JP2000017028A - Curable resin composition and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition capable of forming cured films excellent in clarity, low in refractive index and, in addition, excellent in mar resistance and anti-fouling properties, and an antireflection film by using the cured film. SOLUTION: The curable resin composition comprises (A) an olefinic polymer having a polysiloxane segment in the main chain, a fluorine content of not less than 30 wt.% and a number average molecular weight of not less than 5,000 in terms of polystyrene, (B) a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups in the molecule, (C) a radiation polymerization initiator, and a solvent. It is possible to add a fluoropolymer other than the component (A) at this composition. A desired antireflection film is composed of a cured product of the curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more particularly to a curable resin composition capable of forming a cured film having excellent curability, abrasion resistance, transparency and low reflectance. Related to the prevention film.

[0002]

2. Description of the Related Art At present, with the development of multimedia, various developments are being made in various display devices (display devices). Among various types of display devices, in particular, those used outdoors, mainly for portable use, are becoming more and more important to improve the visibility. This is a technical issue as it is.

Conventionally, as one means for improving the visibility of a display device, an antireflection film made of a low-refractive index material is coated on a substrate of the display device. For example, a method of forming a thin film of a fluorine compound by a vapor deposition method is known. However, in recent years, there has been a demand for a technique capable of forming an antireflection film on a large-sized display device at low cost, mainly for a liquid crystal display device. However, in the case of the evaporation method, it is difficult to form a uniform antireflection film with high efficiency on a large-area substrate,
Moreover, it is difficult to reduce the cost because a vacuum device is required.

Under such circumstances, a liquid composition is prepared by dissolving a fluoropolymer having a low refractive index in an organic solvent,
A method of forming an anti-reflection film by applying this to the surface of a substrate has been studied. For example, Japanese Patent Application Laid-Open
No. 1527 proposes applying a fluorinated alkylsilane to the surface of a substrate.
No. 15023 proposes a method of applying a fluoropolymer having a specific structure. Further, Japanese Unexamined Patent Publication No.
No. 100136 proposes a method of applying a UV-curable fluorine-containing coating material.

[0005]

However, the conventional antireflection film formed by coating a fluorine-based material has a drawback that since it is a thermosetting type, the curing speed is low and the productivity is poor. In addition, the UV-curable fluorine-based coating material has a problem that the resulting coating does not have sufficient scratch resistance, and the antireflection film layer is peeled off, especially when repeatedly rubbed. On the other hand, the anti-reflection film is often located on the outermost layer of the display device. For this reason, it is desirable to be able to easily wipe off dirt such as fingerprints attached to the anti-reflection film, but in order to reduce the surface energy of the film. When an attempt is made to increase the fluorine content, the composition becomes difficult to dissolve in a common solvent, and as a result, there is a disadvantage that a halogen-containing solvent which is expensive and environmentally problematic must be used. Was.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to exhibit excellent transparency, a low refractive index, and a good antireflection effect.
It is still another object of the present invention to provide a curable resin composition which can continuously form a cured film having excellent scratch resistance and stain resistance and can be dissolved in a general hydrocarbon solvent. Another object of the present invention is to provide an antireflection film having high transparency and excellent scratch resistance.

[0007]

The curable resin composition of the present invention comprises (A) a polysiloxane segment in the main chain, a fluorine content of 30% by weight or more, and a number average molecular weight in terms of polystyrene. An olefin polymer having a molecular weight of 5,000 or more (hereinafter referred to as “component (A)”), (B) 1
Multifunctional (meth) acrylate compound containing two or more (meth) acryloyl groups in the molecule (hereinafter referred to as “component (B)”)
That. ) And (C) a radiation polymerization initiator (hereinafter, referred to as “component (C)”). Further, the antireflection film of the present invention is characterized by comprising a cured product of the above curable resin composition.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Olefin Polymer> The curable resin composition of the present invention has a polysiloxane segment in the main chain, has a fluorine content of 30% by weight or more, and has a number average in terms of polystyrene. The component (A) consisting of an olefin polymer having a molecular weight of 5,000 or more (hereinafter, referred to as “specific fluoropolymer”) is contained as an essential component. In the present invention, the specific fluoropolymer is an olefin polymer having a polysiloxane segment represented by the following general formula 1 in the main chain, and the ratio of the polysiloxane segment in the specific fluoropolymer is: Usually, it is 0.1 to 10 mol%.

[0009]

Embedded image In the formula, R ¹ and R ² may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.

The specific fluorine-containing polymer has a fluorine content of 30% by weight or more, preferably 30 to 70% by weight, and has a number average molecular weight of 5,000 in terms of polystyrene obtained by gel permeation chromatography. Above, preferably 10,000-5000
00. Here, the fluorine content is a value measured by the alizarin complex method, and the number average molecular weight is a value when tetrahydrofuran is used as a developing solvent.

The specific fluorine-based polymer in the present invention is:
(A) a fluorine-containing olefin compound (hereinafter, referred to as “component (a)”), and (b) another monomer compound copolymerizable with component (a) (hereinafter, referred to as “component (b)”). And (c) an azo group-containing polysiloxane compound (hereinafter referred to as “component (c)”) and, if necessary, (d) a reactive emulsifier (hereinafter referred to as “component (d)”). Obtainable.

