KR101298381B1 - Radiation-curable resin composition and antireflection coating - Google Patents

Abstract

The present invention provides a radiation curable resin composition containing the following components (A), (B), (C) and (D).

(A) Ethylenic unsaturated group containing fluorine-containing polymer

(B) (meth) acrylate compound

(C) Silicone compound containing the structure represented by following formula (I)

(D) Particles whose main component is silica having a number average particle diameter of 1 to 100 nm

<Formula I>

-(O-SiR ³¹ R ³² ) _c- (CH ₂ ) _d -OR ³³

[Wherein, R ³¹ and R ³² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³³ is a monovalent organic group having one or more groups selected from the group consisting of a hydroxyl group, an amino group, a (meth) acryloyl group and a vinyl group C is an integer of 1 or more, wherein the molecular weight of the silicone compound is in the range of 500 to 30,000, and d is an integer of 1 to 4;

Radiation curable resin composition, cured film, antireflection film

Description

Radiation curable resin composition and anti-reflective coating TECHNICAL FIELD [RADIATION-CURABLE RESIN COMPOSITION AND ANTIREFLECTION COATING}

The present invention relates to a radiation curable resin composition and an antireflection film. More specifically, the low-refractive-index layer containing an ethylenically unsaturated group containing fluorine-containing polymer, and when hardened | cured, and obtained the cured film excellent in abrasion resistance, coatability, and durability is obtained, and such a cured film. It is related with the anti-reflective film containing.

Various display panels, such as a liquid crystal display panel, a cold cathode ray tube panel, and a plasma display, WHEREIN: The low refractive index which consists of a cured film excellent in low refractive index, abrasion resistance, coating property, and durability, in order to prevent the reflection of external light and to improve image quality. There is a need for an antireflection film including a layer.

These display panels require surface characteristics that can easily remove attached fingerprints and dust (antifouling), and often require wiping with a gauze impregnated with ethanol to remove dust. It is becoming.

As the material for the low refractive index layer of the antireflection film, for example, a fluorine resin paint containing a hydroxyl group-containing fluorine-containing polymer is known (for example, Patent Documents 1 to 3 below).

However, in such a fluororesin-based paint, in order to cure the coating film, it is necessary to crosslink the hydroxyl group-containing fluorine-containing polymer and a curing agent such as melamine resin by heating under an acid catalyst, and the curing time is excessively long depending on the heating conditions. There was a problem that the kind of base material that can be limited.

Moreover, also about the obtained coating film, although it was excellent in weatherability, there existed a problem which was lacking in antifouling property, abrasion resistance, or durability.

Moreover, although the antifouling material containing an acryl-type monomer, a silica particle, and a silane coupling agent is known, it cannot be said that low refractive index property is enough as a material of the low refractive index layer of an antireflection film (patent document 4 below).

For this reason, although the coating composition containing this polymer enables low temperature and hardening in a short time, it was necessary to harden | cure further using hardening | curing agents, such as melamine resin, in order to react the remaining hydroxyl group. Moreover, there existed a subject that the coating film obtained from the said antifouling material was not enough also about coating property, antifouling property, and abrasion resistance.

In addition, in order to improve the scratch resistance of the antireflection film, a technique of adding silica particles to the low refractive index film that is the outermost layer of the antireflection film is widely used (for example, Patent Documents 5 and 6 below), but sufficient scratch resistance is obtained. I didn't get to lose.

Patent Document 1: Japanese Patent Laid-Open No. 57-34107

Patent Document 2: Japanese Patent Laid-Open No. 59-189108

Patent Document 3: Japanese Patent Laid-Open No. 60-67518

Patent Document 4: Japanese Patent Application Laid-Open No. 2001-49236

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-265866

Patent Document 6: Japanese Patent Application Laid-Open No. 10-316860

Accordingly, an object of the present invention is to provide a radiation curable resin composition and an antireflection film having a low refractive index and excellent in scratch resistance, antifouling property, and in particular, wiping property of an oily dye.

According to this invention, the following radiation curable resin compositions, cured films, and antireflection films are provided.

[1] A radiation curable resin composition containing the following components (A), (B), (C) and (D).

(A) Ethylenic unsaturated group containing fluorine-containing polymer

(B) (meth) acrylate compound

(C) Silicone compound containing the structure represented by following formula (I)

(D) Particles whose main component is silica having a number average particle diameter of 1 to 100 nm

-(O-SiR ³¹ R ³² ) _c- (CH ₂ ) _d -OR ³³

[Wherein, R ³¹ and R ³² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³³ is a monovalent organic group having one or more groups selected from the group consisting of a hydroxyl group, an amino group, a (meth) acryloyl group and a vinyl group C is an integer of 1 or more, wherein the molecular weight of the silicone compound is in the range of 500 to 30,000, and d is an integer of 1 to 4;

[2] The radiation curable resin composition according to the above [1], wherein R ^{33 in} the formula (I) is a monovalent organic group having a (meth) acryloyl group.

[3] The radiation curable resin composition according to the above [1] or [2], wherein the molecular weight of the silicone compound (C) is 5,000 or more.

[4] The radiation curable resin composition according to any one of the above [1] to [3], wherein the silicone compound including the structure represented by the formula (I) has a (meth) acryloyl group at both ends thereof.

[5] The (A) ethylenically unsaturated group-containing fluorine-containing polymer is

An ethylenically unsaturated group-containing isocyanate compound and

Hydroxyl-containing fluorine-containing polymer

The radiation curable resin composition in any one of said [1]-[4] which is an ethylenically unsaturated group containing fluorine-containing polymer obtained by making it react.

[6] The radiation curable resin composition according to any one of the above [1] to [5], wherein the particles (D) having silica as a main component have a polymerizable unsaturated group.

[7] The radiation curable resin composition according to any one of the above [1] to [6], which is for an antireflection film.

[8] A cured film obtained by curing the radiation curable resin composition according to any one of the above [1] to [7].

[9] An antireflection film having a low refractive index layer containing the cured film according to the above [8].

According to the radiation curable resin composition of this invention, the cured film which is low in refractive index, and has the outstanding antifouling property and abrasion resistance, and the antireflective film containing the same is obtained.

1 is a cross-sectional view of an antireflection film according to an embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION [

Embodiments of the radiation curable resin composition, the cured film, and the antireflection film of the present invention will be described below.

1. Radiation curable resin composition

The radiation curable resin composition (henceforth a composition of this invention) of this invention can contain the following components (A)-(G). Among these components, (A) to (D) are essential components, and (E) to (G) are optional components that may be included as appropriate.

(A) Ethylenic unsaturated group containing fluorine-containing polymer

(B) (meth) acrylate compound

(C) Silicone compound containing the structure represented by following formula (I)

(D) Particles whose main component is silica having a number average particle diameter of 1 to 100 nm

(E) Compounds that generate active species by radiation or heat

(F) Organic solvent

(G) other additives

<Formula I>

-(O-SiR ³¹ R ³² ) _c- (CH ₂ ) _d -OR ³³

[Wherein, R ³¹ and R ³² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³³ is a monovalent organic group having one or more groups selected from the group consisting of a hydroxyl group, an amino group, a (meth) acryloyl group and a vinyl group C is an integer of 1 or more, wherein the molecular weight of the silicone compound is in the range of 500 to 30,000, and d is an integer of 1 to 4;

These components are demonstrated below.

(A) Ethylenic unsaturated group containing fluorine-containing polymer

The ethylenically unsaturated group-containing fluorine-containing polymer (A) is a polymer of fluorine-based olefins. With the component (A), the composition of the present invention exhibits basic performance as a low refractive index material for an antireflection film such as low refractive index, antifouling property, chemical resistance, and water resistance.

It is preferable that (A) component has a (meth) acryl group in a side chain. Thereby, it can co-crosslink with a radically polymerizable (meth) acryl compound, and abrasion resistance improves.

The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by reacting an ethylenically unsaturated group-containing isocyanate compound with a hydroxyl group-containing fluorine-containing polymer. In other words, the hydroxyl group of the hydroxyl group-containing fluorine-containing polymer is modified by an ethylenically unsaturated group-containing isocyanate compound.

(1) ethylenically unsaturated group-containing isocyanate compound

The ethylenically unsaturated group-containing isocyanate compound is not particularly limited as long as it is a compound containing one isocyanate group and one or more ethylenically unsaturated groups in the molecule.

On the other hand, when two or more isocyanate groups are contained, there is a possibility of causing gelation when reacting with a hydroxyl group-containing fluorine-containing polymer.

Moreover, as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable at the point which can harden | cure the curable resin composition mentioned later more easily.

As an ethylenically unsaturated group containing isocyanate compound, 1 type (s) or 2 or more types of combinations of 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate are mentioned.

In addition, an ethylenically unsaturated group containing isocyanate compound can also be synthesize | combined by making a diisocyanate and hydroxyl group containing (meth) acrylate react.

As an example of diisocyanate, 2, 4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), and 1, 3-bis (isocyanate methyl) cyclohexane are preferable.

As an example of hydroxyl group containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.

On the other hand, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, For example, brand name HEA of Osaka Yuki Chemical Co., Ltd. make, brand name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. make. (Trade name) Aronix M-215, M-233, M-305, M-400 etc. are available.

(2) hydroxyl-containing fluorine-containing polymer

The hydroxyl group-containing fluorine-containing polymer preferably includes the following structural units (a), (b) and (c).

(a) The structural unit represented by following formula (1).

(b) The structural unit represented by following formula (2).

(C) The structural unit represented by following formula (3).

[In Formula 1, R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ² (R ² represents an alkyl group or a fluoroalkyl group.)

