# US 9,518,154 B2 · Fluorine-containing surface treatment agent and an article treated with the same

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- Number: US 9,518,154 B2
- Document ID: US9518154B2
- Status: Granted
- Kind: B2
- Application number: 14/304,152
- Filed: 2014-06-13
- Published: 2015-01-01
- Granted: 2016-12-13
- Earliest claimed: 2013-07-01
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Yuji Yamane; Noriyuki Koike
- Web page: https://patentgrep.com/patent/US9518154B2

## CPC

- C08G 77/24: halogen-containing groups
- C09D 183/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
- C09D 183/14: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C09D183/10 takes precedence)
- C08G 77/46: containing polyether sequences
- C08G 77/52: containing aromatic rings
- C08K 5/03: aromatic {, e.g. C6H5-CH2-Cl}
- Y10T 428/31612: As silicone, silane or siloxane
- Y10T 428/31663: As siloxane, silicone or silane
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The invention provides a surface treatment agent wherein a fluorooxyalkylene group-containing polymer or a fluorooxyalkylene group-containing polymer composition comprising the polymers, which is controlled of a temperature range of vaporization of fluorooxyalkylene group-containing polymer(s). The fluorooxyalkylene group-containing polymer has a fluorooxyalkylene structure represented by —(OCF2)p(OCF2CF2)q— and hydrolysable groups bond to a silicon atom represented by the formula at least one terminal. The polymer composition shows a decrease of 75% or more in weight, relative to the total weight of the polymer, in a temperature range of from 150 to 350 degrees C. when this is heated at a rate of 2 degrees C. per minute and a pressure of 0.1 Pa or less. The present surface treatment agent forms a coating having water- and oil-repellency and scratch resistance regardless of a vapor deposition conditions, in particularly by a vapor deposition at a mild temperature such as 350 degrees C.

## Claims

### Claim 1

A surface treatment agent comprising a fluorooxyalkylene group-containing polymer and/or a product obtained by partial hydrolysis and condensation of the polymer, wherein the fluorooxyalkylene group-containing polymer has a fluorooxyalkylene structure represented by —(OCF2)p(OCF2CF2)q—;
wherein p and q are, independently of each other, an integer of from 5 to 80 and a total of p and q is 10 to 100, and these parenthesized units may be sequenced at random; and
at least one group represented by the following formula (1) at at least one terminal;
wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolysable group, a is 2 or 3, and c is an integer of from 1 to 10;
and shows a decrease of 75% or more in weight, relative to the total weight of the polymer, in a temperature range of from 150 to 350 degrees C. when heated at a rate of 2 degrees C. per minute and a pressure of 0.1 Pa or less.

### Claim 2 (depends on 1)

The surface treatment agent according to claim 1, the fluorooxyalkylene group-containing polymer is represented by the following formula (2):
wherein Rf is —(CF2)d—(OCF2)p(OCF2CF2)q(OCF2CF2CF2)r(OCF2CF2CF2CF2)s—O(CF2)d−, A is a fluorine atom, a hydrogen atom, or a monovalent fluorinated group having a —CF3 group or a —CF2H group at a terminal, Q is a divalent organic group, Z is a divalent to octavalent organopolysiloxane residue having siloxane bonds, R, X, a and c are as defined for the aforesaid formula (1), b is an integer of from 1 to 7, α is 0 or 1, d is an integer of from 0 to 5, p and q are, independently of each other, an integer of from 5 to 80, r and s are, independently of each other, an integer of from 0 to 80, and a total of p, q, r and s is 10 to 100, and these parenthesized units may be sequenced at random.

### Claim 3

A surface treatment agent comprising a fluorooxyalkylene group-containing polymer composition, wherein the composition comprises
a fluorooxyalkylene group-containing polymer having
a fluorooxyalkylene structure represented by —(OCF2)p(OCF2CF2)q−;
wherein p and q are, independently of each other, an integer of from 5 to 80 and a total of p and q is 10 to 100, and these parenthesized units may be sequenced at random; and
at least one group represented by the following formula (1) at at least one terminal;
wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolysable group, a is 2 or 3, and c is an integer of from 1 to 10; and/or
a product obtained by partial hydrolysis and condensation of said polymer; and
an another polymer represented by the following formula (3):
A-Rf-A (3)
wherein Rf is —(CF2)d—(OCF2)p(OCF2CF2)q(OCF2CF2CF2)r(OCF2CF2CF2CF2)s—O(CF2)d−, d is an integer of from 0 to 5, p and q are, independently of each other, an integer of from 5 to 80, r and s are, independently of each other, an integer of from 0 to 80, and a total of p, q, r and s is 10 to 100, A is a fluorine atom, a hydrogen atom, or a monovalent fluorinated group having a —CF3 group or a —CF2H group at a terminal, and these parenthesized units may be sequenced at random,
and shows a decrease of 75% or more in weight, relative to the total weight of the polymer composition, in a temperature range of from 150 to 350 degrees C. when heated at a rate of 2 degrees C. per minute and a pressure of 0.1 Pa or less.