Examples of the component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom. Fluoroolefins such as fluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene and chlorotrifluoroethylene;
(2) alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; (3)
Perfluoro (alkyl vinyl ether) s such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); and (4) perfluoro (propoxypropyl vinyl ether) etc. (Alkoxyalkyl vinyl ethers); (5) fluorine-containing (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, and heptadecafluorodecyl (meth) acrylate Kind;
Others can be mentioned. These compounds can be used alone or in combination of two or more. Of these, fluoroolefins, perfluoro (alkyl vinyl ether) s, and perfluoro (alkoxyalkyl vinyl ether) s are particularly preferable, and furthermore, it is preferable to use them in combination. Specifically, it is preferable to use one or two or more selected from hexafluoropropylene, perfluoropropyl vinyl ether and perfluoropropoxypropyl vinyl ether.

Specific examples of the component (b) copolymerizable with the component (a) include (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and tert-butyl. Vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, ethylene glycol butyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol methyl vinyl ether, cyclohexyl vinyl ether Such as alkyl vinyl ethers or cycloalkyl vinyl ethers (2) vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate and benzoic acid; (3) α such as ethylene, propylene and isobutene -Olefins;
(4) styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methylstyrene
tert-butylstyrene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, Vinyl aromatic compounds such as N-diethyl-p-aminostyrene, vinylpyridine, vinylimidazole; (5) carboxyl group-containing compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid;

(6) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate,
Isodecyl (meth) acrylate, undecyl (meth)
Alkyl (meth) acrylates such as acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate; (7) hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate and hydroxybutyl (meth) acrylate;
(8) Phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate;
(9) alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and methoxybutyl (meth) acrylate;

(10) polyethylene glycol such as polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate; (11) polypropylene glycol (meth) acrylates such as (11) polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate; (12) Cyclohexyl (meth)
Acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate,
Dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth)
Cycloalkyl (meth) acrylates such as acrylate, isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate; (13) benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the following general formulas 2 to 2 (Meth) acrylates such as the compound represented by Formula 4;

[0016]

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 12
Is an integer. )

[0017]

Embedded image (In the formula, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group having 2 to 8 carbon atoms, and n is an integer of 1 to 8.)

[0018]

Embedded image (In the formula, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents an alkylene group having 2 to 8 carbon atoms, R ¹⁰ represents a hydrogen atom or a methyl group, and p is an integer of 1 to 8. )

(14) Acryloylmorpholine, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, tert-octyl (15) (meth) acrylamides such as (meth) acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide; Methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, diethyl itaconate, maleic acid Methyl, diethyl maleate, dimethyl fumarate, unsaturated carboxylic acid esters such as diethyl fumarate;

(16) (meth) acrylonitrile, α-
Chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, nitrile crotonic acid, nitrile cinnamate, dinitrile itaconic acid, dinitrile maleate,
Unsaturated nitriles such as fumaric acid dinitrile; (17)
2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 3-hydroxypropyl vinyl ether, 3-hydroxybutyl vinyl ether,
(18) hydroxyl-containing vinyl ethers such as -hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether;
Hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; (19) N-vinyl lactams such as N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam And the like. Among them, 2-hydroxyethyl vinyl ether and 2-hydroxybutyl vinyl ether are preferably used. These compounds can be used alone or in combination of two or more. Furthermore, a specific fluorine-containing polymer having a functional group can be obtained by copolymerizing a monomer containing an epoxy group, an isocyanate group, and other various functional groups in addition to the above-mentioned monomer.

Of the above-mentioned monomer compounds, alkyl vinyl ethers, cycloalkyl vinyl ethers, or vinyl carboxylate are preferred from the viewpoint of increasing the yield in the polymerization reaction for obtaining a specific fluoropolymer. It is preferably used. On the other hand, from the viewpoint of increasing the fluorine content in a specific fluoropolymer, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, vinyl acetate, vinyl propionate,
It is preferable to use low molecular weight monomers such as vinyl butyrate and vinyl pivalate. Further, in order to increase the hardness of the thin film after curing of the curable resin composition and reduce the refractive index, a branched monomer such as isopropyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, or vinyl pivalate is used. It is effective to use an alicyclic monomer such as cyclohexyl vinyl ether.

The azo group-containing polysiloxane compound of the component (c) is a compound containing an azo group easily decomposable by -N = N- and having a polysiloxane segment represented by the above general formula 1. For example, see JP-A-6-9
It can be produced by the method described in JP-A-3100. As a specific example of the component (c), a compound represented by the following general formula 5 can be given.

[0023]

Embedded image In the formula, y = 10 to 500 and z = 1 to 50. (C)
Commercially available compounds that can be used as components include, for example, “VPS-0501” and “VPS-100”.
1 "(all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

Preferred combinations of the above components (a), (b) and (c) are, for example, (1) a fluoroolefin / alkyl vinyl ether / polydimethylsiloxane unit, (2) a fluoroolefin / perfluoro (alkyl vinyl ether) ) / Alkyl vinyl ether / polydimethylsiloxane unit, (3) fluoroolefin / perfluoro (alkoxyalkyl) vinylether / alkylvinylether / polydimethylsiloxane unit, (4) fluoroolefin / (perfluoroalkyl) vinylether / alkylvinylether / polydimethylsiloxane Unit, (5) fluoroolefin / (perfluoroalkoxyalkyl) vinyl ether / alkyl vinyl ether / polydimethylsiloxane unit.

In the specific fluoropolymer of the present invention,
The structural unit derived from the component (a) is 20 to 70 mol%, preferably 25 to 65 mol%, and more preferably 30 to 6 mol%.
0 mol%. When the proportion of the structural monomer derived from the component (a) is less than 20 mol%, the fluorine content in the obtained specific fluorine-based copolymer tends to be too low, and the cured product of the curable resin composition obtained has a refractive index of Is low enough. On the other hand, the ratio of the structural unit derived from the component (a) is 7
When the amount exceeds 0 mol%, the solubility of the obtained specific fluoropolymer in an organic solvent is significantly reduced, and the obtained curable resin composition has low transparency and low adhesion to a substrate. Become.