In Formula 2, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group,-(CH ₂ ) _x -OR ^5, or a group represented by -OCOR ⁵ (R ⁵ represents an alkyl group or glycidyl group, x Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

(i) structural units (a)

In the general formula (1), as the fluoroalkyl group of R ¹ and R ² , a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorocyclohex C1-C6 fluoroalkyl groups, such as a real group, are mentioned. Moreover, as an alkyl group of R <^2> , C1-C6 alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, are mentioned.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as the polymerization component. The fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; Alkyl perfluorovinyl ether or alkoxyalkyl perfluorovinyl ether; Perfluoro (alkyl vinyl), such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butyl vinyl ether), and perfluoro (isobutyl vinyl ether) Ethers); 1 type of single or 2 or more types of perfluoro (alkoxy alkyl vinyl ether), such as perfluoro (propoxy propyl vinyl ether), is mentioned.

Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxy alkyl vinyl ether) are more preferable, and it is more preferable to use them in combination.

In addition, the content rate of a structural unit (a) is 20-70 mol%, when the total amount of structural units (a)-(c) in a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that if the content is less than 20 mol%, it may be difficult to express low refractive index, which is an optical characteristic of the fluorine-containing material intended for the present invention, while on the other hand, if the content is more than 70 mol%, It is because the solubility, transparency, or adhesiveness with respect to a base material of a hydroxyl-containing fluoropolymer in an organic solvent may fall.

For this reason, the content of the structural unit (a) is more preferably 25 to 65 mol%, more preferably 30 to 60 mol%.

(ii) structural units (b)

In the formula (2), examples of the alkyl group represented by R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group and lauryl group, and examples of the alkoxycarbonyl group include methoxycarbonyl group. And ethoxycarbonyl group.

The structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include 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 and n- Alkyl vinyl ethers or cycloalkyl vinyl ethers such as hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether; Allyl ethers such as ethyl allyl ether and butyl allyl ether; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl pivalate, a vinyl caproate, a vinyl versatate, and a vinyl stearate; Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) (Meth) acrylic acid esters such as acrylate and 2- (n-propoxy) ethyl (meth) acrylate; 1 type single or 2 types or more combinations, such as unsaturated carboxylic acids, such as (meth) acrylic acid, a crotonic acid, a maleic acid, a fumaric acid, and itaconic acid, are mentioned.

On the other hand, the content rate of a structural unit (b) is 10-70 mol% when the sum total of structural units (a)-(c) in a hydroxyl-containing fluoropolymer is 100 mol%. The reason is that the solubility of the hydroxyl group-containing fluorine-containing polymer in the organic solvent may be lowered if the content is less than 10 mol%. On the other hand, if the content is more than 70 mol%, the transparency of the hydroxyl-containing fluorine-containing polymer, And optical properties such as low reflectivity may be deteriorated.

For this reason, the content of the structural unit (b) is more preferably 20 to 60 mol%, more preferably 30 to 60 mol%.

(iii) structural units (c)

In the general formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxy A hydroxypentyl group and a 6-hydroxyhexyl group are mentioned.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5- Hydroxyl group-containing allyl ethers such as hydroxyl group-containing vinyl ethers such as hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, and allyl Alcohol etc. are mentioned.

As the hydroxyl group-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and caprolactone (meth) acrylate , Polypropylene glycol (meth) acrylate and the like can be used.

On the other hand, when the content rate of a structural unit (c) makes 100 mol% the sum total of structural units (a)-(c) in a hydroxyl-containing fluoropolymer, it is preferable to set it as 5-70 mol%. The reason for this is that the solubility of the hydroxyl group-containing fluorine-containing polymer in the organic solvent may be lowered if the content is less than 5 mol%. On the other hand, the transparency of the hydroxyl-containing fluorine-containing polymer is more than 70 mol%. This is because optical characteristics such as, and low reflectivity may be degraded.

For this reason, the content of the structural unit (c) is more preferably 5 to 40 mol%, more preferably 5 to 30 mol%.

(iv) structural units (d) and structural units (e)

It is also preferable that the hydroxyl-containing fluorine-containing polymer further comprises the following structural unit (d).

(d) The structural unit represented by following formula (4).

[In Formula 4, R ⁸ and R ⁹ may be the same or different, and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.]

In the general formula (4), an alkyl group of R ⁸ or R ⁹ is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, and a halogenated alkyl group is a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluoro group. A phenyl group, a benzyl group, a naphthyl group etc. are mentioned as an aryl group etc. as a C1-C4 fluoroalkyl group, such as a robutyl group, respectively.

The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the above formula (4). As an example of such an azo-group containing polysiloxane compound, the compound represented by following formula (5) is mentioned.

In Formula 5, R <^10> -R <^13> may be same or different, and represents a hydrogen atom, an alkyl group, or a cyano group, R <^14> -R <^17> may be the same or different, represents a hydrogen atom or an alkyl group, p, q represents a number from 1 to 6, s, t represents a number from 0 to 6, y represents a number from 1 to 200, and z represents a number from 1 to 20.]

In the case of using the compound represented by the formula (5), the structural unit (d) is included in the hydroxyl group-containing fluorine-containing polymer as part of the structural unit (e).

(e) The structural unit represented by following formula (6).

[Formula 6, R ¹⁰ to R ¹³ , R ¹⁴ to R ¹⁷ , p, q, s, t and y are the same as in the above formula (5)]

In Chemical Formulas 5 and 6, R ¹⁰ To the alkyl group of R ^13, methyl, ethyl, propyl group, hexyl group, cyclohexyl may be mentioned an alkyl group having 1 to 12 carbon atoms such as a group, R ¹⁴ to the alkyl group of R ^17, methyl, ethyl, carbon atoms, such as propyl group 1 And alkyl groups of 3 to 3 are mentioned.

In the present invention, the compound represented by the following formula (7) is particularly preferable as the azo group-containing polysiloxane compound represented by the formula (5).

[In Formula 7, y and z are the same as said Formula 5]

On the other hand, when the content rate of the structural unit (d) is 100 mol parts based on the total of the structural units (a) to (c) in the hydroxyl group-containing fluorine-containing polymer, it is preferably 0.1 to 10 mol parts. The reason is that if the content is less than 0.1 mol part, the surface slip resistance of the coated film after curing may be lowered, and the scratch resistance of the coating film may be reduced. On the other hand, if the content is more than 10 mol parts, the transparency of the hydroxyl group-containing fluoropolymer This is because repulsion etc. may arise easily at the time of application | coating when using this as a coating material.

For this reason, the content of the structural unit (d) is more preferably from 0.1 to 5 moles, more preferably from 0.1 to 3 moles. For the same reason, the content rate of the structural unit (e) is preferably determined so that the content rate of the structural unit (d) contained therein is within the above range.

(v) structural units (f)

It is also preferable that the hydroxyl-containing fluorine-containing polymer further comprises the following structural unit (f).

(f) The structural unit represented by following formula (8).

In formula (8), R ¹⁸ represents a group having an emulsifying action.

In the formula (8), the group having an emulsifying action of R ¹⁸ is preferably a group having both a hydrophobic group and a hydrophilic group while the hydrophilic group is a polyether structure such as polyethylene oxide and polypropylene oxide.

Examples of the group having such an emulsifying action include groups represented by the following formula (9).

[Wherein n represents a number from 1 to 20, m represents a number from 0 to 4, and u represents a number from 3 to 50]

The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. As such a reactive emulsifier, the compound represented by following formula (10) is mentioned.

[In Formula 10, n, m and u are the same as in Formula 9]

On the other hand, when the content rate of the structural unit (f) is 100 mol parts based on the total of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer, it is preferably 0.1 to 5 mol parts. The reason is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluorine-containing polymer in the solvent is improved. On the other hand, when the content is less than 5 mole parts, the adhesiveness of the curable resin composition does not increase excessively and handling becomes easy, and the coating material It is because moisture resistance does not fall even if it uses for etc.

For this reason, the content of the structural unit (f) is more preferably from 0.1 to 3 mol parts, more preferably from 0.2 to 3 mol parts.

(vi) molecular weight

The hydroxyl group-containing fluorine-containing polymer preferably has a polystyrene reduced number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography using tetrahydrofuran as a solvent. The reason is that the mechanical strength of the hydroxyl group-containing fluorine-containing polymer may be lowered when the number average molecular weight is less than 5,000. On the other hand, when the number average molecular weight exceeds 500,000, the viscosity of the curable resin composition described later becomes high and the thin film coating This is because it may become difficult.

For this reason, the polystyrene reduced number average molecular weight of the hydroxyl group-containing fluorine-containing polymer is more preferably 10,000 to 300,000, more preferably 10,000 to 100,000.

(3) reaction molar ratio

The ethylenically unsaturated group-containing fluorine-containing polymer is preferably obtained by reacting the above-mentioned ethylenically unsaturated group-containing isocyanate compound with a hydroxyl group-containing fluorine-containing polymer in a ratio of a molar ratio of isocyanate group / hydroxyl group of 1.1 to 1.9. This is because if the molar ratio is less than 1.1, the scratch resistance and durability may decrease. On the other hand, if the molar ratio exceeds 1.9, the scratch resistance after immersion of the aqueous alkali solution of the coating film of the curable resin composition may decrease. .

For this reason, the molar ratio of isocyanate group / hydroxyl group is preferably 1.1 to 1.5, and more preferably 1.2 to 1.5.

Although it does not restrict | limit especially about the addition amount of (A) component, It is 10 to 60 weight% normally with respect to composition whole quantity other than the organic solvent. The reason for this is that when the addition amount is less than 10% by weight, the refractive index of the cured coating film of the radiation curable resin composition may increase, and a sufficient antireflection effect may not be obtained. On the other hand, when the addition amount exceeds 60% by weight, the radiation curable resin This is because the scratch resistance of the cured coating film of the composition may not be obtained.

Moreover, for this reason, it is more preferable to make the addition amount of (A) component into 15 to 55 weight%, and it is still more preferable to set it as the value within 20 to 50 weight% range.

