JPWO2018212263A1 - Photocurable composition containing fluoropolymer - Google Patents

Abstract

Provided is a photocurable composition which has excellent transparency and abrasion resistance and is useful as a protective coating agent for optical members such as glasses and sunglasses and displays of portable electronic devices. A photocurable composition containing a fluoropolymer (A), a urethane (meth) acrylate (B) and a photopolymerization initiator (C), wherein the fluoropolymer (A) has one molecule per molecule. Structural unit A-1 derived from a fluorosilsesquioxane having an addition-polymerizable functional group, and structural unit A derived from an addition-polymerizable monomer and having a group having a polymerizable unsaturated bond in a side chain A photocurable composition, which is a polymer containing -2, wherein the structural unit A-1 is derived from a fluorosilsesquioxane represented by the following formula (1). (Wherein, Rf1 to Rf7 are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is replaced by fluorine or trifluoromethyl, A fluoroarylalkyl having 6 to 20 carbon atoms; or a fluoroarylalkyl having 7 to 20 carbon atoms in which at least one hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and A1 represents an addition-polymerizable functional group. )

Description

  The present invention relates to a photocurable composition containing a fluoropolymer. Further, the present invention relates to a cured film obtained from the photocurable composition containing a fluoropolymer.

Conventionally, various researches have been conducted on surface modifiers that form a coating on the surface of various types of substrates to provide protection, water repellency, oil repellency, insulation, non-adhesion, antifouling properties, etc. of the substrate. I have. As a method, for example, there is a method in which a coating material made of a fluorine resin, a silicone resin, or the like is applied to a base material to improve water repellency.
For example, Patent Document 1 discloses a coating film composed of a silicone-containing fluorine-based copolymer or a composition containing the same, wherein the number of Si atoms and the number of F atoms existing on the coating film surface measured by XPS Coating films having a certain percentage of number have been proposed.
Patent Document 2 discloses a structural unit derived from a fluorosilsesquioxane having one addition-polymerizable functional group in a molecule, a structural unit derived from an organopolysiloxane having an addition-polymerizable functional group, and an addition-polymerizable compound. An addition copolymer comprising a monomer-derived structural unit having a group having a polymerizable unsaturated bond in a side chain as an essential component has excellent water and oil repellency, and has a surface modified property. It is disclosed as being useful as a bulking agent.
Patent Document 3 discloses a polymerizable unsaturated monomer having a fluorinated alkyl group having 4 to 6 carbon atoms, a polymerizable unsaturated monomer having a silicone group, and a polymer having a reactive functional group. A polymer obtained by copolymerizing a polymerizable unsaturated monomer with an essential monomer component is reacted with a compound having a functional group reactive with the reactive functional group and a compound having a polymerizable unsaturated group. An active energy ray-curable composition containing a fluorinated polymerizable resin comprising a polymer obtained by the above method has been proposed.

JP 2006-167490 A International Publication No. 2008/072766 JP 2013-87213 A

The cured film obtained from the active energy ray-curable composition proposed in Patent Document 2 can have properties such as repelling stains due to magic and the like and good wiping properties.
In recent years, as electronic devices have become smaller and thinner, the demand for coating materials to protect their displays has increased more and more, especially for displays of mobile electronic devices such as smartphones and tablets that are often used outdoors. A high level of protection from dirt and scratches is required for comfortable use. In addition, optical members such as eyeglasses and sunglasses have been reduced in thickness and performance, and requirements for transparency and wear resistance of protective materials have been further required.
Therefore, the present invention has high transparency that can be used for displays of mobile electronic devices such as smartphones and tablets, and optical members such as eyeglasses and sunglasses, and can sufficiently protect from dirt and scratches. It is an object of the present invention to provide a resin composition and a coating material for highly-functional coating.

  The present inventors have made intensive studies from the above viewpoint, and as a result, by combining a specific fluoropolymer (A) and urethane (meth) acrylate (B), the composition can be obtained by curing a composition containing the same. The inventors have found that the cured film has excellent transparency and abrasion resistance, and have completed the present invention.

That is, the embodiments of the present invention include the following configurations.
[1] A photocurable composition containing a fluoropolymer (A), a urethane (meth) acrylate (B) and a photopolymerization initiator (C),
A structural unit A-1 derived from a fluorosilsesquioxane having one addition-polymerizable functional group in a molecule represented by the formula (1) and a fluorine-containing polymer (A), A photocurable composition which is a polymer containing a structural unit A-2 which is a structural unit derived from a monomer and has a group having a polymerizable unsaturated bond in a side chain.

(Wherein, R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoromethyl replaced, fluoroaryl having 6 to 20 carbon atoms; at least one hydrogen or in the aryl is replaced by fluorine or trifluoromethyl, indicates fluoroarylalkyl 7 to 20 carbon atoms, a ¹ is addition polymerizable Shows a functional group.)
[2] R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4 , 4,5,5,6,6,6-Nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosa Fluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α The photocurable composition according to [1], which is selected from the group consisting of, α, α-trifluoromethylphenyl.
[3] R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nona The photocurable composition according to [1], which is selected from the group consisting of fluorohexyl and tridecafluoro-1,1,2,2-tetrahydrooctyl.
[4] The method according to any one of [1] to [3], wherein the group having a polymerizable unsaturated bond of the structural unit A-2 is (meth) acrylic bonded to a main chain via a urethane bond. Photocurable composition.
[5] The fluorine-based polymer (A) is a polymer further including a structural unit A-3 derived from an organopolysiloxane having an addition-polymerizable functional group represented by the following formula (2), [1]. The photocurable composition according to any one of [1] to [4].

Wherein n is an integer from 1 to 1,000; R ¹ and R ² are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ³ and R ⁴ are Each independently methyl or phenyl; R ⁵ is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3 , 3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl , Henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, penta Le Oro phenylpropyl, pentafluorophenyl, and alpha, alpha, selected from the group consisting of α- trifluoromethylphenyl; A ² is an addition-polymerizable functional group).
[6] The photocurable composition according to [5], wherein R ¹ , R ² , R ³ and R ⁴ in the formula (2) are each simultaneously methyl and A ² is (meth) acrylic.
[7] The photocurable composition according to any one of [1] to [6], further comprising inorganic fine particles (D).
[8] The photocurable composition according to [7], wherein the inorganic fine particles (D) are surface-modified colloidal silica.
[9] The light according to any one of [1] to [8], wherein the urethane (meth) acrylate (B) is a hexafunctional urethane (meth) acrylate having a viscosity at 40 ° C of 20,000 mPa · s or less. Curable composition.
[10] The photocurable composition according to [9], comprising 50% to 98% by weight of the urethane (meth) acrylate (B) based on 100% by weight of the total solids.
[11] A cured film obtained by curing the photocurable composition according to any one of [1] to [10].
[12] Including a fluoropolymer (A), a hexafunctional urethane (meth) acrylate (B) having a viscosity at 40 ° C. of 20,000 mPa · s or less, a photopolymerization initiator (C), and inorganic fine particles (D). A cured film obtained by curing the photocurable composition,
A cured film having a Δ haze of 3 or less in Evaluation Method 1 for the photocurable composition.
A fluorine-containing polymer (A) represented by the formula (1), a structural unit A-1 derived from fluorosilsesquioxane having one addition-polymerizable functional group in a molecule, an addition-polymerizable monomer Structural unit A-2 derived from a structural unit derived from an organopolysiloxane having a group having a polymerizable unsaturated bond in a side chain and an addition polymerizable functional group represented by the formula (2) -3 is a polymer containing
In the formula (1), R _f ^{1 to} R _f ⁷ are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl Or Tridecafluoro-1,1,2,2-tetrahydrooctyl; A ¹ is an addition polymerizable functional group,
A-2 is a (meth) acryl in which a group having a polymerizable unsaturated bond is bonded to a main chain via a urethane bond,
In the formula (2), n is an integer of ^{1 to} 1,000, R ¹ , R ² , R ³ and R ⁴ are each simultaneously methyl, R ⁵ is butyl, and A ² is (meth) Acrylic.


[Evaluation method 1]
On a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm, a cured film of the photocurable composition having a thickness of 5 μm is formed.
The turbidity (haze) (%) of the PET with the cured film was measured in accordance with ASTM D1044, and a Taber abrasion test was performed with a load of 1 kg (9.8 N) applied, followed by ASTM D1044. Then, the haze (%) is measured, and the difference Δhaze (%) is obtained.
ΔHaze (%) = (Haze (%) after performing Taber abrasion test under a load of 1 kg (9.8 N)) − (Haze (%) before performing Taber abrasion test)
[13] A laminate comprising the cured film according to [11] or [12].
[14] An optical member including the cured film according to [11] or [12], or the laminate according to [13].

  The cured film obtained by curing the fluoropolymer-containing photocurable composition of the present invention has excellent transparency and abrasion resistance.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents. Further, the embodiments of the present invention can be appropriately combined.
In the present invention, the addition-polymerizable means that it can undergo addition polymerization, the addition-polymerizable monomer means a monomer that can undergo addition polymerization, and the addition-polymerizable functional group means that it is addition-polymerizable. Means a functional group.
The photocurable composition (hereinafter, also referred to as the composition of the present invention), which is one embodiment of the present invention, includes a fluoropolymer (A) (hereinafter, also referred to as polymer A or (A) component), It contains a urethane (meth) acrylate (B) (hereinafter, also referred to as a component (B)) and a photopolymerization initiator (C) (hereinafter, also referred to as a component (C)). A, a structural unit A-1 derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule, a structural unit derived from an addition-polymerizable monomer, and having a polymerizable unsaturated bond in a side chain. A polymer containing a structural unit A-2 having a group, wherein the structural unit A-1 is derived from a fluorosilsesquioxane represented by the following formula (1). In addition, "derived from" means a polymerized residue when each monomer constitutes the fluoropolymer (A).

(Wherein, R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoromethyl replaced, fluoroaryl having 6 to 20 carbon atoms; at least one hydrogen or in the aryl is replaced by fluorine or trifluoromethyl, indicates fluoroarylalkyl 7 to 20 carbon atoms, a ¹ is addition polymerizable Shows a functional group.)
The “molar fraction (%) of the structural unit A-1 in the fluoropolymer (A)” is represented by “a”, and the “molar fraction (%) of the structural unit A-2 in the polymer” is “ b "," the molar fraction (%) of the structural unit A-3 in the polymer described later "is denoted by" c ", and the" structural unit D (the structural unit A-1 described later) in the polymer " The molar fraction (%) of the structural units other than -A-3) is represented by “d”, where 0 <a <100, 0 <b <100, 0 ≦ c <100, and 0 ≦ d <100, respectively. , A + b + c + d = 100.
The fluoropolymer (A) of the present invention includes, for example, an addition polymerizable monomer (α) having a fluorine atom and an addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond. Is preferably copolymerized to obtain a precursor polymer, and is obtained by introducing a group having a polymerizable unsaturated bond into the precursor via this functional group.

