KR20080050335A - Curable resin composition and antireflection film - Google Patents

Abstract

A curable resin composition is provided to form a cured film having a low refraction index and excellent scratch resistance even under a low irradiation dose, and useful as a low-refraction index layer for an anti-reflective film. A curable resin composition comprises: (A) an ethylenically unsaturated group-containing fluoropolymer; (B) a (meth)acrylate compound; (C) silica particles having a number average particle diameter of 1-100 nm; and (D) a photopolymerization initiator represented by the following formula. In formula, each of R1, R2, R4 and R5 represents a C1-C4 alkyl group; and R3 is a C1-C4 alkylidene group or C2-C3 alkylene group.

Description

Curable Resin Composition and Anti-Reflection Film {CURABLE RESIN COMPOSITION AND ANTIREFLECTION FILM}

The present invention relates to a curable resin composition and an antireflection film.

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, abrasion resistance, coating property, and the durability which consisted of a cured film excellent in low refractive index, in order to prevent the reflection of external light, and to improve image quality. There is a need for an antireflection film including a refractive index layer.

In these display panels, the surface is often wiped off with a gauze impregnated with ethanol in order to remove fingerprints, dust, and the like, and thus scratch resistance is required.

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

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

Moreover, also about the obtained coating film, although it was excellent in weather resistance, there existed a problem of being scratch-resistant and lacking in durability.

Therefore, in order to solve the above problem, the isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition polymerizable unsaturated group and the hydroxyl group-containing fluorine-containing polymer are 0.01 to 1.0 The coating composition containing the unsaturated group containing fluorine-containing vinyl polymer obtained by making it react by the ratio was proposed (for example, following patent document 4).

However, the above publication does not use an isocyanate group-containing unsaturated compound in an amount sufficient to react all hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer when producing the unsaturated group-containing fluorine-containing vinyl polymer, and actively reacts the unreacted hydroxyl group in the polymer. It was to remain.

For this reason, although the coating composition containing this polymer enables hardening at low temperature and 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 by the said publication is not enough also about coating property and abrasion resistance.

Moreover, in order to improve the scratch resistance of an antireflection film, the technique of adding a silica particle to the low refractive index film which is the outermost layer of an antireflection film is used widely (for example, following patent documents 5 and 6). However, in most cases, since one type of silica particles having a relatively uniform particle size is used, the filling rate of the particles cannot be increased and sufficient scratch resistance cannot be obtained.

In addition, a low refractive index film material having a lower refractive index than in the prior art is desired in order to provide a lower antireflection film. Therefore, the technique using the particle | grains which have a space | gap inside a particle | grains, such as porous particle | grains and hollow particle | grains (henceforth collectively called a "hollow particle") is known using the point that the refractive index of air is lower than resin components, such as acrylic. (For example, following patent documents 7-9).

However, the use of hollow particles has the drawback that the scratch resistance of the cured film is lowered compared to the particles (solid particles) having no such voids.

In addition, various types of radiation curable materials have been proposed in view of high productivity and curing at room temperature. However, in the conventional radiation curable resin composition, sufficient scratch resistance was not obtained with a low irradiation light amount of 0.2 J / cm ² or less.

[Patent Document 1] Japanese Unexamined Patent Publication No. 57-34107

[Patent Document 2] Japanese Unexamined Patent Publication No. 59-189108

[Patent Document 3] Japanese Unexamined Patent Publication No. 60-67518

[Patent Document 4] Japanese Unexamined Patent Publication No. 61-296073

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

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

[Patent Document 7] Japanese Unexamined Patent Publication No. 2003-139906

[Patent Document 8] Japanese Unexamined Patent Publication No. 2002-317152

[Patent Document 9] Japanese Unexamined Patent Publication No. 10-142402

Therefore, an object of this invention is to provide the antireflection film which has a low refractive index layer containing the curable resin composition which provides the cured film which is low in refractive index and excellent in abrasion resistance even if it is a low irradiation light quantity.

In order to achieve the above object, the present inventors earnestly researched and cured resin which added the photoinitiator which has a specific structure to the particle | grains which have an ethylenically unsaturated group containing fluorine-containing polymer, a (meth) acrylate compound, and a silica as a main component. The present invention has been found to provide a cured film having excellent scratch resistance even when the composition is cured with a low irradiation light amount.

According to the present invention, the following curable resin compositions and antireflection films are provided.

1. Curable resin composition containing following component (A)-(D).

(A) Ethylenic unsaturated group containing fluorine-containing polymer

(B) (meth) acrylate compound

(C) Silica particles having a number average particle diameter of 1 to 100 nm

(D) photoinitiator which has a structure represented by following General formula (d-1)

<Formula d-1>

In formula d-1, R <^1> , R <^2> , R <^4> and R <^5> represent a C1-C4 alkyl group each independently, R <^3> is a C1-C4 alkylidene group or C2-C3 alkylene Flag]

2. Said (B) curable resin composition as described in said 1 in which (meth) acrylate compound contains at least 2 or more (meth) acryloyl group in a molecule | numerator.

3. Curable resin composition as described in said 1 or 2 in which the said (B) (meth) acrylate compound contains a fluorine atom in a molecule | numerator.

4. Curable resin composition in any one of said 1-3 whose said (C) silica particle is 1 or more types chosen from hollow particle, porous particle, and solid particle.

5. Curable resin composition in any one of said 1-4 in which the said (C) silica particle is surface-treated with the organic compound containing a polymerizable unsaturated group.

6. Furthermore, curable resin composition in any one of said 1-5 containing (E) surface modifier.

7. Curable resin composition in any one of said 1-6 which is for antireflection films.

8. Cured film obtained by hardening | curing curable resin composition in any one of said 1-6.

9. Antireflection film which has low refractive index layer containing cured film of 8 above.

According to this invention, curable resin composition which provides the cured film which has a low refractive index while having excellent scratch resistance, even if it hardens | cures with low irradiation light quantity is obtained.

