CA1295770C - Chalk adhesion polymer composition and method of preparation - Google Patents
Chalk adhesion polymer composition and method of preparationInfo
- Publication number
- CA1295770C CA1295770C CA000529151A CA529151A CA1295770C CA 1295770 C CA1295770 C CA 1295770C CA 000529151 A CA000529151 A CA 000529151A CA 529151 A CA529151 A CA 529151A CA 1295770 C CA1295770 C CA 1295770C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- weight
- methacrylate
- chalk
- acrylic
- 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 - Fee Related
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Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
Abstract
ABSTRACT OF THE DISCLOSURE
A chalk-adhesion polymer latex for exterior coatings especially suitable for blending with an acrylic formulation, such as vinyl acetate/acrylic copolymers. The polymer is derived from a monomer precursor composition, including an acrylic moiety, such as an acrylate and a methacrylate, together with small amounts of a nitrogen containing alkyl acrylate, an acrylamide and propylene glycol. The method of preparing the chalk adhesion polymer includes emulsification stages to accomplish the polymerization.
A chalk-adhesion polymer latex for exterior coatings especially suitable for blending with an acrylic formulation, such as vinyl acetate/acrylic copolymers. The polymer is derived from a monomer precursor composition, including an acrylic moiety, such as an acrylate and a methacrylate, together with small amounts of a nitrogen containing alkyl acrylate, an acrylamide and propylene glycol. The method of preparing the chalk adhesion polymer includes emulsification stages to accomplish the polymerization.
Description
~2~ 71D
BACRGROUND OF TEIE INVENTION
1. FIELD OF T~E INVENTION
The present invention relates to a chalk adhesion polymer latex, comprisiny acrylates and methacrylates, and its method of preparation from a monomer composition~ The polymer latex can be blended with vinyl acetate/acrylic copolymer coatings to form a finished latex coating composition with improv~d chalk adhesion properties.
BACRGROUND OF TEIE INVENTION
1. FIELD OF T~E INVENTION
The present invention relates to a chalk adhesion polymer latex, comprisiny acrylates and methacrylates, and its method of preparation from a monomer composition~ The polymer latex can be blended with vinyl acetate/acrylic copolymer coatings to form a finished latex coating composition with improv~d chalk adhesion properties.
2. DESCR:I:PTION OF TlqE PRIOR ART
Chalkinq has been defined as the formation of a friable powder on the surface of a paint film, caused by the disintegration of the binding medium due to disruptive factors during weathering~ Chalking resistance is the ability of a coating to resist the formation of a friable powder on the surface of its film caused by the disintegration of the bindin~ medium due to degradative weather factors.
one of the principal problems encountered in the ormulation of paints, especially exterior house paints, is the improvement of chalk adhesion properties.
An exterior paint coating with good chalk adhesion properties has the ability to penetrate a chalky coating, such as weathered paint, and to adhere to the surface beneath the chalky coatingO
One of the primary uses for alkyd resins as components of water-based coatings is the modification of exterior latex house paints. Oleoresinous modifiers have been favored for this purpose because many paint manufacturers and users seek the added adhesion properties that alkyds impart to exterior formulations.
Acrylic emulsions normally afford good adhesion to chalky surfaces under moderate exposure conditions, but under severe conditions failures can occur. Alkyds have '70 therefore been employed in exterior latex paints to provide an extra safety factor of added adhesion.
However, alkyds also have shortcomings. While fully cured alkyds can provide an acrylic paint with extra adhesion on certain problem substrates, they adversely affect the fast-dry characteristics of the acrylic. An alkyd generally requires several days, the number varying with ambient conditions, to dry to a full cure and to develop optimum adhesion and blister resistance. As a result, an allcyd-modified paint has a greater chance of failure should inclement weather occur during the first few days following application. Even without rainr prolonged tackiness can provide sites for early dirt pickup.
Alkyd modification can also make acrylic latex paints more susceptible to the damaging effects of exposure. Tests have shown that the durability of modified paints decrease as the level of alkyd modification increases. Both tint retention and chalk resistance diminish because the alkyd breaks down rather rapidly on exposure. Also, problems in paint manufacture and storage can arise because the alkyd can absorb the sur~actants and dispersants used for stability in the formulation. These and other problems related to alkyd modification are well known. See Mattei et al, "Chalk Adhesion Polymer for Exterior House Paints", R~SI~ R~VIEW,-vol. 24, no. 4, pages 14-22 (April 1975).
U.S. Patent 4,504,609 to Kuwajima et al discloses an aqueous coating composition comprisin~ a resinous vehicle composed of at least one aqueous resin and at least one water insoluble component. The aqueous resin can be polyester, alkyd, acrylic, acryl-modified polyester, and acyl-modified alkyd. The water insoluble resinous component is obtained by polymerization or copolymerization of alpha, beta-ethylenically unsaturated monomers.
~.S. Patent 4,529,765 to DenHartog et al ;7~
discloses a coating composition containing about 20-80 percent by weight of a binder and 80-20 percent by weight of a solvent for the binder. The binder comprises an acrylic amino ester polymer of polymerized monomers of methyl methacrylate and monomers of alkyl methacrylake or alkyl acrylate, and an acrylate polymer having pendent polymerizable ethylenically unsaturated groups.
U.S. Patent 4,199,400 to Bakule et al discloses migration-resistant binder compositions mixed with an anionically stabilized polymer latex and a volatile base.
U.S. Patent 3,454,516 to Victorius discloses coating compositions comprising soft phase polymers which have infused or dissolved in them hard phase polymers.
SUMMARY OF THE INV~TION
The present invention relates to an acrylic emulsion chalk adhesion polymer which, alone or when blended with vinyl acetate/acrylic copolymer coatings, significantly improves chalk adhesion properties.
DESCRIPTIO~I OF T~E PREFEl~RED EMRODIMENTS
In accordance with the present invention, a chalk-adhesion polymer for exterior coatings, such as house paints or the like, is derived from a monomer composition precursor comprising an acrylic moiety, together with small amounts of a secondary amine-containing alkyl acrylate, and an acrylamide. A glycol can also be included in the composition to improve blister resistant properties.
