CA2482898A1 - Highly crosslinked polymer particles and coating compositions containing the same - Google Patents
Highly crosslinked polymer particles and coating compositions containing the same Download PDFInfo
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- CA2482898A1 CA2482898A1 CA002482898A CA2482898A CA2482898A1 CA 2482898 A1 CA2482898 A1 CA 2482898A1 CA 002482898 A CA002482898 A CA 002482898A CA 2482898 A CA2482898 A CA 2482898A CA 2482898 A1 CA2482898 A1 CA 2482898A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
A latex emulsion that includes crosslinked polymeric microparticles dispersed in an aqueous continuous phase. The microparticles are prepared from a monomer mix of a crosslinking monomer, a monomer having hydrophilic functional groups, and one or more other monomers. Also disclosed is a thermosetting composition that includes a first reactant that has reactive functional groups; a curing agent that has at least two functional groups reactive with the functional groups of the first reactant; and the latex emulsion of crosslinked polymeric microparticles dispersed in an aqueous continuous phase. The thermosetting composition may be used to coat a substrate. The coating may be a multi-layer composite coating that includes a base coat layer deposited from a pigmented film-forming base coat composition containing the thermosetting composition;
and a substantially pigment free top coat layer deposited over a portion of the base coat layer from a substantially pigment free top coat composition.
and a substantially pigment free top coat layer deposited over a portion of the base coat layer from a substantially pigment free top coat composition.
Claims (55)
1. A latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase in latex emulsion form, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 5 weight percent of a polymerizable ethylenically unsaturated monomer having hydrophiiic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2 -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH
where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30, D
is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other, wherein the crosslinking monomer having two or more sites of reactive unsaturation in (a) is one or more selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 5 weight percent of a polymerizable ethylenically unsaturated monomer having hydrophiiic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2 -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH
where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30, D
is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other, wherein the crosslinking monomer having two or more sites of reactive unsaturation in (a) is one or more selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
2. The latex emulsion of claim 1, wherein the crosslinking monomer (a) has two sites of reactive unsaturation.
3. The latex emulsion of claim 1, wherein the monomers having one or more functional groups capable of reacting to form crosslinks after polymerization the are selected from the group consisting of N-alkoxymethyl(meth)acrylamides, y-(meth)acryloxytrialkoxysilane, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, (meth)acryliclactones, N-substituted (meth)acrylamide lactones, (meth)acryliclactams, N-substituted (meth)acrylamide lactams and glycidyl (meth)acrylate.
4. The latex emulsion of claim 1 wherein the polymerizable ethylenically unsaturated monomer (c) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
5. The latex emulsion of claim 1, wherein the polymerizable ethylenically unsaturated monomer (b) comprises one or monomers of structure 1.
6. The latex emulsion of claim 1, wherein the polymerizable ethylenically unsaturated monomer (b) having hydrophilic functional groups comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate and dimethylaminoethyl (meth)acrylate.
7. The latex emulsion of claim 1, wherein the aqueous continuous phase includes from 0.01 to 5 weight percent of a surface active agent.
8. The latex of claim 1, wherein the crosslinking monomer (a) comprises a monomer selected from glycol di(meth)acrylates and glycol tri(meth)acrylates; the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises (meth)acrylamide; and the polymerizable ethylenically unsaturated monomer (c) comprises one or more alkyl(meth)acrylates.
9. The latex of claim 1, wherein the average particle size of the polymeric microparticles ranges from 0.01 to 1 microns.
10. The latex of claim 1, wherein the latex emulsion is substantially free of polymeric emulsifiers and/or protective colloids.
11. A latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared by:
(I) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 2 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino; -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2CH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(II) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to 20 weight percent of (c) to form polymeric seedy dispersed in the contiguous phase; and (III) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles;
wherein the crosslinking monomer in (a) is one or more selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 9,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydraxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate; triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
(I) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 2 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino; -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2CH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(II) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to 20 weight percent of (c) to form polymeric seedy dispersed in the contiguous phase; and (III) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles;
wherein the crosslinking monomer in (a) is one or more selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 9,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydraxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate; triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
12. A thermosetting composition comprising:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from ~NR1R2, -OR3 and ~SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH
where n is 0 to 30, and, -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30, D
is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other.
