JPWO2006057297A1 - Curable resin composition and antireflection film - Google Patents

Abstract

(A) An ethylenically unsaturated group-containing fluoropolymer, (B) a (meth) acrylate compound, and (C) an organic solvent. (C) As an organic solvent, an organic solvent (C1) at 25 ° C. and 1 atm ( An organic solvent having a boiling point of less than 100 ° C. at 1.013 × 105 Pa) and a surface tension of less than 2.1 × 10 −4 N / cm, and (C2) a boiling point of 130 ° C. or more and 200 ° C. at 25 ° C. and 1 atm. Provided are a curable resin composition and an antireflection film which contain an organic solvent which is the following and give a cured product having a low refractive index of 1.50 or less and excellent scratch resistance.

Description

  The present invention relates to a curable resin composition and an antireflection film. More specifically, a curable resin composition containing an ethylenically unsaturated group-containing fluorine-containing polymer and capable of obtaining a cured product having excellent scratch resistance, coating property, and durability when cured, and The present invention relates to an antireflection film including a low refractive index layer made of such a cured product.

In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays (PDP), etc., in order to prevent reflection of external light and improve image quality, low refractive index, scratch resistance, coating properties, and There is a demand for an antireflection film including a low refractive index layer made of a cured product having excellent durability.
These display panels are also required to have excellent coating properties free from coating defects such as coating unevenness and repellency.
In particular, in a liquid crystal display panel and a PDP panel, the coating property of the antireflection film is an important factor that affects the appearance of the display of the final product.

As a material for a low refractive index layer of an antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known (for example, Patent Documents 1 to 3).
However, in such a fluororesin-based paint, it is necessary to heat and crosslink a hydroxyl group-containing fluoropolymer and a curing agent such as melamine resin under an acid catalyst in order to cure the coating film. Depending on the conditions, there are problems that the curing time becomes excessively long and the types of base materials that can be used are limited.
Moreover, although the obtained coating film was excellent in the weather resistance, there was a problem that it was poor in scratch resistance and durability.

  Therefore, in order to solve the above-mentioned problems, an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition polymerizable unsaturated group and a hydroxyl group-containing fluoropolymer are converted into an isocyanate group. A coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio of number / hydroxyl number of 0.01 to 1.0 has been proposed (for example, Patent Document 4). .

However, in the above publication, when preparing the unsaturated group-containing fluorine-containing vinyl polymer, an isocyanate group-containing unsaturated compound in an amount sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer is not used, Actively left unreacted hydroxyl groups in the polymer.
Therefore, a coating composition containing such a polymer can be cured at a low temperature in a short time, but is further cured using a curing agent such as a melamine resin in order to react the remaining hydroxyl groups. There was a need. Furthermore, the coating film obtained by the said gazette had the subject that it could not be said that coating property and abrasion resistance were sufficient.

  In addition, in order to improve the scratch resistance of the antireflection film, a technique of adding silica particles to a low refractive index film that is the outermost layer of the antireflection film is widely used (for example, Patent Documents 5 and 6).

Furthermore, in order to provide an antireflection film having a lower reflectivity, a material for a low refractive index film having a lower refractive index than before is desired. Therefore, by utilizing the fact that the refractive index of air is lower than that of a resin component such as acrylic, a technique using particles having voids inside the particles such as porous particles and hollow particles (hereinafter collectively referred to as hollow particles). Is known (for example, Patent Documents 7 to 9).
However, in these conventional techniques, since a fluoropolymer is used, it is difficult to obtain a uniform and defect-free coating film because coating unevenness or foreign matter is likely to occur during coating.

JP 57-34107 A JP 59-189108 A JP-A-60-67518 JP 61-296073 A JP 2002-265866 A JP-A-10-316860 JP 2003-139906 A JP 2002-317152 A JP-A-10-142402

  Accordingly, an object of the present invention is to provide a curable resin composition, a cured film, and an antireflection film including the cured resin composition that provide a cured film having excellent coating properties, a low refractive index, and excellent scratch resistance.

According to the present invention, the following curable resin composition, a cured film comprising the same, and an antireflection film are provided.
[1] The following components (A), (B) and (C):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) (meth) acrylate compound,
(C) contains an organic solvent,
(C) The organic solvent contains the following organic solvents (C1) and (C2), and
A curable resin composition that gives a cured product having a refractive index of 1.50 or less.
(C1) Organic solvent having a boiling point of less than 100 ° C. and a surface tension of less than 2.5 × 10 ⁻⁴ N / cm at 25 ° C. and 1 atm (1.013 × 10 ⁵ Pa) (C2) 25 ° C. 1 Organic solvent having a boiling point at atmospheric pressure of 130 ° C. or higher and 200 ° C. or lower [2] Further, (C3) Curing according to the above [1] containing an organic solvent having a boiling point at 25 ° C. of 1 atmospheric pressure of 100 ° C. or higher and lower than 130 ° C. Resin composition.
[3] The proportion of (C1) in the total amount of (C) 100% by weight of the organic solvent is 10 to 99.5% by weight, the proportion of (C2) is 0.5 to 90% by weight, and (C3) Curable resin composition as described in said [1] or [2] whose ratio is 0 to 89.5 weight%.
[4] A cured film obtained by curing the curable resin composition according to any one of [1] to [3] by heating and / or irradiating with radiation.
[5] An antireflection film having a low refractive index layer comprising the cured film according to [4].

The curable resin composition of the present invention has good coatability, and by curing it, a cured product (cured film) having a low refractive index and excellent scratch resistance can be produced.
The cured film of the present invention has a low refractive index and excellent scratch resistance.
The antireflection film of the present invention includes the cured film of the present invention having a low refractive index and scratch resistance, and has good antireflection characteristics and scratch resistance.

It is sectional drawing of the antireflection film by one Embodiment of this invention.