The present chalk adhesion polymer has been found to exhibit good chalk adhesion and to improve the chalk adhesion properties of vinyl acetate/acrylic copolymer coatings when blended in proportions of about o ~
10 to 30 weight ~ chalk adhesion polymer.
The chalk adhesion polymer comprises a monomer precursor composition which contains an acrylic moiety usually including at least one alkyl acrylate and one alkyl methacrylate, together with small but effective amounts of a secondary amine-containing alkyl acrylate and an acrylamide.
Generally, the monomer precursor composition includes a minor pro~ortion of a glycol such as propylene glycol, butylene glycol, dipropylene glycol, diethylene glycol, 1,4-butanediol, lr2-propanediol and ethylene glycol. The glycols are used primarily as surface active agents and depress the surface tension of aqueous solutions. Additionally, the glycols assist the latex to achieve improved blister resistant properties.
Preferably, the acrylic moiety includesr in combinationr butyl acrylater methyl methacrylate and 2-ethyl-hexyl acrylate.
The secondary amine-containing alkyl acrylates can be selected from dimethylaminoethyl methacrylater diethylamino- ethyl methacrylater t-butylaminoethyl methacrylate, and an allylic monomer containing amino and ureido functionality (WAM~ monomerr Alcolac CO.r Baltimorer MD). The polymerizable amide can be selected ~5 from N-methylol acrylamider acrylamide, methyl acrylamidoglycolate methyl ether (MAGME) and NrN-dimethyl acrylamide. Preferablyr the secondary amine-containing alkyl acrylate is dimethylaminoethyl methacrylater and the preferred polymerizable amide is N-methylol acrylamide.
Usually the acrylic moiety comprises more than 90% by weight of the monomer composition~
The monomer precursor composition, when polymerized to form the chalk adhesion polymer latex can be used alone or blended with a vinyl-acrylic or all acrylic formulation to provide a latex coating composition. Preferably, about 10-30% of the latex coating composition comprises the chalk adhesion polymer ~.i2~ 7~
latex. For a vinyl acetate/acrylic latex, the greater the amount of chalk adhesion polymer used, the more improved chalk adhesion and blister resistance properties are found.
The dimethylaminoethyl methacrylate (DMAEMA) is used together with a small amount of N-methylol acrylamide (NMA). It is believed that the presence of the DMAEMA and NMA act synergistically and are responsible for the chalk adhesion properties of the chalk adhesion polymer.
In the monomer composition, the amount of butyl acrylate can vary rom about 0-80%, preferably 40-60%, methyl methacrylate can vary from about 5-40%, pre~erably 10-30%, and the 2-ethylhexyl acrylate can vary from about 0-40~, preferably 5-20%. It has also been found that the total amount of butyl acrylate plus 2-ethylhexyl acrylate should vary from about 40-80~.
The minor but highly significant components dimethylaminoethyl methacrylate can vary from about 0.5-5%, N-methylol acrylamide can vary from about 0.5-5%, and propylene glycol can vary from about 0.5-5%. All parts and percentages are by weight of the monomer composition. The method for preparing the chalk adhesion polymer latex involves a sequence of steps which includes providing a monomer composition as a precursor to the chalk adhesion polymer latex. The components include the compounds mentioned above, namely, butyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, and dimethylamino-ethyl methacrylate, which are pre-emulsified or preformed~ to form a monomer pre-emulsion. A minor portion of about 3-10% of the methyl methacrylate is initially polymerized, to function as a seed component during the initial stage of polymerization.
The N-methylol acrylamide is pre-emulsified in the presence of polyethylene glycol octylphenyl ether and may be power fed or force fed to the monomer pre-emulsion continuously over a period of time to obtain ~ 7~
the final pre-emulsified monomer mixture which forms the product chalk adhesion polymer latex with improved chalk adhesion properties.
Typically, the total amount of the monomer pre-emulsion is added continuously to the reactor over a period of about 3 to 6 hours, preferably 4 hours. The pre-emulsified N-methylol acrylamide may be power ed to the reactor over a period of 3-4 hours, preferably 3.5 hours. The product polymer latex can be used alone or blended with a vinyl/acrylic and/or acrylic formulation, such as vinyl acetate/acrylic copolymers, to form a latex coating composition. As mentioned earlier, the chalk adhesion polymer latex comprises about 10-30% of the latex coating composition.
The following examples serve to illustrate the present invention, and all parts and percentages are by weight, unless otherwise indicated.
~3,5~
A monomer composition consisting of 50 parts of butyl acrylate, 35 parts of methyl methacrylate, 13 parts of 2-ethylhexyl acrylate, 1 part of dimethylamin~ethyl methacrylate, 1 part of N-methylol ~crylamide and 0.05 parts of tert-dodecyl mercaptan were dispersed in 22 parts of water containing 1 part of polyethylene glycol octylpheny:L ether t30 moles EO), 1.7 parts of sodium dodecyldiphenyl~oxide disulPonate and 2.5 parts of sodium lauryl sulfate to form a pre-emulsion. The polymerization was initiated by adding 5%
of the pre-emulsion and 0.2 parts of sodium persulfate to the reaction vessel containing 44 parts of water, 0.9 parts of sodium dodecyldiphenyloxide disulfonate, 0.4 parts of ethylenediaminetetraacetic acid and 1.5 parts of propylene glycol at 75C. The ~emperature was allowed to reach 78-80C and held for 10 minutes.
Subsequently, the remainder of the pre-emulsion was continuously fed to the reactor over 4 hours while the reactor temperature was kept at 78-80C. After completion of the addition, the reaction mixture was kept at 78-80C for another 30 minutes and then two streams of aqueous solutions of 0.1 part tert-butyl hydrQperoxide in 1.5 parts of water and O.l parts of sodium formaldehyde sulfoxylate in 1.5 parts of water were simultaneously added to the reaction vessel over 30 minutes. This produced a latex having a total solid of 55.5%, a Brookfield viscosity (spindle 3, 50 rpm) of 60 cps and a p~ of 7.3.