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more groups of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from ~NR1R2, -OR3 and ~SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH
where n is 0 to 30, and, -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30, D
is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other.
13. The thermosetting composition of claim 12, wherein the crosslinking monomer (a) has two or more sites of reactive unsaturation.
14. The thermosetting composition claim 12 wherein the crosslinking monomer (a) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate; triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
15. The thermosetting composition claim 12, wherein the monomers having one or more functional groups capable of reacting to form crosslinks.
after polymerization the are selected from the group consisting of N-alkoxymethyl(meth)acrylamides, .gamma.-(meth)acryloxytrialkoxysilane, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, (meth)acryliclactones, N-substituted (meth)acrylamide lactones, (meth)acryliclactams, N-substituted (meth)acrylamide lactams and glycidyl(meth)acrylate,
after polymerization the are selected from the group consisting of N-alkoxymethyl(meth)acrylamides, .gamma.-(meth)acryloxytrialkoxysilane, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, (meth)acryliclactones, N-substituted (meth)acrylamide lactones, (meth)acryliclactams, N-substituted (meth)acrylamide lactams and glycidyl(meth)acrylate,
16. The thermosetting composition claim 12, wherein the polymerizable ethylenically unsaturated monomer (c) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobomyl (meth)acrylate, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
17. The thermosetting composition of claim 12, wherein the polymerizable ethylenically unsaturated monomer (b) comprises one or monomers of structure 1.
18. The thermosetting composition claim 12, wherein the ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate.
19. The thermosetting composition of claim 12, wherein the aqueous continuous phase includes from 0.01 to 5 weight percent of a surface active agent.
20. The thermosetting composition of claim 12, wherein the crosslinking monomer (a) comprises at least one of glycol di(meth)acrylates and glycol tri(meth)acrylates; the polymerizable ethylenically unsaturated monomers having hydrophilic functional groups (b) comprises (meth)acrylamide; and the monomer (c) comprises one or more alkyl(meth)acrylates.
21. The thermosetting composition of claim 12, wherein the average particle size of the polymeric microparticles ranges from 0.01 to 1 microns.
22. The thermosetting composition of claim 12, wherein said thermosetting composition is a liquid composition.
23. The thermosetting composition of claim 12, wherein said thermosetting composition is a coating composition.
24. The thermosetting composition of claim 12, wherein the latex emulsion is substantially free of polymeric emulsifers and/or protective colloids.
25. The thermosetting composition of claim 12, wherein the functional groups of the first reactant (I) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylol, amino, methylol ether, carbamate and mixtures thereof.
26. The thermosetting composition of claim 12, wherein the functional groups of curing agent (II) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, beta-hydroxyalkylamide and mixtures thereof.
27. The thermosetting composition of claim 12, wherein the functional groups of crosslinking agent (II) are different from and reactive with those of the first reactant (I).
28. The thermosetting composition of claim 12, wherein the first reactant (I) is a polymer containing hydroxyl functional groups, and the curing agent (II) comprises one or more materials selected from polyamines, aminoplast resins and polylsocyanates.
29. The thermosetting composition of claim 12, further comprising one or more aqueous polyurethane dispersions.
30. The thermosetting composition of claim 12, further comprising one or more effect pigments.
31. The thermosetting composition of claim 30, wherein the latex emulsion (III) is present in an amount sufficient to provide a Flop Index rating of 10 or greater.
32. A thermosetting composition comprising:
(A) a first reactant comprising reactive functional groups;
(B) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (A); and (C) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared by:
(I) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 2 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from ~NR1R2, -OR3 and ~SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(II) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to weight percent of (c) to form polymeric seeds dispersed in the continuous phase; and (III) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles.
(A) a first reactant comprising reactive functional groups;
(B) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (A); and (C) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared by:
(I) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 2 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from ~NR1R2, -OR3 and ~SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(II) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to weight percent of (c) to form polymeric seeds dispersed in the continuous phase; and (III) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles.
