Liquid repellent composition, liquid repellent processing method, and article having liquid repellent film

Patent metadata

Field	Value
Publication number	US-9834633-B2
Application number	US-21271608-A
Country	US
Kind code	B2
Filing date	Sep 18, 2008
Priority date	Mar 30, 2006
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

To provide a liquid repellent composition which is excellent in liquid repellency and durability and an article having a liquid repelling film. A liquid repellent composition comprising a copolymer (I) and a copolymer (II), characterized in that the copolymer (I) containing from 65 to 95 mass % of a polymerized unit (a) (referred to as “[a 1 ]”) and from 1 to 30 mass % of a polymerized unit (b); and the copolymer (II) containing from 25 to 80 mass % of a polymerized unit (a) (referred to as “[a 2 ]”) and from 1 to 50 mass % of a polymerized unit (c) are contained in an amount of the copolymer (I)/the copolymer (II)=10/90 to 95/5 (mass ratio), and [a 1 ]−[a 2 ]≧10 (mass %).

First claim

What is claimed is:

1. A liquid repellent composition comprising a copolymer (I) and a copolymer (II),
wherein the copolymer (I) comprises from 65 to 95 mass % of a polymerized unit (a), from 1 to 30 mass % of a polymerized unit (b), and from 0.1 to 20 mass % of a polymerized unit (d) based on the mass of the copolymer (I), wherein polymerized units of a monomer comprising a polyfluoroalkyl group having 7 or more carbon atoms are excluded, and the copolymer (I) does not comprise a polymerized unit (c);
the copolymer (II) comprises from 25 to 80 mass % of a polymerized unit (a) and from 1 to 50 mass % of a polymerized unit (c) based on the mass of the copolymer (II), wherein the copolymer (II) further comprises a polymerized unit (b) and a polymerized unit (d);
when a mass ratio of the polymerized unit (a) in the copolymer (I) to the copolymer (I) is [a 1 ], and a mass ratio of the polymerized unit (a) in the copolymer (II) to the copolymer (II) is [a 2 ], [a 1 ]−[a 2 ]≧10 (mass %); and
the copolymer (I) and the copolymer (II) are contained in a ratio of [mass ratio of the copolymer (I)]/[mass ratio of the copolymer (11)]=10/90 to 95/5:
polymerized unit (a): a polymerized unit derived from a monomer represented by (Z A —Y A ) n X A provided that Z A is a polyfluoroalkyl group having at most 6 carbon atoms, n is 1 or 2, provided that when n is 2, two (Z A —Y A ) may be the same or different, X A is —CR═CH 2 , —COOCR═CH 2 , —OCOCR═CH 2 , —OCH 2 —N—CR═CH 2 or —OCH═CH 2 when n is 1, and ═CH(CH 2 ) m CR═CH 2 , ═CH(CH 2 ) m COOCR═CH 2 , ═CH(CH 2 ) m OCOCR═CH 2 or —OCOCH═CHCOO— when n is 2, wherein R is a hydrogen atom, a methyl group or a halogen atom, N is a phenylene group, and m is an integer of from 0 to 4, and Y A is a bivalent organic group or a single bond;
polymerized unit (b): a polymerized unit derived from a monomer represented by Z B —X B provided that Z B is a hydrocarbon group having at least 14 carbon atoms, and X B is the same as X A ;
polymerized unit (c): a polymerized unit derived from a monomer having no polyfluoroalkyl group and having a cross-linkable functional group;
nonionic surfactant made of a compound having at least one carbon-carbon triple bond and at least one hydroxyl group in its molecule; and
polymerized unit (d): a polymerized unit derived from a monomer having a polymerizable group, other than the polymerized units (a), (b) and (c).

2. The liquid repellent composition according to claim 1 , further comprising a surfactant (e3):
Surfactant (e3): a cationic surfactant represented by formula s 71 :
[(R 21 ) 4 N + ].X −   (formula s 71 ),

wherein R 21 is a hydrogen atom, a C 1-22 alkyl group, a C 2-22 alkenyl group, a C 1-9 fluoroalkyl group or a polyoxyalkylene chain having a hydroxyl group at a terminal, four R 21 may be the same or different, provided that four R 21 may not be hydrogen atoms at the same time, and X − is a counter ion.

3. A liquid repellent processing method, comprising applying to a surface, the liquid repellent composition as defined in claim 1 .

