JP2008001872A - Curable resin composition and antireflection film - Google Patents

Abstract

Provided are a curable resin composition that gives a cured product having a low refractive index and excellent scratch resistance when cured, and an antireflection film having a low refractive index layer comprising the same.
The following components (A) and (B):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) inorganic fluoride particles,
A curable resin composition containing A cured product obtained by curing the curable resin composition can be used for the antireflection film 10 as the low refractive index layer 18.
[Selection] Figure 1

Description

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

In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, it has low refractive index, scratch resistance, coatability, and durability. There is a need for an antireflection film including a low refractive index layer made of an excellent cured product.
In these display panels, the surface is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like, and scratch resistance is required.
In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, for example, triacetyl cellulose is used as the base material. However, in an antireflection film using such a base material, an alkali is usually used in order to increase the adhesiveness when being bonded to the polarizing plate. It is necessary to saponify with an aqueous solution.
Therefore, in the use of a liquid crystal display panel, an antireflection film excellent in alkali resistance is particularly required in terms of durability.

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 method described in the above publication has a problem that the coating property and scratch resistance are not 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). However, in many cases, since one type of silica particle having a relatively uniform particle size is used, the filling rate of the particles cannot be increased, and sufficient scratch resistance has not been obtained.

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, when hollow particles are used, there is a drawback that the scratch resistance of the cured film is reduced as compared with particles having no voids (solid particles).

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

  Therefore, the present invention provides a curable resin composition that gives a cured film having a refractive index lower than that of conventional silica particles and excellent in scratch resistance, and an antireflection film having the cured film. Objective.

  In order to achieve the above object, the present inventors have intensively studied and combined inorganic fluoride particles having a low refractive index almost equal to silica particles and a fluorine-containing polymer containing an ethylenically unsaturated group as a binder resin. The curable resin composition found that a cured film having a low refractive index and excellent scratch resistance was obtained, and the present invention was completed.

That is, this invention provides the following curable resin composition, the film | membrane and antireflection film which hardened it.
1. The following components (A) and (B):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) inorganic fluoride particles,
A curable resin composition containing
2. When the total of the (A) ethylenically unsaturated group-containing fluoropolymer and the (B) inorganic fluoride particles in the curable resin composition is 100 parts by mass, the (A) ethylenically unsaturated group-containing The curable resin composition according to 1, which contains 20 to 95 parts by mass of a fluoropolymer and 5 to 80 parts by mass of the (B) inorganic fluoride particles.
3. The (A) ethylenically unsaturated group-containing fluoropolymer reacts a compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluoropolymer. 3. The curable resin composition according to 1 or 2, which is a fluorine-containing polymer containing an ethylenically unsaturated group.
4). The curable resin composition according to any one of 1 to 3, wherein the (B) inorganic fluoride particles are particles made of an inorganic fluoride having a refractive index of less than 1.45 at a wavelength of 589 nm.
By using (B) inorganic fluoride particles having a refractive index of less than 1.45, a cured film having a lower refractive index can be obtained, and an antireflection film having better antireflection performance can be obtained.
5. The curable resin composition according to any one of 1 to 4, wherein the (B) inorganic fluoride particles are magnesium fluoride particles.
6). The curable resin composition according to any one of 1 to 5, wherein the (B) inorganic fluoride particles are surface-treated with an organic compound containing a polymerizable unsaturated group.
(B) By having a polymerizable unsaturated group on the surface of the inorganic fluoride particles, the (B) component becomes photocrosslinkable, and the photopolymerizable (A) component and the photopolymerizable (D) component described below. In the case of a cured film, the scratch resistance is further improved.
7). Furthermore, (C) Curable resin composition as described in any one of 1-6 containing the compound which generate | occur | produces active species by irradiation of an active energy ray.
8). Furthermore, (D) the compound containing 1 or more (meth) acryloyl group is contained in a molecule | numerator, The curable resin composition as described in any one of 1-7 characterized by the above-mentioned.
By adding the component (D), the scratch resistance of the obtained cured film and the antireflection film using the cured film can be further enhanced.
9. The film | membrane obtained by hardening the curable resin composition as described in any one of said 1-8, and the refractive index in wavelength 589nm is 1.45 or less.
10. 10. An antireflection film having the film according to 9 above.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which gives the cured film which has a low refractive index, a low reflectance, and the outstanding abrasion resistance, and the antireflection film which has this cured film are obtained.

  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 the present invention (hereinafter sometimes referred to as “the composition of the present invention”) may include the following components (A) to (F). Among these components, (A) and (B) are essential components, and (C) to (F) are optional components that can be appropriately contained.
(A) Ethylenically unsaturated group-containing fluoropolymer (B) Inorganic fluoride particles (C) Compound that generates active species upon irradiation with active energy rays (photopolymerization initiator)
(D) Compound containing one or more (meth) acryloyl groups in the molecule (E) Organic solvent (F) Other additives

In the composition of the present invention, the component (A) can exhibit excellent functions as an antireflection film such as a low refractive index, water repellency, oil repellency, dust wiping property, and fingerprint wiping property.
By adding inorganic fluoride particles (component (B)), a cured film having a low refractive index and a high hardness can be obtained.
Moreover, by making (A) component and (B) component into photocrosslinkability, it can bridge | crosslink with photopolymerizable (D) component and scratch resistance improves.
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. By such modification, it can be co-crosslinked with the radical polymerizable (meth) acrylic compound, and the scratch resistance of the resulting cured film is improved. Here, “(meth) acryl” means acrylic or methacrylic.

