# US 2010/0168319 A1 · Fluorocopolymer and water and oil proofing composition, and processes for their production

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- Number: US 2010/0168319 A1
- Document ID: US20100168319A1
- Status: Published application
- Kind: A1
- Application number: 12/695,246
- Filed: 2010-01-28
- Published: 2010-07-01
- Earliest claimed: 2007-11-01
- Assignees: Asahi Glass Company, Limited
- Inventors: Shuichiro Sugimoto; Takao Hirono; Eiji Morimoto
- Web page: https://patentgrep.com/patent/US20100168319A1

## CPC

- C09D 133/16: Homopolymers or copolymers of esters containing halogen atoms
- C08F 214/18: Monomers containing fluorine
- C08F 220/24: containing perhaloalkyl radicals
- C08J 3/07: from polymer solutions
- C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
- C08F 220/10: Esters
- C08F 220/16: of phenols or of alcohols containing two or more carbon atoms
- C08F 222/02: Acids; Metal salts or ammonium salts thereof {, e.g. maleic acid or itaconic acid}
- C08J 2333/16: Homopolymers or copolymers of esters containing halogen atoms
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

A fluorocopolymer capable of exhibiting excellent water and oil resistance even with its perfluoroalkyl group being a short chain, and a water and oil proofing composition containing it, are provided. A water and oil proofing composition containing a fluorocopolymer (A) comprising from 40 to 98 mass % of polymerized units (a′) having a C1-6 perfluoroalkyl group, from 1 to 50 mass % of polymerized units (b′) having an alkylene oxide and from 1 to 10 mass % of polymerized units (c′) based on a monomer represented by CH2═C(COOH)-Q-COOH (wherein Q is a C1-4 alkylene group, etc.).

## Claims

### Claim 1

A fluorocopolymer comprising from 40 to 98 mass % of polymerized units (a′) based on the following monomer (a), from 1 to 50 mass % of polymerized units (b′) based on the following monomer (b) and from 1 to 10 mass % of polymerized units (c′) based on the following monomer (c):
Monomer (a): a compound represented by (Z—Y)nX, wherein Z is a C1-6 perfluoroalkyl group or a monovalent group represented by CmF2m+1O(CFWCF2O)dCFK— (wherein m is an integer of from 1 to 6, d is an integer of from 1 to 4, and each of W and K which are independent of each other, is a fluorine atom or a trifluoromethyl group), Y is a single bond or a bivalent organic group containing no fluorine atom, n is 1 or 2, provided that when n is 1, X is —CR═CH2, —COOCR═CH2, —OCOCR═CH2, —OCH2-φ-CR═CH2 or —OCH═CH2, and when n is 2, X is —CH[—(CH2)pCR═CH2]—, —CH[—(CH2)pCOOCR═CH2]—, —CH [—CH2)pOCOCR═CH2]— or —OCOCH═CHCOO—, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, p is an integer of from 0 to 4, and when n is 2, two (Z—Y) present in one molecule may be the same or different from each other;
Monomer (b): a compound represented by CH2═CR1-G-(R2O)q—R3, wherein R1 is a hydrogen atom or a methyl group, R2 is a C2-4 alkylene group, or a C2-3 alkylene group having some or all of its hydrogen atoms substituted by hydroxyl groups, q is an integer of from 1 to 10, G is —COO(CH2)r— or —COO(CH2)t—NHCOO— (wherein r is an integer of from 0 to 4, and t is an integer of from 1 to 4), and R3 is a hydrogen atom, a methyl group, an acryloyl group, a methacryloyl group or an allyl group;
Monomer (c): a compound represented by CH2═C(COOH)-Q-COOH, wherein Q is a C1-4 alkylene group, or a C2-3 alkylene group having some or all of its hydrogen atoms substituted by hydroxyl groups, and in the monomer (c), some or all of the carboxyl groups may form at least one salt selected from an ammonium salt and an organic amine salt.

### Claim 2 (depends on 1)

The fluorocopolymer according to claim 1, which further contains from 0.1 to 10 mass % of polymerized units (d′) of the following monomer (d):
Monomer (d): a monomer which is copolymerizable with the above monomers (a), (b) and (c) and is not included in any of the monomers (a), (b) and (c) and which has at least one functional group selected from the group consisting of a carboxyl group, an isocyanate group, a blocked isocyanate group, a urethane group, an alkoxysilyl group, an epoxy group, an N-methylol group and an N-alkoxymethyl group and has no polyfluoroalkyl group.

### Claim 3 (depends on 1)

The fluorocopolymer according to claim 1, wherein in the above (Z—Y)nX, Z is a C1-6 perfluoroalkyl group, Y is a bivalent organic group containing no fluorine atom, n is 1 and X is —OCOCR═CH2, or n is 2 and X is —OCOCH═CHCOO— (wherein R is a hydrogen atom, a methyl group or a halogen atom).

### Claim 4 (depends on 3)

The fluorocopolymer according to claim 3, wherein the monomer (a) is a compound represented by F(CF2)sY1OCOCR═CH2 (wherein s is an integer of from 1 to 6, R is a hydrogen atom, a methyl group or a halogen atom, and Y1 is a C1-10 alkylene group).

