Aqueous plastic dispersions, method for producing the same and their use
View Patent ↗Multistage polymers predominantly stabilized by nonionic emulsifiers and derived from hard and soft monomer compositions containing vinyl esters, of which at least one monomer composition must contain an unsaturated compromisable organosilicon compound, are described. The plastic dispersions can be used as binders in emulsion paints and finishes and impart to these excellent scrub resistance in addition to good blocking resistance.
1. An aqueous plastic dispersion based on a vinyl ester copolymer having a solids content of up to 80% by weight and a minimum film formation temperature below 20° C., the vinyl ester copolymer being characterized by the following features:
it is a multistage polymer and is derived from at least one homo- or copolymer A and at least one homo- or copolymer B,
the copolymer A is derived from a monomer composition A which would give a copolymer having a glass transition temperature in the range from 0 to 20° C.,
the homo- or copolymer B is derived from a monomer composition B which would give a homo- or copolymer having a glass transition temperature in the range from 20 to 50° C.,
monomer compositions A and B which give polymers A and B whose glass transition temperatures differ by at least 10 K are used,
the sum of the proportions of the polymers A and B in the vinyl ester copolymer are at least 50% by weight, based on the vinyl ester copolymer,
the weight ratio of monomer composition A to monomer composition B is in the range from 95/5 to 5/95,
the monomer composition A contains from 50 to 100% by weight of at least one vinyl ester of carboxylic acids having 1 to 18 carbon atoms (M1), based on the total mass of the monomers used in monomer composition A,
the monomer composition B contains from 50 to 100% by weight of at least one vinyl ester of carboxylic acids having 1 to 18 carbon atoms (M1), based on the total mass of the monomers used in monomer composition B,
at least one of the monomer compositions A or B contains from 0.05 to 10% by weight of at least one unsaturated, copolymerizable organosilicon compound (M4), based on the total mass of the monomers used in this monomer composition,
the vinyl ester copolymer contains, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, from 0 to 3% by weight of structural units derived from at least one ethylenically unsaturated, ionic monomer (M3),
the vinyl ester copolymer contains, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, from 0 to 10% by weight of structural units derived from at least one ethylenically unsaturated, nonionic monomer (M5),
the aqueous plastic dispersion contains from 0 to 3% by weight, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, of ionic emulsifiers (S1),
the aqueous plastic dispersion contains at least 0.5% by weight, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, of nonionic emulsifiers (S2), and
wherein the ratio of the total mass of ionic components (M3) and (S1) to the total mass of nonionic components (M5) and (S2) used assumes a value of from 0.0 to 0.9.
2. The plastic dispersion as claimed in claim 1 , which has a solids content which is in the range from 20 to 80% by weight.
3. The plastic dispersion as claimed in claim 1 , wherein the sum of the proportions of the homo- or copolymers A and B in the vinyl ester copolymer is from 75 to 100% by weight, based on the total mass of the copolymer.
4. The plastic dispersion as claimed in claim 1 , which has a pH in the range from 2 to 9.
5. The plastic dispersion as claimed in claim 1 , wherein the homo- or copolymers A and/or B contain, as vinyl esters of carboxylic acids having 1 to 18 carbon atoms (M1), vinyl esters of carboxylic acids having 1 to 8 carbon atoms, vinyl esters of saturated, branched monocarboxylic acids having 9, 10 or 11 carbon atoms in the acid radical, vinyl esters of saturated or unsaturated fatty acids, vinyl esters of benzoic acid or of p-tert-butyl benzoic acid and mixtures thereof incorporated in the form of polymerized units.
6. The plastic dispersion as claimed in claim 1 , wherein the homo- or copolymers A and/or B contain vinyl acetate incorporated in the form of polymerized units as vinyl esters of carboxylic acids having 1 to 18 carbon atoms (M1).
7. The plastic dispersion as claimed in claim 1 , wherein the copolymers A and/or B contain monoethylenically unsaturated and optionally halogenated hydrocarbons having 2 to 4 carbon atoms (M2) incorporated in the form of copolymerized units.
8. The plastic dispersion as claimed in claim 7 , wherein the proportion of monoethylenically unsaturated hydrocarbons having 2 to 4 carbon atoms (M2) in the vinyl ester copolymer, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, is less than 20% by weight.
9. The plastic dispersion as claimed in claim 1 , wherein the homo- or copolymers A and/or B contain, as ethylenically unsaturated, ionic monomers (M3), unsaturated monocarboxylic acids, unsaturated dicarboxylic acids or monoesters thereof with alkanols, unsaturated sulfonic acids and/or unsaturated phosphonic acids incorporated in the form of copolymerized units.
10. The plastic dispersion as claimed in claim 1 , wherein the copolymers derived from monomer composition A or the copolymers derived from monomer compositions A and B contain up to 10% by weight, based on the total mass of the monomers used in the monomer composition, structural units derived from at least one unsaturated, copolymerizable organosilicon compound (M4).