EX~MPLE 2 The latex obtained from Example 1 was blended with Wallpol 40-145 (Reichhold Chemicals, Inc.~, a vinyl acrylic latex in 30/70 wei~ht ratio. The latex blend and unblended Wallpol 40-145 as a control were formulated into an unmodified exterior house paint * Trade-mark - lZ~5~
composition and their paint properties were evaluated and recorded in Table 1 which follows:
Table I - U~MO~IFIFD EXTERIQ~_~QUSE PAINT
Component40-145/Example 1 Latex 100%
(70~30 ratio~ ~Q=l~
Pigment Slurry 685.0 grams 685.0 grams 40-145 (55% solids) 243.0 grams 347.0 grams Example 1 (52~ solids) 110.0 grams 2% Thickener (250 MR
solution, Hercules Co.) 54.0 grams 57.0 grams Water 54.0 grams 57.0 grams Total Resin Solids 54.1 grams 55.0 grams Paint Properties pH after 13 hours 8.4 3.5 Visc, KU (Krep units~
after 18 hours 83 86 Contrast Ratio .003" Wet .975 .975 Reflectance .003" Wet .879 .879 20 Wet Adhesion tl8 hour~-~L~l Approximate ~ Film Removed After 2-3 min. 3-5 15-20 After 5-6 min. 3-5 15-20 Blister Resistance (4.5 hrD dry) After 3 hours Excellent Excellent 25 Chalk Adhesion (Li~ht-Medium) ~proximate % Film Removed After 1 day dry 10-15 ~ 100 After 5 days dry 1-2 7Q-75 After 1 week 1-2 50-55 It is evident from the information tabulated in Table 1 that the 40~145/Example l ~lend showed marked improvement over the control, i.e., the 100~ 40-145 i77~
latex formulation in both chalk adhesion and wet adhesion performance.
~X~MPLE 3 Utilizing the process of Example 1, a monomer composition of:
Component ~L~ Y_~cigh~
butyl acrylate 69 methyl methacrylate 30 WAM~ monomer (Alcolac Co., 1.1 Baltimore, MD) was used to prepare a latex having a total solid content of 51%, Brookfield viscosity (spindle 3, 50 rpm) of 700 cps and a pH of 6.7.
EXAMP~E 4 Utilizing the process of Example 1, a monomer composition of:
Component Parts by W~iqht butyl acrylate 54 methyl methacrylate 30 2-Ethylhexyl acrylate 15 WAM~ monomer (Alcolac Co.) 1.1 was used to prepare a latex having a total solid of 51%, a Brookfield viscosity (spindle 31 50 rpm) of 500 cps and a pH of 6.5.
7~
~:E~
The latices obtained from Example 3 and 4 were blended with Wallpol 40-145 (Reichhold Chemicals, Inc.), a vinyl acrylic latex in 30/70 weight ratio and were then formulated into an unmodified exterior house paint composition. The recipes for the formulation and paint properties were evaluated and tabulated in Table II as follow~:
:~L2~;7~
Table II
Example 3 Example 4 Component Control Blend Blend 40-145 (55% solids) 347 g 243 g 243 g Example 3 (51.4% solids) - 11175 g Example 4 (50.9~ solids) - - 112.6 g Total Resin Solids 57.0~ 53.9% 53.7%
Pigment Slurry 685 g 685 g 68S g Total Emulsion 313 g 354.5 y 355.6 g 2% Thickener (250 MR solution, Hercules Co.) 111 g 69.5 g68.4 g Water 37 g 37 g 37 g Blister Resistance (4 hr, dry~ -After 3 hrs.Good to Moderate Excellent Excellent Wet Adhesion (24 hr., dry) After 2-3 min.Good to Moderate Excellent Excellent Chalk Adhesion Slight chalk Overnight 100% 2-3% 2-3%
After 1 week 70-75~ 1-2% 1-2%
Medium Chalk 25 Overnight 100% 90-95% 95-100 After 1 week 100% 25-30~ 20-25 7~
~ 12 -A monomer composition consisting of 50 parts of butyl acrylate, 30 parts of methyl methacrylate, 13 parts of 2-ethylhexyl acrylate, 1 part of dimethylethylaminoethyl me~hacrylate and OD5 parts of t-dodecyl mercaptan were dispersed in 24 parts of water containing 2 parts o~ polyethylene glycol octylphenyl ether (30 moles EO), 1.7 parts of sodium dodecyldiphenyloxide disulfonate and 3.5 parts of sodium polyethy}ene glycol octylphenyl ether sulfonate to form a pre-emulsion~ The polymeriæation was initiated by adding 5 parts of methyl methacrylate and 0.35 parts of sodium persulfate to the reaction vessel containing 44 parts of water, 0.9 parts of sodium dodecyldiphenyloxide disulfonate, 0.4 parts of ethylenediamine-tetraacetic acid and 1.5 parts of propylene glycol at 75C. The temperature was allowed to reach 78-80C and held for 10 minutes. Subsequently, the pre-emulsion was continuously fed to the reactor over 3 hours while an aqueous solution consisting of 1 part of N-methylol acrylamide and 0.5 parts of polyethylene glycol octylphenyl ether in 2.5 parts of water was power fed to the pre-emulsion over 2 hours and 30 minutes. The reaction was kept at 78-80C. After completion of the addition, the reaction mixture was kept at 78-80C for another 30 minutes and then chemically treated as described in Example 1. The resulting latex had a total solids of 54.1~, a Bxookfield viscosity (spindle 3, S0 rpm) of 500 cps and a p~ of 8.1 The latex obtained from Example 6 was blended with Wallpol 40-145 (Reichhold Chemicals, Inc.), a vinyl acrylic latex in 30/70 weight ratio The latex blend and unblended Wallpol 40~145 as a control were formulated into an unmodified house paint composition - 13 ~ 77~
and their paint properties were evaluated as recorded in Table III which follows:
TABLE III
Unmodified House Pa.int Evaluation Example 6 ~Qn~Ql Example 6 Blend Pigment slurry 690.5 g 690.5 g 690.5 g Example 6 (54.1%)347.0 g -- 106.0 g 40-145 (55.0~) -- 347.0 ~ 243.0 g 2% 250 MR soln 70 g 70 g 70 g Water 44 g 42 g 42 g Total Resin Solids (%) 54~7 g 54.7 g 54.7 g pH Value after 18 hrs at room temp 8.8 8.5 8.4 Viscosity/KU after 18 ; 15 hrs at room temp 77 77 77 . Contrast ratio .962 .962 .96g Reflectance .891 .894 .892 ,: .
