Opacifying polymer particles

Patent metadata

Field	Value
Publication number	US-9574103-B2
Application number	US-201314652051-A
Country	US
Kind code	B2
Filing date	Dec 17, 2013
Priority date	Dec 20, 2012
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

An aqueous dispersion of pigmented opacifying polymer particles, the particles comprising: i. an inorganic core comprising dispersed inorganic pigment particle and a dispersant ii. a first layer of base-swellable polymer comprising acid groups encapsulating the core iii. a second layer of non-base-swellable polymer encapsulating the first layer wherein the dispersant comprises or consists of hydroxyl moieties; and carboxyl groups derived from itaconic acid.

First claim

The invention claimed is:

1. An aqueous dispersion of pigmented opacifying polymer particles, the particles comprising:
i) an inorganic core comprising a dispersed inorganic pigment particle and a dispersant,
ii) a first layer of a base-swellable polymer comprising acid groups encapsulating the core, and
iii) a second layer of a non-base-swellable polymer encapsulating the first layer;
wherein the dispersant is a polymer having a weight average molecular weight (Mw) of at least 1000 Daltons, and comprises hydroxyl moieties, and carboxyl groups derived from itaconic acid.

2. The aqueous dispersion according to claim 1 , further comprising an intermediate polymer layer at least one of between the pigment particle and the base-swellable polymer or between the base-swellable polymer and the non-base swellable polymer.

3. The aqueous dispersion according to claim 2 comprising an intermediate polymer layer between the pigment particle and the base swellable polymer layer and which is free of an intermediate polymer layer between the base swellable polymer layer and the non-base swellable polymer layer.

4. The aqueous dispersion according to claim 2 wherein the intermediate polymer layer has an acid value of from 0.1 to 65 mg KOH/g of polymer.

5. The aqueous dispersion according to claim 1 wherein the pigment particle is a titanium dioxide particle.

6. The aqueous dispersion according to claim 1 , wherein the dispersed inorganic particles have a mean particle diameter of from 75 to 300 nm.

7. The aqueous dispersion according to claim 6 , wherein the acid value of the dispersant is from 65 to 400 mg KOH/g non-volatile (non-vol.) dispersant.

8. The aqueous dispersion according to claim 1 , wherein the base swellable polymer is derived from one or more monomers selected from the group consisting of methacrylic acid, acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, cinnamic acid, fumaric acid, and beta carboxy ethyl acrylate.

9. The aqueous dispersion according to claim 1 , wherein the non-base swellable polymer is non-film forming at ambient temperature.

10. The aqueous dispersion according to claim 1 , wherein the Fox Tg of the non-base swellable polymer is at least 60° C.

11. The aqueous dispersion according to claim 1 , wherein said non-base swellable polymer comprises monomers selected from the group consisting of styrene, alpha methyl styrene, tert-butyl styrene, vinyl toluene, methyl methacrylate, acrylonitrile, methacrylonitrile, and mixtures thereof.

12. The aqueous dispersion according to claim 11 , wherein the non-base-swellable polymer contains 90-100% styrene monomer.

13. A coating composition comprising the aqueous dispersion according to claim 1 .

14. A substrate coated with the coating composition according to claim 13 .

15. A method of preparing the aqueous dispersion according to claim 1 , comprising:
i) dispersing an inorganic pigment in an aqueous medium using a dispersant of acid value at least 65 mg KOH/g of dispersant,
wherein the dispersant is a polymer having a weight average molecular weight (Mw) of at least 1000 Daltons and comprises carboxyl acid moieties of differing pKa derived from itaconic acid, and hydroxyl groups, wherein the pH during dispersion is greater than the pKa of the carboxyl moiety having the lower pKa and at least 0.25 pH units above or below the iso-electric point of the pigment, to form a stable aqueous dispersion of the pigment in the aqueous medium;

ii) adjusting the pH of the pigment dispersion to below the pKa of the acid moiety comprising the base swellable polymer of iii while satisfying the pH criteria of i;
iii) forming a first layer of a base swellable polymer on the pigment particles by polymerising monomers comprising acid groups;
iv) forming a second layer of a non-base swellable polymer;
v) optionally polymerising further monomers to form intermediate polymer layers having an acid value between 0 and 65 mg KOH/g polymer between at least one of the pigment and the first layer or the first and second layer;
vi) at least partially neutralising the first polymer, using a base, at a temperature above the Tg eff of the second layer of non-swellable polymer whereby the first layer of polymer is caused to swell; and,
vii) cooling the dispersion to a temperature below the Tg eff of the second layer.

16. The aqueous dispersion according to claim 4 , wherein the intermediate polymer layer comprises sodium styrene sulphonate.

17. The aqueous dispersion according to claim 1 , wherein the dispersed inorganic particles have a mean particle diameter of from 225 to 275 nm.

18. The aqueous dispersion according to claim 1 , wherein the Fox Tg of the non-base swellable polymer is from 90 to 140° C.

19. The aqueous dispersion according to claim 7 , wherein the base swellable polymer is derived from one or more monomers selected from the group consisting of methacrylic acid, acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, cinnamic acid, fumaric acid, and beta carboxy ethyl acrylate.

20. The aqueous dispersion according to claim 8 , wherein said non-base swellable polymer comprises monomers selected from the group consisting of styrene, alpha methyl styrene, tert-butyl styrene, vinyl toluene, methyl methacrylate, acrylonitrile, methacrylonitrile, and mixtures thereof.

Assignees

• Akzo Nobel Coatings Int Bv

Inventors

• Williams Neal St John
• Wheeler Stephen Arthur
• Bradley Robert David

Classifications

• C09C3/10

  Treatment with macromolecular organic compounds {(C09C3/006 takes precedence)} · CPC title

• C09D133/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• C08K2003/2241

  Titanium dioxide · CPC title

• C01P2006/33

  Phase transition temperatures · CPC title

• C09C1/3676

  Treatment with macro-molecular organic compounds · CPC title