JP2008030286A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film which is excellent in abrasion resistance and contamination resistance without spoiling antireflection characteristics. <P>SOLUTION: A laminate has a low refractive index layer made of the cured product of a first curable composition containing an ethylenic unsaturated group-containing fluororesin (A), a (meth)acryloyl group-containing compound (B), and (D), and particles containing silica as a main component (C) and has a refractive index of 1.45 or below and a surface protection layer made of the cured product of a second curable composition containing a (meth)acryloyl group-containing compound (B') and a compound having the structure of poly(dimethyl siloxane) (D) and a thickness of 5-40 nm which are arranged according to a distance from a substrate. The thickness ratio between the low refractive index layer and the surface protection layer is 60:40-95:5. The total thickness of the low refractive index layer and the surface protection layer is 50-200 nm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminate mainly used as an antireflection film. More specifically, the present invention relates to a laminate excellent in antireflection properties and scratch resistance.

  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. These display panels are often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like, and are required to have scratch resistance. 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.

  As a composition for a low refractive index layer of an antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known and disclosed in Patent Document 1, Patent Document 2, Patent Document 3, and the like. . 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 problems, Patent Document 4 discloses 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. A coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio of the number of isocyanate groups / number of hydroxyl groups of 0.01 to 1.0 has been proposed.

JP 57-34107 A JP 59-189108 A JP 60-67518 A Japanese Patent Publication No. 6-35559

However, an antireflection film having a low refractive index layer formed from a conventional composition for a low refractive index layer as an outermost layer does not have sufficient scratch resistance of the low refractive index layer. In addition, it has been difficult to achieve both scratch resistance and antifouling properties such as fingerprint wiping properties and magic repellent properties.
The present invention has been made against the background of the above situation, and its object is to provide an antireflection film that achieves both excellent scratch resistance and antifouling properties without impairing antireflection properties. It is.

  In order to achieve the above object, the present inventors have intensively studied, have a film thickness on the low refractive index layer that does not impair the antireflection property, and have higher hardness and antifouling than the low refractive index layer. By providing a layer having excellent properties, it was found that scratch resistance and antifouling properties can be improved while maintaining antireflection properties, and the present invention has been completed.

That is, the present invention provides the following laminate and antireflection film.
1. A low refractive index layer comprising a cured product of the first curable composition containing the following components (A), (B) and (C) and having a refractive index of 1.45 or less, and the following components (B ′) and A laminate having a surface protective layer having a film thickness of 5 nm or more and 40 nm or less made of a cured product of the second curable composition containing (D) in this order from the side closer to the substrate,
The film thickness ratio of the low refractive index layer and the surface protective layer is in the range of 60:40 to 95: 5, and the total film thickness of the low refractive index layer and the surface protective layer is 50. Laminate in the range of ~ 200 nm.
(A) Ethylenically unsaturated group-containing fluorine-containing polymer (B) Compound containing (meth) acryloyl group (C) Silica-based particle (B ′) Compound containing (meth) acryloyl group (D 1) Compound containing polydimethylsiloxane structure 2. The laminate according to 1 above, wherein the second curable composition further contains (C ′) particles containing silica as a main component.
3. 3. The laminate according to 1 or 2 above, wherein a mantel hardness value of the surface protective layer measured by a microhardness meter is 1.2 times or more that of the low refractive index layer.
4). (C) The laminate according to any one of the above items 1 to 3, wherein a particle having silica as a main component has a spherical shape or a chain sphere shape.
5. The laminate according to any one of 2 to 4 above, wherein the shape of the particles containing (C ′) silica as a main component is a sphere or a chain sphere.
6). The laminate according to any one of 1 to 5 above, wherein the particles having (C) silica as a main component have a (meth) acryloyl group on the surface.
7). The laminate according to any one of 2 to 6 above, wherein the particles containing (C ′) silica as a main component have a (meth) acryloyl group on the surface.
8). Any of (1) to (7) above, wherein the (B) (meth) acryloyl group-containing compound and the (B ′) (meth) acryloyl group-containing compound contain two or more (meth) acryloyl group-containing compounds. The laminated body of crab.
9. The laminate according to any one of 1 to 8 above, wherein the first curable composition contains a compound that generates active species upon irradiation with active energy rays.
10. The laminate according to any one of 1 to 9 above, wherein the second curable composition contains a compound that generates active species upon irradiation with active energy rays.
11. The antireflection film which consists of a laminated body in any one of said 1-10.

According to the present invention, it is possible to obtain a laminate having low reflectance and excellent scratch resistance and antifouling properties.
According to the present invention, an antireflection film having excellent scratch resistance and antifouling properties can be obtained.

  Hereinafter, the laminate of the present invention will be specifically described.

I. Structure of Laminate The laminate of the present invention is characterized by having at least a substrate, a low refractive index layer having a refractive index of 1.45 or less, and a surface protective layer in this order. The low refractive index layer is a layer that exhibits low reflectance, which is the basic performance as an antireflection film, and the surface protective layer protects the low refractive index layer from external impact, abrasion, and friction, and is a laminate. This is a layer that imparts high scratch resistance to the (antireflection film). Furthermore, the surface protective layer also plays a role of imparting antifouling performance such as prevention of adhesion of dirt such as fingerprints and magic throats or easy wiping.
The low refractive index layer needs to have a refractive index of 1.45 or less, preferably 1.40 or less, and more preferably 1.37 or less. If the refractive index is higher than 1.45, sufficient antireflection performance may not be obtained. In addition, the refractive index in this invention means the refractive index of the Na-D line | wire (wavelength 589nm) in 25 degreeC.

  The refractive index of the surface protective layer is within the same refractive index to 1.65 as the low refractive index layer, preferably within the same refractive index to 1.60 as the low refractive layer, more preferably the same as the low refractive layer. The rate is in the range of 1.55. If the refractive index is higher than 1.65, the antireflection effect may be impaired.