  The ethylenically unsaturated group-containing fluoropolymer can be obtained by reacting a compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer. preferable.

(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, as said ethylenically unsaturated group, since the curable resin composition mentioned later can be hardened more easily, a (meth) acryloyl group is more preferable. Here, the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
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 at a ratio of 1: 1 to 1: 1.5 (molar ratio). Here, “(meth) acrylate” means acrylate or methacrylate.
As the diisocyanate, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferable.

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, Osaka Organic Chemical Industry Co., Ltd. product name HEA, Nippon Kayaku Co., Ltd. product name KAYARAD DPHA, PET-30, Sartomer product Name SR-399E, Toagosei Co., Ltd. product name Aronix M-215, M-233, M-305, M-400, etc. are mentioned.

(2) Hydroxyl group-containing fluorine-containing polymer The hydroxyl group-containing fluorine-containing polymer usually contains 30% by mass or more and preferably 40% by mass or more of fluorine. When the fluorine content is 40% by mass or more, a cured film having a lower refractive index can be obtained. The fluorine content can be calculated from the composition obtained by analyzing the composition of the polymer by ¹³ C-NMR.

The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a) and / or (b), and (c) and / or (d). However, when it consists of only the structural unit (b) and the structural unit (c), in the following general formula (2) representing the structural unit (b), when the substituent R ⁵ is an acrylic group or a glycidyl group, Excluded because it is not a fluoropolymer.
(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).
(D) A structural unit represented by the following formula (4).

［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、フルオロ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）、−Ｏ−(ＣＨ₂)_x’−Ｒ^5’で表される基（Ｒ^5’はパーフルオロアルキル基を、ｘ’は１〜１０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, fluoroalkyl A group or a glycidyl group, x represents a number of 0 or 1, and a group represented by —O— (CH ₂ ) _{x ′} —R ^{5 ′} (R ^{5 ′} represents a perfluoroalkyl group, x ′ represents 1 -10 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]

［式（４）中、Ｒｆはフッ素を含有する炭素数２〜１０の２価の有機基を示す。］

[In Formula (4), Rf shows a C2-C10 bivalent organic group containing a fluorine. ]

(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 three fluorine atoms. 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 structural unit (a) is 20-70 mol% with respect to the total amount of structural unit (a)-(d) in a hydroxyl-containing fluoropolymer. The reason for this is that when the content 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 intended by the present application. This is because when the ratio 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 this reason, the content of the structural unit (a) is set to 25 to 65 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferably, it is more preferably 30 to 60 mol%.

(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. Examples of the fluoroalkyl group for R ⁵ include groups in which one or more hydrogen atoms of the alkyl group are substituted with fluorine atoms. In addition, R ^{5 ′} perfluoroalkyl group includes perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluoro group. Examples include an octyl group, a perfluorooctyl group, and a perfluorodecyl 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 such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; 3,3,3-propyldecafluoropropyl vinyl ether, 3,3,4,4,4-heptafluorobutyl vinyl ether, 3, 3,4,4,5,5,5-heptylfluoropentyl vinyl ether, 3,3,4,4,5,5,6,6,6-nonylfluorohexyl vinyl ether -Tel 3,3,4,4,5,5,6,6,7,7,7-dodecafluoroheptyl vinyl ether, 3,3,4,4,5,5,6,6,7,7,8, 8,8-propadecafluorooctyl vinyl ether 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl vinyl ether, 3,3,4 , 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-fluoroalkyl vinyl ethers such as heptadecafluorodecanyl vinyl ether; cycloalkyl vinyl ethers; ethyl allyl ether; Allyl ethers such as butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate, etc. Stealth; 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% with respect to the total amount of the structural units (a)-(d) in a hydroxyl-containing fluoropolymer. 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 this reason, the content of the structural unit (b) is set to 15 to 60 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferred is 20 to 60 mol%.

(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% with respect to the total amount of the structural units (a)-(d) in a hydroxyl-containing fluoropolymer. 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 this reason, the content of the structural unit (c) is set to 5 to 40 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferably, it is more preferably 5 to 30 mol%.

構造単位（ｄ）を含有することによりフッ素含有量が高まり、さらに低屈折率を示す硬化膜が得られる。
構造単位（ｄ）は、含フッ素ビニル単量体を重合成分として用いることにより導入することができる。このような含フッ素ビニル単量体としては、ユニマテック製 商品名ＦＶＥＰ等が挙げられる。 (Iv) Structural unit (d)
In the formula (4), examples of Rf include a tetrafluoroethylene group, a hexafluoropropylene group, and a structure represented by the following formula (14).