In the specific fluorine-containing polymer, the structural unit derived from the component (b) is 10 to 70 mol%, preferably 15 to 65 mol%, more preferably 30 to 60 mol%.
It is. When the proportion of the structural unit derived from the component (b) is less than 10 mol%, the specific fluoropolymer has poor solubility in an organic solvent, and when the proportion exceeds 70 mol%, curing with the curable resin composition is performed. The object has deteriorated transparency and optical characteristics of low reflectance.

The azo group-containing polysiloxane of the component (c) itself is a thermal radical generator and has a function as a polymerization initiator in a polymerization reaction for obtaining a specific fluorine-containing polymer. A radical initiator may be used in combination. The proportion of the structural unit derived from the component (c) in the specific fluoropolymer is such that the polysiloxane segment represented by the general formula 1 is 0.1 to 20 mol%, preferably 0.1 to 15 mol%, Preferably 0.1 to 10
It is the ratio to be mol%. When the proportion of the polysiloxane segment represented by the general formula 1 exceeds 20 mol%, the obtained specific fluoropolymer has poor transparency, and when it is used as a coating agent, cissing occurs at the time of coating. Are likely to occur.

In the present invention, a reactive emulsifier is preferably used as a monomer component as the component (d) in addition to the components (a) to (c). By using the component (d), when a specific fluoropolymer is used as a coating agent, good coating properties and leveling properties can be obtained. As this reactive emulsifier, it is particularly preferable to use a nonionic reactive emulsifier. Specific examples of the nonionic reactive emulsifier include, for example, a compound represented by the following general formula 6.

[0029]

Embedded image In the formula, n, m and s represent a repeating unit, and n = 1 to
20, m = 0-4 and s = 3-50 are preferred. Commercially available compounds that can be used as component (d) include, for example, "Adecaria Soap NE-5",
"Adecaria Soap NE-10", "Adecaria Soap NE-20", "Adecaria Soap NE-30", "Adecaria Soap NE-40" (all manufactured by Asahi Denka Kogyo Co., Ltd.)
And the like.

In the specific fluoropolymer, the proportion of the constituent unit derived from the component (d) is usually 0 to 10 mol%, preferably 0.1 to 5 mol%. This ratio is 1
If the amount exceeds 0 mol%, the resulting curable resin composition becomes tacky, which makes it difficult to handle, and reduces the moisture resistance when used as a coating agent.

Preferred combinations when component (d) is contained are as follows. (1) Fluoroolefin /
Alkyl vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier, (2) fluoroolefin /
Perfluoro (alkyl vinyl ether) / alkyl vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier, (3) fluoroolefin / perfluoro (alkoxyalkyl) vinyl ether / alkylvinylether / polydimethylsiloxane unit / nonionic reactive emulsifier, (4) Fluoroolefin / (perfluoroalkyl) vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier, (5) fluoroolefin / (perfluoroalkoxyalkyl) vinyl ether /
Alkyl vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier.

In the present invention, as a polymerization method for producing a specific fluoropolymer, any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and a solution polymerization method using a radical polymerization initiator is used. As the polymerization operation, an appropriate operation can be selected from a batch operation, a semi-continuous operation, a continuous operation, and the like.

Examples of the radical polymerization initiator which can be used in combination with the component (c) include (1) diacyl peroxides such as acetyl peroxide and benzoyl peroxide; and (2) methyl acyl ketone peroxide and cyclohexanone peroxide. Ketone peroxides; (3) hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; (4) di-tert
Dialkyl peroxides such as -butyl peroxide, dicumyl peroxide, dilauroyl peroxide; (5) peroxyesters such as tert-butylperoxyacetate and tert-butylperoxypivalate; (6) azobis Azo compounds such as isobutyronitrile and azobisisovaleronitrile; (7) persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; and others.

Specific examples of the above radical polymerization initiator include, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide , Heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5
Methylhexyl iodide, 2- (perfluoro-5-
Methylhexyl) ethyl iodide, perfluoro-7
-Methyloctyl iodide, 2- (perfluoro-7
-Methyloctyl) ethyl iodide, perfluoro-
9-methyldecyl iodide, 2- (perfluoro-9
-Methyldecyl) ethyl iodide, 2,2,3,3
-Tetrafluoropropyl iodide, 1H, 1H, 5
H-octafluoropentyl iodide, 1H, 1H,
7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-
Examples thereof include iodine-containing fluorine compounds such as diiodobutane and dodecafluoro-1,6-diiodohexane. The iodine-containing fluorine compound can be used alone or in combination with the above organic peroxides, azo compounds or persulfates. Among these radical polymerization initiators that can be used in combination with the component (c), dilauroyl peroxide is particularly preferably used.

The polymerization reaction for obtaining a specific fluoropolymer is preferably carried out in a solvent system using a solvent. Here, preferred organic solvents include, for example, (1) esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and cellosolve acetate; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; (3) cyclic ethers such as tetrahydrofuran and dioxane; (4) N, N
Amides such as -dimethylformamide and N, N-dimethylacetamide; (5) aromatic hydrocarbons such as toluene and xylene; and others. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used. Among them, ethyl acetate, methyl isobutyl ketone and the like are preferably used from the viewpoint of solubility of each component.

