US 7,001,952 B2Granted

Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles

AssigneePPG Industries Ohio, Inc.

InventorsDennis L. Faler, Karen A. Barkac, M. Frank Haley, Deena M. McHenry, Edward S. Pagac, Shanti Swarup, Cathy A. Taylor, Elizabeth A. Zezinka

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Abstract

An aqueous polyurethane dispersion and thermosetting compositions containing them. The aqueous polyurethane dispersion includes an aqueous medium with dispersed polyurethane-acrylate particles, which include the reaction product obtained by polymerizing a pre-emulsion formed from hydrophobic polymerizable ethylenically unsaturated monomers, a crosslinking monomer, and an active hydrogen-containing polyurethane acrylate prepolymer, which is a reaction product obtained by reacting a polyol, a polymerizable, ethylenically unsaturated monomer containing at least one hydroxyl group, a compound that includes an alkyl group having at least one hydroxyl group and optionally a carboxylic acid group, and a polyisocyanate. The prepolymer includes at least 30 percent by weight of polyurethane acrylate prepolymers with at least one terminal ethylenic unsaturation at one end of the molecule, and at least one active hydrogen-containing group at the opposite end; and at least 10 percent by weight of prepolymers having at least one terminal ethylenic unsaturation at each end of the molecule.

Claims57

Dependent claims

A thermosetting composition comprising:

(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(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) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
and
(IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable, ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1–C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group;
and
(iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers;
and
(C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule;
and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.

20 more elements

A substrate coated by a method 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
(D) curing the thermosetting composition, wherein the thermosetting composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(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) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
and
(IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing functional polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1–C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group;
and
(iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers;
and
(C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule;
and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.

21 more elements

A multi-layer composite coating comprising:

(A) a base coat layer deposited from an effect pigment-containing base coat composition, wherein said base coat composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(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)m—OH where n is 0 to 30, and —CH2CH2—(OC(CH3)HCH2)n—OH where m is 0 to 30;
and
(c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
and
(IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1–C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group;
and
(iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers;
and
(C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule;
and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule;
and
(B) a substantially pigment free top coat layer deposited over at least a portion of said base coat layer from a substantially pigment free top coat composition.

23 more elements

A multi-layer composite coating comprising:

(A) a base coat layer deposited from a base coat composition, wherein said base coat composition comprises:
(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(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)m—OH where n is 0 to 30, and —CH2CH2—(OC(CH3)HCH2)n—OH where m is 0 to 30;
and
(c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
and
(IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1–C30 alkyl group comprising at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group;
and
(iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers;
and
(C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule;
and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule;
and
(B) a substantially pigment free top coat layer wherein said top coat layer comprises a substantially pigment free powder coating composition deposited over at least a portion of said base coat layer from the powder coating composition.

23 more elements

A thermosetting composition comprising:

(I) a first reactant comprising reactive functional groups;
(II) a curing agent having functional groups reactive with the functional groups of the first reactant in (I);
(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 selected from the group consisting of(meth)acrylamide, hydroxyethy(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl (meth)acrylate, allyl glycerol ether, methallyl glycerol ether and polyethyleneoxide allyl ether;
and
(c) optionally, the balance comprised of one or more polymerizable ethylenically unsaturated monomers, wherein (a), (b) and (c) are different from each other;
and
(IV) an aqueous polyurethane dispersion, comprising polyurethane-acrylate particles dispersed in an aqueous medium, said particles comprising the reaction product obtained by polymerizing the components of a pre-emulsion formed from:
(A) an active hydrogen-containing polyurethane acrylate prepolymer, comprising a reaction product obtained by reacting:
(i) a polyol;
(ii) a polymerizable, ethylenically unsaturated monomer containing at least one hydroxyl group;
(iii) a compound comprising a C1–C30 alkyl group having at least two active hydrogen groups selected from carboxylic acid groups and hydroxyl groups, wherein at least one active hydrogen group is a hydroxyl group;
and
(iv) a polyisocyanate;
(B) one or more hydrophobic polymerizable ethylenically unsaturated monomers;
and
(C) a crosslinking monomer;
wherein the active hydrogen functional polyurethane acrylate prepolymer of (A) includes at least 30 percent by weight of polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation, at one end of the molecule and at least one active hydrogen-containing group at the opposite end of the molecule;
and at least 10 percent by weight of the polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.

17 more elements

Dependencies are inferred from the claim text.

Facts

Application: 10/126,903Filed 19 Apr 2002
Published: US 2003/0220446 A127 Nov 2003
Granted: 21 Feb 2006
Term ends: Not estimatedThe source records don’t support an estimate.

Classification13 codes

C09D 175/04
Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers: polyurethanes
C08G 18/0823
Containing anionic or anionogenic groups: containing carboxylate salt groups or groups forming them
C08G 18/0866
In the presence of a dispersing phase for the polymers or a phase dispersed in the polymers: the dispersing or dispersed phase being an aqueous medium
C08G 18/4288
Polycondensates having carboxylic or carbonic ester groups in the main chain: modified by higher fatty oils or their acids or by resin acids