Resin compositions for thermosetting powder coating compositions
View Patent ↗The invention relates to a resin composition comprising at least an organophosphorous compound and a branched amorphous carboxylic acid functional polyester, said polyester having a T g of at least 40° C., said polyester comprising at least 1 to 45% mol of 2,2-dimethyl-1,3-propanediol; a C 3 to C 5 aliphatic diol AD1 not including 2,2-dimethyl-1,3-propanediol; a C 6 to C 50 aliphatic or cycloaliphatic diol AD2; 0.1 to 10% mol of an at least trifunctional monomer; 1 to 55% mol of terephthalic acid, wherein the % mol is based on the polyester. The powder coatings of the present invention derived upon curing at low temperature of the thermosetting powder coating compositions of the invention that were storage stable and comprised said resin composition and a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester, have limited or no blooming, good smoothness sufficient reverse impact resistance and preferably have also good degassing limit.
1. A resin composition comprising at least:
(a) an organophosphorous compound; and
(b) a branched amorphous carboxylic acid functional polyester, said polyester having a Tg of at least 40° C. as measured by Differential Scanning calorimetry at a heating rate of 5° C./min, wherein said polyester comprises polycondensed residues derived from at least the following monomers:
bi) 8 to 40% mol of 2,2-dimethyl-1,3-propanediol;
bii) 3 to 21% mol of a C 3 to C 5 aliphatic diol AD1 not including 2,2-dimethyl-1,3-propanediol, wherein the C 3 to C 5 aliphatic diol AD1 is a saturated diol having only hydrogen carbon bonds, carbon carbon single bonds and two hydroxyl groups which are each attached to a carbon atom;
biii) 1 to 10% mol of a C 6 to C 50 aliphatic or cycloaliphatic diol AD2;
biv) 0.5 to 10% mol of an at least trifunctional monomer;
bv) 10 to 55% mol of terephthalic acid; wherein
the % mol is based on the polyester, and wherein
the molar ratio of AD1 to AD2 (=mol AD1/mol AD2) in the polyester is at least equal or higher to 1 and at most equal to 10, and wherein
the polyester has:
an acid value (AV) as measured titrimetrically according to the ISO 2114-2000, between 14 and 120 mg KOH/g polyester, and
a hydroxyl value (OHV) as measured titrimetrically according to the ISO 4629-1978, less than 13 mg KOH/g polyester, and
a viscosity measured at 160° C. using as a cone and plate rheometer the Brookfield CAP 2000+, with spindle CAP-S-05 at 21 rpm (shear rate 70 s-1) of at most 150 Pa·s.
2. The composition according to claim 1 , wherein the polyester comprises 8 to 35% mol of 2,2-dimethyl-1,3-propanediol.
3. The composition according to claim 1 , wherein the polyester comprises 32 to 55% mol of terephthalic acid.
4. The composition according to claim 1 , wherein the polyester further comprises 2 to 15% mol of adipic acid.
5. The composition according to claim 1 , wherein said composition also comprises a tertiary amine and/or a quaternary ammonium salt.
6. The composition according to claim 5 , wherein the tertiary amine is selected from the group consisting of octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, didodecylmonomethylamine, ditetradecylmonomethylamine, dihexadecylmonomethylamine, di-tallow alkylmonomethylamine, (hydrogenated tallow alkyl)-dimethylamine, trioctylamine, tridecylamine, tridodecylamine and mixtures thereof.
7. The composition according to claim 1 , wherein the organophosphorous compound is selected from the group of phosphonium salts having at least one phosphorous carbon bond and/or organophosphines having at least one phosphorous carbon bond.
8. The composition according to claim 7 , wherein the resin composition further comprises: c) a tertiary amine and/or an amine salt and wherein the tertiary amine is selected from the group consisting of octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, didodecylmonomethylamine, ditetradecylmonomethylamine, dihexadecylmonomethylamine, di-tallow alkylmonomethylamine, (hydrogenated tallow alkyl)-dimethylamine, trioctylamine, tridecylamine, tridodecylamine and mixtures thereof.
9. The composition according to claim 1 , wherein the resin composition further comprises: c) a tertiary amine and/or an amine salt.
10. The composition according to claim 9 , wherein the tertiary amine is selected from the group consisting of octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, didodecylmonomethylamine, ditetradecylmonomethylamine, dihexadecylmonomethylamine, di-tallow alkylmonomethylamine, (hydrogenated tallow alkyl)-dimethylamine, trioctylamine, tridecylamine, tridodecylamine and mixtures thereof.
11. The composition according to claim 1 , wherein the amount of organophosphorous compound; and any tertiary amine and/or quaternary ammonium salt present is in the range of from at least 0.1 to at most 5% w/w based on the total weight of polyester and organophosphorous compound; and any tertiary amine and/or quaternary ammonium salt present.
12. The composition according to claim 1 , wherein the organophosphorous compound is selected from the group of phosphonium salts having at least one phosphorous carbon bond and/or organophosphines having at least one phosphorous carbon bond, and wherein the resin composition further comprises: c) a tertiary amine and/or an amine salt and wherein the tertiary amine is selected from the group consisting of octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, didodecylmonomethylamine, ditetradecylmonomethylamine, dihexadecylmonomethylamine, di-tallow alkylmonomethylamine, (hydrogenated tallow alkyl)-dimethylamine, trioctylamine, tridecylamine, tridodecylamine and mixtures thereof, and wherein the amount of organophosphorous compound; and any tertiary amine and/or quaternary ammonium salt present is in the range of from at least 0.1 to at most 5% w/w based on the total weight of polyester and organophosphorous compound; and any tertiary amine and/or quaternary ammonium salt present.