The specific fluoropolymer obtained as described above can be used as a curable resin composition as it is in the reaction solution obtained by the polymerization reaction in some cases. On the other hand, an appropriate post-processing may be freely performed. As this post-treatment, for example, a general purification method represented by a purification method in which a polymerization reaction solution is added dropwise to an insolubilizing solvent for the specific fluoropolymer, such as alcohol, to solidify the specific fluoropolymer. A reprecipitation treatment can be performed, and then, a solution of a specific fluorine-based polymer can be prepared by dissolving the obtained solid copolymer in a solvent. A solution obtained by removing the residual monomer from the polymerization reaction solution can be used as it is as a solution of a specific fluoropolymer.

<Specific Fluorinated Polymer Modified> The component (A) composed of the specific fluorinated polymer constituting the composition of the present invention is a copolymer modified by introducing a crosslinkable functional group. A polymer (hereinafter, also referred to as a “crosslinkable functional group-containing copolymer”) may be used, or a copolymer modified by the introduction of a photopolymerizable group (hereinafter, referred to as a copolymer).
Also referred to as a “photopolymerizable group-containing copolymer”. ).

(1) Crosslinkable Functional Group-Containing Copolymer The crosslinkable functional group-containing copolymer is used as the component (b)
It can be obtained by using a copolymerizable monomer containing a crosslinkable functional group. Here, as the crosslinkable functional group, for example, a hydroxyl group, a carboxyl group, an anhydride group of a dicarboxylic acid, an epoxy group, an amino group, a hydrolyzable silyl group,
Examples thereof include a silanol group, an isocyanate group, and a thiol group.

Preferred specific examples of the copolymerizable monomer containing a crosslinkable functional group include monomers containing a hydroxyl group such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and hydroxyethyl (meth) acrylate; Carboxy group-containing monomers such as acetic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and (meth) acrylic acid, and anhydrides of dicarboxylic acids such as maleic anhydride and phthalic anhydride Monomer containing epoxy group, monomer containing epoxy group such as vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, glycidyl crotonate, methyl glycidyl maleate, vinyl trimethoxysilane, etc. Monomers containing hydrolyzable silyl groups It can be mentioned. By using a crosslinkable functional group-containing polymer as the specific fluoropolymer (A) and adding a crosslinkable compound described below to prepare the composition of the present invention, a cured film formed by the composition is prepared. Since the crosslinked structure can be introduced into the cured film, the cured film has a high hardness and further excellent solvent resistance and chemical resistance.

(2) Photopolymerizable Group-Containing Copolymer: The photopolymerizable group-containing copolymer is the same as the above-mentioned crosslinkable functional group-containing copolymer.
It can be obtained by reacting the crosslinkable functional group with a compound containing a group capable of reacting and a photopolymerizable group and introducing the photopolymerizable group into the copolymer. Here, as the photopolymerizable group, for example, a (meth) acryloyl group, an alkenyl group, a cinnamoyl group, a cinnamylideneacetyl group,
Benzalacetophenone group, styrylpyridine group, α-
Phenylmaleimide group, phenylazide group, sulfonylazide group, carbonylazide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,
Examples thereof include a 2,3-thiadiazole group, a cyclopropene group, and an azadioxabicyclo group.
Not only the species but also two or more species may be used. Of these,
A (meth) acryloyl group and a cinnamoyl group are preferred, and a (meth) acryloyl group is particularly preferred.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods. A method of reacting (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group to perform esterification, and adding an isocyanate group to the crosslinkable functional group-containing copolymer containing a hydroxyl group. A method of reacting a (meth) acrylic acid ester to form a urethane, a method of reacting a (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group, and a method of esterifying the carboxyl group A method comprising reacting a (meth) acrylate containing an epoxy group with a crosslinkable functional group-containing copolymer containing the same to esterify the copolymer.

According to the composition of the present invention obtained by using the specific fluoropolymer, that is, the polymer having a photopolymerizable group as the component (A), the coating film obtained from the composition is irradiated with radiation. As a result, the photopolymerization reaction of the component (A) occurs together with the photopolymerization reaction of the component (B) and the component (D) described below, and as a result, the formed cured film has a crosslinked structure introduced therein. It has high hardness, and has even better solvent resistance and chemical resistance.

The component (A) is selected from the viewpoints of appropriately maintaining the optical properties of the cured product, the coating properties of the composition, and the abrasion resistance of the coating film.
When the total amount of the composition is 100% by weight (hereinafter referred to as "specific conditions"), it is preferably blended at a ratio of 1 to 80% by weight, particularly preferably 3 to 80% by weight.

The polyfunctional (meth) acrylate compound as the component (B) of the composition of the present invention contains (meth)
It contains two or more acryloyl groups, preferably 3 to 10, more preferably 3 to 6 acryloyl groups. Specific examples of such a compound include, for example, (1) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4 -Butanediol di (meth)
Alkylene glycol di (meth) acrylates such as acrylate, 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate; (2) trimethylolpropane tri (meth) acrylate, trimethylol propane trihydroxy Ethyl tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentylglycol dihydroxypivalate Poly (meth) acrylates of polyhydric alcohols such as acrylates; (3) isocyanurate tri (meth) acrylate, tris (2-
Poly (meth) acrylates of isocyanurate such as (hydroxyethyl) isocyanurate di (meth) acrylate and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate;

(4) poly (meth) acrylates of cycloalkane such as tricyclodecanediyldimethyldi (meth) acrylate; (5) di (meth) acrylate of ethylene oxide adduct of bisphenol A, propylene oxide of bisphenol A Di (meta) of adduct
Acrylate, di (meth) acrylate of alkylene oxide adduct of bisphenol A, di (meth) acrylate of ethylene oxide adduct of hydrogenated bisphenol A, di (meth) acrylate of propylene oxide adduct of hydrogenated bisphenol A, hydrogenation Bisphenol A
Di (meth) acrylate of alkylene oxide adduct of bisphenol A diglycidyl ether and (meth)
(Meth) acrylate derivatives of bisphenol A such as (meth) acrylate obtained from acrylic acid;
(6) 3,3,4,4,5,5,6,6-octafluorooctanedi (meth) acrylate, 3- (2-perfluorohexyl) ethoxy-1,2-di (meth) acryloylpropane, Fluorine-containing (meth) acrylates such as Nn-propyl-N-2,3-di (meth) acryloylpropylperfluorooctylsulfonamide can be mentioned. These can be used alone or in combination of two or more. Of these, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate are particularly preferred.

