JP2016124945A - Water-repellent and oil-repellent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which imparts water and oil repellency and can form a cured film having excellent adhesiveness on at least a part of both surfaces of an inorganic and organic base materials.SOLUTION: There is provided a composition which comprises a fluorine-containing a compound (A) having at least one ethylenically unsaturated group and a perfluoropolyether structure, a compound (B) having at least two ethylenically unsaturated groups and containing no fluorine and a compound (C) having at least one polar group and one ethylenically unsaturated group and having no perfluoropolyether structure, wherein the polar group is selected from a carboxy group, a phosphate group, an amino group, an isocyanate group, a hydrolyzable silyl group and a thiol group.SELECTED DRAWING: None

Description

  The present invention relates to a water / oil repellent composition and an article having a cured film formed from the composition on at least a part of the surface of a substrate.

  Perfluoropolyether compounds (hereinafter referred to as “PFPE compounds”) are not only excellent in heat resistance and chemical resistance, but also have characteristics such as water and oil repellency, antifouling properties, and low refractive index. Widely used for surface treatment of materials. Particularly in recent years, with the spread of smartphones and tablet-type terminals, surface treatment with a PFPE compound has been studied as an antifouling coating such as a touch panel and fingerprint adhesion prevention technology.

  These characteristics of the PFPE compound are considered to be due to its low surface energy, however, the durability and adhesion of the obtained cured film are sufficient even when used for surface treatment of non-fluorine-based substrates. There was a drawback of not. In order to eliminate such drawbacks, various derivatives of PFPE compounds have been studied so far.

  For example, a composition containing a silicon-containing organic fluorine-containing polymer containing a perfluoroether structure and a reactive silicon atom is known (Patent Document 1). And (A) a triisocyanate obtained by trimerizing diisocyanate, and (B) a carbon-carbon double bond-containing composition comprising an active hydrogen-containing compound, wherein component (B) is at least two kinds (B-1) a perfluoropolyether having one active hydrogen, and (B-2) a carbon- consisting essentially of a monomer having an active hydrogen and a carbon-carbon double bond. A composition containing a polymer containing PFPE formed from a carbon double bond-containing composition and an acrylate (2-hydroxyethyl acrylate, triethylene glycol diacrylate, etc.) is known (Patent Document 2). .

International Publication No. 1997/007155 International Publication No. 2003/002628

  Patent Document 1 discloses an example using an inorganic base material such as a glass plate, but the adhesiveness of the cured film has not been evaluated, and the description of the example using an organic base material is as follows. Absent. Moreover, although the Example using organic base materials, such as a polycarbonate board, is disclosed by patent document 2, and the adhesiveness of a cured film is evaluated, there is no description of the Example using an inorganic base material. However, according to the present inventor, the cured film formed from the composition described in Patent Document 1 has insufficient adhesion to an organic substrate such as plastic and is formed from the composition described in Patent Document 2. The cured film was insufficient in adhesion to an inorganic base material such as glass or steel plate (for example, refer to Examples 5 and 7 in Examples described later for the latter). Therefore, there are a wide variety of types of base materials for which water and oil repellency and antifouling properties are desired, and those skilled in the art will change the composition to be used according to the type of base material to which a cured film is to be applied. Complicated work was required, such as having to do.

  The present invention provides a composition capable of forming a cured film having water and oil repellency and antifouling properties and having excellent adhesion on at least a part of both surfaces of the inorganic and organic substrates, and at least the surface of the substrate. An object is to provide an article having a cured film formed in part from the composition.

  The present invention provides compositions and articles having the following configurations [1] to [10].

[1] A fluorine-containing compound (A) having at least one ethylenically unsaturated group and a perfluoropolyether structure, a fluorine-free compound (B) having at least two ethylenically unsaturated groups, and at least one A composition comprising a polar group and a compound (C) having one ethylenically unsaturated group and not having a perfluoropolyether structure, wherein the polar group is a carboxy group, a phosphate group, an amino group, an isocyanate. A composition characterized in that it is selected from a narate group, a hydrolyzable silyl group and a thiol group.

[2] The composition of [1], wherein the ethylenically unsaturated group is selected from a vinyl group, an allyl group, a (meth) acryloyl group, a styryl group, and a cinnamoyl group.

[3] The composition according to [1] or [2], wherein the fluorine-containing compound (A) is a compound represented by the following formula (1).
_{[D- (C m F 2m O} ) n -] o -E ··· (1)
Where
D is D ¹ —R ^f1 —O—CH ₂ — or D ² —O—;
here,
D ¹ is CF ₃ — or CF ₃ —O—,
R ^f1 represents a fluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon-carbon atoms, an alkylene group having 1 to 20 carbon atoms, or a carbon-carbon atom. An alkylene group having 2 to 20 carbon atoms having an etheric oxygen atom in between;
D ² is a C 1-6 perfluoroalkyl group;
m is an integer from 1 to 6;
n is an integer of 1 to 200, and when n is 2 or more, (C _m F _2m O) _n may be composed of two or more types of C _m F _2m O different from _m ;
o is an integer greater than or equal to 1;
E is an o-valent organic group having one or more —C (═O) —CR ¹ ═CH ₂ (wherein R ¹ is a hydrogen atom or a methyl group).

[4] The composition according to any one of [1] to [3], wherein the fluorine-containing compound (A) is at least one selected from the group consisting of the following compounds (A1) to (A3).
(A1) A fluorine-containing polymer having an ethylenically unsaturated group and a perfluoropolyether structure independently in the side chain.
(A2) A fluorine-containing polymer having an ethylenically unsaturated group in the side chain and a perfluoropolyether structure at both ends or one end of the main chain.
(A3) A fluorine-containing compound having an ethylenically unsaturated group and a perfluoropolyether structure independently at the end of the main chain or at the side chain of the cyclic compound.

[5] The content of the fluorine-containing compound (A) is 0.01 to 5% by mass with respect to the total amount of the fluorine-containing compound (A), the compound (B), and the compound (C). ] The composition in any one of [4].
[6] The content of the compound (B) is 90 to 99.98% by mass with respect to the total amount of the fluorine-containing compound (A), the compound (B), and the compound (C). The composition according to any one of [5].
[7] The content of the compound (C) is 0.01 to 5% by mass with respect to the total amount of the fluorine-containing compound (A), the compound (B), and the compound (C). The composition according to any one of [6].
[8] The composition according to any one of [1] to [7], further comprising a photopolymerization initiator.

[9] An article having a cured film formed from the composition of any one of [1] to [8] on at least a part of the surface of the substrate.
[10] The article according to [9], wherein the substrate is an inorganic substrate.

According to the composition of the present invention, it is possible to form a cured film having water and oil repellency and antifouling properties and excellent adhesion to at least a part of both surfaces of the inorganic and organic substrates.
The article of the present invention has a cured film having water and oil repellency and antifouling properties and excellent adhesion on at least a part of the surfaces of both inorganic and organic substrates.

[Definition of terms]
In this specification, for example, the fluorine-containing compound represented by the formula (1) may be referred to as a (fluorine-containing) compound (1). The same applies to groups, compounds and the like represented by other formulas.
The following definitions of terms apply throughout this specification and the claims.
The “ethylenically unsaturated group” means a group containing a carbon-carbon double bond structure, but does not include a double bond in a stable aromatic ring like a benzene ring.
“Perfluoropolyether structure” means a group consisting of two or more oxyperfluoroalkylene units. Here, the chemical formula of oxyperfluoroalkylene represents that the oxygen atom is arranged on the right side of the perfluoroalkylene group.
“Polar group” means a polar atomic group.
The “hydrolyzable silyl group” means a silyl group that can form one or more silanol groups (Si—OH) by a hydrolysis reaction.
The “(meth) acryloyl group” includes both methacryloyl groups and acryloyl groups. Similarly, “(meth) acrylate” encompasses both methacrylate and acrylate embodiments.
“Fluoroalkyl group” means a group in which some or all of the hydrogen atoms in the alkyl group are substituted with fluorine atoms, and “perfluoroalkyl group” means that all of the hydrogen atoms in the alkyl group are substituted with fluorine atoms. Means the group formed. The “fluoroalkyl group” includes a “perfluoroalkyl group”.
“Fluoroalkylene group” means a group in which some or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms. “Perfluoroalkylene group” means that all of the hydrogen atoms in the alkylene group are substituted with fluorine atoms. Means the group formed. The “fluoroalkylene group” includes a “perfluoroalkylene group”.
The “etheric oxygen atom” means an oxygen atom that forms an ether bond (—O—) between carbon-carbon atoms.
“Organic group” means a group having one or more carbon atoms.
“Molecular chain” is a portion composed of a plurality of units connected in a linear or branched manner.
The “main chain” is a linear molecular chain in which all molecular chains other than the main chain are regarded as side chains.
The “side chain” is a molecular chain branched from the main chain, or a cyclic compound that is a molecular chain bonded to a ring.
A “unit” is an atomic group that forms part of the basic structure of a molecular chain.