  The antireflection film is usually composed of two layers of a high refractive index layer and a low refractive index layer, and by forming this on a substrate, a laminate suitable as an antireflection film can be formed. The schematic diagram of the laminated body which is one Embodiment of this invention is shown in FIG. In the laminate 1 of the present invention, a hard coat layer 12 is provided on a substrate 10, and a first curable composition (hereinafter referred to as “low refractive index layer forming composition”) described later is sometimes provided thereon. ) Is applied and cured, and a second curable composition (hereinafter also referred to as a “surface protective layer forming composition”) described below is further cured thereon. Thus, a high-hardness surface protective layer 16 is formed.

  The antireflection film may further include layers other than these. For example, a plurality of combinations of a high refractive index film and a low refractive index film are provided to provide a relatively uniform reflectance with respect to light in a wide wavelength range. A so-called wideband antireflection film having characteristics may be used, and an antistatic layer may be provided.

  Although there is no restriction | limiting in particular as a base material, When using as an antireflection film, the above-mentioned plastics (a polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, an epoxy resin, a melamine resin, a triacetyl cellulose (TAC) resin, for example are mentioned. , ABS resin, AS resin, norbornene resin, etc.).

  A surface protective layer obtained by applying a composition for forming a surface protective layer, which will be described later, onto a substrate and UV-curing it is excellent in scratch resistance (steel wool resistance), haze, and has high hardness.

The film thickness ratio of the low refractive index layer and the surface protective layer in the laminate of the present invention needs to be in the range of 60:40 to 95: 5. When deviating from this range, the reflectance characteristics may be impaired, or the laminate may be inferior in scratch resistance. For these reasons, the film thickness ratio is more preferably in the range of 70:30 to 95: 5.
Furthermore, the total film thickness of the low refractive index layer and the surface protective layer needs to be in the range of 50 to 200 nm. If the total film thickness is less than 50 nm or exceeds 200 nm, sufficient antireflection performance may not be obtained. For this reason, the total film thickness is more preferably in the range of 70 to 150 nm.

  In the laminate of the present invention, the Mantel hardness value of the surface protective layer measured by a microhardness meter is preferably 1.2 times or more that of the low refractive index layer, and preferably 1.5 times or more. More preferred. When the hardness of the surface protective layer is 1.2 times or more that of the low refractive index layer, good scratch resistance is exhibited. In addition, as a device used for the measurement of the microhardness, there is a Picodenter (registered trademark) HM500 and a Fisher scope (registered trademark) H100C (both manufactured by Fischer). The microhardness is measured using a Vickers indenter with a maximum load of 0.1 mN.

II. First curable composition (composition for forming a low refractive index layer)
The first curable composition (low refractive index layer forming composition) used in the present invention is (A) an ethylenically unsaturated group-containing fluoropolymer, (B) a compound containing a (meth) acryloyl group, (C) The particle | grains which have a silica as a main component are included.

1. Each component of the composition for forming a low refractive index layer will be specifically described.

(A) Ethylenically unsaturated group-containing fluoropolymer (A) The ethylenically unsaturated group-containing fluoropolymer is a polymer of a fluorine-based olefin. By the component (A), the composition of the present invention exhibits basic performance as a low refractive index composition for an antireflection film such as low refractive index, antifouling property, chemical resistance, and water resistance.
Preferably, the component (A) is modified with a (meth) acrylic compound having a side chain hydroxyl group having an isocyanate group, an acid chloride group or a carboxylic acid group. Such modification allows co-crosslinking with the radically polymerizable (meth) acrylic compound and improves the scratch resistance.

  The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by reacting a compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group with a hydroxyl group-containing fluoropolymer.

(1) A compound containing at least one ethylenically unsaturated group and a group capable of reacting with a hydroxyl group. Such a compound is a compound containing at least one ethylenically unsaturated group in the molecule. Any functional group capable of reacting with a hydroxyl group of the fluoropolymer is not particularly limited.
Moreover, as said ethylenically unsaturated group, since the curable resin composition mentioned later can be hardened more easily, the compound which has a (meth) acryloyl group is more preferable.
Such compounds include (meth) acrylic acid, (meth) acryloyl chloride, anhydrous (meth) acrylic acid, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1- (Bisacryloyloxymethyl) ethyl isocyanate may be used alone or in combination of two or more.
In addition, as a commercial item of (meth) acrylate which has an isocyanate group, Showa Denko Co., Ltd. brand name Karenz MOI, Karenz AOI, Karenz BEI is mentioned, for example.

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

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

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

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

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

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

[In Formula (2-1), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _d —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or A glycidyl group, d represents a number of 0 or 1, and a carboxyl group or an alkoxycarbonyl group]

［式中、Ｒ^３は式（２−１）で定義した通りであり、Ｒ^２４はフルオロアルキル基を示し、ｘは０〜２の数を示す］

[Wherein R ³ is as defined in formula (2-1), R ²⁴ represents a fluoroalkyl group, and x represents a number of 0 to 2]

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

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

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

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluororefines such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Perfluoro (alkoxyalkyl vinyl ether) s such as perfluoro (propoxypropyl vinyl ether) These may be used alone or in combination of two or more.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and it is more preferable to use these in combination.

The content of the structural unit (a) is 30 when the total of the structural unit (a), (b-1) and / or (b-2), and (c) is 100 mol%. -65 mol%. The reason for this is that when the content is less than 30 mol%, it is difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present invention, whereas This is because when the ratio exceeds 65 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
Moreover, for such reasons, the content of the structural unit (a) is set to 100 mol% of the total of the structural unit (a), (b-1) and / or (b-2), and (c). When it is, it is more preferable to set it as 35-60 mol%, and it is more preferable to set it as 40-55 mol%.

