Claims
- 1. Method of preparing aqueous microemulsions of vinyl resins having carboxylic or sulfonic groups therein which comprises vigorously blending said resins with a water-miscible base, water, at least one organic water-miscible solvent which has an affinity for said resins and a boiling point below about 160.degree. C., and an organic, water-miscible co-solvent which is a poor solvent for said resins but is miscible with the organic solvent and has a boiling point above that of the organic solvents and water.
- 2. Method of preparing aqueous microemulsions of vinyl resins having an average particle size of about 0.02 to about 0.14 microns which comprises blending:
- (A) a normally solid vinyl resin containing carboxylic or sulfonic acid groups and having the following moieties copolymerized herein ##STR14## wherein m and n are percentages each having a value of 0-99%; t is a percentage having a value of 0-59%;
- p is a percentage having a value of 1-30%; when q=0;
- q is a percentage having a value of 1-30%; when p=0 with the proviso that m+n+t is .gtoreq.70 and .ltoreq.99%, that m+n+t+p+q=100%, that when m=0, n is at least 1 and that when n=0, m is at least 1; wherein X is a monovalent radical selected from the group consisting of --H and lower alkyls having 1-4 carbons;
- W is a monovalent radical selected from the group consisting of --H, lower alkyls, aryl having 6 to about 9 carbons, ##STR15## wherein a is an integer having values of 1-3, ##STR16## --OR wherein R is a C.sub.1 -C.sub.18 alkyl, ##STR17## wherein R.sub.1 is a monovalent radical selected from the group consisting of --H, methyl or ethyl, and --CN;
- Y is a monovalent radical selected from the group consisting of --H, methyl; ##STR18## wherein b is an integer having values of 0-4; and Z is a monovalent radical selected from the group consisting of ##STR19## --SO.sub.3 H and --C.sub.6 H.sub.4 --SO.sub.3 H, with the proviso that Y and Z are never --COOH and --SO.sub.3 H at the same time,
- (B) sufficient water miscible base to neutralize about 10% to 100% of said carboxylic or sulfonic acid groups,
- (C) 1 to about 200 parts, per 100 parts by weight of vinyl resin of a water-miscible normally liquid solvent for said vinyl resin having a boiling point of up to 160.degree. C., selected from the group consisting of lower aliphatic ketones, esters or ethers having 3 to about 6 carbon atoms and cycloaliphatic ketones or ethers having 4 to about 6 carbon atoms;
- (D) 1 to about 200 parts, per 100 parts by weight of vinyl resin, of a normally liquid co-solvent which is a poor solvent for said vinyl resin and miscible with water and solvent (C), having a boiling point greater than that of solvent (C), selected from the group consisting of:
- (1) glycol monoalkyl ethers having the formula:
- HO--CHR"CHR'"O).sub.r R""
- where each of R", R'" is H or CH.sub.3, r is an integer having values of 1 to 3 and R"" is an alkyl group having 1 to about 4 carbon atoms,
- (2) aliphatic acidic ethers having the formula:
- R""' O--CH.sub.2).sub.r COOH
- wherein R""' is an alkyl group having 1 to 4 carbon atoms
- (3) amino esters having the formula: ##STR20## (4) amino ketones having the formula: ##STR21## (5) aliphatic alcohols having the formula:
- R.sub.2 OH, where R.sub.2 is alkyl having 1 to 5 carbons,
- (6) aliphatic carboxylic acids having the formula: ##STR22## where R.sub.3 is H or alkyl having 1 to 4 carbons, (7) aliphatic amines having the formula: ##STR23## where R.sub.4 and R.sub.5 are H or alkyl having 1 to 6 carbons and R.sub.6 is alkyl having 1 to 6 carbons with the proviso that the total number of carbons in the sum of R.sub.4 +R.sub.5 +R.sub.6 .ltoreq.6,
- (8) aliphatic amino ethers having the formula:
- R.sub.7 O--CH.sub.2).sub.g ].sub.r NH.sub.3-r
- where R.sub.7 is methyl or ethyl, and g has values of 1-4,
- (9) aliphatic dialkyl amides having the formula:
- R.sub.8 CON(R.sub.7).sub.2
- where R.sub.8 is H or alkyl having 1 to 5 carbons,
- (10) N-(Hydroxymethyl)acrylamide and N-hydroxymethyl(methacrylamide having the formula:
- CH.sub.2 .dbd.CR.sub.9 CONHCH.sub.2 OH
- where R.sub.9 is H or --CH.sub.3,
- (11) cycloaliphatic ether alcohols having the formula: ##STR24## where R.sub.10 is alkylene having 1 to 3 carbons and v is an integer having values of 1 to 5,
- (12) hydroxy esters having the formula: ##STR25## (13) hydroxy ketones having the formula: ##STR26## (E) sufficient water to provide an aqueous microemulsion having a total solids content of up to about 60% by weight.