<Fluorine-based polymer (A)>
Description of Structural Unit A-1 <Fluorosilsesquioxane (α) having one addition-polymerizable functional group in the molecule>
Fluorosilsesquioxane has a silsesquioxane skeleton in the molecular structure. The silsesquioxane is _{[(R-SiO 1.5) n} ] represented by (the R is any substituent) generic term of polysiloxane. The structure of the silsesquioxane is generally classified into a random structure, a ladder structure, and a cage structure according to its Si-O-Si skeleton. Furthermore, cage structures are classified into such _{T 8, T 10, T 12} type. Among them, fluoro silsesquioxanes used in the present invention, having a cage structure of _{T 8} type _{[(R-SiO 1.5) 8} ].

The above-mentioned fluorosilsesquioxane is characterized by having one addition-polymerizable functional group. That is, one is an addition polymerizable functional group of R of the silsesquioxane _{[(R-SiO 1.5) n} ].
Examples of the above addition-polymerizable functional groups include groups having a terminal polymerizable functional group of an terminal olefin type or an internal olefin type; groups having a cationic polymerizable functional group such as vinyl ether and propenyl ether; and vinyl carboxyl and cyanoacryloyl. Although a group having an anionic polymerizable functional group is included, a radical polymerizable functional group is preferable.

  The radically polymerizable functional group is not particularly limited as long as it is a radically polymerizable group. Examples include vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide and the like, and among them, a group containing (meth) acrylic or styryl is preferable. Here, (meth) acryl is a general term for acryl and methacryl, and means acryl and / or methacryl. The same applies hereinafter.

Examples of the radical polymerizable functional group having (meth) acryl include a group represented by the following formula (3).
In the formula (3), Y ¹ represents alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms, and more preferably alkylene having 3 carbon atoms (propylene). R ⁶ represents hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons, preferably hydrogen or alkyl having 1 to 3 carbons, and more preferably hydrogen or methyl. Here, the alkyl having 1 to 5 carbon atoms may be linear or branched.

Examples of the radically polymerizable functional group having styryl include a group represented by the following formula (5). In the formula (5), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms, preferably a single bond or alkylene having 1 to 6 carbon atoms, more preferably a single bond or alkylene having 1 or 2 carbon atoms, A bond or alkylene (ethylene) having 2 carbon atoms is particularly preferred. The vinyl is bonded to any carbon of the benzene ring, preferably bound to a carbon of the para position relative to Y ^2.

  In the above-mentioned fluorosilsesquioxane, Rs other than the above-mentioned addition-polymerizable functional groups are all fluoroalkyl, fluoroarylalkyl and / or fluoroaryl.

The above fluoroalkyl may be linear or branched. The fluoroalkyl has 1 to 20 carbon atoms, preferably 3 to 14 carbon atoms. Further, any methylene of the fluoroalkyl may be replaced by oxygen. Here, _methylene, -CH 2 _-, - CFH-, or -CF ₂ - containing. In other words, the "arbitrary methylene may be replaced by _oxygen", -CH 2 -, - -CFH- or -CF ₂ - which means that may be substituted with -O-. However, in a fluoroalkyl, two oxygens are not bonded (—O—O—). That is, the fluoroalkyl may have an ether bond. In a preferred fluoroalkyl, the methylene adjacent to Si is not replaced by oxygen, and the terminal opposite to Si is CF ₃ . Furthermore, -CH ₂ - or, more -CFH- is replaced by oxygen, -CF ₂ - Write is replaced by oxygen is preferred. Preferred specific examples of such fluoroalkyl include 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6 6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrododecyl, henicosafluoro-1,1,2,2-tetrahydro Dodecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl and the like. Among these, perfluoroalkyl ethyl are preferred examples, -CH 2 _-CH 2 _- to the fluoroalkyl group may be bonded groups via, -CH 2 _- fluoroalkyl group is linked via a It may be a group.

  The fluoroarylalkyl is an alkyl containing a fluorine-containing aryl, and preferably has 7 to 20 carbon atoms, and more preferably 7 to 10 carbon atoms. The fluorine contained is preferably one in which one or more hydrogens in the aryl are replaced by fluorine or trifluoromethyl. Examples of aryl moieties include phenyl, naphthyl and the like, as well as heteroaryl, and examples of alkyl moieties include methyl, ethyl and propyl.

  Further, the above-mentioned fluoroaryl is one in which any one or more hydrogen in the aryl is replaced by fluorine or trifluoromethyl, and preferably has 6 to 20 carbon atoms, more preferably Is 6. Examples of such aryl include phenyl, naphthyl and the like, as well as heteroaryl. Specific examples include fluorophenyl such as pentafluorophenyl and trifluoromethylphenyl.

  Among the above-mentioned fluoroalkyl, fluoroarylalkyl or fluoroaryl contained in the fluorosilsesquioxane, a preferred group is fluoroalkyl, more preferably perfluoroalkylethyl.

As described above, fluorosilsesquioxane has a structure of type ₈ T has one addition polymerizable functional group, and R _f ¹ to R _f ⁷ each independently, fluoroalkyl, fluoroaryl It has alkyl and / or fluoroaryl and is represented by the following structural formula (1).

In the above formula (1), A ¹ is an addition polysynthetic functional group, preferably the above-mentioned radical polymerizable functional group, and R _f ^{1 to} R _f ⁷ are each independently any methylene represented by oxygen. A fluoroalkyl having 1 to 20 carbon atoms, which is optionally substituted with; a fluoroaryl having 6 to 20 carbon atoms, wherein at least one hydrogen is replaced by fluorine or trifluoromethyl; or at least one hydrogen in the aryl is it is replaced by fluorine or trifluoromethyl, fluoro arylalkyl having 7 to 20 carbon atoms, R _f ¹ ~R _f ^7, even each divergent groups may all be the same group.
R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4, 5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1 , 1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, It is preferable to be selected from the group consisting of α-trifluoromethylphenyl, and R _f ^{1 to} R _f ⁷ are each independently 3,3,3-trifluoropropyl More preferably, it is selected from the group consisting of pill, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and tridecafluoro-1,1,2,2-tetrahydrooctyl.
The fluorosilsesquioxane (α) having one addition-polymerizable functional group in the molecule can be synthesized with reference to, for example, JP-A-2004-123698.

Description of Structural Unit A-2 <Addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond>
As described above, the polymer (A) containing a group having a polymerizable unsaturated bond in a side chain can be obtained as a precursor of a polymer having a functional group into which a group having a polymerizable unsaturated bond can be introduced. Examples of such a functional group into which a group having a polymerizable unsaturated bond can be introduced include a group having an active hydrogen and a monovalent functional group including a cyclic ether. Active hydrogen refers to hydrogen bonded to an atom whose electronegativity value is equal to or higher than carbon (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) among the hydrogen atoms present in the molecule of an organic compound. It is. Therefore, a preferred precursor for obtaining the polymer (A) is a polymer containing a group having an active hydrogen, and the fluorosilsesquioxane (α) having one addition-polymerizable functional group in the molecule is used as a precursor. An addition polymerizable monomer (ε) containing a monovalent functional group containing a group having hydrogen or a cyclic ether as an essential component, preferably together with an organopolysiloxane (γ) having an addition polymerizable functional group described later. A precursor of the polymer used in the composition of the invention can be obtained.

Examples of the group having an active _{hydrogen, -OH, -SH, -COOH, -NH} , -NH 2, -CONH 2, -NHCONH -, - NHCOO-, Na + [CH (COOC 2 H 5)], - CH ₂ NO ₂ , —OOH, —SiOH, —B (OH) ₂ , —SH, and the like. Carboxyl, amino, and hydroxyl are preferable, and hydroxyl is more preferable. The addition-polymerizable monomer (ε) containing a group having an active hydrogen may be a compound having a group having an active hydrogen and an addition-polymerizable double bond in a molecule, and includes a group having an active hydrogen. , A vinyl compound, a vinylidene compound, or a vinylene compound. Preferably, it is an acrylic acid derivative or a styrene derivative containing a group having active hydrogen.

  Examples of the monovalent functional group containing a cyclic ether include groups such as glycidyl, epoxycyclohexyl, and oxetanyl.

Examples of the addition polymerizable monomer containing a group having an active hydrogen include the monomers disclosed in JP-A-9-208681, JP-A-2002-348344, and JP-A-2006-158961.
Specific examples include the following monomers.
Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, (anhydride) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itacone Acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, (meth) acrylic acid hexadecane, cinnamic acid and the like.
Examples of the hydroxyl group-containing vinyl monomer include a hydroxyl group-containing monofunctional vinyl monomer and a hydroxyl group-containing polyfunctional vinyl monomer. As the hydroxyl group-containing monofunctional vinyl monomer, a vinyl monomer having one vinyl group is used. For example, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate (HEMA), hydroxypropyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, -Buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether (2-propenoxyethanol), 16-hydroxyhexadecane methacrylate Etc. Relate and sucrose allyl ether. As the hydroxyl group-containing polyfunctional vinyl monomer, a vinyl monomer having a plurality of vinyl groups is used. For example, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, Diglycerin tri (meth) acrylate, sorbitan tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetraglycerin penta (meth) acrylate, glycerin di (meth) allyl ether, trimethylolpropane di (meth) allyl ether, Pentaerythritol tri (meth) allyl ether, diglycerin tri (meth) allyl ether, sorbitan tri (meth) allyl ether, dipentaerythritol penta (meth) allyl ether and Such as tigers glycerol penta (meth) allyl ether.
As the amino group-containing vinyl monomer, for example, aminoethyl (meth) acrylate, aminoisopropyl (meth) acrylate, aminobutyl (meth) acrylate, aminohexyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, crotylamine , Aminostyrene, methyl α-acetoaminoacrylate, N-allylphenylenediamine, 16-methacryloylhexadecaneamine and the like.

