US 6,613,436 B2Granted

Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers

AssigneePPG Industries Ohio, Inc.

InventorsRonald R. Ambrose, Anthony M. Chasser, Shengkui Hu, Jackie L. Smith

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Abstract

The present invention provides a crosslinking agent which may have reactive benzoxazine groups prepared from (a) at least one aromatic compound, (b) at least one aminotriazine compound, and (c) at least one other compound having active hydrogen groups reactive with aminoplast compound (b). The crosslinking agent is essentially free of hydroxyl functionality and has a glass transition temperature of at least 25° C. The present invention is further directed to a method for preparing the above-described crosslinking agent, and a curable powder coating composition comprising a mixture of (A) a polymer having functional groups reactive with aminotriazine and/or benzoxazine groups having a glass transition temperature of at least 30° C.; and (B) the above crosslinking agent. Multilayer composite coating compositions are also provided including a basecoat deposited from a film-forming composition and a topcoat over the basecoat, deposited from the curable powder coating composition described above. Coated substrates are also provided.

Claims132

Dependent claims

A crosslinking agent having reactive benzoxazine groups comprising an ungelled reaction product of the following reactants:

(a) at least one mono-hydroxy aromatic compound having the following structure (I-A):
wherein R1 represents a monovalent hydrocarbon group, COOR5 where R5 represents H or a monovalent hydrocarbon group, NO2, halogen or XR4, where X represents O or S and R4 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms;
R3, R′3, R2 and R′2 can be the same or different and each independently represents a substituent selected from H, a monovalent hydrocarbon group, COOR5, NO2, halogen and XR4, provided that at least one of R3 and R′3 is H;
or
when R3 is non-hydrogen substituted and R′3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R2 taken together with the non-hydrogen substituted R3 represent fused aliphatic or aromatic ring structures, or
when R′3 is non-hydrogen substituted and R3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R′2 taken together with the non-hydrogen substituted R′3 represent fused aliphatic or aromatic ring structures;
(b) at least one aminoplast compound;
and
(c) at least one compound different from (a) having active hydrogen groups reactive with aminoplast compound (b), said compound (c) selected from at least one of:
(1) compounds having the following structure (II):
wherein X is aromatic;
R6, R7, and R8 can be the same or different and each independently represents H, (cyclo)alkyl having from 1 to 12 carbon atoms, aryl, alkaryl, aralkyl, or an active hydrogen-containing group,
provided that at least one of R6, R7, and R8 represents an active hydrogen-containing group which is reactive with the aminoplast resin (b);
(2) compounds having the following structure (III) or (IV):
where R′ and R″ are the same or different and each independently represents an aromatic group or an alkyl group having 1 to 12 carbon atoms;
and
(3) compounds different from (1) and (2) and having a melting point of at least 80° C.;
wherein said crosslinking agent is essentially free of hydroxyl functionality and has a glass transition temperature of at least 25° C.

15 more elements

A method for forming a powder crosslinking agent having reactive benzoxazine groups comprising the following steps:

(1) combining the following reactants:
(a) at least one mono-hydroxy aromatic compound having the following structure (I):
wherein R1 represents a monovalent hydrocarbon group, COOR5 where R5 represents H or a monovalent hydrocarbon group, NO2, halogen or XR4, where X represents O or S and R4 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms;
R3, R′3 R2 and R′2 can be the same or different and each independently represents a substituent selected from H, a monovalent hydrocarbon group, COOR5, NO2, halogen and XR4, provided that at least one of R3 and R′3 is H;
or
when R3 is non-hydrogen substituted and R′3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R2 taken together with the non-hydrogen substituted R3 represent fused aliphatic or aromatic ring structures, or
when R′3 is non-hydrogen substituted and R3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R′2 taken together with the non-hydrogen substituted R′3 represent fused aliphatic or aromatic ring structures;
(b) at least one aminoplast compound;
and
(c) at least one compound different from (a) having active hydrogen groups reactive with aminoplast compound (b), said compound (c) selected from at least one of:
(i) compounds having the following structure (II):
wherein X is aromatic;
R6, R7, and R8 can be the same or different and each independently represents H, (cyclo)alkyl having from 1 to 12 carbon atoms, aryl, alkaryl, aralkyl, or an active hydrogen-containing group,
provided that at least one of R6, R7, and R8 represents an active hydrogen-containing group which is reactive with the aminoplast compound (b);
(ii) compounds having the following structure (III) or (IV):
where R′ and R″ are the same or different and each independently represents an aromatic group or an alkyl group having 1 to 12 carbon atoms;
and
(iii) compounds different from (i) and (ii) and having a melting point of at least 80° C. to form a reaction admixture;
(2) heating the reaction admixture formed in step (1) to a temperature ranging from 90° C. to 135° C.;
and
(3) maintaining the temperature achieved in step (2) for a time sufficient to produce an ungelled reaction product having a glass transition temperature of at least 25° C. which is essentially free of hydroxyl functionality as determined by infrared spectroscopy.