Moreover, according to this invention, the antireflection film which has the low refractive index layer containing the said cured film, and has the outstanding scratch resistance is obtained.

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

1. Curable Resin Composition

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) Silica particles having a number average particle diameter of 1 to 100 nm

(D) a photoinitiator having a structure represented by the formula d-1

(E) surface modifiers

(F) organic solvent

(G) other additives

In the composition of this invention, sufficient hardenability is obtained even if it hardens | cures with the low irradiation light quantity of 0.2 J / cm <^2> or less by using the photoinitiator which has a specific structure of (D) component.

In addition, by using the particles having a porous or hollow structure as the (C) silica particles, a lower reflectance can be obtained.

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 the side chain hydroxyl group modified by the (meth) acrylic-type compound. Moreover, it is preferable to modify | denature by the (meth) acrylic-type compound which has an isocyanate group. By such modification, 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 a compound containing at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer.

(1) Compounds containing at least one ethylenically unsaturated group

The compound containing at least one ethylenically unsaturated group is not particularly limited as long as it is a compound containing at least one ethylenically unsaturated group in its molecule and has a functional group capable of reacting with a hydroxyl group of the fluoropolymer.

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 such a compound, (meth) acrylic acid, (meth) acryloyl chloride, (meth) acrylic anhydride, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1 Single or single or 2 or more types of-(bisacryloyloxymethyl) ethyl isocyanate is mentioned.

On the other hand, as a commercial item of the (meth) acrylate which has an isocyanate group, the brand name Kalens MOI, AOI, BEI etc. made by Showa Denko Corporation are mentioned, for example.

Moreover, such a compound can also be synthesize | combined by making a diisocyanate and hydroxyl-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-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 Kayarrad DPHA, PET-30, Toagosei (manufactured by Nippon Kayaku Co., Ltd.) Note) It can obtain as brand names Aronix M-215, M-233, M-305, M-400, etc. of manufacture.

(2) hydroxyl-containing fluorine-containing polymer

The hydroxyl group-containing fluorine-containing polymer preferably comprises 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 group represented by a fluorine atom, a fluoroalkyl group, or -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 -OCOR ⁵ (R ⁵ represents an alkyl group or glycidyl group, x is 0 or 1 Represents a number, 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; Alkylperfluorovinylether or alkoxyalkylperfluorovinylethers; 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 these in combination.

On the other hand, the content rate of the structural unit (a) is preferably 20 to 70 mol% when the total amount of the structural units (a) to (c) in the hydroxyl group-containing fluorine-containing polymer is 100 mol%. The reason for this is that when 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, as intended by the present invention. On the other hand, when the content is more than 70 mol%, hydroxyl group-containing This is because the solubility in an organic solvent of a fluoropolymer, transparency, or adhesiveness to a base material 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% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(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 the structural unit (b) is preferably 10 to 70 mol% when the total amount of the structural units (a) to (c) in the hydroxyl group-containing fluorine-containing polymer is 100 mol%. This is because the solubility in the organic solvent of a hydroxyl-containing fluorine-containing polymer may fall when content rate is less than 10 mol%, On the other hand, when content rate exceeds 70 mol%, transparency of a hydroxyl-containing fluoropolymer and It is because optical characteristics, such as low reflectivity, may fall.

For this reason, the content of the structural unit (b) is more preferably 20 to 60 mol%, more preferably 30 to 60 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(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 vinyl ethers such as hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, and allyl Alcohol etc. are mentioned.

In addition, as hydroxyl group containing vinyl monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and caprolactone (meth) acryl Elate, polypropylene glycol (meth) acrylate, etc. can be used.

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

For this reason, the content rate of the structural unit (c) is more preferably 5 to 40 mol%, more preferably 5 to 30 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(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), examples of the alkyl group represented by R ⁸ or R ⁹ include an alkyl group having 1 to 3 carbon atoms such as methyl group, ethyl group, and propyl group, and a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, and purple as a halogenated alkyl group. A phenyl group, a benzyl group, a naphthyl group, etc. are mentioned, respectively, as a C1-C4 fluoroalkyl groups, such as a fluorobutyl group, and an aryl 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 formulas (5) and (6), examples of the alkyl group of R ¹⁰ to R ¹³ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group and cyclohexyl group, and methyl group as R ¹⁴ to R ¹⁷ alkyl group. And alkyl groups having 1 to 3 carbon atoms such as ethyl group and propyl group.

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 that of Formula 5]

On the other hand, the content rate of the structural unit (d) is preferably 0.1 to 10 mol% when the total amount of the structural units (a) to (c) in the hydroxyl group-containing fluorine-containing polymer is 100 mol%. The reason for this is that when the content is less than 0.1 mol%, the surface slip resistance of the coating film after curing may decrease, and the scratch resistance of the coating film may decrease. On the other hand, when the content is more than 10 mol%, the hydroxyl group-containing fluorine-containing polymer This is because, when used as a coating material, the transparency of the resin is poor, and craters tend to be generated during coating.

For this reason, the content of the structural unit (d) is more preferably 0.1 to 5 mol%, more preferably 0.1 to 3 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer. 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), a group having an emulsifying action of R ¹⁸ is preferably a group having both a hydrophobic group and a hydrophilic group and a hydrophilic group having 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, the content rate of the structural unit (f) is preferably 0.1 to 5 mol% when the total amount of the structural units (a) to (c) in the hydroxyl group-containing fluorine-containing polymer is 100 mol%. The reason is that when the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluorine-containing polymer in the solvent is improved, while when the content is within 5 mol%, the adhesiveness of the curable resin composition does not increase excessively, and handling becomes easy. It is because moisture resistance does not fall even if it uses for a coating material.