[Composition]
The composition of the present invention (hereinafter also referred to as “the present composition”) comprises at least one ethylenically unsaturated group and a fluorine-containing compound (A) having a perfluoropolyether structure; at least two ethylenically unsaturated groups A fluorine-free compound (B) having at least one polar group selected from a carboxy group, a phosphate group, an amino group, an isocyanate group, a hydrolyzable silyl group and a thiol group, and one ethylenic group The compound (C) which has an unsaturated group and does not have a perfluoropolyether structure is contained.

(Fluorine-containing compound (A))
The fluorine-containing compound (A) in the present invention has at least one ethylenically unsaturated group and a perfluoropolyether structure.
Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a (meth) acryloyl group, a styryl group, and a cinnamoyl group, and a (meth) acryloyl group is preferable because curing by light irradiation proceeds more rapidly. .

  The number average molecular weight (Mn) of the present fluorine-containing compound (A) is preferably 500 to 80,000, more preferably 600 to 40,000, still more preferably 600 to 30,000, and particularly preferably 800 to 10,000. . When the number average molecular weight is within this range, the fluorine-containing compound (A) is excellent in compatibility with other components in the composition.

The perfluoropolyether structure imparts antifouling properties to the cured film. Examples of the perfluoropolyether structure include (C _m F _2m O) _n , where m is an integer of 1 to 6, n is an integer of 1 to 200, and n is 2 or more. , (C _m F _2m O) _n may be composed of two or more types of C _m F _2m O with different _m . When n is 2 or more, the permutation of (C _m F _2m O) may be any of block, random, and alternating. _{(C m F 2m O) C} m F 2m in _n may be either linear or branched.
Examples of (C _m F _2m O) include: (CF ₂ O); (CF ₂ CF ₂ O), (CF (CF ₃ ) O); (CF ₂ CF ₂ CF ₂ O), (C (CF ₃ ) ₂ O), (CF (CF ₃ ) CF ₂ O), (CF ₂ CF (CF ₃ ) O); (CF ₂ CF ₂ CF ₂ CF ₂ O), (CF (CF ₃ ) CF ₂ CF ₂ O ), (CF ₂ CF (CF ₃ ) CF ₂ O), (CF ₂ CF ₂ CF (CF ₃ ) O), (C (CF ₃ ) ₂ CF ₂ O), (CF ₂ C (CF ₃ ) ₂ O ), (CF (CF ₃ ) CF (CF ₃ ) O), (CF (C ₂ F ₅ ) CF ₂ O), (CF ₂ CF (C ₂ F ₅ ) O), or combinations thereof (for example, ( CF ₂ CF ₂ O—CF ₂ CF ₂ CF ₂ CF ₂ O) and the like.

As the fluorine-containing compound (A) of the present invention, a fluorine-containing compound represented by the following formula (1) is preferable.
_{[D- (C m F 2m O} ) n -] o -E ··· (1)
Where
D is D ¹ —R ^f1 —O—CH ₂ — or D ² —O—;
here,
D ¹ is CF ₃ — or CF ₃ —O—,
R ^f1 represents a fluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon-carbon atoms, an alkylene group having 1 to 20 carbon atoms, or a carbon-carbon atom. An alkylene group having 2 to 20 carbon atoms having an etheric oxygen atom in between;
D ² is a C 1-6 perfluoroalkyl group;
m is an integer from 1 to 6;
n is an integer of 1 to 200, and when n is 2 or more, (C _m F _2m O) _n may be composed of two or more types of C _m F _2m O different from _m ;
o is an integer greater than or equal to 1;
E is an o-valent organic group having one or more —C (═O) —CR ¹ ═CH ₂ (wherein R ¹ is a hydrogen atom or a methyl group).

The perfluoroalkyl group for D ² may be linear or branched. Specific _{examples, CF 3 -, CF 3 CF} 2 -, CF 3 (CF 2) 2 -, CF 3 CF (CF 3) -, CF 3 (CF 2) 3 -, CF 3 (CF 2) 4 - , CF ₃ (CF ₂ ) ₅ — and the like.
D ² is preferably a C ¹ to C 3 perfluoroalkyl group, particularly preferably CF ₃ — or CF ₃ CF ₂ — from the viewpoint of imparting excellent antifouling properties to the cured film.

R ^f1 represents a fluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon-carbon atoms, an alkylene group having 1 to 20 carbon atoms, or a carbon-carbon atom. It is a C2-C20 alkylene group which has an etheric oxygen atom in between. From the viewpoint of sufficiently imparting antifouling properties to the cured film, a fluoroalkylene group having 1 to 20 carbon atoms and a fluoroalkylene group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon-carbon atoms are preferred. From the viewpoint of particularly excellent antifouling properties, a C 1-20 perfluoroalkylene group and a C 2-20 perfluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms are particularly preferred. In addition, from the viewpoint of excellent compatibility between the fluorine-containing compound (A) and other components, a C1-C20 fluoroalkylene group containing one or more hydrogen atoms, or an etheric oxygen atom between carbon-carbon atoms And a C2-C20 fluoroalkylene group containing at least one hydrogen atom is particularly preferred.
The number of hydrogen atoms in R ^f1 is preferably 1 or more. The number of hydrogen atoms in R ^f1 is (the number of carbon atoms in R ^f1 ) × 2 or less, and is preferably (the number of carbon atoms in R ^f1 ) or less from the viewpoint that the antifouling property of the cured film is sufficiently excellent.
When R ^f1 has a hydrogen atom, the compatibility between the fluorine-containing compound (A) and other components in the present composition is excellent.

When R ^f1 has one or more hydrogen atoms, R ^f1 is a group represented by the following formula (1-1) or a formula (1-2) from the viewpoint of easy production of the fluorine-containing compound (A). Or a group represented by the following formula (1-3). R ^F is a group bonded to D ¹ .
-R ^F -O-CHFCF _2- (1-1)
-R ^F -CHFCF _2- (1-2)
-R ^F -C _z H _2z- (1-3)
However,
R ^F is a single bond, a ^C 1-15 perfluoroalkylene group, or a C 2-15 perfluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms,
z is an integer of 1-4.

R ^F is a perfluoroalkylene group having 1 to 9 carbon atoms or a perfluoroalkylene having 2 to 13 carbon atoms having an etheric oxygen atom between carbon-carbon atoms from the viewpoint of sufficiently imparting antifouling properties to the cured film. Groups are preferred. The perfluoroalkylene group may be linear or branched.
z is preferably an integer of 1 to 3. When z is 3 or more, C _z H _2z may be linear or branched, and is preferably linear.

When R ^f1 is represented by the formula (1-1), specific examples of the D ¹ -R ^f1 -group include the following groups.
CF ₃ -O-CHFCF ₂ -,
_{CF 3 -CF 2 -O-CHFCF 2} -,
_{CF 3 -CF 2 CF 2 -O-} CHFCF 2 -,
_{CF 3 -CF 2 CF 2 CF 2} -O-CHFCF 2 -,
_{CF 3 -CF 2 CF 2 CF 2} CF 2 CF 2 -O-CHFCF 2 -,
_{CF 3 -O-CF 2 CF 2} -O-CHFCF 2 -,
_{CF 3 -CF 2 OCF 2 CF 2} -O-CHFCF 2 -,
_{CF 3 -O-CF 2 CF 2} OCF 2 CF 2 -O-CHFCF 2 -,
_{CF 3 -CF 2 OCF 2 CF 2} OCF 2 CF 2 -O-CHFCF 2 -,
_{CF 3 -CF 2 CF 2 OCF (} CF 3) CF 2 -O-CHFCF 2 -,
_{CF 3 -CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) CF 2 -O-CHFCF 2 -.

Specific examples of the D ¹ -R ^f1 — group in the case where R ^f1 is represented by the formula (1-2) include the following groups.
CF ₃ -CHFCF ₂ -,
CF ₃ -CF ₂ -CHFCF _2- ,
_{CF 3 -CF 2 CF 2 -CHFCF 2} -,
_{CF 3 -CF 2 CF 2 CF 2} -CHFCF 2 -.