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

  The structural unit (b-1) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid vinyl, vinyl caproate, vinyl vinyl versatate, vinyl stearate Tellurium; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc. The combination of is mentioned.

（式中、Ｒ^３は水素原子又はメチル基であり、ｘは０〜２の数を表す。また、上記式中、芳香環の中にFと記した基は、５つの水素の全てがフッ素原子で置換されていることを示す。） (Iii) Structural unit (b-2)
In the copolymer of the present invention, the structural unit (b-2) can be used together with the structural unit (b-1) or in place of the structural unit (b-1). The structural unit (b-2) can be introduced by using a vinyl monomer represented by the formula (2-2) as a polymerization component. Specific examples of such vinyl monomers include those having the following structural formula.

(In the formula, R ³ represents a hydrogen atom or a methyl group, and x represents a number from 0 to 2. In the above formula, the group marked F in the aromatic ring is all five hydrogens are fluorine. Indicates that the atom is substituted.)

The content of the structural unit (b-1) and / or (b-2) is the sum of the structural unit (a), (b-1) and / or (b-2), and (c). When the content is 100 mol%, it is 1 to 50 mol%. The reason for this is that when the content rate is less than 1 mol%, the solubility of the hydroxyl group-containing fluorine-containing copolymer in the organic solvent may be reduced, whereas when the content rate exceeds 50 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluorine-containing copolymer may deteriorate.
For these reasons, the content of the structural units (b-1) and / or (b-2) is changed to the structural units (a), (b-1) and (b-2), and (c )) Is more preferably from 1 to 45 mol%. Moreover, the content rate of (b-1) and / or (b-2) shown above is the structural unit when the structural unit (b-1) or (b-2) is used alone. It means the content of either (b-1) or (b-2), and when the structural units (b-1) and (b-2) are used together, it means the total content of both. .

(Iv) 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.

The content of the structural unit (c) is 5 when the total of the structural units (a), (b-1) and / or (b-2), and (c) is 100 mol%. It is preferable to set it as -60 mol%. The reason for this is that when the content is less than 5 mol%, the hydroxyl group content of the fluoropolymer is lowered, and sufficient hardness of the cured coating film may not be obtained. On the other hand, the content is 60 mol. This is because if it exceeds%, optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
For these reasons, the content of the structural unit (c) is set to 100 mol% of the total of the structural units (a), (b-1) and / or (b-2), and (c). When it is, it is more preferable to set it as 5-55 mol%, and it is more preferable to set it as 10-50 mol%.

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

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

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

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

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

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

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

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

［式（６）中、Ｒ¹⁰〜Ｒ¹³、Ｒ¹⁴〜Ｒ¹⁷、ｐ、ｑ、ｓ、ｔ及びｙは、上記式（５）と同じである。］ (E) A structural unit represented by the following formula (6).

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

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

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

［式（７）中、ｙ及びｚは、上記式（５）と同じである。］

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

In addition, the content rate of the structural unit (d) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as 10 mol part. 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.
Moreover, for such reasons, the content of the structural unit (d) is adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-5 mol part, and it is further more preferable to set it as 0.1-3 mol part. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

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

［式（８）中、Ｒ¹⁸は乳化作用を有する基を示す］ (F) A structural unit represented by the following formula (8).

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

In the formula (8), the group having an emulsifying action of R ¹⁸ 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（９−１）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］

［式（９−２）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］ Examples of the group having such an emulsifying action include groups represented by the following formula (9-1) or (9-2).

[In Formula (9-1), 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]

[In Formula (9-2), n, m, and u are the same as in Formula (9-1) above]

  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such a reactive emulsifier include compounds represented by the following formula (10-1) or (10-2).

［式（１０−１）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］

［式（１０−２）中、ｎ、ｍ及びｕは、上記式（９−１）と同様である］

[In Formula (10-1), n, m, and u are the same as in Formula (9-1) above]

[In Formula (10-2), n, m, and u are the same as in Formula (9-1) above]

In addition, the content rate of the structural unit (f) is 0.1 to the total 100 mol parts of the structural unit (a), (b-1) and / or (b-2), and (c). It is preferable to set it as -5 mol part. 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 such reasons, the content of the structural unit (f) is adjusted to 100 mol parts in total of the structural unit (a), (b-1) and / or (b-2), and (c). On the other hand, it is more preferable to set it as 0.1-3 mol part, and it is further more preferable to set it as 0.2-3 mol part.

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

Although it does not restrict | limit especially about the addition amount of (A) component, It is 5-80 mass% normally with respect to composition whole quantity other than an organic solvent. The reason for this is that when the addition amount is less than 5% by mass, the refractive index of the cured coating film of the curable resin composition is increased, and a sufficient antireflection effect may not be obtained. This is because if the amount exceeds 80% 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 5 to 70% by mass, and even more preferably 5 to 60% by mass.

(B) Compound containing (meth) acryloyl group A compound having (meth) acryloyl group (hereinafter sometimes referred to as "(meth) acrylate compound") is obtained by curing the first curable composition. It has a function of enhancing the scratch resistance of the cured product and the antireflection film using the cured product.

  Compounds containing one (meth) acryloyl group include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth). Acrylates, cyclohexyl (meth) acrylate and other alicyclic structure-containing (meth) acrylates, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isop Pill (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, Heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Toxiethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, Ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (Meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Examples thereof include relate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like. As these commercial products, Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, manufactured by Toa Gosei Co., Ltd.); Biscote LA, STA, IBXA, 2 -MTA, # 192, # 193 (Osaka Organic Chemical Co., Ltd.); NK Ester AMP-10G, AMP-20G, AMP-60G (above, Shin-Nakamura Chemical Co., Ltd.); Light acrylate LA, S-A, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (hidden, Hitachi Chemical) Kogyo Co., Ltd.).