The component (B) may be mixed at a specific ratio of 1
The proportion is preferably from 0 to 70% by weight, particularly preferably from 20 to 60% by weight. This ratio is 1
When the amount is less than 0% by weight, the hardness and scratch resistance of the cured product are not sufficient. When the amount is more than 70% by weight, the refractive index of the composition becomes high and the antireflection effect becomes insufficient.

Specific examples of the radiation polymerization initiator (C) used in the composition of the present invention include, for example, 1
-Hydroxycyclohexyl phenyl ketone, 2,2-
Dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole,
-Methylacetophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
On, thioxanthone, diethylthioxanthone, 2-
Isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholino-propan-1-one, 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butan-1-one, 1- [4-
(2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like. These compounds can be used alone or
More than one species can be used in combination. Of these compounds, 2-methyl-1- [4- (methylthio) phenyl]
2-Morifolino-propan-1-one, diethylthioxanthone and the like are preferred.

By blending the component (C), the composition obtained has sufficient curability.
Excessive blending of the component (C) is not economical and also causes embrittlement of the cured product. Therefore, the blending ratio of the component (C) is preferably 0.1 to 10% by weight under specific conditions. And particularly preferably 0.2 to 5% by weight.

The curable resin composition of the present invention may further comprise one or more unsaturated groups in the molecule for the purpose of further improving the properties of the cured product, in addition to the components (A), (B) and (C).
A component (D) consisting of a compound having the same number (provided that they are other than the components (A), (B) and (C)) can be blended. It is preferable to use a component (D) having a functional group, in particular, for improving the adhesion to the substrate. Examples of the component (D) include a compound having one (meth) acryloyl group in one molecule and other polymerizable monomers copolymerizable with the component (B).

Specific examples of the component (D) include the compounds exemplified as the component (a) and the component (b), which are components in the specific fluoropolymer (A), and 2,2,2 2
Trifluoroethyl (meth) acrylate, 2,2
3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) )
Examples thereof include fluorine-containing (meth) acrylates such as acrylate and 2- (perfluorodecyl) ethyl (meth) acrylate. These copolymerizable monomers can be used alone or in combination of two or more. Further, fluorine-containing (meth) acrylate is used from the viewpoint of keeping the refractive index of the cured product low, and N-vinyl lactam is used from the viewpoint of increasing the compatibility of the whole composition and enhancing the adhesion of the coating film to the substrate. It is particularly preferable to use heptadecafluorodecyl (meth) acrylate, octafluoropentyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and trifluoroethyl (meth) acrylate. , N-vinyl-2-pyrrolidone,
N-vinyl-2-caprolactam and the like.

The component (D) is blended under specific conditions at a ratio of 0 to 20% by weight, preferably 0 to 10% by weight. If this ratio is excessive, the hardness of the cured film tends to be low. Further, the ratio of the total amount of the component (B) and the component (D) is preferably 20 to 80% by weight under specific conditions.

The curable resin composition of the present invention can be obtained by homogenizing a specific fluoropolymer, a polymerizable monomer, and a radiation polymerization initiator by stirring or the like in an organic solvent. In the curable resin composition of the present invention, these mixtures can be used as they are, or can be used by blending various additives as necessary.

<Fluorine-Containing Polymer> The curable composition of the present invention is formed from a material other than the specific fluorine-containing polymer in order to obtain a uniform coating film and to improve the adhesion of the cured film to the substrate. It is preferable to add a polymer containing a fluorine atom (hereinafter, simply referred to as “fluorine-containing polymer”).
The fluorine-containing polymer is obtained by polymerizing the same fluorine-containing olefin compound as that used as the component (a) constituting the specific fluorine-containing polymer alone in the presence of a radical polymerization initiator, or as necessary. Accordingly, copolymerization is performed with another monomer copolymerizable with the fluorine-containing olefin compound similar to that used as the component (b) and / or a reactive emulsifier similar to that used as the component (d). Can be obtained by:

The following are examples of particularly preferred specific compositions. (1) a copolymer of vinylidene fluoride / tetrafluoroethylene / hexafluoroethylene,
(2) fluoroolefin / alkyl vinyl ether,
(3) fluoroolefin / perfluoro (alkyl vinyl ether) / alkyl vinyl ether, (4) fluoroolefin / perfluoro (alkoxyalkyl) vinyl ether / alkyl vinyl ether, (5) fluoroolefin / (perfluoroalkyl) vinyl ether / alkyl vinyl ether, (6) Fluoroolefin / (perfluoroalkoxyalkyl) vinyl ether / alkyl vinyl ether Examples of the above (1) are particularly preferable in that they have high compatibility with the component (B) and the solvent and have good scratch resistance. The examples (2) to (6) are preferable in that various functional groups are introduced into the polymer to improve properties such as adhesion to a substrate. Commercially available compounds that can be used as (1) above include “KYN
AR ADS "(manufactured by Elf Atchem).

