JP2002145952A - Hardening resin composition and anti-reflection coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hardening resin composition soluble in general hydrocarbon solvent and capable of forming a hardened film excellent in transparency, anti-reflecting effect and resistance to scuffing. SOLUTION: This hardening resin composition comprises (A) a fluorocopolymer including >=30% of fluorine and having an average molecular weight >=5,000 and (B) a fluoro ureathane compound having 3 or more polymerizable unsaturated groups.

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, scratch resistance, transparency and low reflectance characteristics. The present invention relates to a cured product and an antireflection film made of the cured product.

[0002]

2. Description of the Related Art Hitherto, as a 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.
As a method of forming an antireflection film, for example, a method of forming a thin film of a fluorine compound by an evaporation method is known.
In recent years, as a method excellent in productivity and low cost, a liquid composition is prepared by dissolving a fluorine-based polymer having a low refractive index in a solvent, and this is applied to the surface of a substrate to form an antireflection film. Methods for forming are being studied. However, when trying to increase the fluorine content, the composition becomes difficult to dissolve in a general solvent, and as a result, a halogen-containing solvent which is expensive and environmentally problematic has to be used. There was also.

For example, JP-A-2000-17028 discloses a radiation-curable resin composition comprising a fluoropolymer, a polyfunctional (meth) acrylate, and a radiation polymerization initiator as an antireflection film material. ing.

However, conventional polyfunctional (meth) acrylates have poor compatibility with fluoropolymers and have a high refractive index, so that conventional polyfunctional (meth) acrylates are contained in a large amount in the composition. When the composition has a low refractive index, it is difficult to obtain a cured product. Conversely, when the content of the polyfunctional (meth) acrylate in the composition is small, the cross-linking density of the obtained antireflection film decreases and the scratch resistance is reduced. As a result, there is a problem that it is difficult to sufficiently achieve both a low refractive index of the cured film and an improvement in scratch resistance.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide excellent transparency and a better antireflection effect. An object of the present invention is to provide a curable resin composition that can form a cured film having excellent scratch resistance and that 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.

[0006]

According to the present invention, (A) a fluorine content of 30% by weight or more and a number average molecular weight of 5,
A curable resin composition containing a fluorinated copolymer having a molecular weight of at least 000 and (B) a fluorinated urethane compound having at least three polymerizable unsaturated groups.

In the curable resin composition of the present invention, the component (A) is represented by (a) a structural unit containing a fluorine atom represented by the following general formula 1, and (b) a structural unit represented by the following general formula 2. It is a fluorinated copolymer comprising structural units.

[0008]

Embedded image (1)

Wherein R ¹ is a fluorine atom, a chlorine atom, a fluoroalkyl group having 1 to 10 carbon atoms, or a group represented by —OR ² (R ² is an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group) Represents a group). ]

[0010]

Embedded image (2)

Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkyl group having 1 to 15 carbon atoms, an alkoxycarbonyl group, a carboxyl group, a group represented by — (CH ₂ ) _X —OR ⁵ (R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group or a glycidyl group, and X represents a number of 0 or 1), or a group represented by —OCOR ⁵ (R ⁵
Represents the same as described above). ]

Further, the curable resin composition of the present invention comprises:
The component (A) is further characterized in that the component (c) is a fluorine-containing copolymer having a siloxane structural unit represented by the following general formula 3. With this configuration, a cured product having excellent surface smoothness and surface sliding properties can be obtained.

[0013]

Embedded image (3)

[Wherein R ⁶ and R ⁷ may be the same or different and each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
It represents a halogenated alkyl group or an aryl group having 6 to 20 carbon atoms. ]

Further, the curable resin composition of the present invention comprises:
Component (B) is a fluorine-containing urethane compound obtained by reacting a polyisocyanate compound, a polymerizable unsaturated group-containing hydroxy compound and a fluoroalkyl group-containing hydroxy compound.

Further, the curable resin composition of the present invention comprises:
Component (B) is a fluorine-containing urethane compound obtained by reacting a polyisocyanate compound, a polymerizable unsaturated group-containing hydroxy compound and a fluoroalkyl group-containing hydroxy compound. With this configuration, the compatibility of the composition is good, the fluorine content is high, the refractive index is low, and the crosslink density can be improved, so that the cured product has excellent transparency, low reflectance, and scratch resistance. Properties can be obtained effectively.

Further, the curable resin composition of the present invention comprises:
(B) The component is a fluorine-containing urethane compound represented by the following general formula 4.

[0018]

Embedded image (4)

[In the formula, R ⁸ represents a fluoroalkyl group or a divalent organic group having 1 to 20 carbon atoms having a fluoroalkylene group, A represents an acryloyl group or a methacryloyl group,
B ¹ and B ² each independently represent an (n + 1) -valent or (m + 1) -valent organic group having 1 to 20 carbon atoms, wherein n is 1 to 5 and m is 1 to 5;
And 3 ≦ n + m ≦ 10. ]

B ¹ and B ² are preferably an organic group having 2 to 10 carbon atoms, and particularly preferred examples are —CH ₂ —C (CH ₂
—) ₂ CH ₂ —.

Further, the curable resin composition of the present invention comprises:
As a particularly preferred specific example of the component (B), the composition contains a fluorine-containing urethane compound represented by the following chemical formula 5.

