being observed for at least one month following admix¬ ing.
EXAMPLE 9 Several compositions containing .latex poly¬ mers other than that in Example 8 are admixed in separate tests with the sol of Example 1. The follow- ing commercially available UCD compositions containing latex polymer derived by emulsion polymerization are all compatible (i.e., form stable, noncoagulated % product admixtures) with the cupric acetate sol when admixed in the same manner as in Example 8: (76 RES 3103) polyvinylacetate, (76 RES 1019) styrene/acry- late, (76 RES 9608) acrylic, (76 RES 701) polyvinyli- dene chloride and (76 RES 661) vinyl acrylics.
EXAMPLE 10 Citric acid/ethylene glycol/nitric acid sols from Examples 1 and 2 are compatibly combined with 76 RES 4400 in the same manner as in Example 8. The product admixture is prepared in a 3.5 inch Petri dish and air dried at room temperature for 1 week. The dried resultant latex polymer/salt films contain¬ ing the various salts (and/or cations and/or anions) have the electrical conductivity properties summarized in Table F. The Biddle Model No. 22005 Electric Testing Equipment is used to test the dried resultant latex polymer/salt films. The Biddle Testing Equip¬ ment contains brass strips which are placed one inch * apart and voltage is applied while determining current
* flow. The voltage required to produce an alternating electrical current flow of five thousand microamperes is summarized in Table F.
TABLE F
Voltage AC volts to give
Sol Used 5K microamps
76 RES 4400 None 5K*
Aluminum Acetate 2700 Aluminum Nitrate 1000 Ammonium Acetate 950 Ammonium Molybdate 1700 Ammonium Molybdocobaltate 1700 Ammonium Nitrate 1500 Antimony Acetate 2000 Antimony Ethyleneglycoxide 2300
Bismuth Nitrate 950
Boron Acetate 1800
Cadmium Acetate 1050
Calcium Acetate 1300
Cerium Acetate 1850
Cerium Nitrate 2700
Cesium Acetate 1900
Chromium Acetate 1800
Cobalt Acetate 2200
Cobalt Silylmolybdate 3100
Cupric Acetate 1800
Dysprosium Chloride 1000
Dysprosium Nitrate 1000
Ferric Citrate 2400
Lanthanum Acetate 2100
Lanthanum Chloride 2000
Lanthanum Nitrate 3000
Lanthanum Oxide 3000
Lead Acetate 1450
Lithium Acetate 1600
Magnesium Acetate 2300
Mercuric Acetate 4500
Neodymium Chloride 1150
Neodymium Nitrate 1500
Nickel Acetate 1400 TABLE F (continued)
Sol Used
Nickel Phosphomolybdate Nickel Silylmolybdate Nickel Tetrafluoroborate Potassium Acetate Praseodymium Acetate Silicon Acetate Silver Acetate Sodium Acetate Sodium Chromate Sodium Molybdate Sodium Vanadate Strontium Acetate Tetraethylammonium Acetate Tetraethylammonium Chloride Thallium Acetate Thorium Nitrate Titanium Butoxide Titanium Isopropoxide Uranyl Acetate Yttrium Acetate Yttrium Chloride Yttrium Formate Yttrium Nitrate Zinc Acetate
Figure imgf000095_0001
* 5000 AC volts gave *0.5 microamp reading
EXAMPLE 11 Some cupric acetate/ethylene glycol/nitric acid sols from Examples 5 and 6 using different non¬ ionic surfactants as stabilizers of the sol are com¬ patibly admixed with 76 RES 4400 SBR latex and dried in the same manner as in Example 10. The dried re¬ sultant latex polymer/salt compositions are tested as in Example 10 and the observed current flow data summarized in Table G.
TABLE G
Nonionic Surfactant
9 mol EO octylphenol 12.5 mol EO octylphenol
7.5 mol EO nonylphenol 8.5 mol EO nonylphenol 9 mol EO nonylphenol 10 mol EO nonylphenol 10.5 mol EO nonylphenol 12 mol EO nonylphenol
10 mol EO oleyl alcohol 10 mol EO cetyl alcohol 20 mol EO oleyl alcohol 20 mol EO cetyl alcohol
Polyoxyethylene glycol 400 Polyoxyethylene glycol 600 Polyoxyethylene glycol 1000 Polyoxyethylene glycol 1500
Figure imgf000096_0001
Polypropylene glycol 425
80 mol EO sorbitan monolaurate 20 mol EO sorbitan monooleate 20 mol EO sorbitan monolaurate
Figure imgf000096_0002
95
TABLE G (Continued)
AC volts AC current,
Nonionic Surfactant Applied microamperes
10 wt. % Pluronic L31 + 90 Wt. % L35 4000 990
90 wt. % Pluronic L35 + 10 wt. % F38 5000 1880
50 wt. % Igepal CO530 + 50 wt. % Igepal CO890 800 5000
EXAMPLE 12 Sols prepared in Example 4 are admixed with 76 RES 4400 SBR latex, dried, and the resultant latex polymer/salt compositions tested for electrical con¬ ductivity in the same manner as in Example 10. The dried sol/latex products are tested as in Example 10 and the observed current flow data summarized in Table H.
Salt
Aluminum Acetate Ammonium Acetate Cobalt Acetate Cupric Acetate Mercuric Acetate Nickel Acetate Uranyl Acetate
Figure imgf000097_0001
EXAMPLE 13 Acetate salts in the citric acid/ethylene glycol/nitric acid-prepared sols of Example 2 are admixed with a commercially available UCD composition containing a polyvinylidene chloride latex (76 RES P546 PVDC latex) , dried and tested in the same manner as in Example 10. The dried sol/latex products are tested as in Example 10 and the observed current flow data summarized in Table J.
Cation
None
Aluminum
Ammonium
Cadmium
Calcium
Chromium
Cobalt
Cupric
Lanthanum
Lead
Lithium
Magnesium
Nickel
Potassium
Praseodymium
Silicon
Sodium
Strontium
Figure imgf000098_0001
TABLE J (Continued)
AC Volts AC current,
Cation Applied microamperes
Uranium 5000 111 Yttrium 4000 75000 Zinc 5000 75000
EXAMPLE 14 A sol containing neodymium nitrate is prepared as follows: to a 1 liter container is added 492 grams of ethylene glycol solvent, 332 grams of 9 mol EO nonyl¬ phenol surfactant stabilizer (i.e., a nonionic sur¬ factant which is a polyethoxylated nonylphenol sur¬ factant having 9 moles of ethylene oxide per mole) and 100 grams of neodymium nitrate (pentahydrate) . From room temperature (about 25°C), the mixture is slowly heated to 40°C. and held at 40°C. for 4 hours. A clear, transparent product sol is formed having a violet color. The transparent violet colored sol contains neodymium cations (Nd3+) , nitrate anions and colloidal size neodymium nitrate salt particles dis¬ persed in the liquid medium. Such a product is then cooled to room temperature. The transparent product is a stable sol having a pH of 2.73 and a viscosity of 98
180 cps .
EXAMPLE 15 A neodymium nitrate salt is admixed with 76 RES 4400 to produce a noncoagulated product admixture composition containing the stable, latex polymer together with the neodymium nitrate salt uniformly dispersed in the product admixture. The neodymium nitrate salt is added to the composition containing the latex polymer by addition of the sol prepared in Example 1 containing the neodymium nitrate salt.
One part by weight (30 grams) of the neodymium nitrate containing sol is admixed with 9 parts by weight (270 grams) of the composition containing the latex polymer to produce a stable, noncoagulated product admixture composition containing neodymium nitrate salt, including neodymium (Nd3+) cations, uniformly dispersed in the latex polymer. The stable product admixture indicates the sol and latex polymer are compatible, with the resultant latex polymer product admixture being not coagulated. No coagula¬ tion of the latex polymer composition is observed for at least four months following admixing.
The resultant latex polymer product admixture is then compounded with a filler material containing calcium carbonate (CaC03) to produce a compounded latex/salt product. The compounding is done by blend¬ ing 31 grams of the resultant latex polymer/salt product admixture with 67 grams Franklin limestone filler material, 0.16 grams sodium vinyl sulfonate frothing agent, and 2.1 grams water. The blend is then thickened to 6000 cps. by the addition of 35 grams of a polyacrylic acid/polyacrylamide product thickener (i.e., Jarco 1111). Thirty grams of this compounded latex/salt product is poured into a 3 inch Petri dish and air dried.
EXAMPLE 16 Several sols prepared according to the pro¬ cedure in Example 14 are compatibly combined with 76 RES 4400 in the same manner as in Example 15. Each product admixture is prepared in a 3.5 inch Petri dish and air dried at room temperature for 1 week. The dried resultant latex polymer/salt films containing the various salts (and/or cations cations and/or anions) have the electrical conductivity properties summarized in Table K. The Biddle Model No. 22005 Electric Testing Equipment is used to test the dried resultant latex polymer/salt films. The Biddle Test¬ ing Equipment contains brass strips which are placed one inch apart and voltage is applied while determin¬ ing current flow. The observed alternating electrical current flow (microamperes) at the indicated applied voltage (kilovolts, KV) as summarized in Table K for several compounded dried resultant latex polymer/salt films is as follows:
TABLE K
Current Flow as a Function of Applied Voltage for Several Compounded Sol-Latexes
Observed Current (microamps) at Applied Voltage (KV)
Figure imgf000102_0001
TABLE K (Continued)
Figure imgf000103_0001
In a procedure similar to that in Example 15 a 1-liter reactor is charged with 246 grams ethylene glycol, 166 grams citric acid (monohydrate) , 50 grams neodymium nitrate (pentahydrate) , and 21 grams nitric acid. The mixture is heated at 40° C. for 6 hours. The transparent product when cooled to room tempera¬ ture has a pH of 0.1 and a Brookfield viscosity of 193 cps.
Dysprosium nitrate and ammonium nitrate are used to prepare citric acid sols in the same manner. The dysprosium sol has a pH of *0.1 and a Brookfield viscosity of 326 cps. The ammonium sol has a pH of 0.1 and a Brookfield viscosity of 396 cps.
EXAMPLE 18 Sols from Example 17 using citric acid as a stabilizer of the sol are compatibly admixed with 76 RES 4400 SBR latex and dried in the same manner as in Example 15. The dried resultant latex polymer/salt compositions are tested as in Example 16 and the observed current flow data summarized in Table L.
TABLE L
Current Flow as a Function of Applied Voltage for Citric Acid Compounded Sol-Latexes
Observed Current (microamps) at Applied Voltage (KV)
Figure imgf000104_0001
Using the method of Examples 15 and 16, the weight percent of neodymium nitrate/nonionic sol of Example 14 is varied in the 76 RES 4400 SBR latex of Example 15 and evaluated by the Biddle testing method of Example 16.
TABLE M
Current Flow as a Function of Applied Voltage for Variations of Neodymium Nitrate/Nonionic Sol in Resulting Latex Polymer Product Admixtures
Observed Current (microamps) at Applied Voltage (KV)
Amt. Sol in
Figure imgf000105_0001
A compounded latex/salt product composition obtained from a 15% neodymium nitrate/nonionic sol admixed with 76 RES SBR 4400 latex of Example 15 (Sol No. 4 in Table M of Example 19) which is compounded with limestone (CaC03) , sodium lauryl sulfonate and water in the manner of Example 2 is placed on the backing of a square yard of continuous fiber carpet. The amount of compounded latex/salt product composi¬ tion used is 80 grams, which is applied to the carpet backing using a #40 drawdown rod.
The textile composition (i.e., dried carpet) is evaluated using the Biddle testing equipment in a similar manner as in Example 16. Measurements are made in three directions: (1) the cross direction, (2) the machine direction, and (3) on a diagonal line using a 36 inch spacing between the brass electrodes. The values for 5 KV applied voltage are: cross, 3100 microamps; machine, 500 microamps; diagonal, 3200 microamps.
A sample of carpet treated similarly but without the neodymium sol component shows the follow¬ ing current flows at 5 KV applied voltage: ^ cross, 4 microamps; machine, 11 microamps; diagonal, 4 mi¬ croamps.
EXAMPLE 21 A 1-liter kettle is charged with 50g lanthanum nitrate, 246g ethylene glycol, 166g citric acid, and 15ml (21.4g) concentrated nitric acid. The mixture is heated at 50° C. for 6 hours, and then cooled to room temperature. The clear, straw colored sol had a pH <0.1 and a Brookfield viscosity 226 cps. The sol'contains about 10 weight percent of the lan¬ thanum nitrate salt. Various other sols are prepared in the same manner. These sols are blended with vinyl acrylic latex (76 RES 3077, available from UCD, Schau - burg, Illinois). For each 75g latex, 2.6g sol is used, i.e., about 3.35 weight percent of sol in the latex. The sol/latex product admixture is then made into formulated paint useful for semi-gloss architec¬ tural coatings applications.
The following materials are blended at 400 rpm using a 4-inch Cowels blade: 1845g water, 610g 1,3-propylene glycol, 31g Natrasol 250HR, 8.9 colloid 681-F, 70.9g Tanol 731, 26.6g Igepal CO630, 8.9g phenylmercuric acetate, and 2215 Tronox CR800. The blend is then ground at 1800 rpm for 2 hours to achieve a grind gauge value of 7NS. The material is cooled to room temperature and the following ingredi¬ ents are added at 400 rpm: 117g Texanol, 17.7 col¬ loid, 681-F, and 886g water. The resulting material is a paste stock for paint.
The formulated paint is prepared using 124.3g paste stock, 75.3g sol/latex, and 0.38g Triton GR-5. These ingredients are blended at 400 rpm for 20 minutes.
EXAMPLE 22 Determination of Gloss Values for Compounded Sol/Latex Paints
Plain white Leneta Charts Form WB (Leneta Company, Ho-Ho-Kus, New Jersey) is coated with com¬ pounded paints from Example 21 using a 6 mil drawdown bar (Gardner, Bethesda, Maryland) . The panels are air dried under controlled conditions for 1 week under conditions including 50% humidity and 73° F. The gloss readings in the following Table N are made using a 60° Glossgard II meter (Gardner, Bethesda, Maryland) .
TABLE N
Salt Used in Sol Gloss Percent Reflectance* blank (w/o sol) 63 none (sol w/o salt) 64 aluminum acetate 72 ammonium acetate 74 antimony ethyleneglycoxide 67 barium acetate 64 cadium acetate 69 calcium acetate 70 cerium acetate 67 chromium acetate 71 cobalt acetate 72 cupric acetate 72 dyprosium acetate 71 ferric acetate 75 lanthanum acetate 72 lanthanum chloride 69 lanthanum nitrate 74 lanthanum oxide 70 lead acetate 72 TABLE N (Continued) Salt Used in Sol Gloss Percent Reflectanc
lithium acetate 73 magnesium acetate 70 magnesium nitrate 68 nickel acetate 72 potassium acetate 73 praseodymium acetate 71 silicon acetate 70 silver acetate 76 sodium acetate 73 strontium acetate 68 tetraethylammonium bromide 75 thorium nitrate 68 titanium isopropoxide 67 uranium acetate 71 yttrium acetate 65 yttrium nitrate 71 zinc acetate 73 scale: higher numbers are better
♦Readings of gloss are (1-2)
The data summarized in Table N indicate that enhanced gloss is found in compositions employing salt-containing sols in the compounded latex paints.
EXAMPLE 23 Scrub Performance of Compounded Sol/Latex Paints
Black scrub test panels (Leneta, Ho-Ho-Kus, New Jersey) Form P-121-10N are coated with compounded paints from Example 21 using a 6 mil drawdown bar (Gardner, Bethesda, Maryland) . The panels are dried l week at 73° F. and 50% humidity. The scrub performance is determined in accordance with the procedure of ASTM D2486-79 using a straight line washability and abra¬ sion machine (Model MA1492, Gardner, Bethesda, Mary¬ land) and standard scrub medium SC-2, abrasive type (Leneta, Ho-Ho-Kus, New Jersey) .
TABLE O
Salt Used in Sol Average Cycles to Failure* blank (w/o sol) 2500 none (sol w/o salt) 2650 aluminum acetate 2250 ammonium acetate 2300 antimony ethyleneglycoxide 2400 barium acetate 2200 cadium acetate 2300 calcium acetate 2350 cerium acetate 2200 chromium acetate 2350 cobalt acetate 2200 cupric acetate 2200 dyprosium acetate 2450 ferric acetate 2250 lanthanum acetate 2650 lanthanum chloride 2700 lanthanum nitrate 2650 lanthanum oxide 2700 lead acetate 2300 lithium acetate 2400 magnesium acetate 2400 magnesium nitrate 2400 nickel acetate 2300 potassium acetate 2450 praseodymium acetate 2300 silicon acetate 2650 silver acetate 2450 sodium acetate 2400 TABLE 0 Continued
Figure imgf000111_0001
*Scrub measurements are l50 cycles at 2500 total cycles; 2300 and 2400 are the same.
The summarized data in Table O suggest scrub is slightly depressed by the addition of sols, except for lanthanum, silicon and thorium salt-containing sols, which do not affect the normal scrub.
EXAMPLE 24 Wet Adhesion Performance of Compounded Sol/Latex Paints
Plain white Leneta Charts Form WB (Leneta Company, Ho-Ho-Kus, New Jersey) are coated with black enamel paint (such as interior/exterior 54-309 from Pittsburgh Paints, Pittsburgh, Pennsylvania) prepared from sols in the same manner as in Examples 21 and 22 while using a 10 mil drawdown bar (Gardner, Bethesda, Maryland) , and dried for 1 week at 73° F. and 50% humidity. The wet adhesion performance is determined using the wet pick and peel procedure of ASTM D3359- 83.