<Various Additives> The curable resin composition of the present invention is used for the purpose of improving the coating properties of the curable resin composition and the physical properties of the thin film after curing, imparting photosensitivity to the coating film, and the like. For example, coloring agents such as pigments or dyes, stabilizers such as antioxidants and ultraviolet absorbers, crosslinkable compounds,
Various additives such as a thermal acid generator, a photoacid generator, a surfactant, a solvent, and a polymerization inhibitor can be contained. In particular,
It is preferable to add a crosslinkable compound for the purpose of improving the hardness and durability of the formed cured film. In using these, it is preferable to select one that does not decrease the transparency of the curable resin composition of the present invention after curing and that is uniformly dissolved in the solution.

<Colorants such as Pigments or Dyes> Examples of the colorants that can be incorporated into the curable resin composition of the present invention include (1) extenders such as alumina white, clay, barium carbonate, and barium sulfate. (2) zinc white, lead white,
(3) Organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue and phthalocyanine green; (4) inorganic pigments such as yellow-white, ultramarine blue, titanium oxide, zinc chromate, red iron and carbon black; ) Magenta,
Basic dyes such as rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acid dyes such as roserine and methanyl yellow; and others.

<Stabilizers such as anti-aging agent and ultraviolet absorber> As the anti-aging agent and ultraviolet absorber which can be added to the curable resin composition of the present invention, known agents can be used. . Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-
Butyl catechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n
-Butylphenol, phenol, hydroquinone monopropyl ether, 4,4 '-[1- {4- (1- (4-
(Hydroxyphenyl) -1-methylethyl) phenyl
Ethylidene] diphenol, 1,1,3-tris (2
5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole, and the like.

Specific examples of the UV absorber include salicylic acid UV absorbers represented by phenyl salicylate, benzophenone UV absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and benzotriazole UV absorbers. UV absorbers used as additives for various plastics, such as agents and cyanoacrylate UV absorbers, can be used.

<Crosslinkable Compound> The curable resin composition of the present invention may optionally contain another crosslinkable compound to improve the hardness of a film formed from the composition. it can. Specific examples of the crosslinkable compound include, for example, various amino compounds, hydroxyl group-containing compounds such as pentaerythritol, polyphenol, and glycol, and the like. The amino compound used as the crosslinkable compound includes an amino group capable of reacting with a hydroxyl group or an epoxy group present in the fluoropolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total of two. These are compounds contained above, and specific examples thereof include melamine compounds, urea compounds, benzoguanamine compounds, and glycoluril compounds. The amount of the crosslinkable compound to be used is 100 parts by weight or less based on 100 parts by weight of the curable resin composition, and is preferably 0 to 30 parts by weight. If the use ratio of this crosslinkable compound exceeds 50 parts by weight, the cured product is brittle, the film strength is reduced, and the refractive index is undesirably high.

<Thermal acid generator> The thermal acid generator which can be added to the curable resin composition of the present invention is obtained by curing a coating film of the curable resin composition by irradiation with ultraviolet rays, and then heating it. When promoting the crosslinking of the coating film, it is a substance that can improve the heating conditions to a milder one, such as when a component whose curing is accelerated by an acid is blended in the curable resin composition. It is effective when added. Specific examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aromatic carboxylic acids such as benzoic acid and phthalic acid and salts thereof, alkylbenzenesulfonic acid and ammonium salts thereof, various metal salts, and phosphorus compounds. Examples include acids and phosphoric acid esters of organic acids.

<Photoacid Generator> The photoacid generator that can be added to the curable resin composition of the present invention is obtained by adding an acid-accelerated component to the curable resin composition. Is a substance capable of initiating and accelerating the curing reaction. Examples of the photoacid generator include (1)
Various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones and sulfone compounds for these α-diazo compounds; (3) alkyls Sulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters,
Sulfonic esters such as iminosulfonates; (4)
Sulfonimide compounds represented by the following general formula 7;
(5) diazomethane compounds represented by the following general formula 8;
Others can be mentioned. The photoacid generator alone,
Alternatively, two or more kinds can be used in combination, and further, the above-mentioned thermal acid generator can be used in combination.

[0062]

Embedded image In the formula, X represents a divalent group such as an alkylene group, an arylene group, an alkoxylene group, and R ¹¹ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group.

[0063]

Embedded image In the formula, R ¹² and R ¹³ may be the same or different and represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group.

<Polymerization Inhibitor> Examples of the thermal polymerization inhibitor that can be blended in the curable resin composition of the present invention include, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone. , Amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-
[1- [4- (1- (4-hydroxyphenyl) -1-
Methylethyl) phenyl] ethylidene] diphenol,
1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and the like can be mentioned. The use ratio of this thermal polymerization inhibitor is preferably 5 parts by weight or less based on 100 parts by weight of the curable resin composition.

<Surfactant> A surfactant may be added to the curable resin composition of the present invention for the purpose of improving the coatability of the curable resin composition. Known surfactants can be used as the surfactant, and specifically,
For example, various anionic surfactants, cationic surfactants, nonionic surfactants can be used,
In particular, in order to make the cured film have excellent strength and good optical characteristics, it is preferable to use a fluorine-based surfactant. The usage ratio of the surfactant is preferably 5 parts by weight or less based on 100 parts by weight of the curable resin composition.