Specific examples of the D ¹ -R ^f1 — group in the case where R ^f1 is represented by the formula (1-3) include the following groups.
CF ₃ —CH ₂ —,
CF ₃ —CF ₂ —CH ₂ —,
_{CF 3 -CF 2 CF 2 -CH 2} -,
CF ₃ -CF ₂ CF ₂ CF ₂ -CH _2- ,
_{CF 3 -CF 2 CF 2 CF 2} CF 2 -CH 2 -,
_{CF 3 -CF 2 CF 2 CF 2} CF 2 CF 2 -CH 2 -,
CF ₃ —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —CH ₂ —,
CF ₃ -CH ₂ CH ₂ -,
_{CF 3 -CF 2 -CH 2 CH 2} -,
_{CF 3 -CF 2 CF 2 -CH 2} CH 2 -,
CF ₃ —CF ₂ CF ₂ CF ₂ —CH ₂ CH ₂ —,
_{CF 3 -CF 2 CF 2 CF 2} CF 2 -CH 2 CH 2 -,
_{CF 3 -CF 2 CF 2 CF 2} CF 2 CF 2 -CH 2 CH 2 -,
CF ₃ —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —CH ₂ CH ₂ —,
_{CF 3 -CH 2 CH 2 CH 2} -,
_{CF 3 -CF 2 -CH 2 CH 2} CH 2 -,
_{CF 3 -CF 2 CF 2 -CH 2} CH 2 CH 2 -,
CF ₃ —CF ₂ CF ₂ CF ₂ —CH ₂ CH ₂ CH ₂ —,
CF ₃ —CF ₂ CF ₂ CF ₂ CF ₂ —CH ₂ CH ₂ CH ₂ —,
CF ₃ —CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —CH ₂ CH ₂ CH ₂ —,
_{CF 3 -CF 2 CF 2 CF 2} CF 2 CF 2 CF 2 -CH 2 CH 2 CH 2 -,
_{CF 3 -O-CF 2 -CH 2} -,
_{CF 3 -CF 2 OCF 2 -CH 2} -,
CF ₃ —O—CF ₂ CF ₂ OCF ₂ —CH ₂ —,
_{CF 3 -CF 2 OCF 2 CF 2} OCF 2 -CH 2 -,
_{CF 3 -O-CF 2 CF 2} OCF 2 CF 2 OCF 2 -CH 2 -,
_{CF 3 -CF 2 OCF 2 CF 2} OCF 2 CF 2 OCF 2 -CH 2 -.

R ^f1 is preferably a group represented by the formula (1-1) from the viewpoint of ease of production of the compound (1), and the D ¹ -R ^f1 -group may be CF ₃ -CF ₂ CF _2. -O-CHFCF ₂ - or _{CF 3 -CF 2 CF 2 CF 2} CF 2 CF 2 -O-CHFCF 2 - is particularly preferred.

Examples of the fluorine-containing compound represented by the formula (1) include the following compounds (A1) to (A3).
(A1) A fluorine-containing polymer having a perfluoropolyether structure and an ethylenically unsaturated group independently in the side chain.
(A2) A fluorine-containing polymer having a perfluoropolyether structure at both ends or one end of the main chain and having an ethylenically unsaturated group in the side chain.
(A3) A fluorine-containing compound having a perfluoropolyether structure and an ethylenically unsaturated group independently at the end of the main chain or in the side chain of the cyclic compound.

<Fluorine-containing compound (A1)>
The fluorine-containing compound (A1) is preferably a copolymer containing a unit (U1) having a perfluoropolyether structure and a unit (U2) having an ethylenically unsaturated group. The copolymer includes, for example, a monomer (M1) having a perfluoropolyether structure, a monomer (M2) having an ethylenically unsaturated group, and other monomers (M1 and M2 as necessary). Is obtained by copolymerization.

<< Monomer (M1) >>
As the monomer (M1), a compound represented by the following formula (M11) (hereinafter also referred to as monomer (M11)) is preferable.
^{G 1 -C (= O) C} (R 11) = CH 2 ··· (M11)
In formula (M11),
R ¹¹ is a hydrogen atom or a methyl group,
G ¹ is a group represented by the following formula (G1).
_{^{D 2 -O- (C m F 2m}} O) n -R f2 -Y 11 -Q 11 -Y 12 - ··· (G1)
Here, in the formula (G1),
D ² , m and n are the same as in formula (1), and the preferred range is also the same,
R ^f2 is a fluoroalkylene group having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms,
Y ¹¹ is a single bond, —C (═O) NH— (where Q ¹¹ is bound to N), —OC (═O) NH— (where Q ¹¹ is bound to N), — O—, —C (═O) O— (wherein Q ¹¹ is bonded to O), —OC (═O) O—, —NHC (═O) NH— or —NHC (═O) O— (Where Q ¹¹ binds to O),
Q ¹¹ is a single bond or a divalent organic group,
Y ¹² is —O—, —NH— or —NHC (═O) O— (C _k H _2k ) —O— (where k is an integer of 1 to 10, preferably 2 to 3, preferably 2). Particularly preferred, and Q ¹¹ binds to N).
However, in Formula (G1), Y ¹¹ is —C (═O) NH—, —OC (═O) NH—, —O—, —C (═O) O—, —OC (═O) O— , —NHC (═O) NH— or —NHC (═O) O—, Q ¹¹ is a divalent organic group. When Y ¹¹ and Y ¹² are —O—, Q ¹¹ is a divalent organic group.

In formula (M11), R ¹¹ is preferably a methyl group from the viewpoint of excellent oil repellent properties.

In the formula ^{(G1), -R f2 -Y 11} -Q 11 -Y 12 - as a combination of ^{Y 11, Q 11} and ^{Y 12} in the formula (G1) preferably has the following 1-5.
1. Y ¹¹ : single bond, Q ¹¹ : single bond, Y ¹² : —O—
2. Y ¹¹ : —C (═O) NH—, Q ¹¹ : divalent organic group, Y ¹² : —O— or —NH—
3. Y ¹¹ : —OC (═O) NH—, Q ¹¹ : divalent organic group, Y ¹² : —O—, —NH— or —NHC (═O) O— (CH ₂ ) ₂ —O—.
4). Y ¹¹ : —O—, Q ¹¹ : Divalent organic group, Y ¹² : —O—
5). Y ¹¹ : —C (═O) O—, Q ¹¹ : divalent organic group, Y ¹² : —O—

R ^f2 is preferably a fluoroalkylene group having 1 to 10 carbon atoms, and particularly preferably a fluoroalkylene group having 1 to 6 carbon atoms. For _{example, -CF 2 CF 2 CF 2 -} , - CF 2 CF 2 CF 2 CH 2 - and the like.

Q ¹¹ is a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group, a poly (oxyalkylene) group, a cycloalkylene group, an arylene group, and a group in which a part of hydrogen atoms of the alkylene group is substituted with a hydroxyl group. Q ¹¹ is preferably an alkylene group having 2 to 6 carbon atoms or a group in which part of the hydrogen atoms of the alkylene group is substituted with a hydroxyl group from the viewpoint of easy industrial production.

As the monomer (M11), and preferably ^{D 2} mentioned above it is preferably a combination of a preferred _{(C m} F 2m _{O) n} described above, industrially easy to manufacture, easy to handle, excellent in cured film A compound represented by the following formula is particularly preferable from the viewpoint of imparting antifouling properties.