### Claim 4 (depends on 3)

The surface treatment agent according to claim 3, wherein the fluorooxyalkylene group-containing polymer is
represented by the following formula (2):
wherein Rf is —(CF2)d—(OCF2)p(OCF2CF2)q(OCF2CF2CF2)r(OCF2CF2CF2CF2)s—O(CF2)d−, A is a fluorine atom, a hydrogen atom, or a monovalent fluorinated group having a —CF3 group or a —CF2H group at a terminal, Q is a divalent organic group, Z is a divalent to octavalent organopolysiloxane residue having siloxane bonds, R, X, a and c are as defined for the aforesaid formula (1), b is an integer of from 1 to 7, α is 0 or 1, d is an integer of from 0 to 5, p and q are, independently of each other, an integer of from 5 to 80, r and s are, independently of each other, an integer of from 0 to 80, and a total of p, q, r and s is 10 to 100, and these parenthesized units may be sequenced at random; or represented by the following formula (4):
wherein Rf is —(CF2)d—(OCF2)p(OCF2CF2)q(OCF2CF2CF2)r(OCF2CF2CF2CF2)s—O(CF2)d−, and Q, Z, R, X, a, b, c, d, α, p, q, r and s are as defined for said formula (2), or is a mixture of the polymers represented by the formulas (2) and (4).

### Claim 5 (depends on 2)

The surface treatment agent according to claim 2 or , wherein Q is a hydrocarbon group having 2 to 12 carbon atoms and may have one or more bonds selected from the group consisting of an amide bond, an ether bond, an ester bond, a silphenylene bond, a silethylene bond and an alkylene bond.

### Claim 6 (depends on 1)

The surface treatment agent according to claim 1, further comprising a fluorinated solvent.

### Claim 7 (depends on 1)

An article treated by vapor deposition with the surface treatment agent according to claims 1.

### Claim 8 (depends on 7)

The article according to claim 7 wherein the article is one selected from a glass, a hard coat film, a highly hard film, an anti-reflection film, an ophthalmic lens, an optical lens and a quartz substrate.

### Claim 9 (depends on 8)

The article according to claim 8 wherein the glass is a tempered glass.

### Claim 10 (depends on 8)

The article according to claim 8 wherein the glass is an anti-reflection coating glass.

### Claim 11 (depends on 3)

A method for preparing the surface treatment agent according to claim 3 wherein the method comprises a step of subjecting a fluorooxyalkylene group-containing polymer composition comprising a fluorooxyalkylene group-containing polymer having at least one group represented by said formula (1) and/or a product obtained by partial hydrolysis and condensation of said polymer and a polymer represented by said formula (3) to molecular distillation at a temperature in a range from 100 to 400 degrees C. to thereby remove low boiling components and/or high boiling components.

### Claim 12 (depends on 1)

The surface treatment agent according to claim 1, wherein the fluorooxyalkylene group-containing polymer has one group represented by said formula (1) at at least one terminal.

### Claim 13 (depends on 2)

The surface treatment agent according to claim 2, wherein the fluorooxyalkylene group-containing polymer has one group represented by said formula (1) at at least one terminal.

### Claim 14 (depends on 3)

The surface treatment agent according to claim 3, wherein the fluorooxyalkylene group-containing polymer has one group represented by the said formula (1) at at least one terminal.

### Claim 15 (depends on 4)

The surface treatment agent according to claim 4, wherein the fluorooxyalkylene group-containing polymer has one group represented by said formula (1) at at least one terminal.

### Claim 16 (depends on 1)

The surface treatment agent according to claim 1, wherein the fluorooxyalkylene group-containing polymer has more than one group represented by said formula (1) at at least one terminal.

### Claim 17 (depends on 2)

The surface treatment agent according to claim 2, wherein the fluorooxyalkylene group-containing polymer has more than one group represented by said formula (1) at at least one terminal.

### Claim 18 (depends on 3)

The surface treatment agent according to claim 3, wherein the fluorooxyalkylene group-containing polymer has more than one group represented by said formula (1) at at least one terminal.

### Claim 19 (depends on 4)

The surface treatment agent according to claim 4, wherein the fluorooxyalkylene group-containing polymer has more than one group represented by formula (1) at at least one terminal.