By containing the structural unit (d), the fluorine content is increased and a cured film having a low refractive index can be obtained.
The structural unit (d) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. As such a fluorine-containing vinyl monomer, Unimatec brand name FVEP etc. are mentioned.

The content of the structural unit (d) is preferably 5 to 60 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. The reason for this is that when the content is less than 5 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 application. This is because if the rate exceeds 50 mol%, the solubility in an organic solvent such as methyl isobutyl ketone may decrease.
For these reasons, the content of the structural unit (d) is more preferably 10 to 60 mol% with respect to the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer. More preferably, it is 25-60 mol%.

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

［式（５）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］ (E) A structural unit represented by the following formula (5).

[In Formula (5), 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 (5), 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 (e) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (5). An example of such an azo group-containing polysiloxane compound is a compound represented by the following formula (6).

［式（６）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 (6), R ^{10 to} R ¹³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group; R ^{14 to} R ¹⁷ may be the same or different; 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 (6) is used, the structural unit (e) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (f).

［式（７）中、Ｒ¹⁰〜Ｒ¹³、Ｒ¹⁴〜Ｒ¹⁷、ｐ、ｑ、ｓ、ｔ及びｙは、上記式（６）と同じである。］ (F) A structural unit represented by the following formula (7).

[In formula (7), R ^{10 to} R ¹³ , R ^{14 to} R ¹⁷ , p, q, s, t, and y are the same as those in the above formula (6). ]

In formulas (6) and (7), 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 (6) is particularly preferably a compound represented by the following formula (8).

［式（８）中、ｙ及びｚは、上記式（６）と同じである。］

[In formula (8), y and z are the same as the above formula (6). ]

The content of the structural unit (e) is 0.1 to 10 mole parts when the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer is 100 mole parts. Is preferred. The reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing is lowered, and the scratch resistance of the coated film may be lowered. If the amount exceeds 10 parts by mole, 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 (e) is more preferably 0.1 to 5 mole parts relative to the total amount of the hydroxyl group-containing fluoropolymer, More preferably, the molar part. For the same reason, the content of the structural unit (f) is desirably determined so that the content of the structural unit (e) contained therein falls within the above range.

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

［式（９）中、Ｒ¹⁸は乳化作用を有する基を示す］ (G) A structural unit represented by the following formula (9).

[In formula (9), R ¹⁸ represents a group having an emulsifying action]

In the formula (9), 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.

［式（１０）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］ Examples of the group having such an emulsifying action include a group represented by the following formula (10).

[In Formula (10), 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 (g) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (11).

［式（１１）中、ｎ、ｍ及びｕは、上記式（１０）と同様である］

[In formula (11), n, m, and u are the same as those in formula (10) above]

The content of the structural unit (g) is 0.1 to 5 mole parts when the total amount of the structural units (a) to (d) in the hydroxyl group-containing fluoropolymer is 100 mole parts. Is preferred. The reason for this is that when the content is 0.1 mol part 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 parts, 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 these reasons, the content of the structural unit (g) is more preferably 0.1 to 3 mole parts relative to the total amount of the hydroxyl group-containing fluoropolymer, and 0.2 to 3 More preferably, the molar part.

(Vii) 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. It is preferable to obtain by reacting. At this time, it is preferable to carry out the reaction 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 isocyanate group / hydroxyl molar ratio is more preferably 1.1 to 1.5, and still more preferably 1.2 to 1.5.

Although it does not restrict | limit especially about the addition amount of (A) component, When the sum total of (A) component and (B) component is 100 mass parts, it is 20-95 mass parts normally. The reason for this is that when the addition amount is less than 20 parts by mass, 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 95 parts by mass, 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 25 to 85 parts by mass, and still more preferably 30 to 80 parts by mass.

(B) Inorganic fluoride particles (1) Inorganic fluoride particles The inorganic fluoride particles used in the present invention preferably have a refractive index of less than 1.45 at a wavelength of 589 nm. The component (B) has an effect of improving the strength of the cured film and lowers the refractive index of the cured film by using particles having a refractive index of less than 1.45 at a wavelength of 589 nm than when silica particles are used. Therefore, an antireflection film having excellent antireflection characteristics can be obtained. As such inorganic fluoride particles, aluminum fluoride particles (refractive index: 1.38), calcium fluoride particles (refractive index: 1.23-1.45), lithium fluoride particles (refractive index: 1. 30), magnesium fluoride particles (refractive index: 1.38 to 1.40), and the like. Among these, lithium fluoride particles, calcium fluoride particles, and magnesium fluoride particles are preferable. Magnesium fluoride particles Is particularly preferred.

  In view of particle hardness, hygroscopicity, and refractive index, magnesium fluoride is most preferable. Commercially available magnesium fluoride particles include Stella Chemifa magnesium fluoride, magnesium fluoride OP, magnesium fluoride G1, magnesium fluoride H, and Sanwa polished magnesium fluoride.