[0022]

Embedded image (5)

Further, the present invention provides a cured product obtained by curing the above-mentioned curable resin composition. When the cured product is configured in this manner, the compatibility of each component is good, the content of fluorine is high, the refractive index is low, and the crosslink density can be improved, so that the cured product has excellent transparency, low reflectance, and high resistance. Abrasion can be obtained effectively.

Further, the present invention provides an antireflection film obtained by curing the above-mentioned curable resin composition. The antireflection film configured as described above has excellent antireflection performance, and also has excellent scratch resistance and solvent resistance.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises
(A) a fluorine-containing copolymer having a fluorine content of 30% by weight or more and a number average molecular weight in terms of polystyrene of 5,000 or more (hereinafter also referred to as “component (A) component”);
And (B) a fluorine-containing urethane compound having at least three polymerizable unsaturated groups (hereinafter, also referred to as “component B”). <(A) Fluorine-Containing Copolymer> The fluorine-containing copolymer as the component (A) has a fluorine content of 30% by weight or more, preferably 30 to 70% by weight, and is further subjected to gel permeation chromatography (GPC). Is 5,000 or more, preferably 10,000 to 500,000, and more preferably 15,000 to 200,000 in terms of polystyrene obtained by the above method. Here, the fluorine content is a value measured by the alizarin complex method,
The number average molecular weight is a value when tetrahydrofuran is used as a developing solvent.

The component (A) in the present invention comprises (a) a fluorine-containing monomer component containing a structural unit represented by the general formula 1 (hereinafter referred to as “component (a)”) and (b) this component (a). And a monomer compound containing a structural unit represented by Formula 2 (hereinafter, referred to as “component (b)”) copolymerizable with:
If necessary, it can be obtained by reacting (c) a monomer compound containing a structural unit represented by the general formula 3 (hereinafter, referred to as “component (c)”).

<Component (a)> The component (a) is a compound having a polymerizable unsaturated double bond and at least three fluorine atoms. Specific examples thereof include (1) tetrafluoroethylene, Hexafluoropropylene, 3,
Fluoroolefins such as 3,3-trifluoropropylene, chlorotrifluoroethylene; (2) alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; (3) perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (Propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (alkyl vinyl ether) such as perfluoro (isobutyl vinyl ether); (4) perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether); and others. .
These compounds can be used alone or in combination of two or more. Of the above, fluoroolefins,
Perfluoro (alkyl vinyl ether) s or perfluoro (alkoxyalkyl vinyl ethers) are preferred, and more preferably used in combination. Specifically, it is preferable to use one or two or more selected from hexafluoropropylene, perfluoropropyl vinyl ether and perfluoropropoxypropyl vinyl ether.

<Component (b)> The component (b) is a compound copolymerizable with the component (a). After copolymerization, the compound may be a compound having the groups of R ³ and R ^{4 represented} by the general formula (2). Specific examples thereof include (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, and n Octyl vinyl ether,
alkyl vinyl ethers or cycloalkyl vinyl ethers such as n-dodecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether; (2) vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, Carboxylic acid vinyl esters such as vinyl versatate, vinyl stearate and benzoic acid; (3) α-olefins such as ethylene, propylene and isobutene; (4) styrene, α-methylstyrene, o-methylstyrene, m-
Methylstyrene, p-methylstyrene, p-tert-
Butylstyrene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, N-
Vinyl aromatic compounds such as diethyl-p-aminostyrene, vinylpyridine, vinylimidazole; (5) (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid,
Carboxyl group-containing compounds such as 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 6 to general (Meth) acrylates such as the compound represented by Formula 8;

[0031]

Embedded image (6)

Wherein R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents an alkylene group having 2 to 6 carbon atoms,
¹¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. p is an integer of 0-12. ]

[0033]

Embedded image (7)

[In the formula, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents an alkylene group having 2 to 8 carbon atoms.
q is an integer of 1 to 8. ]

[0035]

Embedded image (8)

[Wherein, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ represents an alkylene group having 2 to 8 carbon atoms,
R ¹⁶ represents a hydrogen atom or a methyl group. r is an integer of 1 to 8. ]

(14) Acryloyl morpholine, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, tert-octyl ( (Meth) acrylamide, 7-
Amino-3,7-dimethyloctyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N,
(15) Methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, silicic acid such as N-diethyl (meth) acrylamide; Unsaturated carboxylic esters such as butyl cinnamate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate and 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 group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; and others. Among them, 2-hydroxyethyl vinyl ether, 2-hydroxybutyl vinyl ether and ethyl vinyl ether are preferably used. These compounds can be used alone or in combination of two or more. Furthermore, a fluorine-containing copolymer 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.

Among the above monomer compounds, alkyl vinyl ethers, cycloalkyl vinyl ethers, and vinyl carboxylate are preferred from the viewpoint of increasing the yield in the polymerization reaction for obtaining a fluorine-containing copolymer. Used for On the other hand, from the viewpoint of increasing the fluorine content copolymerized in the fluorine-containing copolymer, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, It is preferable to use a low molecular weight monomer such as 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.

