CA1105183A - Resinous particles for coating composition and its production - Google Patents
Resinous particles for coating composition and its productionInfo
- Publication number
- CA1105183A CA1105183A CA273,814A CA273814A CA1105183A CA 1105183 A CA1105183 A CA 1105183A CA 273814 A CA273814 A CA 273814A CA 1105183 A CA1105183 A CA 1105183A
- Authority
- CA
- Canada
- Prior art keywords
- resin
- process according
- groups
- coating composition
- water
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/904—Powder coating compositions
Abstract
ABSTRACT OF THE DISCLOSURE
The specification discloses a process for preparing resinous particles for a coating composition including the following steps. Firstly, a resin containing an ionic group, or a mixture of another type of resin and a dispersing agent containing an ionic group, is dissolved or ispersed in water by treatment with a neutralizing agent for the ionic group.
Secondly, the resin is removed from solution or dispersion by the use of a powdering agent and the resin thus deposited is pulverized in the aqueous medium. Thirdly the powder thus formed is removed from the aqueous medium. The resulting powder can then be used to preparing coating compositions or can be used directly for spray coating. The advantage of this type of powdered material is that it is produced entirely without the use of organic solvents and their attendant pollution, health and fire hazards etc.
The specification discloses a process for preparing resinous particles for a coating composition including the following steps. Firstly, a resin containing an ionic group, or a mixture of another type of resin and a dispersing agent containing an ionic group, is dissolved or ispersed in water by treatment with a neutralizing agent for the ionic group.
Secondly, the resin is removed from solution or dispersion by the use of a powdering agent and the resin thus deposited is pulverized in the aqueous medium. Thirdly the powder thus formed is removed from the aqueous medium. The resulting powder can then be used to preparing coating compositions or can be used directly for spray coating. The advantage of this type of powdered material is that it is produced entirely without the use of organic solvents and their attendant pollution, health and fire hazards etc.
Description
~?r.~t~
The present invention relates to a process for preparing resinous particles for a coating composition. More particularly, it relates to an improved process for preparing a coating composition in a slurry or powder form.
From the viewpoint of avoiding the use of organic solvents which may cause environmental pollution, various types of al-ternative coating compositions have been proposed, such as water-soluble coating compositions, emulsion coating compositions, slurry coating compositions and powder coating compositions. Of these, the last two coating compositions are particularly advantageous because of their reduced content of harmful or polluting materials, their simplicity of post treatment, and easy recovery for reuse, etc.
For the preparation of slurry coating compositions and powder coating compositions, a method is known which comprises mixing a liquid composition comprising a resin dissolved in an organic solvent with a coagulating liquid which is miscible with the organic solvent and precipitates : the resin from solution, collecting the coagulated resin and drying the resin or dispersing it into an aqueous medium.
ternatively, the liqui.d composition may be subjected to spra,~ i drying, optionally followed by dispersing the resulting dried resin into an aqueous mediu~.. However, both these methods re-~;r~
~uitc the use of organic solvents in large amounts and are therefore disadvantageous from the viewpoints of environmental polIution, fire hazard and economy, etc.
The present invention is directed to the improvement of the said conventional methods for production of a coating ~ -composition in a slurry or powder form substantially without the use of any organic solvent.
Thus, a main advantage of the pr.esent invention, at least in preferred forms, is that it pro~ides an improved ,~ I .
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:
process for preparing resinous particles suitable for a coating composition substantially without using any organic solvent. Another advantage of this invention, at least in preferred forms, is that it provides an im-proved process Eor preparing a slurry or powder coating composition substantially without using any organic solvent.
According to the invention there ls provided a process for preparing resinous particles for a coating composition which comprises the steps oE (1) treating (A) an aqueous resin dispersion or solution, which comprises (a) a resin having carboxyl groups or primary secondary or tertiary amino groups and no material dispersibility or solubility in water, which resin has been rendered dispersible or soluble in water by at least partly neutralizing the carboxyl groups or the amino groups with a base or an acid, respectively, and (b)a water-insoluble crosslinking agent which is crosslinkable with functional groups in the resin, with (B) an acidic substance or a basic substance as a powdering agent, said acidic substance being used when the resin is one having carboxyl groups, said basic substance being used when the resin is one having primary, secondary or tertiary amino yroups, under conditions which will deposit the resin in particulate form toagether with the crosslinking agent uniformly dispersed therein, and
The present invention relates to a process for preparing resinous particles for a coating composition. More particularly, it relates to an improved process for preparing a coating composition in a slurry or powder form.
From the viewpoint of avoiding the use of organic solvents which may cause environmental pollution, various types of al-ternative coating compositions have been proposed, such as water-soluble coating compositions, emulsion coating compositions, slurry coating compositions and powder coating compositions. Of these, the last two coating compositions are particularly advantageous because of their reduced content of harmful or polluting materials, their simplicity of post treatment, and easy recovery for reuse, etc.
For the preparation of slurry coating compositions and powder coating compositions, a method is known which comprises mixing a liquid composition comprising a resin dissolved in an organic solvent with a coagulating liquid which is miscible with the organic solvent and precipitates : the resin from solution, collecting the coagulated resin and drying the resin or dispersing it into an aqueous medium.
ternatively, the liqui.d composition may be subjected to spra,~ i drying, optionally followed by dispersing the resulting dried resin into an aqueous mediu~.. However, both these methods re-~;r~
~uitc the use of organic solvents in large amounts and are therefore disadvantageous from the viewpoints of environmental polIution, fire hazard and economy, etc.
The present invention is directed to the improvement of the said conventional methods for production of a coating ~ -composition in a slurry or powder form substantially without the use of any organic solvent.
Thus, a main advantage of the pr.esent invention, at least in preferred forms, is that it pro~ides an improved ,~ I .
~ -2- !~
:
process for preparing resinous particles suitable for a coating composition substantially without using any organic solvent. Another advantage of this invention, at least in preferred forms, is that it provides an im-proved process Eor preparing a slurry or powder coating composition substantially without using any organic solvent.
According to the invention there ls provided a process for preparing resinous particles for a coating composition which comprises the steps oE (1) treating (A) an aqueous resin dispersion or solution, which comprises (a) a resin having carboxyl groups or primary secondary or tertiary amino groups and no material dispersibility or solubility in water, which resin has been rendered dispersible or soluble in water by at least partly neutralizing the carboxyl groups or the amino groups with a base or an acid, respectively, and (b)a water-insoluble crosslinking agent which is crosslinkable with functional groups in the resin, with (B) an acidic substance or a basic substance as a powdering agent, said acidic substance being used when the resin is one having carboxyl groups, said basic substance being used when the resin is one having primary, secondary or tertiary amino yroups, under conditions which will deposit the resin in particulate form toagether with the crosslinking agent uniformly dispersed therein, and
(2) recovering the deposited resinous particles contain-ing the crosslin~ing agent from the aqueous medium.
In the process of the invention, at least in a preferred form, a resin is dissolved or dispersed in an aqueous medium by utilization of a neutralization reac-tion. Thus, the resin may be of any type conventionally
In the process of the invention, at least in a preferred form, a resin is dissolved or dispersed in an aqueous medium by utilization of a neutralization reac-tion. Thus, the resin may be of any type conventionally
- 3 -' employed for the formation of a coating fi]m but it is required to have at least one ionic group in the molecule so as to be soluble or dispersible in an aqueous medium by neutralization of a part or all of the ionic groups.
Examples of suitable ionic groups include acidic groups such as carboxyl and basic groups such as primary, secondary and tertiary amino. In addition to the ionic group, the resin may include any other functional group such as an epoxy group or a hydroxyl group.
Specific examples of the resin wherein the ionic group is acidic are acrylic resins having carboxyl groups, :- - - ' ,, - 3a -: ~
. .
.: : , -:
alkyd resins having carboxyl groups, acrylic resins having carboxyl groups and crosslinkable functional groups (e.g.
epoxy, hydroxyl), alkyd resins having carboxyl groups and crosslinkable functional groups (e.g. epoxy, hydroxyl), and acryl-modified alkyd resins obtained by copolymerization of said alkyd resins with polymerizable acrylic monomers.