  By adding a compound containing one (meth) acryloyl group, it is possible to improve the adhesion with the base hard coat. Specifically, among the above compounds, (meth) acryloylmorpholine, benzyl (meth) acrylate, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4- (meta ) Acrylyloxymethyl-2,2-dimethyl-1,3-dioxolane and the like. Of these compounds, (meth) acryloylmorpholine and benzyl (meth) acrylate are particularly preferred. Examples of commercially available products of these compounds include MMDOL30, MEDOL30, MIBDOL30, CHDOL30, MEDOL10, MIBDOL10, MIBDOL10, CHDOL10, Biscote 150, Biscote 160 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), ACMO (above ) Manufactured by Kojin).

  Examples of the compound containing two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tri Cyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate Nurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, pro Renoxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether at both ends (meth) acrylic acid Adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, Polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate , Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di ( (Meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, etc. It can be illustrated. Examples of commercially available products of these multifunctional monomers include SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA 20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M- 309, M-310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF 400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  In addition, among these, the compound containing 2 or more (meth) acryloyl groups in a molecule | numerator is preferable for the composition of this invention. Examples of the compound containing two or more (meth) acryloyl groups include tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds and hexa (meth) acrylate compounds exemplified above. Among these, pentaerythritol hydroxytriacrylate and trimethylolpropane triacrylate are particularly preferable. Each of the above compounds can be used alone or in combination of two or more.

  Moreover, these (meth) acrylate compounds may contain fluorine. Examples of such compounds are perfluoro-1,6-hexanediol di (meth) acrylate, octafluorooctane-1,6-di (meth) acrylate, octafluorooctanediol and 2- (meth) acryloyloxyethyl. One type of isocyanate, addition of 2- (meth) acryloyloxypropyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, triacryloylheptadecafluorononenylpentaerythritol (LINC-3A, manufactured by Kyoeisha Chemical Co., Ltd.), etc. Single or 2 or more types of combinations are mentioned.

Although it does not restrict | limit especially about the addition amount of (B) component, it is 5-50 mass% normally with respect to composition whole quantity other than an organic solvent. The reason for this is that when the addition amount is less than 5% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained. On the other hand, when the addition amount exceeds 50% by mass, This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained.
For this reason, the amount of component (B) added is more preferably 5 to 40% by mass, and still more preferably 10 to 40% by mass.

(C) Particles mainly composed of silica Solid particles or hollow particles can be used as particles mainly composed of silica (hereinafter sometimes referred to as “silica particles”). The particles have a function of developing the coating strength of the low refractive index layer. Further, when hollow particles are used, the refractive index can be lowered. Furthermore, by using irregular particles such as chain spherical particles, the refractive index can be lowered due to internal voids and surface irregularities.

The dispersion medium of silica particles is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.
Commercially available products of solid spherical particles mainly composed of silica include, for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, MEK-ST-S, MEK. -ST-L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST -OL etc. can be mentioned. Moreover, as an amorphous particle, Nissan Chemical Industries Ltd. brand name: Snowtex-PS-M, PS-S, PS-SO, UP, OUP, Sakai Chemical Industry Co., Ltd. brand name: PL-1 , PL-2, PL-3, PL-3H and the like. Moreover, as a hollow particle, the catalyst chemical industry Co., Ltd. brand name: JX1008SIV, JX1009SIV, JX1010SIV, JX1011SIV etc. can be mentioned.

In addition, these colloidal silica surfaces that have been subjected to surface treatment such as chemical modification can be used, for example, those containing hydrolyzable silicon compounds having one or more alkyl groups in the molecule or hydrolysates thereof. Etc. can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane and the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane and the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane and the like having a thiocyanate group 3 As thiocyanate propyltrimethoxysilane and the like having an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having a thiol group 3 -Mercaptopropyltrimethoxy Sisilane etc. can be mentioned. A preferred compound is 3-mercaptopropyltrimethoxysilane.

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

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

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

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

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

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

(Iii) A silanol group or a group that generates a silanol group by hydrolysis The specific organic compound is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or by hydrolysis. A compound that generates a silanol group (hereinafter sometimes referred to as a “silanol group-generating compound”) is preferable. Examples of such a silanol group-forming compound include compounds having an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, etc. on the silicon atom, but an alkoxy group or aryloxy group on the silicon atom. In other words, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-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 Specific examples of the specific organic compound include compounds represented by the following formula (12).

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

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

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

R ²² is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (11). Can also be included.

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

  Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

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

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

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

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

  Examples of such polyisocyanate compounds include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4 Xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4, 4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl) Isocyanato), 2,2,4-trimethylhexamethylene diisocyanate, bis (2 Isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3- Bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and the like can be mentioned. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane and the like are preferable. These can be used alone or in combination of two or more.

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

Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythr Litholtri (meth) acrylate, dipentaerythritol penta Meth) acrylate - door, and the like can be given. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable.
These compounds can be used individually by 1 type or in mixture of 2 or more types.

(3) Surface treatment method of particles mainly composed of silica with a specific organic compound (hereinafter also referred to as particles) The surface treatment method of particles with a specific organic compound is not particularly limited. It is also possible to manufacture by mixing, heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-forming site of the specific organic compound with the particles. However, when the specific organic compound has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.

  The reaction amount of the particles and the specific organic compound is preferably 0.01% by 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 (12) as an example of the specific organic compound.
The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment may be an amount that allows at least one alkoxy group on silicon in one molecule to be hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface, and particles composed of such components are not included. In the hardened | cured material of the composition to contain, the effect of expression of high hardness and abrasion resistance is low.

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

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

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

In addition, an acid, a salt or a base may be added as a catalyst to promote the reaction during the surface treatment.
Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, and itacone An unsaturated organic acid such as an acid, as a salt, for example, an ammonium salt such as tetramethylammonium hydrochloride or tetrabutylammonium hydrochloride, and as a base, for example, aqueous ammonia, diethylamine, triethylamine, dibutylamine, Primary, secondary or tertiary aliphatic amines such as cyclohexylamine, aromatic amines such as pyridine, quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide Etc.
Among these, preferred examples of the acid include organic acids and unsaturated organic acids, and the base includes tertiary amine or quaternary ammonium hydroxide. The amount of these acids, salts or bases added is preferably 0.001 to 1.0 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.

