# US 11,897,989 B2 · Fluorine-containing curable composition and article

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- Number: US 11,897,989 B2
- Document ID: US11897989B2
- Status: Granted
- Kind: B2
- Application number: 17/618,171
- Filed: 2020-05-26
- Published: 2022-07-14
- Granted: 2024-02-13
- Earliest claimed: 2019-06-11
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Yasunori Sakano
- Web page: https://patentgrep.com/patent/US11897989B2

## CPC

- C08F 290/06: Polymers provided for in subclass C08G
- C09D 183/10: Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00)
- C08F 222/104: {of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate}
- C08F 230/08: containing silicon
- C08F 259/08: on to polymers containing fluorine
- C08F 283/06: on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)}
- C08F 290/062: {Polyethers}
- C08G 65/336: containing silicon
- C08G 77/385: containing halogens
- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C09D 4/06: {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
- C09D 5/1668: {Vinyl-type polymers}
- C08G 77/442: containing vinyl polymer sequences
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

A fluorine-containing curable composition which contains, as essential components, component (A) that is composed of a compound which is a linear polymer having a fluoropolyether in the main chain, while having a trifluoromethyl group at one end of the molecular chain and two or more (meth)acryl groups at the other end, component (B) that is composed of a compound which is a linear polymer having a fluoropolyether in the main chain, while having two or more (meth)acryl groups at each end of the molecular chain, and which has four to ten (meth)acryl groups in each molecule on average, and component (C) that is composed of a non-fluorinated acrylic compound which contains no fluoropolyether structure, while having two or more (meth)acryl groups in each molecule on average; the total blending amount of component (A) and component (B) relative to 100 parts by mass of component (C) is from 0.05 to 50 parts by mass; and the blending amount of component (A) relative to 100 parts by mass of component (B) is 1 to 100 parts by mass. This fluorine-containing curable composition is capable of forming a cured film that exhibits excellent antifouling properties and excellent water repellency, while having a low coefficient of kinetic friction.

## Claims

### Claim 1

A curable fluorinated composition comprising as essential components, component (A) which is a fluorinated acrylic compound in the form of a linear polymer having a fluoropolyether backbone, having a trifluoromethyl group at one end of the molecule and at least two (meth)acryloyl groups at the other end of the molecule, and having the general formula (1):
RfA—Z1-Q1[X1]a (1)
wherein RfA is a monovalent perfluoropolyether group having a trifluoromethyl group at the opposite end to the end of attachment to Z1, which is represented by Rf1—O—Rf2—CF2—,
wherein Rf1 is a C1-10 perfluoroalkyl group having a trifluoromethyl group at the opposite end to the end of attachment to the oxygen atom, which may contain oxygen, and Rf2 is a divalent perfluoropolyether group consisting of randomly arranged repeat units of one or more types selected from the following four types:
—CF2O—,
—CF2CF2O—,
—CF2CF2CF2O—, and
—CF2CF2CF2CF2O—,
Z1 is a linking group in the form of a C1-20 divalent hydrocarbon group which may contain at least one heteroatom selected from oxygen, nitrogen, and silicon, which may contain a cyclic structure therein, and in which some carbon-bonded hydrogen may be substituted by fluorine,
Q1 is a (a+1)-valent linking group containing at least (a+1) number of silicon atoms, which may take a cyclic structure,
“a” is an integer of 2 to 5, and
X1 is independently a monovalent organic group having a (meth)acryloyl group which may contain at least one heteroatom selected from oxygen, nitrogen, and silicon,
component (B) which is a compound in the form of a linear polymer having a fluoropolyether backbone, having at least two (meth)acryloyl groups at each end of the molecule, and having on the average 4 to 10 (meth)acryloyl groups per molecule, and
component (C) which is a non-fluorinated acrylic compound free of fluoropolyether structure and having on the average at least two (meth)acryloyl groups per molecule,
wherein the total amount of components (A) and (B) blended is 0.05 to 50 parts by weight per 100 parts by weight of component (C), and the amount of component (A) blended is 1 to 100 parts by weight per 100 parts by weight of component (B).

### Claim 2 (depends on 1)

The curable fluorinated composition of claim 1, further comprising (D) a photopolymerization initiator.

