Surface treatment composition, method of producing the surface treatment composition, and surface-treated article

Patent metadata

Field	Value
Publication number	US-9045647-B2
Application number	US-201113884452-A
Country	US
Kind code	B2
Filing date	Nov 10, 2011
Priority date	Nov 10, 2010
Publication date	Jun 2, 2015
Grant date	Jun 2, 2015

Abstract

A surface treatment composition comprises a polyfluoropolyether silane. The polyfluoropolyether silane and the surface treatment composition are produced by reacting a perfluoropolyether-containing compound and a hydrosilane in the presence of a hydrosilylation catalyst and an isomer reducing agent.

First claim

What is claimed is:

1. A surface treatment composition comprising a polyfluoropolyether silane having the following general formula (A):
Y—Z a —([(OC 3 F 6 ) b —(OCF(CF 3 )CF 2 ) c —(OCF 2 CF(CF 3 )) d —(OC 2 F 4 ) e —(CF(CF 3 )) f —(OCF 2 ) g ]—(CH 2 ) h —X—(C n H 2n )—((SiR 2 —O) m —SiR 2 ) i —(C j H 2j )—Si—(X′) 3-z (R 1 ) z   (A);

wherein Z is independently selected from —(CF 2 )—, —(CF(CF 3 )CF 2 O)—, —(CF 2 CF(CF 3 )O)—, —(CF(CF 3 )O)—, —(CF(CF 3 )CF 2 )—, —(CF 2 CF(CF 3 ))—, and —(CF(CF 3 ))—; a is an integer from 1 to 200; b, c, d, e, f, and g are integers each independently selected from 0 to 200; h, n and j are integers each independently selected from 0 to 20; i and m are integers each independently selected from 0 to 5; X is a bivalent organic group or an oxygen atom; R is a hydrocarbon group having from 1 to 22 carbon atoms; z is an integer independently selected from 0 to 2; X′ is an independently selected hydrolysable group; R 1 is an independently selected hydrocarbon group having from 1 to 22 carbon atoms which is free of aliphatic unsaturation; and Y is selected from F and Si—(X′) 3-z (R 1 ) z (C j H 2j )—((SiR 2 —O) m —SiR 2 ) i —(C n H 2n )—X—(CH 2 ) h —; wherein X′, z, R 1 , j, m, i, n and h are as defined above;
provided that when subscript i is 0, subscript j is also 0; when subscript i is an integer greater than 0, subscript j is also an integer greater than 0; and when subscript i is an integer greater than 0, m is also an integer greater than 0;
with the proviso that when Y is F; Z is —(CF 2 )—; a is an integer from 1 to 3; and subscripts c, d, f and i are 0; fluorine-containing compounds represented by the general formula (B) below are present in said surface treatment composition in an amount of at least 25 mol % based on the total amount of said surface treatment composition
F—(CF 2 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) e —(OCF 2 ) g —F  (B);

and with the proviso that fluorine-containing compounds represented by the general formula (C) below are present in said surface treatment composition in an amount of less than 40 mol % based on the total amount of said surface treatment composition
Y′—Z a —[(OC 3 F 6 ) b —(OCF(CF 3 )CF 2 ) c —(OCF 2 CF(CF 3 )) d —(OC 2 F 4 ) e —(CF(CF 3 )) f —(OCF 2 ) g ]—(CH 2 ) h —X—(C n′ H 2n′ )—CR 5 ═CR 5 —CH 3   (C);

wherein Y′ is selected from F and CH 3 —CR 5 ═CR 5 —(C n′ H 2n′ )—X—(CH 2 ) h ; n′ is an integer independently selected from 0 to 17; R 5 is independently selected from a hydrogen atom and a methyl group; and Z, a, b, c, d, e, f, g, h and X are as defined above.

2. A surface treatment composition as set forth in claim 1 wherein said hydrolysable group represented by X′ in general formula (A) of said polyfluoropolyether silane is independently selected from a halide group, an alkoxy (—OR 2 ) group, an alkylamino (—NHR 2 or —NR 2 R 3 ) group, a carboxy (—OOC—R 2 ) group, an alkyliminoxy (—O—N═CR 2 R 3 ) group, an alkenyloxy (O—C(═CR 2 R 3 )R 4 ) group, or an N-alkylamido (—NR 2 COR 3 ) group, wherein R 2 , R 3 and R 4 are each independently selected from H and a hydrocarbon having from 1 to 22 carbon atoms, and wherein R 2 and R 3 optionally can form a cyclic amine in the alkylamino group.

3. A method for producing a surface treatment composition which comprises a polyfluoropolyether silane, said method comprising the steps of:
providing a perfluoropolyether-containing compound having at least one aliphatically unsaturated group;
providing a hydrosilane compound;
providing a hydrosilylation catalyst;
providing an isomer reducing agent; and
reacting the perfluoropolyether-containing compound and the hydrosilane compound in the presence of the hydrosilylation catalyst and the isomer reducing agent, thereby producing the polyfluoropolyether silane and the surface treatment composition;
with the proviso that when the polyfluoropolyether silane has the following general formula (G),
Y—Z′ a′ —[(OC 3 F 6 ) b —(OC 2 F 4 ) e —(OCF 2 ) g ]—(CH 2 ) h —X—(C n H 2n )—Si—(X′) 3-z (R 1 ) z   (G);

wherein Z′ is —(CF 2 )—; a′ is an integer from 1 to 3; b, e, and g are integers each independently selected from 0 to 200; h and n are integers each independently selected from 0 to 20; X is a bivalent organic group or an oxygen atom; z is an integer independently selected from 0 to 2; X′ is an independently selected hydrolysable group; R 1 is an independently selected hydrocarbon group having from 1 to 22 carbon atoms which is free of aliphatic unsaturation; and Y is F;
fluorine-containing compounds represented by the general formula (B) below are present in the surface treatment composition in an amount of at least 25 mol % based on the total amount of the surface treatment composition
F—(CF 2 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) e —(OCF 2 ) g —F  (B);

wherein a is from 1 to 3 in general formula (B) and b, e and g are as defined above.

4. A method as set forth in claim 3 wherein the polyfluoropolyether silane has the following general formula (A):
Y—Z a —[(OC 3 F 6 ) b —(OCF(CF 3 )CF 2 ) c —(OCF 2 CF(CF 3 )) d —(OC 2 F 4 ) e —(CF(CF 3 )) f —(OCF 2 ) g ]—(CH 2 ) h —X—(C n H 2n )—((SiR 2 —O) m —SiR 2 ) i —(C j H 2j )—Si—(X′) 3-z (R 1 ) z   (A);

wherein Z is independently selected from —(CF 2 )—, —(CF(CF 3 )CF 2 O)—, —(CF 2 CF(CF 3 )O)—, —(CF(CF 3 )O)—, —(CF(CF 3 )CF 2 )—, —(CF 2 CF(CF 3 ))—, and —(CF(CF 3 ))—; a is an integer from 1 to 200; b, c, d, e, f, and g are integers each independently selected from 0 to 200; h, n and j are integers each independently selected from 0 to 20; i and m are integers each independently selected from 0 to 5; X is a bivalent organic group or an oxygen atom; R is a hydrocarbon group having from 1 to 22 carbon atoms; z is an integer independently selected from 0 to 2; X′ is an independently selected hydrolysable group; R 1 is an independently selected hydrocarbon group having from 1 to 22 carbon atoms which is free of aliphatic unsaturation; and Y is selected from F and Si—(X′) 3-z (R 1 ) z (C j H 2j )—((SiR 2 —O) m —SiR 2 ) i —(C n H 2n )—X—(CH 2 ) h —; wherein X′, z, R 1 , j, m, i, n and h are as defined above;
provided that when subscript i is 0, subscript j is also 0; when subscript i is an integer greater than 0, subscript j is also an integer greater than 0; and when subscript i is an integer greater than 0, m is also an integer greater than 0;
with the proviso that when Y is F; Z is —(CF 2 )—; a is an integer from 1 to 3; and subscripts c, d, f and i are 0; fluorine-containing compounds represented by the general formula (B) below are present in the surface treatment composition in an amount of at least 25 mol % based on the total amount of the surface treatment composition
F—(CF 2 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) e —(OCF 2 ) g —F  (B).

5. A method as set forth in claim 4 wherein the hydrolysable group represented by X′ in general formula (A) of the polyfluoropolyether silane is independently selected from a halide group, an alkoxy (—OR 2 ) group, an alkylamino (—NHR 2 or —NR 2 R 3 ) group, a carboxy (—OOC—R 2 ) group, an alkyliminoxy (—O—N═CR 2 R 3 ) group, an alkenyloxy (O—C(═CR 2 R 3 )R 4 ) group, or an N-alkylamido (—NR 2 COR 3 ) group, wherein R 2 , R 3 and R 4 are each independently selected from H and a hydrocarbon having from 1 to 22 carbon atoms, and wherein R 2 and R 3 optionally can form a cyclic amine in the alkylamino group.

6. A method as set forth in claim 3 wherein the isomer reducing agent comprises a carboxylic acid compound.

7. A method as set forth in claim 3 wherein the isomer reducing agent comprises one or more silylated carboxylic acids.

8. A method as set forth in claim 3 wherein fluorine-containing compounds represented by the general formula (C) below are present in the surface treatment composition

Assignees

• Kleyer Don Lee
• Sugiura Yasushi
• Tachikawa Mamoru
• Taniguchi Yoshinori
• Hupfield Peter
• Itami Yasuo
• Maeda Masahiko
• Masutani Tetsuya
• Yoshida Tomohiro
• Dow Corning
• Daikin Ind Ltd

Inventors

• Kleyer Don Lee
• Sugiura Yasushi
• Tachikawa Mamoru
• Taniguchi Yoshinori
• Hupfield Peter
• Itami Yasuo
• Maeda Masahiko
• Masutani Tetsuya
• Yoshida Tomohiro

Classifications

• C08G65/336

  containing silicon · CPC title

• C07F7/188

  by reactions involving the formation of Si-O linkages · CPC title

• C07F7/14 Primary

  Preparation thereof from {optionally substituted} halogenated silanes and hydrocarbons {hydrosilylation reactions} · CPC title

• C08G65/007

  containing fluorine · CPC title

• C09D171/02 Primary

  Polyalkylene oxides · CPC title