For this reason, the content rate of the structural unit (f) is more preferably 0.1 to 3 mol%, more preferably 0.2 to 3 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(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, measured by gel permeation chromatography using tetrahydrofuran as a solvent. If the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluorine-containing polymer may be lowered. On the other hand, if the number average molecular weight is more than 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.

Although it does not restrict | limit especially about the addition amount of (A) component, It is 1-80 weight% normally 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 1% by weight, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antifouling effect may not be obtained. On the other hand, when the addition amount exceeds 80% by weight, curing of the curable resin composition This is because the scratch resistance of the coating film may not be obtained.

Moreover, for this reason, it is more preferable to make the addition amount of (A) component into 1 to 70 weight%, and it is still more preferable to set it as the value within the range of 5 to 60 weight%.

(B) (meth) acrylate compound

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

Although it will not restrict | limit especially if it is a compound containing 1 or more (meth) acryloyl group in a molecule | numerator as a (meth) acrylate compound, It is preferable that it is a compound which has 2 or more (meth) acryloyl group.

As a compound which has one (meth) acryloyl group, for example, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclo decanyl (meth) acrylate, and dicyclopentanyl (meth) acryl Latex, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinyl Pyridine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylic Late, isoamyl (meth) ah Relate, hexyl (meth) acrylate, heptyl (meth) arc relate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate , Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol (meth) acrylate, ethoxy ethyl (meth) acrylate, methoxy polyethylene glycol (meth) Acrylate, methoxy polypropylene glycol (meth) acrylate, etc. are mentioned. As these commercial items, Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, Toagosei Co., Ltd. product); Biscotti LA, STA, IBXA, 2-MTA, # 192, # 193 (manufactured by Osaka Yuki Chemical Co., Ltd.); NK ester AMP-10G, AMP-20G, AMP-60G (above, Shin-Nakamura Chemical Co., Ltd. make); Light acrylates L-A, S-A, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (above, manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (above, Hitachi Kasei Kogyo Co., Ltd. product) etc. are mentioned.

Examples of the compound having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, and tetraethylene glycol di (meth). ) Acrylate, tricyclodecanediyldimethylene di (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, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as "EO") modification Trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as "PO") modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neophene Glycol di (meth) acrylate, both terminal (meth) acrylic acid adducts of bisphenol A diglycidyl ether, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, di Trimethylolpropane tetra (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified hydrogenated bis Examples of phenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, and (meth) acrylates of phenol novolac polyglycidyl ether can do. Examples of commercially available products of these polyfunctional monomers include SA1002 (above, manufactured by Mitsubishi Chemical Corporation), Biscot 195, Biscot 230, Biscot 260, Biscot 215, Biscot 310, Biscot 214HP, Bis Coat 295, Biscuit 300, Biscuit 360, Biscuit GPT, Biscuit 400, Biscuit 700, Biscuit 540, Biscuit 3000, Biscuit 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, Doa Kosei Co., Ltd.) Manufacture), light acrylates BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (above, Kyoeisha Kagaku Co., Ltd., New Frontier BPE-4, BR-42M, GX-8345 (above, Dai-ichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, Shinnitetsu Kagaku 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 ( As above, Shin-Nakamura Kagaku Kogyo Co., Ltd.) etc. are mentioned.

On the other hand, the composition containing 3 or more (meth) acryloyl groups in a molecule is more preferable in the composition of this invention. Examples of the compound having three or more (meth) acryloyl groups include the tri (meth) acrylate compound, tetra (meth) acrylate compound, penta (meth) acrylate compound, and hexa (meth) acrylate compound exemplified above. Etc., among these, pentaerythritol hydroxytriacrylate and trimethylolpropane triacrylate are particularly preferable. The said compound can be used individually by 1 type or in combination of 2 or more types, respectively.

Moreover, it is preferable that these (meth) acrylate compounds contain fluorine. By containing a fluorine atom, the cured film of a lower refractive index is obtained. Examples of such compounds include perfluoro-1,6-hexanediol di (meth) acrylate, octafluorooctane-1,6-di (meth) acrylate, octafluorooctanediol and 2- (meth) Acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, adduct with 1,1- (bisacryloyloxymethyl) ethyl isocyanate, triacryloylheptadecafluorononenylpentaeryte 1 type single, or 2 or more types of combinations, such as a lititol, are mentioned.

Although it does not restrict | limit especially about the addition amount of (B) component, It is 5 to 70 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 curable resin composition may not be obtained when the addition amount is less than 5% by weight. On the other hand, when the addition amount exceeds 70% by weight, the refractive index of the cured coating film of the curable resin composition is increased. This is because 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 10 to 60 weight%, and it is still more preferable to set it as the value within 15 to 50 weight% range.

(C) silica particles

(1) silica particles

In the composition of the present invention, silica particles (C) having a number average particle diameter of 1 to 100 nm are blended. The particle diameter of a silica particle is measured by a transmission electron microscope.

By mix | blending a silica particle (C), low refractive index and abrasion resistance can be expressed in the cured film which hardens the composition of this invention.

Moreover, it can also mix | blend the silica particle (C) from which a number average particle diameter differs.

As these silica particles, well-known ones can be used. If the shape is spherical, the silica particles are not limited to ordinary colloidal silica, and hollow particles, porous particles, core shell particles, solid particles, and the like may also be used. However, hollow particles or porous particles are preferable in terms of reducing the refractive index of the composition. Moreover, it is not limited to spherical form, Amorphous particle may be sufficient.

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 silica as a main component, it is a solid 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- As 50, ST-OL and a hollow colloidal silica, brand name: JX1008SIV, JX1009SIV, JX1012SIV etc. by Shokubai Kasei Kogyo Co., Ltd. are mentioned.