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

1. Curable resin composition The curable resin composition of this invention may contain the following component (A)-(F). The refractive index of the cured product obtained by curing the curable resin composition of the present invention with respect to light having a wavelength of 589 nm needs to be 1.50 or less. When the refractive index is within this range, the cured film obtained by curing the curable resin composition of the present invention is suitable as a low refractive index film constituting the antireflection film.
(A) ethylenically unsaturated group-containing fluoropolymer (B) (meth) acrylate compound (C) organic solvent (D) particles mainly composed of silica,
(E) Compound that generates active species by irradiation of active energy rays or heat (F) Other additives These components will be described below.

(A) Ethylenically unsaturated group-containing fluorinated polymer The ethylenically unsaturated group-containing fluorinated polymer (A) is a polymer of a fluorinated olefin. By 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.
Preferably, in the component (A), the side chain hydroxyl group is modified with a (meth) acrylic compound. More preferably, it is modified with a (meth) acrylic compound having an isocyanate group. Such modification allows co-crosslinking with the radically polymerizable (meth) acrylic compound and improves the scratch resistance.

  The ethylenically unsaturated group-containing fluorine-containing polymer comprises an isocyanate group / hydroxyl molar ratio of a compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. Is obtained at a ratio of 1.1 to 1.9.

(1) A compound containing one isocyanate group and at least one ethylenically unsaturated group As a compound containing one isocyanate group and at least one ethylenically unsaturated group, The compound is not particularly limited as long as it is a compound containing one isocyanate group and at least one ethylenically unsaturated group.
In addition, when two or more isocyanate groups are contained, there is a possibility of causing gelation when reacting with a hydroxyl group-containing fluoropolymer.
Moreover, since the curable resin composition mentioned later can be hardened more easily as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable.
As such a compound, 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate may be used singly or in combination of two or more.

Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
As examples of diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferred.

As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.
In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, for example, Osaka Organic Chemical Co., Ltd. product name HEA, Nippon Kayaku Co., Ltd. product name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. Product name Aronix M-215, M-233, M-305, M-400 and the like can be obtained.

(2) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
(A) A structural unit represented by the following formula (1).
(B) A structural unit represented by the following formula (2).
(C) A structural unit represented by the following formula (3).

［式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基又は−ＯＲ²で表される基（Ｒ²はアルキル基又はフルオロアルキル基を示す）を示す］

[In formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

［式（２）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_x−ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基又はアルコキシカルボニル基を示す］

[In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group. , X represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group]

［式（３）中、Ｒ⁶は水素原子又はメチル基を、Ｒ⁷は水素原子又はヒドロキシアルキル基を、ｖは０又は１の数を示す］

[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 unit (a)
In the above formula (1), examples of the fluoroalkyl group represented by R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorocyclohexyl group, and the like. A C1-C6 fluoroalkyl group is mentioned. The alkyl group R ^2, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a 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 fluororefines such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Perfluoro (alkoxyalkyl vinyl ether) s such as perfluoro (propoxypropyl vinyl ether) These may be used alone or in combination of two or more.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and it is more preferable to use these in combination.

In addition, the content rate of a structural unit (a) is 20-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that when the content rate is less than 20 mol%, it is sometimes difficult to develop a low refractive index, which is the characteristic of the optically fluorine-containing material as intended by the present invention, This is because if the content exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
For these reasons, the content of the structural unit (a) is more preferably 25 to 65 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Ii) Structural unit (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. Examples of the group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The structural unit (b) can be introduced by using the above-mentioned 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, n-hexyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid vinyl, vinyl caproate, vinyl vinyl versatate, vinyl stearate Tellurium; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc. The combination of is mentioned.

In addition, the content rate of a structural unit (b) is 10-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because if the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (b) is more preferably 20 to 60 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iii) Structural unit (c)
In the 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-hydroxypentyl group , 6-hydroxyhexyl group.

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-hydroxypentyl vinyl ether, Examples include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
Moreover, as a hydroxyl-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene Glycol (meth) acrylate or the like can be used.

In addition, it is preferable that the content rate of a structural unit (c) shall be 5-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because if the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (c) is more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iv) Structural unit (d) and structural unit (e)
The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).

  (D) A structural unit represented by the following formula (4).

［式（４）中、Ｒ⁸及びＲ⁹は、同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン化アルキル基又はアリール基を示す］

[In formula (4), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]

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

  The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following formula (5).

［式（５）中、Ｒ¹⁰〜Ｒ¹³は、同一でも異なっていてもよく、水素原子、アルキル基又はシアノ基を示し、Ｒ¹⁴〜Ｒ¹⁷は、同一でも異なっていてもよく、水素原子又はアルキル基を示し、ｐ、ｑは１〜６の数、ｓ、ｔは０〜６の数、ｙは１〜２００の数、ｚは１〜２０の数を示す。］

[In the formula (5), R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ^{14 to} R ¹⁷ may be the same or different and represent a hydrogen atom. Alternatively, it represents an alkyl group, p and q are numbers 1 to 6, s and t are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20. ]

  When the compound represented by the formula (5) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

  (E) A structural unit represented by the following formula (6).

［式（６）中、Ｒ¹⁰〜Ｒ¹³、Ｒ¹⁴〜Ｒ¹⁷、ｐ、ｑ、ｓ、ｔ及びｙは、上記式（５）と同じである。］

[In the 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 the formulas (5) and (6), examples of the alkyl group represented by R ^{10 to} R ¹³ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. Examples of the alkyl group of ^{14 to} R ¹⁷ include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

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

［式（７）中、ｙ及びｚは、上記式（５）と同じである。］

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

In addition, it is preferable that the content rate of a structural unit (d) shall be 0.1-10 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the cured coating film is lowered, and the scratch resistance of the coating film may be lowered. If the amount exceeds 10 mol%, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling and the like are likely to occur during coating.
For these reasons, the content of the structural unit (d) is more preferably 0.1 to 5 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer, More preferably, it is mol%. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

(V) Structural unit (f)
It is also preferred that the hydroxyl group-containing fluoropolymer further comprises the following structural unit (f).

  (F) A structural unit represented by the following formula (8).

［式（８）中、Ｒ¹⁸は乳化作用を有する基を示す］

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

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

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

［式（９）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］

[In Formula (9), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]

  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (10).