33. A method of coating a substrate comprising:
(A) applying a thermosetting composition over at least a portion of the substrate;
(B) coalescing said thermosetting composition to form a substantially continuous film on the substrate; and (C) curing the thermosetting composition;
wherein the thermosetting composition comprises:
(I) a first reactant containing one or more reactive functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups; and (c) the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other.
(A) applying a thermosetting composition over at least a portion of the substrate;
(B) coalescing said thermosetting composition to form a substantially continuous film on the substrate; and (C) curing the thermosetting composition;
wherein the thermosetting composition comprises:
(I) a first reactant containing one or more reactive functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 2 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups; and (c) the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other.
34. The method of claim 33, wherein the crosslinking monomer (a) has two or more sites of reactive unsaturation.
35. The method of claim 33, wherein the crosslinking monomer (a) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,9-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1 tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
36. The method of claim 33, wherein the monomers having one or more functional groups capable of reacting to form crosslinks after polymerization the are selected from the group consisting of N-alkoxymethyl(meth)acrylamides, .gamma.-(meth)acryloxytrialkoxysilane, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, (meth)acryliclactones, N-substituted (meth)acrylamide lactones, (meth)acryliclactams, N-substituted (meth)acrylamide lactams and glycidyl(meth)acrylate.
37. The method of claim 33; wherein the polymerizable ethylenically unsaturated monomer(c) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, N-butoxy methyl (meth)acrylamide, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
38. The method of claim 33, wherein the polymerizable ethylenically unsaturated monomer, (b) comprises one or monomers of structure 1.
39. The method of claim 33, wherein the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and dimethylaminoethyl (meth)acrylate.
40. The method of claim 33, wherein the aqueous continuous phase includes from 0.01 to 5 weight percent of a surface active agent.
41. The method of claim 33, wherein the crosslinking monomer (a) is selected from glycol di(meth)acrylates and glycol tri(meth)acrylates; the polymerizable ethylenically unsaturated monomers having hydrophilic functional groups (b) comprises (meth)acrylamide; and the polymerizable ethylenically unsaturated monomer (c) comprises one or more alkyl(meth)acrylates.
42. The method of claim 33, wherein the average particle size of the polymeric microparticles ranges from 0.01 to 1 micron.
43. The method of claim 33, wherein the thermosetting composition is a liquid composition.
44. The method of claim 33, wherein the functional groups of the first reactant (I) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylol, amino, methylol ether, carbamate and mixtures thereof.
45. The method of claim 33, wherein the functional groups of curing agent (II) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, beta-hydroxyalkylamide and mixtures thereof.
46. The method of claim 33, wherein the functional groups of curing agent (II) are different from and reactive with those of the first reactant (I).
47. The method of claim 33, wherein the first reactant (I) comprises a polymer containing hydroxyl functional groups, and the curing agent (II) comprises one ar more materials selected from aminoplast resins and polyisocyanates.
48. A substrate coated by the method of claim 33.
49. A method of coating a substrate comprising:
(A) applying a thermosetting composition over at least a portion of the substrate;
(B) coalescing said thermosetting composition to form a substantially continuous film on the substrate; and (C) curing the thermosetting composition, wherein the thermosetting composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared by:
(i) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 5 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30; D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(ii) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to 20 weight percent of {c) to form polymeric seeds dispersed in the continuous phase; and (iii) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles,
(A) applying a thermosetting composition over at least a portion of the substrate;
(B) coalescing said thermosetting composition to form a substantially continuous film on the substrate; and (C) curing the thermosetting composition, wherein the thermosetting composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared by:
(i) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 5 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30; D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(ii) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to 20 weight percent of {c) to form polymeric seeds dispersed in the continuous phase; and (iii) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles,
50. A multi-layer composite coating comprising:
(A) a base coat layer deposited from an effect pigment-containing film-forming base coat composition, wherein said base coat composition comprises:
(I) a first reactant containing one or more functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 5 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II) wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-CH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-CH
where m is 4 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30;; and (c) the balance comprised of one or more non-hydrophilic polymerizable ethylenicailly unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (B) a substantially pigment free top coat layer deposited aver at least a portion of said base coat layer from a substantially pigment free top coat composition.