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 at least one alkyl group, 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 compound having at least one reactive group in the molecule, for example, a reactive group as having an NH _2, elements trimethoxysilane, N- (2- aminoethyl) -3-aminopropyltrimethoxysilane, etc. And 3-thiocyanate propyl as having a thiocyanate group such as 3-isocyanate propyltrimethoxysilane as having an isocyanate group such as bis (2-hydroxyethyl) -3 aminotripropylmethoxysilane as having an OH group 3-mercaptopropyl as having a thiol group, such as (3-glycidoxypropyl) trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as having an epoxy group, such as trimethoxysilane Trimethoxysilane etc. are mentioned. As a preferable compound, 3-mercaptopropyl trimethoxysilane is mentioned.

It is preferable that a silica particle (C) is surface-treated with the organic compound (Hereinafter, a "specific organic compound" may be called.) 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

Particular organic compounds used in the present invention are polymerizable compounds containing a polymerizable unsaturated group in a molecule. It is preferable that the said compound is a compound containing the group further represented by following formula (11) 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 11, X represents NH, O (oxygen atom) or S (sulfur atom), and 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, maleate A group and an acrylamide group are mentioned as a preferable example.

The said polymerizable unsaturated group is a structural unit which performs addition polymerization with active radical species.

(ii) a group represented by formula (11)

It is preferable that a specific organic compound further contains the group represented by the said Formula (11) in a molecule | numerator. The group [-XC (= Y) -NH-] represented by the formula (11) is specifically [-OC (= O) -NH-], [-OC (= S) -NH-], [-SC] (= O) -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-], and [-SC (= S) -NH-]. 6 species. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, in view of thermal stability, at least one of [-OC (= O) -NH-] group, [-OC (= S) -NH-] group and [-SC (= O) -NH-] group is used in combination. It is preferable.

The group [-XC (= Y) -NH-] represented by the above formula (11) generates moderate cohesive force by hydrogen bonding between molecules, and when it is a cured film, excellent mechanical strength, adhesion to a substrate and heat resistance, etc. It is thought to give characteristics.

(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 a "silanol group-containing compound") or a compound which 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, that is, The alkoxysilyl group containing compound or the aryloxysilyl group containing compound is preferable.

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

(iv) preferred embodiments

As a preferable specific example of a specific organic compound, the compound represented by following formula (12) 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.

Examples of the group represented by [(R ¹⁹ O) _a R ²⁰ _{3 - a} Si-] include trimethoxysilyl group, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmeth A oxysilyl group etc. are mentioned. 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 include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and further, a group represented by Formula 11 above. It may be.

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. Of these, acryloyl (oxy) groups and methacryloyl (oxy) groups are preferable. In addition, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

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) It can carry out by addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group containing polymerizable 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 represented by the said Formula (12), (a) of these methods is used preferably. More specifically, for example

(a) Method: First, by reacting a mercaptoalkoxysilane and a polyisocyanate compound, an intermediate containing an alkoxysilyl group, a [-SC (= 0) -NH-] group and an isocyanate group is formed in a molecule, and then an intermediate A method of reacting an active hydrogen-containing polymerizable unsaturated compound with an isocyanate remaining in the compound and bonding the unsaturated compound through a [-OC (= 0) -NH-] group,

Method (b): First, a polyisocyanate compound and an active hydrogen-containing polymerizable unsaturated compound are reacted to form an intermediate containing a polymerizable unsaturated group, a [-OC (= 0) -NH-] group and an isocyanate group in a molecule thereof. And a method in which the mercaptoalkoxysilane is reacted to bind the mercaptoalkoxysilane via the [-SC (= O) -NH-] group.

Etc. can be mentioned. Moreover, in both, the method (a) is preferable at the point which does not reduce the polymerizable unsaturated group by Michael addition reaction.

In the synthesis of the compound represented by the above formula (12), examples of the alkoxysilane capable of forming a [-SC (= O) -NH-] group by reaction with an isocyanate group include one alkoxysilyl group and a mercapto group in the molecule. The compound which has the above 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-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyane 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 an isocyanate group 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 Hydroxy-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, neopentylglycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) Acrylate, 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, and 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 performed in the presence of water in order to efficiently bond the silanol group generating site and the particles included in the specific organic compound. However, water may not be present when a specific organic compound has a silanol group. Therefore, it can surface-treat by the method containing the operation of mixing particle | grains and a specific organic compound at least.

The reaction amount of the particles and the specific organic compound is 100% by weight in total, preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 1% by weight or more. If it is less than 0.01 weight%, the dispersibility of the particle | grains in a composition will not be enough, and the transparency and the scratch resistance of the cured film obtained may become insufficient.

Hereinafter, the surface treatment method will be described in more detail by taking an alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (12) 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 the amount by which one or more of the alkoxy groups on the silicon in one molecule are 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 silicon, and more preferably at least one third and less than three times the number of moles of alkoxy groups. The product obtained by mixing an alkoxysilane compound and particle | grains on condition that water does not exist completely is a product which the alkoxysilane compound physically adsorbed on the particle surface, and has a high diameter 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 adding the said alkoxysilane compound to a hydrolysis operation separately, this is a method of mixing a powder dispersion or a 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. The temperature at the time of surface treatment 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. The treatment time is usually in the range of 5 minutes to 24 hours.

At the time of surface treatment, when using powdery powder, an organic solvent can be added for the purpose of making reaction with the said alkoxysilane compound smooth and uniform. 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 γ-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 is suitable for 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, an organic solvent which is homogeneously compatible with water can be added for the purpose of ensuring uniformity of the initial reaction and smoothly proceeding the reaction.

In addition, at the time 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 tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride, As a base, For example, ammonia water, diethylamine, triethylamine Primary, secondary or tertiary aliphatic amines such as dibutylamine and cyclohexylamine, aromatic amines such as pyridine, quaternary such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide Ammonium hydroxide, etc. are mentioned.

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 reduction% when the dry powder is completely burned in air normally, and can be calculated | required by thermogravimetric analysis from 110 degreeC to 800 degreeC in air.