<Component (c)> The component (c) is a compound having a structural unit represented by the general formula 3, and is not particularly limited as long as it can be introduced into the fluorinated copolymer. For this reason, the component (c) is preferably an azo group-containing polysiloxane compound, and the azo group-containing polysiloxane compound is a compound containing an azo group that is easily decomposable by -N = N-. JP-A-6-9
It can be produced by the method described in JP-A-3100. As a commercially available compound that can be used as the component (c), for example, “VPS-050”
1 "and" VPS-1001 "(all manufactured by Wako Pure Chemical Industries, Ltd.).

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 fluorine-containing copolymer of the present invention,
The structural unit derived from the component (a) is 20 to 90 mol%, preferably 25 to 85 mol%, and more preferably 30 to 7 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 fluorine-containing copolymer tends to be too low, and the cured product of the obtained curable resin composition has a refractive index of It is hard to be low enough. On the other hand, the ratio of the structural unit derived from the component (a) is 90%.
When the amount exceeds mol%, the solubility in an organic solvent in the obtained fluorine-containing copolymer is significantly reduced, and the obtained curable resin composition has low transparency and low adhesion to a substrate. .

In the fluorine-containing copolymer of the present invention,
The structural unit derived from the component (b) is 10 to 80 mol%, preferably 15 to 75 mol%, and more preferably 30 to 7 mol%.
0 mol%. When the proportion of the structural unit derived from the component (b) is less than 10 mol%, the resulting fluorine-containing copolymer has poor solubility in an organic solvent, and when it exceeds 80 mol%, the curable resin composition The cured product of the above has deteriorated optical properties of transparency and low reflectance.

The azo group-containing polysiloxane compound, which is a preferred component (c), is itself a thermal radical generator and has a function as a polymerization initiator in a polymerization reaction for obtaining a fluorine-containing copolymer. Other radical initiators can be used in combination. The proportion of the structural unit represented by the general formula 3 derived from the component (c) in the fluorinated copolymer is generally from 0 to 20 mol%, preferably from 0.1 to 15 mol%, more preferably from 0.1 to 15 mol%. This is a ratio of 10 mol%. When the proportion of the structural unit represented by the general formula 3 exceeds 20 mol%, the obtained fluorocopolymer becomes poor in transparency, and when used as a coating agent, cissing or the like during coating may occur. It is easy to occur.

<Component (d)> In the present invention, in addition to the components (a) to (c), it is preferable to use a reactive emulsifier as a monomer component as the component (d).
By using the component (d), when the fluorocopolymer 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 9.

[0046]

Embedded image (9)

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

In the fluorinated copolymer, the proportion of the constituent unit derived from the component (d) is usually 0 to 10 mol%, preferably 0.01 to 5 mol%, more preferably 0.0 to 5 mol%.
5 to 2 mol%. If this proportion exceeds 10 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 / alkyl vinyl ether / polydimethylsiloxane unit / nonionic reaction (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 fluorine-containing copolymer which is the component (A) of the present invention, copolymer components other than (a) to (d) can be used.

In the present invention, as a polymerization method for producing a fluorine-containing copolymer, 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, or the like. Furthermore, the polymerization conditions are not particularly limited, but may be, for example, 50 to 50.
The polymerization is preferably performed at a temperature of 200 ° C. for 1 to 100 hours.

Examples of the radical polymerization initiator that can be used in combination with the component (c) include: (1) diacyl peroxides such as acetyl peroxide and benzoyl peroxide; and (2) methyl ethyl 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 the fluorinated copolymer 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.

In some cases, the reaction solution obtained by the polymerization reaction of the fluorocopolymer obtained as described above can be used as it is as a curable resin composition. It is also possible to carry out an appropriate post-processing. As this post-treatment, for example, a general reprecipitation represented by a purification method in which a polymerization reaction solution is added dropwise to an insolubilizing solvent for the fluorinated copolymer made of alcohol or the like to solidify the fluorinated copolymer. The treatment can be carried out, and then the solution of the fluorinated copolymer 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 the fluorine-containing copolymer.

The component (A) is selected from the viewpoints of appropriately maintaining the optical properties of the cured product, the applicability of the composition, and the abrasion resistance of the coating film.
The total amount of the active ingredients (components other than the solvent) in the composition was 10
0% by weight, 10 to 95% by weight, preferably 20 to 90% by weight, more preferably 40 to 80% by weight.
It is blended in the ratio as follows.

<(B) Fluorine-containing urethane compound> The component (B) of the present invention may be any fluorine-containing urethane compound having at least three polymerizable unsaturated groups, and specifically, a fluoroalkyl group-containing hydroxy compound. (Hereinafter referred to as “component”), a polyisocyanate compound (hereinafter referred to as “component”), and a polymerizable unsaturated group-containing hydroxy compound (hereinafter referred to as “component”). That is, it is produced by reacting an isocyanate group in the component with a hydroxyl group in the component and a hydroxyl group in the component, respectively.

The reaction includes, for example, a method in which the components, the components, and the components are charged and reacted at once; a method in which the components, the components are reacted, and then the components are reacted; the components, the components, and the components are reacted. And the like.

However, if the fluoroalkyl group-containing hydroxy compound as a component is present in the system as an unreacted substance, the abrasion resistance of the coating film is reduced, so that the component must be sufficiently reacted. Therefore, it is preferred to first react the component fluoroalkyl group-containing hydroxy compound with the component polyisocyanate compound, and then react the component with the polymerizable unsaturated group-containing hydroxy compound.