［式（１０）中、ｎ、ｍ及びｕは、上記式（９）と同様である］

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

In addition, it is preferable that the content rate of a structural unit (f) shall be 0.1-5 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because, when the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol%, the curable resin composition This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
For such reasons, the content of the structural unit (f) is more preferably 0.1 to 3 mol% based on the total amount of the hydroxyl group-containing fluoropolymer, and 0.2 to 3 More preferably, it is mol%.

(Vi) Molecular Weight The hydroxyl group-containing fluoropolymer preferably has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 measured by gel permeation chromatography using tetrahydrofuran as a solvent. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be lowered. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.
For these reasons, the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

(3) Reaction molar ratio The ethylenically unsaturated group-containing fluoropolymer is the above-described compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer. Is obtained at a molar ratio of isocyanate group / hydroxyl group of 1.1 to 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be reduced. On the other hand, if the molar ratio exceeds 1.9, the coating film of the curable resin composition may be deteriorated. This is because the scratch resistance after immersion in an alkaline aqueous solution may be lowered.
For this reason, the molar ratio of isocyanate group / hydroxyl group is preferably 1.1 to 1.5, and more preferably 1.2 to 1.5.

The amount of component (A) added is not particularly limited, but is usually 10 to 90% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 10% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. This is because if the amount exceeds 90% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
For this reason, the amount of component (A) added is more preferably 15 to 90% by weight, and still more preferably 20 to 85% by weight.

(B) (Meth) acrylate Compound The (meth) acrylate compound is used for enhancing the scratch resistance of a cured product obtained by curing a curable resin composition and an antireflection film using the cured product.

The compound is not particularly limited as long as it is a compound containing at least one (meth) acryloyl group in the molecule.
Examples of the monomer having one (meth) acryloyl group include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, and isobornyloxyethyl. (Meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopente (Meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2 -Tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachloropheny Compounds represented by (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate It can be illustrated. Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate are particularly preferable.

  As a commercial item of these monofunctional monomers, for example, Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, manufactured by Toagosei Co., Ltd.) ), KAYARAD TC-110S, R-564, R-128H (above, Nippon Kayaku Co., Ltd.), Biscoat 192, Biscoat 220, Biscoat 2311HP, Biscoat 2000, Biscoat 2100, Biscoat 2150, Biscoat 8F, Biscoat 17F , Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the monomer having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, 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”) modified trimethylolpropane tri (meth) acrylate, Pyrene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, both ends (meth) acrylic of bisphenol A diglycidyl ether Acid adduct, 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, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate Rate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meta) ) Acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, etc. can do.

  Examples of commercially available products of these polyfunctional monomers include SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700 (manufactured by Osaka Organic Chemical Industry 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 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M- 309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF 400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Of these, the composition of the present invention preferably contains a compound containing at least two (meth) acryloyl groups in the molecule. More preferably, a compound containing at least 3 (meth) acryloyl groups in the molecule is particularly preferable. The three or more compounds can be selected from the tri (meth) acrylate compounds exemplified above, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds, and the like. Of these, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylates are particularly preferred. Each of the above compounds can be used alone or in combination of two or more.

  Further, the (meth) acrylate compound may contain fluorine. Examples of such a compound include one kind of perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, or a combination of two or more kinds.

Although it does not restrict | limit especially about the addition amount of (B) component, It is 1 to 88 weight% normally with respect to composition whole quantity other than an organic solvent. The reason for this is that when the addition amount is less than 1% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained, whereas when the addition amount exceeds 88% by weight, This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained.
For this reason, the amount of component (B) added is more preferably 1 to 60% by weight, and even more preferably 1 to 40% by weight.

(C) Organic solvent The curable composition of the present invention needs to contain the following organic solvents (C1) and (C2). By containing these organic solvents, the coating properties of the curable composition can be improved.
(C1) Organic solvent having a boiling point of less than 100 ° C. and a surface tension of less than 2.5 × 10 ⁻⁴ N / cm at 25 ° C. and 1 atm (1.013 × 10 ⁵ Pa) (C2) 25 ° C. 1 Organic solvent having a boiling point at atmospheric pressure of 130 ° C. or higher and 200 ° C. or lower

The organic solvent (C1) reduces the surface tension of the curable resin composition of the present invention and improves the coatability. Specific examples of the organic solvent (C1) include n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, isooctane, and cyclopentane. , Aliphatic hydrocarbons such as methylcyclopentane and cyclohexane, methyl chloride, ethyl chloride, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, t-butyl chloride, sec-butyl chloride, 1,1-dichloroethane, hexafluoro Halogenated hydrocarbons such as benzene, 1,1,2-trichloro-1,2,2, -trifluoroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, methyl ethyl ketone (MEK), Ketones such as acetone, methanol, ethanol, 1-propanol, isopropyl alcohol Alcohol (IPA), 1-butanol, 2-butanol, t-butanol, alcohols such as 2,2,2-trifluoroethanol, diethyl ether, dipropyl ether, diisopropyl ether, butyl vinyl ether, 1,2-dimethoxy Ethers such as ethane and methylal, methyl formate, ethyl formate, isobutyl formate, methyl acetate, ethyl acetate, isopropyl butyrate, methyl propionate, ethyl propionate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine , Amines such as isopropylamine, diisopropylamine, butylamine, isobutylamine, sec-butylamine and t-butylamine. Among these, MEK (surface tension 2.4 × 10 ⁻⁴ N / cm), ketones such as acetone, IPA (surface tension 2.2 × 10 ⁻⁴ N / cm), t-butanol (surface tension 1) .9 × 10 ⁻⁴ N / cm) and the like are preferable, and t-butanol is more preferable.
The surface tension of the organic solvent (C1) needs to be less than 2.5 × 10 ⁻⁴ N / cm at 25 ° C. and 1 atm, and preferably less than 2.1 × 10 ⁻⁴ N / cm. . The surface tension is measured by the well Helmi (plate) method.