^{_{D 2 -O - [(CF 2}} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 O] -CF 2 CF 2 CF 2 CH 2 -O-C (= O) C ( R ¹¹ ) = CH ₂ (M11-1a)
^{_{D 2 -O - [(CF 2}} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 O] -CF 2 CF 2 CF 2 -C (= O) NH-Q 11 -O _{^{-C (= O) C (R}} 11) = CH 2 ··· (M11-2a)
^{_{D 2 -O - [(CF 2}} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 O] -CF 2 CF 2 CF 2 -C (= O) NH-Q 11 -NH ^{-C (= O) C (R} 11) = CH 2
... (M11-2b)
^{_{D 2 -O - [(CF 2}} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 O] -CF 2 CF 2 CF 2 CH 2 -OC (= O) NH-Q 11 _{^{-O-C (= O) C}} (R 11) = CH 2 ··· (M11-3a)
^{_{D 2 -O - [(CF 2}} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 O] -CF 2 CF 2 CF 2 CH 2 -OC (= O) NH-Q 11 —NHC (═O) O— (CH ₂ ) ₂ —O—C (═O) C (R ¹¹ ) ═CH ₂ (M11-3b)
^{_{D 2 -O - [(CF 2}} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 O] -CF 2 CF 2 CF 2 CH 2 -O-Q 11 -O-C ( = O) C (R ¹¹ ) = CH ₂ (M11-4a)
^{_{D 2 -O - [(CF 2}} CF 2 O-CF 2 CF 2 CF 2 CF 2 O) n -CF 2 CF 2 O] -CF 2 CF 2 CF 2 -C (= O) O-Q 11 -O _{^{-C (= O) C (R}} 11) = CH 2 ··· (M11-5a)
However, ^{D 2} is CF ₃ - or _CF 3 CF ₂ - is.

For example, the monomer (M11) includes a compound (α1) represented by the following formula (α1) and Cl—C (═O) C (R ¹¹ ) ═CH _{2 in} the presence of a base (such as triethylamine). It can manufacture by the method of making it react.
_{^{D 2 -O- (C m F 2m}} O) n -R f2 -OH ··· (α1)
Compound ([alpha] 1) or the _{^{like, D 2 -O- (C m F}} 2m O) n - can be prepared by known methods depending on the structure of.

<< Monomer (M2) >>
As the monomer (M2), a compound represented by the following formula (M21) (hereinafter also referred to as monomer (M21)) is preferable.
^{G 2 -C (= O) C} (R 21) = CH 2 ··· (M21)

In formula (M21),
R ²¹ represents a hydrogen atom or a methyl group,
G ² is a group represented by the following formula (G2).
_{^{CH 2 = C (R 22)}} C (= O) -O-R 23 -Y 21 -Q 21 -Y 22 - ··· (G2)
Here, in the formula (G2),
R ²² is a hydrogen atom or a methyl group,
R ²³ is an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms having an etheric oxygen atom between carbon-carbon atoms,
Y ²¹ is a single bond, —C (═O) NH— (where Q ²¹ binds to N), —OC (═O) NH— (where Q ²¹ binds to N), — O—, —C (═O) O— (wherein Q ²¹ is bonded to O), —OC (═O) O—, —NHC (═O) NH— or —NHC (═O) O— (Where Q ²¹ binds to O),
Q ²¹ is a single bond or a divalent organic group (excluding those having (C _m F _2m O) _n ),
Y ²² represents —O—, —NH— or —NHC (═O) O— (C _k H _2k ) —O— (wherein k is the same as in formula (G1), and the preferred range is also the same. And Q ²¹ binds to N).
However, in Formula (G2), Y ²¹ represents —C (═O) NH—, —OC (═O) NH—, —O—, —C (═O) O—, —OC (═O) O—. , —NHC (═O) NH— or —NHC (═O) O—, Q ²¹ is a divalent organic group. When Y ²¹ and Y ²² are —O—, Q ²¹ is a divalent organic group.

In Formula (M21), R ²¹ is preferably a methyl group from the viewpoint of excellent oil repellent properties.
In Formula (G2), R ²² is preferably a hydrogen atom from the viewpoint of excellent reactivity.

In formula ^{(G2), -R 23 -Y 21} -Q 21 -Y 22 - as a combination of ^{Y 21, Q 21} and ^{Y 22} in the formula (G2) preferably has the following 1-4.
1. Y ²¹ : —NHC (═O) O—, Q ²¹ : divalent organic group, Y ²² : —O—
2. Y ²¹ : —OC (═O) NH—, Q ²¹ : divalent organic group, Y ²² : —O—
3. Y ²¹ : single bond, Q ²¹ : single bond, Y ²² : —O—
4). Y ²¹ : —O—, Q ²¹ : divalent organic group, Y ²² : —O—

R ²³ is an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms having an etheric oxygen atom between carbon-carbon atoms. The alkylene group may be linear or branched. R ²³ is preferably an alkylene group having 2 to 6 carbon atoms from the viewpoint of easy industrial production.

Q ²¹ is a single bond or a divalent organic group. The divalent organic group is exemplified and Q ¹¹ is also preferred range is also the same.

G ² is preferably a group represented by the following formula from the viewpoint of easy production of the copolymer and excellent reactivity.
^{_{CH 2 = CHC (= O)}} -O-R 23 -NHC (= O) O-Q 21 -O- ··· (G2-1)
^{_{CH 2 = CHC (= O)}} -O-R 23 -OC (= O) NH-Q 21 -O- ··· (G2-2)
^{_{CH 2 = CHC (= O)}} -O-R 23 -O- ··· (G2-3)
CH ₂ ═CHC (═O) —O—R ²³ —OQ ²¹ —O— (G2-4)
^{However, Q 21} is a divalent organic group (provided _that (excluding those with a _{C m} F 2m _{O) n)} is.

<< Unit composition >>
The proportion of the unit (U1) in the fluorine-containing compound (A1) is preferably from 0.1 to 30 mol%, particularly preferably from 0.1 to 10 mol%, of all the units constituting the fluorine-containing compound (A1). . If the ratio of the unit (U1) is within the above range, the cured film can be provided with excellent antifouling properties, and the fluorine-containing compound (A1) is excellent in compatibility with other components in the composition.

  The proportion of the unit (U2) in the fluorinated compound (A1) is preferably 5 to 99.9 mol%, particularly preferably 5 to 90 mol%, of all the units constituting the fluorinated compound (A1). When the proportion of the unit (U2) is within the above range, the fluorine-containing compound (A1) is excellent in compatibility with other components in the composition.

The proportion of units derived from other monomers (excluding M1 and M2) in the fluorine-containing compound (A1) is preferably 0 to 94.9 mol% of all units constituting the fluorine-containing compound (A1). 0 to 80 mol% is particularly preferable. If the proportion of units derived from other monomers is within the above range, the effects of the present invention will not be impaired.
The most preferred embodiment of the fluorine-containing compound (A1) is as follows.

^{_{G 11: CF 3 -O- (C}} m F 2m O) n -CF 2 CF 2 CF 2 CH 2 -O-
^{_{G 21: CH 2 = CHC (}} = O) -O- (CH 2) 2 -NHC (= O) O- (CH 2) 2 -O-
^{_{G 31: CH 3 CH 2 CH}} 2 CH 2 -O-
^{_{G 32: HO- (CH 2)}} 2 -O-
For example, s1 is 6 mol%, s2 + s4 is 28 mol%, and s3 is 66 mol%. (Calculated from the charged amount of each monomer.)

<Fluorine-containing compound (A2)>
As the fluorine-containing compound (A2), a polymer containing a unit having a perfluoropolyether structure at both ends or one end of the main chain and a unit having an ethylenically unsaturated group is preferable. The polymer uses a compound having a perfluoropolyether structure as a polymerization initiator or a chain transfer agent, and a monomer having an ethylenically unsaturated group and, if necessary, another monomer (ethylenically unsaturated group). Is obtained by polymerization.

<< Polymerization initiator having a perfluoropolyether structure >>
The polymerization initiator having a perfluoropolyether _{structure, D- (C m F 2m O} ) n - organic peroxide having a group, and wherein, D, m and n are as defined in the formula (1) The preferred range is also the same. _{D- (C m F 2m O)} n - Examples of the organic peroxide having a group, the compound represented by the following formula (SA1) (. Hereinafter, also referred to as "Compound (SA1)") can be mentioned.
D ² —O— (C _m F _2m O) _n —CF ₂ —C (═O) —O—O—C (═O) —CF ₂ — (OC _m F _2m ) _n —O—D ^2.・ (SA1)

^D 2, m and n in formula (SA1) is the same as ^D 2, m and n in formula (1), and preferred ranges are also the same. Compound (SA1) can be produced, for example, by the method described in JP-A-2008-44863.

<< Chain transfer agent having a perfluoropolyether structure >>
The chain transfer agent having a perfluoropolyether _{structure, D- (C m F 2m O} ) n - compound having a group and -SH group, and wherein, D, m and n in Formula (1) The preferred range is also the same. _{D- (C m F 2m O)} n - Examples of the compound having a group and -SH group, the compound represented by the following formula (TA1) (. Hereinafter, also referred to as "Compound (TA1)") can be mentioned.
_{D- (C m F 2m O)} n -CF 2 -Q 31 -SH ··· (TA1)

D, m and n in the formula (TA1) are the same as those in the formula (1), and the preferred range is also the same. Q ³¹ is a divalent organic group containing no single bond or fluorine atom other than —S—.