  In the curable resin composition of the present invention, it is preferable to use inorganic fluoride particles having a number average particle diameter of 200 nm or less, preferably 100 nm or less. The particle size is measured with a transmission electron microscope. If the number average particle size is larger than 200 nm, the transparency of the formed coating film may be lowered. In addition, when the cured film obtained by curing the curable resin composition of the present invention is used as the low refractive index layer of the antireflection film, the thickness of the low refractive index layer is about 100 nm, so that the inorganic fluoride particles If the particle size of is larger than the film thickness, the optical properties and mechanical properties of the antireflection film may be deteriorated. Since the commercially available products are coarse particles having a particle size of several μm, in order to use them as the component (B) in the present invention, it is necessary to pulverize and disperse them using a pulverizer or the like.

  Further, these inorganic fluoride particles may be used by dispersing in water or an organic solvent. Examples of organic solvents that can be used as the dispersion medium include alcohols such as methanol, ethanol, isopropyl alcohol, ethylene glycol, butanol, and ethylene glycol monopropyl ether; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and aromatics such as toluene and xylene. Group hydrocarbons; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane Among these, alcohols and ketones are preferable. These organic solvents can be used alone or in admixture of two or more as a dispersion medium. Examples of commercially available magnesium fluoride sol dispersed in such an organic solvent include MFS-10P manufactured by Nissan Chemical Industries.

  (B) The inorganic fluoride particles may have been subjected to surface treatment with an organic compound containing a polymerizable unsaturated group (hereinafter sometimes referred to as “specific organic compound”). Such surface treatment improves the dispersibility of the particles, and can be co-crosslinked with photopolymerizable monomers such as the inorganic fluoride particles and the binder resin (A) component and (D) component described later. , Scratch resistance is improved.

(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 containing a group represented by the following formula (12) in addition to a polymerizable unsaturated group in the molecule and / or a compound having a silanol group in the molecule or silanol- It is preferable that it is a compound which produces | generates a ru group.

［式（１２）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 (12), 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 (12) The specific organic compound preferably further contains a group represented by Formula (12) 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 a silanol group by hydrolysis. It is preferable that it is a compound (hereinafter, sometimes referred to as “silanol group-generating compound”). 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-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment Preferred specific examples of the specific organic compound include, for example, a compound represented by the following formula (13).

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 (12). 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, A maleate group, an acrylamide group, a methacrylamide group, and the like can be given. 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 (13), (i) 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 isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-i Socyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diene Examples include isocyanate, 2,5 (or 2,6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and the like. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) 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, examples of the active hydrogen-containing polymerizable unsaturated compound that can be bonded to the polyisocyanate compound through an [—O—C (═O) —NH—] group by addition reaction include isocyanates in the molecule. Examples thereof include compounds having at least one active hydrogen atom capable of forming a [—O—C (═O) —NH—] group by addition reaction with a group and at least one polymerizable unsaturated group.

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 Rumono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Meth) acrylate, and the like. 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 inorganic fluoride particles (hereinafter also referred to as particles) with a specific organic compound Although there is no particular limitation on the surface treatment method of particles with a specific organic compound, the specific organic compound and particles are mixed, It can also be produced by 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 mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass, where the total of the particles and the specific organic compound is 100% by mass. That's it. If it is less than 0.01% by mass, the dispersibility of the particles in the composition may not be sufficient, and the resulting cured product may not have sufficient transparency and scratch resistance.

Hereinafter, the surface treatment method will be described in more detail using the alkoxysilyl group-containing compound (alkoxysilane compound) represented by the formula (13) 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 addition amount of these acids, salts or bases is preferably 0.001 to 1.0 parts by mass, more preferably 0.01 to 0.1 parts by mass, with respect to 100 parts by mass 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 alkoxysilane compound bonded to the particles is usually a thermogravimetric analysis from 110 ° C. to 800 ° C. in air as a constant value of mass reduction% when the dry powder is completely burned in air. It can ask for.

  The blending amount of the component (B) in the resin composition is usually 5 to 80 parts by mass, preferably 15 to 75 parts by mass when the total of the component (A) and the component (B) is 100 parts by mass. 20-70 mass parts is still more preferable. 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.

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

Examples of the compound that generates active species upon irradiation with active energy rays (hereinafter referred to as “photopolymerization initiator”) include photoradical generators that generate radicals as active species.
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 Although the addition amount of a photoinitiator is not restrict | limited in particular, it is 0.1-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component. preferable. The reason for this is that when the addition amount is less than 0.1 parts by mass, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, when the addition amount of the photopolymerization initiator exceeds 15 parts by mass, the refractive index of the cured product may increase and the antireflection effect may decrease.
For such reasons, the amount of the photopolymerization initiator added is more preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

(D) Compound containing one or more (meth) acryloyl groups in the molecule The compound containing one or more (meth) acryloyl groups in the molecule is a cured product obtained by curing the curable resin composition. And an antireflection film using the same is used for enhancing the scratch resistance.