- 3. Method claimed in claim 2 wherin the vinyl resin contains about 60 to about 91 weight % vinyl chloride, about 10 to about 25 weight % vinyl acetate and about 1 to about 15% carboxyl-containing ethylenically unsaturated hydrocarbon.
- 4. Method claimed in claim 3 wherein the carboxyl-containing ethylenically unsaturated hydrocarbon is maleic acid or fumaric acid.
- 5. Method claimed in claim 3 wherein the vinyl resin contains about 75 to about 99 weight % vinyl chloride about 1 to about 25% acrylic or methacrylic acid copolymerized therein.
- 6. Method claimed in claim 2 wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/glycidyl acrylate or methacrylate terpolymer is used.
- 7. Method claimed in claim 2 wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/hydroxyalkyl acrylate or methyacrylate having 2 to 3 carbons in the alkyl group is used.
- 8. Method claimed in claim 2 wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/vinyl alcohol terpolymer is used.
- 9. Method claimed in claim 2 wherein the vinyl resin is a terpolymer of vinyl chloride, vinylidene chloride and an ethylenically unsaturated carboxylic acid.
- 10. Method claimed in claim 9 wherein the ethylenically unsaturated carboxylic acid is maleic acid or fumaric acid.
- 11. Method claimed in claim 9 wherein the ethylenically unsaturated carboxylic acid is acrylic or methacrylic acid.
- 12. Method claimed in claim 2 wherein the vinyl resin is a copolymer of vinyl chloride and an ethylenically unsaturated carboxylic acid.
- 13. Method claimed in claim 2 wherein the ethylenically unsaturated carboxylic acid is acrylic or methacrylic acid.
- 14. Method claimed in claim 2 wherein the vinyl resin is a copolymer of vinylidene chloride and an ethylenically unsaturated carboxylic acid.
- 15. Method claimed in claim 2 wherein the vinyl resin (A) is first dissolved in the solvent (C) and co-solvent (D), contacted with base (B) and then emulsified with water.
- 16. Method claimed in claim 2 wherein the vinyl resin (A) is pulverized and added to a mixture of base (B), solvent (C), co-solvent (D) and water with vigorous agitation.
- 17. Method claimed in claim 2 wherein a crosslinking amount of a thermosetting resin is blended into the microemulsion.
- 18. Method claimed in claim 17 wherein the thermosetting resin is an epoxy resin.
- 19. Method claimed in claim 17 wherein the thermosetting resin is a hexamethoxymethylmelamine.
- 20. Method claimed in claim 17 wherein the thermosetting resin is a methylated urea-formaldehyde resin.
- 21. Microemulsion obtained by the method claimed in claim 2.
Parent Case Info
This is a continuation-in-part of Ser. No. 846,541 filed Oct. 28, 1977 now abandoned.
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
3146122 |
Renner et al. |
Aug 1964 |
|
3357938 |
Eisenwiener |
Dec 1967 |
|
3694365 |
Custner |
Sep 1972 |
|
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
846541 |
Oct 1977 |
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