18 more elements

A curable powder coating composition comprising a solid particulate, film-forming mixture of the following components:

(A) a polymer having functional groups reactive with benzoxazine groups, said polymer having a glass transition temperature of at least 30° C.;
and
(B) a crosslinking agent having reactive benzoxazine groups comprising an ungelled reaction product of the following reactants:
(1) at least one mono-hydroxy aromatic compound having the following structure (I):
wherein R1 represents a monovalent hydrocarbon group, COOR5 where R5 represents H or a monovalent hydrocarbon group, NO2, halogen or XR4, where X represents O or S and R4 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms;
R3, R′3, R2 and R′2 can be the same or different and each independently represents a substituent selected from H, a monovalent hydrocarbon group, COOR5, NO2, halogen and XR4, provided that at least one of R3 and R′3 is H;
or
when R3 is non-hydrogen substituted and R′3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R2 taken together with the non-hydrogen substituted R3 represent fused aliphatic or aromatic ring structures, or
when R′3 is non-hydrogen substituted and R3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R′2 taken together with the non-hydrogen substituted R′3 represent fused aliphatic or aromatic ring structures;
(2) at least one aminoplast compound;
and
(3) at least one compound different from (1) having active hydrogen groups reactive with aminoplast compound (2), said compound (3) selected from at least one of:
(a) compounds having the following structure (II):
wherein X is aromatic;
R6, R7, and R8 can be the same or different and each independently represents H, (cyclo)alkyl having from 1 to 12 carbon atoms, aryl, alkaryl, aralkyl, or an active hydrogen-containing group,
provided that at least one of R6, R7, and R8 represents an active hydrogen-containing group which is reactive with the aminoplast compound (2);
(b) compounds having the following structure (III) or (IV):
where R′ and R″ are the same or different and each independently represents an aromatic group or an alkyl group having 1 to 12 carbon atoms;
and
(c) compounds different from (a) and (b) and having a melting point of at least 80° C.;
wherein said crosslinking agent is essentially free of hydroxyl functionality and has a glass transition temperature of at least 25° C.

18 more elements

A multilayer composite coating composition comprising a base coat deposited from a film-forming base coat composition and topcoat over the base coat, the topcoat deposited from a transparent curable powder topcoating composition,

the curable powder topcoating composition comprising a film-forming, solid particulate mixture of the following components:
(A) a polymer having functional groups reactive with benzoxazine groups, said polymer having a glass transition temperature of at least 30° C.;
and
(B) a crosslinking agent having reactive benzoxazine groups comprising the ungelled reaction product of the following reactants:
(1) at least one mono-hydroxy aromatic compound having the following structure (I):
wherein R1 represents a monovalent hydrocarbon group, COOR5 where R5 represents H or a monovalent hydrocarbon group, NO2, halogen or XR4, where X represents O or S and R4 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms;
R3, R′3, R2 and R′2 can be the same or different and each independently represents a substituent selected from H, a monovalent hydrocarbon group, COOR5, NO2, halogen and XR4, provided that at least one of R3 and R′3 is H;
or
when R3 is non-hydrogen substituted and R′3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R2 taken together with the non-hydrogen substituted R3 represent fused aliphatic or aromatic ring structures, or
when R′3 is non-hydrogen substituted and R3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R′2 taken together with the non-hydrogen substituted R3 represent fused aliphatic or aromatic ring structures;
and
(2) at least one aminoplast compound;
and
(3) at least one compound different from (1) having active hydrogen groups reactive with aminoplast compound (2), said compound (3) selected from at least one of:
(a) compounds having the following structure (II):
wherein X is aromatic;
R6, R7, and R8 can be the same or different and each independently represents H, (cyclo)alkyl having from 1 to 12 carbon atoms, aryl, alkaryl, aralkyl, or an active hydrogen-containing group,
provided that at least one of R6, R7, and R8 represents an active hydrogen-containing group which is reactive with the aminoplast compound (2);
(b) compounds having the following structure (III) or (IV):
where R′ and R″ are the same or different and each independently represents an aromatic group or an alkyl group having 1 to 12 carbon atoms;
and
(c) compounds different from (a) and (b) and having a melting point of at least 80° C.;
wherein said crosslinking agent is essentially free of hydroxyl functionality and has a glass transition temperature of at least 25° C.

