Fluorochemical coating composition and article treated therewith

Patent metadata

Field	Value
Publication number	US-11053410-B2
Application number	US-201514661256-A
Country	US
Kind code	B2
Filing date	Mar 18, 2015
Priority date	Mar 31, 2014
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

A fluorochemical coating composition is provided comprising (A) a hydrolyzable group-containing silane modified with a fluorooxyalkylene-containing polymer and (B) a fluorooxyalkylene-containing polymer having an average molecular weight not higher than the average molecular weight of component (A) in a weight ratio (A)/(B) of 40/60 to 95/5. The composition forms on a substrate a water/oil repellent layer which does not detract from the visibility of the substrate.

First claim

The invention claimed is:

1. A fluorochemical coating composition comprising:
(A) a hydrolyzable group-containing silane modified with a fluorooxyalkylene-containing polymer and/or a partial hydrolytic condensate thereof, and
(B) a fluorooxyalkylene-containing polymer having an average molecular weight not higher than the average molecular weight of component (A), in a weight ratio (A)/(B) of 40/60 to 95/5,
wherein a weight average molecular weight of component (B) is 0.25 to 1 times a weight average molecular weight of component (A),
wherein the hydrolyzable group-containing silane modified with a fluorooxyalkylene-containing polymer (A) is at least one member selected from fluorooxyalkylene-containing polymer-modified silanes having the general formulae (3), (4), (6) and (7):
A-Rf-QZW α   (3)

Rf-(QZW α ) 2   (4)

wherein Rf is —(CF 2 ) d —(OCF 2 ) p (OCF 2 CF 2 ) q (OCF 2 CF 2 CF 2 ) r —(OCF 2 CF 2 CF 2 CF 2 ) s (OCF(CF 3 )CF 2 ) t —O—(CF 2 ) d —, d is independently an integer of 0 to 5, p, q, r, s and t are each independently an integer of 0 to 200, p+q+r+s+t is an integer of 10 to 200, individual units in parentheses may be randomly arranged,
α is an integer of 1 to 7,
A is fluorine, hydrogen, or a monovalent fluorinated group terminated with —CF 3 , —CF 2 H or —CH 2 F radical,
Q is a single bond or an optionally fluorinated divalent organic group,
Z is a single bond, a trivalent group: -JC=(wherein J is an alkyl, hydroxyl or silyl ether group: K 3 SiO— wherein K is independently hydrogen, alkyl, aryl or alkoxy), a trivalent group: -LSi=(wherein L is alkyl), a tetravalent group: —C≡, a tetravalent group: —Si≡, or a di- to octavalent siloxane residue,
W is a hydrolyzable group-bearing group having the general formula (5b):

wherein R is a C 1 -C 4 alkyl or phenyl, X is a hydrolyzable group, a is 2 or 3, l is an integer of 0 to 10, D is a single bond or an optionally fluorinated C 1 -C 20 divalent organic group, b is an integer of 2 to 6, and Me is methyl,
A-Rf-Q-(Y) β B  (6)

Rf-(Q-(Y) β B) 2   (7)

wherein Rf, A and Q are as defined above,
β is an integer of 1 to 10,
Y is a hydrolyzable group-bearing divalent group having the general formula (9):

wherein R, X and a are as defined above, D is a single bond or an optionally fluorinated C 1 -C 20 divalent organic group, D′ is an optionally fluorinated C 1 -C 10 divalent organic group, R 1 is a C 1 -C 20 monovalent hydrocarbon group, and e is 1 or 2, with the proviso that when β is 1, e is 2 in the general formula (9), and
B is a hydrogen, a C 1 -C 4 alkyl or a halogen.

2. The fluorochemical coating composition of claim 1 wherein component (A) contains 10 to 200 repeating units of the general formula (1):
—C g F 2g O—  (1)

wherein g is independently in each unit an integer of 1 to 6, as the fluorooxyalkylene group, and has at least one hydrolyzable silyl group of the general formula (2):

wherein R is a C 1 -C 4 alkyl or phenyl, X is a hydrolyzable group, and a is 2 or 3, at one or more ends, and
component (B) contains 10 to 100 repeating units of the general formula (1) as the fluorooxyalkylene portion.

3. The fluorochemical coating composition of claim 1 wherein component (B) is a polymer having the general formula (11):
A-Rf-A  (11)

wherein Rf is —(CF 2 ) d —(OCF 2 ) p (OCF 2 CF 2 ) q OCF 2 CF 2 CF 2 ) r —(OCF 2 CF 2 CF 2 CF 2 ) s (OCF(CF 3 )CF 2 ) t —O—(CF 2 ) d —, d is independently an integer of 0 to 5, p, q, r, s and t are each independently an integer of 0 to 100, p+q+r+s+t is an integer of 5 to 100, individual units in parentheses may be randomly arranged, and
A is fluorine, hydrogen, or a monovalent fluorinated group terminated with —CF 3 , —CF 2 H or —CH 2 F radical.

4. The fluorochemical coating composition of claim 1 wherein Q is a single bond or a group selected from divalent groups having the following formulae:

wherein b is an integer of 2 to 6, c is an integer of 1 to 50, and Me is methyl.

5. The fluorochemical coating composition of claim 1 wherein Z is a single bond or a group selected from divalent to octavalent groups having the following formulae:

wherein Me is methyl.

6. The fluorochemical coating composition of claim 1 , further comprising a solvent for dilution.

7. The fluorochemical coating composition of claim 6 wherein the solvent is ethyl perfluorobutyl ether, decafluoropentane, pentafluorobutane or perfluorohexane.

8. The fluorochemical coating composition of claim 1 , wherein the hydrolyzable group-containing silane modified with a fluorooxyalkylene-containing polymer (A) comprises a fluorooxyalkylene-containing polymer-modified silane having the formula (3).

9. The fluorochemical coating composition of claim 1 , wherein the hydrolyzable group-containing silane modified with a fluorooxyalkylene-containing polymer (A) comprises a fluorooxyalkylene-containing polymer-modified silane having the formula (4).

10. The fluorochemical coating composition of claim 1 , wherein the hydrolyzable group-containing silane modified with a fluorooxyalkylene-containing polymer (A) comprises a fluorooxyalkylene-containing polymer-modified silane having the formula (6).

11. The fluorochemical coating composition of claim 1 , wherein the hydrolyzable group-containing silane modified with a fluorooxyalkylene-containing polymer (A) comprises a fluorooxyalkylene-containing polymer-modified silane having the formula (7).

12. An article treated with the fluorochemical coating composition of claim 1 .

13. A touch panel treated with the fluorochemical coating composition of claim 1 .

14. An antireflective coated article treated with the fluorochemical coating composition of claim 1 .

15. A glass, strengthened glass, sapphire glass, quartz glass or SiO 2 -deposited substrate treated with the fluorochemical coating composition of claim 1 .

Assignees

• Shinetsu Chemical Co

Inventors

• Yamane Yuji
• Sato Shinichi
• Koike Noriyuki
• Matsuda Takashi
• Sakoh Ryusuke

Classifications

• C09D183/12

  containing polyether sequences · CPC title

• C09D171/02

  Polyalkylene oxides · CPC title

• C08G65/007

  containing fluorine · CPC title

• C08G77/46

  containing polyether sequences · CPC title

• C08G65/336

  containing silicon · CPC title