13. A thermosetting powder coating composition comprising a resin composition as defined in claim 12 and a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester.
14. A thermosetting powder coating composition comprising a resin composition as defined in claim 1 and a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester.
15. A process for the preparation of the thermosetting powder coating composition as defined in claim 14 , comprising the steps of:
(a) mixing the resin composition comprising the organophosphorous compound and the branched amorphous carboxylic acid functional polyester with a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester of the resin composition, to obtain a premix;
(b) heating the obtained premix in an extruder, to obtain an extrudate;
(c) cooling down the extrudate obtained in step b) to obtain a solidified extrudate;
(d) grinding the obtained solidified extrudate into smaller particles to obtain the thermosetting powder coating composition and classifying the thus prepared powder particles via a sieve and collecting a sieve fraction with particle size below 130 μm.
16. A process for forming a coating on a substrate comprising the steps of applying a composition as defined in claim 14 onto the substrate and curing the composition to form the coating.
17. A powder coating prepared by partial or full cure of a thermosetting powder coating composition according to claim 14 .
18. A coated substrate comprising a coating derived upon curing of a composition as defined in claim 14 .
19. A resin composition comprising at least:
(a) 0.1 to 2% w/w of a quaternary phosphonium salt; and
(b) a branched amorphous carboxylic acid functional polyester, said polyester having a Tg of at least 40° C. as measured by Differential Scanning Calorimetry at a heating rate of 5° C./min, wherein said polyester comprises polycondensed residues derived from at least the following monomers:
bi) 18 to 35% mol of 2,2-dimethyl-1,3-propanediol;
bii) 5 to 17% mol of 1,2-propane diol as diol AD1;
biii) 3 to 7% mol of 1,6-hexanediol as diol AD2;
biv) 0.5 to 2% mol of trimethylol propane as a trifunctional monomer; and
bv) 32 to 45% mol of terephthalic acid; wherein
the % w/w is based on the total weight of the polyester and the quaternary phosphonium salt, and wherein
the % mol is based on the polyester, and wherein
the molar ratio of AD1 to AD2 (=mol AD1/mol AD2) in the polyester is at least equal or higher to 1 and at most equal to 10, and wherein
the polyester has:
an acid value (AV) as measured titrimetrically according to the ISO 2114-2000, between 14 and 120 mg KOH/g polyester, and
a hydroxyl value (OHV) as measured titrimetrically according to the ISO 4629-1978, less than 13 mg KOH/g polyester, and
a viscosity measured at 160° C. using as a cone and plate rheometer the Brookfield CAP 2000+, with spindle CAP-S-05 at 21 rpm (shear rate 70 s −1 ) of at most 150 Pa·s.
20. A resin composition according to claim 19 , wherein the quaternary phosphonium salt is triphenyl ethyl phosphonium bromide.
21. A thermosetting powder coating composition comprising a resin composition as defined in claim 20 and a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester.
22. A process for the preparation of the thermosetting powder coating composition as defined in claim 21 , comprising the steps of:
(a) mixing the resin composition comprising the triphenyl ethyl phosphonium bromide and the branched amorphous carboxylic acid functional polyester with a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester of the resin composition, to obtain a premix;
(b) heating the obtained premix in an extruder, to obtain an extrudate;
(c) cooling down the extrudate obtained in step b) to obtain a solidified extrudate;
(d) grinding the obtained solidified extrudate into smaller particles to obtain the thermosetting powder coating composition and classifying the thus prepared powder particles via a sieve and collecting a sieve fraction with particle size below 130 μm.
23. A process for forming a coating on a substrate comprising the steps of applying a composition as defined in claim 21 onto the substrate and curing the composition to form the coating.
24. A powder coating prepared by partial or full cure of a thermosetting powder coating composition according to claim 21 .
25. A coated substrate comprising a coating derived upon curing of a composition as defined in claim 21 .
26. A thermosetting powder coating composition comprising a resin composition as defined in claim 19 and a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester.
27. A process for the preparation of the thermosetting powder coating composition as defined in claim 26 , comprising the steps of:
(a) mixing the resin composition comprising the quaternary phosphonium salt and the branched amorphous carboxylic acid functional polyester with a crosslinker having functional groups that are reactive with the carboxylic acid groups of the polyester of the resin composition, to obtain a premix;
(b) heating the obtained premix in an extruder, to obtain an extrudate;
(c) cooling down the extrudate obtained in step b) to obtain a solidified extrudate;
(d) grinding the obtained solidified extrudate into smaller particles to obtain the thermosetting powder coating composition and classifying the thus prepared powder particles via a sieve and collecting a sieve fraction with particle size below 130 μm.
28. A process for forming a coating on a substrate comprising the steps of applying a composition as defined in claim 26 onto the substrate and curing the composition to form the coating.
29. A powder coating prepared by partial or full cure of a thermosetting powder coating composition according to claim 26 .
30. A coated substrate comprising a coating derived upon curing of a composition as defined in claim 26 .