The components used here include a dihydroxy compound and a monohydroxy compound.
Examples of the dihydroxy compound include 3- (2-perfluorohexyl) ethoxy-1,2-dihydroxypropane, 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol 2,2,3,3,4,4,5,5,6,6,
7,7-dodecafluoro-1,8-octanediol can be mentioned. The fluorine-containing polyfunctional urethane (meth) acrylate of the present invention preferably has a smaller molecular weight between crosslinking points. Accordingly, the dihydroxy compound containing a fluoroalkyl group used herein is a 3- (2-perfluorohexyl) ethoxy- having a fluoroalkyl group bonded to a side chain.
1,2-dihydroxypropane is preferred.

Examples of the monohydroxy compound include 1H, 1H-trifluoroethanol, 1H, 1H-
Pentafluoropropanol, 6- (perfluoroethyl)
Hexanol, 1H, 1H-heptafluorobutanol,
2- (perfluorobutyl) ethanol, 3- (perfluorobutyl) propanol, 6- (perfluorobutyl) hexanol, 2-perfluoropropoxy-2,3,3,3-
Tetrafluoropropanol, 2- (perfluorohexyl) ethanol, 2- (perfluorohexyl) propanol, 6- (perfluorohexyl) hexanol, 2-
(Perfluorooctyl) ethanol, 3- (perfluorooctyl) propanol, 6- (perfluorooctyl) hexanol, 2- (perfluorodecyl) ethanol, 1H,
1H-2,5-di (trifluoromethyl) -3,6-dioxaundecafluorononanol, 6- (perfluoro-1-methylethyl) hexanol, 2- (perfluoro-3-methylbutyl) ethanol, 2- (Perfluoro-5-methylhexyl) ethanol, 2- (perfluoro-7-methyloctyl) ethanol, 1H, 1H, 3H-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 7H-deca Fluoroheptanol, 1H, 1H, 9H-hexadecafluorononanol,
2H-hexafluoro-2-propanol, 1H, 1H,
3H-hexafluorobutanol, 2,2-bis (trifluoromethyl) propanol, 2- (perfluorooctyl) ethanol, (perfluoro-n-butyl) methanol, (perfluoro-n-hexyl) methanol, (perfluoro-n- (Octyl) methanol, (perfluoro-n
-Decyl) methanol, 3- (perfluoro-n-butyl) -2-propenol, 3- (perfluoro-n-hexyl) -2-propenol, 3- (perfluoro-n-octyl) -2-propenol, 3- ( Perfluoro-n-
Decyl) -2-propenol, 11- (perfluoro-n
-Hexyl) undecanol, 11- (perfluoro-n)
-Hexyl) -10-undecenol, 11- (perfluoro-n-octyl) -10-undecenol, and the like.

Examples of the polyisocyanate compound used as the component include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 1,3
-Xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'- Diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate Cyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate,
2,5 (or 6) -bis (isocyanatomethyl)-
Bicyclo [2.2.1] heptane and the like;
Isophorone diisocyanate is preferred. Since isophorone diisocyanate has a cyclohexane ring,
The glass transition temperature is higher than that of diisocyanate having no ring structure, and the scratch resistance of the coating film is advantageous. Further, the benzene ring has a higher glass transition temperature than the cyclohexane ring, but the benzene ring has a higher refractive index.

These polyisocyanate compounds can be used alone or in combination of two or more.

Examples of the polymerizable unsaturated group-containing hydroxy compound include trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, and pentaerythritol tri (meth) acrylate.
Acrylate, dipentaerythritol penta (meth)
Acrylate and the like. A glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate,
A compound obtained by an addition reaction with (meth) acrylic acid can also be used.

Of these hydroxy compounds containing a polymerizable unsaturated group, pentaerythritol triacrylate (also known as tetramethylolmethane triacrylate) is particularly preferred. When monofunctional hydroxyethyl acrylate is used as the hydroxy compound containing a polymerizable unsaturated group, the number of crosslinking groups in the obtained compound is 1 or 2, and good coating film strength cannot be obtained. In addition, when pentafunctional dipentaerythritol hydroxypentaacrylate is used as the hydroxy compound containing a polymerizable unsaturated group, good coating strength is obtained, but the refractive index of the coating is increased, which is disadvantageous. NK Ester A-TMM-3, NK Ester A-TMM-3 as commercially available pentaerythritol triacrylate
L, NK ester A-TMM-3LM-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

These hydroxy compounds containing a polymerizable unsaturated group can be used alone or in combination of two or more.

The proportion of the dihydroxy compound having a fluoroalkyl group, the polyisocyanate compound and the hydroxy compound having a polymerizable unsaturated group is 1.5 to 3 moles of the polyisocyanate compound per 1 mole of the dihydroxy compound, The ratio is preferably such that the content of the hydroxy compound is 1.5 to 3 mol.
2.5 mol, polymerizable unsaturated group-containing hydroxy compound
A ratio of 8 to 2.5 mol is particularly preferred.

The proportion of the monohydroxy compound having a fluoroalkyl group, the polyisocyanate compound and the hydroxy compound having a polymerizable unsaturated group is 0.7 to 1.
5 mol, polymerizable unsaturated group-containing hydroxy compound 0.7-
The ratio is preferably 1.5 mol, and further, with respect to 1 mol of the hydroxy compound, 0.9 to 1.2 mol of the polyisocyanate compound and 0.9 to 1.2 mol of the polymerizable unsaturated group-containing hydroxy compound. Such a ratio is particularly preferred.