The compounding quantity of (C) component is mix | blended 1-70 weight% normally with respect to composition whole quantity other than the organic solvent, 10-65 weight% is preferable, and its 20-60 weight% is more preferable.

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 dispersion medium.

(D) photoinitiator which has a structure represented by general formula (d-1)

The component (D) used for the composition of this invention is a component used in order to harden the composition of this invention with active energy rays, such as an ultraviolet-ray. On the other hand, an active energy ray is defined as an energy ray which can generate | occur | produce an active species by decomposing the compound (photoinitiator) which generate | occur | produces an active species. Examples of such active energy rays include visible energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, and γ rays. However, since it has a constant energy level, the curing speed is fast, and the irradiation apparatus is relatively inexpensive and compact, it is preferable to use ultraviolet rays.

The photoinitiator of (D) component used for the composition of this invention has a structure represented by following General formula (d-1).

<Formula d-1>

In formula d-1, R <^1> , R <^2> , R <^4> and R <^5> represent a C1-C4 alkyl group each independently, R <^3> is a C1-C4 alkylidene group or C2-C3 alkylene Flag]

Since the compound represented by the said general formula (d-1) has two (alpha)-hydroxy ketone groups, it is highly sensitive, and even the low irradiation light quantity can harden the composition of this invention effectively, and the scratch resistance of the cured film obtained can be improved.

The molecular weight of the photopolymerization initiator (hereinafter referred to as photopolymerization initiator (d-1)) having a structure represented by the formula (d-1) is preferably in the range of 340 to 430, and more preferably in the range of 340 to 400.

Specific examples of the photopolymerization initiator (d-1) include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane- 1-one etc. are mentioned, As a commercial item which can be used as a photoinitiator (d-1), Irgacure 127 (made by Ciba Specialty Chemicals company) etc. which are represented by following General formula (d-1a) etc. are mentioned, for example. .

<Formula d-1a>

The addition amount of (D) component is 0.1-20 weight% normally with respect to the composition whole quantity except the organic solvent. This is because when the addition amount is less than 0.1% by weight, curing failure may be caused. On the other hand, when the addition amount is more than 20% by weight, the excessive amount of components may cause a decrease in the coating film strength.

Moreover, for this reason, it is more preferable to make the addition amount of (D) component into 0.5-10 weight%, and it is still more preferable to set it as the value within the range of 0.5-8 weight%.

(E) surface modifiers

In order to improve the surface slip property, antifouling property, etc. of the cured film obtained, a surface modifier can be added to the composition of this invention as (E) component. As the surface modifier (E), it is preferable to use at least one compound selected from the group consisting of a compound (E-1) having a polydimethylsiloxane skeleton and a fluorine-based surface modifier (E-2).

(E-1) Compound Having Polydimethylsiloxane Skeleton

The compound having a polydimethylsiloxane skeleton has the effect of improving the surface slip resistance and improving the scratch resistance of the cured coating film, and can impart antifouling properties. It is preferable that the compound which has polydimethylsiloxane frame | skeleton further has reactive groups, such as a (meth) acryloyl group and a hydroxyl group. As these specific examples, Cilaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-DA11, FM-DA21 , FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso Co., Ltd.), UV3500, UV3510, UV3530 (manufactured by Big Chemi Japan Co., Ltd.), BY16-004, SF8428 (Toray Dow Corning Silicone Co., Ltd., VPS-1001 (made by Wako Pure Chemical Industries), etc. are mentioned.

The addition amount of (E-1) component is 0.01 to 20 weight% normally with respect to the composition whole quantity except the organic solvent. The reason is that if the addition amount is less than 0.01% by weight, the effect of improving slip properties cannot be sufficiently obtained. On the other hand, if the addition amount is more than 20% by weight, the excessive amount of components causes a decrease in coating film strength and deterioration of coating properties. to be.

Moreover, for this reason, it is more preferable to make the addition amount of (E-1) component into 0.1-10 weight%, and it is still more preferable to set it as the value within the range of 0.5-8 weight%.

(E-2) Fluorine Surface Modifier

The compound having a perfluoroalkyl group has the effect of improving the antifouling property by modifying the surface of the coating film, and also improves the coatability. It is preferable that the compound which has a perfluoroalkyl group further has a ring-opening condensate of ethylene oxide, and a hydrophilic / lipophilic group. As specific examples thereof, Megapack F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478, F479, F480SF, F482 And F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, and R90 (manufactured by Dainippon Ink Chemical Industries, Ltd.).

The addition amount of (E-2) component is 0.01 to 20 weight% normally with respect to the composition whole quantity except the organic solvent. The reason is that if the addition amount is less than 0.01% by weight, the effect of improving slip properties may not be sufficiently obtained. On the other hand, when the addition amount is more than 20% by weight, the excessive amount of components may cause a decrease in coating film strength and deterioration of coating properties. This is because there is concern.

Moreover, for this reason, it is more preferable to make the addition amount of (E-2) component into 0.1-10 weight%, and it is still more preferable to set it as the value within the range of 0.5-8 weight%.

(F) organic solvent

The composition of this invention can contain an organic solvent. The antireflection film of a thin film can be formed uniformly by adding the organic solvent and adjusting the density | concentration of curable resin composition. Specific examples of the organic solvent include ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. , One kind alone or two kinds, such as alcohols such as methanol, ethanol, sec-butanol, t-butanol, 2-propanol, isopropanol, aromatics such as benzene, toluene and chlorobenzene, and aliphatic such as hexane and cyclohexane The above combination is mentioned. Among these, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol, Alcohols, such as ethanol, sec-butanol, t-butanol, 2-propanol, isopropanol, are preferable, More preferably, they are single 1 type or a combination of 2 or more types of methyl isobutyl ketone, methyl amyl ketone, and t-butanol.

