Fluorochemical coating composition and article treated therewith

Patent metadata

Field	Value
Publication number	US-9644115-B2
Application number	US-201514663799-A
Country	US
Kind code	B2
Filing date	Mar 20, 2015
Priority date	Mar 31, 2014
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

A fluorochemical coating composition is provided comprising (A) a hydrolyzable group-containing silane modified with a fluoropolyether-containing polymer and (B) a hydrolyzable group-containing silane modified with a fluoropolyether-polysiloxane copolymer 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 fluoropolyether-containing polymer and/or a partial hydrolytic condensate thereof, and (B) a hydrolyzable group-containing silane modified with a fluoropolyether-polysiloxane copolymer and/or a partial hydrolytic condensate thereof, in a weight ratio (A)/(B) of 40/60 to 95/5.

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 fluoropolyether group, and has at least one hydrolyzable silyl group of the general formula (2):

wherein R is 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 200 repeating units of the general formula (1) as the fluoropolyether portion, and 3 to 200 siloxane bonds as the polysiloxane portion.

3. The fluorochemical coating composition of claim 1 wherein the hydrolyzable group-containing silane modified with a fluoropolyether-containing polymer (A) is at least one member selected from fluoropolyether-containing polymer-modified silanes having the general formulae (3), (4), (5) and (6):
A-Rf-QZ(W) α   (3)

Rf-(QZ(W) α ) 2   (4)

A-Rf-Q-(Y) β B  (5)

Rf-(Q-(Y) β B) 2   (6)

wherein Rf is —(CF 2 ) d —O—(CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r —(CF 2 CF 2 CF 2 CF 2 O) s (CF(CF 3 )CF 2 O) t —(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,
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 (7):

wherein R is C 1 -C 4 alkyl or phenyl, X is a hydrolyzable group, a is 2 or 3, and 1 is an integer of 0 to 10,
α is an integer of 1 to 7,
Y is a hydrolyzable group-bearing divalent group having the general formula (8), (9), (10) or (10′):

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′ is a C 1 -C 20 monovalent hydrocarbon group, R 2 is hydrogen or methyl, and e is 1 or 2,
β is an integer of 1 to 10, and
B is hydrogen, C 1 -C 4 alkyl or halogen.

4. The fluorochemical coating composition of claim 1 wherein the hydrolyzable group-containing silane modified with a fluoropolyether-polysiloxane copolymer (B) is at least one member selected from fluoropolyether-polysiloxane copolymer-modified silanes having the general formulae (11) and (12):
A-Rf′-QZW α   (11)

Rf′-(QZW α ) 2   (12)

wherein Rf′ is a divalent group containing fluoropolyether-polysiloxane copolymer,
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 (7):

wherein R is C 1 -C 4 alkyl or phenyl, X is a hydrolyzable group, a is 2 or 3, and 1 is an integer of 0 to 10, and
α is an integer of 1 to 7.

5. The fluorochemical coating composition of claim 4 wherein Rf′ in formulae (11) and (12) is a group having the general formula (13) or (14):
—(Z′-Q) h -Rf-(Q-Z′) h -  (13)

—Rf-(Q-Z′-Q-Rf) i -  (14)

wherein Q is as defined above,
Rf is —(CF 2 ) d —O—(CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r —(CF 2 CF 2 CF 2 CF 2 O) s (CF(CF 3 )CF 2 O) t —(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,
Z′ is each independently a divalent polysiloxane chain, h is independently 0 or 1, and i is an integer of 1 to 3.

6. The fluorochemical coating composition of claim 5 wherein Z′ in formulae (13) and (14) is a polysiloxane chain having the general formula (15) or (16):

wherein R′ is each independently C 1 -C 4 alkyl, phenyl or phenylethyl, j is an integer of 10 to 200, y is an integer of 1 to 5, u and v are each independently an integer of 1 to 200.

7. The fluorochemical coating composition of claim 1 , further comprising (C) a fluoropolyether-containing polymer having the general formula (17):
A-Rf-A  (17)

wherein Rf is —(CF 2 ) d —O—(CF 2 O) p (CF 2 CF 2 O) q (CF 2 CF 2 CF 2 O) r —(CF 2 CF 2 CF 2 CF 2 O) s (CF(CF 3 )CF 2 O) t —(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, and
A is fluorine, hydrogen, or a monovalent fluorinated group terminated with —CF 3 , —CF 2 H or —CH 2 F radical.

8. The fluorochemical coating composition of claim 1 , further comprising a fluorochemical solvent.

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

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

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

12. A glass treated with the fluorochemical coating composition of claim 1 .

13. A strengthened glass treated with the fluorochemical coating composition of claim 1 .

14. A sapphire glass treated with the fluorochemical coating composition of claim 1 .

15. A quartz glass treated with the fluorochemical coating composition of claim 1 .

16. A SiO 2 -deposited substrate treated with the fluorochemical coating composition of claim 1 .

Assignees

• Shinetsu Chemical Co

Inventors

• Yamane Yuji
• Matsuda Takashi
• Sakoh Ryusuke

Classifications

• C09D183/12 Primary

  containing polyether sequences · CPC title

• Y10T428/31612

  As silicone, silane or siloxane · CPC title

• C08G77/24

  halogen-containing groups · CPC title

• C03C17/30

  with silicon-containing compounds · CPC title

• Y10T428/31663

  As siloxane, silicone or silane · CPC title