Q ³¹ is preferably a divalent organic group represented by the following formula (TA1-1) from the viewpoint of ease of production of the fluoropolymer and easy availability of production raw materials.
^{-Y 31 -R 31 - ··· (TA1-1} )
However, R ³¹ is bonded to S.

As Y ³¹ , —C (═O) NH— (where N binds to R ³¹ ), —OC (═O) NH— (where N binds to R ³¹ ), —O—. , —C (═O) O— (wherein O is bonded to R ³¹ ), —OC (═O) O—, —NHC (═O) NH— or —NHC (═O) O— (wherein , O binds to R ³¹ ). From the viewpoint of excellent compatibility with other components in the composition, —C (═O) NH— (wherein N is bonded to R ³¹ ) is preferable.
R ³¹ includes a single bond or an alkylene group, and an alkylene group having 2 to 6 carbon atoms is preferable from the viewpoint of imparting excellent antifouling properties to the cured film.

The monomer (M2) is preferable as the monomer having an ethylenically unsaturated group.
The most preferred embodiment of the fluorine-containing compound (A2) is as follows.

R ²¹ is the same as formula (M21), and the preferred range is also the same. n1 + n2 is n, and n is the same as the formula (1). t1 is 1 or 2, and exists at one end or both ends.

<Fluorine-containing compound (A3)>
In the fluorine-containing compound (A3) in the present invention, the number of (meth) acryloyl groups of the E group is preferably 1 to 3, and 1 or 2 is particularly preferable.
Examples of the fluorine-containing compound (A3) include compounds in which o in the formula (1) is 1 and E is represented by the following formulas (E1) to (E3).

In formulas (E1) to (E3), Q ⁴¹ is a divalent organic group, Q ⁴² is a trivalent organic group, Q ⁴³ is a tetravalent organic group, and R ^{41 to} R ⁴⁶ are each independently hydrogen. An atom or a methyl group.

1 to 100 is preferable for each of Q ^{41 to} Q ⁴³ , and 10 to 60 is particularly preferable. If the carbon number is not less than the lower limit of the above range, the compatibility of the fluorine-containing compound (A3) and other components in the composition is excellent, and if it is not more than the upper limit of the above range, the antifouling property of the cured film Is better. Q ^{41 to} Q ⁴³ preferably have no fluorine atom. By Q ⁴¹ to Q ⁴³ has no fluorine atom, the compatibility of the fluorine-containing compound in the composition and (A3) and the other ingredients is excellent.
Q ^{41 to} Q ⁴³ may be linear or branched. Further, it may have a ring structure. When it has a ring structure, the ring structure may be an aromatic ring or an aliphatic ring, and an aliphatic ring is preferred.
Q ^{41 to} Q ⁴³ may have a hetero atom such as an etheric oxygen atom, a sulfur atom or a nitrogen atom, or may have a group such as a carbonyl group, an imino group or a sulfonyl group.

Groups represented by the above formula (E1) (hereinafter, referred to as "E1 group.") ^Is represented by the ^{group Q 41} is represented by the following formula (E1-1), the following equation (E1-2) It is preferable to have one or more groups represented by the group or the following formula (E1-3).
_{- (CH 2 CH 2 O)} p1 - ··· (E1-1)
_{- (CH 2 CH (CH 3} ) O) p2 - ··· (E1-2)
_{- {C (= O) C} q H 2q O} p3 - ··· (E1-3)

p1, p2, p3 and q are integers of 1-20.
For example, p1 is preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 3. q is preferably an integer of 1 to 8, and q is more preferably 3 to 6 and particularly preferably 5 from the viewpoint of easy production of the compound (1). p3 is preferably an integer of 1 to 10, particularly preferably an integer of 2 to 8.

Q ⁴¹ preferably has at least a group represented by the formula (E1-3), more preferably a group represented by the following formula (E1-4), from the viewpoint of easy production of the fluorine-containing compound (A3). .
_{-CF 2 CH 2 O- (CH 2} CH 2 O) p1 - {C (= O) CH 2 CH 2 CH 2 CH 2 CH 2 O} p3 - ··· (E1-4)

P1 and p3 in Formula (E1-4) are the same as p1 and p3 in Formula (E1-1) and Formula (E1-3), and the preferred ranges are also the same. In Formula (1), it is preferable that the —CF ₂ CH ₂ O side of the group represented by Formula (E1-4) be bonded to (C _m F _2m O) _n .

The above equation (E2), a group represented by (hereinafter referred to as "E2 group".) As ^is mentioned group ^having a group ^{Q 42} is represented by the following formula (E2-1) ~ (E2-6) It is done.

In formulas (E2-1) to (E2-6), u1, u2, u3, v1 and v2 are each independently an integer of 2 to 10. ^{* 1, *} 2 and ^* 3, a terminal for coupling with other ^groups, one of ^* 1 and ^* 2, combined with ^{-C (= O) -CR 42 =} CH 2 in the formula (E2), -C in the other formula ^(E2) (= O) bonded to ^-CR 43 = CH ^{_2, *} 3 via a single bond or a divalent organic group, in the formula _{(1) (C m F 2m} O) It is preferable to combine with _n . Examples of the divalent organic group include an alkylene group having 1 to 10 carbon atoms, a fluoroalkylene group, and a perfluoroalkylene group. For example, CH ₂ CF ₂ — or —CH ₂ CF ₂ CF ₂ — is preferable. However, _-CH 2 CF ₂ - or _-CH 2 _CF 2 CF ₂ - bonded at the terminal represented by CH ₂ side is ^* 3, _-CH 2 CF ₂ - or _-CH 2 _CF 2 CF ₂ - a CF ₂ side is bound with _{(C m F 2m O) n} .

The (meth) acryloyl group at the end of the E group can be introduced, for example, by applying the following methods (i) to (iii) to the hydroxyl-modified ends of Q ^{41 to} Q ⁴³ . (I) Using a compound having a (meth) acryloyl group such as (meth) acrylic acid or (meth) acrylic acid chloride and having a group capable of forming an ester bond with a hydroxyl group, (meth) acryloyl by an ester bond How to introduce a group. (Ii) A method of introducing a (meth) acryloyl group by a urethane bond using a compound having a (meth) acryloyl group such as (meth) acryloyloxyethyl isocyanate and a group capable of forming a urethane bond with a hydroxyl group . (Iii) A compound having a (meth) acryloyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or hydroxybutyl (meth) acrylate and having a hydroxyl group, together with a bifunctional isocyanate compound, and urethane A method of introducing a (meth) acryloyl group through a bond.

  As the fluorine-containing compound (A3), the following formula (A3-1), the following formula (A3-2), the following formula (A3-3), the following formula (A3-4), the following formula (A3-5), the following formula A compound represented by formula (A3-6) is preferred. Moreover, the compounds represented by the following formulas (A3-7) to (A3-12) are preferred. Among these, the following formula (A3-1), the following formula (A3-2), and the following formula (A3-3) are easy to manufacture industrially, easy to handle, and can sufficiently impart antifouling properties to the cured film. The compounds represented by formula (A3-4), formula (A3-5), formula (A3-6) and formula (A3-7) are particularly preferred.