  In addition, addition-polymerizable monomers that are (meth) acrylic acid derivatives having a monovalent functional group containing a cyclic ether include epoxy-containing (meth) acrylates such as glycidyl (meth) acrylate; and 3,4-epoxycyclohexyl. Alicyclic epoxy-containing (meth) acrylates such as methyl (meth) acrylate; oxetanyl-containing (meth) acrylates such as 3-ethyl-3- (meth) acryloyloxymethyloxetane; 4- (meth) acryloyloxymethyl-2- Dioxolane-containing (meth) acrylates such as methyl-2-ethyl-1,3-dioxolane; and the like.

Description of Structural Unit A-3 <Organopolysiloxane (γ) Having Addition Polymerizable Functional Group>
In the present invention, it is preferable that the fluoropolymer (A) further includes a structural unit A-3 derived from an organopolysiloxane (γ) having an addition-polymerizable functional group represented by the following formula (2).

In the formula (2), n is an integer of ^{1 to} 1,000; R ¹ and R ² are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ³ and R ⁴ Are each independently methyl or phenyl; R ⁵ is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl , 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2- Tetrahydrodecyl, henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy ) Propyl, pentafluoro-phenylpropyl, pentafluorophenyl or alpha,, alpha, it is α- trifluoromethylphenyl; A ² is an addition polymerizable functional group.
Also preferably, A ² in the above formula (2) is a radical polymerizable functional group, more preferably the A ² contains a (meth) acrylic or styryl, A ² is represented by the following formula (3), (4 ) Or (5).
From the viewpoint of slipperiness, it is more preferable that R ¹ , R ² , R ³ and R ⁴ in the formula (2) are each methyl at the same time, and A ² is (meth) acryl. Also, it is preferred that R ⁵ is butyl. n is preferably 50 to 100.

In the formula (3), Y ¹ represents alkylene having 2 to 10 carbon atoms, R ⁶ represents hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons; ⁷ represents hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons, X ₁ represents alkylene having 2 to 20 carbons, and Y represents -OCH ₂ CH _2- , -OCH (CH ₃ ) CH ₂ — or —OCH ₂ CH (CH ₃ ) —, p is an integer of 0 to 3, and in the formula (5), Y ² represents a single bond or an alkylene having 1 to 10 carbon atoms. . Here, the alkyl having 1 to 5 carbon atoms may be linear or branched.

In the present invention, in the formula (3), Y ¹ is preferably alkylene having 2 to 6 carbon atoms, R ⁶ is preferably hydrogen or methyl, and in the formula (4), X ₁ is —CH ₂ CH ₂ CH ₂ —. Is preferable, Y is preferably —OCH ₂ CH ₂ —, p is preferably 0 or 1, R ⁷ is preferably hydrogen or methyl, and in the formula (5), Y ² is a single bond or an alkylene having 1 or 2 carbon atoms. preferable. Further, combinations of the preferred embodiments of the above organic groups are included in the present invention.
Examples of the organopolysiloxane (γ) preferably used in the present invention include Silaplane FM0711 (manufactured by JNC), Silaplane FM0721 (manufactured by JNC), Silaplane FM0725 (manufactured by JNC), Thyraplane TM0701 (manufactured by JNC), Silaplane TM0701T (manufactured by JNC) and the like are included.

Description of Structural Unit A-4 <Optional Addition Polymerizable Monomer (δ)>
In the precursor of the fluoropolymer (A) used in the present invention, in addition to the addition-polymerizable monomers (α), (ε) and (γ), compatibility with resin, leveling property, In order to control the content of the group having a polymerizable unsaturated bond in the polymer, if necessary, an addition polymerizable monomer (δ) other than the monomers (α), (β), and (γ) Can also be used in any proportion.
Examples of the addition-polymerizable monomer (δ) having no group having an active hydrogen include a (meth) acrylic acid compound having one addition-polymerizable double bond and having no group having an active hydrogen, and one addition polymerizable monomer. Styrene compounds having a polymerizable double bond and not having a group having an active hydrogen are exemplified. Specific examples of the (meth) acrylic acid compound include methyl (meth) acrylate (MMA), ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, Alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate; phenyl (meth) acrylate, Aryl (meth) acrylates such as yl (meth) acrylate; arylalkyl (meth) acrylates such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl ( Alkoxyalkyl (meth) acrylates such as (meth) acrylate; ethylene oxide adducts of (meth) acrylic acid; and the like.
Further, examples of the (meth) acrylic acid compound having one addition-polymerizable double bond and having no group having an active hydrogen include a (meth) acrylic acid compound having a silsesquioxane skeleton. Specific examples of such silsesquioxane having a skeleton (meth) acrylic acid compound, 3- (3,5,7,9,11,13,15- hepta ethylpentamethylene cyclo [9.5.1.1 ^{3 , 9.1,15,15,17,13} ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaisobutyl-pentacyclo [9. 5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9, 11,13,15-heptacyclo pliers Pentacyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13 , 15-hepta phenylpent-cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) propyl (meth) acrylate, 3 - [(3,5, 7,9,11,13,15- hepta ethylpentamethylene cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- hepta isobutyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane -1 -Yloxy) dimethylsilyl ] Propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7, 13]} octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9.1 5,15} .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- heptaphenyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy), and the like dimethylsilyl] propyl (meth) acrylate.
Specific examples of the styrene compound having one addition-polymerizable double bond and having no group having an active hydrogen include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene; and the like.

Examples of the styrene compound having one addition-polymerizable double bond and not having a group having an active hydrogen further include a styrene compound containing silsesquioxane. Examples of styrene derivatives containing such silsesquioxane include 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.13 ^{, 9} . ^{15, 15,.} 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hept isobutyl penta cyclo [9.5.1.1 ^{3, 9. 15, 15,.} 17, ¹³ ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 . ^{15, 15,.} 1 ^7,13] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9. 15, 15,.} 17, ¹³ ] octasiloxane and 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 . ^{15, 15,.} 1 ^7,13] such octasiloxane, octasiloxane _{(T 8-inch} silsesquioxane) having a 4-vinylphenyl group; and, 3- (3,5,7,9,11,13,15- Heputaechiru pentacyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15 - hepta isobutyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11, 13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) ethyl styrene, 3- (3,5,7, 9,11,13,15-heptacyclopen Rupentashikuro ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} oct octasiloxane-1-yl) ethyl styrene, 3- (3,5,7,9,11,13,15 - heptaphenyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yl) ethyl styrene, 3 - ((3,5,7,9,11 , 13,15- hepta ethylpentamethylene cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3, 5,7,9,11,13,15- hepta isobutyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene , 3-((3,5 7,9,11,13,15- hepta isooctyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7,13]} octasiloxane-1-yloxy ) dimethylsilyl) ethylstyrene, and 3 - ((3,5,7,9,11,13,15- heptaphenyl penta cyclo ^[9.5.1.1 3,9 ^.1 5,15 ^{.1 7, 13],} such as octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, octasiloxane with 4-vinyl-phenylethyl group (T _8-inch silsesquioxane); and the like.
Further, as an optional addition-polymerizable monomer, styrene, (meth) acrylic acid ester, siloxane, and a main chain derived from an alkylene oxide such as ethylene oxide or propylene oxide may be used. A macromonomer having a bond is also exemplified.

Examples of the addition-polymerizable monomer (δ) include a compound having two addition-polymerizable double bonds.
Examples of the compound having two addition polymerizable double bonds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. Acrylate, polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl Glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, bis [(meth) acryloyloxyethoxy] bisphenol A, bis [(meth) acryloyloxyethoxy] tetrabromobisphenol Of bis [(meth) acryloxypolyethoxy] bisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol compound Di (meth) acrylate monomers such as di (meth) acrylate and bis [(meth) acryloyloxypropyl] tetramethyldisiloxane, and divinylbenzene are included.
Further, a macromonomer having a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide and having two polymerizable double bonds is also exemplified. You.

Examples of the addition polymerizable monomer (δ) include compounds having three or more addition polymerizable double bonds. Examples of the compound having three or more addition polymerizable double bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate. ) Acrylate, tris (2-hydroxyethyl isocyanate) tri (meth) acrylate, tris (diethylene glycol) trimellitate tri (meth) acrylate, 3,7,14-tris [(((meth) acryloyloxypropyl) dimethylsiloxy)] -1,3,5,7,9,11,14- hepta ethyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl ) Dimethylsiloxy)]-1, , 5,7,9,11,14- hepta isobutyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, 3,7,14- tris [(((meth) acryloyloxy propyl) dimethylsiloxy) ] -1,3,5,7,9,11,14-heptaisooctyltricyclo [7.3.3.1 ^5,11 ] heptasiloxane, 3,7,14-tris [(((meth) acryloyl Oxypropyl) dimethylsiloxy)]-1,3,5,7,9,11,14-heptacyclopentyltricyclo [7.3.3.1 ^5,11 ] heptasiloxane, 3,7,14-tris [( ((meth) acryloyloxy propyl) dimethylsiloxy)] - 1,3,5,7,9,11,14- heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept siloxane, O Takis (3- (meth) acryloyloxy propyl dimethylsiloxy) octasilsesquioxane and octakis (3- (meth) acryloyloxy propyl) octasilsesquioxane include.
Furthermore, a macromonomer having a main chain derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide and having three or more polymerizable double bonds is also exemplified. Is done.

  Examples of the addition-polymerizable monomer (δ) include a compound containing fluorine. The compound containing fluorine may be any compound having a group having a fluorine atom in the molecule and an addition polymerizable double bond, and may be any of a vinyl compound having a fluorine atom, a vinylidene compound, and a vinylene compound. Preferably, it is an acrylic acid derivative or a styrene derivative having a fluorine atom.