  The compound is not particularly limited as long as it is a compound containing one or more (meth) acryloyl groups 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 A compound 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 SR399E (manufactured by Sartomer Co., Ltd.), SA1002 (manufactured by Mitsubishi Chemical Co., Ltd.), Biscote 195, Biscote 230, Biscote 260, Biscote 215, Biscote 310, Biscoat 214HP, Biscoat 295, Biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayrad 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-2 , 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 ( Top, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (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 (above, Shin-Nakamura Chemical Co., Ltd.) and the like.

Of these, the composition of the present invention preferably contains a compound containing two or more (meth) acryloyl groups in the molecule. More preferably, a compound containing 3 or more (meth) acryloyl groups in the molecule is particularly preferable. Here, “a compound containing 2 or more or 3 or more (meth) acryloyl groups” includes a compound containing 2 or 3 or more acryloyl groups or 2 or 3 or more methacryloyl groups. Means a compound.
Examples of the compound containing three or more (meth) acryloyl groups in the molecule include the tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, and hexa (meth) acrylates exemplified above. The compound can be selected from among compounds such as trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth). ) Acrylate and ditrimethylolpropane tetra (meth) acrylate are particularly preferred. Each of the above compounds may 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 alone or a combination of two or more kinds such as perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, and trifluoroethyl (meth) acrylate.

Although it does not restrict | limit especially about the addition amount of (D) component, Usually, it is 100 mass parts or less with respect to a total of 100 mass parts of (A) component and (B) component. The reason for this is that when the addition amount exceeds 100 parts by mass, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained.
For this reason, the amount of component (D) added is preferably 1 to 80 parts by mass, and more preferably 1 to 65 parts by mass.

(E) Organic solvent It is preferable to add an organic solvent to the curable resin composition. Thus, by adding an organic solvent, a thin antireflection film can be formed uniformly. Examples of such organic solvents include acetone, methyl isobutyl ketone, methyl ethyl ketone, methyl amyl ketone, methanol, ethanol, t-butanol, isopropanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, One kind alone or a combination of two or more kinds such as toluene and xylene may be mentioned.

  The addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by mass with respect to 100 parts by mass in total of components excluding the organic solvent. The reason for this is that when the addition amount is less than 100 parts by mass, 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 mass, the curable resin is used. This is because the storage stability of the composition may decrease, or the viscosity may decrease excessively, making handling difficult.

(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 component (B), 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 includes the (A) ethylenically unsaturated group-containing fluoropolymer, the (B) component, or the (C) component, the (D) component, and (E) as necessary. It can prepare by adding an organic solvent and (F) additive, respectively, and mixing under room temperature or a heating condition. 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 0.1 to 5 J / cm ² , and more preferably set to a value in the range of 0.3 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 this reason, 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 60 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 a film | membrane 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, a hard coat layer 14 and a low refractive index layer 18 are laminated on a substrate 12.
At this time, a high refractive index layer (not shown) may be directly formed on the substrate 12 without providing the hard coat layer 14, or the hard coat layer 14 and the low refractive index layer 18 may be formed. A high refractive index layer may be provided therebetween.
Further, an intermediate refractive index layer (not shown) may be further provided between the high refractive index layer and the low refractive index layer 18 or between the high refractive index layer and the hard coat layer 14.

(1) Low refractive index layer A low refractive index layer is comprised from the film | membrane 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 at a wavelength of 589 nm of the cured product obtained by curing the curable resin composition (the refractive index of Na-D line, measurement temperature 25 ° C.), that is, the refractive index of the low refractive index film is 1.45 or less. It is preferable to do. 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 outstanding antireflection effect is acquired, it is preferable to make the refractive index difference between a low-refractive-index layer and a lower layer into 0.05 or more value. The reason for this is that when the refractive index difference between the low refractive index layer and the lower layer is a value less than 0.05, the synergistic effect in these antireflection film layers cannot be obtained, and the antireflection effect decreases instead. Because there is.
Therefore, the refractive index difference between the low refractive index layer and the lower layer is more preferably set to a value within the range of 0.1 to 0.5, and the value within the range of 0.15 to 0.5. Is more preferable.

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 Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, epoxy-type resin, phenol-type resin, melamine-type resin, It is preferable to include one kind or a combination of two or more kinds of alkyd resins, cyanate resins, acrylic resins, polyester resins, urethane resins, siloxane resins and the like. 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) And a substrate made of norbornene-based resin or the like. 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.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples.

(Production Example 1)
Synthesis of Hydroxyl-Containing Fluoropolymer 1 A stainless steel autoclave with an internal volume of 2.0 liters equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 400 g of ethyl acetate, 53.2 g of perfluoro (propyl vinyl ether), 36.1 g of ethyl vinyl ether. , Hydroxyethyl vinyl ether 44.0 g, lauroyl peroxide 1.00 g, azo group-containing polydimethylsiloxane represented by the above formula (8) (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) 6.0 g and After charging 20.0 g of nonionic reactive emulsifier (NE-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.) and cooling to −50 ° C. with dry ice-methanol, the oxygen in the system was again nitrogen gas. Removed.