(A) a base coat layer deposited from an effect pigment-containing film-forming base coat composition, wherein said base coat composition comprises:
(I) a first reactant containing one or more functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the first reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase, the polymeric microparticles prepared from a monomer mix comprised of:
(a) at least 20 weight percent of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) at least 5 weight percent of one or more polymerizable ethylenically unsaturated monomers having hydrophilic functional groups having the following structures (I) and/or (II) wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-CH where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-CH
where m is 4 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30;; and (c) the balance comprised of one or more non-hydrophilic polymerizable ethylenicailly unsaturated monomers, wherein (a), (b) and (c) are different from each other; and (B) a substantially pigment free top coat layer deposited aver at least a portion of said base coat layer from a substantially pigment free top coat composition.
51. The multi-layer composite coating of clam 50, wherein the crosslinking monomer (a) has two or more sites of reactive unsaturation.
52. The multi-layer composite coating of claim 50, wherein the crosslinking monomer (a) comprises one or more monomers selected from the group consisting of ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethyiene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolproparie tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol allyloxy di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)ethane tri(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane di(meth)acrylate, 1,1,1-tris(hydroxymethyl)propane tri(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl phthalate, diallyl terephthalate, divinyl benzene, methylol (meth)acrylamide, triallylamine, and methylenebis (meth) acrylamide.
53. The multi-layer composite coating of claim 50, wherein the monomers having one or more functional groups capable of reacting to form crosslinks after polymerization the are selected from the group consisting of N-alkoxymethyl(meth)acrylamides, .gamma.-(meth)acryloxytrialkoxysilane, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, (meth)acryliclactones, N-substituted (meth)acrylamide lactones, (meth)acryliclactams, N-substituted (meth)acrylamide lactams and glycidyl(meth)acrylate.
54. The multi-layer composite coating of claim 50, wherein the polymerizable ethylenically unsaturated monomer (c) comprises one or more monomers selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, N-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl (meth)acrylate, styrene, (meth)acrylonitrile, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethylcyclohexyl (meth)acrylate.
55. The multi-layer composite coating of claim 50, wherein the polymerizable ethylenically unsaturated monomer (b) comprises one or monomers of structure 1.
55. The multi-layer composite coating of claim 50, wherein the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate.
57. The multi-layer composite coating of claim 50, wherein the aqueous continuous phase includes from 0.01 to 5 weight percent of a surface active agent.
58. The multi-layer composite coating of claim 50, wherein the crosslinking monomer (a) comprises at least one of glycol di(meth)acrylates and glycol tri(meth)acrylates; the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises at least one (meth)acrylamide and the monomer (c) comprises at least one alkyl(meth)acrylate.
59. The multi-layer composite coating of claim 50, wherein the average particle size of the polymeric microparticles ranges from 0,01 to 1 micron.
60. The multi-layer composite coating of claim 50, wherein said base coat composition is a liquid composition.
61. The multi-layer composite coating of claim 50, wherein the functional groups of the first reactant (I) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylal, amino, methylol ether, carbamate and mixtures thereof.
62. The multi-layer composite coating of claim 50, wherein the functional groups of curing agent (II) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, beta-hydroxyalkylamide and mixtures thereof.
63. The multi-layer composite coating of claim 50, wherein the functional groups of curing agent (II) are different from and reactive with those of the first reactant (I).
64. The multi-layer composite coating of claim 50, wherein the first reactant (I) comprises a polymer containing hydroxyl functional groups, and the functional groups of the curing agent (II) comprises one or more selected from the group consisting of aminoplast resins and polyisocyanates.
65. The multi-layer composite coating of claim 50, wherein the latex emulsion (III) is present in the basecoat composition in an amount sufficient to provide a Flop Index rating for the multi-layer composite coating of 10 or greater.
66. The multi-layer composite coating of claim 50, wherein the basecoat composition further comprises an aqueous polyurethane dispersion.