Commercially available pentaerythritol triacrylate may contain a mixture of a diacrylate and a tetraacrylate, and may be used after purification, but may be used as a mixture.

In the reaction of these compounds, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin laurate, triethylamine, 1,4
-Diazabicyclo [2.2.2] octane, 2,6,7
-Trimethyl-1,4-diazabicyclo [2.2.2]
It is preferable to use a urethane-forming catalyst such as octane in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the reactants.
The reaction temperature is usually 0 to 90 ° C, particularly 30 to 80 ° C.
It is preferable to carry out. The reaction of these compounds can be carried out without a catalyst.

In producing the compound of the present invention, a solvent may be used. As the solvent, hydrocarbon isolating agents such as methyl isobutyl ketone and methyl ethyl ketone can be used.

The mixing ratio of the component (B) is 5 to 90% by weight, preferably 10 to 80% by weight, when the total amount of the active ingredients (components other than the solvent) in the composition is 100% by weight. More preferably, it is blended at a ratio of 20 to 60% by weight. When this proportion is less than 5% by weight, the hardness and scratch resistance of the cured product are not sufficient, and when it exceeds 90% by weight, the refractive index of the composition becomes high and the antireflection effect becomes insufficient.

<(C) Radiation Polymerization Initiator> When the curable resin composition of the present invention is cured by light, it is preferable to mix a radiation polymerization initiator as the component (C). Specific examples thereof include, for example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone,
-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
-Phenylpropan-1-one, 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) butane-
1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like can be mentioned. These compounds can be used alone or in combination of two or more.
Among these compounds, 2-methyl-
1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, diethylthioxanthone and the like are preferred. Available Irgacure 907 as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, diethylthioxanthone
(Made by Ciba Specialty Chemicals).

By blending the component (C), the composition obtained has sufficient curability.
Excessive blending of component (C) is not only economical, but also causes embrittlement of the cured product. Therefore, the blending ratio of component (C) is based on the total amount of non-volatile components in the composition being 100% by weight. , 0 to 10% by weight, preferably 0.5 to 7% by weight, more preferably 1 to 5% by weight.

<(D) Polymerizable Monomer> The curable resin composition of the present invention is used in addition to the above components (A) and (B) for the purpose of lowering the refractive index and increasing the hardness of the cured product. ,
The component (D) comprising a compound having at least one polymerizable unsaturated group in a molecule other than the components (A) and (B) can be blended. Examples of the component (D) include compounds containing one or more (meth) acryloyl groups in one molecule and other polymerizable monomers copolymerizable with the component (B).

As specific examples of the component (D), the component (a) which is a component in the fluorine-containing copolymer (A),
Compounds exemplified as the component (b) and (1) 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) )
Acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 3,3,4,4,5,5,6,6-
Octafluorooctane di (meth) acrylate, 3-
(2-perfluorohexyl) ethoxy-1,2-di (meth) acryloylpropane, Nn-propyl-N-
Fluorinated (meth) acrylates such as 2,3-di (meth) acryloylpropylperfluorooctylsulfonamide; (2) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate;
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4
-Alkylene glycol di (meth) acrylates such as butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate; (3) trimethylolpropane tri (meth) Acrylate, trimethylolpropane trihydroxyethyl tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Poly (meth) acrylates of polyhydric alcohols such as erythritol penta (meth) acrylate and neopentylglycol di (meth) acrylate hydroxypivalate; 4) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-
(6) isocyanurate poly (meth) acrylates such as (hydroxyethyl) isocyanurate tri (meth) acrylate; (5) cycloalkane poly (meth) acrylates such as tricyclodecanediyldimethyldi (meth) acrylate; Di (meth) acrylate of ethylene oxide adduct of bisphenol A, di (meth) acrylate of propylene oxide adduct of bisphenol A
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; and others. These copolymerizable monomers can be used alone or in combination of two or more.

Further, a fluorine-containing (meth) acrylate is used from the viewpoint of keeping the refractive index of the cured product low, a polyfunctional (meth) acrylate is used from the viewpoint of improving the hardness of the cured film, and the compatibility of the whole composition is improved. It is particularly preferable to use N-vinyl lactam from the viewpoint of increasing the adhesion of the coating film to the base material as well as increasing the H.sub.2. Specific examples of such a compound include heptadecafluorodecyl (meth) acrylate, octafluoro Pentyl (meth) acrylate,
Examples include tetrafluoropropyl (meth) acrylate, trifluoroethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-vinyl-2-caprolactam, and the like.

Component (D) is 0 to 100% by weight based on the total amount of active ingredients (components other than solvent) in the composition.
The content is 50% by weight, preferably 0 to 30% by weight, more preferably 0 to 20% by weight. If this ratio is excessive, the hardness of the cured film tends to be low or the refractive index tends to be high. The ratio of the total amount of the components (B) and (D) is preferably 5 to 90% by weight, where the total amount of the active ingredients in the composition is 100% by weight.

The curable resin composition of the present invention can be obtained by homogenizing the fluorinated copolymer, the polymerizable monomer and, if necessary, the radiation polymerization initiator by stirring or the like in an organic solvent. it can. 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.