In the case of solid particles, the amount of component (C) is usually 1 to 50% by mass, preferably 1 to 40% by mass, and more preferably 1 to 30% by mass with respect to the total amount of the composition other than the organic solvent. . If it is less than 1% by mass, the effect of improving the film strength may not be exhibited, and if it is 50% by mass or more, the refractive index increases and the antireflection ability may not be sufficient. Moreover, when the particle | grains to be used are hollow particles, it is normally mix | blended 1-90 mass% with respect to composition whole quantity except an organic solvent, 10-80 mass% is preferable, and 20-80 mass% is more preferable. In the present invention, solid particles and hollow particles can be used in combination.
The amount of particles means solid content, and when the particles are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of solvent.

(E) Compound that generates active species by irradiation of active energy rays or heat The compound that generates active species by irradiation of active energy rays or heat is used to efficiently cure the first curable composition. it can.

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

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

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

(Ii) Addition amount The addition amount of the photopolymerization initiator is not particularly limited, but the solid content of the first curable composition (total of components (A) to (C) other than the organic solvent) is 100 masses. It is preferable that it is 0.1-20 mass parts with respect to a part. This is because when the amount added is less than 0.1 parts by mass, the curing reaction is insufficient and the scratch resistance may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20 parts by mass, the refractive index of the cured product is increased, the antireflection effect is lowered, and the scratch resistance may be insufficient.
For this reason, it is more preferable to add 1 to 10 parts by mass of the photopolymerization initiator.

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

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

(Ii) Addition amount The addition amount of the thermal polymerization initiator is not particularly limited, but is 0.1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the first curable composition. 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 20 parts by mass, the refractive index of the cured product increases and the antireflection effect may be lowered.
For this reason, it is more preferable to add 1 to 10 parts by mass of the thermal polymerization initiator.

(F) Organic solvent It is preferable that the curable resin composition is further diluted with an organic solvent. By diluting with an organic solvent, a thin antireflection film can be formed uniformly. Examples of such organic solvents include ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl acetate, esters such as methyl amyl ketone, ketones such as methyl isobutyl ketone, methyl ethyl ketone, and acetone, t-butanol, isopropanol, propylene glycol. One kind alone or a combination of two or more kinds of alcohols such as monomethyl ether may be mentioned.

  Although it does not restrict | limit especially also about the dilution amount by an organic solvent, It is preferable to add 100-100,000 mass parts organic solvent with respect to 100 mass parts of total solids. The reason for this is that when the addition amount is less than 100 parts by mass or 100,000 parts by mass or more, the coating properties deteriorate and an optical thin film suitable for an antireflection film cannot be obtained.

(G) Other components In the composition for forming a low refractive index layer, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability, as necessary. An improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, and the like can be appropriately blended.

2. Method for Producing Composition for Forming Low Refractive Index Layer The first curable composition used in the present invention contains (A) an ethylenically unsaturated group-containing fluoropolymer, (B) (meth) acrylic group. The compound component, (C) silica particles and (E) component, (F) organic solvent, and (G) additive are respectively added and mixed at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

3. Method for applying low-refractive-index layer-forming composition The low-refractive-index-layer-forming composition is suitable for use in forming an antireflection film or a coating material. Examples thereof include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. The shape of these substrates may be a plate, film or three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. Can be mentioned.

4). Curing Method for Low Refractive Index Layer Composition The low refractive index layer forming composition can be cured by radiation (light). The radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, a laser, or the like, or visible light is used. As a radiation source, sunlight, a lamp, a fluorescent lamp, a laser, etc. are generated from a commercially available tungsten filament as an ultraviolet ray source, a mercury lamp, a halide lamp, a laser, etc., and as an electron beam source. Examples include a method using thermal electrons, a cold cathode method in which a metal is generated through a high voltage pulse, and a secondary electron method in which secondary electrons generated by collision between ionized gaseous molecules and a metal electrode are used. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

The low refractive index layer of the laminate of the present invention is obtained by curing the first curable composition.
The curing conditions for the first curable composition are not particularly limited. For example, when an active energy ray is used, the exposure amount is set to a value within the range of 0.01 to 10 J / cm ^2. preferable.
This is because when the exposure dose is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure dose exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.
For these reasons, the exposure dose is more preferably set to a value in the range of 0.05 to 5 J / cm ² , and more preferably set to a value in the range of 0.1 to 3 J / cm ^2. .
Further, it is desirable that the curing atmosphere is an inert gas atmosphere in order to prevent polymerization inhibition due to oxygen. Examples of the inert gas include helium, argon, nitrogen, carbon dioxide and the like. The atmosphere of these inert gases preferably has a residual oxygen concentration of 5000 ppm or less, more preferably 1000 ppm or less, and particularly preferably 100 ppm or less. If the residual oxygen concentration exceeds 5000 ppm, poor curing may occur.

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

III. Second curable composition (surface protective layer forming composition)
The second curable composition (surface protective layer forming composition) used in the present invention includes (B ′) a compound containing a (meth) acryloyl group and (D) a compound containing a polydimethylsiloxane structure. . Moreover, it is also preferable that the 2nd curable composition (composition for low-refractive-index layer formation) used by this invention contains the particle | grains which have (C ') silica as a main component.

1. Each component of the composition for forming a surface protective layer will be specifically described.
The composition for forming a surface protective layer used in the present invention is a compound (polyfunctional (meth) acrylate) containing at least two (meth) acryloyl groups among compounds containing (B ′) (meth) acrylic groups. Compound). By containing a polyfunctional (meth) acrylate compound, the hardness as a surface protective layer can be expressed. Specific examples of this compound are as described in the description of the component (B) of the composition for forming a low refractive index layer.