67. A multi-layer composite coating comprising:
(A) a base coat layer deposited from a pigmented film-forming base coat composition, wherein said base coat composition comprises:
(I) a first reactant containing one or more functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the fast reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase,, the polymeric microparticles prepared by:
(1) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 2 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH. where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(2) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to 20 weight percent of (c) to form polymeric seeds dispersed in the continuous phase; and (3) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles; and (B) a substantially pigment free top coat deposited over at least a portion of said base coat layer from a top coat composition.
68. A coated substrate comprising:
(A) a substrate, and (B) the multi-layer composite coating composition of claim 48 aver at least a portion of the substrate.
69. The coated substrate of claim 68, wherein the substrate is selected from a metallic substrate, an elastomeric substrate, and combinations thereof.
70. A coated substrate comprising:
(A) a substrate, and (B) the multi-layer composite casting composition of claim 62 over at least a portion of the substrate.
71. The coated substrate of claim 70, wherein the substrate is selected from a metallic substrate, an elastomeric substrate, and combinations thereof.
55. The multi-layer composite coating of claim 50, wherein the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises one or more monomers selected from the group consisting of (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate.
57. The multi-layer composite coating of claim 50, wherein the aqueous continuous phase includes from 0.01 to 5 weight percent of a surface active agent.
58. The multi-layer composite coating of claim 50, wherein the crosslinking monomer (a) comprises at least one of glycol di(meth)acrylates and glycol tri(meth)acrylates; the polymerizable ethylenically unsaturated monomer having hydrophilic functional groups (b) comprises at least one (meth)acrylamide and the monomer (c) comprises at least one alkyl(meth)acrylate.
59. The multi-layer composite coating of claim 50, wherein the average particle size of the polymeric microparticles ranges from 0,01 to 1 micron.
60. The multi-layer composite coating of claim 50, wherein said base coat composition is a liquid composition.
61. The multi-layer composite coating of claim 50, wherein the functional groups of the first reactant (I) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, amide, oxazoline, aceto acetate, isocyanate, methylal, amino, methylol ether, carbamate and mixtures thereof.
62. The multi-layer composite coating of claim 50, wherein the functional groups of curing agent (II) are selected from the group consisting of epoxy, carboxylic acid, hydroxy, isocyanate, capped isocyanate, amine, methylol, methylol ether, beta-hydroxyalkylamide and mixtures thereof.
63. The multi-layer composite coating of claim 50, wherein the functional groups of curing agent (II) are different from and reactive with those of the first reactant (I).
64. The multi-layer composite coating of claim 50, wherein the first reactant (I) comprises a polymer containing hydroxyl functional groups, and the functional groups of the curing agent (II) comprises one or more selected from the group consisting of aminoplast resins and polyisocyanates.
65. The multi-layer composite coating of claim 50, wherein the latex emulsion (III) is present in the basecoat composition in an amount sufficient to provide a Flop Index rating for the multi-layer composite coating of 10 or greater.
66. The multi-layer composite coating of claim 50, wherein the basecoat composition further comprises an aqueous polyurethane dispersion.