Next, 120.0 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 26.4%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer. This is designated as a hydroxyl group-containing fluoropolymer 1. Table 1 shows the amounts (g) of monomers and solvents used.

It attached to the obtained hydroxyl-containing fluoropolymer 1, and measured the polystyrene conversion number average molecular weight by gel permeation chromatography. Moreover, the ratio of each monomer component which comprises the hydroxyl-containing fluoropolymer 1 was determined from both NMR analysis results and elemental analysis results of ¹ H-NMR and ¹³ C-NMR. Moreover, fluorine content was computed from the composition calculated | required by the composition analysis of the polymer by < ¹³ > C-NMR. The results are shown in Table 2.

VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (8) 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 (11).
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 (g)
Polydimethylsiloxane skeleton (e)

(Production Example 2)
Synthesis of ethylenically unsaturated group-containing fluoropolymer (A-1) (methacryl-modified fluoropolymer) (component (A)) 1-liter separable flask equipped with a magnetic stirrer, glass condenser and thermometer Into this, 50.0 g of the hydroxyl group-containing fluoropolymer 1 obtained in Production Example 1, 0.01 g of 2,6-di-t-butylmethylphenol and 370 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor were charged. Stirring was performed until the hydroxyl group-containing fluoropolymer was dissolved in MIBK at 20 ° C., and the solution became transparent and uniform.
Next, 15.1 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. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer A-1 was obtained by maintaining the temperature at ˜65 ° C. and continuing stirring for 5 hours.
2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.2% by mass. The compounds used, solvent and solid content are shown in Table 3.

(Production Example 3)
Synthesis of Hydroxyl-Containing Fluoropolymer 2 A stainless steel autoclave with an internal volume of 2.0 liters equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 200 g of ethyl acetate, 1-vinyloxy-3,3,4, , 6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecane (FAVE-8) 41.2 g, 1H, 1H-perfluoro-2- (2-vinyloxy) Ethoxy) propanol (FVEP) 58.8 g, lauroyl peroxide 0.5 g, azo group-containing polydimethylsiloxane (VPS1001) represented by the above formula (8) 3.0 g and nonionic reactive emulsifier (NE-30) 5 0.0 g was charged and cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.
Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours. At 20 hours, the reaction was stopped by cooling the autoclave with water. After reaching room temperature, the autoclave was opened to obtain a polymer solution having a solid content concentration of 24.0%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 100 g of a hydroxyl group-containing fluoropolymer. This is designated as a hydroxyl group-containing fluoropolymer 2. Table 4 shows the monomers and solvents used.

It attached to the obtained hydroxyl-containing fluoropolymer 2, and measured the polystyrene conversion number average molecular weight by gel permeation chromatography. Moreover, the ratio of each monomer component which comprises a hydroxyl-containing fluoropolymer was determined from both NMR analysis results and elemental analysis results of ¹ H-NMR and ¹³ C-NMR. Moreover, fluorine content was computed from the composition calculated | required by the composition analysis of the polymer by < ¹³ > C-NMR. The results are shown in Table 5.

In Table 5, the correspondence between the monomer and the structural unit is as follows.
Monomer structural unit FEVE-8 (b)
FVEP (d)
NE-30 (g)
Polydimethylsiloxane skeleton (e)

(Production Example 4)
Synthesis of ethylenically unsaturated group-containing fluoropolymer (A-2) (methacryl-modified fluoropolymer) (component (A)) 1-liter separable flask equipped with electromagnetic stirrer, glass condenser and thermometer Into this, 50.0 g of the hydroxyl group-containing fluoropolymer 2 obtained in Production Example 3 was added, 0.01 g of 2,6-di-t-butylmethylphenol and 350 g of methyl isobutyl ketone (MIBK) were charged as a polymerization inhibitor, Stirring was performed until the hydroxyl group-containing fluoropolymer 2 produced in Production Example 3 was dissolved in MIBK at 20 ° C., and the solution became transparent and uniform.
Next, 9.3 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. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer A-2 was obtained by maintaining the temperature at ˜65 ° C. and continuing stirring for 5 hours.
2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 13.8% by mass. The compounds used, solvent and solid content are shown in Table 6.

(Production Example 5)
Synthesis of specific organic compound (Bb-1) To a mixed solution of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in a vessel equipped with a stirrer, 222 parts of isophorone diisocyanate was added in dry air at 50 ° C for 1 hour. Then, the mixture was further stirred at 70 ° C. for 3 hours.
Subsequently, NK ester A-TMM-3LM-N (made of 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., is involved in the reaction. (Only pentaerythritol triacrylate having a hydroxyl group.) 549 parts were added dropwise at 30 ° C. over 1 hour, and then stirred at 60 ° C. for 10 hours to obtain a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate in the organic compound having a polymerizable unsaturated group was measured by FT-IR and found to be 0.1% by mass or less, and each reaction was performed almost quantitatively. I confirmed that. Infrared absorption spectrum of the product absorption peak characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material - click disappeared, new urethane bond and S ( C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 was observed in group, acryloxy group and -S (C = O) NH as polymerizable unsaturated group It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. Thus, 773 parts of a compound having a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group and a composition (Bb-1) of 220 parts of pentaerythritol tetraacrylate not involved in the reaction were obtained. Obtained.