(B) (meth) acrylate compound

A (meth) acrylate compound is used in order to improve the scratch resistance of the cured film obtained by hardening a radiation curable resin composition, and the anti-reflective film using the same.

The compound is not particularly limited as long as it is a compound containing at least one (meth) acryloyl group in the molecule.

As a monomer which has one (meth) acryloyl group, for example, acrylamide, (meth) acryloyl morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) Acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acryl Amide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclophene Tenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate , Tetrahydrofurfuryl ( Meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylic Latex, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinylpyrrolidone, Phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono The compound represented by (meth) acrylate, bornyl (meth) acrylate, and methyl triethylene diglycol (meth) acrylate can be illustrated. Among these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate and phenoxyethyl (meth) acrylate are particularly preferable.

As a commercial item of these monofunctional monomers, for example, Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, Toagosei Co., Ltd. product) KAYARAD TC-110S, R-564, R-128H 8F, Biscot 17F (above, Osaka Yuki Chemical Co., Ltd. make) etc. are mentioned.

As the monomer having two or more (meth) acryloyl groups, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di ( Meth) acrylate, bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (also called "tricyclodecanediyldimethylenedi (meth) acrylate"), tris (2- Hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, trimethylolpropanetri (meth) acrylate, ethylene oxide (hereinafter referred to as "EO") modified trimethylolpropanetri (meth) acrylate, propylene oxide (hereinafter referred to as "PO") Modified trimethylolpropane tree (meth ) Acrylate, tripropylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, bisphenol A diglycidyl ether both ends (meth) acrylic acid adduct, 1, 4- butanediol di (meth) Acrylate, 1,6-hexanedioldi (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyesterdi (meth) acrylate, polyethylene glycol di (meth ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate , Caprolactone modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modification Bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, phenol novolac poly In addition to the (meth) acrylate of glycidyl ether, the compound etc. which are represented by following formula (11) can be illustrated.

[In Formula 11, "Acryl" represents an acryloyl group.]

Examples of commercially available products of these polyfunctional monomers include SA1002 (above, manufactured by Mitsubishi Chemical Corporation), Biscot 195, Biscuit 230, Biscot 260, Biscot 215, Biscot 310, Biscot 214HP, Biscot 295, Biscot 300, Biscot 360, Biscot GPT, Biscuit 400, Biscot 700, Biscot 540, Biscot 3000, Biscot 3700 (above, Osaka Yuki Chemical Co., Ltd.), Kayarad R -526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C , DPHA-2I, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA -320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (above, manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M- 233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.) ), Light acrylates BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (above, Eisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, Shinnitetsu Chemical Co., Ltd.) Manufacture), Repoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Kobunshi Co., Ltd.), NK ester A-BPE-4 (more than) And Shin-Nakamura Kagaku Kogyo Co., Ltd.) etc. are mentioned.

On the other hand, it is preferable that the composition of this invention contains the compound containing at least 2 or more (meth) acryloyl group in a molecule | numerator among these. More preferably, compounds containing at least three or more (meth) acryloyl groups in the molecule are particularly preferable. As such 3 or more compounds, it can select from the tri (meth) acrylate compound, the tetra (meth) acrylate compound, the penta (meth) acrylate compound, the hexa (meth) acrylate compound, etc. which were illustrated above, among these, Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra ( Meth) acrylates are particularly preferred. The said compound can be used individually by 1 type or in combination of 2 or more types, respectively.

In addition, the (meth) acrylate compound may contain fluorine. As an example of such a compound, single 1 type or 2 or more types of combinations, such as a perfluoro octyl ethyl (meth) acrylate, an octafluoro pentyl (meth) acrylate, and a trifluoroethyl (meth) acrylate, are mentioned. .

Although it does not restrict | limit especially about the addition amount of (B) component, It is 1-88 weight% normally with respect to composition whole quantity other than the organic solvent. The reason is that the scratch resistance of the cured coating film of the radiation curable resin composition may not be obtained when the addition amount is less than 1% by weight. On the other hand, when the addition amount exceeds 88% by weight, the cured coating film of the radiation curable resin composition This is because the refractive index may be high and a sufficient antireflection effect may not be obtained.

Moreover, for this reason, it is more preferable to make the addition amount of (B) component into 1 to 60 weight%, and it is still more preferable to set it as the value within 1 to 40 weight% range.

(C) silicone compound

(C) Silicone compound is mix | blended with the composition of this invention. (C) The silicone compound needs to contain the structure represented by following formula (I).

The silicone compound (C) containing the structure represented by following formula (I) is mix | blended in order to improve the antifouling property of the cured film obtained by hardening | curing the composition of this invention.

<Formula I>

-(O-SiR ³¹ R ³² ) _c- (CH ₂ ) _d -OR ³³

In general formula (I), R <^31> and R <^32> is respectively independently a C1-C3 alkyl group, and a methyl group is preferable.

R ³³ is a monovalent organic group having at least one group selected from the group consisting of a hydroxyl group, an amino group, a (meth) acryloyl group and a vinyl group, preferably a monovalent organic group having an amino group or a (meth) acryloyl group, It is more preferable that it is a monovalent organic group which has a meth) acryloyl group.

c is an integer of 1 or more which molecular weight of (C) silicone compound exists in the range of 500-30,000, and is an integer of 1-550 normally. On the other hand, the larger the molecular weight of the (C) silicone compound, the better the slip property and the higher the antifouling property, but it is preferably 5,000 or more, and most preferably about 10,000. Here, the molecular weight of (C) silicone compound is measured by the gel permeation chromatography method which makes polystyrene the molecular weight standard.

d is an integer of 1-4, 3 is preferable.

(C) A silicone compound will not be specifically limited if it has the said structure. In the formula I - the structural portion of the (CH _{2) d} -OR ^33, it may have only one end of the silicone chain may have at both ends. Moreover, it is preferable not to have a polar group other than this structural part. Since component (C) is a component contributing to antifouling property, it is preferable to bleed out to the surface of a cured film to some extent, but when it has a polar group, it meshes with a nonpolar silicone chain and has an interfacial function, and the antifouling property of a cured film may fall. to be.

It is preferable that R <^33> is a monovalent organic group which has a (meth) acryloyl group, and it is preferable that (C) silicone compound has a (meth) acryloyl group at both ends.

Specific examples of the (C) silicone compound include silaplane FM-7711, FM-7725, FM-0411, FM-0711, and FM-0725 (above, in addition to the silicone compounds represented by the following formulas (12) to (19). Kaisha) etc. are mentioned.

[In Formulas 12-19, Me represents a methyl group, e is independently selected so that the molecular weight of the compound represented by each chemical formula may be in the range of 500-10,000.]

Although it does not restrict | limit especially about the addition amount of (C) component, It is 0.1-20 weight% normally with respect to the composition whole quantity other than the organic solvent. The reason is that when the addition amount is less than 0.1% by weight, the antifouling property of the cured coating film of the radiation curable resin composition may become insufficient. On the other hand, when the addition amount is more than 20% by weight, such as peeling of the silicone compound from the surface of the cured coating film. This is because there is a problem.

Moreover, for this reason, it is more preferable to make the addition amount of (B) component into 0.5 to 10 weight%, and it is still more preferable to set it as the value within 1 to 10 weight% range.

(D) Particles whose main component is silica having a number average particle diameter of 1 to 100 nm

(1) Particles based on silica

The curable resin composition of this invention can mix | blend the particle | grain (D) which has a silica with a number average particle diameter of 1-100 nm as a main component. The particle diameter is measured by a transmission electron microscope. 5-80 nm is preferable and, as for the particle diameter of (D) component, 10-60 nm is more preferable.

Particles (D) containing silica having a number average particle diameter of 1 to 100 nm as a main component are blended to improve scratch resistance, particularly steel wool resistance, of the cured film of the curable resin composition of the present invention.

As particle | grains which have these silica as a main component, a well-known thing can be used and its shape is not specifically limited, either. If it is spherical, it is not limited to normal colloidal silica, It may be a hollow particle, porous particle, core-shell type particle, etc. Moreover, it is not limited to spherical form, Amorphous particle may be sufficient. Colloidal silica having a solid content of 10 to 40% by weight is preferred.

In addition, the dispersion medium is preferably water or an organic solvent. As an organic solvent, Alcohol, such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Organic solvents, such as ethers, such as tetrahydrofuran and a 1, 4- dioxane, are mentioned, Among these, alcohol and ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

As a commercial item of the particle containing a silica as a main component, it is a colloidal silica, for example, Nissan Chemical Co., Ltd. brand name: methanol silicazol, IPA-ST, MEK-ST, MEK-ST-S, MEK-ST -L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50 , ST-OL, and the like.

Moreover, the thing which surface-treated, such as chemical modification, can be used for the colloidal silica surface, For example, what contains the hydrolyzable silicon compound which has one or more alkyl groups, or its hydrolyzate etc. can be made to react. Examples of such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane and dodecyl tree. Methoxysilane, 1,1,1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3 -Trimethyl-1,3-disiloxane, α-trimethylsilyl-ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxanehexamethyl-1,3-disila A glass etc. can be mentioned. It is also possible to use hydrolyzable silicon compounds having at least one reactive group in the molecule. Hydrolyzable silicon compounds having at least one reactive group in the molecule include, for example, NH ₂ groups as reactive groups, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane 3-thiocyanate as having an OH group and having a thiocyanate group such as 3-isocyanatepropyltrimethoxysilane as having an isocyanate group such as bis (2-hydroxyethyl) -3 aminotripropylmethoxysilane 3-mercapto as having a thiol group, such as (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, as having an epoxy group, such as propyltrimethoxysilane Propyl trimethoxysilane, etc. are mentioned. As a preferable compound, 3-mercaptopropyl trimethoxysilane is mentioned.

It is preferable that the particle | grain (D) which has a silica as a main component is surface-treated with the organic compound (Hereinafter, it may be called a "specific organic compound.") Containing a polymerizable unsaturated group. By such a surface treatment, it can co-crosslink with a UV curing acrylic monomer, and abrasion resistance improves.