Representative examples of the addition-polymerizable monomer having a fluorine atom include, for example, fluoroalkyl (meth) acrylate, fluorostyrene, and a fluorine-containing polyether compound.
Examples of such an addition-polymerizable monomer having a fluorine atom include JP-A-10-251352, JP-A-2004-043631, JP-A-2004-155847, JP-A-2005-029743, JP-A-2006-117742, and JP-A-2006-2006. 299016 and the monomers disclosed in JP-A-2005-350560.
Specific examples include the following monomers.
Examples of the fluoroalkyl (meth) acrylate include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth) acrylate, 2,2,3 3-tetrafluoro-t-pentyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,4,4,4-hexafluoro-t- Hexyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4,4-hexa Fluorobutyl (meth) acrylate, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluor Butyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,5-nonafluoro Pentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5 6,6,7,7,8,8-dodecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (Meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl (meth) acrylate, 3,3,4,4,5 5,6,6,7,7,8,8,9,9,10,10-hexadecafluorodecyl (meth) a 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) acrylate, 3,3,4 , 4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-octadecafluoroundecyl (meth) acrylate, 3,3,4,4,5 , 5,6,6,7,7,8,8,9,9,10,10,11,11,11-nonadecafluoroundecyl (meth) acrylate, 3,3,4,4,5,5 , 6,6,7,7,8,8,9,9,10,10,11,11,12,12-eicosafluorododecyl (meth) acrylate and the like.
Examples of the fluorostyrene include fluoroalkylstyrene such as p-trifluoromethylstyrene, p-heptafluoropropylstyrene, and p-pentafluoroethylstyrene.
Specific examples of the fluorinated polyether compound include 1H, 1H-perfluoro-3,6-dioxaheptyl (meth) acrylate, 1H, 1H-perfluoro-3,6-dioxaoctyl (meth) acrylate, 1H , 1H-perfluoro-3,6-dioxadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9-trioxadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9 -Trioxaundecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9-trioxatridecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12-tetra Oxateridecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12-tetraoxatetradecanyl (meth ) Acrylate, 1H, 1H-perfluoro-3,6,9,12-tetraoxahexadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxahexadecanyl (Meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxaheptadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15-penta Oxononadecanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15,18-hexaoxaicosanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9 , 12,15,18-Hexaoxadocosanyl (meth) acrylate, 1H, 1H-perfluoro-3,6,9,12,15,18,21- Data oxa Trichoderma Sa sulfonyl (meth) acrylate, IH, 1H-perfluoro -3,6,9,12,15,18,21- hepta oxa penta Xhosa sulfonyl (meth) can be given acrylate.
Further, such an addition polymerizable monomer having a fluorine atom can also be synthesized by reacting a fluorine compound having a hydroxyl group with an acid halide having an addition polymerizable functional group.
Examples of such a fluorine compound having a hydroxyl group include (HO) C (CF ₃ ) ₂ CH ₃ , (HO) C (CF ₃ ) ₂ CH ₂ CH ₃ , and (HO) C (CF ₃ ) ₂ CH ₂ O— A compound having a CH ₂ — group, (HO) C (CF ₃ ) ₂ CH ₂ CH ₂ O—CH _{3 and the} like can be mentioned.
It is also commercially available from Exfluor Research Corporation and can be purchased and used.
Further, the above-mentioned fluorine compound having a hydroxyl group can also be synthesized and used, and a synthesis method is described in JP-A-10-147639.

  Examples of the addition polymerizable monomer (δ) also include a compound having a hydrophilic group. For example, an oxyalkylene group-containing monomer such as methoxypolyethylene glycol mono (meth) acrylate can be used.

  The above addition polymerizable monomer (δ) may be used alone or in combination of two or more. When a plurality of types are used in combination, various composition ratios can be appropriately adjusted according to the characteristics of the target polymer and used.

<Precursor of fluorinated polymer (A)>
The precursor of the fluoropolymer (A) (hereinafter also referred to as polymer (A)) used in the present invention is derived from fluorosilsesquioxane (α) having one addition-polymerizable functional group in the molecule. An addition-polymerizable monomer having a structural unit (structural unit A-1) and a functional group capable of introducing a group having a polymerizable unsaturated bond, preferably an addition-polymerizable monomer having a group having an active hydrogen (ε ) -Derived structural units (structural units (A-2 ')) as an essential component, and even an orderly copolymer such as a block copolymer may be a random copolymer. It may be present, but is preferably a random copolymer. Further, the fluoropolymer (A) may have a crosslinked structure or may be a graft copolymer.

In the precursor of the polymer (A) used in the present invention, the molar ratio of the structural unit A-1 to the structural unit A-2 ′ is arbitrary, and (a) :( b) = about 0.001: 99. 999 to about 99.999: 0.001. When the structural unit A-3 is included, the molar ratio of the structural unit A-1 to the structural unit A-2 ′ and the structural unit A-3 is arbitrary, and (a) :( b) = about 0.001: 99. 0.999 to about 99.999: 0.001, (b) :( c) = about 0.001: 99.999 to about 99.999: 0.001, (a) :( c) = about 0.001 : 99.999 to about 99.999: 0.001.
The proportion of the structural unit A-2 ′ contained in the polymer (A) used in the present invention is not particularly limited as long as it is within the range of the above (b), and the polymer used in the present invention is used as a coating agent. In order to improve the bonding property with the binder resin to be mixed in the reaction, a group having a polymerizable unsaturated bond may be contained to such an extent that a preferable reactivity with the binder resin monomer is obtained.
As described below, when the composition of the present invention is used as a surface modifier, (a) :( b) is preferably about 1:99 to about 99: 1, and the structural unit A-3 is preferably If included, (a) :( b) = about 1:99 to about 99: 1, (b) :( c) = about 1:99 to about 99: 1, (a) :( c) = about 1 : 99 to about 99: 1.
In the case where the fluoropolymer (A) used in the present invention further contains an optional structural unit (D), the structural unit A-1 or the structural unit contained in the fluoropolymer (A) or a precursor thereof may be used. The above molar ratio of A-2 (or structural unit A-2 ′) and structural unit (A-3) is the same.
The weight average molecular weight of the fluoropolymer (A) varies depending on the content of the structural unit A-2 and the like, but is about 1,000 to 1,000,000 as a guide. On the other hand, the molecular weight distribution (Mw / Mn) of the fluoropolymer (A) is approximately 1.01 to 3.0 as a guide.
The precursor of the fluoropolymer (A) is, for example, a fluorosilsesquioxane (α) having one addition-polymerizable functional group in the molecule, and an addition-polymerizable monomer (ε) having a group having an active hydrogen. )), When an organopolysiloxane having an addition-polymerizable functional group (γ) and a plurality of types of monomers are used as an optional addition-polymerizable monomer (δ), the ratio of each monomer depends on the purpose and It may be appropriately determined according to the properties of the copolymer to be formed. In view of simplicity and versatility, radical copolymerization is preferred.

The addition polymerization can be performed using a polymerization initiator.
Examples of the polymerization initiator used include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-butyronitrile), Azo compounds such as dimethyl-2,2'-azobisisobutyrate and 1,1'-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, diacetyl Peroxides such as t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxy acetate, t-butyl peroxy benzoate, t-butyl peroxy neodecanoate; and tetraethyl Dithiocarbamates such as thiuram disulfide; radicals such as Initiator is included.
Further, examples of the polymerization reaction include living radical polymerization and active energy ray polymerization.

Living radical polymerization is represented by atom transfer radical polymerization; reversible addition-fragmentation chain transfer; iodine transfer polymerization;
・ Cited document A: Mikiharu Kamachi and Tsuyoshi Endo, Radical Polymerization Handbook, published on August 10, 1999, published by NTS).
・ Cited document B: HANDBOOK OF RADICAL POLYMERIZATION, K. Matyjaszewski, T .; P. Davis, Eds. , John Wiley and Sons, Canada 2002
・ Cited document C: JP-A-2005-105265
The active energy ray polymerization can be carried out using the compound described in the cited reference D as an active energy ray polymerization initiator.
-Reference D: Photopolymer Society, Ed., List of Photosensitive Materials, March 31, 1996, published by Bunshin Publishing.

In the present invention, an active energy ray refers to an energy ray that can decompose a compound that generates an active species to generate an active species. Examples of such active energy rays include light energy rays such as visible rays, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, and electron beams.
Specific examples of the active energy ray polymerization initiator used are not particularly limited as long as the compounds generate radicals upon irradiation with ultraviolet light or visible light. Compounds used as the active energy ray polymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, -Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, , 2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropa -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-ethyl 1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di ( t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) ) -4,6-Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bi (Trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)] -2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5 (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis ( 7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazo 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole , 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (η ⁵ − 2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, and the like. These compounds may be used alone or in combination of two or more. 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxy (Carbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone and the like are preferable.
The amount of the polymerization initiator used in the above addition polymerization may be about 0.01 to 10 mol% based on the total number of moles of the monomers.
In the addition polymerization, a chain transfer agent may be used. By using a chain transfer agent, the molecular weight can be appropriately controlled. Examples of chain transfer agents include thio-β-naphthol, thiophenol, butylmercaptan, ethylthioglycolate, mercaptoethanol, mercaptoacetic acid, isopropylmercaptan, t-butylmercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 Mercaptans such as -mercaptopropionate) and pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyldisulfide, diethyldithioglycolate and diethyldisulfide; and the like, toluene, methyl isobutyrate, Carbon tetrachloride, isopropylbenzene, diethylketone, chloroform, ethylbenzene, butyl chloride, s-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, chloride Pyrene, methyl chloroform, t- butyl benzene, butyl alcohol, isobutyl alcohol, acetic acid, ethyl acetate, acetone, dioxane, Four ethane chloride, chlorobenzene, cyclohexane, t- butyl alcohol, benzene and the like. In particular, mercaptoacetic acid can lower the molecular weight of the polymer to make the molecular weight distribution uniform.

The chain transfer agents can be used alone or in combination of two or more.
The specific method for producing the fluorine-containing polymer (A) may be the same as the method for producing an ordinary addition polymer, and includes, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, A bulk-suspension polymerization method and a polymerization method using supercritical CO ₂ can be used.
When the solution polymerization method is used, for example, a fluorosilsesquioxane (α) having one addition-polymerizable functional group in a molecule and an addition-polymerizable monomer containing a group having active hydrogen in an appropriate solvent (Ε), an organopolysiloxane (γ) having an addition-polymerizable functional group that can be used as needed, an optional addition-polymerizable monomer (δ), a polymerization initiator, and a chain transfer agent May be dissolved and heated or irradiated with an active energy ray to cause an addition polymerization reaction.

Examples of the solvent used in the above polymerization reaction include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (chloride, etc.). Methylene, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), nitrile solvents (acetonitrile, Propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents N, N-dimethylformamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (HFCs having 2 to 4, 5 and 6 or more carbon atoms) ), Perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol) ), Aromatic fluorine solvents (α, α, α-trifluorotoluene, hexafluorobenzene) and water. These may be used alone or in combination of two or more.
The amount of the solvent used may be an amount that brings the monomer concentration to about 10 to 80% by weight.

The reaction temperature is not particularly limited, and may be about 0 to 200 ° C as a guide, and is preferably room temperature to about 150 ° C. The polymerization reaction can be performed under reduced pressure, normal pressure or increased pressure, depending on the type of monomer and the type of solvent.
The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. This is because the generated radicals are deactivated by contact with oxygen to suppress a decrease in the polymerization rate, and to obtain a polymer whose molecular weight is appropriately controlled. Further, the polymerization reaction is preferably performed in a polymerization system from which dissolved oxygen has been removed under reduced pressure (the polymerization reaction may be directly performed under reduced pressure after removing dissolved oxygen under reduced pressure).