### Claim 5 (depends on 1)

The fluorocopolymer according to claim 1, wherein in CH2═CR1-G-(R2O)q—R3 of the monomer (b), G is —COO(CH2)r— (wherein r is an integer of from 0 to 4), R2 is a C2-4 alkylene group, q is an integer of from 1 to 10, and R3 is a hydrogen atom.

### Claim 6 (depends on 5)

The fluorocopolymer according to claim 5, wherein the polymerized units (b′) are polymerized units based on 2-hydroxyethyl methacrylate.

### Claim 7 (depends on 1)

The fluorocopolymer according to claim 1, wherein the polymerized units (c′) are polymerized units based on itaconic acid (some or all of carboxyl groups may form at least one salt selected from the group consisting of an ammonium salt and an organic amine salt).

### Claim 8 (depends on 1)

The fluorocopolymer according to claim 1, which has a mass average molecular weight of from 5,000 to 100,000.

### Claim 9 (depends on 1)

A water and oil proofing composition comprising the fluorocopolymer as defined in claim 1 and an aqueous medium.

### Claim 10 (depends on 9)

The water and oil proofing composition according to claim 9, wherein the content of a volatile organic solvent in the aqueous medium is not more than 1 mass %, and in the polymerized units (c′), some or all of carboxyl groups form at least one salt selected from the group consisting of an alkali metal salt, an ammonium salt and an organic amine salt.

### Claim 11 (depends on 9)

The water and oil proofing composition according to claim 9, wherein some or all of carboxyl groups in the polymerized units (c′) form salts with at least one member selected from the group consisting of ammonia, diethanolamine, tris(hydroxymethyl)aminomethane and 2-amino-2-methyl-1-propanol.

### Claim 12 (depends on 9)

A processed article treated with the water and oil proofing composition as defined in claim 9.

### Claim 13

A process for producing a fluorocopolymer, which comprises a step of polymerizing a monomer mixture comprising from 40 to 98 mass % of the following monomer (a), from 1 to 50 mass % of the following monomer (b) and from 1 to 10 mass % of the following monomer (c):
Monomer (a): a compound represented by (Z—Y)nX, wherein Z is a C1-6 perfluoroalkyl group or a monovalent group represented by CmF2m+1O(CFWCF2O)dCFK— (wherein m is an integer of from 1 to 6, d is an integer of from 1 to 4, and each of W and K which are independent of each other, is a fluorine atom or a trifluoromethyl group), Y is a single bond or a bivalent organic group containing no fluorine atom, n is 1 or 2, provided that when n is 1, X is —CR═CH2, —COOCR═CH2, —OCOCR═CH2, —OCH2-φ-CR═CH2 or —OCH═CH2, and when n is 2, X is —CH[—(CH2)pCR═CH2]—, —CH[—(CH2)pCOOCR═CH2]—, —CH [—(CH2)pOCOCR═CH2]— or —OCOCH═CHCOO—, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, p is an integer of from 0 to 4, and when n is 2, two (Z—Y) present in one molecule may be the same or different from each other;
Monomer (b): a compound represented by CH2═CR1-G-(R2O)q—R3, wherein R1 is a hydrogen atom or a methyl group, R2 is a C2-4 alkylene group, or a C2-3 alkylene group having some or all of its hydrogen atoms substituted by hydroxyl groups, q is an integer of from 1 to 10, G is —COO(CH2)r— or —COO(CH2)t—NHCOO—(wherein r is an integer of from 0 to 4, and t is an integer of from 1 to 4), and R3 is a hydrogen atom, a methyl group, an acryloyl group, a methacryloyl group or an allyl group;
Monomer (c): CH2═C(COOH)-Q-COOH, wherein Q is a C1-4 alkylene group, or a C2-3 alkylene group having some or all of its hydrogen atoms substituted by hydroxyl groups, and in the monomer (c), some or all of the carboxyl groups may form at least one salt selected from an ammonium salt and an organic amine salt.

### Claim 14 (depends on 13)

The process for producing a fluorocopolymer according to claim 13, wherein the monomer mixture further contains from 0.1 to 10 mass % of the following monomer (d):
Monomer (d): a monomer which is copolymerizable with the above monomers (a), (b) and (c) and is not included in any of the monomers (a), (b) and (c) and which has at least one functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, a urethane group, an alkoxysilyl group, an epoxy group, an N-methylol group and an N-alkoxymethyl group and has no polyfluoroalkyl group.

### Claim 15 (depends on 14)

A process for producing a water and oil proofing composition, which comprises a salt-forming step of reacting the fluorocopolymer obtained by the process as defined in claim 14 with at least one member selected from the group consisting of ammonia, diethanolamine, tris(hydroxymethyl)aminomethane and 2-amino-2-methyl-1-propanol to convert some or all of carboxyl groups of the fluorocopolymer to a salt or salts, and a step of dispersing the fluorocopolymer after the salt-forming step in an aqueous medium.