<Various Additives> The curable resin composition of the present invention may be used for the purpose of improving the coating properties of the curable resin composition and the physical properties of a 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 added to 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.

<Stabilizing agents such as antioxidants and ultraviolet absorbers> As the antioxidants and ultraviolet absorbers that 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 other crosslinkable compounds 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 fluorine-containing copolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total. It is a compound containing at least one compound, and specific examples include a melamine-based compound, a urea-based compound, a benzoguanamine-based compound, and a glycoluril-based compound. When the total amount of the active ingredients (components other than the solvent) in the curable resin composition is 100% by weight, the amount of the crosslinkable compound used is 50% by weight or less, and preferably 0 to 30% 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 the coating film of the curable resin composition by irradiation with ultraviolet rays, and then heating it. It is a substance that can improve the heating conditions to be milder when promoting the crosslinking of the coating film. 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, which can be added to the curable resin composition of the present invention, imparts photosensitivity to the coating film of the curable resin composition, for example, radiation such as light. Is a substance that enables photo-curing of the coating film by irradiating the film. Examples of the photoacid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) β-ketoester, β
-Sulfonyl sulfones and sulfone compounds for these α-diazo compounds; (3) alkyl sulfonates,
Sulfonic acid esters such as haloalkylsulfonic acid esters, arylsulfonic acid esters and iminosulfonates; (4) sulfonimide compounds represented by the following general formula 10; (5) diazomethane compounds represented by the following general formula 11; Can be mentioned. The photoacid generators can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generators.

[0087]

Embedded image (10)

[0088] [wherein, X represents a divalent group such as alkylene group, arylene group, alkoxylene group, R ¹⁷ represents an alkyl group having an aryl group, a halogen-substituted alkyl group, monovalent, such as a halogen-substituted aryl group Represents a group. ]

[0089]

Embedded image (11)

[Wherein, R ¹⁸ and R ¹⁹ may be the same or different and each represents 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 which 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 the thermal polymerization inhibitor is preferably 5% by weight or less based on 100% by weight of the active ingredient (component other than the solvent) in 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 proportion of the surfactant used is 100% by weight of the active ingredient (component other than the solvent) in the curable resin composition.
Is preferably 5% by weight or less.

<Solvent> The curable resin composition of the present invention is obtained in the form of a solution using the solvent used for producing the fluorine-containing copolymer, and usually contains a 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 ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate, particularly from the viewpoint of solubility and volatility. To methyl isobutyl ketone. These solvents can be used alone or in combination. Further, the solution of the curable resin composition of the present invention, a solvent that does not dissolve the fluorine-containing copolymer, for example, water,
Poor solvents such as alcohols and ethers can be used in combination as long as the fluorine-containing copolymer does not precipitate. This may result in a solution of the curable resin composition having good preservability and favorable coatability. Examples of such a poor solvent include alcohols such as ethyl alcohol, isopropyl alcohol, and tert-butyl alcohol. The solvent is used in an amount of 300 to 5,000 parts by weight, preferably 500 to 3,500 parts by weight, based on 100 parts by weight of the active ingredients (components other than the solvent) in the curable resin composition.

<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 properties 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. As a curing method, radiation curing or thermal curing can be used, and ultraviolet curing and electron beam curing are particularly preferable. In order to surely 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.

[0095]

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. <Synthesis Example 1><Synthesis of fluorinated copolymer> After sufficiently replacing the inside of a 0.5-liter stainless steel autoclave with an electromagnetic stirrer with nitrogen gas, 200 g of ethyl acetate, perfluoro (propyl vinyl ether) (FPVE) 21.3 g,
20.1 g of ethyl vinyl ether (EVE), 10.6 g of 2-hydroxyethyl vinyl ether (HVE) and 0.5 g of dilauroyl peroxide (LPO) were charged. Then, -50 with dry ice-methanol
After cooling to ° C., the atmosphere was replaced with nitrogen gas again. Next, 48.0 g of hexafluoropropylene (HFP) was charged, and the temperature was raised. The temperature inside the autoclave is 60 ° C
At the time when the pressure reached 4.0 × 10 ⁵ Pa.
The reaction was continued at 70 ° C. for 20 hours while stirring as it was. When the pressure dropped to 1.5 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After the temperature was allowed to reach room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution. The nonvolatile content (active ingredient concentration) in this polymer solution was 26.4% by baking at 150 ° C. for 5 minutes on an aluminum dish. 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 88 g of a fluorine-containing copolymer. This fluorinated copolymer is referred to as fluorinated copolymer A1. Table 1
Table 1 shows the charged amount, the yield, the polymerization addition rate, and the nonvolatile content of the monomer for obtaining the fluorocopolymer A1.

Using a 0.5% solution prepared by dissolving the fluorine-containing copolymer A1 in tetrahydrofuran (THF), the number average molecular weight (Mn) in terms of polystyrene was determined by gel permeation chromatography to be 54000. Met. In addition, differential thermal analysis (DS
The glass transition temperature (Tg) according to C), the fluorine content according to the alizarin complex method, and the hydroxyl value according to the acetylation method using acetic anhydride were measured. Also,
^{From 1} H-NMR analysis, FT-IR analysis, and the measured fluorine content, the proportion of each monomer component constituting the fluorine-containing copolymer A1 was determined. Table 1 shows the obtained results.