### Claim 3 (depends on 1)

The curable fluorinated composition of claim 1, wherein component (B) is a fluorinated acrylic compound having the general formula (2):
wherein RfB is a divalent perfluoropolyether group,
Z1 is independently a linking group in the form of a C1-20 divalent hydrocarbon group which may contain at least one heteroatom selected from oxygen, nitrogen, and silicon, which may contain a cyclic structure therein, and in which some carbon-bonded hydrogen may be substituted by fluorine,
Q1 is independently a (a+1)-valent linking group containing at least (a+1) number of silicon atoms, which may take a cyclic structure,
“a” is an integer of 2 to 5,
Z2 is each independently a C1-100 divalent hydrocarbon group which may contain oxygen and/or nitrogen, and which may contain a cyclic structure therein,
R1 is independently hydrogen or a C1-8 monovalent hydrocarbon group,
R2 is independently hydrogen or a monovalent organic group having a (meth)acryloyl group, which may contain oxygen and/or nitrogen,
with the proviso that there are contained at least two monovalent organic groups R2 at each end of the molecule and on the average 4 to 10 monovalent organic groups R2 per molecule.

### Claim 4 (depends on 1)

The curable fluorinated composition of claim 1, wherein in formula (1) representative of component (A), X1 is selected from the following:
CH2CH2CH2OC(═O)NHCH2CH2OC(═O)CH═CH2
—CH2CH2CH2OCH2CH2OC(═O)NHCH2CH2OC(═O)CH═CH2
—CH2CH2CH2OC(═O)NHCH2CH2OC(═O)C(CH3)═CH2
—CH2CH2CH2OCH2CH2OC(═O)NHCH2CH2OC(═O)C(CH3)═CH2
—CH2CH2CH2OC(═O)NHC(CH3)[CH2OC(═O)CH═CH2]2
—CH2CH2CH2OCH2CH2OC(═O)NHC(CH3) [CH2OC(═O)CH═CH2]2
—CH2CH2CH2OC(═O)CH═CH2
—CH2CH2CH2OCH2CH2OC(═O)CH═CH2
—CH2CH2CH2OC(═O)C(CH3)—CH2
—CH2CH2CH2OCH2CH2OC(═O)C(CH3)—CH2
—CH2CH2Si[OSi(CH3)2CH2OC(═O)CH═CH2]3
—CH2CH2Si[Osi(CH3)2CH2OC(═O)C(CH3)—CH2]3

### Claim 5 (depends on 1)

The curable fluorinated composition of claim 1, wherein in formula (1) representative of component (A), Q1 is selected from the following:
wherein “a” is an integer of 2 to 5, and b is an integer of 1 to 5.

### Claim 6 (depends on 1)

The curable fluorinated composition of claim 1, wherein the fluorinated acrylic compound having formula (1) representative of component (A) is selected from compounds having the following formulae:
wherein RfA is as defined above.

### Claim 7 (depends on 3)

The curable fluorinated composition of claim 3 wherein Z1 in formula (2) representative of component (B) is selected from the following
—CH2CH2—
—CH2CH2CH2—
—CH2CH2CH2CH2—
—CH2OCH2CH2—
—CH2OCH2CH2CH2—.

### Claim 8 (depends on 3)

The curable fluorinated composition of claim 3, wherein Q1 in formula (2) representative of component (B) is a group having the following formula:
wherein a1 is 2 or 3.

### Claim 9 (depends on 3)

The curable fluorinated composition of claim 3, wherein the fluorinated acrylic compound having formula (2) representative of component (B) is a fluorinated acrylic compound having the general formula (3) or (4):
wherein Z1, Q1, and “a” are as defined above, RfB′ is —CF2O(CF2O)m(CF2CF2O)nCF2—, m is an integer of 1 to 200, n is an integer of 1 to 170, m+n is an integer of 6 to 201, the arrangement of —(CF2O)— and —(CF2CF2O)— is random, R3 is hydrogen or methyl, d1 and e1 each are an integer of 0 to 10.

### Claim 10 (depends on 1)

The curable fluorinated composition of claim 1, wherein the non-fluorinated acrylic compound as component (C) is a polyfunctional acrylic compound containing at least two (meth)acryloyl groups per molecule, but free of a urethane bond, a polyfunctional urethane (meth)acrylate having at least three (meth)acryloyl groups per molecule which is obtained by reacting said polyfunctional acrylic compound with an aliphatic polyisocyanate and a hydroxy-containing acrylic compound, or a mixture of at least two acrylic compounds including said polyfunctional acrylic compound and said polyfunctional urethane (meth)acrylate.

### Claim 11 (depends on 1)

An article having a cured film of the curable fluorinated composition of claim 1 on its surface.

### Claim 12 (depends on 1)

The curable fluorinated composition of claim 1, wherein Rf2 is a divalent perfluoropolyether group represented by the following formula:
—(CF2O)m(CF2CF2O)n—
wherein m is an integer of 1 to 200, n is an integer of 1 to 170, and m+n is an integer of 6 to 201.