Specific examples of the resin wherein the ionic group is basic are epoxy resins having primary, secondary or tertiary amino groups (prepared, for instance, by adding organic amino compounds to the epoxy groups in epoxy resins or epoxy-modified resins such as copolymers of phenol glycidyl ether, glycidyl ethers of phenol-aldehyde condensates, glycidyl acrylake or glycidyl methacrylate with other polymerizable monomers), acrylic or vinylic resins having primary, secondary or tertiary amino groups (prepared, for instance, by copolymerization of nitrogen containing vinyl compounds such as amino group-containing acrylates, amino group-containing methacrylates, vinylpyridines and vinyl-imidazoles with vinyl compounds having no free carboxyl group), and polyamide resins having primary, secondary or tertiary amino groups (prepared, for instance, by poly-condensing dibasic acids with polyvalent amines~
For neutralization of the ionic group in the resin ~ `
so as to make such resin dissolvable or dispersible in an aqueous medium, there may be used an inorganic basic sub-stance (e.g. potassium hydroxide, sodium hydroxide, potassium carbonate, ammonia) or an organic basic substance (e.g. methylaminel trlethylamine, monoethanolamlne, di-methylethanolamine, triethanolamine, ethylenediamine, diethylenetriamine) when the ionic group is acidic, or an inorganic dC dic xubstance (e.g. hydrochloric acid, sul~uric acid, phosphoric acid, carbonic acid) or an organlc acidic substance (e.g. formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, lactic acid, butyric acid, glycollic acid) when the ionic group is basic. The extent of the neutralization of the ionic group so as to make the resin dissolvable or dispersible in an aqueous medium varies considerab:ly with the kind of resin and may usually be not less than about 10 percent and pre-~ ferably not less than about 30 percent.
- 10 In addition to the resin dissolved or dispersed in an aqueous medium, the aqueous resin composition may comprise any conventional additive(s~ such as a coloring agent, a crosslinking agent and a modifier.
The coloring agent may be selected from pigments, dyes and the like.
As the crosslinking agent, any conventional cross-linkable resin or compound may be used which can react with the functional group `(e.g. carboxyl, primary, secondary or tertiary amino, hydroxyl, epoxy) present in the resin.
Particularly preferred are crosslinking agents having mis-cibility with the resin or being miscible with such resin at :` :
least on baking to afford a unlform coating film. Examples of the crosslinking agent capable of reacting with a carboxyl group or a primary, secondary or tertiary amino group are two or more epoxy group-containing compounds such - -as epoxy resins or triglycidyl isocyanurate. Examples of the crosslinking agent capable of reacting with a hydroxyl group are aminoplast resins such as urea~resins, melamine resins (e.g. hexamethoxymethylmelamine) and benzoguanamine, and polyisocyanate compounds containlng a blocked isocyanate , ~ ' :~ :
~ ~3~ ~ P.~,~
group.
A substance which is miscible with the resin and showing an efEect of improving the quality of a coating film is preferred as the modifier. Specific examples are natural resins, cellulose deri~atives such as cellulose acetate butyrate, alkyd resins, acrylic resins, vinyl resins, etc.
In practice, the crosslinking agent and the modifier may be incorporated as such into the aqueous resin composition when they are in a liquid form. On the other hand, if these agents are solid and of low miscibility, they may be melted or dissolved in a suitable solvent on admixture with the aqueous resin composition.
The preparation of the aqueous resin composition may be effected in a conventional manner. For example, an a~ueous solution or dispersion of the resin may be admixed with a coloring agent and subjected to a conventional dissolving or dispersing treatment, if necessary, followed by addition of a crosslinking agent, a modifier and the like to obtain a desir~d aqueous resin composition. The content of non-volatile components in such aqueous resin composition is usually designed to be from about 5 to 80 ~ by weight, p~eferably from about 10 to 60 % by weight.
` The thus prepared aqueous resin composition is then subjected to treatment with an agent capable of acting on the neutralized ionic group (hereinafter referred to as a "powdering agent") to make it free (hereinafter referred to -~
as a "separation treatment"), if necessary, followed by particle formation treatment.
When the ionic group in the resin is acidic, the ; - 6 -said separation treatment employs an aciclic substance. Any acidic substance can be used which can be dissolved in water to afford hydrogen ions. Specific examples are inorganic acids such as sulfuriC acid, hydrochloric acid, phosphoric acid and carbonic acid, organic acids such as formic acid, acetic acid, monochloroacetiC acid, dichloroacetic acid, trichloroacetic acid, lactic acid, butyric acid and glycolacetic acid, acidic gases such as carbon dioxide and sulfur dio~ide, etc. The inorganic or organic acid may be used as an aqueous solution, usually in a concentration of 1 N or less. The acidic gas may be employed solely or in combination with air or an inert gas such as nitrogen in an appropriate proportion. The amount of the acidic substance to be used may be approximately equivalent to the neutralized ionic groups in the resin.
When the ionic group in the resin is basic, the said separation treat~ent employs a basic substance. Any basic substance may be employed which can be dissolved in water to accept hydrogen ions. Specific examples are inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbon-ate and ammonia, organic bases such as triethylamine and di-methylaminoethanol, basic yases such as gaseous ammonia, etc.
The inorganic or organic base may be used as an aqueous solu-tion~ usually in a concentration of 1 N or less. The basic -~
gas may be employed solely or in combination with air or an inert gas such as nitrogen in an appropriate proportion. --The amount of the basic substance to be used may be approxi-mately equivalent to the neutralized ionic groups in the resin.
. .' : .' .
' ~
The separation treatment may be effected by an appropriate procedure depending on the form and the size of the resinous particles to be formed. For example, the following procedures may be adopted:
(a) A procedure which comprises graduall~ intro-ducing the acidic or basic gas into the aqueous resin com-position while stirring vigorously;
(b) A procedure which comprises gradually adding the aqueous resin composition into an aqueous solution of the acidic or basic substance while stirring vigorously, or vice versa; in this case, the presence of a water-soluble high polymer having a dispersing ability such as poly-ethylene oxide or poval, cellulose derivatives such as hydroxyethylcellulose or a dispersing agent of low molecular weight such as an anionic, cationic or nonionic surfactarlt, in the aqueous solution of the acidic or basic substance makes the resulting resinous particles more spherical, when the coating composition comprising such spherical resin partlcles is applied to the sur~ace of a substrate to be coated, the resin particles are arranged on the surface more densely so that a more smooth and lustrous coating film can be obtained;
(c) A procedure which comprises spraying the aqueous resin composition onto or into an aqueous solution of the acidic or basic substance, if necessary, while stirr-ing; in this case, it is advantageous to make th~ dispersing agent present as in the above mentioned procedure (b);
(d) A procedure which comprises spraying the aqueous resin composition into the atmosphere o~ the acidic or basic gas, ~ ' ; ~ ' ' ' (e) A procedure which eomprises contaeting the aqueous resin eomposit:ion in a mist form with an aqueous solution of the acidie or basic substanee in a mist form.
By the above separation treatment, the neu-tralized ionie groups in the resin are converted to free carboxyl groups, and the resinous particles are separated. As to the particle form of the resinous particles, the procedures (c), (d) and (e~
bring about a more spherical, globular particle form compared with the procedures (a~ and (b). The particle size of the resinous partieles ean be appropriately controlled depending on the conditions of the separation treatment (e.g. the viseosity of the resin, the speed of the stirring, the diameter o~ the spraying nozzle, and the spraying viseosity).
The resinous particles formed in the separation treatment are then recovered by a eonventional separation proeedure sueh as filtration, sieving and eentrifugation.
If neeessary, the mixture after the separation treatment may be treated with a neutralizing agent so as to neutralize the exeessive aeidie or basie substanee.