<Synthesis Example 2> The amount of each component charged was FPVE1
7.3 g, EVE 16.5 g, HEVE 8.6 g, LPO 0.5 g, HFP 39.0 g, and Adecaria Soap NE-3 as a nonionic reactive emulsifier
0 (manufactured by Asahi Denka Kogyo KK) and 2.4 g of VPS-1001 (manufactured by Wako Pure Chemical Industries) as the azo group-containing polydimethylsiloxane, in the same manner as in Synthesis Example 1 except that polysiloxane was used. A fluorinated copolymer having a segment (hereinafter referred to as fluorinated copolymer A2) was obtained.
The evaluation was performed in the same manner as in Synthesis Example 1. Table 1 shows the obtained results.

[0098]

[Table 1]

<Synthesis Example 3><Synthesis of a fluorinated urethane compound having at least three polymerizable unsaturated groups> A 30 equipped with a magnetic stirrer, a reflux condenser equipped with a nitrogen gas inlet tube, and a thermometer.
Isophorone diisocyanate in a 0 ml round bottom flask.
9.87 g (22.5 mmol) of 0 g (45 mmol, 3- (2-perfluorohexyl) ethoxy-1,2-dihydroxypropane (MF100, manufactured by Tochem Products)
l), 39 g of methyl isobutyl ketone were added in order, and the mixture was stirred at room temperature. Further, dibutyltin dilaurate 0.0
7 g was added and the mixture was stirred at 50 ° C. for 2 hours. Then, 22.0 g of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-TMM-3LM-N)
And a mixed solution of methyl isobutyl ketone and 58 g of dibutyltin dilaurate, and stirred at 66 ° C. for 4 hours. When the isocyanate content of this reaction solution was measured, it was 0.08 wt%, and it was confirmed that the reaction had sufficiently proceeded. As described above, the fluorine-containing urethane compound 30.
A 0% MIBK solution was obtained. The nonvolatile component obtained by distilling off the solvent from the reaction solution with an evaporator is referred to as a fluorine-containing urethane compound B1.

<Synthesis Example 4> 5.0 g (22.5 mmol) of isophorone diisocyanate and 2-perfluorooctylethanol were placed in a 300 ml round bottom flask equipped with a magnetic stirrer, a reflux condenser equipped with a nitrogen gas inlet tube, and a thermometer. (Daikin Fine Chemical Laboratory,
A1820) (10.5 g, 22.5 mmol) and methyl isobutyl ketone (40 g) were sequentially added, and the mixture was stirred at room temperature. 0.07 g of dibutyltin dilaurate was added, and 50
Stirred at C for 2 hours. Then, pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A)
-TMM-3LM-N) and a mixed solution of 10.5 g of methyl isobutyl ketone and 30 g of methyl isobutyl ketone and 0.1 g of dibutyltin dilaurate.
06 g was added and the mixture was stirred at 66 ° C. for 5 hours. When the isocyanate content of this reaction solution was measured, it was 0.01 wt%, and it was confirmed that the reaction proceeded sufficiently. Thus, a 30.0% MIBK solution of the fluorinated urethane compound was obtained. The nonvolatile component obtained by removing the solvent from the reaction solution by an evaporator is referred to as a fluorine-containing urethane compound B2.

Fluorine-containing urethane compounds B1, B of the present invention
2 Fourier transform infrared spectrophotometer JIR made by JEOL Ltd.
IR analysis was performed using -5500. From the analysis results and the like, it was determined that the compounds contained in B1 and B2 were compounds represented by the following chemical formulas 5 and 12, respectively.

[0102]

Embedded image (5)

[0103]

Embedded image (12)

<Example 1><Preparation of curable resin composition> 7.00 g of the fluorinated copolymer A1 obtained in Synthesis Example 1 and 30.0 g of the fluorinated urethane compound B1 obtained in Synthesis Example 3 were obtained. 1% 0% MIBK solution
0.00g (3.00 g as B1), 0.20 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals), KAYACURE DETX-S
0.05 g (manufactured by Nippon Kayaku Co., Ltd.) and 153.58 g of methyl isobutyl ketone (MIBK) were dissolved in
By dissolving under stirring for a time, the active ingredient concentration is 6%
A solution of the curable resin composition was obtained.

<Formation and evaluation of coating film of curable resin composition> Measurement of reflectivity After forming a coating film of the curable resin composition on an acrylic plate having a thickness of 3 mm, using a bar coater # 3, A laminated film was formed by irradiating ultraviolet rays of 500 mJ / cm ^{2 in} a nitrogen atmosphere using an ultraviolet curing power supply device manufactured by Eye Graphics Co., Ltd. A matte black spray (immediate dry acrylic lacquer spray, matte black: manufactured by Campeapio) was applied to the back surface of this film and dried. Using this film as a sample, the reflectance was measured using a micro-reflection spectral film thickness meter FTM-1000 (manufactured by Otsuka Electronics Co., 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, 2 under the condition the surface of the load 1 kgf / cm ² of the cured film using a Kimwipe (Jujo manufactured Kimberly Co., Ltd.)
Rubbing was repeated 00 times, and the presence or absence of scratches on the surface was visually checked. AA where no peeling or scratching of the cured film was observed, A where slight streak damage occurred on the surface of the cured film, A where many streak damage occurred on the surface of the cured film Of the cured film was evaluated as C, and the one in which the cured film was peeled was evaluated as C. Table 2 shows the above results.