(2) specific organic compounds

The specific organic compound used for this invention is a polymeric compound containing a polymeric unsaturated group in a molecule | numerator. It is preferable that this compound is a compound which contains the group further represented by following formula (20) in a molecule | numerator, and a compound which has a silanol group in a molecule | numerator, or a compound which produces a silanol group by hydrolysis.

[In Formula 20, X represents NH, O (oxygen atom) or S (sulfur atom), Y represents O or S.]

(i) polymerizable unsaturated groups

Although there is no restriction | limiting in particular as a polymerizable unsaturated group contained in a specific organic compound, For example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, male Eate group and acrylamide group are mentioned as a preferable example.

This polymerizable unsaturated group is a structural unit which performs addition polymerization by active radical species.

(ii) the group represented by the formula (20)

It is preferable that a specific organic compound further contains the group shown by the said Formula (20) in a molecule | numerator. The group [-XC (= Y) -NH-] represented by the formula (20) is specifically [-OC (= O) -NH-], [-OC (= S) -NH-], [-SC (= O) -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-] and [-SC (= S) -NH-]. . These groups can be used individually by 1 type or in combination of 2 or more types. Among them, in terms of thermal stability, at least one of a [-OC (= O) -NH-] group, a [-OC (= S) -NH-] group, and a [-SC (= O) -NH-] group is used in combination. It is desirable to.

The group [-XC (= Y) -NH-] shown in the above formula (20) generates moderate cohesive force due to hydrogen bonding between molecules, and when it is set as a cured film, characteristics such as excellent mechanical strength, adhesion to a substrate and heat resistance It seems to give.

(iii) silanol groups or groups that produce silanol groups by hydrolysis

The specific organic compound may be a compound having a silanol group in the molecule (hereinafter sometimes referred to as "silanol group-containing compound") or a compound that generates a silanol group by hydrolysis (hereinafter referred to as "silanol group generating compound"). Yes). Examples of such silanol group-producing compounds include compounds having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom and the like on a silicon atom, but a compound containing an alkoxy group or an aryloxy group on a silicon atom, namely , An alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.

The silanol group generating site of the silanol group or silanol group generating compound is a structural unit bonded to the oxide particles by a condensation reaction following a condensation reaction or hydrolysis.

(iv) preferred embodiments

As a preferable specific example of a specific organic compound, the compound shown by following General formula (21) is mentioned, for example.

R ¹⁹ and R ²⁰ may be the same or different and represent a hydrogen atom or an alkyl or aryl group having 1 to 8 carbon atoms, and a represents a number of 1, 2 or 3.

As an example of R <^19> , R <^20> , methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl group etc. are mentioned.

As a group represented by [(R ¹⁹ O) _a R ²⁰ _{3 - a} Si-], for example, trimethoxysilyl group, triethoxysilyl, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmethoxy Silyl groups; and the like. Among these groups, trimethoxysilyl group, triethoxysilyl group, and the like are preferable.

R ²¹ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may include a chain, branched or cyclic structure. As such an organic group, methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene, etc. are mentioned, for example. Preferred examples of these are methylene, propylene, cyclohexylene, phenylene and the like.

In addition, R ²² is a divalent organic group, and is usually selected from a divalent organic group having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, Chain polyalkylene groups, such as hexamethylene, octamethylene, and dodecamethylene; Alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; Divalent aromatic groups such as phenylene, naphthylene, biphenylene and polyphenylene; And alkyl group substituents and aryl group substituents thereof. In addition, these divalent organic groups may include atomic groups containing elements other than carbon and hydrogen atoms, and may also include polyether bonds, polyester bonds, polyamide bonds, polycarbonate bonds, and further, the groups represented by the above formula (11). have.

R ²³ is a (b + 1) valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule which undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, A tinyl (oxy) group, a cinnamoyl (oxy) group, a maleate group, an acrylamide group, a methacrylamide group, etc. are mentioned. Among them, acryloyl (oxy) group and methacryloyl (oxy) group are preferable. In addition, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

Specific examples of the compound represented by the formula (21) include compounds represented by the following formulas (22) and (23).

[In Formula 22, 23, "Acryl" represents acryloyl group and "Me" represents a methyl group.]

The synthesis | combination of the specific organic compound used by this invention can use the method of Unexamined-Japanese-Patent No. 9-100111, for example. That is, (a) can be performed by addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group containing polymeric unsaturated compound. Moreover, (b) It can carry out by the direct reaction of the compound which has an alkoxy silyl group and an isocyanate group in a molecule | numerator, and an active hydrogen containing polymerizable unsaturated compound. Moreover, it can also synthesize | combine directly by addition reaction of the compound which has a polymerizable unsaturated group and an isocyanate group in (c) molecule | numerator, and mercaptoalkoxysilane or aminosilane.

In order to synthesize | combine the compound shown by the said General formula (21), (a) is used preferably among these methods. More specifically, for example

(a) method; By first reacting a mercaptoalkoxysilane and a polyisocyanate compound, an intermediate containing an alkoxysilyl group, [-SC (= O) -NH-] group and an isocyanate group is formed in the molecule, and then to the isocyanate remaining in the intermediate. A method of reacting an active hydrogen-containing polymerizable unsaturated compound to bind the unsaturated compound through a [-OC (= 0) -NH-] group,

(b) method; First, an intermediate containing a polymerizable unsaturated group, a [-OC (= 0) -NH-] group, and an isocyanate group is formed in a molecule | numerator by reacting a polyisocyanate compound and an active hydrogen containing polymerizable unsaturated compound, a mercaptoalkoxy here And a method in which the mercaptoalkoxysilane is bonded through a [-SC (= O) -NH-] group by reacting a silane. Among them, the method (a) is preferable in that there is no reduction of the polymerizable unsaturated group due to the Michael addition reaction.

In the synthesis | combination of the compound shown by the said Formula (21), as an example of the alkoxysilane which can form a [-SC (= O) -NH-] group by reaction with an isocyanate group, 1 or more alkoxysilyl groups and a mercapto group are respectively contained in a molecule | numerator. The compound which has is mentioned. Examples of such mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, Mercaptopropyl triphenoxysilane, mercaptopropyl tributoxysilane, etc. are mentioned. In this, mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane are preferable. Moreover, the addition product of an amino substituted alkoxysilane and an epoxy group substituted mercaptan, and the addition product of an epoxysilane and an (alpha), (omega)-dimercapto compound can also be used.

As a polyisocyanate compound used when synthesize | combining a specific organic compound, it can select from the polyisocyanate compound comprised from linear saturated hydrocarbon, cyclic saturated hydrocarbon, and aromatic hydrocarbon.

Examples of such polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 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, methylenebis (4-cyclohexyl isocyanate), 2,2 , 4-trimethylhexamethylene diisocyanate, bis (2-isocyanateethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane di Sociane Agent, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethyl xylylene diisocyanate, 2,5 (or 6) -, and the like [2.2.1] heptane-bis (isocyanatomethyl). Among them, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) cyclohexane and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.

In the synthesis of specific organic compounds, examples of the active hydrogen-containing polymerizable unsaturated compound which can be bonded through the [-OC (= O) -NH-] group by an addition reaction with the polyisocyanate compound include addition of isocyanate groups in a molecule. The compound which contains one or more polymerizable unsaturated groups, having one or more active hydrogen atoms which can form a [-OC (= O) -NH-] group by reaction, is mentioned.

As these active hydrogen containing polymerizable unsaturated compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy, for example 3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1 , 6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylol ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylic The rate, dipentaerythritol penta (meth) acrylate, etc. are mentioned. Moreover, the compound obtained by addition reaction of glycidyl-group containing compounds, such as alkylglycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like are preferable.

These compounds can be used individually by 1 type or in mixture of 2 or more types.

(3) Surface treatment method of particle | grains (henceforth a particle | grain) which have silica as a main component by a specific organic compound

Although there is no restriction | limiting in particular as a surface treatment method of the particle | grains by a specific organic compound, It is also possible to manufacture by mixing, heating, and stirring a specific organic compound and particle | grains. On the other hand, the reaction is preferably carried out in the presence of water in order to efficiently bond the silanol group generating site and the particles possessed by the specific organic compound. However, when a specific organic compound has a silanol group, water may not be necessary. Therefore, it can surface-treat by the method containing the operation of mixing particle | grains and a specific organic compound at least.

Reaction amount of a particle and a specific organic compound makes the sum total of a particle and a specific organic compound 100 weight%, Preferably it is 0.01 weight% or more, More preferably, it is 0.1 weight% or more, Especially preferably, it is 1 weight% or more. . If it is less than 0.01 weight%, the dispersibility of the particle | grains in a composition may not be enough, and transparency and the scratch resistance of the cured film obtained may become insufficient.

Hereinafter, the surface treatment method is explained in more detail by taking an alkoxysilyl group-containing compound (alkoxysilane compound) represented by the above formula (21) as a specific organic compound as an example.

The amount of water consumed by the hydrolysis of the alkoxysilane compound at the time of surface treatment may be an amount by which at least one alkoxy group on the silicon in one molecule is hydrolyzed. Preferably the amount of water added or present at the time of hydrolysis is at least one third of the total number of moles of alkoxy groups on the silicon, and more preferably at least one third and less than three times the number of moles of all alkoxy groups. The product obtained by mixing an alkoxysilane compound and particle | grains on the conditions which do not fully exist in water is a product in which the alkoxysilane compound was physically adsorbed on the particle surface, and is hardened | cured in the cured film of the composition containing the particle | grains comprised by such a component. The effect of expression of degree and scratch resistance is low.