The polymer obtained in the solution may be purified or isolated by a conventional method, and may be used as it is for forming a coating film.
When purifying the fluoropolymer (A), a purification method by a reprecipitation operation is preferable. This purification method is performed as follows. First, in a polymerization reaction solution containing a polymer and an unreacted monomer, a solvent that does not dissolve the polymer but dissolves the unreacted monomer, a so-called precipitant, is added to this solution to remove only the polymer. Let it settle. The preferred use amount of the precipitant is 20 to 50 times based on the weight of the polymerization reaction solution. Preferred precipitants are solvents that are compatible with the solvent used during polymerization, do not dissolve the polymer at all, dissolve only unreacted monomers, and have a relatively low boiling point. Examples of preferred precipitants are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitants are methanol, ethanol, 2-propanol, hexane, and heptane. These may be used alone or as a mixture of two or more. When mixed and used, Solmix AP-1, A-11 or the like, which is commercially available as a denatured alcohol, may be purchased from Japan Alcohol Sales Co., Ltd. and used. Then, in order to further increase the efficiency of removing unreacted monomers, the number of times of reprecipitation operation may be increased. According to this method, only the polymer can be precipitated in the poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

<Fluorine-based polymer (A) used in the present invention>
As described above, the group having a polymerizable unsaturated bond is a functional group (a group having active hydrogen) capable of introducing a precursor of a fluoropolymer and a group having a polymerizable unsaturated bond of the structural unit (E). And a compound having a group having a polymerizable unsaturated bond in the same molecule.
Examples of such a compound having a functional group reactive with a group having an active hydrogen and a group having a polymerizable unsaturated bond in the same molecule include, for example, an isocyanate compound having a polymerizable unsaturated bond and a polymerizable unsaturated bond. Acid halides, carboxylic acid compounds having a polymerizable unsaturated bond, carboxylic acid ester compounds having a polymerizable unsaturated bond, and epoxy compounds. As the group having such a polymerizable unsaturated bond, a radical polymerizable group is preferable, and examples thereof include (meth) acryl, allyl, and styryl.

  As the isocyanate compound having (meth) acryl, a compound having the following structure can be used.

In the formula, R ⁸ and R ⁹ are each independently hydrogen or methyl, B is oxygen, alkylene having 1 to 3 carbon atoms, or —OR ¹⁰ —; R ¹⁰ is alkylene having 2 to 12 carbon atoms. Oxyalkylene having 2 to 12 carbons and arylene having 6 to 12 carbons.

  As an isocyanate compound having styryl, a compound having the following structure can be used.

In the formula, R ¹¹ is alkylene having 1 to 10 carbon atoms, and R ¹² is hydrogen or methyl.
Specific examples of the isocyanate compound having a polymerizable unsaturated bond that can be suitably used include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and 4- ( 2-isocyanatoisopropyl) styrene, preferably 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate.

When reacting an isocyanate compound having a polymerizable unsaturated bond with a group having active hydrogen, a urethanization catalyst can be used for the purpose of accelerating the reaction.
Examples of the urethanization catalyst include an organometallic urethanization catalyst and a tertiary amine-based urethanization catalyst.

  Organometallic urethanization catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, and naphthenic acid An organometallic urethanization catalyst such as cobalt can be used.

Examples of the tertiary amine urethanization catalyst include triethylenediamine, N, N, N ', N', N'-pentamethyldipropylenetriamine, N, N, N ', N', N'-pentamethyldiethylenetriamine, N , N, N ', N'-tetramethylhexamethylenediamine, bis (dimethylaminoethyl) ether, 2- (N, Ndimethylamino) -ethyl-3- (N, Ndimethylamino) propylether, N, N '-Dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, triethylamine, N, N-dimethylacetylamine, N, N-dimethyldodecylamine, N, N-dimethylhexadecylamine, N, N ', N'-tetramethyl-1,3-butanediamine, N, N- Methylbenzylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4,4'-oxydiethylenedimorpholine, N, N'-dimethylpiperazine, N, N'- Diethylpiperazine, N, -methyl-N'-dimethylaminoethylpiperazine, 2,4,6-tri (dimethylaminomethyl) phenol, tetramethylguanidine, 3-dimethylamino-N, N-dimethylpropionamide, N, N , N ', N'-tetra (3-dimethylaminopropyl) methanediamine, N, N-dimethylaminoethanol, N, N, N', N'-tetramethyl-1,3-diamino-2-propanol, N , N, N'-trimethylaminoethylethanolamine, 1,4-bis (2-hydroxy Pyl) -2-methylpiperazine, 1- (2-hydroxypropyl) imidazole, 3,3-diamino-N-methylpropylamine, 1,8-diazabicyclo [5.4.0] -undecene-7, N-methyl —N-hydroxyethylpiperazine and the like.
These can be used alone or in combination of two or more. The catalyst may be used in any amount with respect to the isocyanate groups, but is preferably 0.0001 to 1 mol%, more preferably 0.001 to 1 mol%, based on the isocyanate groups.

  In order to obtain the fluoropolymer (A) using the isocyanate compound having a polymerizable unsaturated bond, a solvent may be used as necessary. The solvent used may be a group having active hydrogen and a solvent inert to isocyanate groups, for example, aromatic hydrocarbon solvents such as toluene and xylene, and ester solvents such as ethyl acetate and butyl acetate. , Methyl ethyl ketone, ketone solvents such as cyclohexanone, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, glycol ether ester solvents such as ethyl-3-ethoxypropionate, tetrahydrofuran, ether solvents such as dioxane, dimethylformamide, Examples thereof include polar solvents such as dimethylacetamide, N-methylpyrrolidone, and furfural. These may be used alone or in combination of two or more. The amount of the solvent used may be such that the concentration of the polymer containing the group having active hydrogen is about 10 to 80% by weight.

The reaction temperature is generally from 0 to 120C, preferably from 20 to 100C. If the temperature is lower than 0 ° C., the reaction becomes very slow. If the temperature exceeds 120 ° C., polymerization may be caused.
The molar ratio at the time of the reaction is isocyanate group: group having active hydrogen = 100: 1 to 0.01: 1, preferably 20: 1 to 0.1: 1.
Further, during the reaction between the isocyanate group and the group having active hydrogen, a polymerization inhibitor may be present for the purpose of suppressing polymerization. Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, phenanthraquinone, p-xyloquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-diacetoxy-p-. Benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-diasiloxy-p-benzoquinone, hydroquinone, pt-butylcatechol, 2,5-t-butylhydroquinone, mono-t-butylhydroquinone or 2,5 -Di-t-amylhydroquinone; and the amount used is 10 to 10, with respect to the total amount of the precursor of the fluoropolymer (A) and the isocyanate compound having a polymerizable unsaturated bond. 000 ppm, preferably 50 to 1,000 ppm.

  On the other hand, examples of the acid halide having a polymerizable unsaturated bond include, for example, acryl chloride, methacryl chloride, styrene carbonyl chloride, styrene sulfonyl chloride, 2-methacryloyloxyethyl succinyl chloride, and 2-methacryloyloxyethyl hexahydrophthalyl chloride. And bromide compounds such as acryl bromide, methacryl bromide, styrene carbonyl bromide, styrene sulfonyl bromide, 2-methacryloyloxyethyl succinyl bromide, and 2-methacryloyloxyethyl hexahydrophthalyl bromide. From the viewpoint of curability, halides of acrylic acid and methacrylic acid are preferred.

  In order to obtain a fluoropolymer (A) having a polymerizable unsaturated bond in a side chain using an acid halide having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a dehydrohalogenation reaction between an acid halide and a group having active hydrogen (preferably a hydroxyl group).

In this reaction, hydrogen halide is by-produced. Generally, in order to remove this hydrogen halide from the reaction system, it is preferable to allow a base to coexist in the reaction system as a hydrogen halide scavenger. The base as the hydrogen halide scavenger is not particularly limited, and a known base can be used. In general, bases that are suitably used include trialkylamines such as trimethylamine, triethylamine, and tripropylamine, pyridine, tetramethylurea, sodium hydroxide, and sodium carbonate. The amount of the base is preferably 1 mol or more per 1 mol of the carboxylic acid chloride.
In this reaction, it is generally preferable to use an organic solvent. Examples of the solvent preferably used include aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene, hexane, heptane, petroleum ether, chloroform, methylene chloride, and ethylene chloride or halogenated hydrocarbons. Ethers such as diethyl ether, dioxane and tetrahydrofuran; N, N-dialkylformamides such as N, N-dimethylformamide and N, N-diethylformamide; dimethyl sulfoxide and the like.
The temperature in this reaction can be selected from a wide range, and may be generally selected from a range of -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C. The reaction time varies depending on the type of the raw material, but may be generally selected from the range of 5 minutes to 24 hours, preferably 1 to 4 hours. It is preferable to carry out stirring during the reaction.
Usually, after the reaction, the reaction product can be separated by water washing and drying, and then the solvent is distilled off. Can be subjected to an esterification reaction.

  Examples of the carboxylic acid compound having a polymerizable unsaturated bond include acrylic acid, methacrylic acid, vinylbenzoic acid, and the like.

  In order to obtain a fluoropolymer (A) having a polymerizable unsaturated bond in a side chain using a carboxylic acid compound having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a dehydration condensation reaction between a carboxylic acid compound and a group having an active hydrogen (preferably a hydroxyl group).

  Examples of the carboxylic acid ester compound having a polymerizable unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 1-butyl (meth) acrylate, and t-butyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, and the like can be given.

  In order to obtain a fluoropolymer (A) having a polymerizable unsaturated bond in a side chain using a carboxylic acid ester compound having a polymerizable unsaturated bond, a known esterification reaction can be used. Here, the esterification reaction is a transesterification reaction between a carboxylic acid ester compound and a group having active hydrogen (preferably a hydroxyl group).

  Examples of the epoxy compound having a polymerizable unsaturated bond include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.

  In order to obtain a fluoropolymer (A) having a polymerizable unsaturated bond in a side chain using a compound having a polymerizable unsaturated bond, a known epoxy ring-opening reaction between a cyclic ether and a hydroxyl group must be used. Can be.

  Further, a part of the isocyanate group of a compound having a plurality of isocyanate groups such as isophorone diisocyanate is urethanized with a hydroxyl group-containing addition polymerizable monomer such as 2-hydroxyethyl acrylate to obtain an isocyanate compound having a polymerizable unsaturated bond. Further, a fluorinated polymer (A) having a polymerizable unsaturated bond in a side chain can be obtained by utilizing a urethanization reaction between the above isocyanate compound and a group having an active hydrogen (preferably a hydroxyl group).