20 more elements

A crosslinking agent comprising an ungelled reaction product of the following reactants:

(a) at least one aromatic compound having the following structure (I-B):
wherein R1 represents a monovalent hydrocarbon group, COOR5 wherein R5 represents H or a monovalent hydrocarbon group, NO2, halogen or XR4, where X represents O or S and R4 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms;
R3, R′3, R2 and R′2 can be the same or different and each independently represents a substituent selected from H, a monovalent hydrocarbon group, COOR5, NO2, halogen and XR4, provided that at least one of R3 and R′3 is H;
or
when R3 is non-hydrogen substituted and R′3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R2 taken together with the non-hydrogen substituted R3 represent fused aliphatic or aromatic ring structures, or
when R′3 is non-hydrogen substituted and R3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R′2 taken together with the non-hydrogen substituted R′3 represent fused aliphatic or aromatic ring structures;
Y represents an active hydrogen-containing group selected from amino, thiol, and urea;
(b) at least one aminoplast compound;
and
(c) at least one compound different from (a) having active hydrogen groups reactive with aminoplast compound (b), said compound (c) selected from at least one of:
(1) compounds having the following structure (II):
wherein X is aromatic;
R6, R7, and R8 can be the same or different and each independently represents H, (cyclo)alkyl having from 1 to 12 carbon atoms, aryl, alkaryl, aralkyl, or an active hydrogen-containing group,
provided that at least one of R6, R7, and R8 represents an active hydrogen-containing group which is reactive with the aminoplast resin (b);
(2) compounds having the following structure (III) or (IV):
where R′ and R″ are the same or different and each independently represents an aromatic group or an alkyl group having 1 to 12 carbon atoms;
and
(3) compounds different from (1) and (2) and having a melting point of at least 80° C.;
wherein said crosslinking agent is essentially free of hydroxyl functionality and has a glass transition temperature of at least 25° C.

16 more elements

A method for forming a powder crosslinking agent having reactive benzoxazine groups comprising the following steps:

(1) combining the following reactants:
(a) at least one mono-hydroxy aromatic compound having the following structure (I-A):
wherein R1 represents a monovalent hydrocarbon group, COOR5 where R5 represents H or a monovalent hydrocarbon group, NO2, halogen or XR4, where X represents O or S and R4 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms;
R3, R′3, R2 and R′2 can be the same or different and each independently represents a substituent selected from H, a monovalent hydrocarbon group, COOR5, NO2, halogen and XR4, provided that at least one of R3 and R′3 is H;
or
when R3 is non-hydrogen substituted and R′3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R2 taken together with the non-hydrogen substituted R3 represent fused aliphatic or aromatic ring structures, or
when R′3 is non-hydrogen substituted and R3 is H, R1 and R2 taken together, R1 and R′2 taken together, or R′2 taken together with the non-hydrogen substituted R′3 represent fused aliphatic or aromatic ring structures;
and
(b) at least one aminoplast compound to form a reaction admixture;
(2) heating the reaction admixture formed in step (1) to a temperature ranging from 90° C. to 135° C.;
(3) maintaining the temperature achieved in step (2) until no free hydroxyl functionality remains;
(4) adding to the reaction admixture formed in step (1) at least one compound different from (a) having active hydrogen groups reactive with aminoplast compound (b), said compound selected from at least one of:
(i) compounds having the following structure (II):
wherein X is aromatic;
R6, R7, and R8 can be the same or different and each independently represents H, (cyclo)alkyl having from 1 to 12 carbon atoms, aryl, alkaryl, aralkyl, or an active hydrogen-containing group,
provided that at least one of R6, R7, and R8 represents an active hydrogen-containing group which is reactive with the aminoplast resin (b);
(ii) compounds having the following structure (III) or (IV):
where R′ and R″ are the same or different and each independently represents an aromatic group or an alkyl group having 1 to 12 carbon atoms;
and
(iii) compounds different from (i) and (ii) and having a melting point of at least 80° C. to form a second reaction admixture;
(5) heating the second reaction admixture formed in step (4) to a temperature ranging from 90° C. to 135° C.;
and
(6) maintaining the temperature achieved in step (5) for a time sufficient to produce an ungelled reaction product having a glass transition temperature of at least 25° C. which is essentially free of hydroxyl functionality as determined by infrared spectroscopy.

20 more elements

Dependencies are inferred from the claim text.

Facts

Application: 09/919,092Filed 31 Jul 2001 · continuation in part
Priority: 21 Sep 2000
Published: US 2002/0071955 A113 Jun 2002
Granted: 2 Sep 2003
Term ends: Not estimatedThe source records don’t support an estimate.