^{_{D 1 -R F -O-CHFCF 2}} -O-CH 2 -CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} -CF 2 CH 2 O- (CH 2 CH 2 O _{) p1 - {C (= O} ) CH 2 CH 2 CH 2 CH 2 CH 2 O} p3 -C (= O) NH-CH 2 CH 2 -O-C (= O) -CH = CH 2 ··· (A3-1)
^{_{D 1 -R F -O-CHFCF 2}} -O-CH 2 -CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} -CF 2 CH 2 O- (CH 2 CH 2 O _{) p1 - {C (= O} ) CH 2 CH 2 CH 2 CH 2 CH 2 O} p3 -C (= O) NH-CH 2 CH 2 -O-C (= O) -C (CH 3) = CH ₂ ... (A3-2)

^{_{D 1 -R F -CHFCF 2 -O-}} CH 2 -CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} -CF 2 CH 2 O- (CH 2 CH 2 O) p1 _{- {C (= O) CH} 2 CH 2 CH 2 CH 2 CH 2 O} p3 -C (= O) NH-CH 2 CH 2 -O-C (= O) -CH = CH 2 ··· (A3 -3)
^{_{D 1 -R F -CHFCF 2 -O-}} CH 2 -CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} -CF 2 CH 2 O- (CH 2 CH 2 O) p1 _{- {C (= O) CH} 2 CH 2 CH 2 CH 2 CH 2 O} p3 -C (= O) NH-CH 2 CH 2 -O-C (= O) -C (CH 3) = CH 2 · .. (A3-4)

^{_{D 1 -R F -C z H 2z}} -O-CH 2 -CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} -CF 2 CH 2 O- (CH 2 CH 2 O _{) p1 - {C (= O} ) CH 2 CH 2 CH 2 CH 2 CH 2 O} p3 -C (= O) NH-CH 2 CH 2 -O-C (= O) -CH = CH 2 ··· (A3-5)
^{_{D 1 -R F -C z H 2z}} -O-CH 2 -CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} -CF 2 CH 2 O- (CH 2 CH 2 O _{) p1 - {C (= O} ) CH 2 CH 2 CH 2 CH 2 CH 2 O} p3 -C (= O) NH-CH 2 CH 2 -O-C (= O) -C (CH 3) = CH ₂ ... (A3-6)

In formulas (A3-1) to (A3-6), D ¹ has the same meaning as D ¹ in formula (1), and the preferred range is also the same. R ^F and z have the same meanings as R ^F and z in formulas (1-1) to (1-3), and preferred ranges are also the same. n1 + n2 is n, and n is the same as n in the formula (1). p1 and p3 are the same as p1 and p3 in Formula (E1-1) and Formula (E1-3), and their preferred ranges are also the same.

In formulas (A3-7) to (A3-9), G ¹⁰ represents D ¹ —R ^f1 —O—CH ₂ CF ₂ O {(CF ₂ O) _n1-1 (CF ₂ CF ₂ O) _n2 } CF. ₂ CH ₂ — or D ² —O— (CF ₂ CF ₂ CF ₂ O) _n3 —CF ₂ CF ₂ CH ₂ —. u1, u2, u3, v1 and v2 have the same meanings as in formulas (E2-1) to (E2-6), and preferred ranges are also the same.

Wherein ^{(A3-10) ~ (A3-12),} G 10 _{^{is, D 1 -R f1 -O-CH}} 2 CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} CF ₂ CH ₂ — or D ² —O— (CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ CH ₂ —. u1, u2, u3, v1 and v2 have the same meaning as in formulas (E2-1) to (E2-6), and preferred ranges are also the same.

As the compound (1), D ^{is, D 1 -R f1 -O-CH} 2 - and ^is, D 1 ^{-R f1} - group _{CF 3 -CF 2 CF 2 -O-} CHFCF 2 - a and, p1 indicates Particularly preferred is a compound of the formula (A3-1) wherein 1 and p3 is 2 (that is, a compound of the following formula (A3-1-1)).
_{CF 3 CF 2 CF 2 -O-} CHFCF 2 -O-CH 2 -CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} CF 2 CH 2 O- (CH 2 CH 2 O _{) - {(C = O)} CH 2 CH 2 CH 2 CH 2 CH 2 O} 2 -C (= O) NH-CH 2 CH 2 -O-C (= O) -CH = CH 2 ··· ( A3-1-1)
Similarly, the compound ^{(1), G 10 _{is, D 2 -O- (CF 2 CF}} 2 CF 2 O) n -CF 2 CF 2 CH 2 - and is, ^{D 2} groups, _CF 3 CF ₂ - Especially preferred are compounds of formula (A3-7), wherein u1, u2 and u3 are each 6, and v1 and v2 are each 2.

The fluorine-containing compound (A3) can be produced, for example, by the method described in International Publication No. 2003/002628 (Patent Document 2).
Here, a method for producing the compound (A3-1) will be described.
In the presence of a basic compound, D ¹ -R ^F —O—CF═CF ₂ is reacted with the compound (β1) represented by the following formula having an OH group at both ends, to give a compound (β2), a compound ( A mixture of β3) and unreacted compound (β1) is obtained.
HOCH ₂ CF ₂ O {(CF ₂ O) _n1-1 (CF ₂ CF ₂ O) _n2 } CF ₂ CH ₂ OH (β1)
_{^{D 1 -R F -O-CHFCF 2}} OCH 2 CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} CF 2 CH 2 OH ··· (β2)
D ¹ -R ^F —O—CHFCF ₂ OCH ₂ CF ₂ O {(CF ₂ O) _n1-1 (CF ₂ CF ₂ O) _n2 } CF ₂ CH ₂ OCF ₂ CHF—O—R ^F —D ^1.・ (Β3)

From the above mixture, a monofunctional compound (β2) having an OH group remaining at one end is isolated, and added in the presence of a basic compound such as cesium carbonate while decarboxylating ethylene carbonate to the compound (β2). To obtain the compound (β4).
^{_{D 1 -R F -O-CHFCF 2}} OCH 2 CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} CF 2 CH 2 O (CH 2 CH 2 O) p1 H ··· (Β4)

Next, in the presence of a metal complex catalyst such as titanium tetraisobutoxide, ε-caprolactone is anionically polymerized with the compound (β4) to obtain a compound (β5).
^{_{D 1 -R F -O-CHFCF 2}} OCH 2 CF 2 O {(CF 2 O) n1-1 (CF 2 CF 2 O) n2} CF 2 CH 2 O (CH 2 CH 2 O) p1 {C (= O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O} _p3 H (β5)

  Next, acryloyloxyethyl isocyanate is reacted with compound (β5) in the presence of a metal catalyst such as tin to introduce an acryloyl group to obtain compound (A3-1).

(Compound (B))
Compound (B) in the present composition is a fluorine-free compound having at least two ethylenically unsaturated groups.
As the ethylenically unsaturated group, a vinyl group, an allyl group, a (meth) acryloyl group, a styryl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable. At least two ethylenically unsaturated groups of the compound (B) form a three-dimensional cross-link in the cured film, imparting abrasion resistance, and giving a film having an excellent appearance. Moreover, it is thought that a compound (B) contributes to the improvement of the adhesiveness between a base material and a cured film, when van der Waals force etc. work between a base material, especially an organic base material.

  The compound (B) preferably has three or more ethylenically unsaturated groups, particularly preferably 3 to 30 from the viewpoint of imparting excellent wear resistance to the cured film.

  Such a compound is a reaction product of trimethylolpropane, pentaerythritol or polypentaerythritol and acrylic acid or methacrylic acid, and has 3 or more, more preferably 4 to 20 (meth) acryloyl groups. The compound which has is mentioned. Specific examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  As the compound (B), the urethane bond acts as a pseudo-crosslinking point due to the action of a hydrogen bond, and imparts excellent wear resistance to the cured film even if the molecular weight per (meth) acryloyl group is not small. A compound having a urethane bond in the molecule and three or more (meth) acryloyl groups in one molecule is also preferable.

Examples of such compounds include tris (acryloyloxyethyl) isocyanurate and the following compounds.
A compound which is a reaction product of pentaerythritol or polypentaerythritol, polyisocyanate, and hydroxyalkyl (meth) acrylate, and has 3 or more, more preferably 4 to 20 (meth) acryloyl groups.
A compound which is a reaction product of pentaerythritol or polypentaerythritol poly (meth) acrylate having a hydroxyl group and polyisocyanate, and has 3 or more, more preferably 4 to 20 (meth) acryloyl groups.

(Compound (C))
Compound (C) in the present composition contains at least one polar group selected from a carboxy group, a phosphate group, an amino group, an isocyanate group, a hydrolyzable silyl group and a thiol group, and one ethylenic unsaturated group. It has a group and does not have a perfluoropolyether structure. In the compound (C), the polar group forms a hydrogen bond or a covalent bond with a polar group (for example, a hydroxyl group) on the surface of a base material, particularly an inorganic base material, thereby causing adhesion between the base material and the cured film. It is thought that it contributes to the improvement.
As the ethylenically unsaturated group, a vinyl group, an allyl group, a (meth) acryloyl group, a styryl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.
When the polar group has two or more, the two or more polar groups may be the same as or different from each other.

  Specific examples of the compound (C) include β-carboxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2-aminoethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3 -(Trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate and the like.