11. The plastic dispersion as claimed in claim 10 , wherein the copolymers derived from monomer composition A or the copolymers derived from monomer compositions A and B contain from 0.1 to 1.5% by weight, based on the total mass of the respective monomer composition, of structural units derived from at least one unsaturated, copolymerizable organosilicon compound (M4).
12. The plastic dispersion as claimed in claim 1 , wherein monomers containing siloxane groups and of the formula RSi(CH 3 ) 0-2 (OR 1 ) 3-1 are used as unsaturated, copolymerizable organosilicon compounds (M4), R having the meaning CH 2 ═CR 2 —(CH 2 ) 0-1 or CH 2 ═CR 2 —CO 2 —(CH 2 ) 1-3 , R 1 being a straight-chain or branched, optionally substituted alkyl radical having 1 to 12 carbon atoms which may optionally be interrupted by an ether group, and R 2 being H or CH 3 .
13. The plastic dispersion as claimed in claim 1 , wherein the vinyl ester copolymer contains up to 30% by weight of at least one further, ethylenically unsaturated monomer (M6), based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, incorporated in the form of copolymerized units.
14. The plastic dispersion as claimed in claim 1 , which contains anionic emulsifiers as ionic emulsifiers (S1).
15. The plastic dispersion as claimed in claim 14 , which contains as anionic emulsifiers, alkali metal and ammonium salts of alkylsulfates, alkylphosphonates, sulfuric acid monoesters or phosphoric acid mono- or diesters of ethoxylated alkanols and of ethoxylated alkylphenols, of alkanesulfonic acids and alkylarylsulfonic acids, and/or compounds of the formula 1
in which R 1 and R 2 are hydrogen or C 4 -C 24 -alkyl and are not simultaneously hydrogen, and X and Y are alkali metal ions and/or ammonium ions.
16. The plastic dispersion as claimed in claim 1 , which contains, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, from 1 to 8% by weight of nonionic emulsifiers (S2).
17. The plastic dispersion as claimed in claim 1 , which contains, as nonionic emulsifiers (S2), araliphatic and aliphatic nonionic emulsifiers.
18. The plastic dispersion as claimed in claim 17 , which contains, as nonionic emulsifiers (S2), ethoxylates of branched or straight-chain alkanols (alkyl radical: C 6 to C 22 , average degree of ethoxylation: from 3 to 50), ethoxylates based on natural alcohols, Guerbet alcohols or oxo alcohols having a linear or branched C 12 -C 18 -alkyl radical and a degree of ethoxylation 10 of from 8 to 50.
19. The plastic dispersion as claimed in claim 1 , which contain protective colloids.
20. The plastic dispersion as claimed in claim 19 , which contain polyvinyl alcohols.
21. A method for producing a plastic dispersion as claimed in claim 1 , wherein a homo- or copolymer B is first prepared by aqueous, free radical emulsion polymerization of a monomer or of a monomer mixture B and then the homo- or copolymer A is prepared in the aqueous dispersion of the homo- or copolymer B by free radical emulsion polymerization of a monomer or of a monomer mixture A, the free radical emulsion polymerization being carried out in the presence of nonionic emulsifiers (S2) and optionally in the presence of ethylenically unsaturated, ionic monomers (M3) and/or ionic emulsifiers (S1) so that the total mass of the nonionic emulsifiers (S2) in the end product is at least 0.5% by weight, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, and wherein the ratio of the total mass of ionic components (M3) and (S1) to the total mass of nonionic components (M5) and (S2) used assumes a value of from 0.0 to 0.9.
22. The method as claimed in claim 21 , wherein the free radical emulsion polymerization is effected in the presence of protective colloids.
23. The method as claimed in claim 21 , wherein the free radical emulsion polymerization is effected in the presence of substances regulating the molecular weight.
24. An aqueous preparation for coating substrates, containing a plastic dispersion as claimed in claim 1 .
25. A pigment-containing, aqueous preparation containing a plastic dispersion as claimed in claim 1 .
26. An emulsion paint containing a plastic dispersion as claimed in claim 1 .
27. A food coating containing a plastic dispersion as claimed in claim 1 .
28. A papercoating slip containing a plastic dispersion as claimed in claim 1 .
29. The plastic dispersion as claimed in claim 7 , wherein the monoethylenically unsaturated hydrocarbon is ethene.
30. A method for producing a plastic dispersion as claimed in claim 1 , wherein a homo- or copolymer A is first prepared by aqueous, free radical emulsion polymerization of a monomer or of a monomer mixture A and then the homo- or copolymer B is prepared in the aqueous dispersion of the homo- or copolymer A by free radical emulsion polymerization of a monomer or of a monomer mixture B, the free radical emulsion polymerization being carried out in the presence of nonionic emulsifiers (S2) and optionally in the presence of ethylenically unsaturated, ionic monomers (M3) and/or ionic emulsifiers (S1) so that the total mass of the nonionic emulsifiers (S2) in the end product is at least 0.5% by weight, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer, and wherein the ratio of the total mass of ionic components (M3) and (S1) to the total mass of nonionic components (M5) and (S2) used assumes a value of from 0.0 to 0.9.