At the time of surface treatment, after attaching the said alkoxysilane compound to a hydrolysis operation separately, this is a method of mixing a powder dispersion or the solvent dispersion sol of particle | grains, and performing a heating and stirring operation; A method of performing hydrolysis of the alkoxysilane compound in the presence of particles; Or the method of surface-treating a particle | grain in presence of another component, for example, a polymerization initiator, etc. can be selected. In this, the method of performing hydrolysis of the said alkoxysilane compound in presence of particle | grains is preferable. At the time of surface treatment, the temperature becomes like this. Preferably they are 0 degreeC or more and 150 degrees C or less, More preferably, they are 20 degreeC or more and 100 degrees C or less. In addition, the treatment time is usually in the range of 5 minutes to 24 hours.

In the case of surface treatment, when a powdery powder is used, an organic solvent may be added for the purpose of smoothly and uniformly reacting with the alkoxysilane compound. As such an organic solvent, For example, Alcohol, such as methanol, ethanol, isopropanol, butanol, an octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate and Y-butyrolactone; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned. Especially, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferable.

The amount of these solvents added is not particularly limited as long as it meets the purpose of smoothly and uniformly reacting.

When using a solvent dispersion sol as particle | grains, it can manufacture by mixing at least a solvent dispersion sol and a specific organic compound. Here, in order to ensure the uniformity of reaction initial stage and to advance reaction smoothly, you may add the organic solvent uniformly compatible with water.

In addition, in the case of surface treatment, an acid, a salt or a base may be added as a catalyst to promote the reaction.

Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; Organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid and oxalic acid; Unsaturated organic acids, such as methacrylic acid, acrylic acid, and itaconic acid, are salts, For example, ammonium salts, such as tetramethyl ammonium hydrochloride and tetrabutylammonium hydrochloride, As a base, For example, ammonia water, diethylamine, triethyl Primary, secondary or tertiary aliphatic amines such as amines, dibutylamine and cyclohexylamine, aromatic amines such as pyridine, 4 such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide And higher ammonium hydroxides.

Preferred examples of these are organic acids as unsaturated acids, unsaturated organic acids and tertiary amines or quaternary ammonium hydroxides as bases. The addition amount of these acids, salts or bases is preferably 0.001 part by weight to 1.0 part by weight, more preferably 0.01 part by weight to 0.1 part by weight based on 100 parts by weight of the alkoxysilane compound.

It is also preferable to add a dehydrating agent to promote the reaction.

As a dehydrating agent, inorganic compounds, such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds, such as methyl ortho formate, ethyl ortho formate, tetraethoxymethane, and tetrabutoxymethane, can be used. Especially, an organic compound is preferable and orthoesters, such as methyl ortho formate and ethyl ortho formate, are more preferable.

In addition, the quantity of the alkoxysilane compound couple | bonded with the particle | grains is a quantity value of the weight loss% when the dry powder is completely burned in air normally, and is calculated | required by the thermogravimetric analysis from 110 degreeC to 800 degreeC in air. Can be.

The compounding quantity of (D) component in the resin composition is mix | blended in 1-40 weight% normally with respect to the composition whole quantity other than the organic solvent, with or without surface treatment, 1-30 weight% is preferable, and 1-10 weight% is More preferred. In addition, the quantity of particle means solid content, and when particle | grains are used in the form of a solvent dispersion sol, the compounding quantity does not contain the quantity of a solvent.

(E) Compounds that generate active species by radiation or heat

Compounds which generate active species by irradiation or heat of radiation are used to cure the curable resin composition.

(1) Compounds that Generate Active Species by Irradiation

As a compound which generate | occur | produces an active species by irradiation of a radiation (henceforth "photoinitiator"), the radical radical generator etc. which generate | occur | produce a radical as an active species are mentioned.

On the other hand, radiation is defined as an energy ray capable of generating active species by decomposing the compound generating the active species. Examples of such radiation include light energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. However, it is preferable to use ultraviolet rays in view of having a constant energy level, fast curing speed, and in addition, the irradiation apparatus is relatively inexpensive and compact.

(i) Type

As an example of an optical radical generating agent, for example, acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone , 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2- Dimethoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropane-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl Propane-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propylether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra -Butyl peroxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenyl Methyl) -1-butanone, 4-benzoyl-4'-methyldiphenylsulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers; Can be.

Among these photoinitiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4, 6-trimethylbenzoyldiphenylphosphineoxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- ( Morpholinyl) phenyl] -2-phenylmethyl) -1-butanone and the like are preferred, and more preferably 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholino propane-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, etc. are mentioned.

(ii) added amount

Although the addition amount of a photoinitiator is not specifically limited, It is preferable to set it as 0.1-10 weight% with respect to the composition whole quantity other than the organic solvent. The reason for this is that when the addition amount is less than 0.1% by weight, the curing reaction may be insufficient, and the scratch resistance and the scratch resistance after immersion in the alkaline aqueous solution may decrease. On the other hand, when the addition amount of a photoinitiator exceeds 10 weight%, it is because the refractive index of a cured film may increase and the antireflection effect may fall.

Moreover, for this reason, it is more preferable to make the addition amount of a photoinitiator into 1 to 5 weight% with respect to the composition whole quantity other than the organic solvent.

(2) Compounds that generate active species by heat

As a compound which generate | occur | produces an active species by heat (henceforth a "thermal polymerization initiator"), the thermal radical generator etc. which generate | occur | produce a radical as an active species are mentioned.

(i) Type

Examples of the thermal radical generator include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert-butyl peroxide , tert-butylhydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) Single 1 type, or 2 or more types of combination is mentioned.

(ii) added amount

Although it does not restrict | limit in particular also about the addition amount of a thermal polymerization initiator, It is preferable to set it as 0.1 to 10 weight% with respect to the composition whole quantity other than the organic solvent. The reason for this is that when the addition amount is less than 0.1% by weight, the curing reaction may be insufficient, and the scratch resistance and the scratch resistance after immersion in the alkaline aqueous solution may decrease. On the other hand, when the addition amount of a photoinitiator exceeds 10 weight%, it is because the refractive index of a cured film may increase and the antireflection effect may fall.

Moreover, it is more preferable to make the addition amount of a thermal polymerization initiator into 1 to 5 weight% with respect to the composition whole quantity other than the organic solvent from such a reason.

(F) Organic solvent

It is preferable to add an organic solvent further to curable resin composition. By adding an organic solvent in this way, the low refractive index layer of the antireflection film which is a thin film can be formed uniformly, and also the thickness of an antireflection film can be formed uniformly. As such an organic solvent, single 1 type, or 2 or more types of combinations, such as methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol, t-butanol, isopropanol, are mentioned.

Although it does not restrict | limit in particular also about the addition amount of an organic solvent, It is preferable to set it as 100-100,000 weight part with respect to 100 weight part of ethylenically unsaturated group containing fluoropolymers. The reason is that when the amount is less than 100 parts by weight, the viscosity adjustment of the curable resin composition may be difficult. On the other hand, when the amount is more than 100,000 parts by weight, the storage stability of the curable resin composition is reduced or the viscosity is too high. It is because it may fall and handling becomes difficult.

(G) Additive

In the curable resin composition, inorganic fillers or pigments and dyes other than the photosensitizer, the polymerization inhibitor, the polymerization initiation aid, the ultraviolet absorber, the antioxidant, the antistatic agent, and the component (D) within a range that does not impair the object or effect of the present invention. It is also preferable to further contain additives such as these.

Next, the manufacturing method and hardening conditions of the composition of this invention are demonstrated.

The composition of the present invention comprises the above-mentioned (A) ethylenically unsaturated group-containing fluorine-containing polymer, (B) component, (C) component and (D) component, or (E) component, (F) organic solvent, if necessary, And (G) additives, respectively, and can be produced by mixing at room temperature or under heating conditions. Specifically, it can manufacture using mixers, such as a mixer, a kneader, a ball mill, and a triaxial roll. However, when mixing under heating conditions, it is preferable to carry out below the decomposition start temperature of a thermal polymerization initiator.

Although it does not restrict | limit especially about hardening conditions of curable resin composition, For example, when radiation is used, it is preferable to make an exposure amount into the value within 0.01-10 J / cm <^2> range.

This is because when the exposure amount is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure amount exceeds 10 J / cm ² , the curing time may be excessively long.

For this reason, it is more preferable to make the exposure amount a value within the range of 0.1 to 5 J / cm ² , and even more preferably to a value within the range of 0.3 to 3 J / cm ² .

In addition, when heating and hardening curable resin composition, it is preferable to heat for 1 to 180 minutes at the temperature within the range of 30-200 degreeC. By heating in this way, an antireflection film excellent in scratch resistance can be obtained more efficiently without damaging the substrate or the like.

Moreover, for this reason, it is more preferable to heat for 2 to 120 minutes at a temperature in the range of 50 to 180 ° C, and more preferably to heat for 5 to 60 minutes at a temperature in the range of 80 to 150 ° C.

2. Anti-reflection film

The antireflection film of this invention contains the low refractive index layer containing the cured film which hardened the said curable resin composition. In addition, the anti-reflection film of the present invention may include a high refractive index layer, a hard coating layer and / or a substrate under the low refractive index layer.

1 shows such an antireflection film 10. As shown in FIG. 1, the hard coating layer 14, the high refractive index layer 16, and the low refractive index layer 18 are laminated | stacked on the base material 12. As shown in FIG.

At this time, the high refractive index layer 16 may be formed directly on the base material 12 without providing the hard coating layer 14.

In addition, a medium refractive index layer (not shown) may be further provided between the high refractive index layer 16 and the low refractive index layer 18 or between the high refractive index layer 16 and the hard coating layer 14.

(1) low refractive index layer

The low refractive index layer is composed of a cured film obtained by curing the curable resin composition of the present invention. Since the structure of curable resin composition etc. are as above-mentioned, the detailed description here is abbreviate | omitted and the refractive index and thickness of a low refractive index layer are demonstrated below.