The thus recovered resinous partieles can be used as a eoating eomposition. For a powder coating eomposition, the resinous particles may be employed as such. For a slurry eoating composition, the resinous particles are dispersed in an aqueous medium and then used. When the resinous partieles are eontaminated with unfavorable im- :
purities sueh as salts, the impurities may be removed by a eonventional elimination proeedure, for instanee, washing with water.
The applieation of the eoating composition in a powder form onto a substrate to be eoated may be earried , ' out by various procedures, e.g. air sprayinc~, electrostatic coating, fluid bed coating, etc. The applied coatiny composition is then dried and baked under suitable condi-tions whereby a smooth and lustrous coating film is formed.
When the coating composition in a slurry form is applied by a conventional spraying or roll coating proce-dure, evaporation of water from the wet film is faster than the case usiny a conventional water-soluble or emulsion type aqueous paint for ~aking, so that a coating film having a larger film thickness is readily obtainable, and thus the workability auring the coating operation is greatly improved.
Besides, it is confirmed that the coating film formed after baking is superior in smoothness and luster to a coating film obtained from a conventional powdery paint.
The coating composition can be obtained accoraing to a ~; preferrea form of the invention without making noise and . .
scattering of dust, explosion of dust and other dangers at the pulverizing st~p, unlike the conventional process which comprises the step of pulverizing a solid composition.
Besides, the particle form and the particle size can be readily controlled as mentioned above, and the kind of the resin to be used can be selected as desired from a wide range.
The formation of a large amount of a solvent mixture as a by-product does not take place, unlike the conventional method in which the resin particles are precipitated by utilizing the difference between the dissolving abilities of solvents with respect to the resin components, so that environ-mental pollution is prevented. Besides, it is advantageous from the economical viewpoint that operations required for recycling, recovery or removal of such solvent mixture in the production of coating step is simplified. In addition, :;:
-: : :, .
.
. ~ -5~3 the risk of explosion which is significant when using acetone or other inflammable solvents can be minimized.
Since the aqueous resin composition is in a solution or dispersion state before the separation treatment, conventional techniques for dispersion of a pigment into a liquid medium can be utilized. The adsorption of the pigment into the resin can thus be effectively attained, compared with a conventional powdery paint or a paint in slurry form obtained by dispersing a powdery paint in water, so that a coating film having excellent luster and smoothness can be obtained. In addition, a conventional color matching pro-cedure can be adopted to effect color matching with ease and high preciseness.
The illustrations as hereinabove described are concerned with the preparation of resinous particles and a coating composition including them by the use of a resin having an ionic group in the molecule. Even when a resin having no ionic group is used in place of the said resin, it is still possible to produce resinous particles and a coating composition including them by applying a technical concept as chemically equivalent thereto.
Thus, an aqueous resin composition wherein a resin having no ionic group and having as such no solubility or dispersibility in water can be dispersed in an aqueous medium in the presence of a dispersing agent having an ionic group by at least partially neutralizing the ionic group in the dispersing agent. The mixture can then be subjected to treatment with a powderin~ agent while applying thPreto an operation for pulverization to deposit the resin in a particulate form, and the deposited resinous particles can then be recovered from the aqueous medium.
~ ' The ionic group in the dispersing agent ma~ be acidic or basic. As hereinabove stated, the neutralization may be carried out by the use of a basic substance in case of the ionic group being acidic or by the use of an acidic substance in case of the ionic group being basic. When the ionic group is acidic, the separation treatment employs an acidic substance. ~hen the ionic group is basic, the separa-tion treatment employs a basic substance.
As the neutralized acidic group-containing dis-persing agent, there may be used an emulsifier or an anionicsurfactant. Speci~ic examples are sodium oleate, potassium oleate, castor oil potassium soap, etc. Examples of the neutralized basic group-containing dispersing agent are cationic surfactants such as alkylammonium salts (e.g.
primary, secondary or tertiary laurylammonium acetate) and alkyl group-containing quaternary ammonium salts.
The aqueous resin composition may be prepared, for instance, by polymerization of polymerizable monomers in an aqueous medium in the presence of a dispersing agent as previously neutralized or by admixing a liquid resin (i.e. a solution of a resin in a water-miscible solvent or a melted resin) with an aqueous medium by the aid of a dispersing agent as previously neutralized.
The subsequent operations may be carried out in ~ .
.` .
~ ~ .
' :
.
.
., . . , - . . . .
the same manner as in case of using a resin having an ionic group. While the thus prepared resinous particles are provided with the same ~ood physical properties as possessed by those obtained by the use of a resin having an ionic group, the former are sometimes obtainable in a finer and more spherical state than the latter.
Practical and presently preferred embodiments of the invention are illustratively shown in the following Examples wherein parts and percentages are by weight.
Example l Thirty parts of an aqueous solution comprising a water-soluble acrylic resin (which comprises units of acrylic acid, hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate, styrene and n-butyl acrylate in a weight ratio of 14.5 : 8.9 : l~.9 : 16.1 : 26 : 16.6, 100 of the carboxyl groups in the molecule being neutralized with dimethylethanolamine) in a concentration of 38 ~, 2.9 parts of hexamethoxymethylmelamine and 0.71 part of water-dispersible aluminum powders are mixed together, and the resulting mixture is admixed with 30 parts of water to make an aqueous resin composition.
The aqueous resin composition (63.61 parts) is dropwise added to a l/20 N aqueous hydrochloric acid solu--tion (500 parts) in about 15 minutes while stirring by a high speed mixer. After completion of the additionl ex-cessive hydrochloric acid in the resulting mixture was neutralized with a l N aqueous potassium hydroxide solution and sieved through a sieve of 250 mesh to obtain a dis-~` ~ persion o~ res:inous particles having a particle size of lO
to 30 ~. The resin particles are washed with water and :.
~ .
~: . , ~' : .' ' ' : ' dispersed in water to make a coating composition in a slurry Eorm havin~ a solid content of 50 ~.
The coating composition in a s~urry form is applied to a polished steel plate by air spraying and baked at 160C for 30 minutes, whereby a smooth and lustrous metallic finish coating film is formed. When the coating film is subjected to an impact test of the DuPont's metho~, a value of 20 cm or more (500 g) is obtained. It is thus confirmed that sufficient crosslinking has been attained.
Example 2 The dispersion of resin particles obtained in Example 1 is washed with water and dried at 50C for 3 hours in a fluidized bed drier to make a powder coating composi-tion. The powder coating composition is applied to a steel plate by electrostatic coating and baked at 160C for 30 minutes, whereby a well crosslinked, smooth and lustrous metallic finish coating film is formed.
Example 3 .
One hundred parts of an isopropanol solution comprising a polyester resin (which has a number average molecular weight of 1500 and an acid value of 110 and wherein 50 % of the carboxyl groups are neutralized with triethylamine) in a concentration of 70 %, 30 parts o benzoguanamine, 60 parts of titanium o~ide ("Tipake R-820", trademark of Ishihara Sangyo Kaisha, Ltd.) and 640 parts o water are mixed together to make an aqueous resin compo sition.
The aqueous resin composition is air sprayed onto the surface of a 1/20 N aqueous hydrochloric acid solution charged in a vessel while stirring. The precipitated .
; . ~. ~ .
materials are collected by centrifugation, washed with water and dispersed in water to make a coating cornposition in a slurry form having a solid content of 50 ~.
The coating composition in a slurry form is applied to a polished steel plate by air spraying and baked at 160C
for 30 minutes, whereby a smooth and lustrous coating film is formed. When the coating film is subjected to the ex-trusion test using an Erichsen tester, a value of 3 mm or more is obtained. It is thus confirmed that sufficient crosslinking has been attained.
Example 4 The aqueous resin composition used in Example 3 is air sprayed onto the surface of a 1/20 N aqueous hydro-chloric acid solution charged in a vessel while stirring.
The precipitated materials are collected by centrifugation, washed with water and dried at 50C for 3 hours in a flui-dized bed drier to prepare a powder coating composition, which is applied to a steel plate by electrostatic coating and baked at 160C for 30 minutes, whereby a well cross-linked, smooth and lustrous coating film is formed.
Exam The polyester resin dispersion as employed in Example 3 (100 parts) and a polyisocyanate compound contain-ing a blocked isocyanate group (14 parts) are melt mixed at a temperature higher than the melting temperature of the ` polyisocyanate compound (e.g. 90C), and 70 % of the carboxyl groups in the resin mixture are neutralized with dimethylethanolamine. The resultant mixture (114 parts~ is admixed with titanium oxide as employed in Example 3 (30 parts) and water (350 parts) to make an aqueous resin .
~; : :
, ~ ' ' . .
composition.
The aqueous resin composition is air sprayed into a stream of carbon dioxide to make resinous spherical particles, which are washed with water and dispersed in water to prepare a coating composition in a slurry form having a solid content of 50 ~. Alternatively, the said resinous spherical particles may be washed with water and dried to prepare a powder coating c:omposition.
E~ample 6 Acrylic acid (15 parts), 2-hydroxyethyl meth-acrylate (15 parts), methyl methacrylate (38 parts), styrene (19 parts) and n-butyl acrylate (8 parts) are mixed together to make a liquid composition. The thus prepared liquid composition (20 parts) is charged in a flask, and while stirring at 130C, a mi~ture of the said liquid composition (75 parts) and azobisisobutyronitrile (1.5 parts) is drop-wise added thereto in 3 hours. After completion of the addition, stirring is continued at the same temperature or 1 hour. Then, a 10 % aqueous solution of sodium hydroxide (36 parts) is added to the resulting mixture at 110C, and after stirring for 30 minutes, water (150 parts) is added thereto ~t a temperature of lower than 100C to obtain a resin mixture. To the resin mixture (100 parts), hexa-methoxymethylmelamine (10 parts) and aluminum powders ("Alpaste 5105 WA", tradema~k of Toyo Aluminium K.K.) (30 parts) are added, and the resultant mixture is dispersed well to make an aqueous resin compositionO
The aqweous rèsin composition (100 parts) is :~-diluted with water t200 parts), and a 1/10 N aqueous hydro-chloric acid solwtion (700 parts) is added thereto, followed : :
:: :
1, , .. . . - : . ' ' .
: ~: , :. , . : ..
"''` ~ '" ' '~ ~ . ' ' ' ;
, by stirring with a labomixer. The rcsultant mixture is neutralized with a l/10 N aqueous so~ium hydroxide solution, an~ the aqueous medium is eliminated to obtain resinous particles having a particle size of lO to 20 ~. The resinous particles are washed with water to eliminate the produced sodium chloride and dispersed in water to make a coating composition in a slurry form having a solid content of 50 %.
The coating composition in a slurry form i5 applied 10 to a polished steel plate by air spraying and baked at 160C
for 30 minutes, whereby a smooth and lustrous coating film is formed.
When the said resinous particles are washed with water and dried at 50C for 3 hours in a fluidized bed drier, there is obtained a powder coating composition, which can also af~ord a coating film o~ satisfactory quality.
Example 7 ~ frac/~ ~ark-B An epoxy resin ("Epicoat 10011 manufactured by Shell Chemical Corp.) (488 parts) and diethanolamine (105 20 parts) are reacted in isopropanol (250 parts) under nitrogen stream at 80C for 3 hours to make an aminoepoxy resin solu-tion. To the aminoepo~y resin solution (143 parts), glacial acetic acid ~62 parts) is added, deionized water (500 parts) is added thereto, and the resultant mixture is admixed with a blocked polyisocyanate resin solution in methylethylketone (solid content, 50 ~; 16 parts) and titanium oxide ("Tipake ~ rkR~ /"h /, k ~
R-820'1 manufactured by Ishihara Sangyo Kaisha, Ltd.) (30 parts) to make an a~ueous resin composition.
` The aqueous resin composition (143 parts) is diluted with water (250 parts), and the resulting dilution :
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.
': :
is dropwise added to 0.05 N aqueous solution of potassium hydroxide while viyorous ~;tirring. After excessive alkali is neutralized with 0.1 N acetic acid, the resultant mixture is subjected to centrifugal separation to collect resinous particles of not more than 50 ~ in diameter. The resinous particles are washed with water and then dispersed in water to make a coating composition in a slurry form having a solid content of 50 ~.
The coating composition in a slurry form is applied to a polished steel plate by air spraying and baked at 180C for 20 minutes, whereby a smooth and lustrous coating film is formed. I~hen the coating film is subjected to the DuPont's impact test, a value of 20 cm or more (500 g) is obtained. It is thus confirmed that sufficient crosslinking has been attained.
Example 8 -An aqueous dispersion comprising an aminoacrylic resin (comprising as the monomeric constituents dimethyl aminoethyl methacrylate, methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate and styrene; glass transition point, 65C; weight average molecular weight, 18,000; content of non-volatile components, 80 ~; dispersing medium, isopropanol : water = 1 : 1 by weight) (100 parts) B is admixed with hexamethoxymethylmelamine ("Cymel 303"~ k manufactured by American Cyanamid) (20 parts), a mixture of ~cf~ k_ ~
powdery aluminum ("L-579'; manufactured by Silverline Mfg. Co.) (5 parts) and isopropanol (5 parts) is added thereto, and the resultant mixture is admixed with 0.1 N hydrochloric acid to make an aqueous resin composition.
To the aqueous resin composition (100 parts), a .
: ~ - . . , .. , :
~,5:~3 mixture of 0.1 N sodium hydroxide solution (500 parts~ and polyethylene o~ide (10 parks) is added, and the resulting mixture is stirred by the aid of a high speed mixer for 15 minutes. After excessive alkali is neutralized with 0.1 N
hydrochloric acid, the resultant mixture is subjected to centrifugal separation to collect resinous particles of not more than 50 ~ in particle size. The resinous particles are washed with water and dispersed in water to make a coating composition in a slurry form having a solid content of 50 %.
The coating composition in a slurry ~orm is applied to a polished steel plate and baked as in Example 7, whereby a smooth and lustrous metallie finish coating film is formed. By the DuPont's impaet test method, it is confirmed that sufficient crosslinking has been attained.
Example 9 The resinous particles as eollected in Example 8 are washed with water and dried by the use of a fluidized bed type dryer to make a eoating eomposition in a powder form. The eoating eomposition is applied onto a polished steel plate eleetrostatieally and then baked at 160C for 20 minutes, whereby a smooth and lustrous eoating film possess-ing a good metallie feeling is formed. By the DuPont's impaet test method, it is eonfirmed that suffieient eross-linking has been attained.
Example 10 Potassium laurate (3.0 parts) and water (150 parts) are eharged into a flask, and a mixture of methyl methaerylate ~30 parts), styrene (30 parts), n-butyl meth-aerylate (20 parts) and 2-h~droxyethyl methacrylate (20 part) and a mixture of ~,4'-abbzis-4-eyanovalerie aeid , ' ~- ` . .
3~
(1.0 part), dimethylethanolamine (1.0 part) and water (50 parts) are dropwise added thereto at 70C for 3 hours. The resultant mixture is kept at the same temperature to make an aqueous liquid composition.
The aqueous liquid composition (100 paxts) is dropwise added to l/20 N hydrochloric acid (500 parts) with vigorous stirxing. After the addition is completed, ex-cessive hydrochloric acid is neutrali~ed with 1/lO N sodium hydroxide solution and subjected to centrifugation, whereby resinous particles of not more than 10 ~ in particle size are collected.
The resinous particles are washed with water and dispersed into water to give a coating composition in a slurry form. The coating composition is sprayed on a polished steel plate and baked at 130C for 20 minutes to make a smooth and lustrous finish coating film.
Separately, the resinous particles as above obtained are washed with water and dried by a fluidized bed dryer to give a coating composition in a powder form. The coating composition is applied onto a polished steel plate by electrostatic coating and baked to make a lustrous, smooCh coating film.
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Examples of suitable ionic groups include acidic groups such as carboxyl and basic groups such as primary, secondary and tertiary amino. In addition to the ionic group, the resin may include any other functional group such as an epoxy group or a hydroxyl group.
Specific examples of the resin wherein the ionic group is acidic are acrylic resins having carboxyl groups, :- - - ' ,, - 3a -: ~
. .
.: : , -:
alkyd resins having carboxyl groups, acrylic resins having carboxyl groups and crosslinkable functional groups (e.g.
epoxy, hydroxyl), alkyd resins having carboxyl groups and crosslinkable functional groups (e.g. epoxy, hydroxyl), and acryl-modified alkyd resins obtained by copolymerization of said alkyd resins with polymerizable acrylic monomers.
Specific examples of the resin wherein the ionic group is basic are epoxy resins having primary, secondary or tertiary amino groups (prepared, for instance, by adding organic amino compounds to the epoxy groups in epoxy resins or epoxy-modified resins such as copolymers of phenol glycidyl ether, glycidyl ethers of phenol-aldehyde condensates, glycidyl acrylake or glycidyl methacrylate with other polymerizable monomers), acrylic or vinylic resins having primary, secondary or tertiary amino groups (prepared, for instance, by copolymerization of nitrogen containing vinyl compounds such as amino group-containing acrylates, amino group-containing methacrylates, vinylpyridines and vinyl-imidazoles with vinyl compounds having no free carboxyl group), and polyamide resins having primary, secondary or tertiary amino groups (prepared, for instance, by poly-condensing dibasic acids with polyvalent amines~
For neutralization of the ionic group in the resin ~ `
so as to make such resin dissolvable or dispersible in an aqueous medium, there may be used an inorganic basic sub-stance (e.g. potassium hydroxide, sodium hydroxide, potassium carbonate, ammonia) or an organic basic substance (e.g. methylaminel trlethylamine, monoethanolamlne, di-methylethanolamine, triethanolamine, ethylenediamine, diethylenetriamine) when the ionic group is acidic, or an inorganic dC dic xubstance (e.g. hydrochloric acid, sul~uric acid, phosphoric acid, carbonic acid) or an organlc acidic substance (e.g. formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, lactic acid, butyric acid, glycollic acid) when the ionic group is basic. The extent of the neutralization of the ionic group so as to make the resin dissolvable or dispersible in an aqueous medium varies considerab:ly with the kind of resin and may usually be not less than about 10 percent and pre-~ ferably not less than about 30 percent.
- 10 In addition to the resin dissolved or dispersed in an aqueous medium, the aqueous resin composition may comprise any conventional additive(s~ such as a coloring agent, a crosslinking agent and a modifier.
The coloring agent may be selected from pigments, dyes and the like.
As the crosslinking agent, any conventional cross-linkable resin or compound may be used which can react with the functional group `(e.g. carboxyl, primary, secondary or tertiary amino, hydroxyl, epoxy) present in the resin.
Particularly preferred are crosslinking agents having mis-cibility with the resin or being miscible with such resin at :` :
least on baking to afford a unlform coating film. Examples of the crosslinking agent capable of reacting with a carboxyl group or a primary, secondary or tertiary amino group are two or more epoxy group-containing compounds such - -as epoxy resins or triglycidyl isocyanurate. Examples of the crosslinking agent capable of reacting with a hydroxyl group are aminoplast resins such as urea~resins, melamine resins (e.g. hexamethoxymethylmelamine) and benzoguanamine, and polyisocyanate compounds containlng a blocked isocyanate , ~ ' :~ :
~ ~3~ ~ P.~,~
group.
A substance which is miscible with the resin and showing an efEect of improving the quality of a coating film is preferred as the modifier. Specific examples are natural resins, cellulose deri~atives such as cellulose acetate butyrate, alkyd resins, acrylic resins, vinyl resins, etc.
In practice, the crosslinking agent and the modifier may be incorporated as such into the aqueous resin composition when they are in a liquid form. On the other hand, if these agents are solid and of low miscibility, they may be melted or dissolved in a suitable solvent on admixture with the aqueous resin composition.
The preparation of the aqueous resin composition may be effected in a conventional manner. For example, an a~ueous solution or dispersion of the resin may be admixed with a coloring agent and subjected to a conventional dissolving or dispersing treatment, if necessary, followed by addition of a crosslinking agent, a modifier and the like to obtain a desir~d aqueous resin composition. The content of non-volatile components in such aqueous resin composition is usually designed to be from about 5 to 80 ~ by weight, p~eferably from about 10 to 60 % by weight.
` The thus prepared aqueous resin composition is then subjected to treatment with an agent capable of acting on the neutralized ionic group (hereinafter referred to as a "powdering agent") to make it free (hereinafter referred to -~
as a "separation treatment"), if necessary, followed by particle formation treatment.
When the ionic group in the resin is acidic, the ; - 6 -said separation treatment employs an aciclic substance. Any acidic substance can be used which can be dissolved in water to afford hydrogen ions. Specific examples are inorganic acids such as sulfuriC acid, hydrochloric acid, phosphoric acid and carbonic acid, organic acids such as formic acid, acetic acid, monochloroacetiC acid, dichloroacetic acid, trichloroacetic acid, lactic acid, butyric acid and glycolacetic acid, acidic gases such as carbon dioxide and sulfur dio~ide, etc. The inorganic or organic acid may be used as an aqueous solution, usually in a concentration of 1 N or less. The acidic gas may be employed solely or in combination with air or an inert gas such as nitrogen in an appropriate proportion. The amount of the acidic substance to be used may be approximately equivalent to the neutralized ionic groups in the resin.
When the ionic group in the resin is basic, the said separation treat~ent employs a basic substance. Any basic substance may be employed which can be dissolved in water to accept hydrogen ions. Specific examples are inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbon-ate and ammonia, organic bases such as triethylamine and di-methylaminoethanol, basic yases such as gaseous ammonia, etc.
The inorganic or organic base may be used as an aqueous solu-tion~ usually in a concentration of 1 N or less. The basic -~
gas may be employed solely or in combination with air or an inert gas such as nitrogen in an appropriate proportion. --The amount of the basic substance to be used may be approxi-mately equivalent to the neutralized ionic groups in the resin.
. .' : .' .
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The separation treatment may be effected by an appropriate procedure depending on the form and the size of the resinous particles to be formed. For example, the following procedures may be adopted:
(a) A procedure which comprises graduall~ intro-ducing the acidic or basic gas into the aqueous resin com-position while stirring vigorously;
(b) A procedure which comprises gradually adding the aqueous resin composition into an aqueous solution of the acidic or basic substance while stirring vigorously, or vice versa; in this case, the presence of a water-soluble high polymer having a dispersing ability such as poly-ethylene oxide or poval, cellulose derivatives such as hydroxyethylcellulose or a dispersing agent of low molecular weight such as an anionic, cationic or nonionic surfactarlt, in the aqueous solution of the acidic or basic substance makes the resulting resinous particles more spherical, when the coating composition comprising such spherical resin partlcles is applied to the sur~ace of a substrate to be coated, the resin particles are arranged on the surface more densely so that a more smooth and lustrous coating film can be obtained;
(c) A procedure which comprises spraying the aqueous resin composition onto or into an aqueous solution of the acidic or basic substance, if necessary, while stirr-ing; in this case, it is advantageous to make th~ dispersing agent present as in the above mentioned procedure (b);
(d) A procedure which comprises spraying the aqueous resin composition into the atmosphere o~ the acidic or basic gas, ~ ' ; ~ ' ' ' (e) A procedure which eomprises contaeting the aqueous resin eomposit:ion in a mist form with an aqueous solution of the acidie or basic substanee in a mist form.
By the above separation treatment, the neu-tralized ionie groups in the resin are converted to free carboxyl groups, and the resinous particles are separated. As to the particle form of the resinous particles, the procedures (c), (d) and (e~
bring about a more spherical, globular particle form compared with the procedures (a~ and (b). The particle size of the resinous partieles ean be appropriately controlled depending on the conditions of the separation treatment (e.g. the viseosity of the resin, the speed of the stirring, the diameter o~ the spraying nozzle, and the spraying viseosity).
The resinous particles formed in the separation treatment are then recovered by a eonventional separation proeedure sueh as filtration, sieving and eentrifugation.
If neeessary, the mixture after the separation treatment may be treated with a neutralizing agent so as to neutralize the exeessive aeidie or basie substanee.
The thus recovered resinous partieles can be used as a eoating eomposition. For a powder coating eomposition, the resinous particles may be employed as such. For a slurry eoating composition, the resinous particles are dispersed in an aqueous medium and then used. When the resinous partieles are eontaminated with unfavorable im- :
purities sueh as salts, the impurities may be removed by a eonventional elimination proeedure, for instanee, washing with water.
The applieation of the eoating composition in a powder form onto a substrate to be eoated may be earried , ' out by various procedures, e.g. air sprayinc~, electrostatic coating, fluid bed coating, etc. The applied coatiny composition is then dried and baked under suitable condi-tions whereby a smooth and lustrous coating film is formed.
When the coating composition in a slurry form is applied by a conventional spraying or roll coating proce-dure, evaporation of water from the wet film is faster than the case usiny a conventional water-soluble or emulsion type aqueous paint for ~aking, so that a coating film having a larger film thickness is readily obtainable, and thus the workability auring the coating operation is greatly improved.
Besides, it is confirmed that the coating film formed after baking is superior in smoothness and luster to a coating film obtained from a conventional powdery paint.
The coating composition can be obtained accoraing to a ~; preferrea form of the invention without making noise and . .
scattering of dust, explosion of dust and other dangers at the pulverizing st~p, unlike the conventional process which comprises the step of pulverizing a solid composition.
Besides, the particle form and the particle size can be readily controlled as mentioned above, and the kind of the resin to be used can be selected as desired from a wide range.
The formation of a large amount of a solvent mixture as a by-product does not take place, unlike the conventional method in which the resin particles are precipitated by utilizing the difference between the dissolving abilities of solvents with respect to the resin components, so that environ-mental pollution is prevented. Besides, it is advantageous from the economical viewpoint that operations required for recycling, recovery or removal of such solvent mixture in the production of coating step is simplified. In addition, :;:
-: : :, .
.
. ~ -5~3 the risk of explosion which is significant when using acetone or other inflammable solvents can be minimized.
Since the aqueous resin composition is in a solution or dispersion state before the separation treatment, conventional techniques for dispersion of a pigment into a liquid medium can be utilized. The adsorption of the pigment into the resin can thus be effectively attained, compared with a conventional powdery paint or a paint in slurry form obtained by dispersing a powdery paint in water, so that a coating film having excellent luster and smoothness can be obtained. In addition, a conventional color matching pro-cedure can be adopted to effect color matching with ease and high preciseness.
The illustrations as hereinabove described are concerned with the preparation of resinous particles and a coating composition including them by the use of a resin having an ionic group in the molecule. Even when a resin having no ionic group is used in place of the said resin, it is still possible to produce resinous particles and a coating composition including them by applying a technical concept as chemically equivalent thereto.
Thus, an aqueous resin composition wherein a resin having no ionic group and having as such no solubility or dispersibility in water can be dispersed in an aqueous medium in the presence of a dispersing agent having an ionic group by at least partially neutralizing the ionic group in the dispersing agent. The mixture can then be subjected to treatment with a powderin~ agent while applying thPreto an operation for pulverization to deposit the resin in a particulate form, and the deposited resinous particles can then be recovered from the aqueous medium.
~ ' The ionic group in the dispersing agent ma~ be acidic or basic. As hereinabove stated, the neutralization may be carried out by the use of a basic substance in case of the ionic group being acidic or by the use of an acidic substance in case of the ionic group being basic. When the ionic group is acidic, the separation treatment employs an acidic substance. ~hen the ionic group is basic, the separa-tion treatment employs a basic substance.
As the neutralized acidic group-containing dis-persing agent, there may be used an emulsifier or an anionicsurfactant. Speci~ic examples are sodium oleate, potassium oleate, castor oil potassium soap, etc. Examples of the neutralized basic group-containing dispersing agent are cationic surfactants such as alkylammonium salts (e.g.
primary, secondary or tertiary laurylammonium acetate) and alkyl group-containing quaternary ammonium salts.
The aqueous resin composition may be prepared, for instance, by polymerization of polymerizable monomers in an aqueous medium in the presence of a dispersing agent as previously neutralized or by admixing a liquid resin (i.e. a solution of a resin in a water-miscible solvent or a melted resin) with an aqueous medium by the aid of a dispersing agent as previously neutralized.
The subsequent operations may be carried out in ~ .
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.
.
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the same manner as in case of using a resin having an ionic group. While the thus prepared resinous particles are provided with the same ~ood physical properties as possessed by those obtained by the use of a resin having an ionic group, the former are sometimes obtainable in a finer and more spherical state than the latter.
Practical and presently preferred embodiments of the invention are illustratively shown in the following Examples wherein parts and percentages are by weight.
Example l Thirty parts of an aqueous solution comprising a water-soluble acrylic resin (which comprises units of acrylic acid, hydroxypropyl acrylate, methyl methacrylate, n-butyl methacrylate, styrene and n-butyl acrylate in a weight ratio of 14.5 : 8.9 : l~.9 : 16.1 : 26 : 16.6, 100 of the carboxyl groups in the molecule being neutralized with dimethylethanolamine) in a concentration of 38 ~, 2.9 parts of hexamethoxymethylmelamine and 0.71 part of water-dispersible aluminum powders are mixed together, and the resulting mixture is admixed with 30 parts of water to make an aqueous resin composition.
The aqueous resin composition (63.61 parts) is dropwise added to a l/20 N aqueous hydrochloric acid solu--tion (500 parts) in about 15 minutes while stirring by a high speed mixer. After completion of the additionl ex-cessive hydrochloric acid in the resulting mixture was neutralized with a l N aqueous potassium hydroxide solution and sieved through a sieve of 250 mesh to obtain a dis-~` ~ persion o~ res:inous particles having a particle size of lO
to 30 ~. The resin particles are washed with water and :.
~ .
~: . , ~' : .' ' ' : ' dispersed in water to make a coating composition in a slurry Eorm havin~ a solid content of 50 ~.
The coating composition in a s~urry form is applied to a polished steel plate by air spraying and baked at 160C for 30 minutes, whereby a smooth and lustrous metallic finish coating film is formed. When the coating film is subjected to an impact test of the DuPont's metho~, a value of 20 cm or more (500 g) is obtained. It is thus confirmed that sufficient crosslinking has been attained.
Example 2 The dispersion of resin particles obtained in Example 1 is washed with water and dried at 50C for 3 hours in a fluidized bed drier to make a powder coating composi-tion. The powder coating composition is applied to a steel plate by electrostatic coating and baked at 160C for 30 minutes, whereby a well crosslinked, smooth and lustrous metallic finish coating film is formed.
Example 3 .
One hundred parts of an isopropanol solution comprising a polyester resin (which has a number average molecular weight of 1500 and an acid value of 110 and wherein 50 % of the carboxyl groups are neutralized with triethylamine) in a concentration of 70 %, 30 parts o benzoguanamine, 60 parts of titanium o~ide ("Tipake R-820", trademark of Ishihara Sangyo Kaisha, Ltd.) and 640 parts o water are mixed together to make an aqueous resin compo sition.
The aqueous resin composition is air sprayed onto the surface of a 1/20 N aqueous hydrochloric acid solution charged in a vessel while stirring. The precipitated .
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materials are collected by centrifugation, washed with water and dispersed in water to make a coating cornposition in a slurry form having a solid content of 50 ~.
The coating composition in a slurry form is applied to a polished steel plate by air spraying and baked at 160C
for 30 minutes, whereby a smooth and lustrous coating film is formed. When the coating film is subjected to the ex-trusion test using an Erichsen tester, a value of 3 mm or more is obtained. It is thus confirmed that sufficient crosslinking has been attained.
Example 4 The aqueous resin composition used in Example 3 is air sprayed onto the surface of a 1/20 N aqueous hydro-chloric acid solution charged in a vessel while stirring.