Blister Resistance (4 1/2 hrs dry) ~ : 20 after 1 hr excellent excellentexcellent :: : . after 3 hrs excellent excellentexcellent ; ~ ~ . : :
Wet Adhesion (18 hr dry3 Approx. % Film Removal after 2 min recovery less than 1 15-20 3-5 :25 after 5 min " :less than 1 15-20 less than 1 . after 10 min " less than 1 15-20 less than 1 :
Chalk Adhesion (medium chalk) Approx, ~ Fi~m Removal : after 1 day dry 0 100 10-15 after 7 day dry 0 70-75 ~5-10
Chalkinq has been defined as the formation of a friable powder on the surface of a paint film, caused by the disintegration of the binding medium due to disruptive factors during weathering~ Chalking resistance is the ability of a coating to resist the formation of a friable powder on the surface of its film caused by the disintegration of the bindin~ medium due to degradative weather factors.
one of the principal problems encountered in the ormulation of paints, especially exterior house paints, is the improvement of chalk adhesion properties.
An exterior paint coating with good chalk adhesion properties has the ability to penetrate a chalky coating, such as weathered paint, and to adhere to the surface beneath the chalky coatingO
One of the primary uses for alkyd resins as components of water-based coatings is the modification of exterior latex house paints. Oleoresinous modifiers have been favored for this purpose because many paint manufacturers and users seek the added adhesion properties that alkyds impart to exterior formulations.
Acrylic emulsions normally afford good adhesion to chalky surfaces under moderate exposure conditions, but under severe conditions failures can occur. Alkyds have '70 therefore been employed in exterior latex paints to provide an extra safety factor of added adhesion.
However, alkyds also have shortcomings. While fully cured alkyds can provide an acrylic paint with extra adhesion on certain problem substrates, they adversely affect the fast-dry characteristics of the acrylic. An alkyd generally requires several days, the number varying with ambient conditions, to dry to a full cure and to develop optimum adhesion and blister resistance. As a result, an allcyd-modified paint has a greater chance of failure should inclement weather occur during the first few days following application. Even without rainr prolonged tackiness can provide sites for early dirt pickup.
Alkyd modification can also make acrylic latex paints more susceptible to the damaging effects of exposure. Tests have shown that the durability of modified paints decrease as the level of alkyd modification increases. Both tint retention and chalk resistance diminish because the alkyd breaks down rather rapidly on exposure. Also, problems in paint manufacture and storage can arise because the alkyd can absorb the sur~actants and dispersants used for stability in the formulation. These and other problems related to alkyd modification are well known. See Mattei et al, "Chalk Adhesion Polymer for Exterior House Paints", R~SI~ R~VIEW,-vol. 24, no. 4, pages 14-22 (April 1975).
U.S. Patent 4,504,609 to Kuwajima et al discloses an aqueous coating composition comprisin~ a resinous vehicle composed of at least one aqueous resin and at least one water insoluble component. The aqueous resin can be polyester, alkyd, acrylic, acryl-modified polyester, and acyl-modified alkyd. The water insoluble resinous component is obtained by polymerization or copolymerization of alpha, beta-ethylenically unsaturated monomers.
~.S. Patent 4,529,765 to DenHartog et al ;7~
discloses a coating composition containing about 20-80 percent by weight of a binder and 80-20 percent by weight of a solvent for the binder. The binder comprises an acrylic amino ester polymer of polymerized monomers of methyl methacrylate and monomers of alkyl methacrylake or alkyl acrylate, and an acrylate polymer having pendent polymerizable ethylenically unsaturated groups.
U.S. Patent 4,199,400 to Bakule et al discloses migration-resistant binder compositions mixed with an anionically stabilized polymer latex and a volatile base.
U.S. Patent 3,454,516 to Victorius discloses coating compositions comprising soft phase polymers which have infused or dissolved in them hard phase polymers.
SUMMARY OF THE INV~TION
The present invention relates to an acrylic emulsion chalk adhesion polymer which, alone or when blended with vinyl acetate/acrylic copolymer coatings, significantly improves chalk adhesion properties.
DESCRIPTIO~I OF T~E PREFEl~RED EMRODIMENTS
In accordance with the present invention, a chalk-adhesion polymer for exterior coatings, such as house paints or the like, is derived from a monomer composition precursor comprising an acrylic moiety, together with small amounts of a secondary amine-containing alkyl acrylate, and an acrylamide. A glycol can also be included in the composition to improve blister resistant properties.
The present chalk adhesion polymer has been found to exhibit good chalk adhesion and to improve the chalk adhesion properties of vinyl acetate/acrylic copolymer coatings when blended in proportions of about o ~
10 to 30 weight ~ chalk adhesion polymer.
The chalk adhesion polymer comprises a monomer precursor composition which contains an acrylic moiety usually including at least one alkyl acrylate and one alkyl methacrylate, together with small but effective amounts of a secondary amine-containing alkyl acrylate and an acrylamide.
Generally, the monomer precursor composition includes a minor pro~ortion of a glycol such as propylene glycol, butylene glycol, dipropylene glycol, diethylene glycol, 1,4-butanediol, lr2-propanediol and ethylene glycol. The glycols are used primarily as surface active agents and depress the surface tension of aqueous solutions. Additionally, the glycols assist the latex to achieve improved blister resistant properties.
Preferably, the acrylic moiety includesr in combinationr butyl acrylater methyl methacrylate and 2-ethyl-hexyl acrylate.
The secondary amine-containing alkyl acrylates can be selected from dimethylaminoethyl methacrylater diethylamino- ethyl methacrylater t-butylaminoethyl methacrylate, and an allylic monomer containing amino and ureido functionality (WAM~ monomerr Alcolac CO.r Baltimorer MD). The polymerizable amide can be selected ~5 from N-methylol acrylamider acrylamide, methyl acrylamidoglycolate methyl ether (MAGME) and NrN-dimethyl acrylamide. Preferablyr the secondary amine-containing alkyl acrylate is dimethylaminoethyl methacrylater and the preferred polymerizable amide is N-methylol acrylamide.
