Coating composition
The present invention relates to an aqueous coating composition comprising a multi-aziridine compound and a carboxylic acid functional polymer, characterized in that (i) the composition is an aqueous dispersion having a pH ranging from 8 to 14, (ii) the aqueous dispersion comprises particles X which particles X comprise multi aziridine compound and particles Y which particles Y comprise carboxylic acid functional polymer, and (iii) said multi-aziridine compound has: a) from 2 to 6 of the following structural units A: b) one or more linking chains wherein each one of these linking chains links two of the structural units A; and c) a molecular weight in the range from 500 to 10000 Daltons.
1 . An aqueous coating composition comprising a multi-aziridine compound and a carboxylic acid functional polymer, wherein
(i) the aqueous coating composition is an aqueous dispersion having a pH ranging from 8 to 14,
(ii) the aqueous dispersion comprises particles X which particles X comprise multi-aziridine compound and particles Y which particles Y comprise carboxylic acid functional polymer, whereby the carboxylic acid functional polymer contains carboxylic acid groups and/or carboxylate groups, and
(iii) said multi-aziridine compound has:
a) from 2 to 6 of the following structural units A:
whereby
R 1 is H,
R 2 and R 4 are independently chosen from H or an aliphatic hydrocarbon group containing from 1 to 4 carbon atoms,
R 3 is an aliphatic hydrocarbon group containing from 1 to 4 carbon atoms,
m is an integer from 1 to 6,
R′ and R″ are according to (1) or (2):
(1) R′=H or an aliphatic hydrocarbon group containing from 1 to 14 carbon atoms, and
R″=an aliphatic hydrocarbon group containing from 1 to 14 carbon atoms, a cycloaliphatic hydrocarbon group containing from 5 to 12 carbon atoms, an aromatic hydrocarbon group containing from 6 to 12 carbon atoms, CH 2 —O—(C═O)—R′″, CH 2 —O—R″″, or CH 2 —(OCR′″″HCR′″″H) n —OR″″″, whereby R′″ is an aliphatic hydrocarbon group containing from 1 to 14 carbon atoms and R″″ is an aliphatic hydrocarbon group containing from 1 to 14 carbon atoms or an aromatic hydrocarbon group containing from 6 to 12 carbon atoms, n being from 1 to 35, R′″″ independently being H or an aliphatic hydrocarbon group containing from 1 to 14 carbon atoms and R″″″ being an aliphatic hydrocarbon group containing from 1 to 4 carbon atoms,
(2) R′ and R″ form together a saturated cycloaliphatic hydrocarbon group containing from 5 to 8 carbon atoms,
t is an integer from 0 to 3,
R 5 is H or CH 3 ,
X and Y are according to (I), (II) or (III):
(I) X and Y are both N—R 6 ;
(II) X is O and Y is N—R 6 ;
(III) X is N—R 6 and Y is O,
whereby R 6 is H or a linear or branched hydrocarbon group containing from 1 to 4 carbon atoms;
b) one or more linking chains wherein each one of these linking chains links two of the structural units A, whereby a linking chain is the shortest chain of consecutive atoms that links two structural units A; and
c) a calculated molecular weight in the range from 500 to 10000 Daltons, wherein the calculated molecular weight is the sum of the atomic masses of all atoms present in the structural formula of the multi-aziridine compound.
2 . The aqueous coating composition according to claim 1 , wherein R 2 is H, R 3 is CH 3 and R 4 is H.
3 . The aqueous coating composition according claim 1 , wherein R 2 is H, R 3 is CH 3 and R 4 is CH 3 .
4 . The aqueous coating composition according to claim 1 , wherein X is O, Y is NH, m is 1 and t is 0.
5 . The aqueous coating composition according to claim 1 , wherein the linking chains consist of from 4 to 300 atoms and the linking chains are a collection of atoms covalently connected which collection of atoms consists of i) carbon atoms, ii) carbon and nitrogen atoms, or iii) carbon, oxygen and nitrogen atoms.
6 . The aqueous coating composition according to claim 1 , wherein the multi-aziridine compound contains 2 or 3 structural units A.
7 . The aqueous coating composition according to claim 1 , wherein
R′ is H and R″=an alkyl group containing from 1 to 4 carbon atoms, CH2-O—(C═O)—R′″, CH2-O—R″″, or CH2-(OCH2CH2)n-OCH3, whereby R′″ is an alkyl group containing from 3 to 12 carbon atoms and R″″ is an alkyl group containing from 1 to 14 carbon atoms.
8 . The aqueous coating composition according to claim 1 , wherein the multi-aziridine compound comprises one or more connecting groups wherein each one of these connecting groups connects two of the structural units A, whereby the connecting groups consist of at least one functionality selected from:
aliphatic hydrocarbon functionality, cycloaliphatic hydrocarbon functionality, aromatic hydrocarbon functionality, functionality, isocyanurate iminooxadiazindione functionality, urethane functionality, urea functionality, biuret functionality and any combination thereof.
9 . The aqueous coating composition according to claim 8 , wherein the connecting groups consist of at least one aliphatic hydrocarbon functionality and/or at least one cycloaliphatic hydrocarbon functionality and optionally at least one aromatic hydrocarbon functionality and optionally an isocyanurate functionality or an iminooxadiazindione functionality.
10 . The aqueous coating composition according to claim 8 , wherein the connecting groups consist of at least one aliphatic hydrocarbon functionality and/or at least one cycloaliphatic hydrocarbon functionality and an isocyanurate functionality or an iminooxadiazindione functionality.