Measurement of Transparency To evaluate the transparency of the coating film, the film on which the above-mentioned cured film was formed was used as a sample, and the appearance was visually observed.

Examples 2 to 6 and Comparative Examples 1 to 6 Curable resin compositions were prepared in the same manner as in Example 1 except that the contents of the compositions were changed to those shown in Tables 2 and 3. Prepared. A cured film was formed from these curable resin compositions in the same manner as described above, and various physical properties were measured. The results are shown in Tables 2 and 3.

[0109]

[Table 2]

[0110]

[Table 3]

The abbreviations in the table indicate the following contents. KAYARAD DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd.) Biscoat 17F: heptadecafluorodecyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2 -Morifolino-propan-1-one (manufactured by Ciba Specialty Chemicals) KAYACURE DETX-S: diethylthioxanthone (manufactured by Nippon Kayaku)

[0112]

According to the curable resin composition of the present invention, a cured film having excellent transparency, durability and low refractive index is formed. Accordingly, the curable resin composition of the present invention is particularly useful for forming optical materials such as an antireflection film and an optical fiber sheath material, and also for a coating material, a weather resistant film material, and a coating material utilizing the weather resistance which is an inherent characteristic of a fluorine material. It can be suitably used as an application material. 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. And
Since the curable resin composition of the present invention is dissolved in a general hydrocarbon-based solvent, it can 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) C08G 18/67 C08G 18/67 4J100 C09D 127/12 C09D 127/12 175/16 175/16 183/08 183 / 08 G02B 1/11 G02B 1/10 A F term (reference) 2K009 AA04 CC26 DD02 4J011 PA66 PA67 PA69 PA95 PC02 PC08 QA03 QA12 QA13 QA15 QA17 QA22 QA32 QB16 RA10 SA01 SA21 SA27 SA31 SA41 SA51 SA64 UA04 WA10 AG CB10 CC08 4J034 CA04 CB03 CC03 CC26 CD12 FA01 FA02 FB01 FC01 FC02 HA07 HC12 HC17 HC61 HC64 HC71 HC73 RA04 RA14 4J038 CD091 CD092 CD121 CD122 CD131 CD132 DG051 DG052 DG071 DG072 DG091 DG091 GA 272 DG211 DG211 DG211 DG071 NA24 PA17 PC03 PC08 4J100 AA02Q AA03Q AB02Q AB03Q AC27P AC28P AE04Q AE10Q AE39P AG04Q AG05Q AG06Q AG08Q AL02Q AL08 Q BA02Q BA08Q BA15Q BC43Q BC53Q CA04 FA08 HC54 HC77

Claims (8)

[Claims] (A) a fluorine-containing copolymer having a fluorine content of 30% by weight or more and a number average molecular weight of 5,000 or more; and (B) having at least three polymerizable unsaturated groups. A curable resin composition comprising a fluorine-containing urethane compound. 2. The component (A) comprises: (a) a structural unit containing a fluorine atom represented by the following general formula 1, and (b):
The curable resin composition according to claim 1, wherein the curable resin composition is a fluorine-containing copolymer comprising a structural unit represented by the following general formula 2. Embedded image (1) [In the formula, R ¹ is a fluorine atom, a chlorine atom, and has 1 to 10 carbon atoms.
Or a group represented by —OR ² (R ²
Represents an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group). ] (2) [wherein, R ³ represents a hydrogen atom or a methyl group; R ⁴ represents an alkyl group having 1 to 15 carbon atoms, an alkoxycarbonyl group, a carboxyl group, or a group represented by — (CH ₂ ) _X —OR ⁵ ; (R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group or a glycidyl group, and X represents a number of 0 or 1), or a group represented by —OCOR ⁵ (R ⁵ is as defined above). Show. ] 3. The composition of claim 1, wherein the component (A) further comprises (c)
The curable resin composition according to any one of claims 1 and 2, wherein the curable resin composition is a fluorine-containing copolymer having a siloxane structural unit represented by the formula: Embedded image (3) wherein R ⁶ and R ⁷ may be the same or different;
It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an aryl group having 6 to 20 carbon atoms. ] 4. The component (B) is a fluorine-containing urethane compound obtained by reacting a polyisocyanate compound, a polymerizable unsaturated group-containing hydroxy compound and a fluoroalkyl group-containing hydroxy compound. ~
4. The curable resin composition according to any one of 3. 5. The composition according to claim 1, wherein the component (B) is a fluorine-containing urethane compound represented by the following general formula 4.
5. The curable resin composition according to any one of 4. Embedded image (4) wherein R ⁸ is a fluoroalkyl group or a divalent organic group having 1 to 20 carbon atoms having a fluoroalkylene group, A is an acryloyl group or a methacryloyl group, and B ¹ and B ² are each independently (N + 1) -valent, (m + 1) -valent carbon number of 1 to 20
Wherein n is a number from 1 to 5, m is a number from 1 to 5,
3 ≦ n + m ≦ 10. ] 6. The composition according to claim 1, wherein the component (B) is a fluorine-containing urethane compound represented by the following chemical formula 5.
The curable resin composition according to any one of items 5 to 5. Embedded image (5) 7. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 6. 8. An anti-reflection film comprising a cured product of the curable resin composition according to claim 1. Description: