Aqueous binder compositions
The present invention relates to aqueous binder compositions which are based on aqueous multistage polymer dispersions, to the uses of such binder compositions, and to coating compositions comprising them. The aqueous binder composition comprises: a) a polymer P in the form of an aqueous multistage polymer dispersion of dispersed polymer particles, where the polymer particles comprise a first polymer having a glass transition temperature of at least 30° C. and being made of ethylenically unsaturated monomers M-A, and a second polymer having a glass transition temperature of not more than 20° C. and being made of ethylenically unsaturated monomers M-B, where the ethylenically unsaturated monomers M-A and M-B together comprise: i. 85% to 99.45% by weight, preferably 87.5% to 97% by weight and in particular 90% to 95.5% by weight, based in each case on the total amount of monomers M-A+M-B, of at least one neutral, monoethylenically unsaturated monomer M1 having a solubility in water of at most 50 g/l at 25° C. and 1 bar; ii. 0.5% to 10% by weight, preferably 1% to 7.5% by weight and in particular 1.5% to 6.5% by weight, based in each case on the total amount of monomers M-A+M-B, of at least one neutral, monoethylenically unsaturated monomer M2 having a solubility in water of at least 100 g/l at 25° C. and 1 bar; iii. 0.05 to 0.5% by weight, preferably 0.15% to 0.5% by weight and in particular 0.3% to 0.5% by weight, based in each case on the total amount of monomers M-A+M-B, of one or more monoethylenically unsaturated monomers M3 having an acidic group; and iv. optionally from 0 to 5% by weight and in particular from 0 to 4.5% by weight, based in each case on the total amount of monomers M-A+M-B, of one or more monomers M4 having at least two non-conjugated ethylenically unsaturated double bonds; and b) at least one carbodiimide having at least two carbodiimide moieties, which are bound to an aliphatic carbon atom.
1. An aqueous binder composition, comprising:
a) a polymer P in a form of an aqueous multistage polymer dispersion of dispersed polymer particles,
and
b) a carbodiimide comprising at least two carbodiimide moieties, which are bound to an aliphatic carbon atom,
wherein
the polymer particles comprise
a first polymer having a glass transition temperature of at least 30° C. and being made of ethylenically unsaturated monomers M-A, and
a second polymer having a glass transition temperature of not more than 20° C. and being made of ethylenically unsaturated monomers M-B; and
the ethylenically unsaturated monomers M-A and M-B together comprise
i. from 85% to 99.45% by weight, based on a total amount of monomers M-A and M-B, of at least one neutral, monoethylenically unsaturated monomer M1 having a solubility in water of at most 50 g/l at 25° C. and 1 bar,
ii. from 0.5% to 10% by weight, based on the total amount of monomers M-A and M-B, of at least one neutral, monoethylenically unsaturated monomer M2 having a solubility in water of at least 100 g/l at 25° C. and 1 bar,
iii. from 0.05 to 0.5% by weight, based on the total amount of monomers M-A and M-B, of one or more monoethylenically unsaturated monomers M3 comprising an acidic group, and
iv. optionally from 0 to 5% by weight, based on the total amount of monomers M-A and M-B, of one or more monomers M4 comprising at least two non-conjugated ethylenically unsaturated double bonds.
2. The aqueous binder composition of claim 1 , wherein the first polymer is present in an amount of from 5 to 50% by weight, based on a total weight of the first polymer and the second polymer.
3. The aqueous binder composition of claim 1 , wherein the monomers M-A comprise
i. from 80 to 99.4% by weight, based on a total amount of monomers M-A of at least one neutral, monoethylenically unsaturated monomer M1 having a solubility in water of at most 50 g/l at 25° C. and 1 bar;
ii. from 0.5% to 20% by weight, based on the total amount of monomers M-A, of at least one neutral, monoethylenically unsaturated monomer M2 having a solubility in water of at least 100 g/l at 25° C. and 1 bar, and
iii. from 0.1 to 2% by weight, based on the total amount of monomers M-A, of one or more monoethylenically unsaturated monomers M3 comprising an acidic group.
4. The aqueous binder composition of claim 1 , wherein the monomers M-B comprise from 90 to 100% by weight, based on a total amount of monomers M-B, of at least one neutral, monoethylenically unsaturated monomer M1 having a solubility in water of at most 50 g/l at 25° C. and 1 bar.
5. The aqueous binder composition of claim 4 , wherein the monomers M-B comprise from 0.1 to 10% by weight, based on the total amount of monomers M-B, of one or more monomers M4 comprising at least two non-conjugated ethylenically unsaturated double bonds.
6. The aqueous binder composition of claim 1 , wherein the first polymer has a number average molecular weight of from 2000 to 100000 g/mol.
7. The aqueous binder composition of claim 1 , wherein the polymer P has an acid number of not more than 10 mg KOH.
8. The aqueous binder composition of claim 1 , wherein the polymer particles of the aqueous multistage polymer dispersion have a volume average diameter, determined by light scattering, of from 10 to 500 nm.
9. The aqueous binder composition of claim 1 , wherein the aqueous multistage polymer dispersion is obtained by aqueous radical emulsion polymerization of the monomers M-B in the presence of the first polymer.
10. The aqueous binder composition of claim 1 , wherein the aqueous multistage polymer dispersion is obtained by sequential aqueous radical emulsion polymerization, which comprises
(1) aqueous emulsion polymerization of the monomers M-A to obtain an aqueous dispersion of the first polymer and
(2) aqueous emulsion polymerization of the monomers M-B in the aqueous dispersion of the first polymer.
11. The aqueous binder composition of claim 1 , wherein the monomers M1 are selected from the group consisting of esters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids with C 1 -C 10 alkanols, and vinylaromatic hydrocarbons.
12. The aqueous binder composition of claim 1 , wherein the monomers M2 are selected from the group consisting of hydroxy-C 2 -C 4 alkyl esters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, primary amides of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, esters of hydroxy-C 3 -C 10 -alkylketones with monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, amides of amino-C 3 -C 10 -alkylketones with monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, monoesters of monoethylenically unsaturated C 3 -C 8 carboxylic acids with polyoxy-C 2 -C 4 alkylene ethers, and monoethylenically unsaturated monomers comprising a urea group.
13. The aqueous binder composition of claim 1 , wherein the monomers M3 are selected from the group consisting of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, and monoethylenically unsaturated C 4 -C 8 dicarboxylic acids.
14. The aqueous binder composition of claim 1 , wherein the monomers M4 are selected from the group consisting of diesters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids with saturated aliphatic or cycloaliphatic diols, monoesters of monoethylenically unsaturated C 3 C 8 monocarboxylic acids with monoethylenically unsaturated aliphatic or cycloaliphatic monohydroxy compounds, and divinyl aromatic compounds.
15. The aqueous binder composition of claim 1 , wherein the carbodiimide is present in an amount of from 0.1 to 30% by weight, based on a weight of the polymer P.
16. The aqueous binder composition of claim 1 , wherein the carbodiimide comprises poly-C 2 -C 3 -alkylene oxide groups.
17. The aqueous binder composition of claim 1 , wherein the carbodiimide is an aliphatic carbodiimide, which comprises a structural unit represented by:
18. The aqueous binder composition of claim 1 , wherein the carbodiimide comprises from 2 to 20% by weight of N═C≡N moieties, based on a weight of the carbodiimide.