<Solvent> The curable resin composition of the present invention is obtained in the form of a solution using the solvent used in the production of the specific fluoropolymer, and usually contains the solvent as an essential component.
Further, a solvent can be separately added and blended for the purpose of improving the coatability of the curable resin composition and the like, and for other purposes. Preferred solvents contained in the curable resin composition of the present invention include methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate,
Esters such as butyl acetate can be mentioned. These solvents can be used alone or in combination. Further, in the solution of the curable resin composition of the present invention, a solvent that does not dissolve a specific fluoropolymer, for example, a poor solvent such as water, alcohols, and ethers, a range in which the specific fluoropolymer is not precipitated. Can be used together. This may result in a solution of the curable resin composition having good preservability and favorable coatability. Examples of such poor solvents include ethyl alcohol, isopropyl alcohol, and tert-butyl alcohol.

<Method for Forming Coating Film> The curable resin composition of the present invention can be applied as a solution to various substrates, and particularly when the substrate is a transparent substrate, excellent reflection can be obtained. A barrier film is formed. Here, as the transparent substrate, specifically,
For example, in addition to inorganic glass, various transparent plastic plates and films of polyester resin, polycarbonate resin, acrylic resin, styryl resin, arylate resin, norbornane resin, triacetyl cellulose and the like can be mentioned. As the coating method, a known method can be used, and in particular, various methods such as a coater method, a dipping method, and a printing method can be applied. In order to reliably obtain the durability of the cured film, which is a feature of the present invention, it is preferable that the ultraviolet curing is performed in an inert gas atmosphere.

[0068]

EXAMPLES Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.
In the following, “parts” and “%” indicate parts by weight and% by weight, respectively, unless otherwise specified. <Production Example 1><Production of Specific Fluoropolymer> After sufficiently replacing a 1.5-liter stainless steel autoclave with an electromagnetic stirrer with an inner volume of nitrogen gas with 600 g of ethyl acetate, perfluoro (propyl vinyl ether) (FPVE) 91 .5g,
57.9 g of ethyl vinyl ether (EVE), 30.3 g of 2-hydroxyethyl vinyl ether (HVE),
Nonionic reactive emulsifier "Adecaria Soap NE-3"
0 "(manufactured by Asahi Denka Kogyo KK), 60.0 g of azo group-containing polydimethylsiloxane" VPS-1001 "(manufactured by Wako Pure Chemical Industries, Ltd.) 5.0 g and dilauroyl peroxide (L
PO) was charged and cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas. Next, hexafluoropropylene (HFP) 1
44.4 g was charged and the temperature was raised. When the temperature in the autoclave reaches 60 ° C., the pressure is 4.7 kgf.
/ Cm ² . Thereafter, the reaction was continued under stirring at 60 ° C. for 25 hours. When the pressure dropped to 2.5 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution. The obtained polymer solution was poured into methanol to precipitate a polymer, followed by washing with methanol, followed by vacuum drying at 50 ° C. to obtain 306 g.
Was obtained. Table 1 shows the charged amount, the yield, the polymerization conversion, and the solid content of the monomer for obtaining the fluorocopolymer A1.

Using a 0.5% solution prepared by dissolving this fluorine-based copolymer A1 in tetrahydrofuran (THF), the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography.
8000. Further, the glass transition temperature (Tg) according to the differential thermal analysis (DSC), the fluorine content according to the alizarin complex method, and the hydroxyl value according to the acetylation method using acetic anhydride were measured. Also, ¹ H-N
Perform both NMR analysis and elemental analysis of MR and ¹³ C-NMR,
Further, the content of inorganic silica was measured from the fluorine content, hydroxyl value, and remaining weight after calcination at 600 ° C., and from these results, the proportion of each monomer component constituting the fluorine-based copolymer A1 was determined. The results are as shown in Table 2.

<Production Examples 2 and 3 and Comparative Production Examples 1 and 2> Fluorine-based copolymers were produced in the same manner as in Production Example 1 except that the types and charged amounts of the respective monomers were changed as shown in Table 1. Polymers A2 and A3 and comparative copolymers B1 and B2 were prepared. Table 2 shows the proportions and physical properties of the respective monomer components constituting these copolymers. Comparative Production Example 1 was not the component (A) in that it did not contain the azo group-containing polysiloxane compound of the component (c), and Comparative Production Example 2 was a component (A) in which the fluorine content was too small. It is not a component.

[0071]

[Table 1]

[0072]

[Table 2]

Example 1 <Preparation of Curable Resin Composition> 32.0 g of the specific fluoropolymer obtained in Production Example 1 was mixed with a 2F / 4F / 6F copolymer “KYNAR ADS” (manufactured by Elf Atchem Co., Ltd.). 3)
2.0 g, 29.0 g of dipentaerythritol hexaacrylate (DPHA), N-vinylpyrrolidone (V
P), 4.5 g of a radiation polymerization initiator “Irgacure 90
7 "(Irg. 907) (manufactured by Ciba Specialty Chemicals Co., Ltd.) together with 2.0 g of diethylthioxanthone (DETX) together with 0.5 g of diethylthioxanthone (DETX) were dissolved in 900 g of methyl isobutyl ketone (MIBK) at room temperature By dissolving under stirring for 2 hours, a solution of the curable resin composition having an effective concentration of 10% was obtained.

<Formation and Evaluation of Coating Film of Curable Resin Composition> Measurement of refractive index As an evaluation of optical properties, MIB of the above curable resin composition was measured.
A sample obtained by applying the K solution onto a silicon wafer with a spin coater so that the thickness after drying becomes about 0.1 μm was measured at 25 ° C. using an ellipsometer.
Was measured for the refractive index (n _D ²⁵ ) at a wavelength of 539 nm. Measurement of Pencil Hardness Pencil hardness was measured according to JIS K5400.