It is preferable that the refractive index (refractive index of Na-D line | wire, 25 degreeC of measurement temperature) of the cured film obtained by hardening | curing curable resin composition, ie, the refractive index of a low refractive index film shall be 1.47 or less. The reason is that when the refractive index of the low refractive index film exceeds 1.47, when combined with the high refractive index film, the antireflection effect may remarkably decrease.

Further, the refractive index of the low refractive index film is more preferably 1.46 or less.

On the other hand, in the case where a plurality of low refractive index films are provided, at least one of them may have a value of the refractive index within the above-mentioned range, and thus, the other low refractive index films may have a value exceeding 1.47.

In addition, when providing a low refractive index layer, since the outstanding antireflection effect is acquired, it is preferable to make the refractive index difference between a high refractive index layer and a value 0.05 or more. The reason is that, when the refractive index difference between the low refractive index layer and the high refractive index layer is less than 0.05, synergistic effects in these antireflection film layers are not obtained, but the antireflection effect may be lowered.

Therefore, it is more preferable that the refractive index difference between the low refractive index layer and the high refractive index layer is in the range of 0.1 to 0.5, and more preferably in the range of 0.15 to 0.5.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as the base may be reduced. On the other hand, when the thickness exceeds 300 nm, optical interference occurs and the antireflection effect is lowered. This is because there is a case.

Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and more preferably 60 to 200 nm.

On the other hand, in order to obtain a higher antireflection property, in the case where a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness thereof is preferably set to 50 to 300 nm.

(2) high refractive index layer

Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, Epoxy resin, a phenol resin, melamine resin, alkyd resin, cyanate resin, acrylic resin, polyester resin, It is preferable to include 1 type individually or 2 or more types of combinations, such as a urethane type resin and a siloxane resin. It is because if it is these resin, a strong thin film can be formed as a high refractive index layer, and as a result, the scratch resistance of an antireflection film can be improved significantly.

However, the refractive index of these resins alone is 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to mix | blend high refractive index inorganic particle, for example, metal oxide particle. In addition, although the curable composition which can thermoset, ultraviolet-ray curing, and electron beam hardening can be used as a hardening form, the ultraviolet curable composition with favorable productivity is used more suitably.

Although the thickness of a high refractive index layer is not specifically limited, For example, it is preferable that it is 50-30,000 nm. The reason is that when the thickness of the high refractive index layer is less than 50 nm, when combined with the low refractive index layer, the antireflection effect and the adhesion to the substrate may decrease, while when the thickness exceeds 30,000 nm, This is because optical interference may occur, and conversely, the antireflection effect may be lowered.

Therefore, the thickness of the high refractive index layer is more preferably 50 to 1,000 nm, more preferably 60 to 500 nm.

In addition, in order to obtain a higher antireflection property, when providing a multi-layered structure by providing two or more high refractive index layers, it is preferable to make the sum total the thickness into 50-30,000 nm.

On the other hand, when providing a hard-coat layer between a high refractive index layer and a base material, the thickness of a high refractive index layer can be 50-300 nm.

(3) hard coating layer

There is no particular limitation on the constituent material of the hard coat layer used for the antireflection film of the present invention. As such a material, single 1 type, or 2 or more types of combinations, such as a siloxane resin, an acrylic resin, a melamine resin, an epoxy resin, are mentioned.

The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 50 µm, more preferably 5 to 10 µm. The reason is that when the thickness of the hard coating layer is less than 1 m, the adhesion of the antireflection film to the substrate may not be improved. On the other hand, when the thickness exceeds 50 m, it may be difficult to form uniformly. Because there is.

(4) mention

Although the kind of base material used for the antireflection film of this invention is not restrict | limited, For example, the base material containing glass, a polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC), etc. is mentioned. Can be. By using the antireflection film containing these base materials, excellent antireflection effects can be obtained in the field of use of a wide range of antireflection films such as a lens part of a camera, a screen display part of a television (CRT), or a color filter in a liquid crystal display device.

Hereinafter, although the Example of this invention is described in detail, the scope of the present invention is not limited to description of these Examples.

(Production Example 1)

Synthesis of hydroxyl-containing fluorine-containing polymer

After fully replacing a 2.0 liter stainless steel autoclave with an electronic stirrer with nitrogen gas, 400 g of ethyl acetate, 53.2 g of perfluoro (propyl vinyl ether), 36.1 g of ethyl vinyl ether, and 44.0 g of hydroxyethyl vinyl ether , 1.0 g of lauroyl peroxide, 6.0 g of azo group-containing polydimethylsiloxane (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and a nonionic reactive emulsifier (NE-30 (trade name), Asahi 20.0 g of Denka Kogyo Co., Ltd. was added, cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed with nitrogen gas again.

Subsequently, 120.0 g of hexafluoropropylene was put, and temperature rising was started. The pressure at the point where the temperature in the autoclave reached 60 ° C. showed 5.3 × 10 ⁵ Pa. After that, the reaction was continued under stirring at 70 ° C. for 20 hours, and the autoclave was cooled with water at the time when the pressure dropped to 1.7 × 10 ⁵ Pa, and the reaction was stopped. After reaching room temperature, the unreacted monomer was released, the autoclave was opened, and the polymer solution of 26.4% of solid content concentration was obtained. The obtained polymer solution was thrown into methanol, and the polymer was deposited, washed with methanol, and dried in vacuo at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluorine-containing polymer. This was set as the hydroxyl-containing fluorine-containing polymer. The monomers and solvents used are shown in Table 1 below.

About the obtained hydroxyl-containing fluorine-containing polymer, the polystyrene reduced number average molecular weight by gel permeation chromatography and the fluorine content by the alizarin complexon method were respectively measured. Moreover, the ratio of each monomer component which comprises a hydroxyl-containing fluorine-containing polymer was determined from the results of two NMR analysis, elemental analysis, and fluorine content of ¹ H-NMR and ¹³ C-NMR. The results are shown in Table 2 below.

On the other hand, VPS1001 is an azo group-containing polydimethylsiloxane represented by the formula (7) wherein the number average molecular weight is 7 to 90,000 and the molecular weight of the polysiloxane moiety is about 10,000. NE-30 is a nonionic reactive emulsifier in formula 10, wherein n is 9, m is 1, and u is 30.

In addition, in Table 2, the correspondence relationship of a monomer and a structural unit is as follows.

     Monomeric structural units

Hexafluoropropylene (a)

Perfluoro (propylvinylether) (a)

Ethyl vinyl ether (b)

Hydroxyethyl vinyl ether (c)

NE-30 (f)

Polydimethylsiloxane skeleton (d)

(Production Example 2)

Synthesis of ethylenically unsaturated group-containing fluorine-containing polymer A-1 (methacryl-modified fluoropolymer) (component (A))

In a 1-liter separate flask equipped with an electronic stirrer, a glass cooling tube, and a thermometer, 50.0 g of the hydroxyl group-containing fluorine-containing polymer obtained in Production Example 1 and 0.01 g of 2,6-di-t-butylmethylphenol as a polymerization inhibitor. And 370 g of methyl isobutyl ketones (MIBK) were put, and it stirred until the hydroxyl group containing fluorine-containing polymer melt | dissolved in MIBK, and a solution became transparent and uniform at 20 degreeC.

Subsequently, 15.1 g of 2-methacryloyloxyethyl isocyanate was added to the system, stirred until the solution became uniform, and then 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was increased. The stirring was continued for 5 hours while maintaining the temperature at 55 to 65 ° C to obtain a MIBK solution of the ethylenically unsaturated group-containing fluorine-containing polymer A-1.

After weighing 2 g of this solution to the aluminum dish, it dried for 5 minutes on the 150 degreeC hotplate, and weighed and calculated | required solid content, and it was 15.2 weight%. The compound, solvent and solid content used are shown in Table 3 below.

(Production Example 3)

Synthesis of Specific Organic Compound (S-1)

To the solution containing 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate were dripped at 50 degreeC over 1 hour, stirring at 70 degreeC, The mixture was heated and stirred for 3 hours. It contains NK ester A-TMM-3LM-N (60 mass% of pentaerythritol triacrylate and 40 mass% of pentaerythritol tetraacrylates) by Shin-Nakamura Chemical Co., and among these, a hydroxyl group is involved in reaction. 549 parts of pentaerythritol triacrylate having a) was added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound containing a polymerizable unsaturated group. Analysis of the amount of remaining isocyanate in the product by FT-IR showed 0.1% or less, indicating that the reaction was almost quantitatively terminated. Infrared absorption spectra of the product lose the absorption peak of the 2550 kaiser characteristic of the mercapto group in the raw material and the absorption peak of the 2260 kaiser characteristic of the raw isocyanate compound and newly 1660 characteristic of the urethane bond and S (C═O) NH-group. The peak of Kaiser and the peak of 1720 Kaiser characteristic of the acryloxy group were observed, indicating that an acryloxy group-modified alkoxysilane having an acryloxy group, -S (C = 0) NH-, and a urethane bond as a polymerizable unsaturated group was produced. It was. Thus, 993 parts of mixture (S-1) containing the compound represented by the said Formula (22) and Formula (23) including 220 parts of pentaerythritol tetraacrylate which were not involved in reaction were obtained.

(Production Example 4)

Synthesis of Specific Organic Compound (S-2)

In dry air, 60.0 parts of isophorone diisocyanate was dripped over 1 hour at 50 degreeC with stirring with respect to the solution containing 23.0 parts of mercaptopropyl trimethoxysilane and 0.5 part of dibutyltin dilaurates, and then at 70 degreeC The mixture was heated and stirred for 3 hours. It contains NK ester A-TMM-3LM-N (60 mass% of pentaerythritol triacrylate and 40 mass% of pentaerythritol tetraacrylates) by Shin-Nakamura Chemical Co., and among these, a hydroxyl group is involved in reaction. 202.0 parts of pentaerythritol triacrylate which has only the following) was dripped at 30 degreeC over 1 hour, and the organic compound containing a polymerizable unsaturated group was obtained by heating and stirring at 60 degreeC for 10 hours.