Usually the acrylic moiety comprises more than 90% by weight of the monomer composition~
The monomer precursor composition, when polymerized to form the chalk adhesion polymer latex can be used alone or blended with a vinyl-acrylic or all acrylic formulation to provide a latex coating composition. Preferably, about 10-30% of the latex coating composition comprises the chalk adhesion polymer ~.i2~ 7~
latex. For a vinyl acetate/acrylic latex, the greater the amount of chalk adhesion polymer used, the more improved chalk adhesion and blister resistance properties are found.
The dimethylaminoethyl methacrylate (DMAEMA) is used together with a small amount of N-methylol acrylamide (NMA). It is believed that the presence of the DMAEMA and NMA act synergistically and are responsible for the chalk adhesion properties of the chalk adhesion polymer.
In the monomer composition, the amount of butyl acrylate can vary rom about 0-80%, preferably 40-60%, methyl methacrylate can vary from about 5-40%, pre~erably 10-30%, and the 2-ethylhexyl acrylate can vary from about 0-40~, preferably 5-20%. It has also been found that the total amount of butyl acrylate plus 2-ethylhexyl acrylate should vary from about 40-80~.
The minor but highly significant components dimethylaminoethyl methacrylate can vary from about 0.5-5%, N-methylol acrylamide can vary from about 0.5-5%, and propylene glycol can vary from about 0.5-5%. All parts and percentages are by weight of the monomer composition. The method for preparing the chalk adhesion polymer latex involves a sequence of steps which includes providing a monomer composition as a precursor to the chalk adhesion polymer latex. The components include the compounds mentioned above, namely, butyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, and dimethylamino-ethyl methacrylate, which are pre-emulsified or preformed~ to form a monomer pre-emulsion. A minor portion of about 3-10% of the methyl methacrylate is initially polymerized, to function as a seed component during the initial stage of polymerization.
The N-methylol acrylamide is pre-emulsified in the presence of polyethylene glycol octylphenyl ether and may be power fed or force fed to the monomer pre-emulsion continuously over a period of time to obtain ~ 7~
the final pre-emulsified monomer mixture which forms the product chalk adhesion polymer latex with improved chalk adhesion properties.
Typically, the total amount of the monomer pre-emulsion is added continuously to the reactor over a period of about 3 to 6 hours, preferably 4 hours. The pre-emulsified N-methylol acrylamide may be power ed to the reactor over a period of 3-4 hours, preferably 3.5 hours. The product polymer latex can be used alone or blended with a vinyl/acrylic and/or acrylic formulation, such as vinyl acetate/acrylic copolymers, to form a latex coating composition. As mentioned earlier, the chalk adhesion polymer latex comprises about 10-30% of the latex coating composition.
The following examples serve to illustrate the present invention, and all parts and percentages are by weight, unless otherwise indicated.
~3,5~
A monomer composition consisting of 50 parts of butyl acrylate, 35 parts of methyl methacrylate, 13 parts of 2-ethylhexyl acrylate, 1 part of dimethylamin~ethyl methacrylate, 1 part of N-methylol ~crylamide and 0.05 parts of tert-dodecyl mercaptan were dispersed in 22 parts of water containing 1 part of polyethylene glycol octylpheny:L ether t30 moles EO), 1.7 parts of sodium dodecyldiphenyl~oxide disulPonate and 2.5 parts of sodium lauryl sulfate to form a pre-emulsion. The polymerization was initiated by adding 5%
of the pre-emulsion and 0.2 parts of sodium persulfate to the reaction vessel containing 44 parts of water, 0.9 parts of sodium dodecyldiphenyloxide disulfonate, 0.4 parts of ethylenediaminetetraacetic acid and 1.5 parts of propylene glycol at 75C. The ~emperature was allowed to reach 78-80C and held for 10 minutes.
Subsequently, the remainder of the pre-emulsion was continuously fed to the reactor over 4 hours while the reactor temperature was kept at 78-80C. After completion of the addition, the reaction mixture was kept at 78-80C for another 30 minutes and then two streams of aqueous solutions of 0.1 part tert-butyl hydrQperoxide in 1.5 parts of water and O.l parts of sodium formaldehyde sulfoxylate in 1.5 parts of water were simultaneously added to the reaction vessel over 30 minutes. This produced a latex having a total solid of 55.5%, a Brookfield viscosity (spindle 3, 50 rpm) of 60 cps and a p~ of 7.3.
EX~MPLE 2 The latex obtained from Example 1 was blended with Wallpol 40-145 (Reichhold Chemicals, Inc.~, a vinyl acrylic latex in 30/70 wei~ht ratio. The latex blend and unblended Wallpol 40-145 as a control were formulated into an unmodified exterior house paint * Trade-mark - lZ~5~
composition and their paint properties were evaluated and recorded in Table 1 which follows:
Table I - U~MO~IFIFD EXTERIQ~_~QUSE PAINT
Component40-145/Example 1 Latex 100%
(70~30 ratio~ ~Q=l~
Pigment Slurry 685.0 grams 685.0 grams 40-145 (55% solids) 243.0 grams 347.0 grams Example 1 (52~ solids) 110.0 grams 2% Thickener (250 MR
solution, Hercules Co.) 54.0 grams 57.0 grams Water 54.0 grams 57.0 grams Total Resin Solids 54.1 grams 55.0 grams Paint Properties pH after 13 hours 8.4 3.5 Visc, KU (Krep units~
after 18 hours 83 86 Contrast Ratio .003" Wet .975 .975 Reflectance .003" Wet .879 .879 20 Wet Adhesion tl8 hour~-~L~l Approximate ~ Film Removed After 2-3 min. 3-5 15-20 After 5-6 min. 3-5 15-20 Blister Resistance (4.5 hrD dry) After 3 hours Excellent Excellent 25 Chalk Adhesion (Li~ht-Medium) ~proximate % Film Removed After 1 day dry 10-15 ~ 100 After 5 days dry 1-2 7Q-75 After 1 week 1-2 50-55 It is evident from the information tabulated in Table 1 that the 40~145/Example l ~lend showed marked improvement over the control, i.e., the 100~ 40-145 i77~
latex formulation in both chalk adhesion and wet adhesion performance.