19. A n aqueous multistage polymer dispersion of dispersed polymer particles, wherein
polymer P particles comprise a first polymer having a glass transition temperature of at least 30° C. and being made of ethylenically unsaturated monomers M-A, and a second polymer having a glass transition temperature of not more than 20° C. and being made of ethylenically unsaturated monomers M-B,
the polymer particles comprise:
a) the first polymer of from 5 to 50% by weight, based on a total weight of the first polymer and the second polymer, where the monomers M-A consist of:
i. from 80 to 99.4% by weight, based on a total amount of monomers M-A of at least one neutral, monoethylenically unsaturated monomer M1 having a solubility in water of at most 50 g/l at 25° C. and 1 bar;
ii. from 0.5% to 20% by weight, based on the total amount of monomers M-A, of at least one neutral, monoethylenically unsaturated monomer M2 having a solubility in water of at least 100 g/l at 25° C. and 1 bar; and
iii. from 0.1 to 2% by weight, based on the total amount of monomers M-A, of one or more monoethylenically unsaturated monomers M3 having an acidic group; and
b) the second polymer of from 50 to 95% by weight, based on the total weight of the first polymer and the second polymer where the monomers M-B comprise
iv. from 90 to 100% by weight, based on a total amount of monomers M-B, of at least one neutral, monoethylenically unsaturated monomer M1 having a solubility in water of at most 50 g/l at 25° C. and 1 bar; and
v. optionally from 0 to 10% by weight, based on the total amount of monomers M-B, of one or more monomers M4 comprising at least two non-conjugated ethylenically unsaturated double bonds, and
the polymer P is defined in claim 1 .
20. The aqueous multistage polymer dispersion of claim 19 , wherein the monomers M-B comprise from 0.1 to 10% by weight, based on the total amount of monomers M-B, of one or more monomers M4 comprising at least two non-conjugated ethylenically unsaturated double bonds.
21. The aqueous multistage polymer dispersion of claim 19 , wherein the first polymer has a number average molecular weight of from 2000 to 100000 g/mol.
22. The aqueous multistage polymer dispersion of claim 19 , wherein the polymer P has an acid number of not more than 10 mg KOH.
23. The aqueous multistage polymer dispersion of claim 19 , wherein the polymer particles of the aqueous multistage polymer dispersion have a volume average diameter, determined by light scattering, of from 10 to 500 nm.
24. The aqueous multistage polymer dispersion of claim 19 , wherein the aqueous multistage polymer dispersion is obtained by aqueous radical emulsion polymerization of the monomers M-B in the presence of the first polymer.
25. The aqueous multistage polymer dispersion of claim 19 , wherein the aqueous multistage polymer dispersion is obtained by sequential aqueous radical emulsion polymerization, which comprises
(1) aqueous emulsion polymerization of the monomers M-A to obtain an aqueous dispersion of the first polymer, and
(2) aqueous emulsion polymerization of the monomers M-B in the aqueous dispersion of the first polymer.
26. The aqueous multistage polymer dispersion of claim 19 , wherein the monomers M1 are selected from the group consisting of esters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids with C 1 -C 10 alkanols, and vinylaromatic hydrocarbons.
27. The aqueous multistage polymer dispersion of claim 19 , wherein the monomers M2 are selected from the group consisting of hydroxy-C 2 -C 4 alkyl esters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, primary amides of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, esters of hydroxy-C 3 -C 10 -alkylketones with monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, amides of amino-C 3 -C 10 -alkylketones with monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, monoesters of monoethylenically unsaturated C 3 -C 8 carboxylic acids with polyoxy-C 2 -C 4 alkylene ethers, and monoethylenically unsaturated monomers comprising a urea group.
28. The aqueous multistage polymer dispersion of claim 19 , wherein the monomers M3 are selected from the group consisting of monoethylenically un-saturated C 3 -C 8 monocarboxylic acids and monoethylenically unsaturated C 4 -C 8 dicarboxylic acids.
29. The aqueous multistage polymer dispersion of claim 19 , wherein the monomers M4 are selected from the group consisting of diesters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids with saturated aliphatic or cycloaliphatic diols, monoesters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids with monoethylenically unsaturated aliphatic or cycloaliphatic monohydroxy compounds, and divinyl aromatic compounds.
30. A coating composition, comprising: the aqueous binder composition of claim 1 .
31. The coating composition according to claim 30 , further comprising: at least one additional binder selected from the group consisting of a polyurethane binder, a polyester binder, and an aldehyde resin.