  The organic solvent (C2) prevents whitening of the coating film in the step of removing the organic solvent after applying the curable resin composition of the present invention. Specific examples of the organic solvent (C2) include aliphatic hydrocarbons such as nonane, decane, dodecane, ethylcyclohexane, p-menthane, o-xylene, m-xylene, p-xylene, ethylbenzene, cumene, mesitylene, n- Aromatic hydrocarbons such as butylbenzene, sec-butylbenzene, t-butylbenzene, p-cymene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-pentylbenzene, 1,1,2,2-tetrachloroethane Halogenated hydrocarbons such as pentachloroethane, hexachloroethane, 1,2,3-trichloropropane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chlorotoluene, p-chlorotoluene, -Pentanol, 2-methoxyethanol 2-ethoxyethanol, 1-ethoxy-2-propanol, isopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3,5,5-trimethyl-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylhexanol, 3 -Methylhexanol, 4-methylhexanol, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 2-methyl-2,4-pentanediol, phenol, o-cresol, 2-ethoxy Ethanol, 2- (methoxyethoxy) ethanol 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol monomethyl ether, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Alcohols such as ether, diacetone alcohol, 1,3-dichloro-2-propanol, 2-aminoethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, zobutyl ether, anisole, phenetole, o-methoxy Toluene, m-methoxytoluene, p-methoxytoluene, benzyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Ethers such as ether and bis (2-chloroethyl) ether, ketones such as 2-heptanone (MAK), 4-heptanone, diisobutyl ketone, acetonylacetone, cyclohexanone and methylcyclohexanone, pentyl formate, pentyl acetate, isopentyl acetate 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, butyl propionate, isopentyl propionate, butyl butyrate, isobenzyl butyrate, isobutyl isobutyrate, ethyl isovalerate, isoyoshi Isopentyl herbate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl lactate, ethyl lactate, butyl lactate, 2-ethoxyethyl acetate, 2-methoxyethyl acetate Esters of 2-butoxyethyl acetate, methyl acetoacetate, ethyl acetoacetate, propylene glycol monomethyl ether acetate (PGMEA), 1-nitropropane, 2-nitropropane, valeronitrile, benzonitrile, dibutylamine, diisobutylamine, Tripentylamine, 2-ethylhexylamine, aniline, N-methylaniline, N, N-dimethylaniline, cyclohexylamine, pyrrole, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N, N -Nitrogen compounds such as dimethylacetamide, N-methylpropionamide, N, N, N ', N'-tetramethylurea and N-ethylmorpholine, and sulfur compounds such as dimethylsulfoxide. Among these, ketones such as MAK, 4-heptanone, diisobutylketone, acetonylacetone, cyclohexanone, methylcyclohexanone, ethyl lactate, butyl lactate, 2-ethoxyethyl acetate, 2-methoxyethyl acetate, 2-butoxyethyl acetate Esters such as methyl acetoacetate, ethyl acetoacetate, and propylene glycol monomethyl ether acetate (PGMEA) are preferable, and MAK, cyclohexanone, ethyl lactate, and PGMEA are more preferable.

  Furthermore, the curable resin composition of the present invention includes an organic solvent having a boiling point at 25 ° C. and 1 atm of 100 ° C. or more and less than 130 ° C. in addition to the organic solvents (C1) and (C2) as necessary Can be blended. By mix | blending an organic solvent (C3), the curable composition after coating can be dried rapidly. Specific examples of the organic solvent (C3) include aliphatic hydrocarbons such as octane, 2,2,3-trimethylpentane, 2,2,5-trimethylhexane, and methylcyclohexane, aromatic hydrocarbons such as toluene, 1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1-chloropentane, benzotrifluoride, halogenated hydrocarbons such as 1-bromo-2-chloroethane, 2-pentanone, 3-pentanone, 2- Ketones such as hexanone, methyl isobutyl ketone (MIBK), 1-butanol, isobutyl alcohol, 2-pentanol, 3-pentanol, t-pentyl alcohol, 2-methyl-1-butanol, 3-methyl-2-butanol Neopentyl alcohol, 4-methyl-2-pentanol, 2-methoxyethanol, 1 Alcohols such as methoxy-2-propanol, 2-chloroethanol, 1-chloro-2-propanol, propylene glycol monomethyl ether, ethers such as dioxane, trioxane, 1,2-diethoxyethane, acetal, butyl formate, Esters such as propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, methyl butyrate, ethyl butyrate, diethyl carbonate, pentyl lactate, nitromethane, nitroethane, butyronitrile, isobutyronitrile, pentylamine, dicyclohexylamine, pepyridine , Nitrogen compounds such as pyridine, ethylenediamine, propylenediamine, and morpholine. Among these, ketones such as 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone (MIBK), butyl formate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, methyl butyrate, ethyl butyrate In addition, esters such as diethyl carbonate and pentyl lactate are preferable, and butyl acetate and MIBK are more preferable.

The blending amount (total amount) of the (C) organic solvent in the curable resin composition of the present invention is not particularly limited, but is 100 parts by weight of all components other than the (C) organic solvent in the composition. Usually, it is 100 to 100,000 parts by weight, preferably 300 to 20,000 parts by weight, and more preferably 1000 to 10,000 parts by weight.
The blending amounts of the component (C1), the component (C2) and the component (C3) contained in 100% by weight of all the components (C) are 10 to 99.5% by weight, 0.5 to 90% by weight and 0%, respectively. To 89.5% by weight, preferably 20 to 98.5% by weight, 0.5 to 80% by weight and 1 to 79.5% by weight, more preferably 30 to 80% by weight, 1 to 60% by weight and 1-69% by weight.

(D) Particles mainly composed of silica (D) Particles mainly composed of silica can be blended in the curable resin composition of the present invention. The particle size is measured with a transmission electron microscope.
By mix | blending particle | grains (D), the abrasion resistance of the hardened | cured material of the curable resin composition of this invention, especially steel wool tolerance can be improved.
As these particles mainly composed of silica, known particles can be used, and if the shape is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, core-shell particles And so on. However, from the viewpoint of reducing the refractive index of the resulting cured product, hollow particles and porous particles are preferable, and it is particularly preferable that part or all of the component (D) is hollow particles. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a solid content of 10 to 40% by weight is preferred.

The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.
As a commercial item of the particle | grains which have a silica as a main component, as a colloidal silica, for example, Nissan Chemical Industries Ltd. brand name: Methanol silica sol, IPA-ST, MEK-ST, MEK-ST-S, MEK-ST- L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL etc. can be mentioned.