  From the viewpoint of the abrasion resistance of the obtained cured film, the total solid content (in the present invention, the remaining components excluding the solvent from the photocurable composition is referred to as “solid content”) is 100% by weight in the resin composition. On the other hand, the fluorine-containing polymer (A) is preferably contained in an amount of 0.01 to 3% by weight, more preferably 0.5 to 2% by weight.

<Urethane (meth) acrylate (B)>
The photocurable resin composition according to one embodiment of the present invention contains hexafunctional urethane (meth) acrylate (B). In the above-mentioned Patent Document 2, the fluorine-based polymer can be used alone as a surface modifier, and if necessary, another resin (hereinafter, referred to as a binder resin) or a resin monomer (hereinafter, referred to as a binder resin). Monomer), and can be used as a surface modifier (so-called coating agent) by dissolving or dispersing it in various solvents as needed. Specifically, it repels dirt due to magic and the like, Although the property that the wiping property is also good is described, the present inventors have surprisingly found that the specific fluorine-based polymer (A) and the hexafunctional urethane (meth) acrylate (B) are combined. In particular, they have found that a cured film having high transparency and excellent wear resistance can be obtained.
In light of the effects of the present invention, the urethane (meth) acrylate (B) is hexafunctional and preferably has a viscosity at 40 ° C. of 20,000 mPa · s or less, more preferably 10,000 mPa · s or less. And more preferably 8,000 mPa · s or less. Preferably, the viscosity at 40 ° C. is 2,000 mPa · s or more. The viscosity is measured at 40 ° C. with an E-type viscometer.
The urethane (meth) acrylate (B) may be synthesized and used, or a commercially available urethane (meth) acrylate may be used.
Commercially available products include, for example, EXCELATE RUA-076MG, EXCELATE
RUA-071 (manufactured by Asia Industry Co., Ltd.), EBECRYL 1290, KRM 8200 (manufactured by Daicel Ornex Co., Ltd.), and Shikko UV-7605B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
Further, from the viewpoint of the abrasion resistance of the obtained cured film, the urethane (meth) acrylate (100% by weight based on the total solid content (the remaining components excluding the solvent from the photocurable composition) in the resin composition) B) is preferably contained in an amount of 50% by weight to 98% by weight, more preferably 53% by weight to 98% by weight, and still more preferably 55% by weight to 97% by weight.

<Photopolymerization initiator (C)>
In the present invention, the photopolymerization initiator (C) is used for the purpose of mixing the fluoropolymer (A) and the urethane (meth) acrylate (B) and promoting the curing thereof. As such a photopolymerization initiator, a photopolymerization initiator that generates a radical by ultraviolet light or visible light is preferable.
As the photopolymerization initiator, the active energy ray polymerization initiator described in the section of <Fluorine-based polymer (A)> can be used.

<Other ingredients>
The fluorine-containing polymer-containing photocurable composition according to one embodiment of the present invention is other than (A) to (C) from the viewpoint of adjusting various physical properties of the composition and from the viewpoint of curing during subsequent film formation. May be further contained. Examples of such other components include a solvent, a resin other than the fluororesin (A), and inorganic fine particles. In addition, as long as the antifouling property and abrasion resistance of the fluorine-containing resin-containing photocurable composition are not adversely affected, an active energy ray sensitizer, a polymerization inhibitor, a polymerization initiation aid, a leveling agent, and an improvement in wettability are provided. An optional component such as an agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler represented by silica or alumina, and an organic filler may be further contained. .

Inorganic fine particles (D)
The composition of the present invention preferably contains inorganic fine particles (D) (hereinafter, also referred to as component (D)) from the viewpoint of improving abrasion resistance. Examples of the inorganic fine particles (D) include silica and alumina.
The average particle size of the inorganic fine particles (D) is not limited as long as it is on the order of nanometers, but is preferably from 1 to 100 nm, more preferably from 1 to 40 nm, and still more preferably from 1 to 20 nm, from the viewpoint of transparency. Further, it is preferable that the particle size distribution is narrow.
The shape of the inorganic fine particles (D) is not particularly limited, but may be any shape such as a spherical shape, an irregular shape, and a scaly shape. From the viewpoint of improving adhesion and transparency, a spherical shape is preferred. When the shape of the inorganic fine particles (D) is not spherical, the average particle diameter of the inorganic fine particles (D) means the average maximum diameter of the inorganic fine particles (D).
Further, the inorganic fine particles (D) may be surface-treated with a silane coupling agent or the like, and a surface-modified colloidal silica is preferable.
In the composition of the present invention, the content of the inorganic fine particles (D) as the component (D) is preferably 5 to 50% by weight, more preferably 10 to 45% by weight in terms of% by weight based on the total solid content of the composition. Is more preferable.
In the present embodiment, the inorganic fine particles (D) may be added to the resin composition and used, or a commercial product in which the inorganic fine particles (D) are dispersed in the resin may be used.
Examples of such commercially available products include nano silica-dispersed epoxy resin [Nanopox (registered trademark) series (C620, F400, E500, E600, E430)] manufactured by EVONIK INDUSTRIES, in which 40% by mass of nano silica is dispersed in an epoxy resin. Nanocryl (registered trademark) series (C130, C140, C145, C146, C150, C153, C155, C165, C350) in which 50% by mass of nanosilica is dispersed in a resin.

In order to form a film on the surface of a base material such as plastics, glass, and metal, and to exhibit abrasion resistance, 1) a composition containing only the components (A) to (C) may be used. ) Further, it may be used in combination with a binder resin and a binder resin monomer. In order to express these functions on the surface of the substrate, it is important to adhere to the substrate, and in order to further fix the polymer with the substrate, it is preferable to use the polymer in combination with a binder resin. And 3) a binder resin having a functional group capable of reacting with the polymer (hereinafter, referred to as a reactive binder resin), and a component that crosslinks the polymer and the reactive binder resin by reaction. The polymer can be more firmly immobilized on the substrate via the polymer. For applications that require properties such as heat resistance, light resistance, and scratch resistance, by selecting a binder resin with these characteristics, the surface can be modified without impairing the inherent characteristics of the resin. can do.
As described above, the composition of the present invention may be used as a coating agent (such as a protective coating agent) in the composition containing only the components (A) to (C) as in the above 1), but may be used in the above 2). May be used as a coating agent by mixing with another binder resin as described above, and a binder resin monomer (hereinafter referred to as a reactive binder resin) capable of reacting with the fluoropolymer (A) as described in 3) above. (Also referred to as a monomer) and used as a coating agent.

The binder resin may be any of a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin, and may be a plurality of types of resins.
Examples of the binder resin include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly (meth) acrylate resin, ultrahigh molecular weight polyethylene, poly-4-methyl Penten, syndiotactic polystyrene, polyamide (nylon 6: Dupont brand name, nylon 6,6: Dupont brand name, nylon 6,10: Dupont brand name, nylon 6, T: Dupont brand name, nylon MXD6: Polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, etc.), polyacetal, polycarbonate, polyphenylene oxide Fluororesin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyarylate (U polymer: trade name of Unitika Ltd., Vectra: polyplastics Ltd.) Brand name, etc.), polyimide (Kapton: Toray Industries, Inc., Aurum: Mitsui Chemicals, Inc., etc.), polyetherimide, polyamideimide, phenolic resin, alkyd resin, melamine resin, epoxy resin, urea Resins, bismaleimide resins, polyester urethane resins, polyether urethane resins, silicone resins and the like are included.
These resins may be used alone, or a plurality of resins may be used in combination.

Further, as in the above 3), a reactive binder resin monomer may be mixed and used. In particular, the fluoropolymer having a polymerizable unsaturated bond in the side chain, and the reactive binder resin monomer, the resin obtained by curing and the fluoropolymer are cross-linked, as a result, mechanical properties, surface -A composite resin having excellent interface characteristics and compatibility can be obtained.
Specifically, a fluoropolymer (A) having a polymerizable unsaturated bond in a side chain, a urethane (meth) acrylate (B), a reactive binder resin monomer, and a photopolymerization initiator (C) are used. By applying the solution containing the composition to the substrate, and drying and curing the coating film, a film (composite film) made of a composite resin with a binder resin can be formed on the substrate.
The formed composite film has high antifouling property and abrasion resistance.
Preferred examples of the reactive binder resin monomer include a monomer that forms a UV-curable resin that can be radically cured by ultraviolet irradiation.

<Monomer forming UV-curable resin>
Resins that can be cured by ultraviolet irradiation include (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins other than component (B). And a resin having an unsaturated bond capable of radical polymerization.

  Examples of the (meth) acrylate monomer include compounds obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (Meth) acrylate, trimethylolpropanediethoxytri (meth) acrylate, trimethylolpropanetriethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropanepentaethoxytri (meth) acrylate, tetra Methylol methanetetra (meth) acrylate, tetramethylolpropanetetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Further, a compound having a silsesquioxane skeleton and having a (meth) acrylate group as a functional group may also be used.

As the unsaturated polyester resin, a condensation product (unsaturated polyester) obtained by an esterification reaction between a polyhydric alcohol and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) was dissolved in a polymerizable monomer. Things.
The unsaturated polyester can be produced by polycondensing an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or an anhydride thereof is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane -1,4-dimethanol, ethylene oxide adduct of bisphenol A, polyhydric alcohol such as propylene oxide adduct of bisphenol A are reacted as an alcohol component, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, Tetrahydrophthalic acid, adipic acid, sebacic acid Polymerizable not have an unsaturated bond or a polybasic acid anhydrides may include those prepared by adding as an acid component.

As the polyester (meth) acrylate resin, (1) a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol contains an α, β-unsaturated carboxylic acid ester group. (Meth) acrylate obtained by reacting an epoxy compound to be reacted, and (2) a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or unsaturated polybasic acid and a polyhydric alcohol, and reacting with a hydroxyl group-containing acrylate. (Meth) acrylates obtained by reacting (meth) acrylic acid with (3) a polyester having a terminal hydroxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol. Can be
Examples of the saturated polybasic acid used as a raw material of the polyester (meth) acrylate include polybasic acids having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Acids and anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid, and itaconic acid and anhydrides thereof are exemplified. Further, the polyhydric alcohol component is the same as the unsaturated polyester.