11 . The aqueous coating composition according to claim 1 , wherein the multi-aziridine compound comprises one or more connecting groups wherein each one of these connecting groups connects two of the structural units A, wherein the connecting groups consist of (i) at least two aliphatic hydrocarbon functionality and (ii) an isocyanurate functionality or an iminooxadiazindione functionality and wherein a pendant group is present on a connecting group, whereby the pendant group has the following structural formula:
wherein
n′ is the number of repeat units and is an integer from 1 to 50,
X is O or NH, preferably X is O,
R 7 and R 8 are independently H or CH 3 in each repeating unit,
R 9 is an aliphatic hydrocarbon group, preferably containing from 1 to 8 carbon atoms, and
R 10 is an aliphatic hydrocarbon group containing from 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon group containing from 5 to 20 carbon atoms or an aromatic hydrocarbon group containing from 6 to 20 carbon atoms.
12 . The aqueous coating composition according to claim 1 , wherein structural units A are according to the following structural formula D:
13 . The aqueous coating composition according to claim 1 , wherein the multi-aziridine compound is obtained by reacting at least a polyisocyanate and a compound B with the following structural formula:
whereby the molar ratio of compound B to polyisocyanate is from 2 to 6.
14 . The aqueous coating composition according to claim 13 , wherein the polyisocyanate is a polyisocyanate with aliphatic reactivity in which all of the isocyanate groups are directly bonded to aliphatic or cycloaliphatic hydrocarbon groups, irrespective of whether aromatic hydrocarbon groups are also present.
15 . The aqueous coating composition according to claim 12 , wherein the number of consecutive C atoms and optionally O atoms between the N atom of the urethane group in a structural unit D and the next N atom which is either present in the linking chain or which is the N atom of the urethane group of another structural unit D is at most 9.
16 . The aqueous coating composition according to claim 1 , wherein the multi-aziridine compound has a calculated molecular weight of from 600 to 5000 Daltons.
17 . The aqueous coating composition according to claim 1 , wherein the aqueous coating composition comprises aziridine functional molecules having a molecular weight lower than 580 Daltons in an amount lower than 0.5 wt. %, on the total weight of the aqueous coating composition, whereby the molecular weight is determined using LC-MS.
18 . The aqueous coating composition according to claim 1 , wherein the pH of the aqueous coating composition is in the range from 9.5 to 11.5.
19 . The aqueous coating composition according to claim 1 , wherein the amount of water in the aqueous coating composition is at least 15 wt. % on the total weight of the aqueous dispersion and at most 90 wt. % on the total weight of the aqueous coating composition.
20 . The aqueous coating composition according to claim 1 , wherein the amount of said multi-aziridine compound in the aqueous coating composition is at least 0.5 wt. % and at most 50 wt. % on the total solids content of the aqueous coating composition.
21 . The aqueous coating composition according to claim 1 , wherein the amounts of aziridinyl groups and of carboxylic acid groups and carboxylate groups are chosen such that the stoichiometric amount (SA) of aziridinyl groups on carboxylic acid groups and carboxylate groups is from 0.1 to 2.0.
22 . The aqueous coating composition according to claim 1 , wherein the solids content of the aqueous coating composition is at least 5 wt. %.
23 . The aqueous coating composition according to claim 1 , wherein the particles X comprising said multi-aziridine compound have a scatter intensity based average hydrodynamic diameter from 30 to 500 nanometer, determined using a method derived from ISO 22412:2017.
24 . The aqueous coating composition according to claim 1 , wherein the particles Y comprising said carboxylic acid functional polymer have a scatter intensity based average hydrodynamic diameter from 30 to 30000 nanometer, determined using a method derived from ISO 22412:2017.
25 . The aqueous coating composition according to claim 1 , wherein the carboxylic acid functional polymer is selected from the group consisting of vinyl polymers, polyacrylates, polymethacrylates, poly(acrylate-co-methacrylate)s and mixtures thereof.
26 . The aqueous coating composition according to claim 1 , wherein the carboxylic acid functional polymer is selected from the group consisting of polyurethanes, poly(urethane-co-acrylate)s, poly(urethane-co-methacrylate)s, poly(urethane-co-acrylate-co-methacrylate), polyureas, and mixtures thereof.
27 . The aqueous coating composition according to claim 1 , wherein the carboxylic acid functional polymer has an acid value of from 2 to 135 mg KOH/gram of the carboxylic acid functional polymer.
28 . The aqueous coating composition according to claim 1 , wherein the aqueous coating composition comprises a dispersant.
29 . The aqueous coating composition according to claim 1 , wherein the aqueous coating composition comprises a separate surface-active molecule component as dispersant in an amount ranging from 0.1 to 20 wt. %, on the total weight of the aqueous coating composition.
30 . The aqueous coating composition according to claim 29 , wherein the dispersant is a polymer having a number average molecular weight of at least 2000 Daltons and at most 1000000 Daltons and the polymer is a polyether, wherein the number average molecular weight is determined using MALDI-TOF mass spectrometry.
31 . The aqueous coating composition according to claim 1 , wherein the particles X neither comprise the carboxylic acid functional polymer nor other compounds crosslinkable with the multi-aziridine compound, and the particles Y do not comprise the multi-aziridine compound.
32 . The aqueous coating composition according to claim 31 , wherein the particles Y neither comprise the multi-aziridine compound nor other crosslinking compounds able to crosslink carboxylic acid functionality of the carboxylic acid functional polymer.
33 . The aqueous coating composition according to claim 32 , wherein the particles Y neither comprise the multi-aziridine compound nor other crosslinking compounds.
34 . The aqueous coating composition according to claim 1 , wherein the particles X neither comprise the carboxylic acid functional polymer nor other compounds crosslinkable with the multi-aziridine compound, and the particles Y neither comprise the multi-aziridine compound nor other compounds crosslinkable with carboxylic acid functionality of the carboxylic acid functional polymer.