(Production Example 6)
Synthesis of polyfunctional acrylate (D-1) NK ester A-TMM-3LM manufactured by Shin-Nakamura Chemical Co., Ltd. was used for a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer. 93 parts of N (only pentaerythritol triacrylate having a hydroxyl group is involved in the reaction) was added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 6 hours. It was.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 5 and found to be 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
As a result, 75 parts of a urethane hexaacrylate compound was obtained, and a composition (D-1) in which 37 parts of pentaerythritol tetraacrylate that was not involved in the reaction was mixed was obtained.

(Production Example 7)
Preparation of Magnesium Fluoride Particle-Dispersed Sol (B-1) (Component (B)) 1400 parts of methyl isobutyl ketone, 10 parts of a polymeric surfactant (Marialim AAB0851 manufactured by NOF Corporation), magnesium fluoride sol A liquid obtained by mixing 190 parts of magnesium fluoride OP (number average particle diameter 5 μm, refractive index 1.38) with a homomixer was dispersed using a disperser (Ultra Aspec Mill manufactured by Kotobuki Industries). As pre-dispersion, 600 parts of zirconia beads (particle size 0.5 mm) were added to the previous mixed solution, and dispersion was performed at a peripheral speed of 5 m / s for 1 hour. Thereafter, the pre-dispersion liquid was collected, and zirconia beads were filtered off. As the main dispersion using the filtrate, 600 parts of zirconia beads (particle size: 0.2 μm) were added to the filtrate, and dispersed at a peripheral speed of 10 m / s for 2 hours to obtain a white transparent particle dispersion B-1. . After weighing 2 g of B-1 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 12% by mass.
The number average particle diameter of the magnesium fluoride-based particles was 20 to 50 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 8)
Preparation of acrylic modified magnesium fluoride particles (B-2) (component (B)) 8.7 parts of specific organic compound (Bb-1) synthesized in Production Example 5, magnesium fluoride sol obtained in Production Example 7) A mixture of 760 parts (solid content 91.3 parts) and ion-exchanged water 0.1 parts was stirred at 80 ° C. for 3 hours, and then 1.4 parts of orthoformate methyl ester was added and heated at the same temperature for 1 hour. By stirring, a colorless transparent particle dispersion B-2 was obtained. After weighing 2 g of B-2 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 14% by mass.

(Production Example 9)
Preparation of acrylic modified magnesium fluoride particles (B-3) (component (B)) 8.7 parts of the specific organic compound (Bb-1) synthesized in Production Example 5, magnesium fluoride sol (manufactured by Nissan Chemical Co., Ltd. MFS-10P) After stirring 830 parts (solid content 91.3 parts) and ion-exchanged water 0.1 parts at 80 ° C. for 3 hours, 1.4 parts of orthoformate methyl ester is added and heated at the same temperature for 1 hour. By stirring, a colorless transparent particle dispersion B-3 was obtained. After weighing 2 g of B-3 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 12% by mass.
The number average particle diameter of the magnesium fluoride particles was 20 nm. Here, the number average particle diameter was measured with a transmission electron microscope.

(Production Example 10)
Preparation of acrylic modified silica particles (B′-1) 8.7 parts of specific organic compound (Bb-1) synthesized in Production Example 5, methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST (number) (Average particle size 0.022 μm, silica concentration 30%)) 91.3 parts (solid content 27.4 parts), isopropanol 0.2 part and ion-exchanged water 0.1 part were mixed at 80 ° C. for 3 hours. Thereafter, 1.4 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain colorless and transparent particle dispersion B′-1. After weighing 2 g of B′-1 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 35% by mass.
The average particle diameter of the silica-based particles was 20 nm. Here, the average particle diameter was measured with a transmission electron microscope.

(Production Example 11)
Preparation of composition for silica particle-containing hard coat layer In a container shielded from ultraviolet rays, 86 parts of B′-1 synthesized in Production Example 10 (30 parts as a solid content), 65 parts of dipentaerythritol hexaacrylate, 2- A composition for a hard coat layer having a uniform solution was obtained by stirring 5 parts of methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 44 parts of MIBK at 50 ° C. for 2 hours. . 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 mass.

(Production Example 12)
Preparation of base material for coating curable resin composition Single-sided easy-adhesive polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) on the easy-adhesion treated surface of silica particle-containing hard coat layer prepared in Production Example 11 The coating composition was coated with a wire bar coater to a film thickness of 3 μm and dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, ultraviolet rays were irradiated under the light irradiation conditions of 0.9 J / cm ² using a high-pressure mercury lamp in the air to prepare a curable resin composition coating substrate.