The epoxy (meth) acrylate resin usable in the present invention includes a polymer formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. A compound in which a compound having a unsaturated bond (vinyl ester) is dissolved in a polymerizable monomer.
The vinyl ester is produced by a known method, and includes an epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.
Further, various epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Chemicals, Inc.) to impart flexibility.
Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether, its high molecular weight homologues, and novolak glycidyl ethers.

As the urethane (meth) acrylate resin, for example, after a polyisocyanate is reacted with a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound are further reacted. And a radical-polymerizable unsaturated group-containing oligomer that can be obtained by the reaction.
Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and isomers thereof, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, and triphthalene diisocyanate. Phenylmethane triisocyanate, Burnock D-750, Crisbon NK (trade name; manufactured by DIC Corporation), Desmodur L (trade name; manufactured by Sumika Covest Lourethane Co., Ltd.), Coronate L (trade name; Tosoh Corporation) ), Takenate D102 (trade name; manufactured by Mitsui Chemicals, Inc.), Isonate 143L (trade name; manufactured by Dow Chemical Japan Co., Ltd.), and the like.
Examples of the polyhydroxy compound include polyester polyol, polyether polyol, and the like.Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, Trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaethritol-ethylene oxide adduct, dipentaethri Tall-propylene oxide adduct, dipentaethritol-tetrahydrofuran adduct, dipentaethritol-ethylene oxide De - propylene oxide adduct and the like.
Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3- Butanediol, adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexaneglycol, 1,3 -Cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol and the like. .
The hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable. Specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, pentaethritol tri ( (Meth) acrylate and the like.

As the acrylate monomer, for example, as disclosed in Japanese Patent No. 2655683, chlorosilane having a polymerizable unsaturated group is obtained by polymerizing silanol having a fluorinated hydrocarbon group and hexamethylcyclotrisiloxane. And fluorine-based silicon compounds that can be obtained by stopping the polymerization by reacting. Preferred examples of the fluorine-based silicon compound include compounds represented by the following formulas (I-1) and (I-2) (both n represents 0 to 500 and R ¹³ represents hydrogen or methyl). Can be

The resin composition of the present invention has a viewpoint of adjusting the concentration of the fluoropolymer and various physical properties of the fluoropolymer-containing photocurable composition, and the fluoropolymer-containing photocurable resin composition during the subsequent film formation. May be contained from the viewpoint of hardening.
Further, a fluorine-based polymer and a binder resin monomer may be dissolved in a solvent before use. Examples of the solvent used include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), and halogenated hydrocarbon solvents (methylene chloride, chloroform, chlorobenzene). ), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butyl alcohol, t-butyl alcohol, etc.), glycol ether solvents (ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether , Propylene glycol monobutyl ether, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide), hydrochlorofluorocarbon-based solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) -based solvents (having 2 to 4, 5 and 6 or more carbon atoms) HFCs), perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (full Roeteru, fluoropolyether, fluoroalkyl ketone, fluoroalcohol), aromatic fluorine solvent (alpha, alpha, alpha-trifluorotoluene, hexafluorobenzene), water. These may be used alone or in combination of two or more.
The amount of the solvent used may be such that the total amount of the fluoropolymer and the binder resin monomer is about 1 to 50% by weight.

  Examples of the curing aid that is contained in the composition of the present invention and that improves the curability of the fluororesin-containing photocurable composition and the adhesion to the substrate include, for example, two thiols in one molecule. Compounds having the above are mentioned. More specifically, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, Methylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglyconate, trishydroxyethyltristhiopropionate, 1,4-bis (3-mercaptobutyi) (Riloxy) butane (trade name: Karenz MT BD1, manufactured by Showa Denko KK), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz M) PE1, manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (product) Name: Karenz MT NR1, manufactured by Showa Denko KK) and the like.

<Coatings and laminates>
The film of the present invention and the laminate having the film are obtained from the composition of the present invention described above. More specifically, the film of the present invention is obtained by a step of forming a film of the composition of the present invention and a step of curing the film. The film can be formed by, for example, coating, and the curing of the film can be usually performed by one or more of drying, heating, and irradiation with active energy rays.

The method of applying the composition of the present invention to a substrate is not particularly limited, but includes spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating, rod coating, and bar coating. There are a coating method, a die coating method, a kiss coating method, a reverse kiss coating method, an air knife coating method, a curtain coating method and the like.
Examples of the substrate to be applied include transparent glass substrates such as white sheet glass, blue sheet glass, and silica-coated sheet glass; polycarbonate, polyester, acrylic resin, vinyl chloride resin, polyamide resin, polyamideimide, polyimide, triacetate, diacetate, and the like. Synthetic resin sheet and film; cycloolefin-based resin containing norbornene-based resin (trade name: ZEONOR, ZEONEX, Nippon Zeon Co., Ltd., trade name: ARTON, JSR, methacrylstyrene, polysulfone, alicyclic acrylic) Transparent resin substrates used for optical applications such as resins and polyarylates; metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates; other ceramic plates; semiconductor substrates having photoelectric conversion elements; urethane rubber, styrene rubber, and the like. .
These substrates may be pre-treated. Examples of the pre-treatment include chemical treatment with a silane coupling agent or the like, sand blast treatment, corona discharge treatment, ultraviolet treatment, plasma treatment, ion plating, sputtering, gas treatment. Phase reaction methods, vacuum deposition, and the like.
Drying of the applied solution can be performed in an environment at room temperature to about 200 ° C.
In the present invention, since a photopolymerization initiator is used, after application and drying, curing is performed by irradiating a photoactive energy ray with an active energy ray source.
The active energy ray source is not particularly limited, but may be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, or a solid laser, depending on the nature of the active energy ray polymerization initiator used. , An electron beam irradiation device, an LED lamp, and the like.

As one embodiment of the present invention, a base material, a fluoropolymer (A), a hexafunctional urethane (meth) acrylate (B) having a viscosity at 40 ° C. of 20,000 mPa · s or less, a photopolymerization initiator ( A cured film obtained by curing a photocurable composition containing (C) and inorganic fine particles (D), wherein a cured film having a Δ haze of 3% or less in Evaluation Method 1 for the photocurable composition is preferable. . Δ haze is more preferably 2.5% or less.
The fluorine-based polymer (A) is a structural unit A-1 derived from fluorosilsesquioxane having one addition-polymerizable functional group in the molecule represented by the formula (1), and an addition-polymerizable monomer Structural unit A-2 derived from a structural unit derived from an organopolysiloxane having a group having a polymerizable unsaturated bond in a side chain and an addition polymerizable functional group represented by the formula (2) It is a polymer containing -3.
[Evaluation method 1]
On a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm, a cured film of the photocurable composition having a thickness of 5 μm is formed.
The turbidity (haze) of the PET with the cured film was measured in accordance with ASTM D1044, and a Taber abrasion test was performed under a load of 1 kg (9.8 N), and then the haze was measured in accordance with ASTM D1044. (%), And the difference Δhaze is determined.
ΔHaze (%) = (Haze (%) after performing Taber abrasion test under a load of 1 kg (9.8 N)) − (Haze (%) before performing Taber abrasion test)

As one embodiment of the present invention, a laminate including a cured film obtained by curing the composition of the present invention is also preferable. Further, an optical member including the above laminate is also preferable.
That is, as a use of a film (cured film) obtained by the composition of the present invention, coating of a resin for optical use used for a top coat, a hard coat, a lens, etc. for an automobile for preventing contamination, and protection used for a display. Coating of a film, a protective film, coating for preventing a touch panel from being damaged, and the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but these descriptions do not limit the scope of the present invention. The data of the weight average molecular weight in this example was obtained by GPC (gel permeation chromatography) using poly (methyl methacrylate) as a standard substance. In the following examples, the polyfunctional urethane acrylate is described as the component (B) regardless of the number of functional groups.

The following measurement method was used in the present invention.
1) Viscosity of urethane (meth) acrylate The viscosity at 40 ° C. was measured using an E-type viscometer “TV-22” manufactured by Toki Sangyo Co., Ltd.
2) Film thickness The film thickness of the coated surface and that of the uncoated surface were measured with a digital micro “MF-501 + Counter TC-101” manufactured by Nikon Corporation, and calculated from the difference in film thickness.
3) Turbidity (haze)
Haze was measured based on ASTM D1003 using a haze meter “NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd.
4) Total light transmittance The total light transmittance was measured based on ASTM D1003 using a haze meter “NDH5000” manufactured by Nippon Denshoku Industries Co., Ltd.
5) Abrasion resistance (Taber abrasion test)
Using a Taber abrasion tester “No. 101” manufactured by Yasuda Seiki Seisakusho Co., Ltd., based on ASTM D1044, using a CS-10 abrasion wheel, applying a load of 1 kg (9.8 N) on the cured film. The haze after 100 rotations was measured, and the difference from the haze value measured before the test was calculated. When the haze difference was 3% or less in the evaluation standard, the abrasion resistance was determined to be good.

[Production Example 1]
.gamma.-methacryloxypropyl hepta (trifluoropropyl) -T 8 _- silsesquioxane, _- silsesquioxanes represented by San synthetic formula (11) .gamma.-methacryloxypropyl hepta (trifluoropropyl) -T 8 It was synthesized by the same method as described in paragraph 0087 of WO 2008/072766.

[Production Example 2] Synthesis of fluorinated polymer (A1) <Polymerization>
In a 500 mL four-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel, 50.00 g of the compound (11) synthesized in Production Example 1, 37.50 g of methyl methacrylate (MMA), 25.00 g of ethyl methacrylate (HEMA), 12.50 g of dimethyl silicone modified with a methacryloxy group at one end (FM-0721, molecular weight of about 6,300), and 123.89 g of 2-butanone (MEK) were introduced, followed by nitrogen sealing. The mixture was set in an oil bath maintained at 80 to 85 ° C., refluxed, and deoxygenated for 15 minutes. Next, a solution in which 1.00 g of 2,2'-azobisisobutyronitrile (AIBN) and 0.11 g of mercaptoacetic acid were dissolved in 10.02 g of MEK was introduced, and polymerization was started while maintaining the reflux temperature. did. After polymerization for 3 hours, a solution in which 1.00 g of AIBN was dissolved in 9.01 g of MEK was introduced, and polymerization was continued for another 5 hours.
Subsequently, 0.70 g of p-methoxyphenol (MEHQ) and 0.21 g of di-n-butyltin dilaurate (DBTDL) were introduced, followed by sealing with nitrogen. The solution was set in an oil bath, the temperature was raised, and when the solution temperature reached 35 ° C., 35.24 g of acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was introduced, and the reaction was started. After reacting at 45 ° C. for 5 hours, the reaction was cooled to room temperature, and 12.00 g of methanol (MeOH) was introduced to terminate the reaction. 4-Methyl-2-pentanone (MIBK) was added and diluted to 30% by weight. The weight average molecular weight determined by GPC analysis of the obtained polymer (A1) was 39,700, and the molecular weight distribution was 1.85. The composition mole fraction of each monomer unit (derived from a monomer component) determined by ¹ H-NMR measurement of the polymer (A1) is Compound (11): MMA: HEMA: FM-0721 = a: b: c: d = 653: 5971: 3340: 35, and the methacryloyl group equivalent was 757 g / eq.