Measurement of Transmittance / Reflectance Using the curable resin composition, a coating film was formed on a polyethylene terephthalate film with a bar coater, and then irradiated with ultraviolet rays of 1 J / cm ² under a nitrogen atmosphere to obtain a laminated film. Was molded. Using this film as a sample, a wavelength of 340
The transmittance of light at ７００700 nm was measured. Further, a matte black spray “immediately dry acrylic lacquer spray matte black” (manufactured by Kanpeapio Co., Ltd.) was applied to the back surface of the film and dried. Using this film as a sample, a spectrophotometer “U-3410 with a 60 mm diameter integrating sphere” was used.
The reflectance was measured using a mold (manufactured by Hitachi, Ltd.).

Measurement of Adhesion As an evaluation of the adhesion of the coating film to the substrate, a scratch resistance test was performed using the film on which the above cured film was formed as a sample. That is, the surface of the cured film was repeatedly rubbed 25 times using “Kimwipe” (manufactured by Jujo Kimberly) under the condition of a load of 1 kg / cm ² , and the presence or absence of scratches on the surface was visually checked. When the peeling of the cured film and the occurrence of scratches were not recognized, it was evaluated as “O”, and when the peeling occurred on a part of the cured film or a streak-like scratch occurred on the surface of the cured film, it was evaluated as “X”. did. Further, the contact angle of pure water was measured. Table 4 shows the above results.

Examples 2 to 6 and Comparative Examples 1 to 4 Curable resin compositions were produced in the same manner as in Example 1 except that the contents of the composition were changed to those shown in Table 3. . A cured film was formed from these curable resin compositions in the same manner as described above, and various physical properties were measured. Table 4 shows the results
Shown in Here, Comparative Example 1, Comparative Example 3 and Comparative Example 4 do not contain the component (A) essential for the present invention, and Comparative Example 2 does not contain the component (B) essential for the present invention. .

[0078]

[Table 3]

[0079]

[Table 4]

The abbreviations in the table indicate the following contents. (A) Component HFP: Hexafluoropropylene FPVE: Perfluoro (propyl vinyl ether) FPOVE: Perfluoro (propoxypropyl vinyl ether) CTFE: Chlorotrifluoroethylene (b) Component EVE: Ethyl vinyl ether HEVE: Hydroxyethyl vinyl ether HBVE: Hydroxybutyl vinyl ether BVE: isobutyl vinyl ether CHVE: cyclohexyl vinyl ether VPi: vinyl pivalate VAc: vinyl acetate

(C) Component VPS-1001: represented by the above general formula 5, having a number average molecular weight of 70,000 to 90,000 and a polysiloxane moiety having a molecular weight of about 100
Azo group-containing polydimethylsiloxane of 00 (manufactured by Wako Pure Chemical Industries, Ltd.) (d) Component NE-10: represented by the aforementioned general formula 6, n = 9, m = 1,
Nonionic reactive emulsifier “Adecaria Soap NE-10” (manufactured by Asahi Denka Kogyo Co., Ltd.) with s = 10, NE-30: represented by the general formula 6, n = 9, m = 1,
Nonionic reactive emulsifier "Adecaria Soap NE-30" with s = 30 (manufactured by Asahi Denka Kogyo Co., Ltd.)

(Thermal polymerization initiator) LPO: dilauroyl peroxide (fluorine-containing polymer) “KYNAR ADS”: copolymer of vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene (manufactured by Elf Atochem)

(B) Component DPHA: dipentaerythritol hexaacrylate PETA: pentaerythritol triacrylate TMPTA: trimethylolpropane triacrylate

(C) Component Irg. 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd.) DETX: diethylthioxanthone (D) component VP: N-vinyl -2-pyrrolidone 17F: heptadecafluorodecyl acrylate (solvent) MIBK: methyl isobutyl ketone

[0085]

According to the curable resin composition of the present invention, a cured film having excellent transparency, durability, antifouling property and low refractive index is formed. Accordingly, the curable resin composition of the present invention is particularly suitable for forming an optical material such as an antireflection film and an optical fiber sheath material, a material for an antifouling coating, a material for a coating material utilizing the weather resistance which is a characteristic of a fluorine material, It can be suitably used as a material for weather resistant films and a material for coating. Further, the coating film obtained from the curable resin composition of the present invention is excellent in water repellency and weather resistance, and can be suitably used as a coating material for water repellency and moisture proof and a material for super weather resistant paint. Since the curable resin composition of the present invention dissolves in a general hydrocarbon-based solvent, it is possible to provide a material that is inexpensive and has little effect on the environment, and exhibits good radiation curability.

The antireflection film of the present invention comprises a cured film obtained from the above curable resin composition, and has excellent scratch resistance, low refractive index and excellent transparency to visible light. And a good anti-reflection effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/10 C08L 83/10 G02B 1/11 C08F 214/18 // C08F 214/18 C09D 4/06 C09D 4/06 G02B 1/10 A (72) Inventor Akira Nishikawa 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Hozumi Sato 2-11-24 Tsukiji, Chuo-ku, Tokyo Jay SRL Co., Ltd.

Claims (2)

[Claims] 1. (A) an olefin polymer having a polysiloxane segment in the main chain, a fluorine content of 30% by weight or more, and a number average molecular weight in terms of polystyrene of 5,000 or more, (B) one molecule A curable resin composition comprising: a polyfunctional (meth) acrylate compound containing two or more (meth) acryloyl groups therein; and (C) a radiation polymerization initiator. 2. An antireflection film comprising a cured product of the curable resin composition according to claim 1.