  The content of the compound (B ′) in the composition for forming a surface protective layer is usually in the range of 10 to 99% by mass, preferably in the range of 20 to 99% by mass, based on the total amount of the composition excluding the organic solvent. More preferably, it is in the range of 20 to 95% by mass. If the content of the compound (B ′) is less than 20% by mass, a cured film having the desired hardness may not be obtained.

The composition for forming a surface protective layer contains (D) a compound containing a polydimethylsiloxane structure. By containing the compound, it is possible to improve the practicality of the resulting cured film (surface protective layer) as an antireflection film such as slipperiness, antifouling property, and oil repellency.
Specific examples of the compound containing a polydimethylsiloxane structure include Chisso Corporation trade names: Iraplain FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411. , FM-0421, FM-0425, FM-DA11, FM-DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T, manufactured by Big Chemie Japan Co., Ltd. Trade names: UV3500, UV3510 , UV3530, BY16-004, manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: SF8428, manufactured by Wako Pure Chemical Industries, Ltd., trade name: VPS-1001, and the like.

  (D) The addition amount of a component is 0.01-50 mass% normally with respect to the composition whole quantity except an organic solvent. The reason for this is that when the addition amount is less than 0.01% by mass, the effect of improving the slipperiness cannot be sufficiently obtained. On the other hand, when the addition amount exceeds 50% by mass, the coating properties deteriorate due to an excessive amount of components. Because. For this reason, the amount of component (D) added is more preferably 0.5 to 40% by mass, and even more preferably 1.0 to 30% by mass.

The composition for forming a surface protective layer may further contain (C ′) particles containing silica as a main component (hereinafter sometimes referred to as silica particles). By containing particles mainly composed of silica, the hardness of the surface protective layer can be increased, and the scratch resistance of the laminate can be further increased.
Moreover, it is preferable that the silica particle is couple | bonded with the organic compound (specific organic compound) which has the said polymerizable unsaturated group. By having a polymerizable unsaturated group on the particle surface, crosslinking with the compound (B ′) can be formed, and the scratch resistance is further improved.
Specific examples of the silica particles and reactive silica particles are as described in the description of the component (C) of the composition for forming a low refractive index layer.

  The content of the silica particles in the composition for forming a surface protective layer is usually 0 to 70% by mass with respect to the total amount of the composition excluding the organic solvent, whether it is the silica particles themselves or the reactive silica particles. If the silica particle content exceeds 70% by mass, preferably 0 to 60% by mass, more preferably 0 to 50% by mass, the coating strength may be lowered.

  The composition for forming a surface protective layer used in the present invention includes (E) a radical photopolymerization initiator, (F) an organic solvent, and (G) an additive used in the composition for forming a low refractive index layer in addition to the above components. Can be contained.

  The content of the photo radical polymerization initiator in the composition for forming a surface protective layer is usually 0.5 to 20% by mass, preferably 0.5 to 15% by mass, more preferably based on the total amount of the composition excluding the organic solvent. Is 0.5 to 10% by mass. If the radical photopolymerization initiator is less than 0.5% by mass, curing failure may occur, and if it exceeds 20% by mass, the coating strength may be reduced due to the plasticizing effect.

  The amount of dilution with the organic solvent in the composition for forming the surface protective layer is not particularly limited, but it is preferable to add 100 to 100,000 parts by mass of the organic solvent with respect to 100 parts by mass of the total solid content. . The reason for this is that when the addition amount is less than 100 parts by mass or 100,000 parts by mass or more, the coating properties deteriorate and an optical thin film suitable for an antireflection film cannot be obtained.

2. Manufacturing method of surface protective layer forming composition The surface protective layer forming composition used in the present invention is manufactured, for example, as follows.
(B ′) component, (C ′) component, (D) component, and if necessary, a photopolymerization initiator, an organic solvent, other additives, etc. are placed in a reaction vessel equipped with a stirrer at 35 to 45 ° C. The surface protective layer-forming composition can be obtained by stirring for about an hour.

3. Method for Applying (Coating) Surface Protective Layer Forming Composition The surface protective layer forming composition is applied on the low refractive index layer. Examples of the coating method include ordinary coating methods such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, and brush coating.

4). Curing Method for Surface Protecting Layer Forming Composition The curing method for the surface protecting layer forming composition is the same as the curing method for the low refractive index layer forming composition.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to description of these Examples. In the examples, unless otherwise specified, the amount of each component means “parts” by mass and “%” means mass%.

(Production Example 1)
Synthesis of hydroxyl group-containing fluoropolymer After a 2.0 liter stainless steel autoclave with a magnetic stirrer was sufficiently replaced with nitrogen gas, 11544 g of ethyl acetate, 3464 g of perfluoro (propyl vinyl ether), 938 g of ethyl vinyl ether, 1145 g of hydroxyethyl vinyl ether , 37.5 g of lauroyl peroxide, azo group-containing polydimethylsiloxane (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) 225 g and nonionic reactive emulsifier (ER-30 (trade name), Asahi Denka Kogyo ( 1125 g of a product obtained by distilling off all the solvent in advance was prepared, cooled to −50 ° C. with dry ice-methanol, and oxygen in the system was removed again with nitrogen gas.

Next, 1953 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 about 5 kg of a hydroxyl group-containing fluoropolymer. Table 1 shows the amounts of monomers and solvents used.

It attached to the obtained hydroxyl-containing fluoropolymer, 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. The results are shown in Table 2.

VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (7) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. ER-30 is a nonionic reactive emulsifier wherein n is 10 to 14, m is 1 and u is 14 to 45 in the above formula (10-2).
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-1)
Hydroxyethyl vinyl ether (c)
ER-30 (f)
Polydimethylsiloxane skeleton (d)

(Production Example 2)
Synthesis of Ethylenically Unsaturated Group-Containing Fluoropolymer (Methacryl-Modified Fluoropolymer) (Component (A)) Production Example in a 1-liter separable flask equipped with a magnetic stirrer, glass condenser and thermometer 120 g of the hydroxyl group-containing fluoropolymer obtained in 1 and 0.02 g of 2,6-di-t-butylmethylphenol and 862 g of methyl isobutyl ketone (MIBK) as a polymerization inhibitor were charged at 20 ° C. Stirring was performed until the polymer was dissolved in MIBK and the solution became transparent and uniform.
Next, to this system, 32.1 g of 2-methacryloyloxyethyl isocyanate was added and stirred until the solution became homogeneous, then 0.3 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. A MIBK solution of an ethylenically unsaturated group-containing fluoropolymer was obtained by maintaining the temperature at 65 ° C. and continuing stirring for 5 hours.
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 15.0% by mass.

(Production Example 3)
Production of specific organic compound (Cb) In a dry air solution, a solution consisting of 23.0 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate is stirred at 50 ° C for 1 hour with 60.0 parts of isophorone diisocyanate. After dropping, the mixture was stirred at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Of these, it is pentaerythritol having a hydroxyl group that is involved in the reaction. (Only triacrylate.) After adding 202.0 parts dropwise at 30 ° C. over 1 hour, specific organic compound (Cb) was obtained by heating and stirring at 60 ° C. for 3 hours.
In the infrared absorption spectrum of the product, the absorption peak at 2550 cm ⁻¹ characteristic for the mercapto group in the raw material and the absorption peak at 2260 cm ⁻¹ characteristic for the isocyanate group disappear, and [−O—C (= O) -NH-] group and [-S-C (= O) -NH-] peak characteristic 1720 cm ^-1 to the carbonyl in the group the peak and acryloyl groups characteristic 1660 cm ^-1 - click is observed And a specific organic compound having both an acryloyl group as a polymerizable unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group is formed. Showed that.

(Production Example 4)
Production of acrylic-modified solid silica particles (component (C ′)) 8.7 parts of the specific organic compound (Cb) synthesized in Production Example 3, 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 parts and ion-exchanged water 0.1 parts were mixed at 80 ° C. for 3 hours. After stirring, 1.4 parts of methyl orthoformate was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a colorless transparent particle dispersion C′-1. When 2 g of C′-1 was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, it 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 5)
Production of composition for forming surface protective layer 129 g of acrylic-modified solid silica particles C′-1 synthesized in Production Example 4 (45 g as a solid content), 41 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one 4 g, polydimethylsiloxane compound (FM0725 manufactured by Chisso) 10 g, MIBK9816 parts by mass for 2 hours at room temperature for 2 hours, a uniform solution composition for the surface protective layer Got. 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 1% by mass.
On the TAC film, the prepared composition for a surface protective layer was applied with a wire bar coater so as to have a film thickness of 100 nm, and dried in an oven at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.3 J / cm ² using a high-pressure mercury lamp under nitrogen. When the mantel hardness value of the cured coating film at an indentation depth of 10 nm was measured with HS100 manufactured by Fischer Instruments, it was 3000 N / mm ² .

(Production Example 6)
Production of composition for forming low refractive index layer 33.5 g (5 g as the solid content of component (A)) of MIBK solution of ethylenically unsaturated group-containing fluoropolymer obtained in Production Example 2, and MIBK of hollow silica particles 375 g of sol (JX1009SIV manufactured by Catalytic Chemical Industry) (75 g as the solid content of the component (C1)), 17 g of triacryloylheptadecafluorononenylpentaerythritol (LINC-3A, manufactured by Kyoeisha Chemical Co., Ltd.), 2-hydroxy 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Irgacure 127, manufactured by Ciba Specialty Chemicals) and MIBK 1000 g , 1100 g of t-butanol was charged into a glass separable flask equipped with a stirrer, The mixture was stirred at room temperature for 1 hour to obtain a uniform curable resin composition (low refractive index layer forming composition). Further, the solid content concentration determined by the method of Production Example 2 was 4.0% by mass.
On the TAC film, the prepared composition for forming a low refractive index layer was coated with a wire bar coater so as to have a film thickness of 100 nm, and dried in an oven at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 0.3 J / cm ² using a high-pressure mercury lamp under nitrogen. When the mantel hardness value of the cured coating film at an indentation depth of 10 nm was measured with HS100 manufactured by Fischer Instruments, it was 1500 N / mm ² . Moreover, the refractive index estimated from the reflectance which measured the obtained cured coating film using the reflection spectrophotometer was 1.33.

(Production Example 7)
Preparation of composition for forming hard coat layer In a container shielded from ultraviolet rays, 95 parts by mass of pentaerythritol hydroxytriacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one By stirring 5 parts by mass and 100 parts by mass of MIBK at 50 ° C. for 2 hours, a composition for forming a hard coat layer having a uniform solution was obtained. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 50% by mass.

(Production Example 8)
Preparation of substrate for coating curable composition A composition for forming a hard coat layer prepared in Production Example 7 was applied to a TAC film (thickness 50 μm) with a wire bar coater so as to have a film thickness of 6 μm. Medium was dried at 80 ° C. for 1 minute to form a coating film. Subsequently, ultraviolet rays were irradiated under the light irradiation conditions of 0.3 J / cm ² using a high-pressure mercury lamp in the air to prepare a substrate for coating a curable composition.

Example 1
(1) Formation of low refractive index layer On the hard coat layer of the base material for coating obtained in Production Example 8, a low refractive index obtained in Production Example 6 above using a wire bar coater (# 3). After coating the rate layer forming composition, it was dried in an oven at 80 ° C. for 1 minute. Subsequently, a cured film layer having a thickness of 90 nm was formed by irradiating ultraviolet rays under a light irradiation condition of 0.3 J / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere.