Although it does not restrict | limit especially 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 solid content. The reason for this is that when the addition amount is less than 100 parts by weight, it may be difficult to adjust the viscosity of the curable resin composition. On the other hand, when the addition amount exceeds 100,000 parts by weight, the storage stability of the curable resin composition is lowered or the viscosity is too low to handle. This may be difficult.

(G) additive

In the composition of the present invention, inorganic particles other than silica particles, photopolymerization initiators other than the photopolymerization initiator (d-1), photosensitizers, thermal polymerization initiators, polymerization inhibitors, and polymerization, within a range that does not impair the objects and effects of the present invention. It is also preferable to further contain additives such as starting aids, leveling agents, wettability improving agents, surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, pigments, dyes, slip agents.

In particular, the inorganic particles are effective to improve the strength of the coating film, and when added, it is preferable that the number average particle diameter is in the range of 1 to 100 nm, and spherical, beads, and amorphous particles can be used, and voids are formed in the internal structure. The porous and hollow particles which may be used can also be used. As an inorganic particle which can be used, an inorganic oxide or a fluoride is preferable, For example, alumina, titania, zirconia, magnesium fluoride, etc. are mentioned. In addition, the surface of these inorganic particles may be surface-modified with an arbitrary organic group, and by modifying with a (meth) acryl group, compatibility with the curable resin composition is improved, and it becomes possible to co-crosslink with other curable compositions at the time of curing, It is possible to improve the scratch resistance of the cured film.

As an example of photoinitiators other than a component (D), for example, acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carboxe Bazole, xanthone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydioxybenzoin, 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-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4' -Tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl ) Phenyl] -2-phenylmethyl) -1-butanone, 4-benzoyl-4'-methyldiphenylsulfide, benzyl, or BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, other pigment sensitization Combination with an agent, etc. are mentioned.

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- (mor Polyyl) 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.

As a commercial item of the said photoinitiator, Irgacure 369 (Ciba Specialty Chemicals make, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1), Irgacure, for example 907 (made by Ciba Specialty Chemicals, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) is preferable.

A thermal polymerization initiator is a compound which generate | occur | produces an active species by heat, and a thermal radical generator etc. which generate a radical as an active species are mentioned. 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.

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

Curable resin composition of this invention can be manufactured by adding (E)-(G) component, respectively, according to said (A)-(D) and a situation, and mixing on room temperature or 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 the hardening conditions of the composition of this invention, For example, when using an active energy ray, it is preferable to make the irradiation light quantity into the value within 0.01-10 J / cm <^2> .

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

On the other hand, when the photoinitiator of general formula g-1 of component (G) is mix | blended with the composition of this invention, the cured film which has the outstanding scratch resistance also can be obtained even with the low irradiation light quantity of 0.2 J / cm <^2> or less. Therefore, the low irradiation light amount can be selected in consideration of the irradiation time and the production efficiency.

In addition, the composition of the present invention may be further cured by heating, and in this case, it is preferable to heat 0.5 to 180 minutes at a temperature within the range of 30 to 200 ° C. By heating in this way, an antireflection film excellent in scratch resistance can be obtained more efficiently without damaging the substrate or the like.

Further, for this reason, it is more preferable to heat 0.5 to 120 minutes at a temperature in the range of 50 to 180 ° C, and even more preferably 1 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, the cross section of such an antireflection film is shown. As shown in FIG. 1, the hard coat layer 3 and the low refractive index layer 4 are laminated | stacked on the base material 2. As shown in FIG.

At this time, a high refractive index layer may be formed directly on the substrate 2 instead of the hard coating layer 3. In addition, a high refractive index layer 5 may be provided between the hard coating layer 3 and the low refractive index layer 4 (FIG. 2). In addition, the middle refractive index layer 6 may be provided between the hard coating layer 3 and the high refractive index layer 5 (FIG. 3).

(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 etc. of curable resin composition 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 of this invention, ie, the refractive index of a low refractive index film, shall be 1.50 or less. The reason is that when the refractive index of the low refractive index film exceeds 1.50, the antireflection effect may be significantly reduced. Therefore, the refractive index of the low refractive index film is more preferably 1.48 or less, and even more preferably 1.45 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. Therefore, the refractive index of the other low-refractive index films may be a value exceeding 1.50.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 200 nm. The reason is that when the thickness of the low refractive index layer is less than 50 nm, the antireflection effect may not be sufficiently obtained. On the other hand, when the thickness exceeds 200 nm, optical interference may occur and the antireflection effect may be lowered. Because.

Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and more preferably 70 to 150 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 remarkably.

However, in general, 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. Moreover, although thermosetting, ultraviolet curing, and electron beam hardening can be used as hardening form, Among these, the ultraviolet curable composition with favorable productivity is used.

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 for this 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 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, and more preferably 60 to 500 nm.

In order to obtain higher antireflection, when a plurality of high refractive index layers are provided to form a multilayer structure, the total of the thicknesses of the plurality of high refractive index layers may be set to 50 to 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

It does not restrict | limit especially about the structural material of the hard coat layer used for the antireflection film of this 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.

In addition, the thickness of the hard coat layer is not particularly limited, but is preferably 1 to 100 m, more preferably 3 to 30 m. The reason is that when the thickness of the hard coating layer is less than 1 μm, the hardness as a hard coating may decrease. On the other hand, when the thickness exceeds 100 μm, the substrate may be deformed by hardening shrinkage of the hard coating. to be.

(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 anti-reflection film containing these base materials, excellent anti-reflection effects can be obtained in the field of use of a wide range of anti-reflection 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. have.

<Example>

Hereinafter, although an Example is given and this invention is demonstrated in detail, the scope of the present invention is not limited to description of these Examples. "Parts" and "%" mean "parts by weight" and "% by weight" unless otherwise specified.