(Photopolymerization initiator)
This composition may contain the photoinitiator as needed. A known photopolymerization initiator can be used as the photopolymerization initiator. For example, aryl ketone photopolymerization initiators such as acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoylbenzoates, α-acyloxime esters; sulfides And sulfur-containing photopolymerization initiators such as thioxanthones; acylphosphine oxides such as acyl diarylphosphine oxides. A photoinitiator may be used individually by 1 type and may use 2 or more types together. The photopolymerization initiator may be used in combination with a photosensitizer such as amines.

(Medium)
The present composition may contain a medium as required. By including the medium, the form, viscosity, surface tension and the like of the present composition can be adjusted, and the liquid physical properties suitable for the coating method can be controlled.
As the medium, an organic solvent is preferable. The organic solvent may be a fluorinated organic solvent, a non-fluorinated organic solvent, or may contain both solvents.

Examples of the fluorine-based organic solvent include fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, fluoroalkylamines, and fluoroalcohols. As commercial products, C ₆ F ₁₃ H (AC-2000: product name, manufactured by Asahi Glass Co., Ltd.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name, manufactured by Asahi Glass Co., Ltd.), C ₂ F ₅ CHFCHFCF ₃ (Bertrell: product name, manufactured by DuPont), 1,1,2,2,3,3,4-heptafluorocyclopentane (Zeorolla H: product name, manufactured by Nippon Zeon), CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (Novec-7100: product name, manufactured by 3M Company), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, 3M Company _{Ltd.), C 6 F 13 OCH 3} ( Novec -7300: product name, 3M Co., Ltd.).
From the viewpoint that the fluorine-containing compound (A) is easily dissolved, fluoroalkane, fluoroalcohol and fluoroalkyl ether are preferred. In addition, you may use these organic solvents individually or in mixture of 2 or more types.

  As the non-fluorine organic solvent, a compound consisting only of a hydrogen atom and a carbon atom, a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and a glycol ether organic is preferable in that the fluorine-containing compound (A) is easily dissolved. A solvent and a ketone organic solvent are particularly preferable.

(Other additives)
The present composition may contain other additives as required.
Other additives include colloidal silica, photosensitizers, UV absorbers, light stabilizers, thermosetting stabilizers, antioxidants, leveling agents, antifoaming agents, thickeners, antisettling agents, pigments, dyes , Dispersants, antistatic agents, surfactants (antifogging agents, leveling agents, etc.), metal oxide particles, various resins (epoxy resins, unsaturated polyester resins, polyurethane resins, etc.) and the like.
Moreover, when using a fluorine-containing compound (A), you may accompany the compound (henceforth "impurity") unavoidable on manufacture of a fluorine-containing compound. Specifically, it is a by-product generated in the manufacturing process of the fluorine-containing compound and a component mixed in the manufacturing process of the fluorine-containing compound. The content of impurities is preferably 5% by mass or less, particularly preferably 2% by mass or less, with respect to the fluorine-containing compound (100% by mass). When the impurity content is within the above range, the cured film can be provided with extremely excellent antifouling properties and lubricity.

(composition)
The content of the fluorine-containing compound (A) in the composition is preferably 0.01 to 5% by mass in the total (100% by mass) of the fluorine-containing compound (A), the compound (B) and the compound (C). 0.02 to 4% by mass is more preferable, and 0.05 to 3% by mass is particularly preferable. When the content of the fluorine-containing compound (A) is within the above range, the composition is excellent in storage stability, appearance of the cured film, abrasion resistance and antifouling property (oil-based ink repellency).

  The content of the compound (B) in the composition is preferably 90 to 99.98% by mass in the total (100% by mass) of the fluorine-containing compound (A), the compound (B) and the compound (C), and 92 -99.96 mass% is more preferable, and 94-99.9 mass% is especially preferable. When the content of the compound (B) is within the above range, the composition is excellent in storage stability, appearance of the cured film, abrasion resistance and antifouling property (oil-based ink repellency).

  The content of the compound (C) in the composition is preferably 0.01 to 5% by mass in the total (100% by mass) of the fluorine-containing compound (A), the compound (B) and the compound (C), and 0 0.02 to 4% by mass is more preferable, and 0.05 to 3% by mass is particularly preferable. When the content of the compound (C) is within the above range, the composition is excellent in storage stability, appearance of the cured film, abrasion resistance and antifouling property (oil-based ink repellency).

  When this composition contains a photoinitiator, the content is 0.01-5 mass parts with respect to the sum total (100 mass parts) of a fluorine-containing compound (A), a compound (B), and a compound (C). Is preferable, 0.02 to 4 parts by mass is more preferable, and 0.05 to 3 parts by mass is particularly preferable. If content of a photoinitiator is in the said range, it is excellent in compatibility with each component in this composition. Moreover, it is excellent in sclerosis | hardenability of this composition, and the cured film to form is excellent in hardness.

When this composition contains a medium, 5-80 mass% is preferable among this composition (100 mass%), 10-70 mass% is more preferable, and its content is 20-60 mass% especially preferable.
When this composition contains another additive, content of the additive in this composition is with respect to the sum total (100 mass%) of a fluorine-containing compound (A), a compound (B), and a compound (C). 0.5-20 mass% is preferable, 1-15 mass% is more preferable, and 1-10 mass% is especially preferable.

[Goods]
The article of the present invention is preferably an article having a cured film formed from the present composition on at least a part of the surface of the substrate.
The thickness of the cured film is preferably from 0.5 to 20 μm, particularly preferably from 1 to 15 μm, from the viewpoint of wear resistance and antifouling properties.

(Base material)
The base material is a main body part of various articles (optical lenses, displays, optical recording media, etc.) that require water / oil repellency and antifouling properties, or a member constituting the surface of the article.
The material of the base material is metal or metal oxide (for example, iron, copper, aluminum, ITO, sapphire, etc.), inorganic materials such as glass; polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate resin (PET) ), Polyethylene naphthalate resin (PEN), polymethyl methacrylate resin (PMMA), polystyrene resin (PSt), polycarbonate resin (PC), organic materials such as acrylonitrile-butadiene-styrene resin (ABS); or a composite material thereof Is mentioned.
As the glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically strengthened. Borosilicate glass is particularly preferred.

(Product manufacturing method)
The article is produced, for example, through a process of applying the present composition to the surface of a substrate to obtain a coating film, removing the medium as necessary, and photocuring to form a cured film.

  Coating methods include bar coating, spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, ink jet, flow coating, roll coating, casting, Langmuir-Blodget Method, gravure coating method and the like.

Examples of the method for removing the medium include heating, reduced pressure, and heating under reduced pressure. In addition, it is preferable that the obtained dry film contains less than 10 mass% of a medium, and it is especially preferable that it contains less than 1 mass%.
The temperature for heating is preferably 50 to 120 ° C.
The solvent removal time is preferably 0.5 minutes to 3 hours.

The photocuring is preferably performed on the coating film when the composition does not contain a medium, and on a dry film obtained by removing the medium from the coating film when the composition contains a medium.
Photocuring is performed by irradiating active energy rays.
Examples of active energy rays include ultraviolet rays, electron beams, X-rays, radiation, high-frequency rays, etc., and ultraviolet rays having a wavelength of 180 to 500 nm are economically preferable.
Active energy ray sources include ultraviolet irradiation devices (xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, etc.), electron beam irradiation devices, X-ray irradiation devices, high-frequency generators, etc. Can be used.
The irradiation time of the active energy ray is the conditions such as the type of the fluorine-containing compound (A), the compound (B) and the compound (C), the type of the photopolymerization initiator, the thickness of the coating film or the dried film, the active energy ray source, etc. Can be changed as appropriate. Usually, the object is achieved by irradiation for 0.1 to 60 seconds.
For the purpose of completing the curing reaction, heating may be performed after irradiation with active energy rays. The heating temperature is preferably 50 to 120 ° C.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to these Examples. In the following, “%” is “% by mass” unless otherwise specified. Examples 1, 2, and 6 are examples, and examples 3-5 and 7 are comparative examples.

Evaluation of the cured film obtained in each example was performed as follows.
[Evaluation method]
(Appearance of cured film)
According to the following criteria, the appearance of the cured film was visually evaluated.
○ (Good): No foreign matter can be confirmed, and the film thickness is uniform.
Δ (possible): Foreign matter cannot be confirmed, but the film thickness is uneven.
X (defect): Foreign matter is confirmed, and the film thickness is uneven.