As a result of measuring the amount of remaining isocyanate by FT-IR in the same manner as in Production Example 3, that is, Production Example 3, the reaction was confirmed to be almost quantitative as 0.1 mass% or less. In addition, it was confirmed that the molecule contains a urethane bond and an acryloyl group (ethylenically unsaturated group).

Thus, 285 parts of mixture (S-2) containing 80.8 parts of pentaerythritol tetraacrylate containing the compound represented by the said General formula (22) and General formula (23) were obtained.

(Production Example 5)

Synthesis of Polyfunctional Acrylate (Component (B)) Represented by Formula 11

For a solution containing 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container with a stirrer, NK ester A-TMM-3LM-N manufactured by Shinnakamura Chemical Co., Ltd. 93 parts of pentaerythritol triacrylate which had only) was dripped on 10 degreeC and the conditions of 1 hour, and it stirred on the conditions of 60 degreeC and 6 hours, and used as the reaction liquid.

As a result of measuring the amount of remaining isocyanate in FT-IR in the same manner as in Production Example 3, that is, Production Example 3, it was confirmed that the reaction was performed almost quantitatively at 0.1 mass% or less. In addition, it was confirmed that the molecule contains a urethane bond and an acryloyl group (ethylenically unsaturated group).

As a result, 75 parts of the compound represented by the above formula (11) were obtained, and 37 parts of pentaerythritol tetraacrylate not involved in the reaction were mixed.

(Production Example 6)

Preparation of Particles D-1 (component (D)) containing silica as a main component

8.7 parts of specific organic compounds (S-1) synthesized in Production Example 3, methyl ethyl ketone silicazol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST (number average particle diameter 0.022 µm, silica concentration 30%)) After stirring the mixture liquid of 91.3 parts (solid content 27.4 parts), 0.2 parts of isopropanol, and 0.1 parts of ion-exchanged water at 80 degreeC for 3 hours, 1.4 parts of methyl ortho formates are added, and also it is colorless and transparent particle | grains by heating and stirring at the same temperature for 1 hour. Dispersion D-1 was obtained. After weighing 2 g of D-1 in the aluminum dish, it dried on 1 hour hotplate at 120 degreeC, and weighed, and obtained solid content, and it was 35 weight%. Furthermore, after weighing 2 g of the dispersion liquid (D-1) in a magnetic crucible, preliminarily drying for 30 minutes on a hot plate at 80 ° C, and burning the inorganic content in solid content from the inorganic residue after firing for 1 hour in a muffle furnace at 750 ° C. It was 90% as a result.

The average particle diameter of this silica particle was 20 nm. Here, the average particle diameter was measured by the transmission electron microscope.

(Production Example 7)

Preparation of Particle D-2 (Component (D)) Based on Silica

8.7 parts of specific organic compounds (S-2) synthesized in Production Example 4, methyl ethyl ketone silicazol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST (number average particle diameter 0.022 µm, silica concentration 30%)) After stirring the mixture liquid of 91.3 parts (solid content 27.4 parts), 0.2 parts of isopropanol, and 0.1 parts of ion-exchanged water at 80 degreeC for 3 hours, 1.4 parts of ortho formate methyl esters are added, and it heat-stirred at the same temperature for 1 hour, and it is colorless and transparent particle | grains. Dispersion D-1 was obtained. After weighing 2 g of D-2 on an aluminum dish, the resultant was dried for 1 hour on a hot plate at 120 ° C. and weighed to obtain a solid content, which was 35% by weight. Furthermore, after weighing 2 g of the dispersion liquid (D-2) in a magnetic crucible, the inorganic content in the solid content was determined from the inorganic residue after preliminary drying on a hot plate at 80 ° C. for 30 minutes and firing for 1 hour in a muffle furnace at 750 ° C. It was 90% as a result.

The average particle diameter of this silica particle was 20 nm. Here, the average particle diameter was measured by the transmission electron microscope.

(Preparation Example 8)

Synthesis of Compound C-1 (Component (C)) Represented by Formula 12

In dry air, a solution of 71.4 parts of α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-0411) and 0.1 parts of dibutyltin laurylate About 10.6 parts of 2, 4- tolylene diisocyanate was dripped over 1 hour, stirring at 30 degreeC, stirring, and it heated and stirred at 60 degreeC for 3 hours. Then, 17.8 parts of pentaerythritol triacrylates were dripped over 1 hour, and it stirred by heating at 60 degreeC for 3 hours. The obtained compound was set to C-1. The number average molecular weight of compound C-1 measured by the gel permeation chromatography method was 1242.

(Preparation Example 9)

Synthesis of Compound C-2 (Component (C)) Represented by Formula 13

In dry air, to a solution of 29.9 parts of α, ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Co., Ltd., product name: Silaplane FM-4411) and 17.8 parts of dibutyltin laurate And 17.8 parts of 2, 4- tolylene diisocyanate were dripped over 1 hour, stirring at 30 degreeC, stirring, and it heated and stirred at 60 degreeC for 3 hours. Then, after dropping 29.9 parts of pentaerythritol triacrylates over 1 hour, it stirred by heating at 60 degreeC for 3 hours. The obtained compound was set to C-2. The number average molecular weight of compound C-2 was 1350.

(Preparation Example 10)

Synthesis of Compound C-3 (Component (C)) Represented by Formula 14

In dry air, a solution of 80.0 parts of α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Co., Ltd., trade name: Silaplane FM-0411) and 0.1 part of dibutyltin laurate About 29.8 parts of 2, 4- tolylene diisocyanate was dripped over 1 hour with stirring at 30 degreeC, and it stirred by heating at 60 degreeC for 3 hours. Then, 19.9 parts of hydroxyethyl acrylates were dripped over 1 hour, and it stirred by heating at 60 degreeC for 3 hours. The obtained compound was set to C-3. The number average molecular weight of compound C-3 was 1200.

(Preparation Example 11)

Synthesis of Compound C-4 (Component (C)) Represented by Formula 15

In dry air, 63.7 parts of α, ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Co., Ltd., brand name: Silaplane FM-4411) and 0.1 part of dibutyltin laurate 21.7 parts of 2,4-tolylene diisocyanate were dripped over 1 hour, stirring at 30 degreeC, stirring, and it heated and stirred at 60 degreeC for 3 hours. Then, 14.5 parts of hydroxyethyl acrylates were dripped over 1 hour, and it stirred by heating at 60 degreeC for 3 hours. The obtained compound was set to C-4. The number average molecular weight of compound C-4 was 1090.

(Production Example 12)

Synthesis of Compound C-5 (Component (C)) Represented by Chemical Formula 16

In dry air, a solution of 88.3 parts of α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Co., Ltd., product name: Silaplane FM-0411) and 0.1 part of dibutyltin laurate About 11.6 parts of 2-methacryloyloxy isocyanate (Showa Denko Co., Ltd., brand name: Carens MOI) was dripped over 1 hour, stirring at 30 degreeC, stirring, and it heated and stirred at 60 degreeC for 3 hours. . The obtained compound was set to C-5. The number average molecular weight of compound C-5 was 980.

(Preparation Example 13)

Synthesis of Compound C-6 (Component (C)) Represented by Chemical Formula 17

In dry air, a solution of 89.2 parts of α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Co., Ltd., trade name: Silaplane FM-0411) and 0.1 part of dibutyltin laurylate About 10.7 parts of 2-acryloyloxy isocyanate was dripped over 1 hour, stirring at 30 degreeC, stirring, and it heated and stirred at 60 degreeC for 3 hours. The obtained compound was set to C-6. The number average molecular weight of compound C-6 was 970.

(Preparation Example 14)

Synthesis of Compound C-7 (Component (C)) Represented by Chemical Formula 18

In dry air, 76.8 parts of α, ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corp., trade name: Silaplane FM-4411) with respect to a solution of 0.1 parts of dibutyltin laurate 23.1 parts of 2-methacryloyloxyisocyanate (Showa Denko Corporation, brand name: Carens MOI) were dripped over 1 hour, stirring at 30 degreeC, stirring, and it heated and stirred at 60 degreeC for 3 hours. The obtained compound was set to C-7. The number average molecular weight of compound C-7 was 1250.

(Preparation Example 15)

Synthesis of Compound C-8 (Component (C)) Represented by Formula 19

In dry air, 79.9 parts of (alpha)-butyl- (omega)-(2, 2'-methanol butoxy)-polydimethylsiloxane (made by Chisso Corporation, brand name: Silaplane FM-DA11), dibutyltin laurate 20.0 parts of 2-methacryloyloxyisocyanate were dripped over 1 hour with stirring at 30 degreeC, stirring, and it stirred at 60 degreeC for 3 hours with respect to 0.1 part of solution. The obtained compound was set to C-8. The number average molecular weight of compound C-8 was 1150.

(Production Example 16)

Preparation of Silica Particle-Containing Hard Coating Layer Composition

In the container which shielded ultraviolet-ray, 86 parts (30 parts as solid content) of D-1 synthesize | combined in manufacture example 6, 65 parts of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl ] 5 parts of morpholino propane-1-one and 44 parts of MIBK were stirred at 50 degreeC for 2 hours, and the composition for hard-coat layers of a uniform solution was obtained. After weighing 2g of this composition to the aluminum dish, it dried on 1 hour hotplate at 120 degreeC and weighed, and calculated | required solid content, and it was 50 weight%.

(Preparation Example 17)

Preparation of base material for coating curable resin composition

The composition for the silica particle-containing hard coating layer prepared in Production Example 16 was used as a wire bar coater on a surface treated to facilitate adhesion of a single-sided adhesive easy polyethylene terephthalate film A4100 (manufactured by Toyo Boseki Co., Ltd., film thickness of 188 μm). The coating was carried out so as to have a thickness of 3 µm, and dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, ultraviolet rays were irradiated under light irradiation conditions of 0.9 J / cm ² using a high pressure mercury lamp under air to prepare a substrate for coating curable resin composition.