(Manufacture 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 , 1.00 g of lauroyl peroxide, 6.0 g of an 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. Thereafter, 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 to stop the reaction. After reaching room temperature, the unreacted monomer was discharged and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. 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. Table 1 shows the dosages of the used monomers and solvents.

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 quantity NMR analysis result, elemental analysis result, and fluorine content of ¹ H-NMR and ¹³ C-NMR. The results are shown in Table 2.

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)

(Manufacture 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 ketone (MIBK) were added and stirred until the hydroxyl group-containing fluorine-containing polymer 1 was dissolved in the MIBK at 20 ° C. and the solution became transparent and uniform.

Subsequently, 15.1 g of 2-methacryloyloxyethyl isocyanate is added to this system, and it is stirred until the solution becomes uniform, and then 0.1 g of dibutyltin dilaurate is added to start the reaction, and the temperature of the system is 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 15.0 weight%. Table 3 shows the compound, solvent and solid content used.

(Manufacture example 3)

Preparation of Composition for Hard Coating Layer

95 parts by weight of pentaerythritol hydroxytriacrylate, 5 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one in a container shielded from ultraviolet rays, MIBK The composition for hard-coat layers of a uniform solution was obtained by stirring 100 weight part at 50 degreeC for 2 hours. After weighing 2 g of this composition in the aluminum dish, it dried on 1 hour hotplate at 120 degreeC, weighed, and calculated | required solid content, and it was 50 weight%.

(Manufacture example 4)

Preparation of base material for coating curable resin composition

The TAC film (50 micrometers in thickness) was apply | coated so that the composition for hard-coat layers manufactured by the manufacture example 3 might be set to 6 micrometers in film thickness with a wire bar coater, and it dried in 80 degreeC for 1 minute in oven, and formed the coating film. Subsequently, under air, ultraviolet rays were irradiated under a light irradiation condition of 300 mJ / cm ² using a high pressure mercury lamp to prepare a substrate for coating curable resin composition.

(Manufacture example 5)

Preparation of Specific Organic Compounds (S1)

In dry air, it dripped at 50 degreeC over 1 hour, stirring 60.0 parts of isophorone diisocyanate with respect to the solution containing 23.0 parts of mercaptopropyl trimethoxysilane and 0.5 part of dibutyltin dilaurate, and then at 70 degreeC Stir 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 Industries. Of 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 specific organic compound (S1) was obtained by heat-stirring at 60 degreeC for 3 hours.

The infrared absorption spectrum of the product is that the absorption peak of 2550 cm ^-1 characteristic of the mercapto group in the raw material and the absorption peak of 2260 cm ^-1 characteristic of the isocyanate group are lost, and the [-OC (= 0) -NH-] group and A peak of 1660 cm ⁻¹ characteristic to the carbonyl and a 1720 cm ⁻¹ characteristic characteristic to the acryloyl group in the [-SC (= O) -NH-] group were observed to form acryloyl group as the polymerizable unsaturated group. It showed that the specific organic compound which has [-SC (= O) -NH-] group and [-OC (= O) -NH-] group together was produced.

(Manufacture example 6)

Preparation of Acrylic Modified Hollow Silica Particles C-2 ((C) Component)

3 parts of the specific organic compound (S1) synthesized in Production Example 5, 137 parts (C-1) of hollow silica particles (C-1) which are JX1009SIV manufactured by Shokubai Kasei Kogyo Co., Ltd., 0.1 parts of ion-exchanged water, 0.05 mol / L Particle dispersion C-2 was obtained using 0.01 part of dilute sulfuric acid and 1.4 part of ortho formic acid methyl esters. It was 25 weight% when the solid content of C-2 was calculated | required.

The average particle diameter of this silica particle was 50 nm. Here, the average particle diameter was measured by the transmission electron microscope.

(Manufacture example 7)

Preparation of Acrylic Modified Solid Silica Particles C-3 ((C) Component)

9 parts of specific organic compound (S1) synthesized in Production Example 5, 137 parts (44 parts solid) of MEK-ST manufactured by Nissan Chemical Industries, 0.1 part of ion-exchanged water, 0.01 part of dilute sulfuric acid of 0.05 mol / L, methyl orthoformate methyl ester Particle dispersion C-3 was obtained using 1.4 parts. It was 35 weight% when the solid content of C-3 was calculated | required.

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

(Example 1)

As shown in Table 4, 67 g of the MIBK solution of the ethylenically unsaturated group-containing fluorine-containing polymer A-1 obtained in Production Example 2 (10 g as a solid content of component (A)) and pentaerythritol hydroxytriacrylate ( 29 g of PET-30, Nippon Kayaku Co., Ltd. (B component), and 259 g (57 g of solid content of (C) component) of hollow silica particle (C-1) which is JX1009SIV by Shokubai Kasei Kogyo Co., Ltd., 2 -Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1-one (irgacure 127, Ciba Specialty Chemical) 3 g, (D) component), 1 g and MIBK 869 g, and propylene glycol monomethyl ether acetate (1629 g) of Cilaplane FM-0725 (trade name, manufactured by Chisso), were attached with a stirrer. It put in the glass separating flask which made it, and stirred at room temperature for 1 hour, and obtained uniform curable resin composition. Moreover, it was 3.5 weight% when solid content concentration was calculated | required by the method of manufacture example 2.

(Examples 2 to 7 and Comparative Examples 1 to 6)

Except having set it as the composition shown in Table 4 and Table 5, it carried out similarly to Example 1, and obtained curable resin composition, respectively.

(Evaluation Example 1)

Evaluation of appearance

Each curable resin composition obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was coated using a wire bar coater so as to have a film thickness of 0.1 μm on the hard coating of the substrate for coating the curable resin composition obtained in Production Example 4, It dried at 80 degreeC for 1 minute, and formed the coating film. Subsequently, under an airflow of nitrogen, ultraviolet rays were irradiated with an irradiation light amount (mJ / cm ² ) shown in Tables 4 and 5 using a high-pressure mercury lamp to prepare an antireflection film. The external appearance of the obtained antireflection film was visually evaluated. Evaluation criteria are as follows. The results are shown in Tables 4 and 5.