~X~MPLE 3 Utilizing the process of Example 1, a monomer composition of:
Component ~L~ Y_~cigh~
butyl acrylate 69 methyl methacrylate 30 WAM~ monomer (Alcolac Co., 1.1 Baltimore, MD) was used to prepare a latex having a total solid content of 51%, Brookfield viscosity (spindle 3, 50 rpm) of 700 cps and a pH of 6.7.
EXAMP~E 4 Utilizing the process of Example 1, a monomer composition of:
Component Parts by W~iqht butyl acrylate 54 methyl methacrylate 30 2-Ethylhexyl acrylate 15 WAM~ monomer (Alcolac Co.) 1.1 was used to prepare a latex having a total solid of 51%, a Brookfield viscosity (spindle 31 50 rpm) of 500 cps and a pH of 6.5.
7~
~:E~
The latices obtained from Example 3 and 4 were blended with Wallpol 40-145 (Reichhold Chemicals, Inc.), a vinyl acrylic latex in 30/70 weight ratio and were then formulated into an unmodified exterior house paint composition. The recipes for the formulation and paint properties were evaluated and tabulated in Table II as follow~:
:~L2~;7~
Table II
Example 3 Example 4 Component Control Blend Blend 40-145 (55% solids) 347 g 243 g 243 g Example 3 (51.4% solids) - 11175 g Example 4 (50.9~ solids) - - 112.6 g Total Resin Solids 57.0~ 53.9% 53.7%
Pigment Slurry 685 g 685 g 68S g Total Emulsion 313 g 354.5 y 355.6 g 2% Thickener (250 MR solution, Hercules Co.) 111 g 69.5 g68.4 g Water 37 g 37 g 37 g Blister Resistance (4 hr, dry~ -After 3 hrs.Good to Moderate Excellent Excellent Wet Adhesion (24 hr., dry) After 2-3 min.Good to Moderate Excellent Excellent Chalk Adhesion Slight chalk Overnight 100% 2-3% 2-3%
After 1 week 70-75~ 1-2% 1-2%
Medium Chalk 25 Overnight 100% 90-95% 95-100 After 1 week 100% 25-30~ 20-25 7~
~ 12 -A monomer composition consisting of 50 parts of butyl acrylate, 30 parts of methyl methacrylate, 13 parts of 2-ethylhexyl acrylate, 1 part of dimethylethylaminoethyl me~hacrylate and OD5 parts of t-dodecyl mercaptan were dispersed in 24 parts of water containing 2 parts o~ polyethylene glycol octylphenyl ether (30 moles EO), 1.7 parts of sodium dodecyldiphenyloxide disulfonate and 3.5 parts of sodium polyethy}ene glycol octylphenyl ether sulfonate to form a pre-emulsion~ The polymeriæation was initiated by adding 5 parts of methyl methacrylate and 0.35 parts of sodium persulfate to the reaction vessel containing 44 parts of water, 0.9 parts of sodium dodecyldiphenyloxide disulfonate, 0.4 parts of ethylenediamine-tetraacetic acid and 1.5 parts of propylene glycol at 75C. The temperature was allowed to reach 78-80C and held for 10 minutes. Subsequently, the pre-emulsion was continuously fed to the reactor over 3 hours while an aqueous solution consisting of 1 part of N-methylol acrylamide and 0.5 parts of polyethylene glycol octylphenyl ether in 2.5 parts of water was power fed to the pre-emulsion over 2 hours and 30 minutes. The reaction was kept at 78-80C. After completion of the addition, the reaction mixture was kept at 78-80C for another 30 minutes and then chemically treated as described in Example 1. The resulting latex had a total solids of 54.1~, a Bxookfield viscosity (spindle 3, S0 rpm) of 500 cps and a p~ of 8.1 The latex obtained from Example 6 was blended with Wallpol 40-145 (Reichhold Chemicals, Inc.), a vinyl acrylic latex in 30/70 weight ratio The latex blend and unblended Wallpol 40~145 as a control were formulated into an unmodified house paint composition - 13 ~ 77~
and their paint properties were evaluated as recorded in Table III which follows:
TABLE III
Unmodified House Pa.int Evaluation Example 6 ~Qn~Ql Example 6 Blend Pigment slurry 690.5 g 690.5 g 690.5 g Example 6 (54.1%)347.0 g -- 106.0 g 40-145 (55.0~) -- 347.0 ~ 243.0 g 2% 250 MR soln 70 g 70 g 70 g Water 44 g 42 g 42 g Total Resin Solids (%) 54~7 g 54.7 g 54.7 g pH Value after 18 hrs at room temp 8.8 8.5 8.4 Viscosity/KU after 18 ; 15 hrs at room temp 77 77 77 . Contrast ratio .962 .962 .96g Reflectance .891 .894 .892 ,: .
Blister Resistance (4 1/2 hrs dry) ~ : 20 after 1 hr excellent excellentexcellent :: : . after 3 hrs excellent excellentexcellent ; ~ ~ . : :
Wet Adhesion (18 hr dry3 Approx. % Film Removal after 2 min recovery less than 1 15-20 3-5 :25 after 5 min " :less than 1 15-20 less than 1 . after 10 min " less than 1 15-20 less than 1 :
Chalk Adhesion (medium chalk) Approx, ~ Fi~m Removal : after 1 day dry 0 100 10-15 after 7 day dry 0 70-75 ~5-10
Claims (15)
1. An aqueous chalk adhesion latex coating composition consisting essentially of:
(a) about 10 to 30% of an aqueous polymer dispersion comprising:
(i) major amounts of an acrylic moiety selected from the group consisting of an alkyl acrylate, an alkyl methacrylate, and mixtures thereof, and (ii) minor, but effective amounts of a secondary amine containing alkyl acrylate and an acrylamide; and (b) the remainder comprising a vinyl-acrylic or all acrylic formulation, wherein said composition exhibits chalk adhesion properties of about 1 to 30% film removed after one week, and excellent blister resistance.
(a) about 10 to 30% of an aqueous polymer dispersion comprising:
(i) major amounts of an acrylic moiety selected from the group consisting of an alkyl acrylate, an alkyl methacrylate, and mixtures thereof, and (ii) minor, but effective amounts of a secondary amine containing alkyl acrylate and an acrylamide; and (b) the remainder comprising a vinyl-acrylic or all acrylic formulation, wherein said composition exhibits chalk adhesion properties of about 1 to 30% film removed after one week, and excellent blister resistance.
2. The composition of claim 1, wherein the acrylic moiety comprises, in combination, butyl acrylate, methyl methacrylate, and 2-ethylhexyl acrylate.
3. The composition of claim 1, wherein the secondary amine-containing alkyl acrylate is selected from the group consisting of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, an allylic monomer containing amino and ureido functionality and mixtures thereof.
4. The composition of claim 3, wherein the secondary amine containing alkyl acrylate is dimethylaminoethyl methacrylate.
5. The composition of claim 1, wherein the acrylamide is selected from the group consisting of N-methylol acrylamide, methyl acrylamidoglycolate methyl ether, N,N-dimethyl acrylamide, and mixtures thereof.
6. The composition of claim 5, wherein the acrylamide is N-methylol acrylamide.
7. The composition of claim 1, wherein the acrylic moiety comprises more than 90% by weight of the copolymer.
8. The composition of claim 1, wherein the precursor for the aqueous polymer dispersion comprises in weight %, about 40-80% butyl acrylate, about 5-40% methyl methacrylate, about 5-40% 2-ethylhexyl acrylate, about 0.5-5% dimethylaminoethyl methacrylate and about 0.5-5%
N-methylol acrylamide.
N-methylol acrylamide.
9. A method for preparing an aqueous chalk adhesion polymer capable of penetrating a chalky coating and adhering to the surface beneath said chalky coating which comprises:
(a) forming a monomer composition consisting essentially of about 40 to 80 weight % butyl acrylate, about 5 to 40 weight % methyl methacrylate, about 5 to 40 weight % 2-ethylhexyl acrylate, about 0.5 to 5 weight %
dimethylaminoethyl methacrylate and about 0.5 to 5 weight % N-methylol acrylamide;
(b) pre-emulsifying the components of step (a) to form an aqueous monomer pre-emulsion;
(c) charging about 3 to 10% of the monomer pre-emulsion to a reactor to initiate the reaction at a temperature below about 80°C.;
(d) slowly adding the remaining portion of the monomer pre-emulsion to the reactor at a temperature below about 80°C. until the reaction is completed to form said chalk adhesion polymer in aqueous dispersion;
(e) wherein said chalk adhesion polymer exhibits chalk adhesion properties of about 1 to 30%
film removed after 1 week, and excellent blister resistance.
(a) forming a monomer composition consisting essentially of about 40 to 80 weight % butyl acrylate, about 5 to 40 weight % methyl methacrylate, about 5 to 40 weight % 2-ethylhexyl acrylate, about 0.5 to 5 weight %
dimethylaminoethyl methacrylate and about 0.5 to 5 weight % N-methylol acrylamide;
(b) pre-emulsifying the components of step (a) to form an aqueous monomer pre-emulsion;
(c) charging about 3 to 10% of the monomer pre-emulsion to a reactor to initiate the reaction at a temperature below about 80°C.;
(d) slowly adding the remaining portion of the monomer pre-emulsion to the reactor at a temperature below about 80°C. until the reaction is completed to form said chalk adhesion polymer in aqueous dispersion;
(e) wherein said chalk adhesion polymer exhibits chalk adhesion properties of about 1 to 30%
film removed after 1 week, and excellent blister resistance.
10. The method of claim 9, wherein the chalk adhesion polymer is blended with an acrylic formulation to form a chalk adhesion latex coating composition comprising about 10-30% by weight of the chalk adhesion polymer.
11. The method of claim 9, wherein the monomer composition of step (a) comprises in weight % about 40-60% butyl acrylate, about 10-30% methyl methacrylate, about 5-20% 2-ethylhexyl acrylate, about 0.5-5%
dimethylamino-ethyl methacrylate, and about 0.5-5% N-methylol acrylamide.
dimethylamino-ethyl methacrylate, and about 0.5-5% N-methylol acrylamide.
12. The method of claim 9, wherein the monomer is emulsified in the presence of about 0.5-5% by weight of a glycol.
13. The method of claim 12, wherein the glycol is selected from the group consisting of propylene glycol, butylene glycol, dipropylene glycol, diethylene glycol, 1,4-butanediol, 1,2-propanediol and ethylene glycol.
14. The method of claim 9, wherein the monomer pre-emulsion of step (b) is charged to the reactor over a period of about 3 to 6 hours.
15. The product formed by the method of claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/832,832 US4722965A (en) | 1986-02-24 | 1986-02-24 | Chalk adhesion polymer composition and method of preparation |
| US832,832 | 1986-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1295770C true CA1295770C (en) | 1992-02-11 |
Family
ID=25262730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000529151A Expired - Fee Related CA1295770C (en) | 1986-02-24 | 1987-02-06 | Chalk adhesion polymer composition and method of preparation |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4722965A (en) |
| EP (1) | EP0239213A3 (en) |
| JP (1) | JPS62205170A (en) |
| AU (1) | AU589496B2 (en) |
| BR (1) | BR8700729A (en) |
| CA (1) | CA1295770C (en) |
| NZ (1) | NZ219364A (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808660A (en) * | 1986-04-03 | 1989-02-28 | Gencorp Inc. | Latex containing copolymers having a plurality of activatable functional ester groups therein |
| US4727119A (en) * | 1986-09-15 | 1988-02-23 | The Dow Chemical Company | Halogenated epoxy resins |
| US5212225A (en) * | 1989-08-29 | 1993-05-18 | Rohm And Haas Company | Binder synthesis process |
| US5134186A (en) * | 1989-08-29 | 1992-07-28 | Union Oil Company Of California | Latex paints |
| US5219917A (en) * | 1989-08-29 | 1993-06-15 | Rohm And Haas Company | Latex-paints |
| US5213901A (en) * | 1989-08-29 | 1993-05-25 | Rohm And Haas Company | Coated articles |
| US5124393A (en) * | 1989-08-29 | 1992-06-23 | Union Oil Company Of California | Latex paints |
| US5157071A (en) * | 1989-08-29 | 1992-10-20 | Union Oil Company Of California | Paints and polymers for use therein |
| US5227423A (en) * | 1989-08-29 | 1993-07-13 | Rohm And Haas Company | Paints and binders for use therein |
| US5142019A (en) * | 1991-10-03 | 1992-08-25 | Ppg Industries, Inc. | Oligomers formed from reaction of acrylamidoglycolate alkyl ethers with β-hydroxyalkylamines |
| US6166127A (en) * | 1997-06-27 | 2000-12-26 | The Sherwin-Williams Company | Interpenetrating networks of polymers |
| US6022925A (en) * | 1998-06-23 | 2000-02-08 | The Sherwin-Williams Company | Partial interpenetrating networks of polymers |
| WO2000008077A1 (en) * | 1998-08-07 | 2000-02-17 | Reichhold, Inc. | Novel latex compositions for deposition on various substrates |
| US20050065284A1 (en) * | 1999-08-06 | 2005-03-24 | Venkataram Krishnan | Novel latex compositions for deposition on various substrates |
| US6509064B2 (en) | 2000-10-11 | 2003-01-21 | Rohm And Haas Company | Aqueous coating composition with improved adhesion to friable surfaces |
| EP1203796B1 (en) * | 2000-11-01 | 2004-06-30 | Rohm And Haas Company | Aqueous coating composition with improved adhesion to friable surfaces |
| US7981946B2 (en) * | 2003-07-03 | 2011-07-19 | Mallard Creek Polymers, Inc. | Antimicrobial and antistatic polymers and methods of using such polymers on various substrates |
| US7781498B2 (en) * | 2003-07-03 | 2010-08-24 | Mallard Creek Polymers, Inc. | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
| US7491753B2 (en) * | 2003-07-03 | 2009-02-17 | Mallard Creek Polymers, Inc. | Antimicrobial and antistatic polymers and methods of using such polymers on various substrates |
| US20070048249A1 (en) | 2005-08-24 | 2007-03-01 | Purdue Research Foundation | Hydrophilized bactericidal polymers |
| US7642314B2 (en) * | 2005-12-30 | 2010-01-05 | Columbia Insurance Company | Emulsion polymers having multimodal molecular weight distributions |
| US20080207774A1 (en) * | 2006-08-24 | 2008-08-28 | Venkataram Krishnan | Anionic latex as a carrier for active ingredients and methods for making and using the same |
| US20080233062A1 (en) * | 2006-08-24 | 2008-09-25 | Venkataram Krishnan | Cationic latex as a carrier for active ingredients and methods for making and using the same |
| EP2061481B1 (en) * | 2006-08-24 | 2012-12-12 | Mallard Creek Polymers, Inc | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
| RU2448990C2 (en) | 2006-08-24 | 2012-04-27 | Маллард Крик Полимерс, Инк. | Anionic latex as carrier for bioactive ingredients and methods of producing and using said latex |
| US20180340046A1 (en) | 2017-05-27 | 2018-11-29 | Poly Group LLC | Dispersible antimicrobial complex and coatings therefrom |
| EP3638740A1 (en) | 2017-06-16 | 2020-04-22 | Poly Group LLC | Polymeric antimicrobial surfactant |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2666044A (en) * | 1951-03-09 | 1954-01-12 | Du Pont | Alkyl acrylate/n-hydrocarbon-substituted acrylamide/unsaturated tertiary amino compound copolymers |
| NL294927A (en) * | 1962-07-05 | |||
| GB1166682A (en) * | 1965-12-23 | 1969-10-08 | Johnson & Johnson | Pressure-Sensitive Acrylate Adhesives |
| US3732184A (en) * | 1971-04-22 | 1973-05-08 | Tanner Co Chas S | Emulsion polymerization method |
| JPS5374554A (en) * | 1976-12-15 | 1978-07-03 | Kyowa Gas Chem Ind Co Ltd | Water-soluble and hydrophilic composition |
| JPS6030348B2 (en) * | 1978-06-15 | 1985-07-16 | 東レ株式会社 | paint composition |
| FR2443473A1 (en) * | 1978-12-08 | 1980-07-04 | Corona Peintures | NOVEL ACRYLIC COPOLYMERS FOR USE IN VARNISHES AND PRINTING INKS AND PREPARATION METHOD |
| JPS5641270A (en) * | 1979-09-10 | 1981-04-17 | Kyowa Gas Chem Ind Co Ltd | Composition for antifouling paint |
| FR2511009A1 (en) * | 1981-08-10 | 1983-02-11 | Rhone Poulenc Spec Chim | VINYL ACETATE POLYMER LATEX AND PROCESS FOR PREPARING THE SAME |
| US4504609A (en) * | 1982-10-04 | 1985-03-12 | Nippon Paint Co., Ltd. | Aqueous coating composition |
| US4529765A (en) * | 1984-04-09 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Coating composition of an acrylic polymer having ethylenically unsaturated groups and an acrylic polymer having primary amine groups |
-
1986
- 1986-02-24 US US06/832,832 patent/US4722965A/en not_active Expired - Fee Related
-
1987
- 1987-02-06 CA CA000529151A patent/CA1295770C/en not_active Expired - Fee Related
- 1987-02-11 EP EP87301165A patent/EP0239213A3/en not_active Withdrawn
- 1987-02-17 BR BR8700729A patent/BR8700729A/en unknown
- 1987-02-23 NZ NZ219364A patent/NZ219364A/en unknown
- 1987-02-23 JP JP62039988A patent/JPS62205170A/en active Pending
- 1987-02-24 AU AU69179/87A patent/AU589496B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU589496B2 (en) | 1989-10-12 |
| EP0239213A3 (en) | 1989-03-15 |
| NZ219364A (en) | 1989-11-28 |
| US4722965A (en) | 1988-02-02 |
| AU6917987A (en) | 1987-08-27 |
| JPS62205170A (en) | 1987-09-09 |
| EP0239213A2 (en) | 1987-09-30 |
| BR8700729A (en) | 1987-12-15 |
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