[Experimental example 1]
(Coating preparation)
As the component (A), the polymer (A1) obtained in Production Example 1, and as the component (B), a hexafunctional urethane acrylate EXCELATE RUA- having a viscosity of 7,700 mPa · s at 40 ° C. measured with an E-type viscometer. 076MG (manufactured by Asia Kogyo Co., Ltd.) and Irgacure 127 (manufactured by BASF Japan Co., Ltd.) as the component (C) were mixed with propylene glycol monomethyl ether so that the solid content concentration was 35% by weight at the compounding amount shown in Table 1. To obtain a coating solution.
(Creating a cured film)
The obtained coating solution was applied to R.I. D. Using a coating rod (# 10) manufactured by Specialtys Co., Ltd., it was applied to one side of a 210 cm × 297 cm polyethylene terephthalate film (thickness: 100 μm, Cosmoshine (trade name) A4300) manufactured by Toyobo Co., Ltd.
The obtained film with a coating film was dried in a high-temperature chamber at 80 ° C. for 3 minutes, and using a conveyor type UV irradiation apparatus equipped with a high pressure mercury lamp (H08-L41, rated 160 W / cm) manufactured by Iwasaki Electric Co., Ltd. UV light was irradiated at an illuminance of 200 mW / cm ² and an exposure of 500 mJ / cm ² to obtain a laminate having a 5 μm-thick transparent hard coat layer. The exposure was measured with an illuminometer (UVPF-A1 / PD-365) manufactured by Iwasaki Electric Co., Ltd.
The obtained cured film was evaluated for optical properties (total light transmittance, haze) and mechanical properties (abrasion resistance) by the methods described above. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 2]
The coating was performed in the same manner as in Experimental Example 1 except that the blending amount of the component (B) was changed, and the propylene glycol monomethyl ether dispersed silica sol PGM-AC-2140Y (manufactured by Nissan Chemical Industries, Ltd.) was blended as the component (D). A liquid was prepared, a coating film was formed and cured, and the obtained cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 3]
Coating was carried out in the same manner as in Experimental Example 1 except that a polyfunctional monomer other than urethane (meth) acrylate, NK ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) was blended and the blending amount of the component (B) was changed. A liquid was prepared, a coating film was formed and cured, and the obtained cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 4]
An alicyclic acrylate monomer SR217 (manufactured by Sartomer Co., USA) which is a monofunctional monomer was blended, and a coating solution was prepared in the same manner as in Experimental Example 1 except that the blending amount of the component (B) was changed. It was prepared and cured, and the resulting cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 5]
A coating solution was prepared, a coating film was formed and cured in the same manner as in Experimental Example 1 except that the component (A) was not blended, and the obtained cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 6]
(B) A coating solution was prepared, a coating film was prepared and cured in the same manner as in Experimental Example 1 except that the amount of the component was changed and NK ester A-DPH was blended. evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 7]
The component (B) was changed to a hexafunctional urethane acrylate purple light (registered trademark) UV-7600B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) whose viscosity measured by an E-type viscometer at 40 ° C. was 35,300 mPa · s. A coating solution was prepared, a coating film was formed and cured in the same manner as in Experimental Example 1 except that the coating was performed, and the obtained cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 8]
Experimental example except that the component (B) was changed to a 10-functional urethane acrylate EXCELATE RUA-077 (manufactured by Asia Industry Co., Ltd.) whose viscosity measured by an E-type viscometer at 40 ° C. was 11,300 mPa · s. In the same manner as in Example 1, a coating liquid was prepared, a coating film was formed and cured, and the obtained cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 9]
The component (B) was converted into a 10-functional urethane acrylate Shikko (registered trademark) UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) having a viscosity measured by an E-type viscometer at 40 ° C. of 11,000 mPa · s. A coating solution was prepared, a coating film was formed and cured in the same manner as in Experimental Example 1 except for the change, and the obtained cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

[Experimental example 10]
The component (B) is a 4- to 5-functional urethane acrylate having a viscosity measured by an E-type viscometer at 40 ° C. of 63,700 mPa · s. ), A coating liquid was prepared, a coating film was formed and cured in the same manner as in Experimental Example 1, and the obtained cured film was evaluated. Table 1 shows the composition of the coating liquid, and Table 2 shows the evaluation results.

  From Experimental Examples 1-4, a cured film obtained from a composition obtained by combining a fluoropolymer (A) and a hexafunctional urethane (meth) acrylate (B) having a viscosity at 40 ° C. of 20,000 mPa · s or less, In particular, it was shown to be excellent in transparency and abrasion resistance.

  The cured film obtained from the photocurable composition of the present invention has high transparency, excellent abrasion resistance, and is very useful as a coating. Used for coating of resin for optical applications such as top coats, hard coats and lenses for automobiles to prevent scratches, coating of protective films and protective films for displays, and coatings for preventing scratches on touch panels. It is possible to In particular, by using a cured film obtained from the photocurable composition of the present invention, to protect portable electronic devices such as smartphones and tablets used outdoors and eyeglasses and sunglasses from scratches, to use more comfortably. Can be done.

Claims (14)

A photocurable composition containing a fluoropolymer (A), a urethane (meth) acrylate (B) and a photopolymerization initiator (C),
A structural unit A-1 derived from a fluorosilsesquioxane having one addition-polymerizable functional group in a molecule represented by the formula (1) and a fluorine-containing polymer (A), A photocurable composition which is a polymer containing a structural unit A-2 which is a structural unit derived from a monomer and has a group having a polymerizable unsaturated bond in a side chain.

(Wherein, R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen; at least one hydrogen is fluorine or trifluoromethyl replaced, fluoroaryl having 6 to 20 carbon atoms; at least one hydrogen or in the aryl is replaced by fluorine or trifluoromethyl, indicates fluoroarylalkyl 7 to 20 carbon atoms, a ¹ is addition polymerizable Shows a functional group.) R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4, 5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1 , 1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl, and α, α, The photocurable composition according to claim 1, which is selected from the group consisting of α-trifluoromethylphenyl. R _f ^{1 to} R _f ⁷ in the formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, The photocurable composition according to claim 1, which is selected from the group consisting of and tridecafluoro-1,1,2,2-tetrahydrooctyl.   The photocurable composition according to any one of claims 1 to 3, wherein the group having a polymerizable unsaturated bond of the structural unit A-2 is (meth) acrylic bonded to a main chain via a urethane bond. Composition. The fluoropolymer (A) is a polymer further comprising a structural unit A-3 derived from an organopolysiloxane having an addition-polymerizable functional group represented by the following formula (2). The photocurable composition according to claim 1.

Wherein n is an integer from 1 to 1,000; R ¹ and R ² are each independently methyl, phenyl or 3,3,3-trifluoropropyl; R ³ and R ⁴ are Each independently methyl or phenyl; R ⁵ is methyl, ethyl, propyl, butyl, isobutyl, phenyl, 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3 , 3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl , Henicosafluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, penta Le Oro phenylpropyl, pentafluorophenyl, and alpha, alpha, selected from the group consisting of α- trifluoromethylphenyl; A ² is an addition-polymerizable functional group). ^{R 1,} R 2, ^{R 3} and ^{R 4} in formula (2) are each simultaneously methyl, ^{A 2} is (meth) acrylic photocurable composition according to claim 5.   The photocurable composition according to any one of claims 1 to 6, further comprising inorganic fine particles (D).   The photocurable composition according to claim 7, wherein the inorganic fine particles (D) are surface-modified colloidal silica.   The photocurable composition according to any one of claims 1 to 8, wherein the urethane (meth) acrylate (B) is a hexafunctional urethane (meth) acrylate having a viscosity at 40 ° C of 20,000 mPa · s or less. Stuff.   The photocurable composition according to claim 9, comprising 50% to 98% by weight of the urethane (meth) acrylate (B) based on 100% by weight of the total solids.   A cured film obtained by curing the photocurable composition according to claim 1. A photocurable composition containing a fluoropolymer (A), a hexafunctional urethane (meth) acrylate (B) having a viscosity at 40 ° C. of 20,000 mPa · s or less, a photopolymerization initiator (C), and inorganic fine particles (D). A cured film obtained by curing the composition,
A cured film having a Δ haze of 3 or less in Evaluation Method 1 for the photocurable composition.
A fluorine-containing polymer (A) represented by the formula (1), a structural unit A-1 derived from fluorosilsesquioxane having one addition-polymerizable functional group in a molecule, an addition-polymerizable monomer Structural unit A-2 derived from a structural unit derived from an organopolysiloxane having a group having a polymerizable unsaturated bond in a side chain and an addition polymerizable functional group represented by the formula (2) -3 is a polymer containing
In the formula (1), R _f ^{1 to} R _f ⁷ are each independently 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl , And tridecafluoro-1,1,2,2-tetrahydrooctyl; A ¹ is an addition polymerizable functional group,
A-2 is a (meth) acryl in which a group having a polymerizable unsaturated bond is bonded to a main chain via a urethane bond,
In the formula (2), n is an integer of ^{1 to} 1,000, R ¹ , R ² , R ³ and R ⁴ are each simultaneously methyl, R ⁵ is butyl, and A ² is (meth) Acrylic.


[Evaluation method 1]
On a polyethylene terephthalate (PET) film substrate having a thickness of 100 μm, a cured film of the photocurable composition having a thickness of 5 μm is formed.
The turbidity (haze) (%) of the PET with the cured film was measured in accordance with ASTM D1044, and a Taber abrasion test was performed with a load of 1 kg (9.8 N) applied, followed by ASTM D1044. Then, the haze (%) is measured, and the difference Δhaze (%) is obtained.
ΔHaze (%) = (Haze (%) after performing Taber abrasion test under a load of 1 kg (9.8 N)) − (Haze (%) before performing Taber abrasion test)   A laminate comprising the cured film according to claim 11.   An optical member comprising the cured film according to claim 11 or a laminate according to claim 13.