Fluorine-containing, silicon-containing polymer and surface treatment agent

Patent metadata

Field	Value
Publication number	US-9951166-B2
Application number	US-201414784444-A
Country	US
Kind code	B2
Filing date	Mar 31, 2014
Priority date	Apr 15, 2013
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

The present invention provides a fluorine-containing and silicon-containing polymer of the general formula (A) or (B) (wherein each symbol is as defined in the description) which is useful for forming a surface treatment layer having water-repellency, oil-repellency and antifouling property and excellent surface slip property.

First claim

The invention claimed is:

1. A fluorine-containing and silicon-containing polymer of the general formula (A) or (B):

wherein:
Rf 1 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;
R 1 is —(OC 4 F 8 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) c —(OCF 2 ) d —
wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least 1, and the occurrence order of the respective repeating units in parentheses is not limited in the formula;
R 2 is each independently at each occurrence a 2- to 7-valent organic group;
R 3 is each independently at each occurrence a divalent organic group;
R 4 is each independently at each occurrence R 4a or R 4b : provided that at least one of R 4 is R 4a ;
R 4a is each independently at each occurrence a divalent organic group having a curable moiety;
R 4b is each independently at each occurrence a divalent organic group having no curable moiety;
R 5 is each independently at each occurrence —O—, —S—, —NH— or a single bond;
R 6 is each independently at each occurrence a 2- to 7-valent organic group;
R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are, each independently, an alkyl group or an aryl group;
n1 is an integer of 1-50;
n3 and n4 are each independently an integer of 0-50, and the sum of n3 and n4 is one or more;
n2, n5 and n6 are each independently an integer of 0-500;
α is each independently an integer of 1-6; and
β is each independently an integer of 1-6.

2. The fluorine-containing and silicon-containing polymer according to claim 1 wherein in the formulae (A) and (B), R 2 is a divalent organic group, and α is 1.

3. The fluorine-containing and silicon-containing polymer according to claim 1 wherein in the formulae (A) and (B), R 6 is a divalent organic group, and β is 1.

4. The fluorine-containing and silicon-containing polymer according to claim 1 wherein in the formulae (A) and (B), R 2 is a divalent organic group, R 6 is a divalent organic group, and α and β are 1.

5. The fluorine-containing and silicon-containing polymer according to claim 1 wherein R 2 is
—(Q) e -(CFZ) f —(CH 2 ) g —
wherein Q is each independently at each occurrence an oxygen atom, phenylene, carbazolylene, —NR a — (wherein R a represents a hydrogen atom or an organic group) or a divalent organic group, Z is each independently at each occurrence a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, e, f and g are each independently an integer of 0-10, the sum of e, f and g is one or more, and the occurrence order of the respective repeating units in parentheses is not limited in the formula.

6. The fluorine-containing and silicon-containing polymer according to claim 1 which is a fluorine-containing and silicon-containing polymer of the following formula (A1) or (B1):

wherein:
Rf 1 , R 1 , R 3 , R 5 , R 7 , R 8 , R 9 , R 10 ,R 11 ,R 12 , R 13 , Z, n1, n2, n3, n4, n5 and n6 are as defined in claim 1 ;
R 6′ is a divalent organic group corresponding to R 6 in claim 1 ;
X 1 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1-10 carbon atoms which may be substituted by a fluorine atom;
f′ is each independently at each occurrence 0 or 1;
g′ is each independently at each occurrence 1 or 2; and
q1 is each independently at each occurrence an integer of 1-10.

7. The fluorine-containing and silicon-containing polymer according to claim 1 which is a fluorine-containing and silicon-containing polymer of the following formula (A2):

wherein:
Rf 1 , R 1 , R 6 , R 13 , n1 and n2 are as defined in claim 1 , and
R 6′ is a divalent organic group corresponding to R 6 in claim 1 .

8. The fluorine-containing and silicon-containing polymer according to claim 1 wherein R 1 is —(OCF 2 CF 2 CF 2 ) b — and b is an integer of 1-200.

9. The fluorine-containing and silicon-containing polymer according to claim 1 wherein R 1 is —(OCF 2 CF 2 CF 2 CF 2 ) a —(OCF 2 CF 2 CF 2 ) b —(OCF 2 CF 2 ) c —(OCF 2 ) d —, a and b are each independently an integer of 0-30, c and d are each independently an integer of 1-200, and the occurrence order of the respective repeating units in parentheses is not limited in the formula.

10. The fluorine-containing and silicon-containing polymer according to claim 1 wherein Rf 1 is a perfluoroalkyl group having 1-16 carbon atoms.

11. A process for producing the fluorine-containing and silicon-containing polymer of the formulae (A) and (B) according to claim 1 comprising
(1) cationic polymerizing a cationic polymerizable monomer in the presence of a perfluoropolyether group-containing cationic polymerization initiator and a Lewis acid, and
(2) stopping the cationic polymerization reaction by using an alkanol group-containing polysiloxane.

12. The process according to claim 11 wherein the alkanol group-containing polysiloxane is a compound

wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are as defined in claim 1 ;
n′ is an integer of 0-500; and
r″ is an integer of 1-20.

13. The process according to claim 12 wherein the alkanol group-containing polysiloxane has an average molecular weight of 100-20,000.

14. The process according to claim 11 wherein the alkanol group-containing polysiloxane has an average molecular weight of 100-20,000.

15. A surface treatment agent comprising one or more fluorine-containing and silicon-containing polymers according to claim 1 .

16. The surface treatment agent according to claim 15 further comprising at least one fluorine-containing oil of the following general formula (C):
Rf 2 —(OC 4 F 8 ) a′ —(OC 3 F 6 ) b′ —(OC 2 F 4 ) c′ —(OCF 2 ) d′ —Rf 3   (C)

wherein Rf 2 represents an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms,
Rf 3 represents a hydrogen atom, a fluorine atom, or an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms,
a′, b′, c′ and d′ are each independently an integer of 0 or more and 200 or less, the sum of a′, b′, c′ and d′ is at least one, and the occurrence order of the respective repeating units in parentheses is not limited in the formula,
at 40% by mass or less with respect to the total mass of the fluorine-containing and silicon-containing polymer and the fluorine-containing oil.

17. The surface treatment agent according to claim 16 further comprising a solvent at 5-10,000 parts by mass with respect to the total 100 parts by mass of the fluorine-containing and silicon-containing polymer, and the fluorine-containing oil.

18. The surface treatment agent according to claim 15 further comprising a solvent at 5-10,000 parts by mass with respect to the total 100 parts by mass of the fluorine-containing and silicon-containing polymer.

19. The surface treatment agent according to claim 15 further comprising an active energy curing initiator.

20. A curable composition comprising the fluorine-containing and silicon-containing polymer according to claim 1 ; and
a matrix forming composition.

21. The curable composit

Assignees

• Daikin Ind Ltd

Inventors

• Fukami Dai
• Yoshida Tomohiro
• Irita Tomomi
• Nagai Takabumi

Classifications

• C09D171/00

  Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain (based on polyacetals C09D159/00; based on epoxy resins C09D163/00; based on polythioether-ethers C09D181/02; based on polyethersulfones C09D181/06); Coating compositions based on derivatives of such polymers · CPC title

• C08G65/007

  containing fluorine · CPC title

• C08J5/00

  Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00) · CPC title

• C08G81/02

  at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds · CPC title

• C08J2343/04

  Homopolymers or copolymers of monomers containing silicon · CPC title