(Oil-based ink repellency)
A line was drawn on the surface of the cured film with a felt pen (manufactured by Zebra Co., Ltd., product name: Mackie extra-black), and the adhesion state of the oil-based ink was visually observed for evaluation. The evaluation criteria are as follows.
◎ (Excellent): Repels oil-based ink in a ball shape.
○ (Good): Oil-based ink is not repelled in a ball shape, repelled in a linear shape, and the line width is less than 50% of the width of the pen tip of the felt pen.
Δ (possible): The oil-based ink is not repelled in a ball shape but is repelled in a linear shape, and the line width is 50% or more and less than 100% of the width of the pen tip of the felt pen.
X (defect): The oil-based ink is not repelled in a ball shape or a linear shape, and a clean line can be drawn on the surface.

(Pencil hardness)
The obtained cured film was measured according to JIS K 5600.

(Adhesion)
About the obtained cured film, it evaluated by the Goban eyes cellophane tape peeling test by the general test method of JIS K-5400. Make 100 pieces of 1mm substrate (10x10) on the test specimen, attach cellophane adhesive tape (width 18mm) completely on the substrate, immediately hold one end of the tape at right angle to the cured film, and pull it away instantly. We examined the number of bases left without being completely removed. The greater the percentage of the grids left unpeeled, the better the adhesion of the cured film. In the table, for example, “70/100” means that the number of bases that remain without being completely peeled out of 100 bases is 70.

[Used compounds]
(A-1): OPTOOL DAC-HP (Product name, active ingredient concentration: 20% by mass, manufactured by Daikin Industries, Ltd.)
(B-1): Pentaerythritol triacrylate (manufactured by Shin-Nakamura Kogyo Co., Ltd.)
(C-1): 3-acryloxypropyltrimethoxysilane (product name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
(I-1): 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one (S-1): methyl isobutyl ketone

[Example 1]
In a 100 mL vial tube, 1.5 g of (A-1), 29.4 g of (B-1), 0.3 g of (C-1), 0.03 g of photopolymerization initiator (I-1), 68.8 g of the organic solvent (S-1) was added, and the mixture was stirred for 1 hour at room temperature and in the light-shielded state to obtain a composition (1).
Next, the composition (1) is applied by bar coating on a steel plate (manufactured by Nippon Steel & Sumikin Co., Ltd., thickness 10 mm, length 210 mm, width 297 mm) to form a coating film, and dried on a hot plate at 50 ° C. for 1 minute. And a dry film was formed on the surface of the substrate. Next, ultraviolet rays (light quantity: 300 mJ / cm ² , ultraviolet accumulated energy amount having a wavelength of 365 nm) were irradiated using a high pressure mercury lamp to form a cured film having a thickness of 5 μm on the surface of the substrate.
Table 1 shows the composition of the composition (1) and the evaluation results of the cured film.

[Example 2]
The composition (1) is coated on a PET film (Toyobo Co., Ltd., product name: A4300, thickness 125 μm, length 210 mm, width 297 mm) by bar coating to form a coating film, and then heated on a hot plate at 50 ° C. for 1 minute. It dried and formed the dry film | membrane on the surface of a base material. Next, ultraviolet rays (light quantity: 300 mJ / cm ² , ultraviolet accumulated energy amount having a wavelength of 365 nm) were irradiated using a high pressure mercury lamp to form a cured film having a thickness of 5 μm on the surface of the substrate.
Table 1 shows the evaluation results of the cured film.

[Examples 3 to 7]
Compositions (2) to (6) were obtained in the same manner as in Example 1 except that the type and amount of each compound were changed as shown in Table 1, and a cured film having a thickness of 5 μm was formed. Table 1 shows the composition of each composition and the evaluation results of the cured film.

From Table 1, the cured films of Examples 1, 2, and 6 formed from the composition containing the fluorine-containing compound (A), the compound (B), and the compound (C) have excellent appearance and oil-based ink repellency, and adhesion. It was also excellent. From Examples 1 and 2, if the composition of the present invention is a steel plate as an inorganic substrate or a PET film as an organic substrate, the cured film has excellent adhesion to the substrate. I can confirm that.
On the other hand, the cured film of Example 3 formed from a composition containing no fluorine-containing compound (A) was insufficient in oil-based ink repellency. This is considered to be due to the high surface energy of the cured film and the high affinity between the oil-based ink and the cured film because there is no fluorine compound on the surface of the cured film. The cured film of Example 4 formed from a composition containing no compound (B) had an insufficient film appearance. This is considered to be because when the compound having two or more curable sites is not included, the compound does not crosslink in the three-dimensional direction, so that a film cannot be formed. The cured films of Examples 5 and 7 formed from a composition containing no compound (C) had insufficient adhesion. This is considered because a hydrogen bond and a covalent bond are not formed between the cured film and the substrate surface.

  The composition of the present invention imparts water and oil repellency and antifouling properties to inorganic and organic substrates, and can form a cured film with excellent adhesion and appearance. Can be expected. For example, the composition can be used for the purpose of sealing treatment after aluminum anodization, hard coating, coloring, antiseptic, and the like. Moreover, it is suitable also as a member which comprises a touch panel. The touch panel is an input device of an input / display device (touch panel device) that combines a display device and a device that inputs contact position information by contact with a finger or the like. The touch panel is composed of a base material and a transparent conductive film, an electrode, a wiring, an IC, and the like depending on the input detection method. By using the surface having the cured film of the article as the input surface of the touch panel, a touch panel having excellent antifouling properties (oil-based ink repellency and fingerprint stain removability) can be obtained.

Claims (10)

At least one ethylenically unsaturated group, a fluorine-containing compound (A) having a perfluoropolyether structure, a fluorine-free compound (B) having at least two ethylenically unsaturated groups, and at least one polar group A composition comprising one ethylenically unsaturated group and a compound (C) having no perfluoropolyether structure,
A composition wherein the polar group is selected from a carboxy group, a phosphate group, an amino group, an isocyanate group, a hydrolyzable silyl group and a thiol group.   The composition according to claim 1, wherein the ethylenically unsaturated group is selected from a vinyl group, an allyl group, a (meth) acryloyl group, a styryl group and a cinnamoyl group. The composition according to claim 1 or 2, wherein the fluorine-containing compound (A) is a compound represented by the following formula (1).
_{[D- (C m F 2m O} ) n -] o -E ··· (1)
Where
D is D ¹ —R ^f1 —O—CH ₂ — or D ² —O—;
Here, D ¹ is CF ₃ — or CF ₃ —O—,
R ^f1 represents a fluoroalkylene group having 1 to 20 carbon atoms, a fluoroalkylene group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon-carbon atoms, an alkylene group having 1 to 20 carbon atoms, or a carbon-carbon atom. An alkylene group having 2 to 20 carbon atoms having an etheric oxygen atom in between;
D ² is a C 1-6 perfluoroalkyl group;
m is an integer from 1 to 6;
n is an integer of 1 to 200, and when n is 2 or more, (C _m F _2m O) _n may be composed of two or more types of C _m F _2m O different from _m ;
o is an integer greater than or equal to 1;
E is an o-valent organic group having one or more —C (═O) —CR ¹ ═CH ₂ (wherein R ¹ is a hydrogen atom or a methyl group). The composition according to any one of claims 1 to 3, wherein the fluorine-containing compound (A) is at least one selected from the group consisting of the following compounds (A1) to (A3).
(A1): A fluorinated polymer having an ethylenically unsaturated group and a perfluoropolyether structure independently in the side chain.
(A2) A fluorine-containing polymer having an ethylenically unsaturated group in the side chain and a perfluoropolyether structure at both ends or one end of the main chain.
(A3) A fluorine-containing compound having an ethylenically unsaturated group and a perfluoropolyether structure independently at the end of the main chain or in the side chain of the cyclic compound.   Content of the said fluorine-containing compound (A) is 0.01-5 mass% with respect to the total amount of a fluorine-containing compound (A), a compound (B), and a compound (C). The composition as described in any one of these.   Any of Claims 1-5 whose content of the said compound (B) is 90-99.98 mass% with respect to the total amount of a fluorine-containing compound (A), a compound (B), and a compound (C). A composition according to claim 1.   Any of Claims 1-6 whose content of the said compound (C) is 0.01-5 mass% with respect to the total amount of a fluorine-containing compound (A), a compound (B), and a compound (C). A composition according to claim 1.   Furthermore, the composition as described in any one of Claims 1-7 containing a photoinitiator.   An article having a cured film formed from the composition according to any one of claims 1 to 8 on at least a part of a surface of a substrate.   The article of claim 9, wherein the substrate is an inorganic substrate.