The precipitated materials are collected by centrifugation, washed with water and dried at 50C for 3 hours in a flui-dized bed drier to prepare a powder coating composition, which is applied to a steel plate by electrostatic coating and baked at 160C for 30 minutes, whereby a well cross-linked, smooth and lustrous coating film is formed.
Exam The polyester resin dispersion as employed in Example 3 (100 parts) and a polyisocyanate compound contain-ing a blocked isocyanate group (14 parts) are melt mixed at a temperature higher than the melting temperature of the ` polyisocyanate compound (e.g. 90C), and 70 % of the carboxyl groups in the resin mixture are neutralized with dimethylethanolamine. The resultant mixture (114 parts~ is admixed with titanium oxide as employed in Example 3 (30 parts) and water (350 parts) to make an aqueous resin .
~; : :
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composition.
The aqueous resin composition is air sprayed into a stream of carbon dioxide to make resinous spherical particles, which are washed with water and dispersed in water to prepare a coating composition in a slurry form having a solid content of 50 ~. Alternatively, the said resinous spherical particles may be washed with water and dried to prepare a powder coating c:omposition.
E~ample 6 Acrylic acid (15 parts), 2-hydroxyethyl meth-acrylate (15 parts), methyl methacrylate (38 parts), styrene (19 parts) and n-butyl acrylate (8 parts) are mixed together to make a liquid composition. The thus prepared liquid composition (20 parts) is charged in a flask, and while stirring at 130C, a mi~ture of the said liquid composition (75 parts) and azobisisobutyronitrile (1.5 parts) is drop-wise added thereto in 3 hours. After completion of the addition, stirring is continued at the same temperature or 1 hour. Then, a 10 % aqueous solution of sodium hydroxide (36 parts) is added to the resulting mixture at 110C, and after stirring for 30 minutes, water (150 parts) is added thereto ~t a temperature of lower than 100C to obtain a resin mixture. To the resin mixture (100 parts), hexa-methoxymethylmelamine (10 parts) and aluminum powders ("Alpaste 5105 WA", tradema~k of Toyo Aluminium K.K.) (30 parts) are added, and the resultant mixture is dispersed well to make an aqueous resin compositionO
The aqweous rèsin composition (100 parts) is :~-diluted with water t200 parts), and a 1/10 N aqueous hydro-chloric acid solwtion (700 parts) is added thereto, followed : :
:: :
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"''` ~ '" ' '~ ~ . ' ' ' ;
, by stirring with a labomixer. The rcsultant mixture is neutralized with a l/10 N aqueous so~ium hydroxide solution, an~ the aqueous medium is eliminated to obtain resinous particles having a particle size of lO to 20 ~. The resinous particles are washed with water to eliminate the produced sodium chloride and dispersed in water to make a coating composition in a slurry form having a solid content of 50 %.
The coating composition in a slurry form i5 applied 10 to a polished steel plate by air spraying and baked at 160C
for 30 minutes, whereby a smooth and lustrous coating film is formed.
When the said resinous particles are washed with water and dried at 50C for 3 hours in a fluidized bed drier, there is obtained a powder coating composition, which can also af~ord a coating film o~ satisfactory quality.
Example 7 ~ frac/~ ~ark-B An epoxy resin ("Epicoat 10011 manufactured by Shell Chemical Corp.) (488 parts) and diethanolamine (105 20 parts) are reacted in isopropanol (250 parts) under nitrogen stream at 80C for 3 hours to make an aminoepoxy resin solu-tion. To the aminoepo~y resin solution (143 parts), glacial acetic acid ~62 parts) is added, deionized water (500 parts) is added thereto, and the resultant mixture is admixed with a blocked polyisocyanate resin solution in methylethylketone (solid content, 50 ~; 16 parts) and titanium oxide ("Tipake ~ rkR~ /"h /, k ~
R-820'1 manufactured by Ishihara Sangyo Kaisha, Ltd.) (30 parts) to make an a~ueous resin composition.
` The aqueous resin composition (143 parts) is diluted with water (250 parts), and the resulting dilution :
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is dropwise added to 0.05 N aqueous solution of potassium hydroxide while viyorous ~;tirring. After excessive alkali is neutralized with 0.1 N acetic acid, the resultant mixture is subjected to centrifugal separation to collect resinous particles of not more than 50 ~ in diameter. The resinous particles are washed with water and then dispersed in water to make a coating composition in a slurry form having a solid content of 50 ~.
The coating composition in a slurry form is applied to a polished steel plate by air spraying and baked at 180C for 20 minutes, whereby a smooth and lustrous coating film is formed. I~hen the coating film is subjected to the DuPont's impact test, a value of 20 cm or more (500 g) is obtained. It is thus confirmed that sufficient crosslinking has been attained.
Example 8 -An aqueous dispersion comprising an aminoacrylic resin (comprising as the monomeric constituents dimethyl aminoethyl methacrylate, methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate and styrene; glass transition point, 65C; weight average molecular weight, 18,000; content of non-volatile components, 80 ~; dispersing medium, isopropanol : water = 1 : 1 by weight) (100 parts) B is admixed with hexamethoxymethylmelamine ("Cymel 303"~ k manufactured by American Cyanamid) (20 parts), a mixture of ~cf~ k_ ~
powdery aluminum ("L-579'; manufactured by Silverline Mfg. Co.) (5 parts) and isopropanol (5 parts) is added thereto, and the resultant mixture is admixed with 0.1 N hydrochloric acid to make an aqueous resin composition.
To the aqueous resin composition (100 parts), a .
: ~ - . . , .. , :
~,5:~3 mixture of 0.1 N sodium hydroxide solution (500 parts~ and polyethylene o~ide (10 parks) is added, and the resulting mixture is stirred by the aid of a high speed mixer for 15 minutes. After excessive alkali is neutralized with 0.1 N
hydrochloric acid, the resultant mixture is subjected to centrifugal separation to collect resinous particles of not more than 50 ~ in particle size. The resinous particles are washed with water and dispersed in water to make a coating composition in a slurry form having a solid content of 50 %.
The coating composition in a slurry ~orm is applied to a polished steel plate and baked as in Example 7, whereby a smooth and lustrous metallie finish coating film is formed. By the DuPont's impaet test method, it is confirmed that sufficient crosslinking has been attained.
Example 9 The resinous particles as eollected in Example 8 are washed with water and dried by the use of a fluidized bed type dryer to make a eoating eomposition in a powder form. The eoating eomposition is applied onto a polished steel plate eleetrostatieally and then baked at 160C for 20 minutes, whereby a smooth and lustrous eoating film possess-ing a good metallie feeling is formed. By the DuPont's impaet test method, it is eonfirmed that suffieient eross-linking has been attained.
Example 10 Potassium laurate (3.0 parts) and water (150 parts) are eharged into a flask, and a mixture of methyl methaerylate ~30 parts), styrene (30 parts), n-butyl meth-aerylate (20 parts) and 2-h~droxyethyl methacrylate (20 part) and a mixture of ~,4'-abbzis-4-eyanovalerie aeid , ' ~- ` . .
3~
(1.0 part), dimethylethanolamine (1.0 part) and water (50 parts) are dropwise added thereto at 70C for 3 hours. The resultant mixture is kept at the same temperature to make an aqueous liquid composition.
The aqueous liquid composition (100 paxts) is dropwise added to l/20 N hydrochloric acid (500 parts) with vigorous stirxing. After the addition is completed, ex-cessive hydrochloric acid is neutrali~ed with 1/lO N sodium hydroxide solution and subjected to centrifugation, whereby resinous particles of not more than 10 ~ in particle size are collected.
The resinous particles are washed with water and dispersed into water to give a coating composition in a slurry form. The coating composition is sprayed on a polished steel plate and baked at 130C for 20 minutes to make a smooth and lustrous finish coating film.
Separately, the resinous particles as above obtained are washed with water and dried by a fluidized bed dryer to give a coating composition in a powder form. The coating composition is applied onto a polished steel plate by electrostatic coating and baked to make a lustrous, smooCh coating film.