○: no coating unevenness

△: slightly uneven coating

×: coating unevenness on the entire surface

(Evaluation Example 2)

Haze

About the antireflection film obtained in the evaluation example 1, haze was measured and evaluated by the color haze meter. Evaluation criteria are as follows. The results are shown in Tables 4 and 5.

○: 0.3% or less haze

Δ: more than 0.3% of haze and 1.0% or less

X: more than 1.0% of haze

(Evaluation Example 3)

Refractive Index of Cured Film

Each curable resin composition was coated on a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and then irradiated with ultraviolet light under a light irradiation condition of 0.3 J / cm ² using a high pressure mercury lamp under nitrogen to cure. I was. The obtained cured film using the ellipsometer to measure the refractive index (n _D ²⁵⁾ at a wavelength of 589 ㎚ at 25 ℃. The results are shown in Tables 4 and 5.

(Evaluation Example 4)

Reflectivity of Anti-Reflection Film

The back surface of the antireflection film obtained in Evaluation Example 1 was painted with a 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) By measuring, the reflectance was measured and evaluated from the substrate side in the wavelength range of 340-700 nm. Specifically, the reflectance of the antireflective laminate (antireflection film) at each wavelength is measured with the reflectance in the aluminum vapor deposition film as a reference (100%), and among them, the antireflection property is determined from the reflectance of light at a wavelength of 550 nm. Was evaluated based on the following criteria. The results are shown in Tables 4 and 5.

◎: reflectance is 1.5% or less

○: reflectance is greater than 1.5% and 3.0% or less

(Triangle | delta): Reflectance is more than 3.0% and 4.0% or less

X: reflectance exceeds 4.0%

(Evaluation Example 5)

Scratch Resistance (Steel Wool Resistance Test)

Steel wool (Bonstar No. 0000, Nippon Steel Wool Co., Ltd.) was attached to the cured film obtained in Evaluation Example 1 to a Hakjin type friction fastness tester (AB-301, Tester Sangyo Co., Ltd.), and the surface of the cured film was Ten times was rubbed under conditions 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. Evaluation criteria are as follows. The results are shown in Tables 4 and 5.

(Double-circle): Scratches do not arise in a cured film.

(Circle): Peeling and a flaw generation of a cured film are hardly seen, or a fine flaw is 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)

Pollution resistance

Fingerprints were affixed to the antireflection film obtained in Evaluation Example 1, and the coating film surface was wiped off with a nonwoven fabric (Asahi Kasei Co., Ltd. make, brand name: Bencoat S-2). The stain resistance was evaluated by the following criteria. The results are shown in Tables 4 and 5.

○: The fingerprint on the surface of the coating film is completely wiped off.

X: The fingerprint mark remained on the sample surface without wiping.

From the result of Table 4 and Table 5, it turns out that in the Example containing (D) component, even if the irradiation light quantity is low as 100 mJ / cm <^2> , it is excellent in scratch resistance. On the other hand, in the composition of the comparative example which does not contain (D) component, even if it hardens | cures with the irradiation light quantity of 300 mJ / cm <^2> , it turns out that scratch resistance is inadequate.

The components in Table 4 and Table 5 are as follows.

Fluorine acrylate: triacryloylheptadecafluorononenyl pentaerythritol, manufactured by Kyoeisha

Pentaerythritol hydroxyacrylate: PET-30, manufactured by Nippon Kayaku

Acryloyl morpholine: ACMO, Kouzin manufacture

Irgacure 127: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1-one, Ciba Specialty Chemicals manufacturing

Irgacure 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone manufactured by Ciba Specialty Chemicals

Irgacure 907: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one manufactured by Ciba Specialty Chemicals

Acrylic-Modified Polydimethylsiloxane: Cyraplane FM-0725, manufactured by Chisso

Hollow particle C-1: JX-1009SIV (Showkubai Kasei Kogyo Co., Ltd., solid content concentration 22%, average particle diameter 50nm)

Curable resin composition of this invention can provide the cured film excellent in scratch resistance, coating property, and durability, and is especially useful as an antireflective film material.

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

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

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

Explanation of symbols for the main parts of the drawings

2: description

3: hard coating layer

4: low refractive index layer

5: high refractive index layer

6: medium refractive index layer

Claims (9)

Curable resin composition containing following component (A)-(D). (A) Ethylenic unsaturated group containing fluorine-containing polymer (B) (meth) acrylate compound (C) Silica particles having a number average particle diameter of 1 to 100 nm (D) photoinitiator which has a structure represented by following General formula (d-1) <Formula d-1>

In formula d-1, R <^1> , R <^2> , R <^4> and R <^5> represent a C1-C4 alkyl group each independently, R <^3> is a C1-C4 alkylidene group or C2-C3 alkylene Flag] The curable resin composition according to claim 1, wherein the (B) (meth) acrylate compound contains at least two or more (meth) acryloyl groups in a molecule. The curable resin composition according to claim 1 or 2, wherein the (B) (meth) acrylate compound contains a fluorine atom in a molecule thereof. The curable resin composition according to any one of claims 1 to 3, wherein the silica particles (C) are at least one member selected from hollow particles, porous particles, and solid particles. The curable resin composition according to any one of claims 1 to 4, wherein (C) the silica particles are surface treated with an organic compound containing a polymerizable unsaturated group. The curable resin composition according to any one of claims 1 to 5, further comprising (E) a surface modifier. The curable resin composition according to any one of claims 1 to 6, which is for an antireflection film. The cured film obtained by hardening | curing curable resin composition of any one of Claims 1-6. The antireflection film which has a low refractive index layer containing the cured film of Claim 8.

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