(2) Formation of surface protective layer Composition for forming surface protective layer obtained in Production Example 6 above using the wire bar coater (# 3) on the low refractive index layer obtained in (1) above. After coating, the film was dried in an oven at 80 ° C. for 1 minute. Subsequently, a cured film layer having a thickness of 10 nm was formed by irradiating ultraviolet rays under a light irradiation condition of 0.3 J / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere.

Examples 2-3 and Comparative Examples 1-3
A laminate was prepared in the same manner as in Example 1 except that the film thickness ratio between the low refractive index layer and the surface protective layer was changed as shown in Table 3.

<Evaluation of laminate>
The following characteristics of the laminates obtained in the above examples and comparative examples were evaluated. The results are shown in Table 3.

(Evaluation example 1)
Appearance Evaluation The appearance of the laminate obtained by the above method was visually confirmed and evaluated according to the following criteria.
○: No coating unevenness Δ: Some coating unevenness ×: Coating unevenness on the entire surface

(2) Haze Turbidity (haze value) in the obtained laminate was measured with a color haze meter and evaluated according to the following criteria.
○: Haze value is 1% or less.
(Triangle | delta): A haze value exceeds 1% and is 3% or less.
X: Haze value exceeds 3%.

(3) Reflectance The back side of the obtained laminate was painted with black spray, and a spectral reflectance measuring device (self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, Hitachi, Ltd. )), The reflectance was measured from the substrate side in the wavelength range of 340 to 700 nm and evaluated according to the following criteria. 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 light source D65, viewing angle is measured from the reflectance curve. The luminous reflectance at 10 ° was calculated.
◎: Reflectance is 1.0% or less ○: Reflectance exceeds 1.0% and 1.5% or less △: Reflectance exceeds 1.5% and 2.0% or less ×: Reflectance is 2.0 %Super

(4) Scratch resistance (steel wool resistance)
The steel wool resistance test of the cured film on the surface of the obtained laminate was carried out by the following method. That is, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded with a load of 500 g. Under the above conditions, rubbing was repeated 10 times, and the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated according to the following criteria.
A: The cured film is not damaged.
◯: Almost no peeling or scratching of the cured film is observed, or 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.

(5) Contamination resistance A fingerprint was attached to the surface of the cured film of the obtained laminate, and the surface of the coating film was wiped off with a non-woven fabric (trade name: Bencot S-2, manufactured by Asahi Kasei). Contamination resistance was evaluated according to the following criteria.
○: The fingerprint on the surface of the coating film was completely wiped off.
(Triangle | delta): The fingerprint of the coating-film surface remains slightly.
X: Fingerprint traces remained on the sample surface without being wiped off.

From the results of Table 3, it can be seen that better scratch resistance and contamination resistance are obtained in Examples 1 to 3 than in Comparative Example 1 having no surface protective layer.
In Comparative Example 2, which is only the surface protective layer, the reflectance characteristics are poor and the basic performance as an antireflection film is not provided, whereas in Examples 1 to 3 having the surface protective layer on the low refractive index layer, It can be seen that the scratch resistance is improved without impairing the antireflection property.
It can be seen that Comparative Example 3 in which the film thickness ratio between the surface protective layer and the low refractive index layer is 50:50 is inferior in reflectance characteristics.

The laminate of the present invention is particularly suitable for antireflection film applications.
Moreover, the laminated body of this invention can be used for optical components, such as a lens and a selectively permeable film filter, besides an antireflection film, for example.

It is a schematic diagram which shows one Embodiment of the laminated body of this invention.

Explanation of symbols

1: Antireflection film laminate 10: Base material 12: Hard coat layer 14: Low refractive index layer 16: Surface protective layer

Claims (11)

A low refractive index layer comprising a cured product of the first curable composition containing the following components (A), (B) and (C) and having a refractive index of 1.45 or less, and the following components (B ′) and A laminate having a surface protective layer having a film thickness of 5 nm or more and 40 nm or less made of a cured product of the second curable composition containing (D) in this order from the side closer to the substrate,
The film thickness ratio of the low refractive index layer and the surface protective layer is in the range of 60:40 to 95: 5, and the total film thickness of the low refractive index layer and the surface protective layer is 50. Laminate in the range of ~ 200 nm.
(A) Ethylenically unsaturated group-containing fluorine-containing polymer (B) Compound containing (meth) acryloyl group (C) Silica-based particle (B ′) Compound containing (meth) acryloyl group (D ) Compounds containing polydimethylsiloxane structure   The laminate according to claim 1, wherein the second curable composition further contains (C ′) particles containing silica as a main component.   The laminate according to claim 1 or 2, wherein a mantel hardness value of the surface protective layer measured by a microhardness meter is 1.2 times or more that of the low refractive index layer.   The laminate according to any one of claims 1 to 3, wherein a shape of the particle (C) having silica as a main component is a sphere or a chain sphere.   The laminate according to any one of claims 2 to 4, wherein a shape of the particle containing (C ') silica as a main component is a sphere or a chain sphere.   The laminate according to any one of claims 1 to 5, wherein the particles containing (C) silica as a main component have a (meth) acryloyl group on the surface.   The laminate according to any one of claims 2 to 6, wherein the particles containing (C ') silica as a main component have (meth) acryloyl groups on the surface.   The compound having (B) (meth) acryloyl group and the compound having (B ′) (meth) acryloyl group contains a compound containing two or more (meth) acryloyl groups. The laminated body of any one of Claims.   The laminate according to any one of claims 1 to 8, wherein the first curable composition contains a compound that generates active species upon irradiation with active energy rays.   The laminate according to any one of claims 1 to 9, wherein the second curable composition contains a compound that generates active species upon irradiation with active energy rays. The antireflection film which consists of a laminated body of any one of Claims 1-10.

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