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Claims (12)
1. A process for preparing resinous particles for a coating composition which comprises the steps of (1) treating (A) an aqueous resin dispersion or solution, which comprises (a) a resin having carboxyl groups or primary secondary or tertiary amino groups and no material dispersibility or solubility in water, which resin has been rendered dis-persible or soluble in water by at least partly neutralizing the carboxyl groups or the amino groups with a base or an acid, respectively, and (b) a water-insoluble crosslinking agent which is crosslinkable with functional groups in the resin, with (B) an acidic substance or a basic substance as a powdering agent, said acidic substance being used when the resin is one having carboxyl groups, said basic sub-stance being used when the resin is one having primary, secondary or tertiary amino groups, under conditions which will deposit the resin in particulate form together with the crosslinking agent uniformly dispersed therein, and (2) recovering the deposited resinous particles contain-ing the crosslinking agent from the aqueous medium.
2. The process according to claim 1, wherein the aqueous resin dispersion or solution further comprises a pigment.
3. The process according to claim 1, wherein the resin is a carboxyl group-containing resin, in which the carboxyl groups are at least partly neutralized with an organic or inorganic base and the powdering agent is an acidic substance.
4. The process according to claim 1, wherein the resin is an amino group-containing resin, in which the amino groups are at least partly neutralized with an organic or inorganic acid and the powdering agent is a basic substance.
5. The process according to claim 1, wherein the resin contains, in addition to the carboxyl or amino groups, other functional groups.
6. The process according to claim 5, wheren the other functional groups are epoxy or hydroxyl groups.
7. The process according to claim 1, wherein the crosslinking agent is a compound containing at least two epoxy groups, an aminoplast resin, a melamine resin, benzoguanamine or a polyisocyanate compound containing a blocked isocyanate group.
8. A process for preparing a coating composition in a slurry form which comprises dispersing the resinous particles prepared by the process according to claim 1 in an aqueous medium.
9. A process for preparing a coating composition in a powdery form which comprises drying the resinous particles prepared by the process according to claim 1.
10. A resinous particle prepared by the process according to claim 1.
11. A coating composition in a slurry form prepared by the process according to claim 8.
12. A coating composition in a powdery form prepared by the processs according to claim 9.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27936/1976 | 1976-03-12 | ||
| JP27935/1976 | 1976-03-12 | ||
| JP2793676A JPS6042259B2 (en) | 1976-03-12 | 1976-03-12 | Method for producing thermosetting solid resin composition |
| JP2793576A JPS52110732A (en) | 1976-03-12 | 1976-03-12 | Method of manufacturing coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1105183A true CA1105183A (en) | 1981-07-14 |
Family
ID=26365940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA273,814A Expired CA1105183A (en) | 1976-03-12 | 1977-03-11 | Resinous particles for coating composition and its production |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4365043A (en) |
| CA (1) | CA1105183A (en) |
| DE (1) | DE2710421A1 (en) |
| FR (1) | FR2343773A1 (en) |
| GB (1) | GB1579299A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5859266A (en) * | 1981-10-05 | 1983-04-08 | Nippon Paint Co Ltd | Water paint composition |
| US4752499A (en) * | 1985-05-16 | 1988-06-21 | Ibiden Co. Ltd. | Adhesive for electroless plating and method of preparation of circuit board using this adhesive |
| US4839403A (en) * | 1987-07-28 | 1989-06-13 | Desoto, Inc. | Cross-linked emulsion copolymers in thermosetting aqueous coatings |
| DE3913966B4 (en) * | 1988-04-28 | 2005-06-02 | Ibiden Co., Ltd., Ogaki | Adhesive dispersion for electroless plating, and use for producing a printed circuit |
| US5247029A (en) * | 1988-08-30 | 1993-09-21 | Kansai Paint Co., Ltd. | Cationically electrodepositable paint comprising hydroxyl and cationic group-containing resin and alicyclic epoxy resins |
| US6455132B1 (en) | 1999-02-04 | 2002-09-24 | Kodak Polychrome Graphics Llc | Lithographic printing printable media and process for the production thereof |
| US6603391B1 (en) * | 1999-03-09 | 2003-08-05 | Micron Technology, Inc. | Phase shifters, interrogators, methods of shifting a phase angle of a signal, and methods of operating an interrogator |
| US6360974B1 (en) | 1999-05-19 | 2002-03-26 | Basf Corporation | Powder slurry coating composition |
| DE10053931A1 (en) * | 2000-10-31 | 2002-05-16 | Basf Coatings Ag | Color and / or effect powder slurries, process for their production and mixing system for color and / or effect powder slurries |
| DE10060765A1 (en) * | 2000-12-07 | 2002-06-20 | Basf Coatings Ag | Color and / or effect powder slurry, process for their preparation and their use |
| DE10126651A1 (en) | 2001-06-01 | 2002-12-12 | Basf Coatings Ag | Use of copolymers with diphenylethylene units as emulsifiers for the production of powder slurry and coating powder for use in coating materials, adhesives and sealants, e.g. for painting cars |
| DE10353638A1 (en) | 2003-11-17 | 2005-06-23 | Basf Coatings Ag | Pseudoplastic, aqueous dispersions, process for their preparation and their use |
| CA2593037A1 (en) * | 2004-12-27 | 2006-07-06 | Kaneka Corporation | Process for producing aggregated latex particle |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2940960A (en) * | 1960-06-14 | Process for recovering polymers | ||
| FR1393776A (en) * | 1963-04-16 | 1965-03-26 | Rohm & Haas | Water-insoluble powdered polymers dispersible in aqueous media |
| FR1536944A (en) * | 1966-02-07 | 1968-09-02 | American Cyanamid Co | Polymer-based compositions for coatings of electrically conductive objects |
| US3483174A (en) * | 1966-06-30 | 1969-12-09 | Firestone Tire & Rubber Co | Process for coagulating latices of copolymers and terpolymers of conjugated dienes and carboxylic acids |
| US3494903A (en) * | 1967-08-02 | 1970-02-10 | Gulf Research Development Co | Process for the recovery of ethylene polymers |
| US3799901A (en) * | 1971-03-12 | 1974-03-26 | Dow Chemical Co | Preparation of latexes by direct dispersion of acidic organic polymers into aqueous alkaline media |
| BE788826A (en) * | 1971-10-05 | 1973-01-02 | Crow Chem Corp | PROCESS FOR MANUFACTURING POWDER PAINTS |
| FR2276340A1 (en) * | 1974-06-25 | 1976-01-23 | Du Pont | Acrylic interpolymer colloidal dispersions - in which particle size is reduced with tert amines and opt. ammonium hydroxide |
| JPS545825B2 (en) * | 1974-09-25 | 1979-03-22 | ||
| US3925181A (en) * | 1974-10-31 | 1975-12-09 | Scm Corp | Cathodic electrocoating process |
| US3993849A (en) * | 1974-12-24 | 1976-11-23 | E. I. Du Pont De Nemours And Company | Metal substrate coated with a thermosetting powder coating composition of an acrylic polymer, a hydroxy functional plasticizer and a blocked polyisocyanate cross-linking agent |
| US4049744A (en) * | 1975-09-29 | 1977-09-20 | Celanese Polymer Specialties Company | Process for making powder coatings |
-
1977
- 1977-03-10 GB GB10151/77A patent/GB1579299A/en not_active Expired
- 1977-03-10 DE DE19772710421 patent/DE2710421A1/en active Granted
- 1977-03-11 FR FR7707387A patent/FR2343773A1/en active Granted
- 1977-03-11 CA CA273,814A patent/CA1105183A/en not_active Expired
- 1977-03-14 US US05/777,548 patent/US4365043A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2343773B1 (en) | 1983-11-10 |
| GB1579299A (en) | 1980-11-19 |
| DE2710421C2 (en) | 1990-05-31 |
| DE2710421A1 (en) | 1977-09-22 |
| US4365043A (en) | 1982-12-21 |
| FR2343773A1 (en) | 1977-10-07 |
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