Moreover, what carried out surface treatments, such as chemical modification, on the colloidal silica surface can be used, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or one containing a hydrolyzate thereof. Can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 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-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. Moreover, the hydrolyzable silicon compound which has 1 or more reactive groups in a molecule | numerator can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane or the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane or the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane or the like having a thiocyanate group 3 As thiocyanate propyltrimethoxysilane and the like having an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having a thiol group 3 -Mercaptopropyltrimethoxy Sisilane etc. can be mentioned. A preferred compound is 3-mercaptopropyltrimethoxysilane.

  The particles (D) containing silica as a main component are preferably those that have been surface-treated with an organic compound containing a polymerizable unsaturated group (hereinafter, also referred to as “specific organic compound”). Such surface treatment enables co-crosslinking with the UV curable acrylic monomer and improves the scratch resistance.

(2) Specific organic compound The specific organic compound used in the present invention is a polymerizable compound containing a polymerizable unsaturated group in the molecule. This compound is a compound further containing a group represented by the following formula (11) in the molecule, and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. preferable.

［式（１１）中、ＸはＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、ＹはＯ又はＳを示す。］

[In the formula (11), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the specific organic compound is not particularly limited. For example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, A cinnamoyl group, a maleate group, and an acrylamide group can be mentioned as preferred examples.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) Group represented by Formula (11) The specific organic compound preferably further includes a group represented by Formula (11) in the molecule. Specific examples of the group [—X—C (═Y) —NH—] represented by the formula (11) include [—O—C (═O) —NH—], [—O—C (═S). ) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [ -S-C (= S) -NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups.
The group [—X—C (═Y) —NH—] represented by the formula (11) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iii) A silanol group or a group that generates a silanol group by hydrolysis The specific organic compound is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or by hydrolysis. A compound that generates a silanol group (hereinafter sometimes referred to as a “silanol group-generating compound”) is preferable. Examples of such a silanol group-forming compound include compounds having an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, etc. on the silicon atom, but an alkoxy group or aryloxy group on the silicon atom. In other words, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-forming site of the silanol group or the silanol group-generating compound is a structural unit that binds to particles mainly composed of silica by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment Specific examples of the specific organic compound include compounds represented by the following formula (12).

R ¹⁹ and R ²⁰ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and a represents a number of 1, 2 or 3.
Examples of R ¹⁹ and R ²⁰ include methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl groups and the like.

Examples of the group represented by [(R ¹⁹ O) _a R ²⁰ _3-a Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

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

R ²² is a divalent organic group, and is usually selected from divalent organic groups 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, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (11). Can also be included.

R ²³ is a (b + 1) -valent organic group, 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 that 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, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  For the synthesis of the specific organic compound used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (i) it can be carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. (B) The reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

In order to synthesize the compound represented by the formula (12), (a) is preferably used among these methods. More specifically, for example,
Method (a): First, a mercaptoalkoxysilane and a polyisocyanate compound are reacted to form an intermediate containing an alkoxysilyl group, [—S—C (═O) —NH—] group and an isocyanate group in the molecule. Next, an active hydrogen-containing polymerizable unsaturated compound is reacted with the isocyanate remaining in the intermediate, and this unsaturated compound is bonded via a [—O—C (═O) —NH—] group. How to
Method (b): First, a polyisocyanate compound and an active hydrogen-containing polymerizable unsaturated compound are reacted to form a polymerizable unsaturated group, [—O—C (═O) —NH—] group, and isocyanate in the molecule. Forming an intermediate containing a group, reacting this with a mercaptoalkoxysilane, and bonding the mercaptoalkoxysilane via a [—S—C (═O) —NH—] group,
Etc. Further, among them, the method (a) is preferable in that there is no decrease in polymerizable unsaturated groups due to the Michael addition reaction.

  In the synthesis of the compound represented by the formula (12), examples of the alkoxysilane capable of forming a [—S—C (═O) —NH—] group by reaction with an isocyanate group include an alkoxysilyl group. And compounds having at least one mercapto group in the molecule. Examples of such mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxy silane, mercapto Mention may be made of propyltributoxysilane. Among these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Moreover, an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan and an addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

  The polyisocyanate compound used when synthesizing the specific organic compound can be selected from polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons.

  Examples of such polyisocyanate compounds include, for example, 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, methylene bis (4-cyclohexyl) Isocyanato), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate) Til) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (Isocyanatemethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatemethyl) -bicyclo [2.2.1] heptane, and the like. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, and the like are preferable. These can be used alone or in combination of two or more.

  In the synthesis of a specific organic compound, as an example of an active hydrogen-containing polymerizable unsaturated compound that can be bonded to the polyisocyanate compound via an [—O—C (═O) —NH—] group by an addition reaction, Examples of compounds having at least one active hydrogen atom capable of forming a [—O—C (═O) —NH—] group by addition reaction with an isocyanate group and at least one polymerizable unsaturated group Can do.

Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- 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, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythr Litholtri (meth) acrylate, dipentaerythritol penta Data) acrylate - door, and the like can be given. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl 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 particles mainly composed of silica with a specific organic compound (hereinafter also referred to as particles) The surface treatment method of particles with a specific organic compound is not particularly limited. It is also possible to manufacture by mixing, heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-forming site of the specific organic compound with the particles. However, when the specific organic compound has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.

  The reaction amount of the particles and the specific organic compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 1% by weight, with the total of the particles and the specific organic compound being 100% by weight. That's it. If it is less than 0.01% by weight, the dispersibility of the particles in the composition is not sufficient, and the transparency and scratch resistance of the resulting cured product may not be sufficient.

Hereinafter, the surface treatment method will be described in more detail using the alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (12) as an example of the specific organic compound.
The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment may be an amount that allows at least one alkoxy group on silicon in one molecule to be hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface, and particles composed of such components are not included. In the hardened | cured material of the composition to contain, the effect of expression of high hardness and abrasion resistance is low.

  At the time of surface treatment, after subjecting the alkoxysilane compound to a separate hydrolysis operation, this is mixed with powder particles or solvent dispersion sol of particles, followed by heating and stirring operations; hydrolysis of the alkoxysilane compound; Can be selected in the presence of particles; or a method in which particles are surface-treated in the presence of other components such as a polymerization initiator. In this, the method of hydrolyzing the said alkoxysilane compound in presence of particle | grains is preferable. During the surface treatment, the temperature is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 20 ° C. or higher and 100 ° C. or lower. The processing time is usually in the range of 5 minutes to 24 hours.

In the case of using a powdery powder during the surface treatment, an organic solvent may be added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. Esters 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 . Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.

  When a solvent-dispersed sol is used as the particles, it can be produced by mixing at least a solvent-dispersed sol and a specific organic compound. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring the uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

In addition, an acid, a salt or a base may be added as a catalyst to promote the reaction during the surface treatment.
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 succinic acid; methacrylic acid, acrylic acid, and itacone An unsaturated organic acid such as an acid, as a salt, for example, an ammonium salt such as tetramethylammonium hydrochloride or tetrabutylammonium hydrochloride, and as a base, for example, aqueous ammonia, diethylamine, triethylamine, dibutylamine, Primary, secondary or tertiary aliphatic amines such as cyclohexylamine, aromatic amines such as pyridine, quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide Etc.
Among these, preferred examples of the acid include organic acids and unsaturated organic acids, and the base includes tertiary amine or quaternary ammonium hydroxide. The amount of these acids, salts or bases added is preferably 0.001 to 1.0 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound. It is.

In order to accelerate the reaction, it is also preferable to add a dehydrating agent.
As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Of these, organic compounds are preferable, and orthoesters such as methyl orthoformate and ethyl orthoformate are more preferable.
The amount of the alkoxysilane compound bonded to the particles is usually a thermogravimetric analysis from 110 ° C. to 800 ° C. in air as a constant value of weight loss% when the dry powder is completely burned in air. It can ask for.

  The blending amount of the component (D) in the resin composition is usually 0 to 40% by weight, preferably 1 to 30% by weight, and more preferably 1 to 10% by weight based on the total amount of the composition other than the organic solvent. The amount of particles means solid content, and when the particles are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of solvent.

(E) Compound that generates active species by irradiation of active energy rays or heat A compound that generates active species by irradiation of active energy rays or heat is used to cure the curable resin composition.

(1) Compounds that generate active species upon irradiation with active energy rays Compounds that generate active species upon irradiation with active energy rays (hereinafter referred to as “photopolymerization initiators”) include light that generates radicals as active species. A radical generator etc. are mentioned.
The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, a high curing speed, and a relatively inexpensive irradiation apparatus, and a small size.

(I) Kind Examples of the photo radical generator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4- Chlorobenzophenone, 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecyl) Phenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3, 3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4 Examples thereof include -benzoyl-4'-methyldiphenyl sulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers.

  Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2 -Phenylmethyl) -1-butanone and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl ) -1-butanone, and the like.

(Ii) Addition amount The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.1% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured product increases and the antireflection effect may be lowered.
For this reason, the amount of photopolymerization initiator added is more preferably 1 to 5% by weight based on the total amount of the composition other than the organic solvent.

(2) Compound that generates active species by heat Examples of the compound that generates active species by heat (hereinafter referred to as “thermal polymerization initiator”) include a thermal radical generator that generates radicals as the active species.

(I) Type Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert -One kind of butyl peroxide, tert-butyl hydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Single or 2 or more types of combinations can be mentioned.

(Ii) Addition amount The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.1% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured product increases and the antireflection effect may be lowered.
For this reason, it is more preferable to add 1 to 8% by weight of the thermal polymerization initiator based on the total amount of the composition other than the organic solvent.

(F) Additive In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surfactant, as long as the object and effect of the present invention are not impaired. It is also preferable to further contain additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the components (C) and (D), pigments, and dyes.

Next, the preparation method and curing conditions of the curable resin composition of the present invention will be described.
The curable resin composition of the present invention comprises the (A) ethylenically unsaturated group-containing fluoropolymer, the (B) component and the (C) component or, if necessary, the (D) component and the (E) component. , And (F) additives can be added and mixed at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

The curing conditions of the curable resin composition are not particularly limited, but for example, when an active energy ray is used, the exposure amount is preferably set to a value within the range of 0.01 to 10 J / cm ² .
This is because when the exposure dose is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure dose exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.
For these reasons, the exposure dose is more preferably set to a value in the range of 0.05 to 5 J / cm ² , and more preferably set to a value in the range of 0.1 to 3 J / cm ^2. .

Moreover, when making a curable resin composition heat and harden | cure, it is preferable to heat for 1 to 180 minutes at the temperature within the range of 30-200 degreeC. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.
For these reasons, it is more preferable to heat at a temperature in the range of 50 to 180 ° C. for 2 to 120 minutes, and further to heat at a temperature in the range of 80 to 150 ° C. for 5 to 60 minutes. preferable.

2. Antireflective film The antireflective film of this invention contains the low-refractive-index layer which consists of hardened | cured material which hardened the said curable resin composition. Furthermore, the antireflection film of the present invention can contain a high refractive index layer, a hard coat layer, and / or a substrate under the low refractive index layer.
FIG. 1 shows such an antireflection film 10. As shown in FIG. 1, the hard coat layer 14 and the low refractive index layer 18 are laminated on the substrate 12.
At this time, a high refractive index layer 16 (not shown) may be formed between the hard coat layer 14 and the low refractive index layer 18. Alternatively, the low refractive index layer 18 may be formed directly on the substrate 12 without providing the hard coat layer 14.
Further, an intermediate refractive index layer (not shown) may be further provided between the high refractive index layer 16 and the low refractive index layer 18 or between the high refractive index layer 16 and the hard coat layer 14.

(1) Low refractive index layer A low refractive index layer is comprised from the hardened | cured material obtained by hardening | curing the curable resin composition of this invention. Since the configuration and the like of the curable resin composition are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the low refractive index layer will be described below.

The refractive index of the cured product obtained by curing the curable resin composition (refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film is 1.50 or less. .45 or less is preferable. The reason for this is that when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be significantly reduced when combined with a high refractive index film.
Therefore, the refractive index of the low refractive index film is more preferably 1.44 or less, and further preferably 1.43 or less.
In the case where a plurality of low refractive index films are provided, at least one of the low refractive index films only needs to have a refractive index value within the above-described range. Therefore, the other low refractive index films exceed 1.45. It may be a value.

Moreover, when providing a low refractive index layer, since the more excellent antireflection effect is acquired, it is preferable to make the refractive index difference between high refractive index layers into 0.05 or more values. The reason for this is that when the refractive index difference between the low refractive index layer and the high refractive index layer is less than 0.05, a synergistic effect in these antireflective film layers cannot be obtained. This is because there is a case in which the lowering may occur.
Therefore, it is more preferable to set the refractive index difference between the low refractive index layer and the high refractive index layer to a value within the range of 0.1 to 0.5, and within the range of 0.15 to 0.5. More preferably, it is a value.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm, for example. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as the base may be reduced. On the other hand, when the thickness exceeds 300 nm, optical interference occurs. This is because the antireflection effect may be reduced.
Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and further preferably 60 to 200 nm.
In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 300 nm.

(2) High Refractive Index Layer The antireflective film of the present invention may form a high refractive index layer between the hard coat layer and the low 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, an epoxy resin, phenol resin, melamine resin, alkyd resin, cyanate resin It is preferable to include one kind alone or a combination of two or more kinds such as acrylic resin, polyester resin, urethane resin, and siloxane resin. If these resins are used, a strong thin film can be formed as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved.
However, the refractive index of these resins alone is usually 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles. Moreover, as a hardening form, although the curable composition which can be thermosetting, ultraviolet curing, and electron beam curing can be used, the ultraviolet curable composition with favorable productivity is used more suitably.

The thickness of the high refractive index layer is not particularly limited, but is preferably 50 to 30,000 nm, for example. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, the antireflection effect and adhesion to the substrate may be reduced when combined with the low refractive index layer, while the thickness is If the thickness exceeds 30,000 nm, optical interference may occur, and the antireflection effect may be reduced.
Therefore, the thickness of the high refractive index layer is more preferably 50 to 1,000 nm, and further preferably 60 to 500 nm.
Further, in order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 30,000 nm.
In addition, 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 coat layer The constituent material of the hard coat layer used in the antireflection film of the present invention is not particularly limited. Examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds.

  Moreover, although it does not restrict | limit especially also about the thickness of a hard-coat layer, it is preferable to set it as 1-50 micrometers, and it is more preferable to set it as 5-10 micrometers. The reason for this is that when the thickness of the hard coat layer is less than 1 μm, the adhesion of the antireflection film to the substrate may not be improved. On the other hand, when the thickness exceeds 50 μm, it is uniform. This is because it may be difficult to form.

(4) Substrate The type of the substrate used for the antireflection film of the present invention is not particularly limited. For example, glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC) The base material which consists of etc. can be mentioned. By using an antireflection film containing these base materials, excellent reflection can be achieved in a wide range of application areas of antireflection films such as camera lens parts, television (CRT) screen display parts, and color filters in liquid crystal display devices. The prevention effect can be obtained.
[Example]

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to the description of these examples.

(Production Example 1)
Synthesis of hydroxyl group-containing fluoropolymer After a 2.0-liter stainless steel autoclave with an electromagnetic stirrer was sufficiently replaced with nitrogen gas, 1200 g of ethyl acetate, 346 g of perfluoro (propyl vinyl ether), 94 g of ethyl vinyl ether, 115 g of hydroxyethyl vinyl ether 4 g of lauroyl peroxide, 23 g of azo group-containing polydimethylsiloxane represented by the above formula (7) (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and nonionic reactive emulsifier (NE-30 (product) Name), manufactured by Asahi Denka Kogyo Co., Ltd.) 450 g, cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

Next, 215 g of hexafluoropropylene was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 30%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 850 g of a hydroxyl group-containing fluoropolymer. Table 1 shows the monomers and solvents used.

About the obtained hydroxyl group-containing fluoropolymer, the polystyrene-equivalent number average molecular weight by gel permeation chromatography and the fluorine content by the alizarin complexone method were measured, respectively. ^{Further, 1 H-NMR, 13 C} -NMR both results of NMR analysis, elemental analysis and fluorine content to determine the percentage of each monomer component constituting the hydroxyl group-containing fluoropolymer. The results are shown in Table 2.

VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (7) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the above formula (10).
Furthermore, in Table 2, the correspondence between the monomer and the structural unit is as follows.
Monomer Structural unit Hexafluoropropylene (a)
Perfluoro (propyl vinyl ether) (a)
Ethyl vinyl ether (b)
Hydroxyethyl vinyl ether (c)
NE-30 (f)
Polydimethylsiloxane skeleton (d)

(Production Example 2)
Synthesis of ethylenically unsaturated group-containing fluoropolymer (methacryl-modified fluoropolymer) Hydroxyl group obtained in Production Example 1 in a 1-liter separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer A fluorine-containing polymer containing 50.0 g, 0.01 g of 2,6-di-t-butylmethylphenol and 370 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor were charged, and the hydroxyl-containing fluorine-containing polymer was MIBK at 20 ° C. The solution was stirred until the solution became clear and uniform.
Next, 13.2 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. A MIBK solution of an ethylenically unsaturated group-containing fluoropolymer was obtained by maintaining the temperature at 65 ° C. and continuing stirring for 5 hours.
The obtained polymer solution was poured into methanol to precipitate a polymer, washed with methanol, and vacuum dried at room temperature to obtain a methacrylic group-containing fluoropolymer. Table 3 shows the raw material monomers used.

(Production Example 3)
Preparation of composition for hard coat layer In a container shielded from ultraviolet rays, 86 parts of MEK-dispersed nanosilica sol (MEK-ST manufactured by Nissan Chemical Industries, 30 parts as solid content), 65 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) DPHA), 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals) and 44 parts MIBK are stirred at 50 ° C. for 2 hours. Thus, a uniform hard coat layer composition was obtained. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 50% by weight.