(Example 1)
As shown in Table 7, 395 g of MIBK solution of ethylenically unsaturated group-containing fluoropolymer A-1 obtained in Production Example 2 (60 g as the solid content of component (A)), dipentaerythritol pentaacrylate (SR399E) (Sartomer Co., Ltd.) (component (D)) 10 g, polyfunctional acrylate D-1 obtained in Production Example 6 3.75 g, acrylic modified magnesium fluoride particle B-2 obtained in Production Example 8 152 g (21.25 g as the solid content of component (B)), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, Ciba 5 g of Specialty Chemicals) and 1434 g of MIBK are charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 1 hour to make uniform A curable resin composition was obtained. Moreover, it was 5 mass% when solid content concentration was calculated | required by the method of manufacture example 2.

(Examples 2-5, Comparative Examples 1-5)
Each curable composition was obtained in the same manner as in Example 1 except that the composition in Table 7 was followed. The unit of composition of the component in a table | surface is the mass%.

(Evaluation example 1)
Appearance Evaluation Each curable resin composition was coated on the hard coat obtained in Production Example 12 using a wire bar coater so as to have a film thickness of 0.1 μm, and dried at 80 ° C. for 1 minute. Formed. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.3 J / cm ² using a high-pressure mercury lamp under a nitrogen stream to form an antireflection film layer. The appearance of the obtained antireflection film was visually evaluated. The evaluation criteria are as follows. The results are shown in Table 7.
○: Transparent and free of coating unevenness Δ: Slightly uneven coating or slightly turbid ×: There is coating unevenness or turbidity on the entire surface

(Evaluation example 2)
Measurement of Refractive Index of Cured Film Each curable resin composition was applied on a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and then a high pressure mercury lamp was added under nitrogen using a high pressure mercury lamp. It was cured by irradiating with ultraviolet rays under light irradiation conditions of ³ J / cm ² . The obtained cured product was measured refractive index at a wavelength of 589nm at 25 ° C. using an ellipsometer to ^{_(n D 25).} The results are shown in Table 7.

(Evaluation example 3)
Reflectivity measurement of antireflection film The back surface of the antireflection film obtained in Evaluation Example 1 was painted with black spray, and a spectral reflectance measurement device (self-recording spectrophotometer U incorporating a large sample chamber integrating sphere attachment device 150-09090 was incorporated. -3410, manufactured by Hitachi, Ltd.), the reflectance was measured from the substrate side in the wavelength range of 340 to 700 nm and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and the reflectance is reflected from the reflectance of light at a wavelength of 589 nm. The prevention was evaluated.

Scratch resistance test (steel wool resistance test)
The cured film obtained in Evaluation Example 1 was attached with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.). The surface of the cured film was repeatedly rubbed 10 times under the condition of a load of 500 g, the presence or absence of scratches on the surface of the cured film was visually confirmed, and evaluated according to the following evaluation criteria. The results are shown in Table 7.
A: Hardened film peeling or scratches are hardly observed.
○: Slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of the cured film occurs.

Photoradical initiator: Trade name Irg. 907; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; polyfunctional acrylic monomer manufactured by Ciba Specialty Chemicals: trade name SR399E; dipentaerythritol pentaacrylate; Sartomer Made by

  The curable resin composition of the present invention is excellent in scratch resistance, coating property and durability, and is particularly useful as an antireflection film.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Antireflection film 12 Base material 14 Hard-coat layer 18 Low refractive index layer

Claims (10)

The following components (A) and (B):
(A) an ethylenically unsaturated group-containing fluoropolymer,
(B) inorganic fluoride particles,
A curable resin composition containing   When the total of the (A) ethylenically unsaturated group-containing fluoropolymer and the (B) inorganic fluoride particles in the curable resin composition is 100 parts by mass, the (A) ethylenically unsaturated group-containing The curable resin composition according to claim 1, comprising 20 to 95 parts by mass of a fluoropolymer and 5 to 80 parts by mass of the (B) inorganic fluoride particles. The (A) ethylenically unsaturated group-containing fluoropolymer is
A compound containing one isocyanate group and at least one ethylenically unsaturated group;
A hydroxyl group-containing fluoropolymer,
The curable resin composition according to claim 1, wherein the curable resin composition is an ethylenically unsaturated group-containing fluoropolymer obtained by reacting.   The curable resin composition according to any one of claims 1 to 3, wherein the (B) inorganic fluoride particles are particles made of an inorganic fluoride having a refractive index of less than 1.45 at a wavelength of 589 nm.   The curable resin composition according to claim 1, wherein the (B) inorganic fluoride particles are magnesium fluoride particles.   The curable resin composition according to any one of claims 1 to 5, wherein the inorganic fluoride particles (B) are surface-treated with an organic compound containing a polymerizable unsaturated group.   Furthermore, (C) Curable resin composition of any one of Claims 1-6 containing the compound which generate | occur | produces active species by irradiation of an active energy ray.   Furthermore, (D) the compound containing 1 or more (meth) acryloyl group is contained in a molecule | numerator, The curable resin composition of any one of Claims 1-7 characterized by the above-mentioned.   A film obtained by curing the curable resin composition according to claim 1 and having a refractive index of 1.45 or less at a wavelength of 589 nm. An antireflection film comprising the film according to claim 9.

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