Aqueous plastic material dispersions method for producing the same and use thereof

• US 20040077782A1
• Filed: 10/06/2003
• Published: 04/22/2004
• Est. Priority Date: 03/15/2001
• Status: Active Grant

• Current Assignee: Celanese Sales Germany GmbH (Celanese Corporation)
• Original Assignee: Carsten Heldmann, Harald Petri, Thomas Wirth
• Inventors: Wirth, Thomas, Petri, Harald, Heldmann, Carsten
• Granted Patent: US 7,078,455 B2
• Time in Patent Office: Days
• US Class Current: 524/804
• CPC Class Codes: C08J 2331/02 Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
• CPC Class Codes: C08J 3/005 Processes for mixing polymers
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C09D 131/04 Homopolymers or copolymers of vinyl acetate
• CPC Class Codes: C09D 143/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: Y10S 525/902 Core-shell

Abstract

Aqueous plastic material dispersions, method for producing the same and use thereof The present invention relates to aqueous plastic material dispersions based on vinyl ester copolymers, having a solids content of up to 80% by weight and a minimum film formation temperature below 20° C., which is substantially stabilized by ionic components, the vinyl ester copolymers containing at least one homo- or copolymer A and at least one homo- or copolymer B, methods for producing the same and the use thereof.

Claims

1. An aqueous plastic material dispersion based on a vinyl ester copolymer P, having a solids content of up to 80% by weight and a minimum film formation temperature below 20°

C., which is substantially stabilized by ionic components, the vinyl ester copolymer P comprising at least one homo- or copolymer A and at least one homo- or copolymer B, and

the homo- or copolymer A having a glass transition temperature in the range from 0 to 20°

C. and the homo- or copolymer B having a glass transition temperature in the range from 20 to 50°

C., provided that the glass transition temperatures of the two homo- or copolymers A and B differ by at least 10 K,

the sum of the amounts of the homo- or copolymers A and B in the vinyl ester copolymer P being at least 50% by weight, based on the copolymer P,

the weight ratio of homo- or copolymer A to homo- or copolymer B being in the range from 95/5 to 5/95 and

the homo- or copolymers A and B, independently of one another, containing in the form of copolymerized units

(a) from 50 to 100% by weight of at least one vinyl ester of carboxylic acids having 1 to 18 C atoms (M1) and

(b) from 0 to 25% by weight of at least one monoethylenically unsaturated, optionally halogen-substituted hydrocarbon having 2 to 4 C atoms (M2), based on the total mass of the monomers used for the preparation of the respective homo- or copolymer A and B,

characterized in that it comprises, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer P,

from 0 to 10% by weight of at least one ethylenically unsaturated, ionic monomer (M3) and

from 0 to 5% by weight of ionic emulsifiers (S1),

the total mass of ethylenically unsaturated, ionic monomers (M3) and ionic emulsifiers (S1) being at least 2% by weight.

2. The plastic material dispersion as claimed in claim 1, characterized in that it has a solids content which is in the range of from 20 to 80% by weight.

3. The plastic material dispersion as claimed in claim 1 or 2, characterized in that the sum of the amounts of the homo- or copolymers A and B in the vinyl ester copolymer P is from 75 to 100% by weight, based on the total mass of the copolymer P.

4. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that it has a pH in the range of from 2 to 9.

5. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the homo- or copolymers A and/or B contain, as vinyl esters of carboxylic acids having 1 to 18 carbon atoms (M1) incorporated in the form of polymerized units, 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 relatively long-chain, saturated and unsaturated fatty acids, vinyl esters of benzoic acid or of p-tert-butylbenzoic acid and mixtures thereof.

6. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the homo- or copolymers A and/or B contain vinyl acetate as vinyl esters of carboxylic acids having 1 to 18 carbon atoms (M1) incorporated in the form of polymerized units.

7. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the copolymers A and/or B contain ethene as monoethylenically unsaturated hydrocarbons having 2 to 4 carbon atoms (M2) incorporated in the form of copolymerized units.

8. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the amount of monoethylenically unsaturated hydrocarbons having 2 to 4 carbon atoms (M2) in the vinyl ester copolymer P is less than 20% by weight, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer P.

9. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the homo- or copolymers A and/or B contain, as ethylenically unsaturated, ionic monomers (M3) incorporated in the form of copolymerized units, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids or the monoesters thereof with C₁-C₁₂-alkanols, unsaturated sulfonic acids and/or unsaturated phosphonic acids.

10. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the vinyl ester copolymer P contains, incorporated as copolymerized units, up to 5% by weight, based on the total mass of the monomers used for the preparation of the vinyl ester copolymer P, at least one unsaturated, copolymerizable organic silicon compound (M4).

11. The plastic material dispersion as claimed in claim 10, characterized in that monomers containing siloxane groups and of the general formula RSi(CH₃)_0-2(OR¹)_3-1, in which R has the meaning CH₂═

CR²—

(CH₂)_0-1 or CH₂═

CR²CO₂—

(CH₂)1-3, R¹ straight-chain or branched, unsubstituted or substituted alkyl radical having 3 to 12 C atoms, which may be interrupted by an ether group, and R² is H or CH₃, are used as unsaturated, copolymerizable organosilicon compounds (M4).

12. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the vinyl ester copolymer P contains, incorporated in the form of copolymerized units, up to 5% by weight of ethylenically unsaturated, nonionic monomers (M5), based on the total mass of the monomers used for the preparation of the vinyl ester copolymer P.

13. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that the vinyl ester copolymers P contain, incorporated in the form of copolymerized units, 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 P.

14. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that it contains from 0.1 to 4% by weight of ionic emulsifiers (S1), based on the total mass of the monomers used for the preparation of the vinyl ester copolymer P.

15. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that it contains anionic emulsifiers as ionic emulsifiers (S1).

16. The plastic material dispersion as claimed in claim 15, characterized in that it contains alkali metal and ammonium salts of alkylsulfates, alkylphosphonates, sulfuric monoesters or phosphoric mono- and diesters of ethoxylated alkanols and ethoxylated alkylphenols, of alkanesulfonic acids and alkylarylsulfonic acids, and/or compounds of the general formula I

17. The plastic material dispersion as claimed in at least one of the preceding claims, characterized in that it contains nonionic emulsifiers (S2).

18. The plastic material dispersion as claimed in claims 12 and 17, characterized in that the ratio of the total amount of ionic components (M3) and (S1) to the total amount of nonionic components (M5) and (S2) used does not fall below the value 1.

19. The method for producing a plastic material dispersion as claimed in at least one of the preceding claims, characterized in that first homo- or copolymer B is prepared by aqueous, free radical emulsion polymerization and then the homo- or copolymer A is prepared in the aqueous dispersion of the homo- or copolymer B.

20. A method for producing a plastic material dispersion as claimed in at least one of claims 1 to 18, characterized in that the homo- or copolymers A and B are prepared separately by aqueous, free radical emulsion polymerization and are then mixed.

21. The use of a plastic material dispersion as claimed in at least one of claims 1 to 18 as an aqueous formulation for coating substrates.

22. The use of a plastic material dispersion as claimed in at least one of claims 1 to 18 as a binder in pigment-containing, aqueous formulations.

23. The use of a plastic material dispersion as claimed in at least one of claims 1 to 18 as a binder in synthetic resin-bound renders, tile adhesives, coating materials, joint sealing compounds, sealing compounds or paper coating slips.

24. The use of a plastic material dispersion as claimed in at least one of claims 1 to 18 as a binder in emulsion paints.

25. An aqueous formulation for coating substrates, comprising a plastic material dispersion as claimed in at least one of claims 1 to 18.

26. A pigment-containing, aqueous formulation comprising a plastic material dispersion as claimed in at least one of claims 1 to 18.

27. An emulsion paint, comprising a plastic material dispersion as claimed in at least one of claims 1 to 18.

28. Food coating, comprising a plastic material dispersion as claimed in at least one of claims 1 to 18.

29. A paper coating slip, comprising a plastic material dispersion as claimed in at least one of claims 1 to 18.