(Production Example 4)
Preparation of substrate for coating curable resin composition A4 size single-sided easy-adhesive polyethylene terephthalate film A4300 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) containing silica particles prepared in Production Example 3 The hard coat layer composition was coated with a wire bar coater to a film thickness of 6 μm, and dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, ultraviolet rays were irradiated under a light irradiation condition of 1 J / cm ² using a high-pressure mercury lamp in the air to prepare a curable resin composition coating substrate.

(Example 1)
8.25 g of (A) ethylenically unsaturated group-containing fluoropolymer obtained in Production Example 2, (B) 1.25 g of dipentaerythritol pentaacrylate (SR399E manufactured by Sartomer), 2-methyl- as a photopolymerization initiator 0.5 g of 1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals), (C) 114 g of methyl ethyl ketone (MEK) as an organic solvent, methyl isobutyl ketone A total of 190 g of (MIBK) and 38 g of propylene glycol monomethyl ether acetate (PGMEA) was charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 1 hour to obtain a curable resin composition. Further, the solid content concentration determined by the method of Production Example 3 was 5% by weight.
The curable resin composition obtained here was applied on a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and then 0.3 J / cm using a high pressure mercury lamp under nitrogen. It was cured by irradiating with ultraviolet rays under the light irradiation conditions of ² . The obtained cured product, the refractive index at a wavelength of 589nm at 25 ° C. using an ellipsometer ^{_(n D 25)} was measured. As a result, the refractive index was 1.43.

Moreover, it apply | coated so that it might become a film thickness of 0.1 micrometer on the hard coat obtained in manufacture example 4 with the wire bar coater, and it dried at 50 degreeC for 1 minute, and formed the coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.2 J / cm ² using a high-pressure mercury lamp under a nitrogen stream to form an antireflection film layer. As a result of evaluating the reflectance of the obtained antireflection film with a reflection spectrometer, the minimum reflectance was 2.5%.

(Examples 2-6, Comparative Examples 1-7)
(C) Except having used the solvent shown in Table 4 and Table 5 as an organic solvent, it carried out similarly to Example 1, and obtained each curable composition. The composition unit in the table is% by weight.

The boiling points and surface tensions of the organic solvents listed in Tables 4 and 5 at 25 ° C. and 1 atm are as follows.
Methyl ethyl ketone (MEK): boiling point 79.6 ° C .; surface tension 2.4 × 10 ⁻⁴ N / cm
Isopropyl alcohol (IPA): boiling point 82.4 ° C .; surface tension 2.2 × 10 ⁻⁴ N / cm
t-butanol: boiling point 82.4 ° C .; surface tension 1.9 × 10 ⁻⁴ N / cm
Methyl isobutyl ketone (MIBK): boiling point 116.2 ° C
Methyl amyl ketone (MAK): boiling point 151.5 ° C
Propylene glycol monomethyl ether acetate (PGMEA): boiling point 146 ° C

(Evaluation example 1)
Evaluation of Uniformity of Coating Liquid After preparing each curable composition obtained in Examples 1 to 6 and Comparative Examples 1 to 7, it was allowed to stand at 25 ° C. for 24 hours. Thereafter, the uniformity was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.
○: Uniform transparent △: Slightly turbid ×: Strongly turbid or partially sedimented

(Evaluation example 2)
Evaluation of coatability On the hard coat obtained in Production Example 4, each curable resin composition was coated with a wire bar coater to a film thickness of 0.1 μm, dried at 50 ° C. for 1 minute, and coated. A film was formed. Subsequently, ultraviolet rays were irradiated under a light irradiation condition of 0.2 J / cm ² using a high-pressure mercury lamp under a nitrogen stream to form a low refractive index film layer. In order to make it easy to see coating film defects, the back surface (base material side) of the obtained antireflection film is completely painted with black spray, and from the low refractive index film side under the three-wavelength white fluorescent lamp (Toshiba EX-N) The appearance was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.
○: Uneven coating and repellency △: Slightly uneven coating and repellency ×: Uneven coating and repellency on the entire surface

(Evaluation example 3)
Measurement of haze The haze of the antireflection film obtained in Evaluation Example 2 was measured with a color haze meter. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.
○: 0.5 or less Δ: 0.5 to 1.0
X: 1.0 or more

(Evaluation example 4)
Evaluation of drying property Each curable resin composition was applied on the hard coat under the same conditions as in Evaluation Example 2, allowed to stand at room temperature, and the time until drying was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.
○: Dried within 30 seconds Δ: Dried within 30 to 2 minutes ×: It took 2 minutes or more to dry

  The curable resin composition of the present invention is a uniform liquid composition and has excellent scratch resistance, antifouling properties, and coating properties, and its cured film is excellent in transparency and is particularly useful as an antireflection film. .

Claims (5)

The following components (A), (B) and (C):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) (meth) acrylate compound,
(C) contains an organic solvent,
(C) The organic solvent contains the following organic solvents (C1) and (C2), and
A curable resin composition that gives a cured product having a refractive index of 1.50 or less.
(C1) Organic solvent having a boiling point of less than 100 ° C. and a surface tension of less than 2.5 × 10 ⁻⁴ N / cm at 25 ° C. and 1 atm (1.013 × 10 ⁵ Pa) (C2) 25 ° C. 1 Organic solvent having a boiling point at atmospheric pressure of 130 ° C. or higher and 200 ° C. or lower   Furthermore, (C3) The curable resin composition of Claim 1 containing the organic solvent whose boiling point in 25 degreeC1 atmosphere is 100 degreeC or more and less than 130 degreeC.   The proportion of (C1) in the total amount of (C) 100% by weight of the organic solvent is 10 to 99.5% by weight, the proportion of (C2) is 0.5 to 90% by weight, and the proportion of (C3) is 0. The curable resin composition according to claim 1, which is ˜89.5 wt%.   The cured film obtained by making it harden | cure by heating the curable resin composition as described in any one of Claims 1-3, and / or irradiating a radiation.   An antireflection film having a low refractive index layer comprising the cured film according to claim 4.

Images