67. A multi-layer composite coating comprising:
(A) a base coat layer deposited from a pigmented film-forming base coat composition, wherein said base coat composition comprises:
(I) a first reactant containing one or more functional groups;
(II) a curing agent having at least two functional groups reactive with the functional groups of the fast reactant in (I); and (III) a latex emulsion comprising crosslinked polymeric microparticles dispersed in an aqueous continuous phase,, the polymeric microparticles prepared by:
(1) providing an overall monomer composition comprising constituent parts of:
(a) a first monomer composition comprising at least 20 weight percent of the overall monomer composition comprised of a crosslinking monomer having two or more sites of reactive unsaturation and/or monomers having one or more functional groups capable of reacting to form crosslinks after polymerization;
(b) a second monomer composition comprising at least 2 weight percent of the overall monomer composition comprised of a polymerizable ethylenically unsaturated monomer having hydrophilic functional groups having the following structures (I) and/or (II):
wherein A is selected from H and C1-C3 alkyl; B is selected from -NR1R2, -OR3 and -SR4, where R1 and R2 are independently selected from H, C1-C18 alkyl, C1-C18 alkylol and C1-C18 alkylamino, R3 and R4 are independently selected from C1-C18 alkylol, C1-C18 alkylamino, -CH2CH2-(OCH2CH2)n-OH. where n is 0 to 30, and , -CH2CH2-(OC(CH3)HCH2)m-OH
where m is 0 to 30, D is selected from H and C1-C3 alkyl; and E is selected from -CH2CHOHCH2OH, C1-C18 alkylol, -CH2CH2-(OCH2CH2)n-OH where n is 0 to 30, and -CH2CH2-(OC(CH3)HCH2)m-OH where m is 0 to 30; and (c) a third monomer composition comprising the balance of the overall monomer composition comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
(2) polymerizing a portion of the overall monomer mix, said portion comprising from 0.1 to 20 weight percent of (a) and from 0.1 to 20 weight percent of (c) to form polymeric seeds dispersed in the continuous phase; and (3) polymerizing the remainder of monomers (a), (b) and (c) in the presence of the dispersed polymeric seeds in (II) to form a latex emulsion of seeded polymeric microparticles; and (B) a substantially pigment free top coat deposited over at least a portion of said base coat layer from a top coat composition.
68. A coated substrate comprising:
(A) a substrate, and (B) the multi-layer composite coating composition of claim 48 aver at least a portion of the substrate.
69. The coated substrate of claim 68, wherein the substrate is selected from a metallic substrate, an elastomeric substrate, and combinations thereof.
70. A coated substrate comprising:
(A) a substrate, and (B) the multi-layer composite casting composition of claim 62 over at least a portion of the substrate.
71. The coated substrate of claim 70, wherein the substrate is selected from a metallic substrate, an elastomeric substrate, and combinations thereof.
Applications Claiming Priority (3)
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|---|---|---|---|
| US10/126,137 | 2002-04-19 | ||
| US10/126,137 US6762240B2 (en) | 2002-04-19 | 2002-04-19 | Highly crosslinked polymer particles and coating compositions containing the same |
| PCT/US2003/011703 WO2003089477A1 (en) | 2002-04-19 | 2003-04-16 | Highly crosslinked polymer particles and coating compositions containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2482898A1 true CA2482898A1 (en) | 2003-10-30 |
| CA2482898C CA2482898C (en) | 2010-08-03 |
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| CA2482898A Expired - Fee Related CA2482898C (en) | 2002-04-19 | 2003-04-16 | Highly crosslinked polymer particles and coating compositions containing the same |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6762240B2 (en) |
| EP (1) | EP1497336B1 (en) |
| JP (2) | JP4227027B2 (en) |
| KR (1) | KR100602478B1 (en) |
| CN (1) | CN100349924C (en) |
| AU (1) | AU2003223633B2 (en) |
| BR (1) | BR0309656A (en) |
| CA (1) | CA2482898C (en) |
| ES (1) | ES2592284T3 (en) |
| WO (1) | WO2003089477A1 (en) |
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| US7765769B2 (en) * | 2003-06-23 | 2010-08-03 | Ppg Industries Ohio, Inc. | Integrated window sash with lattice frame and retainer clip |
| CA2530588C (en) * | 2003-06-23 | 2008-11-18 | Ppg Industries Ohio, Inc. | Integrated window sash and methods of making an integrated window sash |
| US7856791B2 (en) * | 2003-06-23 | 2010-12-28 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
| US7997037B2 (en) * | 2003-06-23 | 2011-08-16 | Ppg Industries Ohio, Inc. | Integrated window sash with groove for desiccant material |
| US7739851B2 (en) * | 2003-06-23 | 2010-06-22 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
| US7588653B2 (en) * | 2003-06-23 | 2009-09-15 | Ppg Industries Ohio, Inc. | Method of making an integrated window sash |
| US7950194B2 (en) | 2003-06-23 | 2011-05-31 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
| US7827761B2 (en) | 2003-06-23 | 2010-11-09 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
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2002
- 2002-04-19 US US10/126,137 patent/US6762240B2/en not_active Expired - Lifetime
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2003
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| US6762240B2 (en) | 2004-07-13 |
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