(Example 1)

As shown in Table 4 below, 395 g of a MIBK solution of the ethylenically unsaturated group-containing fluorine-containing polymer A-1 obtained in Production Example 2 (60 g as a solid content of component (A)) and dipentaerythritol pentaacrylate ( 25 g of SR399E, manufactured by Satomer Co., Ltd. (component (B)), 4.8 g of pentaerythritol tetraacrylate, 6.9 g of polyfunctional acrylate represented by the formula (11), and particles obtained mainly from silica obtained in Production Example 6 22.9 g of dispersion D-1 (8 g as a solid), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (irgacure 907, as a photoinitiator) 2 g of Ciba Specialty Chemicals), 5 g of α-butyl-ω- (3-propylhydroxy) -polydimethylsiloxane (manufactured by Chisso Corporation, trade name: Silaplane FM-0411), and 1622 g of MIBK It put into the glass separation flask with a stirrer, and stirred at room temperature for 1 hour, and obtained uniform curable resin composition. Among these, pentaerythritol tetraacrylate is derived from the pentaerythritol tetraacrylate mixed in the specific organic compound (S1) and the polyfunctional acrylate represented by General formula (11). Moreover, it was 5 weight% when solid content concentration was calculated | required by the method of manufacture example 2.

(Examples 2 to 26, Comparative Examples 1 to 6)

Each curable composition was obtained like Example 1 except having followed the composition of Table 4 and Table 5. The composition unit of a component in a table is a weight part.

(Evaluation Example 1)

Turbidity evaluation of cured film

A cured film was manufactured by the same method as used in Production Example 15. About the obtained cured film, turbidity was evaluated by the measuring method of the permeation | transmission type by the color haze meter SC-3H by the Suga Shikinki Corporation. The evaluation criteria are as follows. The results are shown in Table 4.

○: 0.39 or less

×: 0.40 or more

(Evaluation Example 2)

Refractive Index Measurement of Cured Film

Each curable resin composition was applied onto a silicon wafer by a spin coater so as to have a thickness of about 0.1 μm after drying, and then irradiated with ultraviolet rays under a light irradiation condition of 0.3 J / cm ² using a high pressure mercury lamp under nitrogen. Cured. The obtained cured film was measured for refractive index (n _D ²⁵ ) at a wavelength of 589 nm at 25 캜 using an ellipsometer. The results are shown in Table 4.

(Evaluation Example 3)

Appearance evaluation of antireflection film

Each curable resin composition was coated on the hard coating of the substrate obtained in Production Example 17 using a wire bar coater so as to have a thickness of 0.1 μm, and dried at 80 ° C. for 1 minute to form a coating film. Subsequently, ultraviolet rays were irradiated under a nitrogen stream under a light irradiation condition of 0.3 J / cm ² using a high pressure mercury lamp to prepare an antireflection film layer. The external appearance of the obtained antireflection film was visually evaluated. Evaluation criteria are as follows. The results are shown in Table 4.

○: no coating unevenness

△: slightly uneven coating

×: coating unevenness on the entire surface

(Evaluation Example 4)

Reflectivity Measurement of Anti-reflective Film

The back surface of the antireflection film obtained in Evaluation Example 1 was painted with black spray, and a spectroscopic reflectance measuring device (magnetic spectrophotometer U-3410, manufactured by Hitachi Seisakusho Co., Ltd., incorporating a large sample chamber integrating sphere accessory 150-09090) The reflectance was measured and evaluated from the microlens side in the wavelength range of 340 to 700 nm. Specifically, the reflectance (%) of the antireflection laminate (antireflection film) at each wavelength was measured based on the reflectance in the aluminum vapor deposition film (100%). The results are shown in Table 4.

(Evaluation Example 5)

Scratch Resistance Test of Anti-Reflective Film (Steel Wool Resistance Test)

The anti-reflective film obtained in the evaluation example 1 was attached to the steel wool (Bonstar No.0000, Nippon Steel Wool Co., Ltd.) to the academic type friction fastness tester (AB-301, Tester Sangyo Co., Ltd. product), The surface was repeatedly rubbed 10 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed by the following criteria. The results are shown in Table 4.

(Double-circle): Peeling of a cured film and a generation of a scratch are hardly seen.

(Circle): Fine scratches are seen in a cured film.

(Triangle | delta): A stripe-shaped flaw is seen in the whole cured film.

X: Peeling of a cured film occurs.

(Evaluation Example 6)

Antifouling property evaluation method of antireflection film

About 1 cm ² of the surface of the antireflection film obtained in Evaluation Example 1 was coated with a marking pen of the oil dye ink type (Zebra Co., Ltd. make, brand name) without a gap. After naturally drying for 3 minutes, the portion coated with the marker is wiped with a nonwoven fabric (Bencott S-2: trade name, manufactured by Asahi Kasei Co., Ltd.) (first time).

In addition, the same part was apply | coated with an oily marker, and it observed visually whether it was wiped off by how many wipings when 5 times of wiping was repeated similarly, and it evaluated by ranking according to the following criteria.

(Double-circle): It can be wiped off within 5 times and oily ink will not remain.

(Circle): It can be wiped off within 20 times and oily ink is not left.

(Triangle | delta): It can wipe off within 40 times, and oil-based ink does not remain.

×: Wiping is impossible.

On the other hand, even if the wiping was repeated 40 times or more in the first wiping, when the oil ink was not wiped (when x), the fifth wiping test was not performed.

The structural formula and number average molecular weight of the compound of component (C) shown by the brand name in Table 4 and Table 5 are shown below.

FM-0411: Tosso Co., Ltd., number average molecular weight: 1,000

[Wherein, f is a number such that the number average molecular weight becomes the above value. Below, same]

FM-0711: Tosso Co., Ltd., number average molecular weight: 1,000

FM-7711: Tosso Co., Ltd., number average molecular weight: 1,000

FM-0725: Tosso Co., Ltd., number average molecular weight: 10,000

FM-7725: Tosso Co., Ltd., number average molecular weight: 10,000

VPS1001: Azo-containing polydimethylsiloxane (4,4'-azobis (4-cyanovaleric acid) and α, ω-bis (3-aminopropyl) polydimethylsiloxane produced by Wako Pure Chemical Industries, Ltd. Polycondensates), number average molecular weight: 7-90,000, molecular weight of the polysiloxane moiety is about 10,000

From the result of Table 4 and Table 5, it turns out that the cured film obtained by hardening | curing the curable resin composition of the Example using the silicone compound containing the structure represented by the said Formula (I) is excellent in transparency.

Moreover, it turns out that the antireflection film manufactured from the composition of an Example is excellent in abrasion resistance and also excellent in antifouling property.

Curable resin composition of this invention is excellent in antifouling property, abrasion resistance, coating property, and durability, and is especially useful as an antireflection film.

Claims (9)

The radiation curable resin composition containing following component (A), (B), (C) and (D). (A) 2- (meth) acryloyloxyethyl isocyanate; 2- (meth) acryloyloxypropyl isocyanate; And diisocyanate selected from 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexyl isocyanate) and 1,3-bis (isocyanatemethyl) cyclohexane, and One or two or more ethylene selected from ethylenically unsaturated group-containing isocyanate compounds obtained by reacting a hydroxyl group-containing (meth) acrylate selected from hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate. A unsaturated unsaturated group-containing isocyanate compound, Hydroxyl-containing fluorine-containing polymer Ethylenically unsaturated group-containing fluorine-containing polymer obtained by reacting (B) As a (meth) acrylate monomer containing at least 1 or more (meth) acryloyl groups in a molecule | numerator, Acrylamide, (meth) acryloyl morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobor Neyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) Acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, N, N-dimethyl (meth) acrylamidetetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl ( Meth) acrylic , 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylic Rate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) Acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyl Triethylenediglycol (meth) acrylate, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, bis ( ( Bit) yloxymethyl-acryloyl) tricyclo [5.2.1.0 ^2,6] decane, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Rate tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tree (meth ) Acrylic, propylene oxide modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether both ends (meth ) Acrylic acid adduct, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pole Reester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate , Caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide modified bisphenol A di (meth) Acrylate, propylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide modified hydrogenated bisphenol A di (meth) acrylate, ethylene oxide modified Bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, and the following formula (11) Is said of one or more monomers selected from the group consisting of compounds, &Lt; Formula 11 >

[In Formula 11, "Acryl" represents an acryloyl group.] (C) a silicone compound comprising a structure represented by the following formula (I), <Formula I> -(O-SiR ³¹ R ³² ) _c- (CH ₂ ) _d -OR ³³ [Wherein, R ³¹ and R ³² are each independently an alkyl group having 1 to 3 carbon atoms, R ³³ is a monovalent organic group having a (meth) acryloyl group, and c has a number average molecular weight of 500 to 30,000 of the silicone compound. An integer of 1 or more within the range, and d is an integer of 1 to 4; (D) Particles containing silica with a number average particle diameter of 1-100 nm The radiation curable resin composition of Claim 1 whose number average molecular weights of said (C) silicone compound are 5,000 or more. The radiation curable resin composition of Claim 1 or 2 in which the silicone compound containing the structure represented by the said general formula (I) has a (meth) acryloyl group in the both ends. The radiation curable resin composition of Claim 1 or 2 in which the particle | grains containing the said (D) silica have a polymerizable unsaturated group. The radiation curable resin composition according to claim 1 or 2, which is for an antireflection film. The cured film obtained by hardening | curing the radiation curable resin composition of Claim 1 or 2. The antireflection film which has a low refractive index layer containing the cured film of Claim 6. delete delete