TABLE P
Salt Used in Sol Wet Adhesion Rub/Peel* blank (w/o sol) 3/2 none (sol w/o salt) 3/2 aluminum acetate 3/2 ammonium acetate 5/2 antimony ethyleneglycoxide 3/2 barium acetate 3/2 cadium acetate 3/2 calcium acetate 3/2 cerium acetate 4/3 chromium acetate 3/2 cobalt acetate 3/2 cupric acetate 3/2 dyprosium acetate 5/3 ferric acetate 3/2 lanthanum acetate 4/3 lanthanum chloride 4/2 lanthanum nitrate 4/3 lanthanum oxide 4/2 lead acetate 3/2 lithium acetate 4/2 magnesium acetate 3/2 magnesium nitrate 3/2 nickel acetate 3/2 potassium acetate 4/2 praseodymium acetate 4/3 silicon acetate 5/3 silver acetate 3/2 sodium acetate 4/2 strontium acetate 3/2 tetraethylammonium bromide 4/2 thorium nitrate 3/2 titanium isopropoxide 3/2 uranium acetate 3/2 yttrium acetate 5/2 yttrium nitrate 4/3 zinc acetate 3/2
♦Subjective scale: 5=best, l=worst From the above data summarized in Table P, inorganic and organic nitrogen salts, lanthanide salts, silicon salts, and alkali-metal salts enhance wet adhesion in compounded latex paints.
EXAMPLE 25
Gloss, Scrub and Wet Adhesion Performance of Lanthanum Sol-Containing Compounded Latex Paints as a Function of Lanthanum Concentration
The compounded paint of Example 21 (contain¬ ing 10 weight percent sol in latex which is 3.35 weight percent lanthanum nitrate in the sol/latex) along with other lanthanum nitrate sols containing different amounts of lanthanum nitrate at the same and other sol/latex weight ratios are evaluated for scrub, gloss and wet adhesion as described in Examples 22, 23 and 24.
TABLE O
Figure imgf000114_0001
At 5 weight percent salt in the sol, higher levels of salt in the paint can improve gloss, but can detrimentally affect scrub performance due to the accompanying addition of ethylene glycol and citric acid. A similar impact on wet adhesion is shown, because water sensitivity is also increased. Table Q also shows that an increase of salt content in the sol provides better gloss, scrub and wet adhesion proper¬ ties accompanying the reduced amount of ethylene glycol and citric acid in the paint.
EXAMPLE 26 Performance of Compounded Latex Paints Containing Commercial Lanthanum Nitrate Sols
The method of Example 21 is used to prepare sols from commercial quality lanthanum nitrate (ob¬ tained from Molycorp, Washington, Pennsylvania) . The sols are used to prepare paints as in Example 21, and then tested as described in Examples 22, 23 and 24.
Figure imgf000115_0001
unspec fied
(Lab Quality) from Example 21
The data in Table R indicate that commer¬ cially available impure lanthanum nitrate utilized in paint samples 1, 2 and 3 provide essentially the same gloss, scrub and wet adhesion properties as that for Sample 4 containing a lab quality sample of lanthanum nitrate (<0.5 wt. % of unspecified impurities) in the sol and paint sample.
EXAMPLE 27 A 2 liter resin kettle is charged with 492g ethylene glycol, lOOg aluminum acetate, 333g citric acid, and 30ml concentrated nitric acid. The mixture is heated to 70° C. for 4 hours. The material is then cooled to room temperature. The resulting straw colored sol has a pH of <0.1 and a Brookfield viscosi¬ ty of 450 cps.
The following ingredients are blended to¬ gether to prepare a paint paste stock according to Federal Specification TT-P-19D: 316.5 water, 5.0g Natrosol 250MBR, 10.2g Colloids 226/35, 2.Og Igepal CO630, 3.5g Colloids 640, 2.0g Nuosept 95, 1.5g AMP- 95, 1.5g potassium tripolyphosphate, 250.0g Tronox CR822, 27.8g ethylene glycol, 50.Og Kadox 555, and 175.Og Minex 4. After all ingredients are added and a homogeneous material is obtained, 13.8g Texanol, 3.5g Colloids 643, and 6.0g Polyphase AFl are blended into the paint paste stock. 115
The sol is blended into a commercial sty- rene-vinyl acrylic latex (commercially available as 76 RES 6510 from UCD, herein "Unocal"). The sol to latex weight ratio is 1:10, obtained by using 36.0g sol and 324.Og latex.
The product paint is obtained by blending 360.Og of the sol/latex product admixture composition into 1225.8g of the paint paste stock. The resulting formulation had a viscosity of 95KU, a density of 11.81 lbs/gal and a total solids of 58.1% by weight.
EXAMPLE 28 The rough finished side of redwood clap board is painted by brush with the paint obtained in Example 27. An additional section of board is painted with a paint formulation like that in Example 1, except without the sol, and 360.Og of Unocal 76 RES 6510 styrene-vinyl acrylic latex is used. Single coats of paint are compared subjectively and visually upon drying for 30 minutes. The paint prepared from the aluminum acetate sol and latex hid the redwood grain better than the comparable paint without the sol.
EXAMPLE 29 Several sols containing salts and ethylene glycol solvent are evaluated as tannin block agents. Four latexes are used: a styrene-vinyl acrylic latex (Unocal 76 RES 6510), a polyvinylacetate, i.e., PVA latex (Unocal 76 RES 60011) , a polyvinylacetate, i.e.
PVA latex (Unocal 76 RES 6004) and a styrene butadiene rubber, i.e. SBR latex (Unocal 76 RES 4076). Product admixture compositions containing sol and latex in a 1:10 weight ratio, respectively, are prepared and added to the paint paste stock of Example 27 to pro¬ duce product paints as set forth in Example 27. The sols containing a citric acid stabilizer are prepared in the same manner as in Example 27 and the sols containing nonionic surfactant stabilizers (Igepal C0610, CO620, C0630 - phenoxypolyoxyethylenes) are also prepared in the same manner as in Example 27, except no nitric acid is added. The product paints are evaluated in the same manner as in Example 28.
The following Table S summarizes product paints containing sols having salts and latex polymers which exhibit a suitable tannin blocking property:
TABLE S
Latex 76 RES 6510
76 RES 60011
76 RES 6004
Figure imgf000119_0001
TABLE S Continued
Latex
76 RES 4076
Figure imgf000120_0001
The paint compositions of Table S indicate that several sols in combination with various kinds of latexes give good tannin block performance as freshly painted coatings on redwood board.
All product paints are evaluated for per¬ formance under accelerated weathering conditions. Redwood panels are placed in a QUV Weatherometer for 1 week using 4 hour cycles of light (using UVB-313 lamps, 45° C.) and moist darkness. The panels are again evaluated for tannin block performance. Al¬ though all the product paint compositions exhibit suitable tannin blocking performance, substantially better performance without discoloration of the coat¬ ing is observed in all four latex paints containing the aluminum acetate-containing sol prepared with a citric acid stabilizer.
EXAMPLE 30 Several aluminum salts are utilized to prepare sols containing ethylene glycol solvent using the method of Examples 27 and 29. Using the method of Example 27, paints are prepared with various aluminum- containing salts in respective sols and combined with the latexes of Example 39 and the paint paste stock of Example 27. The product paint compositions are tested as in Examples 28 and 29 and the evaluations summa¬ rized in Table T.
TABLE T
Sol
Figure imgf000122_0001
The accelerated weathering results indicated in Table T suggest the paints derived from the citric acid stabilized sols are better than those derived from the phenoxypolyoxyethylene surfactant-based sols. Furthermore, aluminum acetate and aluminum isopropox¬ ide salts contained in the sols provide paints having superior tannin blocking properties. EXAMPLE 31 In accordance with the method of Exam¬ ple 27, five paints are prepared with four containing 10 weight percent aluminum acetate sol prepared with citric acid as in Example 27 and one without the sol. The four product paints containing the sol contain 5, 15, 25 and 35 weight percent sol, respectively, based on the latex. These paint products are evaluated for tannin blocking under the QUV conditions illustrated in Example 3 and summarized in Table U.
Figure imgf000123_0001
* Subjective rating after 1 week in QUV (5 = best)
The results in Table U indicate that a 10 weight percent aluminum acetate sol blended in a 5 weight percent amount with a latex, and then compounded into a paint paste stock produces a surface coating or paint composition having superior tannin blocking properties.
EXAMPLE 32 A citric acid stabilized sol is prepared using 20 weight of aluminum acetate. The sol is blended with latexes utilized in Example 30 at 5%, 10% and 15 weight percent (based on the latex) , which are then utilized with the paint paste stock of Example 27 to prepare three product paint compositions, which are evaluated under weathering QUV conditions.
Figure imgf000124_0001
* Subjective Rating (5 = best)
Such results indicate that a sol contained in an amount from about 5 to about 10 weight percent of the latex is highly preferred when the sol contains about 15 to about 25 weight percent of aluminum ace¬ tate. EXAMPLE 33 Citric acid stabilized sols prepared by the method of Example 27 containing aluminum acetate are prepared at various concentrations of aluminum ace¬ tate. The sols are blended with the latexes utilized in Example 30 so that the same concentration of alumi¬ num acetate salt is present in each sol/latex product admixture composition. The product admixture composi¬ tions are utilized with the paint paste stock of Example 27 to prepare product paint compositions in accordance with the method of Example 27. The results obtained evaluating the product paint compositions under the QUV weathering conditions of Example 29 are summarized in Table W.
Figure imgf000125_0001
* Subjective Rating (5 = best) The results summarized in Table W indicate that an amount of sol in latex is highly effective for tannin blocking when the sol contains at least about about 15 weight percent, preferably at least about 17 weight percent and more preferably at least about 20 weight percent of aluminum acetate salt.
EXAMPLE 34 The method of Example 27 is used to prepare a tetrapropylammonium bromide-containing sol. Forty nine and nine-tenths grams (49.9g) tetrapropylammonium bromide, 246g ethylene glycol, 166.4g citric acid, and no nitric acid are combined. The admixture is heated at 40° C. for 1 hour. The product sol has a pH <0.1 and a viscosity of 344 cps.
A paint paste is prepared using 397.4g water, 8g Natrosol Plus, 5.5g Colloid 226/35, 2.0g Igepal CO630, 3.0g Colloid 640, 2.0g AMP-95, 1.5g potassium tripolyphosphate, 125g Tronox CR822, 150g Minex 4, lOOg ASP-NC2, 20g ethylene glycol, 1.5g Nuosept 95, 10.g Texanol, 3g Colloid 643, and 6g Polyphase AFl.
Two hundred eighty two (282) grams of a sol/latex product admixture composition, prepared from 30g of the above-prepared sol and 270g of a PVA latex, (Unocal 76 RES 3077) , are blended with equal quanti¬ ties of the above-prepared paint paste, but in one paint the aluminum acetate sol of Example 27 is re¬ placed by tetrapropylammonium bromide sol and no sol is admixed with the latex in the other. The product paint compositions are applied to coat redwood. The tannin blocking property of the paints are observed in Table X.
TABLE X
Sol in Paint Tannin Block Property none very poor blocking tetrapropylammonium bromide good blocking aluminum acetate fair blocking
The tetrapropylammonium bromide sol-containing paint exhibits better tannin blocking properties than the aluminum acetate sol-containing paint when a PVA latex (Unocal 76 RES 3077) is employed in the paint formulation of Example 27. Such results indicate the tannin blocking property of a paint or surface coating composition is dependent on the particular latex and/or the particular paint paste utilized with a given sol or gel composition.
EXAMPLE 35 A 2-liter resin kettle is charged with 491.3g 1,5-pentanediol, 99.82g zinc acetate, 332.7g citric acid and 30 ml concentrated nitric acid. The mixture is heated to 65° C. for 6 hours. The material is cooled to room temperature. The resulting material is a sol having a pH of <0.1.
EXAMPLE 36 A 1-liter resin kettle is charged with 246g ethylene glycol, 50g zinc acetate, and 166g of a nonionic surfactant Igepal CO630 polyoxyethylene nonylphenol. The mixture is heated to 40° C. for 6 hours. Upon cooling to room temperature, the result¬ ing material is a sol having a pH of 2.12 and a vis¬ cosity of 175 cps (Brookfield) .
Sols containing magnesium, manganese, mer- curous, strontium and uranyl nitrates are prepared in the same manner as the above-mentioned sol containing zinc acetate, ethylene glycol and the nonionic sur¬ factant. The pH and viscosity properties of the sols are summarized in Table Y as follows:
Figure imgf000129_0001
The sols of Examples 35 and 36 are each admixed with a latex. Each sol is separately mixed with a styrene-acrylate or and a polyvinylidene chlo¬ ride (commercially available as 76 RES 1018 and 76 RES 5517, respectively, from UCD. The sol to latex weight ratio is 1:9, obtained by using 36.Og sol and 324g latex. The sols are drawn down on steel Q panels using a 10 mil drawdown bar. The panels are dried for 1 week. The panels are then subjected to a salt fog (3%NaCl) at 80° C. for 100 hours in a Model No. 411- 1ACD cabinet manufactured by Industrial Filter & Pump Company of Cicero, Illinois using ASTM B-117 test. Uncoated panels, panels with latex containing no sol, and panels coated with latex admixed with the above described sols are evaluated after the "salt fog" test. The results using SSPC Guide to Vis. 2 are summarized in Table Z.
TABLE Z
Coatincf Rust Grade Description* None 1 approx. 50% of surface rusted
76 RES 1018 w/no sol 5 approx. 3% of surface rusted
w/Zn(OAc)2 citric acid sol 9 approx. 0.03% of surface rust
w/Mg(N03)2 citric acid sol approx. 0.1% of surface ruste
w/Hg(N03) citric acid sol approx. 0.1% of surface ruste
w/Sr(N03)2 citric acid sol approx. 0.1% of surface ruste
76 RES 5517 w/no sol approx. 0.3% of surface rust
w/Zn(OAc)2 CO630 sol approx. 0.1% surface rusted
w/Mg(N03)2 CO630 sol approx. 0.03% of surface rus TABLE Z (Continued)
Coating Rust Grade Description*
w/Mn(N03)2 CO630 sol approx. 0.03% of surface rus
w/Hg(NO3) CO630 sol approx. 0.03% of surface rus
w/U(N03). CO630 so! approx. 0.03% of surface rus
*Steel Structures Painting Council, Guide to Visual Standar No. 2, 1 Nov. 82.
The results in Table Z indicate that the product admixture composition of sol and latex coated on mild steel panels can reduce corrosion on the panel surfaces by a factor of at least about 10 times, and, in some cases, at least about 100 times that of panels coated with the latex containing no sol.
EXAMPLE 38 A 1-liter resin kettle is charged with 246g ethylene glycol, 50g sodium molybdate, 166g citric acid, and 15 ml concentrated citric acid. The mixture is heated at 45° C. for 3 hours. The product is cooled to room temperature to produce a sol. The sol has a pH of 0.1 and a viscosity of 216 cps (Brook¬ field) .
Sols containing sodium chromate and sodium phosphate (monobasic) are similarly prepared. The pH and viscosity properties of the sols are shown in Table AA.
Figure imgf000132_0001
The sols of Example 38 are separately ad¬ mixed with Unocal latexes containing polyvinyl acry¬ late (i.e., Unocal 76 RES 3077 and 76 RES 3083). The sol and latex product admixture compositions are drawn down on steel Q panels using a 10ml drawdown bar. The panels are air dried for 1 week. The panels are then subjected to QUV Weatherometer conditions for 1 week with alternating 4 hour intervals of light and dark¬ ness, and overlapping alternating 4 hour rain Simula- tions (using tap water) . Corrosion evaluations on uncoated panels, panels coated with latex containing no sol, and panels coated with product admixture compositions containing sol and latex are summarized in Table BB.
TABLE BB
Coating Rust Grade Description*
None 3 rust on approx. 17% surface
76 RES 3077 w/no sol 5 rust on approx. 3% surface w/molybdate 8 rust on approx. 0.1% surface w/chromate 9 rust on approx. 0.03% surface w/phosphate. 9 rust on approx. 0.03% surface
76 RES 3083 w/no sol 5 rust on approx. 3% surface w/molybdate 9 rust on approx. 0.03% surface w/chromate 9 rust on approx. 0.03% surface w/phosphate 8 rust on approx. 0.1% surface
*using SSPC Guide to VIS 2 (Nov. 1, 1982)
The results in Table BB indicate that the sol/latex coated panels can reduce corrosion by at least about 10 times and often at least about 100 times that of panels coated with the same latex but containing the salt from the sol.
In view of the foregoing description of the invention including the examples thereof, it is evi¬ dent that many alternatives, modifications, and varia¬ tions can be made by those skilled in the art without departing from the concept of the present invention. Accordingly, it is intended in the invention to em¬ brace all such alternatives, modifications, and varia¬ tions as may fall within the scope of the appended claims.

Claims

I CLAIM :
1. A process for preparing a sol or gel useful for addition to a composition containing at least one starting latex polymer, said process com¬ prising:
(1) admixing
(a) at least one nonaqueous solvent,
(b) at least one stabilizer and
(c) at least one salt, and
(2) heating the admixture at a temperature sufficient to produce a sol or gel composition containing said salt.
2. The process defined in claim 1 further comprising admixing (d) an acidic component prior to heating.
3. The process defined in claim 1 further comprising admixing an acidic component with said admixture after heating the admixture.
4. The process defined in claim 1 wherein said sol or gel has a pH less than about 6.0.
5. The process defined in claim 1 wherein said solvent is an organic solvent selected from the group consisting of a polyol, polyhydroxyl ether and polyhydroxyl alcohol.
6. The process defined in claim 1 wherein said solvent comprises ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyethylene-polyoxypropylene) glycol or blocked (polyoxyethylene-polyoxypropylene) glycol.
7. The process defined in claim 1 wherein said stabilizer comprises a chelator or a nonionic surfactant.
8. The process defined in claim 1 wherein said stabilizer comprises a hydroxycarboxylie acid.
9. The process defined in claim 8 wherein said hydroxycarboxylic acid is selected from the group consisting of citric acid, tartaric acid, mesotartaric acid, glycolic acid, -hydroxybutyric acid, mandelic acid, glyceric acid, malic acid and lactic acid.
10. The process defined in claim 7 wherein said stabilizer is a nonionic surfactant having the formula
R-(EO)χ(PO)y-R1 wherein each of R and Rι is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals,
EO is ethylene oxide, PO is propylene oxide, and x and y are nonnegative integers.
11. The process defined in claim 10 wherein said stabilizer is a glycerine-derived nonionic sur¬ factant having the formula
(EO)χ(PO)y-R glycerine
Figure imgf000137_0001
Figure imgf000137_0002
n-Ri:L wherein each of R, R1 and R11 is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla- ryl, dialkylaryl aliphatic ester and aryl ester radi¬ cals, EO is ethylene oxide, PO is propylene oxide and x, y, a, b, m and n are nonnegative integers, but not simultaneously zero.
12. The process defined in claim 10 wherein said stabilizer is a nonionic surfactant selected from the group consisting of 1-100 percent by weight of ethylene oxide in combination with 0-99 percent by weight of propylene oxide and having a molecular weight from 62 to 5,000, 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco¬ hol, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol EO octyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate, or monocetylate or monomystralate or monostearate.
13. The process defined in claim 1 wherein said salt contains a cation or anion selected from the group consisting of metallic cations or metallic anions, monomeric nonmetallic cations or monomeric nonmetallic anions, and polymeric nonmetallic cations or polymeric nonmetallic anions.
14. The process defined in claim 13 wherein said metallic cation is selected from the group con¬ sisting of antimony, yttrium, cadmium, silver, calci¬ um, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseodymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, strontium, ytterbium, titanium and mercury.
15. The process defined in claim 13 wherein said monomeric nonmetallic cation is selected from the group consisting of ammonium, boron and silicon.
16. The process defined in claim 15 wherein said monomeric nonmetallic anions are selected from the group consisting of nitrates, acetates, halides, borates, phosphates, formates, citrates, benzoates, tartrates, silicates, nitrites, carbonates, oxides and alkoxides.
17. The process defined in claim 2 or 3 wherein said acid component is selected from the group consisting of concentrated nitric acid, concentrated hydrochloric acid and concentrated sulfuric acid.
18. The process defined in claim 1 wherein said sol or gel has a pH less than about 1.0.
19. The process defined in claim 1 wherein the sol or gel composition is admixed with a composi¬ tion containing a latex polymer, said latex polymer is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having
4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a mono-olefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid, (3) olefinically unsaturated carboxylic acid ester polymers containing polymerized, ole¬ finically unsaturated monomers containing polymerized olefinically unsaturated carbox¬ ylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl
chloride with or without other polymer¬ ized, olefinically unsaturated monomers, and
(6) combinations thereof.
20. The process defined in claim 13 wherein said polymeric cations are selected from the group consisting of monoolefinic quaternary ammonium ca¬ tions, diolefinic quaternary ammonium cations, triole- finic quaternary ammonium cations and tetraolefinic quaternary ammonium cations.
21. The process defined in claim 13 wherein said polymeric anions are selected from the group consisting of alkyl, aryl, ether or alkylaryl sulfo- nates, sulfates, phosphates, carboxylates and polycar¬ boxylates.
22. The process defined in claim 19 wherein said conjugated diolefin polymers contain at least 10 weight percent of said conjugated diene monomers.
23. The process defined in claim 19 wherein said latex polymer in (1) further comprises one or more alkenyl- substituted monoaromatic monomers.
24. The process defined in claim 23 wherein said alkenyl-substituted monoaromatic monomers com¬ prise about 1 to about 70 weight percent of said latex polymer in (1) .
25. The process defined in claim 19 wherein said alkenyl or alkenol ester of a saturated carboxyl¬ ic acid in the olefin-ester interpolymers of (2) comprises at least 10 weight percent.
26. The process defined in claim 19 wherein said polymerized olefinically unsaturated carboxylic acid ester monomer comprises at least 10 weight per¬ cent of the latex polymer of (3) .
27. The process defined in claim 19 wherein said alkenyl ether monomer units in the polymers of (4) comprise at least 10 weight percent.
28. The process defined in claim 19 wherein said latex polymer comprises at least 35 weight per¬ cent of the product admixture composition produced from admixing said composition containing a latex polymer with said sol or gel composition.
29. The process defined in claim 3 wherein said sol or gel has a pH less than about 0.1.
30. The process defined in claim 2 or 3 wherein said acidic component is selected from the group consisting of inorganic acids and organic acids and said sol or gel has a pH less than about 4.0.
31. The process defined in claim 13 wherein said nonmetallic anion comprises an element selected from the group consisting of fluorine, oxygen, nitro¬ gen, carbon, tellurium, selenium, phosphorus, sulfur, chlorine, bromine and iodine.
32. The process defined in claim 13 wherein said metallic-containing anion comprises an element selected from the group consisting of arsenic, chromi¬ um, tin, aluminum, titanium, zirconium, vanadium, manganese and molybdenum.
33. The process defined in claim 1 wherein said admixture is heated to a temperature in the range from about 30° C. to about 90° C.
34. A process for admixing a composition containing at least one starting latex polymer with a salt, said process comprising: (A) preparing a substantially nonaqueous sol or gel composition by
(1) admixing (a) at least one nonaqueous
solvent, (b) at least one stabiliz¬ er, and (c) at least one salt, and
(2) heating the admixture to a tempera¬ ture sufficient to produce a substantially nonaqueous sol or gel composition containing said salt; and
(B.) admixing said sol or gel with said composition containing a latex polymer to produce a stable, noncoagulated product admixture composition containing said latex polymer and said salt.
35. The process defined in claim 34 further comprising admixing (d) an acidic component prior to heating.
36. The process defined in claim 34 further comprising admixing an acidic component with said admixture after heating the admixture.
37. The process defined in claim 34 wherein said sol or gel has a pH less than about 7.0.
38. The process defined in claim 34 wherein said solvent is an organic solvent selected from the group consisting of a polyol, polyhydroxyl ether and polyhydroxyl alcohol.
39. The process defined in claim 34 wherein said solvent comprises ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyethylene-polyoxypropylene) glycol or blocked (polyoxyethylene-polyoxypropylene) glycol.
40. The process defined in claim 34 wherein said stabilizer comprises a chelator or a nonionic surfactant.
41. The process defined in claim 34 wherein said stabilizer comprises a hydroxycarboxylic acid.
42. The process defined in claim 41 wherein said hydroxycarboxylic acid is selected from the group consisting of citric acid, tartaric acid, mesotartaric acid, glycolic acid, A-hydroxybutyric acid, mandelic acid, glyceric acid, malic acid and lactic acid.
43. The process defined in claim 40 wherein said stabilizer is a nonionic surfactant having the formula
R-(EO)χ(PO) -RJ
wherein each of R and R is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide, and x and y are nonnegative integers.
44. The process defined in claim 43 wherein said stabilizer is a glycerine-derived nonionic sur¬ factant having the formula (EO ) χ (PO) y-R glycerine ( EO ) a ( PO ) J-.-R1
(EO) m (PO) n-Ri:L
wherein each of R, R1 and R11 is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, onoalkyla- ryl, dialkylaryl aliphatic ester and aryl ester radi¬ cals, EO is ethylene oxide, PO is propylene oxide and X/ yf a, b, m and n are nonnegative integers.
45. The process defined in claim 43 wherein said stabilizer is a nonionic surfactant selected from the group consisting of 1-100 percent by weight of ethylene oxide in combination with 0-99 percent by weight of propylene oxide and having a molecular weight from 62 to 5,000, 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco¬ hol, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol EO qctyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate, or monocetylate or mono ystralate or monostearate.
46. The process defined in claim 34 wherein said salt contains a cation or anion selected from the group consisting of metallic cations or metallic anions, monomeric nonmetallic cations or monomeric nonmetallic anions, and polymeric nonmetallic cations or polymeric nonmetallic anions.
47. The process defined in claim 46 wherein said metallic cation is selected from the group con¬ sisting of antimony, yttrium, cadmium, silver, calci¬ um, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseodymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, strontium, ytterbium, titanium and mercury.
48. The process defined in claim 46 wherein said monomeric nonmetallic cation is selected from the group consisting of ammonium, boron and silicon.
49. The process defined in claim 48 wherein said monomeric nonmetallic anions are selected from the group consisting of nitrates, acetates, halides, borates, phosphates, formates, citrates, benzoates, tartrates, silicates, nitrites, carbonates, oxides and alkoxides.
50. The process defined in claim 35 or 36 wherein said acid component is selected from the group consisting of concentrated nitric acid, concentrated hydrochloric acid and concentrated sulfuric acid.
51. The process defined in claim 34 wherein said sol or gel has a pH less than about 1.0.
52. The process defined in claim 34 wherein the latex polymer is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having
4 to 8 carbon atoms, (2) olefin-ester interpolymers containing a mono olefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymerized, ole¬ finically unsaturated monomers containing polymerized olefinically unsaturated carbox¬ ylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl
chloride with or without other polymer¬ ized, olefinically unsaturated monomers, and
(6) combinations thereof.
53. The process defined in claim 46 wherein said polymeric cations are selected from the group consisting of monoolefinic quaternary ammonium ca¬ tions, diolefinic quaternary ammonium cations, triole- finic quaternary ammonium cations and tetraolefinic quaternary ammonium cations.
54. The process defined in claim 46 wherein said polymeric anions are selected from the group consisting of alkyl, aryl, or ether alkylaryl sulfo- nates, sulfates, phosphates, carboxylates and polycar¬ boxylates.
55. The process defined in claim 52 wherein said conjugated diolefin polymers contain at least 10 weight percent of said conjugated diene monomers.
56. The process defined in claim 52 wherein said latex polymer in (1) further comprises one or more alkenyl- substituted monoaromatic monomers.
57. The process defined in claim 56 wherein said alkenyl-substituted monoaromatic monomers com¬ prise about 1 to about 70 weight percent of said latex polymer in (1) .
58. The process defined in claim 52 wherein said alkenyl or alkenol ester of a saturated carboxyl¬ ic acid in the olefin-ester interpolymers of (2) comprises at least 10 weight percent.
59. The process defined in claim 52 wherein said polymerized olefinically unsaturated carboxylic acid ester monomer comprises at least 10 weight per¬ cent of the latex polymer of (3) .
60. The process defined in claim 52 wherein said alkenyl ether monomer units in the polymers of (4) comprise at least 10 weight percent.
61. The process defined in claim 35 or 36 wherein said acidic component is selected from the group consisting of protic acids and Lewis acids.
62. The process defined in claim 35 wherein said sol or gel has a pH less than about 0.1.
63. The process defined in claim 35 or 36 wherein said acidic component is selected from the group consisting of inorganic acids and organic acids and said sol or gel has a pH less than about 4.0.
64. The process defined in claim 46 wherein said nonmetallic anion comprises an element selected from the group consisting of fluorine, oxygen, nitro¬ gen, carbon, tellurium, selenium, phosphorus, sulfur, chlorine, bromine and iodine.
65. The process defined in claim 46 wherein said metallic-containing anion comprises an element selected from the group consisting of arsenic, chromi¬ um, tin, aluminum, titanium, zirconium, vanadium, manganese and molybdenum.
66. The process defined in claim 34 wherein said admixture is heated to a temperature in the range from about 30° C. to about 90° C.
67. A process for admixing a composition containing at least one starting latex polymer with a salt containing metallic or nonmetallic cations or metallic or nonmetallic anions, said process compris¬ ing the following steps:
(1) admixing (a) at least one nonaqueous solvent
comprising a polyol, (b) at least one stabilizer comprising a chelator or a nonion¬ ic surfactant, and (c) at least one salt con taining a metallic or nonmetallic cation or a metallic or nonmetallic anion, (2) heating the. admixture to a temperature less than about 100° C. for a time sufficient to produce a sol or gel composition containing said metallic cation or metallic anion, and
(3) admixing said sol or gel containing said
metallic cation or metallic anion with said composition containing at least one starting latex polymer to produce a stable, noncoagulated product admixture composition containing said latex polymer and said salt.
68. The process defined in claim 67 further comprising admixing (d) an acidic component prior to heating and wherein said sol or gel has a pH less than 7.0.
69. The process defined in claim 67 further comprising admixing an acidic component with said admixture after heating the admixture.
70. The process defined in claim 67 wherein said sol or gel has a pH less than about 4.0.
71. The process defined in claim 67 wherein said solvent is selected from the group consisting of a polyhydroxyl ether and polyhydroxyl alcohol.
72. The process defined in claim 71 wherein said solvent comprises ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyethylene-polyoxypropylene) glycol or blocked (polyoxyethylene-polyoxypropylene) glycol.
73. The process defined in claim 67 wherein said sol or gel has a pH less than about 1.0.
74. The process defined in claim 67 wherein said chelator comprises a hydroxycarboxylic acid.
75. The process defined in claim 74 wherein said hydroxycarboxylic acid is selected from the group consisting of citric acid, tartaric acid, mesotartaric acid, glycolic acid, -hydroxybutyric acid, mandelic acid, glyceric acid, malic acid and lactic acid.
76. The process defined in claim 71 wherein said nonionic surfactant having the formula
R-(EO) (PO)vy-R
wherei •n each of R and ι is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals,
EO is ethylene oxide, PO is propylene oxide, and x and y are nonnegative integers.
77. The process defined in claim 76 wherein said stabilizer is a glycerine-derived nonionic sur¬ factant having the formula
(EO)χ(PO)y-R glycerine (E0)a(P0)fc)-R1 (EO)m(PO)n-R1:L
wherein each of R, R1 and R11 is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla- ryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide and x, y, a, b, m and n are nonnegative integers.
78. The process defined in claim 76 wherein said stabilizer is a nonionic surfactant selected from the group consisting of 1-100 percent by weight of ethylene oxide in combination with 0-99 percent by weight of propylene oxide and having a molecular weight from 62 to 5,000, 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco- hoi, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol EO octyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate, or onocetylate or monomystralate or monostearate.
79. The process defined in claim 67 wherein said salt further comprises a polymeric nonmetallic cation or polymeric nonmetallic anion.
80. The process defined in claim 67 wherein said monometallic cation is selected from the group consisting of antimony, yttrium, cadmium, silver, calcium, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseodymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, stron¬ tium, ytterbium, titanium and mercury.
81. The process defined in claim 67 wherein said salt further comprises a monomeric nonmetallic cation is selected from the group consisting of ammo¬ nium, boron and silicon.
82. The process defined in claim 67 wherein said monomeric nonmetallic anions are selected from the group consisting of nitrates, acetates, halides, borates, phosphates, formates, citrates, benzoates, tartrates, silicates, nitrites, carbonates, oxides and alkoxides.
83. The process defined in claim 68 or 69 wherein said acidic component is selected from the group consisting of concentrated nitric acid, concen¬ trated hydrochloric acid and concentrated sulfuric acid.
84. The process defined in claim 68 or 69 wherein said sol or gel has a pH less than about 0.1.
85. The process defined in claim 65 wherein the latex polymer is selected from (1) conjugated diolefin polymers containing one or more conjugated diene monomers having
4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a
mono-olefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymerized, ole¬ finically unsaturated monomers containing polymerized olefinically unsaturated carbox¬ ylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl
chloride with or without other polymer¬ ized, olefinically unsaturated monomers, and
(6) combinations thereof.
86. The process defined in claim 79 wherein said polymeric cation is selected from the group consisting of monoolefinic quaternary ammonium ca¬ tions, diolefinic quaternary ammonium cations, triole- finic quaternary ammonium cations and tetraolefinic quaternary ammonium cations.
87. The process defined in claim 79 wherein said polymeric anion is selected from the group con¬ sisting of alkyl, aryl, ether or alkylaryl sulfonates, sulfates, phosphates, carboxylates and polycarboxy¬ lates.
88. The process defined in claim 85 wherein said conjugated diolefin polymers contain at least 10 weight percent of said conjugated diene monomers.
89. The process defined in claim 85 wherein said latex polymer in (1) further comprises one or more alkenyl- substituted monoaromatic monomers.
90. The process defined in claim 89 wherein said alkenyl-substituted monoaromatic monomers com¬ prise about 1 to about 70 weight percent of said latex polymer in (1) .
91. The process defined in claim 85 wherein said alkenyl or alkenol ester of a saturated carboxyl¬ ic acid in the olefin-ester interpolymers of (2) comprises at least 10 weight percent.
92. The process defined in claim 85 wherein said polymerized olefinically unsaturated carboxylic acid ester monomer comprises at least 10 weight per¬ cent of the latex polymer of (3) .
93. The process defined in claim 85 wherein said alkenyl ether monomer units in the polymers of (4) comprise at least 10 weight percent.
94. The process defined in claim 34 or 67 wherein said latex polymer comprises at least 35 weight percent of said product admixture composition.
95. The process defined in claims 67, 68 or 69 wherein said acidic component is selected from the group consisting of protic acids and Lewis acids.
96. The process defined in claim 68 or 69 wherein said acidic component is selected from the group consisting of inorganic acids and organic acids.
97. The process defined in claim 67 wherein said nonmetallic anion comprises an element selected from the group consisting of fluorine, oxygen, nitro¬ gen, carbon, tellurium, selenium, phosphorus, sulfur, chlorine, bromine and iodine.
98. The process defined in claim 67 wherein said metallic-containing anion comprises an element selected from the group consisting of arsenic, chromi¬ um, tin, aluminum, titanium, zirconium, vanadium, manganese and molybdenum.
99. The process defined in claim 67 wherein said admixture is heated to a temperature in the range from about 30° C. to about 90° C.
100. A sol or gel composition comprising:
(1) at least one solvent,
(2) at least one salt, and
(3) a stabilizer comprising a nonionic surfactant.
101. The composition defined in claim 100 further comprising an acidic component.
102. The composition defined in claim 100 having a pH less than 7.0 and being transparent.
103. The composition defined in claim 100 wherein said salt is dispersed as cations and anions or as colloidal salt particulates.
104. The composition defined in claim 100 wherein said solvent is selected from the group con¬ sisting of a polyol, polyhydroxyl ether and polyhy¬ droxyl alcohol.
105. The process defined in claim 1 wherein said solvent comprises ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyethylene-polyoxypropylene) glycol or blocked (polyoxyethylene-polyoxypropylene) glycol.
106. The composition defined in claim 100 wherein said nonionic surfactant has the formula
R-(E0)χ(P0)y-R1
wherein each of R and R1 is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide, and x and y are nonnegative integers.
107. The composition defined in claim 106 wherein said stabilizer is a glycerine-derived nonion¬ ic surfactant having the formula (EO)χ(PO)y-R glycerine (EO)a(PO)^-R1
(EO)m(PO)n-Ri:L
wherein each of R, R and R11 is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla- ryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide and x, y, a, b, m and n are nonnegative integers.
108. The process defined in claim 106 wherein said stabilizer is a nonionic surfactant selected from the group consisting of l-ioo percent by weight of ethylene oxide in combination with 0-99 percent by weight of propylene oxide and having a molecular weight from 62 to 5,000, 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco¬ hol, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol EO octyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate, or monocetylate or monomystralate or monostearate.
109. The composition defined in claim 100 wherein said salt contains a cation or anion selected from the group consisting of metallic cations or metallic anions, monomeric nonmetallic cations or monomeric nonmetallic anions, and polymeric nonmetal¬ lic cations or polymeric nonmetallic anions.
110. The composition defined in claim 109 wherein said metallic cation is selected from the group consisting of antimony, yttrium, cadmium, sil¬ ver, calcium, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseodymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, strontium, ytterbium, titanium and mercury.
111. The composition defined in claim 109 wherein said monomeric nonmetallic cation is selected from the group consisting of ammonium, boron and silicon.
112. The process defined in claim 111 wherein said monomeric nonmetallic anions are selected from the group consisting of nitrates, acetates, halides, borates, phosphates, formates, citrates, benzoates, tartrates, silicates, nitrites, carbonates, oxides and alkoxides.
113. The composition defined in claim 101 wherein said acidic component is selected from the group consisting of concentrated nitric acid, concen¬ trated hydrochloric acid and concentrated sulfuric acid.
114. The composition defined in claim 100 capable of being admixed with a composition containing at least one starting latex polymer to form a stable, noncoagulated composition containing at least 35 weight percent of said latex polymer combined with said salt.
115. The composition defined in claim 114 wherein the latex polymer is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid
ester polymers containing polymerized,olefinically unsaturated monomers containing
polymerized olefinically unsaturated car . boxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride -with or without other polymer¬ ized, olefinically unsaturated monomers, and
(6) combinations thereof.
116. The composition defined in claim 109 wherein said polymeric cations are selected from the group consisting of monoolefinic quaternary ammonium cations, diolefinic quaternary ammonium cations, triolefinic quaternary ammonium cations and tetraole- finic quaternary ammonium cations.
117. The composition defined in claim 109 wherein said polymeric anions are selected from the group consisting of alkyl, aryl, ether or alkylaryl sulfonates, sulfates, phosphates, carboxylates and polycarboxylates.
118. The composition defined in claim 115 wherein said conjugated diolefin polymers contain at least 10 weight percent of said conjugated diene monomers.
119. The composition defined in claim 115 wherein said latex polymer in (1) further comprises one or more alkenyl-substituted monoaromatic monomers.
120. The composition defined in claim 119 wherein said alkenyl-substituted monoaromatic monomers comprise about 1 to about 70 weight percent of said latex polymer in (1) .
121. The composition defined in claim 115 wherein said alkenyl or alkenol ester of a saturated carboxylic acid in the olefin-ester interpolymers of (2) comprises at least 10 weight percent.
122. The composition defined in claim 115 wherein said polymerized olefinically unsaturated carboxylic acid ester monomer comprises at least 10 weight percent of the latex polymer of (3) .
123. The composition defined in claim 115 wherein said alkenyl ether monomer units in the poly¬ mers of (4) comprise at least 10 weight percent.
124. The composition defined in claim 100 wherein said acidic component is selected from the group consisting of protic acids and Lewis acids.
125. The composition defined in claim 101 wherein said acidic component is selected from the group consisting of inorganic acids and organic acids.
126. The composition defined in claim 109 wherein said nonmetallic anion comprises an element selected from the group consisting of fluorine, oxy¬ gen, nitrogen, carbon, tellurium, selenium, phospho¬ rus, sulfur, chlorine, bromine and iodine.
127. The composition defined in claim 109 wherein said metallic-containing anion comprises an element selected from the group consisting of arsenic, chromium, tin, aluminum, titanium, zirconium, vanadi¬ um, manganese and molybdenum.
128. An intermediate composition useful in the preparation of a sol or gel, said composition comprising: (1) at least one solvent,
(2) at least one salt, and
(3) a stabilizer comprising a nonionic surfactan .
129. The composition defined in claim 128 further comprising an acidic component.
130. The composition defined in claim 128 wherein said solvent is nonaqueous.
131. The composition defined in claim 128 having a pH less than 7.0.
132. The composition defined in claim 128 wherein said solvent is an organic solvent selected from the group consisting of a polyol, polyhydroxyl ether and polyhydroxyl alcohol.
133. The process defined in claim 128 wherein said solvent comprises ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyethylene-polyoxypropylene) glycol or blocked (polyoxyethylene-polyoxypropylene) glycol,
134. The composition defined in claim 128 wherein said stabilizer is a nonionic surfactant having the formula
R-(EO)v(PO)v-R-
wherein each of R and R 1 is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide, and x and y are nonnegative integers.
135. The composition defined in claim 128 wherein said stabilizer is a glycerine-derived nonion¬ ic surfactant having the formula
(EO)χ(PO)y-R glycerine (EO) a(PO^-R1
(E0)m(P0)n-R 11 wherein each of R, R1 and R11 is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla- ryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide and x, y, a, b, m and n are nonnegative integers.
136. The process defined in claim 134 wherein said stabilizer is a nonionic surfactant selected from the group consisting of 1-100 percent by weight of ethylene oxide in combination with 0-99 percent by weight of propylene oxide and having a molecular weight from 62 to 5,000, 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco¬ hol, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol EO octyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate, or monocetylate or monomystralate or monostearate.
137. The composition defined in claim 128 wherein said salt contains a cation or anion selected from the group consisting of metallic cations or metallic anions, monomeric nonmetallic cations or monomeric nonmetallic anions, and polymeric nonmetal¬ lic cations or polymeric nonmetallic anions.
138. The composition defined in claim 137 wherein said metallic cation is selected from the group consisting of antimony, yttrium, cadmium, sil¬ ver, calcium, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseodymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, strontium, ytterbium, titanium and mercury.
139. The composition defined in claim 137 wherein said monomeric nonmetallic cation is selected from the group consisting of ammonium, boron and silicon.
140. The process defined in claim 139 wherein said monomeric nonmetallic anions are selected from the group consisting of nitrates, acetates, halides, borates, phosphates, formates, citrates, benzoates, tartrates, silicates, nitrites, carbonates, oxides and alkoxides.
141. The composition defined in claim 129 wherein said acid component is selected from the group consisting of concentrated nitric acid, concentrated hydrochloric acid and concentrated sulfuric acid.
142. The composition defined in claim 128 capable of being heated to form a sol or gel composi¬ tion and wherein said sol or gel forms a stable, noncoagulated product admixture composition containing a latex polymer and said salt when admixed with a composition containing at least one starting latex polymer.
143. The composition defined in claim 142 wherein the latex polymer is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms, (2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymerized, olefin¬ ically unsaturated monomers containing poly¬ merized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl
chloride with or without other polymer¬ ized, olefinically unsaturated monomers, and
(6) combinations thereof.
144. The composition defined in claim 137 wherein said polymeric cations are selected from the group consisting of monoolefinic quaternary ammonium cations, diolefinic quaternary ammonium cations, triolefinic quaternary ammonium cations and tetraole- finic quaternary ammonium cations.
145. The composition defined in claim 137 wherein said polymeric anions are selected from the group consisting of alkyl, aryl, ether or alkylaryl sulfonates, sulfates, phosphates, carboxylates and polycarboxylates.
146. The composition defined in claim 143 wherein said conjugated diolefin polymers contain at least 10 weight percent of said conjugated diene monomers.
147. The composition defined in claim 143 wherein said latex polymer in (1) further comprises one or more alkenyl-substituted monoaromatic monomers.
148. The composition defined in claim 147 wherein said alkenyl-substituted monoaromatic monomers comprise about 1 to about 70 weight percent of said latex polymer in (1) .
149. The composition defined in claim 143 wherein said alkenyl or alkenol ester of a saturated carboxylic acid in the olefin-ester interpolymers of (2) comprises at least 10 weight percent.
150. The composition defined in claim 143 wherein said polymerized olefinically unsaturated carboxylic acid ester monomer comprises at least 10 weight percent of the latex polymer of (3) .
151. The composition defined in claim 143 wherein said alkenyl ether monomer units in the poly¬ mers of (4) comprise at least 10 weight percent.
152. The composition defined in claim 129 wherein said acidic component is selected from the group consisting of protic acids and Lewis acids.
153. The composition defined in claim 129 wherein said acidic component is selected from the group consisting of inorganic acids and organic acids.
154. The composition defined in claim 137 wherein said nonmetallic anion comprises an element selected from the group consisting of fluorine, oxy¬ gen, nitrogen, carbon, tellurium, selenium, phospho¬ rus, sulfur, chlorine, bromine and iodine.
155. The composition defined in claim 137 wherein said metallic-containing anion comprises an element selected from the group consisting of arsenic, chromium, tin, aluminum, titanium, zirconium, vanadi¬ um, manganese and molybdenum.
156. A latex polymer composition comprising the product admixture composition obtained from the process of claim 34.
157. A latex polymer composition comprising the product admixture composition obtained from the process of claim 67.
158. A composition comprising the product admixture composition obtained from admixing the sol or gel obtained from the process of claim 1 with a composition containing at least one starting polymer.
159. A stable, noncoagulated product admix¬ ture composition containing a starting latex polymer and a metallic cation or metallic anion, said product admixture composition prepared from a sol or gel admixed with a composition containing at least one starting latex polymer, said sol or gel composition prepared by the following steps:
(1) admixing
(a) at least one solvent containing ethyl¬ ene glycol,
(b) at least one salt comprising a metallic cation or metallic anion, and
(c) at least one stabilizer comprising citric acid or a nonionic surfactant, and
(2) heating the admixture obtained in step (1) to an elevated temperature in the range from greater than room temperature to about 95° C. and wherein a transparent sol or gel containing a metallic cation or metallic anion is produced.
160. The composition defined in claim 159 further comprising admixing (d) an acidic component prior to heating.
161. The composition defined in claim 159 further comprising admixing an acidic component with said admixture after heating the admixture.
162. The composition defined in claim 159 wherein said sol or gel has a pH less than 4.0.
163. The composition defined in claim 159 wherein said stabilizer is a nonionic surfactant having the formula
R-(EO) (PO) -RJ wherein each of R and Rι is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester and aryl ester radicals,
EO is ethylene oxide, PO is propylene oxide, and x and y are nonnegative integers.
164. The composition defined in claim 163 wherein said stabilizer is a glycerine-derived nonion¬ ic surfactant having the formula
Figure imgf000185_0001
glycerine (EO) .-.(POJj-.-R1
Figure imgf000185_0002
1 I T , , wherein each of R, R-1- and Rx is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla¬ ryl, dialkylaryl aliphatic ester and aryl ester radi¬ cals, EO is ethylene oxide, PO is propylene oxide and x, y, a, b, m and n are nonnegative integers.
165. The process defined in ciaim 163 wherein said stabilizer is a nonionic surfactant selected from the group consisting of 1-100 percent by weight of ethylene oxide in combination with 0-99 percent by weight of propylene oxide and having a molecular weight from 62 to 5,000, 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alco¬ hol, 6-50 mol EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 mol EO octyl phenol, 6- 50 mol EO decyl phenol, 6-50 mol EO dodecyl phenol, 6- 50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate, or monocetylate or onomystralate or monostearate.
166. The composition defined in claim 159 wherein said salt contains a cation or anion selected from the group consisting of metallic cations or metallic anions, monomeric nonmetallic cations or monomeric nonmetallic anions, and polymeric nonmetal¬ lic cations or polymeric nonmetallic anions.
167. The composition defined in claim 166 wherein said metallic cation is selected from the group consisting of antimony, yttrium, cadmium, sil¬ ver, calcium, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseodymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, strontium, ytterbium, titanium and mercury.
168. The composition defined in claim 166 wherein said monomeric nonmetallic cation is selected from the group consisting of ammonium, boron and silicon.
169. The process defined in claim 168 wherein said monomeric nonmetallic anions are selected from the group consisting of nitrates, acetates, halides, borates, phosphates, formates, citrates, benzoates, tartrates, silicates, nitrites, carbonates, oxides and alkoxides.
170. The composition defined in claim 160 or 161 wherein said acid component is selected from the group consisting of concentrated nitric acid, concen¬ trated hydrochloric acid and concentrated sulfuric acid.
171. The composition defined in claim 159 wherein the latex polymer is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene mono¬ mers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymerized, olefin¬ ically unsaturated monomers containing poly¬ merized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl
chloride with or without other polymer¬ ized, olefinically unsaturated monomers, and
(6) combinations thereof.
172. The composition defined in claim 166 wherein said polymeric cations are selected from the group consisting of monoolefinic quaternary ammonium cations, diolefinic quaternary ammonium cations, triolefinic quaternary ammonium cations and tetraole- finic quaternary ammonium cations.
173. The composition defined in claim 166 wherein said polymeric anions are selected from the group consisting of alkyl, aryl, ether or alkylaryl sulfonates, sulfates, phosphates, carboxylates and polycarboxylates.
174. The composition defined in claim 171 wherein said conjugated diolefin polymers contain at least 10 weight percent of said conjugated diene monomers.
175. The composition defined in claim 171 wherein said latex polymer in (1) further comprises one or more alkenyl-substituted monoaromatic monomers.
176. The composition defined in claim 175 wherein said alkenyl-substituted monoaromatic monomers comprise about 1 to about 70 weight percent of said latex polymer in (1) .
177. The composition defined in claim 171 wherein said alkenyl or alkenol ester of a saturated carboxylic acid in the olefin-ester interpolymers of (2) comprises at least 10 weight percent.
178. The composition defined in claim 171 wherein said polymerized olefinically unsaturated carboxylic acid ester monomer comprises at least 10 weight percent of the latex polymer of (3) .
179. The composition defined in claim 171 wherein said alkenyl ether monomer units in the poly¬ mers of (4) comprise at least 10 weight percent.
180. The composition defined in claim 159 wherein said acidic component is selected from the group consisting of protic acids and Lewis acids.
181. The composition defined in claim 160 or 161 wherein said acidic component is selected from the group consisting of inorganic acidε and organic acids.
182. The composition defined in claim 166 wherein said nonmetallic anion comprises an element selected from the group consisting of fluorine, oxy¬ gen, nitrogen, carbon, tellurium, selenium, phospho¬ rus, sulfur, chlorine, bromine and iodine.
183. The composition defined in claim 166 wherein said metallic-containing anion comprises an element selected from the group consisting of arsenic, chromium, tin, aluminum, titanium, zirconium, vanadi¬ um, manganese and molybdenum.
184. An electrically conductive polymer composition comprising a nonconjugated polymer and a salt.
185. A composition containing at least one polymer and an organosol or organogel containing a salt.
186. The composition defined in claim 185 wherein said organosol or organogel comprises an organic solvent, a salt and a stabilizer.
187. The composition defined in claim 186 wherein said salt contains at least one anion and at least one cation dispersed in a latex polymer.
188. A substantially nonaqueous composition containing at least one latex polymer and a salt.
189. The composition defined in claim 188 wherein at least one cation and at least one anion of said salt is dispersed in said latex polymer.
190. The composition defined in claim 188 wherein said salt is an inorganic salt.
191. The composition defined in claim 190 having a pH less than 7.0.
192. The composition defined in claim 188 capable of conducting a greater alternating electrical current flow than that conducted by said composition without said salt.
193. The composition defined in claim 188 capable of conducting at least 0.5 microamperes of alternating electrical current when 5000 volts of electricity are applied between brass electrodes that are one inch apart.
194. The composition defined in claim 188 capable of conducting at least 5,000 microamperes of alternating electrical current when less than 5,000 volts of electricity are applied between brass elec¬ trodes that are one inch apart.
195. A composition obtained from the process defined in claims 156, 157 or 159 wherein said compo¬ sition containing at least one starting latex polymer further comprises water, and substantially all water is removed from said product admixture composition.
196. A resultant latex polymer/salt composi¬ tion obtained by drying said stable, noncoagulated product admixture composition of claims 156, 157 or 159.
197. A process wherein the composition of claim 142 is heated to form a sol or gel composition.
198. A resultant latex polymer/salt composi¬ tion prepared from a stable, noncoagulated product admixture composition containing a starting latex polymer and a dispersed salt, said resultant latex polymer/salt composition prepared by the following steps:
(1) preparing a sol or gel composition (2) admixing said sol or gel composition obtained in step (1) with a composition contain¬ ing a starting latex polymer to produce a stable, noncoagulated product admixture composition; and
(3) drying said stable, noncoagulated product admixture composition obtained from step (2) .
199. The composition defined in claim 198 wherein said sol or gel composition prepared in step (1) comprises the sol or gel composition of claims 1, 34, 67, 100 or 197.
200. The composition defined in claim 199 wherein said sol or gel composition prepared in step
(1) comprises the sol or gel composition of claims 2, 6, 9, 10, 11, 12, 14, 15, 16, 18, 19, 31, 32 or 33.
201. A product composition containing said salt obtained by drying the product admixture composi¬ tion of claims 158 or 185.
202. A textile composition comprising a textile material suffused with sufficient added salt to provide at least 5 percent greater electrical conductivity to said textile composition than that of said textile composition without added salt.
203. The composition defined in claim 202 wherein said added salt provides at least 10 percent greater electrical conductivity.
204. The composition defined in claim 202 wherein said added salt provides at least 25 percent greater electrical conductivity.
205. The composition defined in claim 202 wherein said added salt comprises greater than about 0.1 weight percent.
206. The composition defined in claim 202 wherein said added salt comprises greater than 0.3 weight percent.
207. The composition defined in claim 202 wherein said textile material comprises a carpet material.
208. The composition defined in claim 202 wherein said added salt comprises greater than 0.5 weight percent.
209. The composition defined in claim 202 wherein said added salt is dispersed in a polymer.
210. The composition defined in claim 202 wherein said added salt is dispersed in a latex poly¬ mer.
211. The composition defined in claim 202 further comprising a filler material.
212. The composition defined in claim 211 further comprising a frothing agent.
213. The composition defined in claim 211 further comprising a plasticizer.
214. The composition defined in claim 202 having an electrical conductivity greater than 10 Seimens/cm.
215. The composition defined in claim 202 having an electrical conductivity in the range from about 10 to about 10 Seimens/cm.
216. The composition defined in claim 202 having an electrical conductivity in the range from about 0.1 to about 10 Seimens/cm.
217. A textile composition comprising a textile material and a product admixture composition, said product admixture composition comprising a compo¬ sition (1) containing a polymer, and (2) an added salt contained in a sol or gel composition containing at least one nonaqueous solvent, at least one stabilizer and said added salt, said added salt contained in said product admixture composition in an amount sufficient to provide an antistatic property to said textile composition.
218. The composition defined in claim 217 wherein said polymer comprises a latex polymer.
219. The composition defined in claim 217 wherein said added salt contained in said product admixture composition is greater than about 0.05 weight percent.
220. The composition defined in claim 217 wherein said added salt contained in said product admixture composition is greater than about 0.10 weight percent.
221. The composition defined in claim 217 wherein said added salt contained in said product admixture composition is greater than about 0.5 weight percent.
222. The composition defined in claim 217 wherein said nonaqueous solvent comprises an ether, ester or alcohol.
223. The composition defined in claim 217 wherein said added salt comprises a metallic cation.
224. The composition defined in claim 217 wherein said stabilizer comprises a chelator or non¬ ionic surfactant.
225. The composition defined in claim 223 wherein said metallic cation is selected from the group consisting of neodymium, aluminum, calcium, copper, dysprosium, lithium, magnesium, sodium, yttri¬ um, ytterbium and zinc.
226. The composition defined in claim 217 wherein said added salt comprises a nonmetallic cation selected from the group consisting of ammonium, boron and silicon.
227. The composition defined in claim 217 wherein said sol or gel composition further comprises an acid component.
228. The composition defined in claim 218 further comprising a filler material.
229. The composition defined in claim 218 further comprising a frothing agent.
230. The composition defined in claim 218 further comprising a plasticizer.
231. The composition defined in claim 218 having an electrical conductivity greater than 10 w Seimens/cm.
232. The composition defined in claim 218 having an electrical conductivity in the range from about 10~8 to about 10 Seimens/cm.
233. The composition defined in claim 218 having an electrical conductivity in the range from about 0.1 to about 10 Seimens/cm.
234. The composition defined in claim 217 wherein said textile material comprises carpet.
235. A compounded polymer/salt product compo¬ sition useful for suffusing a textile, said product composition comprising:
(1) a product admixture containing (a) the components of a sol or gel composition containing a salt and (b) a polymer; and
(2) a filler material.
236. The composition defined in claim 235 containing essentially no water.
237. The composition defined in claim 235 further comprising a plasticizer or a frothing agent.
238. The composition defined in claim 235 having an electrical conductivity greater than about 10 ° Seimens/cm.
239. The composition defined in claim 235 wherein said polymer comprises a latex polymer.
240. The composition defined in claim 235 having a pH in the range from about 7.0 to about 9.0.
241. A textile composition containing a salt suffused therein, said textile composition prepared by a method comprising the step of contacting a textile material with a sol or gel composition containing a salt.
242. The textile composition defined in claim
241 wherein said sol or gel composition further com¬ prises a polymer.
243. The textile composition defined in claim
242 wherein said polymer comprises a latex polymer.
244. The textile composition defined in claim 242 wherein said sol or gel composition further com¬ prises a filler material.
245. The textile composition defined in claim 244 wherein said sol or gel composition has a pH less than 4.0 and said filler material has a pH greater than 4.0.
246. The textile composition defined in claim 244 wherein said sol or gel composition further com¬ prises a plasticizer.
247. The textile composition defined in claim 244 wherein said sol or gel composition further com¬ prises a frothing agent.
248. The textile composition defined in claim 241 having an electrical conductivity greater than 10" 10 Seimens/cm.
249. The textile composition defined in claim 241 having an electrical conductivity in the range from about 0.1 to about 10 Seimens/cm.
250. The textile composition defined in claim 241 wherein said method further comprises a subsequent step of drying the textile material contacted with said sol or gel composition.
251. A dried compounded polymer/salt product composition suffused in said textile material and prepared by the method of claim 49.
252. The composition defined in claim 251 comprising at least about 0.03 weight percent of said salt.
253. The composition defined in claim 251 having an electrical conductivity greater than 10 Seimens/cm.
254. The composition defined in claim 252 having an electrical conductivity in the range from about 10~8 to about 10 Seimens/cm.
255. The composition defined in claim 253 having an electrical conductivity in the range from about 0.1 to about 10 Seimens/cm.
256. A textile composition containing a salt suffused therein, said textile composition prepared by a method comprising the step of contacting a textile material with a product admixture composition compris¬ ing (1) a sol or gel composition containing a salt admixed with (2) a polymer.
257. The textile composition defined in claim
256 wherein said polymer comprises a latex polymer.
258. The textile composition defined in claim
257 wherein said product admixture composition further comprises a filler material.
259. The textile composition defined in claim
258 wherein said product admixture composition has a pH less than 4.0 and said filler material has a pH greater than,4.0.
260. The textile composition defined in claim 258 wherein said product admixture composition further comprises a plasticizer.
261. The textile composition defined in claim 258 wherein said product admixture composition further comprises a frothing agent.
262. The textile composition defined in claim 256 having an electrical conductivity in the range from about 10 8 to about 10 Seimens/cm.
263. The textile composition defined in claim 256 having an electrical conductivity in the range from about 0.1 to about 10 Seimens/cm.
264. A dried compounded polymer/salt product composition suffused in said textile material and prepared by the method of claim 56.
265. The composition defined in claim 264 comprising at least about 0.03 weight percent of said salt.
266. The composition defined in claim 264 having an electrical conductivity greater than 10 —T1nU Seimens/cm.
267. A method for preparing a textile compo¬ sition, said method comprising contacting a textile material with (1) a sol or gel composition containing a salt, or (2) a product admixture composition con¬ taining a sol or gel composition containing a salt admixed with a polymer, to produce a textile composi¬ tion containing a salt suffused therein.
268. The method defined in claim 267 wherein said polymer is a latex polymer and said product admixture composition further comprises a filler material.
269. The method defined in claim 267 further comprising drying said textile composition to produce a dried compounded polymer/salt product composition suffused in said textile material.
270. The method defined in claim 269 wherein said product admixture has a pH less than 4.0 and said filler material has a pH greater than 4.0.
271. The method defined in claim 269 wherein said product admixture composition further comprises a frothing agent or a plasticizer.
272. The method defined in claim 269 wherein the amount of said sol or gel composition or said product admixture composition contacting the textile material is sufficient to produce said textile compo¬ sition having an electrical conductivity of about 10~8 to about 10 Seimens/cm.
273. The method defined in claim 269 wherein the amount of said sol or gel composition or said product admixture composition contacting the textile material is sufficient to produce said textile compo¬ sition having electrical conductivity greater than 10" υ Seimens/cm.
274. A textile composition comprising a textile material su fused with su ficient added salt to provide an antistatic property to said composition.
275. A surface coating composition comprising a polymer binder and a salt homogeneously distributed in the composition.
276. The composition defined in claim 275 further comprising water.
277. The composition defined in claim 275 further comprising a surface coating paste stock.
278. The composition defined in claim 276 wherein said polymer is a water-soluble polymer.
279. The composition in claim 276 wherein said polymer is a water-dispersible polymer.
280. The composition in claim 277 wherein said paste stock comprises at least one pigment.
281. The composition defined in claim 277 wherein said paste stock comprises a coalescing aid.
282. The composition defined in claim 277 wherein said paste stock comprises a thickening aid.
283. The composition defined in claim 277 wherein said paste stock comprises a dispersing aid.
284. The composition defined in claim 277 wherein said paste stock comprises a defoamer.
285. The composition defined in claim 277 wherein said paste stock comprises a biocide.
286. The composition defined in claim 279 wherein said water-dispersible polymer is a latex polymer.
287. The composition defined in claim 278 wherein said water-soluble polymer is a water-soluble resin, alkyd, polyurethane, or unsaturated polyester.
288. The composition defined in claim 275 wherein the specular gloss is increased at least about 2 percent reflectance, based upon light having about a 60° angle of incidence, as compared to said composition without said salt.
289. The composition defined in claim 275 wherein said salt comprises a rare earth metallic cation.
290. The composition defined in claim 275 wherein said salt comprises colloidal salt particu¬ lates.
291. The composition defined in claim 275 wherein said salt is contained in a sol or gel compo¬ sition and the concentration of said salt in said sol or gel composition is about 2 to about 50 weight percent.
292. The composition defined in claim 275 wherein the concentration of salt in said coating composition is about 0.05 to about 5 weight percent.
293. The composition defined in claim 291 wherein the concentration of sol or gel composition in said coating composition is about 0.1 to about 2 weight percent.
294. The composition defined in claim 286 wherein said latex polymer is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without .other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
295. The composition defined in claim 275 wherein said salt comprises lanthanum or silicon.
296. The composition defined in claim 275 wherein said salt is selected from the group consist¬ ing of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymi¬ um, antimony, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samari¬ um, tellurium, yttrium, bismuth, gallium, neodymium, rubidium and terbium.
297. The composition defined in claim 275 being a semi-gloss or high-gloss paint composition.
298. A surface coating composition compris¬ ing:
(1) a product admixture composition com¬ prising a sol or gel composition con¬ taining a salt and a polymer binder, and
(2) a surface coating paste stock.
299. The surface coating composition defined in claim 298 being a waterborne surface coating compo¬ sition further comprising water.
300. The waterborne surface coating composi¬ tion defined in claim 299 further comprising at least one pigment.
301. The waterborne surface coating composi¬ tion defined in claim 299 wherein said surface coating paste stock comprises pigment salt particulates of diameter greater than 40 nanometers.
302. The waterborne surface coating composi¬ tion defined in claim 299 further comprising a coa¬ lescing aid.
303. The waterborne surface coating composi¬ tion defined in claim 299 further comprising a thick¬ ening aid.
304. The waterborne surface coating composi¬ tion defined in claim 299 further comprising a dis¬ persing aid.
305. The waterborne surface coating composi¬ tion defined in claim 299 further comprising a defoam¬ er.
306. The waterborne surface coating composi¬ tion defined in claim 299 further comprising a bio- cide.
307. The waterborne surface coating composi¬ tion defined in claim 301 further comprising:
(a) a coalescing aid,
(b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide, and
(f) a filler.
308. The surface coating composition defined in claim 298 wherein said polymer binder comprises a water-dispersible polymer comprising a latex polymer.
309. The waterborne surface coating composi¬ tion defined in claim 298 wherein said polymer binder comprises a water-soluble polymer.
310. The surface coating composition defined in claim 298 further comprising water, a surface coating paste stock and sufficient salt in said sol or gel composition to increase the specular gloss by at least about 2 percent reflectance, based upon light having about a 60° angle of incidence, as compared to the same composition, but not containing said sol or gel composition.
311. The surface coating composition defined in claim 298 wherein said salt comprises a rare earth metallic cation.
312. The surface coating composition defined in claim 298 wherein said salt comprises colloidal salt particulates.
313. The waterborne surface coating composi¬ tion defined in claim 300 wherein said salt is homoge¬ neously distributed in said composition.
314. The surface coating defined in claim 298 wherein the concentration of said salt in said coating composition is about 0.05 to about 5 weight percent.
315. The waterborne surface coating defined in claim 298 wherein the concentration of salt in said sol or gel composition is about 10 to about 20 weight percent.
316. The waterborne surface coating defined in claim 298 wherein the concentration of sol or gel composition in said coating composition is about 0.1 to about 2 weight percent.
317. The waterborne surface coating defined in claim 298 wherein the concentration of sol or gel in said product admixture composition is about 2 to about 20 weight percent.
318. The waterborne surface coating composi¬ tion defined in claim 24 wherein said polymer binder is a water-dispersible polymer binder selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester ofa saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymerized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or .lm32vinyl chloride with or without other polymerized, olefinically unsatu¬ rated monomers, and
(6) combinations thereof.
319. The waterborne surface coating composi¬ tion defined in claim 298 wherein said salt is select¬ ed from the group consisting of the acetates, cit¬ rates, nitrates and halides of ammonium, silver, aluminum, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magne- sium, sodium, nickel, lead, praseodymium, antimony, silicon, strontium, thallium, uranium, zinc, manga¬ nese, gold, germanium, molybdenum, samarium, telluri¬ um, yttrium, bismuth, gallium, neodymium, rubidium and terbium.
320. A paint composition comprising: a paint paste stock, a latex polymer, water, and a gloss-enhancing amount of a salt homogeneously distributed in said com position.
321. A paint composition comprising: water a latex polymer binder. a coalescing aid, a thickening aid, a defoamer, a biocide, a filler, and a gloss-enhancing amount of a salt homogeneously distributed in said composition.
322. A precursor composition useful for preparing a product surface coating composition, said precursor composition comprising:
(1) a polymer,
(2) a surface coating paste stock, and
(3) a sol or gel composition containing a gloss-enhancing amount of a salt.
323. The precursor composition defined in claim 322 wherein said salt is in sufficient amount to increase the specular gloss of said product surface coating composition by at least about 2 percent re¬ flectance, based upon light having about a 60° angle of incidence, as compared to said product surface coating composition without said salt.
324. The precursor composition defined in claim 320 wherein said salt is in sufficient amount to increase the specular gloss of said product surface coating composition by at least about 2 percent re¬ flectance, based upon light having about a 60° angle of incidence, as compared to said product surface coating composition without said salt.
325. The precursor composition defined in claim 321 wherein said salt is in sufficient amount to increase the specular gloss of said product surface coating composition by at least about 2 percent re¬ flectance, based upon light having about a 60° angle of incidence, as compared to said product surface coating composition without said salt.
326. A method for increasing the gloss property of a product surface coating composition, said method comprising the step of admixing a sol or gel composition containing a gloss-enhancing concen¬ tration of a salt with a composition containing a polymer to produce a product surface coating composi¬ tion or a surface coating precursor composition, said product surface coating composition or a product surface coating composition derived from said surface coating precursor composition both having a gloss property which is greater than that of the same product surface coating composition prepared without said salt from said sol or gel composition.
327. The method defined in claim 326 wherein the specular gloss of said product surface coating is increased by at least about 2 percent reflectance, based upon light having about a 60° angle of inci¬ dence.
328. _ The method defined in claim 326 wherein said product surface coating composition is a semi- gloss or high-gloss paint.
329. The method defined in claim 326 wherein said product surface coating composition or said surface coating precursor composition comprises a latex polymer and said salt comprises a rare earth metal.
330. The method defined in claim 338 wherein said product surface coating composition comprises a latex polymer selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) ole in-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
331. The method defined in claim 326 wherein said salt is selected from the group consisting of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymium, antimo¬ ny, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samarium, tellurium, yttrium, bismuth, gallium, neodymium, rubidium and terbium.
332. The method defined in claim 326 wherein said salt comprises lanthanum or silicon.
333. The method defined in claim 326 wherein said salt comprises a rare earth metallic cation.
334. The method defined in claim 52 wherein said finished paint composition comprises:
(a) a coalescing aid, (b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide,
(f) a filler, and
(g) a polymer binder.
335. The method defined in claim 326 wherein said surface coating composition or surface coating precursor composition comprises water and a water- soluble or water-dispersible polymer.
336. The method defined in claim 326 wherein said salt contained in said composition containing said polymer is homogeneously distributed with said polymer.
337. The method defined in claim 326 wherein the concentration of said sol or gel composition in said product surface coating composition is about 0.1 to about 2 weight percent.
338. A method for enhancing the gloss proper¬ ty of a product paint composition, said method com¬ prising the step of admixing a sol or gel composition containing a salt with a paint composition or a paint precursor composition, said paint composition, product paint composition or paint precursor composition each containing a polymer.
339. The method defined in claim 338 wherein the specular gloss of the product paint composition is increased at least about 2 percent reflectance, based upon light having about a 60° angle of incidence, compared to said product paint composition without said salt.
340. The method defined in claim 338 wherein said product paint composition is a semi-gloss or high-gloss paint.
341. The method defined in claim 338 wherein said product paint composition is a semi-gloss paint.
342. The method defined in claim 338 wherein said starting paint or paint precursor composition comprises a latex polymer and said salt comprises a rare earth metal.
343. The method defined in claim 338 wherein said salt in said sol or gel composition comprises colloidal salt particulates.
344. The method defined in claim 338 wherein said product paint composition comprises a latex polymer selected from.
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
345. The method defined in claim 338 wherein said salt is homogeneously distributed with the poly¬ mer contained in said paint composition or said paint precursor composition.
346. The method defined in claim 338 wherein said salt is selected from the group consisting of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymium, antimo¬ ny, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samarium, tellurium, yttrium, bismuth, gallium, neodymium, rubidium and terbium.
347. The method defined in claim 338 wherein said salt comprises lanthanum or silicon.
348. The method defined in claim 338 wherein said salt comprises a rare earth metallic cation.
349. The method defined in claim 338 wherein said product paint composition comprises:
(a) a coalescing aid,
(b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide, and
(f) a filler.
350. The method defined in claim 338 wherein said paint composition or paint precursor composition comprises water and a water-soluble or water-dispersi¬ ble polymer.
351. The method defined in claim 338 wherein said salt contained in said product paint composition is homogeneously dispersed with said polymer.
352. The method defined in claim 338 wherein the concentration of said sol or gel composition in said product paint composition is about 0.1 to about 2 weight percent.
353. The method defined in claim 338 wherein the concentration of said salt in said product paint composition is about 0.05 to about 5 weight percent.
354. The method defined in claim 338 wherein the concentration of salt in said sol or gel composi¬ tion is about 2 to about 50 weight percent.
355. The method defined in claim 349 wherein said polymer is a binder comprising a latex polymer.
356. The method defined in claim 338 wherein sufficient salt is contained in said sol or gel compo¬ sition to increase the specular gloss of said product paint composition by at least about 2 percent reflect¬ ance, based upon light having about a 60° angle of incidence, as compared to said product paint composi¬ tion not containing said sol or gel composition.
357. A method for enhancing the gloss of a surface coating composition, said method comprising the following steps:
(a) admixing a sol or gel composition contain¬ ing a salt with a composition containing a polymer to produce a product admixture composition containing said salt and said polymer; and
(b) blending said product admixture composi¬ tion with a surface coating paste stock to produce a surface coating composition having a specular gloss which is greater by at least about 2 percent reflect¬ ance, based upon light having about a 60° angle of incidence, than substantially the same surface coating composition but not containing said sol or gel compo¬ sition.
358. The method defined in claim 357 wherein said salt in said product admixture composition com¬ prises colloidal salt particulates.
359. The method defined in claim 357 wherein said polymer composition comprises a starting latex polymer.
360. The method defined in claim 357 wherein said polymer composition comprises water.
361. The method defined in claim 357 wherein said surface coating paste stock comprises at least one pigment.
362. The method defined in claim 357 wherein said surface coating composition is a semi-gloss or high-gloss paint.
363. The method defined in claim 357 wherein sufficient salt is added to said sol or gel composi¬ tion to increase said specular gloss by at least about 2.5 percent reflectance.
364. The method defined in claim 357 wherein said polymer in step (a) is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms.
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
365. A resultant dried composition formed by drying said product surface coating composition pre¬ pared by the method of claim 326.
366. A resultant dried composition formed by drying said product paint composition prepared by the method of claim 338
367. A resultant dried composition formed by drying said surface coating composition prepared by the method of claim 357.
368. A resultant dried composition formed by drying said waterborne surface coating composition of claim 298.
369. A coated substrate having a surface at least partially coated with the dried surface coating composition of claim 275.
370. A coated substrate having a surface at least partially coated with the dried paint composi¬ tion of claim 320.
371. A coated substrate having a surface at least partially coated with the dried paint composi¬ tion of claim 321.
372. The coated substrate defined in claim 95 comprising wood, metal, ceramic, plastic, glass, paper, cement and combinations thereof.
373. The coated substrate defined in claim
370 comprising wood, metal, ceramic, plastic, glass, paper, cement and combinations thereof.
374. The coated substrate defined in claim
371 comprising wood, metal, ceramic, plastic, glass, paper, cement and combinations thereof.
375. A product surface coating composition prepared by the method of claim 326.
376. A product paint composition prepared by the method of claim 338.
377. A product surface coating composition prepared by the method of claim 357.
378. A surface coating composition prepared by the method comprising the steps of:
(1) admixing a composition containing a polymer with a surface coating paste stock, and
(2) admixing a sol or gel composition containing a salt with the admixture composition obtained from step (1) to produce a surface coating composition.
379. A surface coating composition prepared ethod comprising the steps of:
(1) admixing a surface coating paste stock with a sol or gel composition contain¬ ing a salt, and
(2) admixing a composition containing a polymer with an admixture composition obtained from step (1) to produce a surface coating composition.
380. A surface coating composition comprising
a surface coating paste stock, a polymer binder, a stabilizer comprising a chelator or a nonionic surfactant, a nonaqueous solvent comprising an ether, ester, alcohol or combination thereof, at least one salt comprising anions, cations
or colloidal particulates, and water.
381. The surface coating composition defined in claim 380 comprising at least about 15 weight percent of water.
382. The surface coating composition defined in claim 380 wherein said chelator comprises citric acid and said nonaqueous solvent comprises ethylene glycol.
383. The surface coating composition defined in claim 380 wherein said salt is selected from the group consisting of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium,
sodium, nickel, lead, praseodymium, antimony, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samarium, tellurium, yttrium, bismuth, gallium, neodymium, rubidium and terbium.
384. A surface coating composition compris¬ ing a polymer binder and at least one salt, said salt homogeneously distributed in the surface coating composition in sufficient concentration to enhance the tannin blocking property of the coating composition.
385. The composition defined in claim 384 further comprising water.
386. The composition defined in claim 384 further comprising a surface coating paste stock.
387. The composition defined in claim 385 wherein said polymer is a water-soluble polymer.
388. The composition in claim 385 wherein said polymer is a water-dispersible polymer.
389. The composition in claim 386 wherein said paste stock comprises at least one pigment.
390. The composition defined in claim 386 wherein said paste stock comprises a coalescing aid.
391. The composition defined in claim 386 wherein said paste stock comprises a thickening aid.
392. The composition defined in claim 386 wherein said paste stock comprises a dispersing aid.
393. The composition defined in claim 386 wherein said paste stock comprises a defoamer.
394. The composition defined in claim 386 wherein said paste stock comprises a biocide.
395. The composition defined in claim 388 wherein said water-dispersible polymer is a latex polymer.
396. The composition defined in claim 387 wherein said water-soluble polymer is a resin.
397. The composition defined in claim 386 wherein said surface coating paste stock comprises pigment salt particulates of diameter greater than 40 nanometers.
398. The composition defined in claim 384 wherein said salt comprises an aluminum metal cation.
399. The composition defined in claim 384 wherein said salt comprises colloidal salt particu¬ lates.
400. The composition defined in claim 384 wherein said salt is contained in a sol or gel compo¬ sition and the concentration of said salt in said sol or gel compositionis about 1 to about 50 weight per¬ cent.
401. The composition defined in claim 384 wherein the concentration of salt in said coating composition is about 0.02 to about 1 weight percent.
402. The composition defined in claim 400 wherein the concentration of sol or gel composition in said coating composition is about 0.1 to about 5 weight percent.
403. The composition defined in claim 395 wherein said latex polymer is selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer- ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
404. The composition defined in claim 384 wherein said salt comprises tetrapropylammonium bro¬ mide.
405. The composition defined in claim 384 wherein said salt is selected from the group consist¬ ing of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, bismuth, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymium, antimony, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samarium, tellurium, thorium, yttrium, bismuth, galli¬ um, neodymium, rubidium, zinc and terbium, tetraethy¬ lammonium bromide, ferric citrate, sodium vanadate, nickel silylmolybdate, cobalt silylmolybdate, nickel phosphomolybdate, titanium ethoxide, ammonium molyb- date, ammonium molybdocobaltate, sodium molybdate, titanium ethylhexoxide, barium carbonate, neodymium nitrate, lanthanum oxide, erbium nitrate, aluminum isopropoxide, and tetrapropylammonium bromide.
406. The composition defined in claim 384 being a paint, primer or stain.
407. A surface coating composition compris- mg:
(1) a product admixture composition com¬ prising a sol or gel composition con¬ taining a salt and a polymer binder, said salt in sufficient amount to enhance the tannin block property of said surface coating composition as compared to the same surface coating composition which does not contain said sol or gel composition, and
(2) a surface coating paste stock.
408. The surface coating composition defined in claim 407 being a waterborne surface coating compo¬ sition further comprising water.
409. The waterborne surface coating composi¬ tion defined in claim 408 further comprising at least one pigment.
410. The waterborne surface coating composi¬ tion defined in claim 408 wherein said surface coating paste stock comprises pigment salt particulates of diameter greater than 40 nanometers.
411. The waterborne surface coating composi¬ tion defined in claim 408 further comprising a coa- lescing aid.
412. The waterborne surface coating composi¬ tion defined in claim 408 further comprising a thick¬ ening aid.
413. The waterborne surface coating composi¬ tion defined in claim 408 further comprising a dis¬ persing aid.
414. The waterborne surface coating composi¬ tion defined in claim 408 further comprising a defoam¬ er.
415. The waterborne surface coating composi¬ tion defined in claim 408 further comprising a bio¬ cide.
416. The waterborne surface coating composi¬ tion defined in claim 410 further comprising:
(a) a coalescing aid, (b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide, and
(f) a filler.
417. The surface coating composition defined in claim 407 wherein said polymer binder comprises a water-dispersible polymer comprising a latex polymer.
418. The waterborne surface coating composi¬ tion defined in claim 407 wherein said polymer binder comprises a water-soluble polymer.
419. The surface coating composition defined in claim 407 further comprising water and a surface coating paste stock.
420. The surface coating composition defined in claim 407 wherein said salt comprises an aluminum metal cation.
421. The surface coating composition defined in claim 407 wherein said salt comprises colloidal salt particulates.
422. The waterborne surface coating composi¬ tion defined in claim 409 wherein said salt is homoge¬ neously distributed in said composition.
423. The surface coating defined in claim 407 wherein the concentration of said salt in said coating composition is about 0.02 to about 1 weight percent.
424. The waterborne surface coating defined in claim 407 wherein the concentration of salt in said sol or gel composition is about 10 to about 20 weight percent.
425. The waterborne surface coating defined in claim 24 wherein the concentration of sol or gel composition in said coating composition is about 0.1 to about 5 weight percent.
426. The waterborne surface coating defined in claim 407 wherein the concentration of sol or gel in said product admixture composition is about 0.5 to about 25 weight percent.
427. The waterborne surface coating composi¬ tion defined in claim 407 wherein said polymer binder is a water-dispersible polymer binder selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
428. The waterborne surface coating composi¬ tion defined in claim 407 wherein said salt is select¬ ed from the group consisting of the acetates, cit¬ rates, nitrates and halides of ammonium, silver, aluminum, bismuth, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymium, antimo¬ ny, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samarium, tellurium, thorium, yttrium, bismuth, gallium, neody¬ mium, rubidium, zinc and terbium, tetraethylammonium bromide, ferric citrate, sodium vanadate, nickel silylmolybdate, cobalt silylmolybdate, nickel phospho- molybdate, titanium ethoxide, ammonium molybdate, ammonium molybdocobaltate, sodium molybdate, titanium ethylhexoxide, barium carbonate, 'neodymium nitrate, lanthanum oxide, aluminum isopropoxide, and tetrapro¬ pylammonium bromide.
429. A paint composition comprising: a paint paste stock, a latex polymer, water, and a tannin block-enhancing amountof a salt homogeneously distributed in said composition.
430. A paint composition comprising:
water a latex polymer binder. a coalescing aid, a thickening aid, a defoamer, a biocide, a filler, and a tannin block-enhancing amount of a salt homogeneously distributed in said composition.
431. A precursor composition useful for preparing a product surface coating composition, said precursor composition comprising:
(1) a polymer,
(2) a surface coating paste stock, and
(3) a sol or gel composition containing a
tannin block-enhancing amount of a salt.
432. The precursor composition defined in claim 4331 wherein the concentration of said salt in said sol or gel composition is about l to about 50 weight percent.
433. The precursor composition defined in claim 429 wherein the concentration of said salt in said paint composition is about 0.02 to about 1 weight percent.
434. The precursor composition defined in claim 430 wherein the concentration of said salt in said paint composition is about 0.02 to about 1 weight percen .
435. A method for increasing the tannin block property of a product surface coating composi¬ tion, said method comprising the step of admixing a sol or gel composition containing a tannin block- enhancing concentration of a salt with a composition containing a polymer to produce a product surface coating composition or a surface coating precursor composition, said product surface coating composition or a product surface coating composition derived from said surface coating precursor composition both having a tannin block property which is greater than that of the same product surface coating composition prepared without said salt from said sol or gel composition.
436. The method defined in claim 435 wherein the said product surface coating exhibits no discolor¬ ation after one week when applied and dried on a wood- containing substrate and subjected to 4 hour intervals of light and moist darkness in a QUV Weatherometer.
437. The method defined in claim 435 wherein said product surface coating composition is a paint, primer or stain.
438. The method defined in claim 435 wherein said product surface coating composition or said surface coating precursor composition comprises a latex polymer and said salt comprises an aluminum metal cation.
439. The method defined in claim 447 wherein said product surface coating composition comprises a latex polymer selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
440. The method defined in claim 435 wherein said salt is selected from the group consisting of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, bismuth, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymium, antimony, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samarium, tellurium, thorium, yttrium, bismuth, gallium, neody¬ mium, rubidium, zinc and terbium, tetraethylammonium bromide, ferric citrate, sodium vanadate, nickel silyl olybdate, cobalt silylmolybdate, nickel phospho- molybdate, titanium ethoxide, ammonium molybdate, ammonium molybdocobaltate, sodium molybdate, titanium ethylhexoxide, barium carbonate, neodymium nitrate, lanthanum oxide, erbium nitrate, aluminum isopropox¬ ide, and tetrapropylammonium bromide.
441. The method defined in claim 435 wherein said salt comprises tetrapropylammonium bromide.
442. The method defined in claim 435 wherein said salt comprises an aluminum metal cation.
443. The method defined in claim 435 wherein said finished paint composition comprises:
(a) a coalescing aid, (b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide,
(f) a filler, and
(g) a polymer binder.
444. The method defined in claim 435 wherein said surface coating composition or surface coating precursor composition comprises water and a water- soluble or water-dispersible polymer.
445. The method defined in claim 435 wherein said salt contained in said composition containing said polymer is homogeneously distributed with said polymer.
446. The method defined in claim 435 wherein the concentration of said sol or gel composition in said product surface coating composition is about 0.1 to about 5 weight percent.
447. A method for enhancing the tannin block property of a product paint composition, said method comprising the step of admixing a sol or gel composi¬ tion containing a salt with a paint composition or a paint precursor composition to produce a product paint composition, said paint composition, product paint composition or paint precursor composition each con¬ taining a polymer, and wherein sufficient salt is contained in said sol or gel composition to increase the tannin block property of said product paint compo¬ sition as compared to said product paint composition not containing said sol or gel composition.
448. The method defined in claim 447 wherein the sol or gel composition further comprises a solvent containing ethylene glycol and a stabilizer containing citric acid or a nonionic surfactant.
449. The method defined in claim 447 wherein said product paint composition is an outdoor paint.
450. The method defined in claim 447 wherein said product paint composition is a latex-based paint.
451. The method defined in claim 447 wherein said starting paint or paint precursor composition comprises a latex polymer and said salt comprises an aluminum metal cation.
452. The method defined in claim 447 wherein said salt in said sol or gel composition comprises colloidal salt particulates.
453. The method defined in claim 447 wherein said product paint composition comprises a latex polymer selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
454. The method defined in claim 447 wherein said salt is homogeneously distributed with the poly¬ mer contained in said paint composition or said paint precursor composition.
455. The method defined in claim 447 wherein said salt is selected from the group consisting of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, bismuth, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymi¬ um, antimony, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samari¬ um, tellurium, thorium, yttrium, bismuth, gallium, neodymium, rubidium, zinc and terbium, tetraethylammo¬ nium bromide, ferric citrate, sodium vanadate, nickel silylmolybdate, cobalt silyl olybdate, nickel phospho- molybdate, titanium ethoxide, ammonium molybdate, ammonium molybdocobaltate, sodium molybdate, titanium ethylhexoxide, barium carbonate, neodymium nitrate, lanthanum oxide, erbium nitrate, aluminum isopropox¬ ide, and tetrapropylammonium bromide.
456. The method defined in claim 447 wherein said salt comprises tetrapropylammonium bromide.
457. The method defined in claim 447 wherein said salt comprises an aluminum metal cation.
458. The method defined in claim 447 wherein said product paint composition comprises:
(a) a coalescing aid,
(b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide, and
(f) a filler.
459. The method defined in claim 447 wherein said paint composition or paint precursor composition comprises water and a water-soluble or water-dispersi¬ ble polymer.
460. The method defined in claim 447 wherein said salt contained in said product paint composition is homogeneously dispersed with said polymer.
461. The method defined in claim 447 wherein the concentration of said sol or gel composition in said product paint composition is about 0.1 to about 5 weight percent.
462. The method defined in claim 447 wherein the concentration of said salt in said product paint composition is about 0.02 to about 1 weight percent.
463. The method defined in claim 447 wherein the concentration of salt in said sol or gel composi¬ tion is about 1 to about 50 weight percent.
464. The method defined in claim 458 wherein said polymer is a binder comprising a latex polymer.
465. The method defined in claim 447 wherein said product paint composition exhibits no discolora¬ tion after one week when applied and dried on a wood- containing substrate and subjected to 4 hour intervals of light and moist darkness in a QUV Weatherometer.
466. A method for enhancing the tannin block property of a surface coating composition, said method comprising the following steps:
(a) admixing a sol or gel composition con- taining a salt with a composition containing a polymer to produce a product admixture composition containing said salt and said polymer, said salt in sufficient amount to increase the tannin block property of the surface coating composition obtained in step (b) ; and
(b) blending said product admixture composi¬ tion with a surface coating paste stock to produce a surface coating composition having a tannin block property which is greater than substantially the same surface coating composition but not containing said sol or gel composition.
467. The method defined in claim 466 wherein said salt in said product admixture composition com¬ prises colloidal salt particulates.
468. The method defined in claim 466 wherein said polymer composition comprises a starting latex polymer.
469. The method defined in claim 466 wherein said polymer composition comprises water.
470. The method defined in claim 466 wherein said surface coating paste stock comprises at least one pigment.
471. The method defined in claim 466 wherein said surface coating composition is a paint, primer or stain.
472. The method defined in claim 466 wherein sufficient salt is added to said sol or gel composi¬ tion such that said surface coating composition exhib¬ its no discoloration after one week when applied and dried on a wood-containing substrate and subjected to 4 hour intervals of light and moist darkness in a QUV Weatherometer.
473. The method defined in claim 466 wherein said polymer in step (a) is selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
474. A resultant dried composition formed by drying said product surface coating composition pre¬ pared by the method of claim 435 on a wood-containing substrate.
475. A resultant dried composition formed by drying said product paint composition prepared by the method of claim 447 on a wood-containing substrate.
476. A resultant dried composition formed by drying said surface coating composition prepared by the method of claim 466 on a wood-containing sub¬ strate.
477. A resultant dried composition formed by drying said waterborne surface coating composition of claim 24 on a wood-containing substrate.
478. A coated wood-containing substrate having a surface at least partially coated with the dried surface coating composition of claim 384.
479. A coated wood-containing substrate having a surface at least partially coated with the dried paint composition of claim 429.
480. A coated wood-containing substrate having a surface at least partially coated with the dried paint composition of claim 430.
481. The coated wood-containing substrate defined in claim 478 comprising redwood, pine, spruce, cedar, maple, walnut, oak, birch, fir, teak, mahogany, pecan, hemlock, aspen, cherry, and combinations there¬ of.
482. The coated wood-containing substrate defined in claim 478 comprising redwood, pine, spruce, cedar, maple, walnut, oak, birch, fir, teak, mahogany, pecan, hemlock, aspen, cherry, and combinations there¬ of.
483. The coated wood-containing substrate defined in claim 479 comprising redwood, pine, spruce, cedar, maple, walnut, oak, birch, fir, teak, mahogany, pecan, hemlock, aspen, cherry, and combinations there¬ of.
484. A product surface coating composition prepared by the method of claim 435.
485. A product paint composition prepared by the method of claim 447.
486. A product surface coating composition prepared by the method of claim 466.
487. A surface coating composition prepared by the method comprising the steps of:
(1) admixing a composition containing a polymer with a surface coating paste stock, and
(2) admixing a sol or gel composition containing a salt with the admixture composition obtained from step (1) to produce a surface coating composition containing said salt in a sufficient amount to enhance the tannin blocking property of said surface coating compo¬ sition.
488. A surface coating composition prepared by the method comprising the steps of:
(1) admixing a surface coating paste stock with a sol or gel composition contain¬ ing a salt, said salt in sufficient amount to block tannin effects on a wood-containing substrate when coated on said substrate and
(2) admixing a composition containing a polymer with an admixture composition obtained from step (1) to produce a surface coating composition having enhanced tannin block properties com¬ pared to the same surface coating composition which does not contain said sol or gel composition.
489. A surface coating composition compris- mg:
a surface coating paste stock, a polymer binder, a stabilizer comprising a chelator or a nonionic surfactant, a nonaqueous solvent comprising an ether,
ester, alcohol or combination thereof, at least one salt comprising anions,cations
or colloidal particulates, said salt in sufficient amount to enhance the tannin block property of said composition when coated on a wood-containing substrate and
water.
490. The surface coating composition defined in claim 489 comprising at least about 15 weight percent of water.
491. The surface coating composition defined in claim 489 wherein said chelator comprises citric acid and said nonagueous solvent comprises ethylene glycol.
492. The surface coating composition defined in claim 489 wherein said salt is selected from the group consisting of the acetates, citrates, nitrates and halides of ammonium, silver, aluminum, bismuth, boron, calcium, cadmium, cerium, cobalt, chromium, cesium, copper, dyprosium, europium, iron, mercury, indium, potassium, lanthanum, lithium, magnesium, sodium, nickel, lead, praseodymium, antimony, silicon, strontium, thallium, uranium, zinc, manganese, gold, germanium, molybdenum, samarium, tellurium, thorium, yttrium, bismuth, gallium, neodymium, rubidium, zinc and terbium, tetraethylammonium bromide, ferric cit¬ rate, sodium vanadate, nickel silylmolybdate, cobalt silylmolybdate, nickel phosphomolybdate, titanium ethoxide, ammonium molybdate, ammonium molybdocobal¬ tate, sodium molybdate, titanium ethylhexoxide, barium carbonate, neodymium nitrate, lanthanum oxide, erbium nitrate, aluminum isopropoxide, and tetrapropylammoni¬ um bromide.
493. A free metal-containing substrate having a surface at least partially coated with a surface coating composition comprising a polymer binder and at least one salt, said salt homogeneously distributed in the surface coating composition in sufficient concentration to inhibit the corrosion of said free metal-containing substrate.
494. The substrate defined in claim 493 wherein said surface coating composition is a paint, lacquer or varnish.
495. The substrate defined in claim 493 wherein said surface coating composition further comprises a surface coating paste stock.
496. The substrate defined in claim 494 wherein said polymer is a water-soluble polymer.
497. The substrate in claim 494 wherein said polymer is a water-dispersible polymer.
498. The substrate in claim 495 wherein said paste stock comprises at least one pigment.
499. The substrate defined in claim 495 wherein said paste stock comprises a coalescing aid.
500. The substrate defined in claim 495 wherein said paste stock comprises a thickening aid.
501. The substrate defined in claim 495 wherein said paste stock comprises a dispersing aid.
502. The substrate defined in claim 495 wherein said paste stock comprises a defoamer.
503. The substrate defined in claim 495 wherein said paste stock comprises a biocide.
504. The substrate defined in claim 497 wherein said water-dispersible polymer is a latex polymer.
505. The substrate defined in claim 496 wherein said water-soluble polymer is a resin.
506. The substrate defined in claim 493 wherein said surface coating paste stock comprises pigment salt particulates of diameter greater than 40 nanometers.
507. The substrate defined in claim 493 wherein said salt comprises a divalent metal cation.
508. The substrate defined in claim 493 wherein said salt comprises colloidal salt particu¬ lates.
509. The substrate defined in claim 493 wherein said salt is derived from a sol or gel compo¬ sition and the concentration of said salt in said sol or gel composition is about 1 to about 50 weight percent .
510. The substrate defined in claim 493 wherein the concentration of salt in said coating composition is about 0.02 to about 1 weight percent.
511. The substrate defined in claim 509 wherein the concentration of sol or gel composition in said coating composition is about 0.1 to about 5 weight percent.
512. The substrate defined in claim 504 wherein said latex polymer is selected from r
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
513. The substrate defined in claim 493 wherein less than 2 percent of the surface area of a free iron metal-concontaining substrate exhibits rust at 100 hours when said surface coating composition is applied and dried on said substrate and subjected to salt fog conditions comprising a temperature of 80° C. and a water vapor atmosphere containing 3 vol. percent sodium chloride and using a 411-lACD cabinet using an ATSM B-117 test.
514. The substrate defined in claim 493 wherein said salt is selected from the group consist¬ ing of the acetates, chromates, molybdates, phos¬ phates, plumbates, and silicates of aluminum, ammoni¬ um, barium, cadmium, calcium, chromium, cobalt, cop¬ per, dysprosium, lead, lithium, magnesium, mercury, potassium, praseodymium, silicon, silver, sodium, strontium, uranium and zinc, tetraethylammonium bro¬ mide, ferric citrate, and yttrium nitrate.
515. The substrate defined in claim 504 wherein a free iron metal-containing substrate exhib¬ its rust on less than one percent of the surface area of said substrate at one week when said surface coat¬ ing composition is applied and dried on said substrate and subjected to 4 hour intervals of light and dark¬ ness with alternating overlapping 4 hour intervals of rain simulation in a QUV Weatherometer.
516. A free metal-containing substrate having a surface at least partially coated with a surface coating composition comprising a product admixture composition comprising a sol or gel composi¬ tion containing a salt and a polymer binder.
517. The substrate defined in claim 516 comprising a waterborne surface coating composition comprising a surface coating paste stock, said salt in sufficient amount to inhibit the corrosion of a metal- containing substrate coated by said surface coating composition as compared to the same surface coating composition which does not contain said sol or gel composition.
518. The substrate defined in claim 517 further comprising at least one pigment.
519. The substrate defined in claim 517 wherein said surface coating paste stock comprises pigment salt particulates of diameter greater than 40 nanometers.
520. The substrate defined in claim 517 further comprising a coalescing aid.
521. The substrate defined in claim 517 further comprising a thickening aid.
522. The substrate defined in claim 517 further comprising a dispersing aid.
523. The substrate defined in claim 517 further comprising a defoamer.
524. The substrate defined in claim 517 further comprising a biocide.
525. The substrate defined in claim 519 wherein said surface coating paste stock further comprises:
(a) a coalescing aid,
(b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer, (e) a biocide, and
(f) a filler.
526. The substrate defined in claim 516 wherein said polymer binder comprises a water-disper¬ sible polymer comprising a latex polymer.
527. The substrate defined in claim 516 wherein said polymer binder comprises a water-soluble polymer or a natural polymer.
528. The substrate defined in claim 516 wherein said surface coating composition is a paint, lacquer or varnish.
529. The substrate defined in claim 516 wherein said salt comprises a divalent metal cation.
530. The substrate defined in claim 516 wherein said salt comprises colloidal salt particu¬ lates.
531. The substrate defined in claim 526 wherein less than 2 percent of the surface area of a free iron metal-containing substrate exhibits rust at 100 hours when said surface coating composition is applied and dried on said substrate and subjected to salt fog conditions comprising a temperature of 80° c. and a water vapor atmosphere containing 3 vol. percent sodium chloride using a 411-lACD cabinet and using an ATSM B-117 test.
532. The substrate defined in claim 516 wherein the concentration of said salt in said surface coating composition is about 0.02 to about 1 weight percent.
533. The substrate defined in claim 516 wherein the concentration of salt in said sol or gel composition is about 10 to about 20 weight percent.
534. The substrate defined in claim 516 wherein the concentration of sol or gel composition in said coating composition is about 0.1 to about 5 weight percent.
535. The substrate defined in claim 516 wherein the concentration of sol or gel in said product admixture composition is about 0.5 to about 25 weight percent.
536. The substrate defined in claim 516 wherein said polymer binder is a water-dispersible polymer binder selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having
4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymerized, olefinically unsaturated monomers contain ing polymerized olefinically unsaturated carboxylic acid ester monomers, (4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymer¬ ized, olefinically unsaturated monomers, and
(6) combinations thereof.
537. The substrate defined in claim 516 wherein said salt is selected from the group consist¬ ing of the molybdates, plumbates, chromates, acetates, phosphates and silicates of ammonium, aluminum, bari¬ um, cadmium, calcium, chromium, cobalt, copper, dys¬ prosium, lead, lithium, magnesium, mercury, potassium, praseodymium, silicon, silver, sodium, strontium, uranium and zinc, tetraethylammonium bromide, ferric citrate, and yttrium nitrate.
538. A free metal-containing substrate having a surface at least partially coated with a paint composition comprising: a paint paste stock, a latex polymer, water, and
a sufficient amount of a salt homogeneously distributed in said composition to inhibit the corrosion of said free metal-containing substrate.
539. A varnish or lacquer composition com¬ prising: a polymer binder, and a sufficient amount of a salt homogene¬ ously distributed in said composition to inhibit the corrosion of a free metal-containing substrate.
540. A precursor composition useful for preparing a product surface coating composition, said precursor composition comprising:
(1) a polymer, and
(2) a sol or gel composition containing suf
ficient amount of a salt to inhibit the corrosion of a metal-containing substrate.
541. The precursor composition defined in claim 540 wherein the concentration of said salt in said sol or gel composition is about 1 to about 50 weight percent.
542. The precursor composition defined in claim 538 wherein the concentration of said salt in said paint composition is about 0.02 to about 1 weight percent.
543. The precursor composition defined in claim 539 wherein the concentration of said salt in said varnish or lacguer composition is about 0.02 to about 1 weight percent.
544. A method for increasing the corrosion inhibiting property of a product surface coating composition, said method comprising the step of admix¬ ing a sol or gel composition containing a sufficient concentration of a salt to inhibit corrosion of a metal-containing substrate with a composition contain- ing a polymer to produce a product surface coating composition or a surface coating precursor composi¬ tion, said product surface coating composition or a product surface coating composition derived from said surface coating precursor composition both having a corrosion inhibiting property which is greater than that of the same product surface coating composition prepared without said salt from said sol or gel compo¬ sition.
545. The method defined in claim 545 wherein said product surface coating composition comprising a rust-inhibiting property wherein a free iron-contain¬ ing substrate exhibits rust on less than one percent of the surface area of said substrate at one week when said composition applied and dried on said substrate and subjected to 4 hour intervals of light and dark¬ ness with alternating overlapping 4 hour intervals of rain simulation in a QUV Weatherometer.
546. The method defined in claim 544 wherein said product surface coating composition comprises a rust-inhibiting property wherein less than 2 percent of the surface area of a free iron metal-containing substrate exhibits rust at 100 hours when said compo¬ sition is applied and dried on said substrate and subjected to salt fog conditions comprising a tempera¬ ture of 80° C. and a water vapor atmosphere containing 3 vol. percent sodium chloride and using a 411-lACD cabinet using an ATSM B-117 test.
547. The method defined in claim 544 wherein said product surface coating composition or said surface coating precursor composition comprises a latex polymer and said salt comprises a divalent metal cation.
548. The method defined in claim 544 wherein said product surface coating composition comprises a latex polymer selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having
4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
549. The method defined in claim 544 wherein said salt is selected from the group consisting of the acetates, chromates, molybdates, phosphates, plumbates and silicates of aluminum, ammonium, barium, cadmium, calcium, chromium, cobalt, copper, dysprosium, lead, lithium, magnesium, mercury, potassium, praseodymium, silicon, silver, sodium, strontium, uranium and zinc, tetraethylammonium bromide, ferric citrate, and yttri¬ um nitrate.
550. The method defined in claim 544 wherein said salt comprises a divalent cation in combination with at least one anion selected from the group con¬ sisting of barium, cadmium, calcium, copper, magnesi¬ um, mercury, strontium and zinc.
551. The method defined in claim 544 wherein said salt comprises a divalent metal cation.
552. The method defined in claim 544 wherein said finished surface coating composition comprises:
(a) a coalescing aid,
(b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide,
(f) a filler, and (g) a polymer binder.
553. The method defined in claim 544 wherein said surface coating composition or surface coating precursor composition comprises water and a water- soluble or water-dispersible polymer.
554. The method defined in claim 544 wherein said salt contained in said composition containing said polymer is homogeneously distributed with said polymer.
555. The method defined in claim 544 wherein the concentration of said sol or gel composition in said product surface coating composition is about 0.1 to about 5 weight percent.
556. A method for enhancing the corrosion- inhibiting property of a product paint composition, said method comprising the step of admixing a sol or gel composition containing a salt with a paint compo¬ sition containing a polymer, and wherein sufficient salt is contained in said sol or gel composition to increase the corrosion inhibiting property of said product paint composition as compared to said product paint composition not containing said sol or gel composition.
557. The method defined in claim 556 wherein the sol or gel composition further comprises a solvent containing ethylene glycol and a stabilizer containing either citric acid or a nonionic surfactant.
558. The method defined in claim 556 wherein said product paint composition is an outdoor paint.
559. The method defined in claim 556 wherein said product paint composition is a latex-based paint.
560. The method defined in claim 556 wherein said starting paint or paint precursor composition comprises a latex polymer and said salt comprises a divalent metal cation.
561. The method defined in claim 556 wherein said salt in said sol or gel composition comprises colloidal salt particulates.
562. The method defined in claim 556 wherein said product paint composition comprises a latex polymer selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
563. The method defined in claim 556 wherein said salt is homogeneously distributed with the poly¬ mer contained in said paint composition.
564. The method defined in claim 556 wherein said salt is selected from the group consisting of the molybdates, plumbates, chromates, acetates, phosphates and silicates of ammonium, aluminum, barium, cadmium, calcium, chromium, cobalt, copper, dysprosium, lead, lithium, magnesium, mercury, potassium, praseodymium, silicon, silver, sodium, strontium, uranium and zinc, tetraethylammonium bromide, ferric citrate, and yttri¬ um nitrate.
565. The method defined in claim 556 wherein said salt comprises a divalent cation in combination with at least one anion selected from the group con¬ sisting of zinc, barium, cadmium, calcium, copper, magnesium, mercury and strontium.
566. The method defined in claim 556 wherein said salt comprises a divalent metal cation.
567. The method defined in claim 556 wherein said product paint composition comprises:
(a) a coalescing aid,
(b) a thickening aid,
(c) a dispersing aid,
(d) a defoamer,
(e) a biocide, and
(f) a filler.
568. The method defined in claim 556 wherein said paint composition comprises water and a water- soluble or water-dispersible polymer.
569. The method defined in claim 559 wherein said product paint composition comprises a rust-inhib¬ iting property wherein less than 2 percent of the surface area of a free iron metal-containing substrate exhibits rust at 100 hours when said composition is applied and dried on said substrate and subjected to salt fog conditions comprising a temperature of 80° C. and a water vapor atmosphere containing 3 vol. percent sodium chloride and using a 411-lACD cabinet using an ATSM B-117 test.
570. The method defined in claim 556 wherein the concentration of said sol or gel composition in said product paint composition is about 0.1 to about 5 weight percent.
571. The method defined in claim 556 wherein the concentration of said salt in said product paint composition is about 0.02 to about 1 weight percent.
572. The method defined in claim 556 wherein the concentration of salt in said sol or gel composi¬ tion is about 1 to about 50 weight percent.
573. The method defined in claim 567 wherein said polymer is a binder comprising a latex polymer.
574. The method defined in claim 559 wherein said product paint composition comprising a rust- inhibiting property wherein a free ion metal-contain¬ ing substrate exhibits rust on less than one percent of the surface area of said substrate at one week when applied and dried on said substrate and subjected to 4 hour intervals of light and darkness with alternating overlapping 4 hour intervals of rain simulation in a QUV Weatherometer.
575. A method for enhancing the corrosion inhibiting property of a surface coating composition, said method comprising admixing the following materi¬ als: (1) a sol or gel composition containing a salt, (2) a polymer-containing composition, and (3) a sur¬ face coating paste stock, to produce a surface coating composition having a corrosion inhibiting property which is greater than substantially the same surface coating composition but not containing said sol or gel composition.
576. The method defined in claim 575 wherein said salt in said surface coating composition com¬ prises colloidal salt particulates.
577. The method defined in claim 575 wherein said polymer-containing composition comprises a start¬ ing latex polymer.
578. The method defined in claim 575 wherein said polymer-containing composition comprises water.
579. The method defined in claim 575 wherein said surface coating paste stock comprises at least one pigment.
580. The method defined in claim 577 wherein said surface coating composition is a paint having a rust-inhibiting property less than 2 percent of the surface area of a free iron metal-containing substrate exhibits rust at 100 hours when said composition is applied and dried on said substrate and subjected to salt fog conditions comprising a temperature of 80° C. and a water vapor atmosphere containing 3 vol. percent sodium chloride and using a 411-lACD cabinet using an ATSM B-117 test.
581. The method defined in claim 577 wherein sufficient salt is added to said sol or gel composi¬ tion such that said surface coating composition com¬ prising a rust-inhibiting property wherein a free iron metal-containing substrate exhibits rust on less than one percent of the surface area of said substrate after one week when applied and dried on said sub¬ strate and subjected to 4 hour intervals of light and darkness with alternating overlapping 4 hour intervals of rain simulation in a QUV Weatherometer.
582. The method defined in claim 575 wherein said polymer in step (a) is selected from the group consisting of:
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer- ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and
(6) combinations thereof.
583. A resultant dried composition formed by drying said product surface coating composition pre¬ pared by the method of claim 544 on a metal-containing substrate.
584. A resultant dried composition formed by drying said product paint composition prepared by the method of claim 556 on a metal-containing substrate.
585. A resultant dried composition formed by drying said surface coating composition prepared by the method of claim 575 on a metal-containing sub¬ strate.
586. A resultant dried surface coating composition formed by drying said waterborne surface coating composition of claim 25 on a metal-containing substrate.
587. A surface coating composition compris¬ ing a polymer binder and at least one salt, said salt homogeneously distributed in the surface coating composition in sufficient concentration to inhibit the corrosion of a free metal-containing substrate.
588. A surface coating composition compris¬ ing a sol or gel composition containing a salt and a polymer binder, said salt being present in said compo¬ sition in a corrosion-inhibiting concentration.
589. The free metal-containing substrate defined in claim 1 selected from the group consisting of iron, mild steel, galvanized steel, stainless steel, cast iron, wrought iron, copper, brass, alumi¬ num and alloys thereof.
590. The free metal-containing substrate defined in claim 516 selected from the group consist¬ ing of iron, mild steel, galvanized steel, stainless steel, cast iron, wrought iron, copper, brass, alumi¬ num and alloys thereof.
591. The free metal-containing substrate defined in claim 46 selected from the group consisting of iron, mild steel, galvanized steel, stainless steel, cast iron, wrought iron, copper, brass, alumi¬ num and alloys thereof.
592. A product surface coating composition prepared by the method of claim 544.
593. A product paint composition prepared by the method of claim 556.
594. A product surface coating composition prepared by the method of claim 575.
595. A surface coating composition compris- mg:
(1) a surface coating paste stock,
(2) a polymer binder,
(3) a stabilizer comprising a chelator or a nonionic surfactant,
(4) a nonaqueous solvent comprising an ether, ester, alcohol or combination thereof,
(5) at least one salt comprising anions, cations or colloidal particulates, said salt in sufficient amount to enhance the corrosion inhibiting property of said composition when coated on a metal-containing substrate, and
(6) water.
596. The surface coating composition defined in claim 103 comprising at least about 15 weight percent of water.
597. The surface coating composition defined in claim 103 wherein said chelator comprises citric acid and said nonaqueous solvent comprises ethylene glycol.
598. The surface coating composition defined in claim 103 wherein said salt is selected from the group consisting of the acetates, chromates, molyb¬ dates, phosphates, plumbates and silicates of alumi¬ num, ammonium, barium, cadmium, calcium, chromium, cobalt, copper, dysprosium, lead, lithium, magnesium, mercury, potassium, praseodymium, silicon, silver, sodium, strontium, uranium and zinc, tetraethylammoni¬ um bromide, ferric citrate, and yttrium nitrate.
599. A process for preparing a stable product admixture composition comprising at least latex one polymer and a salt derived from a sol or gel composition, said process comprising admixing said sol or gel composition containing said salt with a monomer composition containing at least one monomer comprised in said polymer to produce said stable product admix¬ ture composition, said sol or gel composition compris¬ ing a solvent, a stabilizer and at least about 0.001 weight percent of said salt, said sol or gel composi¬ tion and said stable product admixture composition both having a pH less than 7.0.
600. The process defined in claim 599 where¬ in said stabilizer is selected from the group consist¬ ing of nonionic, anionic and cationic surfactant.
601. The process defined in claim 599 where¬ in said solvent is selected from the group consisting of a mono alcohol, monohyroxyl ether, polyol, polyhy¬ droxyl ether and polyhydroxyl alcohol.
602. The process defined in claim 599 where¬ in said solvent comprises ethylene glycol, glycerine, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, mixed (polyethylene-polyoxypropylene) glycol or blocked (polyoxyethylene-polyoxypropylene) glycol.
603. The process defined in claim 599 where¬ in said salt comprises a cation selected from the group consisting of aluminum, calcium, cobalt, copper, lanthanum, iron, cerium, manganese, magnesium, neody¬ mium, antimony, praseodymium, yttrium, uranium, zinc and nickel.
604. The process defined in claim 599 where¬ in said salt comprises an cation selected from the group consisting of tin, titanium, silicon, tantalum, tungsten and zirconium, or an anion selected from the group consisting of acetate, chloride and nitrate.
605. The process defined in claim 599 having a pH less than about 6.0 and a weight percent of said salt greater than about 0.05.
606. The process defined in claim 599 where¬ in said salt is contained in said sol or gel composi¬ tion or in said stable product admixture composition in a concentration which is greater than the lowest concentration of salt which causes destabilization of essentially the same product admixture composition but essentially free of said salt from said sol or gel composition.
607. The process defined in claim 599 where¬ in said stabilizer comprises a hydroxycarboxylic acid.
608. The process defined in claim 607 where¬ in said hydroxycarboxylic acid is selected from the group consisting of citric acid, tartaric acid, meso¬ tartaric acid, glycolic acid A-hydroxybutyriσ acid, mandelic acid, glyceric acid, malic acid, lactic acid, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and aconitic acid.
609. The process defined in claim 599 where¬ in said stable product admixture composition has a pH less than about 6.0.
610. The process defined in claim 599 where- in said stable product admixture composition has a pH less than about 4.0 and a concentration of said salt greater than about 0.01 weight percent.
611. The process defined in claim 599 where¬ in said stable product admixture composition has a pH less than about 2.0.
612. The process defined in claim 599 where¬ in said said sol or gel composition is admixed with said monomer.composition during formation of said latex polymer by delay addition.
613. The process defined in claim 599 where¬ in said sol or gel composition is admixed with said monomer composition before formation of said polymer by charge addition.
614. The process defined in claim 599 where¬ in said sol or gel composition is prepared by heating an admixture of said salt, solvent and stabilizer in the range from room temperature to about 100° C.
615. The process defined in claim 599 where¬ in said stabilizer is a nonionic surfactant having the formula
R-(EO)χ(PO)y-Rx
wherein each of R and R is independently selected from hydrogen, hydroxyl, alkyl, aryl, monoalkylaryl, dialkylaryl, aliphatic ester, aryl ester radicals, and an olefinic moiety capable of polymerizing in an olefinic polymerization reaction, EO is ethylene oxide, PO is propylene oxide, and x and y are nonnega¬ tive integers, but not simultaneously zero.
616. The process defined in claim 599 where¬ in said stabilizer is a glycerine-derived nonionic surfactant having the formula
(EO)χ(PO)y-R glycerine (EO)a(PO)fc-R1 (EO)m(PO)n-Rlx wherein each of R, R1 and R11 is independently select¬ ed from hydrogen, hydroxyl, alkyl, aryl, monoalkyla- ryl, dialkylaryl, aliphatic ester and aryl ester radicals, EO is ethylene oxide, PO is propylene oxide and x, y, a, b, m and n are nonnegative integers, but not all simultaneously zero.
617. The process defined in claim 599 where¬ in said stabilizer is a nonionic surfactant selected from the group consisting of 1-100 percent by weight of ethylene oxide relative to 0-99 percent by weight of propylene oxide and having a molecular weight from 62 to 5,000, 6-50 mol EO lauryl alcohol, 6-50 mol EO cetyl alcohol, 6-50 mol EO mystryl alcohol, 6-50 EO stearyl alcohol, 6-50 mol EO phenol, 6-50 mol EO butyl phenol, 6-50 EO octyl phenol, 6-50 mol EO decyl phe¬ nol, 6-50 mol EO dodecyl phenol, 6-50 mol EO nonyl phenol, and 10-90 mol EO sorbitan monolaurate, or monocetylate or monomystralate or onostearate.
618. The process defined in claim 599 where¬ in said salt contains a cation or anion selected from the group consisting of metallic cations or metallic anions, monomeric metallic or nonmetallic cations, monomeric metallic or nonmetallic anions, polymeric metallic or nonmetallic cations, and polymeric metal¬ lic or nonmetallic anions.
619. The process defined in claim 618 where¬ in said metallic cation is selected from the group consisting of antimony, yttrium, cadmium, silver, calcium, cerium, manganese, nickel, niobium, lead, uranium, barium, chromium, cesium, copper, lithium, sodium, potassium, palladium, praseodymium, aluminum, cobalt, iron, gold, lanthanum, magnesium, thallium, zinc, dysprosium, samarium, gadolinium, erbium, stron¬ tium, ytterbium, titanium and mercury.
620. The process defined in claim 618 where¬ in said monomeric nonmetallic cation is selected from the group consisting of ammonium, boron and silicon and said monomeric nonmetallic anions are selected from the group consisting of nitrates, acetates, halides, borates, phosphates, formates, citrates, benzoates, tartrates, silicates, nitrites, carbonates, oxides and alkoxides.
621. The process defined in claim 599 where¬ in said sol or gel has a pH less than about 1.0.
622. The process defined in claim 599 where¬ in said latex polymer is selected from
(1) conjugated diolefin polymers containing one or more conjugated diene monomers having 4 to 8 carbon atoms,
(2) olefin-ester interpolymers containing a monoolefin monomer having up to 4 carbon atoms and an alkenyl or alkenol ester of a saturated carboxylic acid,
(3) olefinically unsaturated carboxylic acid ester polymers containing polymer¬ ized, olefinically unsaturated monomers containing polymerized olefinically unsaturated carboxylic acid ester monomers,
(4) polymers of olefinically unsaturated monomers containing alkenyl ether monomer units,
(5) polymers of vinylidene chloride or vinyl chloride with or without other polymerized, olefinically unsaturated monomers, and com
(6) binations thereof.
623. The process defined in claim 618 where¬ in said polymeric cations are selected from the group consisting of monoolefinic quaternary ammonium ca¬ tions, diolefinic quaternary ammonium cations, triole¬ finic quaternary ammonium cations and tetraolefinic quaternary ammonium cations.
624. The process defined in claim 618 where¬ in said polymeric anions are selected from the group consisting of alkyl, aryl, ether or alkylaryl sulfo- nates, sulfates, phosphates, carboxylates and polycar¬ boxylates.
625. The process defined in claim 622 where- in said conjugated diolefin polymers contain at least 10 weight percent of said conjugated diene monomers.
626. The process defined in claim 622 where¬ in said latex polymer in (1) further comprises one or more alkenyl-substituted monoaromatic monomers.
627. The process defined in claim 622 where¬ in said alkenyl-substituted monoromatic monomers comprise about 1 to about 70 weight percent of said latex polymer in (1) .
628. The process defined in claim 622 where¬ in said alkenyl or alkenol ester of a saturated car¬ boxylic acid in the olefin-ester interpolymers of (2) comprises at least 10 weight percent.
629. The process defined in claim 622 where¬ in said polymerized olefinically unsaturated carboxyl¬ ic acid ester monomer comprises at least 10 weight percent of the latex polymer of (3) .
630. The process defined in claim 622 where¬ in said alkenyl ether monomer units in the polymers of (4) comprise at least 10 weight percent.
631. The process defined in claim 618 where¬ in said nonmetallic anion comprises an element select¬ ed from the group consisting of fluorine, oxygen, nitrogen, carbon, tellurium, selenium, phosphorus, sulfur, chlorine, bromine and iodine.
632. The process defined in claim 618 where¬ in said metallic-containing anion comprises an element selected from the group consisting of arsenic, chromi¬ um, tin, aluminum, titanium, zirconium, vanadium, manganese and molybdenum.
633. The process defined in claim 618 where¬ in said salt comprises a cation selected from the group consisting of aluminum, calcium, cobalt, copper, lanthanum, iron, cerium, manganese, magnesium, neody¬ mium, antimony, praseodymium nitride, yttrium, urani¬ um, zinc and nickel.
634. The process defined in claim 618 where¬ in said salt comprises an cation selected from the group consisting of tin, titanium, silicon, tantalum, tungsten and zirconium, and an anion selected from the group consisting of acetate, chloride and nitrate.
635. A non-aqueous salt/polymer composition prepared by the process of claim 634.
636. A substrate coated with the sol or gel composition of claim 599.
637. The substrate coated with the non¬ aqueous salt/polymer composition of claim 635.
638. The coated substrate of claim 636 comprising a catalyst. .
639. A process catalyzed by the product admixture composition of claim 34 or 67.
640. The process defined in claim 599 where¬ in said latex polymer comprises at least about 40 weight percent of said stable product admixture compo¬ sition.
641. The process defined in claim 640 where¬ in said stable product admixture composition is a latex.
642. A process for preparing a stable latex comprising a latex polymer and a salt derived from said sol or gel composition of claim 599, said process comprising admixing said sol or gel composition'with a second monomer composition containing at least one monomer comprised in said latex polymer, said admixing being either before or during formation of said latex polymer.
643. The process defined in claim 642 where¬ in said salt is contained in said sol or gel composi¬ tion or in said stable latex in a concentration which is greater than the lowest concentration of salt which causes destabilization of essentially the same latex but essentially free of said salt from said sol or gel composition.
644. A non-aqueous salt/polymer composition prepared by the process of claim 642.
645. A substrate coated with the stable latex prepared by the process of claim 642.
646. A surface coating composition prepared with the sol or gel of claim 599.
647. The surface coating composition of claim 298 comprising a sufficient concentration of salt derived from said sol or gel to effect color.
648. The surface coating composition of claim 379 wherein said sol or gel comprises sufficient salt to effect color.
649. The surface coating composition defined in claim 308 wherein said salt contained in sufficient amount in said sol or gel to effect color.
650. The surface coating composition defined in claim 308 wherein said salt contained in sufficient amount in said sol or gel to reduce oxidation as compared to the same surface coating composition essentially free of salt from said sol or gel.
PCT/US1990/000568 1989-02-01 1990-01-31 Latex/sol or gel systems WO1990008798A1 (en)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US305,451 1989-02-01
US07/305,451 US5004562A (en) 1989-02-01 1989-02-01 Latex/sol or gel systems
US345,029 1989-04-28
US07/345,029 US5004563A (en) 1989-02-01 1989-04-28 Antistatic textile compositions and sol/gel/polymer compositions
US07/373,401 US5041486A (en) 1989-04-28 1989-06-30 Sol/gel polymer surface coatings and gloss enhancement
US373,401 1989-06-30
US387,933 1989-07-31
US07/387,933 US5041487A (en) 1989-06-30 1989-07-31 Sol/gel polymer surface coatings and tannin block enhancement
US412,839 1989-09-26
US07/412,839 US5028489A (en) 1989-02-01 1989-09-26 Sol/gel polymer surface coatings and corrosion protection enhancement

Publications (1)

Publication Number Publication Date
WO1990008798A1 true WO1990008798A1 (en) 1990-08-09

Family

ID=27540911

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/000568 WO1990008798A1 (en) 1989-02-01 1990-01-31 Latex/sol or gel systems

Country Status (2)

Country Link
AU (1) AU5108590A (en)
WO (1) WO1990008798A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960989A (en) * 1971-12-27 1976-06-01 Petrow Henry G Colloidal sol antimony pentaoxide flameproofing compositions
US4731198A (en) * 1985-04-03 1988-03-15 Nissan Chemical Industries, Ltd. Positively charged antimony pentoxide sol and preparation thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960989A (en) * 1971-12-27 1976-06-01 Petrow Henry G Colloidal sol antimony pentaoxide flameproofing compositions
US4731198A (en) * 1985-04-03 1988-03-15 Nissan Chemical Industries, Ltd. Positively charged antimony pentoxide sol and preparation thereof

Also Published As

Publication number Publication date
AU5108590A (en) 1990-08-24

Similar Documents

Publication Publication Date Title
US3914193A (en) Intumescent coating compositions containing crystalline melamine pyrophosphate
US7652087B2 (en) Protective coating
US5041487A (en) Sol/gel polymer surface coatings and tannin block enhancement
US5004562A (en) Latex/sol or gel systems
US5028489A (en) Sol/gel polymer surface coatings and corrosion protection enhancement
US5135780A (en) Method for depositing free metal containing latex
US9346964B2 (en) Paint comprising hydrophobized minerals and related methods
EP0011829B1 (en) Blends of clay, processing oils and ethylene/vinyl ester copolymers and the process for preparing them
TW201736526A (en) Antiviral agent, coating composition, resin composition and antiviral product
US3494878A (en) Stain resistant water-based coating compositions
US5041486A (en) Sol/gel polymer surface coatings and gloss enhancement
US5166248A (en) Sol/gel-containing surface coating polymer compositions
US4111881A (en) Polyoxyhydrocarbylene dihydrocarbyl ethers as coalescing agents for synthetic polymer latexes
CA3172225A1 (en) Aqueous coating compositions
US5173214A (en) Precursor composition for sols and gels
US5004563A (en) Antistatic textile compositions and sol/gel/polymer compositions
CA2572656C (en) Composition for controlling the viscosity of latex compositions that include fly ash
JPS62553A (en) Polymer composition having improved fire retardant property
WO1990008798A1 (en) Latex/sol or gel systems
US7294592B2 (en) Photocatalyst-carrying tent cloth canvas and production method therefor
US3883455A (en) Non-bleeding vinylidene chloride copolymer coatings
JP3880256B2 (en) Antifouling sheet for tent
US5198487A (en) Process for preparing salt-containing surface coating polymer compositions
EP1664210B1 (en) Styrene acrylic copolymer based waterborne coatings
AU2010211112B2 (en) Zinc oxide particles which have been modified with phosphonocarboxylic acid and use of zinc oxide particles

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA FI HU JP KP KR LK MC MG MW NO RO SD SU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BF BJ CF CG CH CM DE DK ES FR GA GB IT LU ML MR NL SE SN TD TG