4. An article comprising a liquid repellent film formed by means of the liquid repellent composition as defined in claim 1 .

5. The liquid repellent composition according to claim 1 , wherein Z A is a polyfluoroalkyl group wherein at least from 20 to 80% of hydrogen atoms in an alkyl group of the polyfluoroalkyl group are substituted by fluorine.

6. The liquid repellent composition according to claim 1 , wherein Z A is at least one group selected from the group consisting of F(CF 2 ) 4 —, F(CF 2 ) 5 —, F(CF 2 ) 6 —, (CF 3 ) 2 CF(CF 2 ) 2 —, H(CF 2 ) 6 —, HCF 2 CF 2 —, Cl(CF 2 ) 4 — and CF 3 CF═CFCF 2 CF═CF—.

7. The liquid repellent composition according to claim 1 , wherein Z B is at least one group selected form the group consisting of a tetradecyl group, a cetyl group, a heptadecyl group, a stearyl group, an icosyl group, a behenyl group, a lauroyl group, a tetracocyl group, a montanyl group and a stearoyl group.

8. The liquid repellent composition according to claim 1 , wherein a content of the polymerized unit (a) in copolymer (I) is 70 to 90 mass %.

9. The liquid repellent composition according to claim 1 , wherein a content of the polymerized unit (a) in copolymer (II) is 30 to 75 mass %.

10. The liquid repellent composition according to claim 1 , wherein a content of the polymerized unit (c) in copolymer (II) is 1 to 35 mass %.

11. The liquid repellent composition according to claim 1 , wherein the copolymer (I) and the copolymer (II) exist as separate particles.

12. The liquid repellent composition according to claim 1 , wherein the copolymer (I) and the copolymer (II) exist in the same particle.

13. The liquid repellent composition according to claim 12 , wherein the copolymer (I) and the copolymer (II) exist as a core-shell structure.

14. The liquid repellent composition according to claim 12 , wherein the copolymer (I) and the copolymer (II) exist as sea-island structure.

15. The liquid repellent composition according to claim 13 , wherein the copolymer (II) is a shell part.

16. The liquid repellent composition according to claim 1 , wherein Z A is a polyfluoroalkyl group having from 4 to 6 carbon atoms.

17. The liquid repellent composition according to claim 1 , wherein Z A is a polyfluoroalkyl group having 6 carbon atoms.

18. The liquid repellent composition according to claim 1 , wherein the copolymer (I) and the copolymer (II) are dispersed in a medium comprising water and at least one compound selected from the group consisting of a glycol and a glycol ether.

19. The liquid repellent composition according to claim 1 , wherein the copolymer (I) and the copolymer (II) are dispersed in a medium comprising water and dipropylene glycol.

20. The liquid repellent composition according to claim 2 , further comprising a surfactant (e1):
Surfactant (e1): at least one surfactant selected from a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, a polyoxyalkylene monoalkapolyenyl ether and a polyoxyalkylene monopolyfluoroalkyl ether.

21. The liquid repellent composition according to claim 1 , wherein [a 1 ]−[a 2 ] is 16 mass % or less.

22. The liquid repellent composition according to claim 1 , wherein the polymerized units (a) included in the copolymer (I) and the copolymer (II) are derived from C 6 F 13 C 2 H 4 OCOC(CH 3 )═CH 2 , the polymerized units (c) included in the copolymer (II) are derived from 3,5-dimethyl pyrazole adduct of 2-isocyanate ethyl methacrylate, and the polymerized units (d) included in the copolymer (I) and the copolymer (II) are derived from vinyl chloride.

Assignees

• Furuta Shoji
• Shimada Minako
• Kaneko Kyouichi
• Sugiyama Kazunori
• Asahi Glass Co Ltd

Inventors

• Furuta Shoji
• Shimada Minako
• Kaneko Kyouichi
• Sugiyama Kazunori

Classifications

• C09D133/16

  Homopolymers or copolymers of esters containing halogen atoms · CPC title

• C08F220/325

  containing glycidyl radical, e.g. glycidyl (meth)acrylate · CPC title

• C09K3/18

  for application to surfaces to minimize adherence of ice, mist or water thereto (rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30); Thawing or antifreeze materials for application to surfaces (used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00) · CPC title

• D06M2200/12

  Hydrophobic properties · CPC title

• C08F220/365

  containing further carboxylic moieties · CPC title