JP2007022071A - Antistatic laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic laminate having a hardened film layer, on the surface of various substrates, that is excellent in antistatic nature, stiffness, abrasion resistance, and transparency. <P>SOLUTION: The laminate comprises at least a base material and a hardened film layer obtained by hardening of a liquid hardenable composition containing the following components (A)-(D): (A) particles composed mainly of tin-containing indium oxide (ITO) wherein the primary particle diameter thereof is 20 nm or less and the secondary particle diameter 50 nm or less, (B) a compound having two or more polymerizable unsaturated groups in each molecule, (C) a photopolymerization initiator, and (D) a solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antistatic laminate. More specifically, it is excellent in curability and various substrates such as plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, (AS resin, norbornene resin, etc.), metal, wood, paper, glass, ceramics, surface, etc., to form a coating (film) with excellent antistatic properties, hardness, scratch resistance and transparency The present invention relates to an antistatic laminate comprising a cured film layer obtained by curing a liquid curable composition to be obtained.

Conventionally, from the viewpoint of ensuring the performance of information communication equipment and taking safety measures, a radiation curable composition has been used on the equipment surface to provide a coating film (hard coat) having scratch resistance and adhesion, and a coating having an antistatic function. A film (antistatic film) is formed.
In addition, in order to impart an antireflection function to an optical article, a multilayer structure (antireflection film) of a low refractive index layer and a high refractive index layer is formed on the surface of the optical article.
In recent years, there has been remarkable development and general use of information communication devices, and further improvements in performance and productivity of hard coats, antistatic films, antireflection films and the like have been demanded.

In particular, optical articles such as plastic lenses are required to prevent the adhesion of dust due to static electricity, and to improve the reduction in transmittance due to reflection, and the display panel also prevents the adhesion of dust due to static electricity. Therefore, prevention of reflection on the screen has been demanded.
In response to these demands, various radiation curable materials have been proposed with a focus on high productivity and curing at room temperature.

  As such a technique, for example, a composition containing a sulfonic acid and a phosphoric acid monomer as an ion conductive component (Patent Document 1), a composition containing a chain metal powder (Patent Document 2), an oxidation A composition mainly composed of tin particles, polyfunctional acrylate, and a copolymer of methyl methacrylate and polyether acrylate (Patent Document 3), and a conductive coating composition containing a pigment coated with a conductive polymer (Patent Document 4) ) A trifunctional acrylic acid ester, a monofunctional ethylenically unsaturated group-containing compound, a photopolymerization initiator, and an optical disk material containing conductive powder (Patent Document 5), antimony-doped dispersed with a silane coupler Conductive paint containing hydrolyzate of tin oxide particles and tetraalkoxysilane, photosensitizer, and organic solvent (Patent Document 6), polymerized in the molecule Reaction product of alkoxysilane containing unsaturated group and metal oxide particles, liquid curable resin composition containing trifunctional acrylic compound and radiation polymerization initiator (Patent Document 7), primary particle diameter is 100 nm The following conductive oxide fine powder, easy-dispersible low-boiling solvent of the conductive oxide fine powder, difficult-dispersible low-boiling solvent of the conductive oxide fine powder, and formation of a transparent conductive film containing a binder resin For example (Patent Document 8).

Furthermore, 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, low refractive index properties, scratch resistance, coating properties, and contamination resistance There is a demand for an antireflection film including a low refractive index layer made of a cured product having excellent properties.
In these display panels, the surface is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust and the like, and scratch resistance is required. In addition, there is a demand for contamination resistance so that attached fingerprints, dust, and the like can be easily wiped off.
In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, for example, triacetyl cellulose is used as the base material. However, in an antireflection film using such a base material, an alkali is usually used in order to increase the adhesiveness when it is bonded to the polarizing plate. It is necessary to saponify with an aqueous solution.
Accordingly, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in durability.

As a material for a low refractive index layer of an antireflection film, for example, a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer is known (for example, Patent Documents 9 to 11).
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 a melamine resin under an acid catalyst in order to cure the coating film. Depending on the conditions, there is a problem 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 weather resistance, there was a problem that scar resistance and durability were poor.

  Therefore, in order to solve the above-mentioned problems, an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition polymerizable unsaturated group and a hydroxyl group-containing fluoropolymer are converted into an isocyanate group. A coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio of number / hydroxyl number of 0.01 to 1.0 has been proposed (for example, Patent Document 12). .

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

JP 47-34539 A JP 55-78070 A Japanese Patent Laid-Open No. 60-60166 Japanese Patent Laid-Open No. 2-194071 JP-A-4-172634 Japanese Unexamined Patent Publication No. Hei 6-264209 JP 2000-143924 A JP 2001-131485 A JP 57-34107 A JP 59-189108 A JP 60-67518 A JP 61-296073 A

  However, although such conventional techniques each exhibit a certain effect, a cured film that is required to have all functions as a hard coat, an antistatic film, and an antireflection film in recent years. As such, it was not always satisfactory.

  For example, the conventional techniques as described in the above prior art documents have the following problems. The composition described in Patent Document 1 uses an ion conductive material, but the antistatic performance is not sufficient, and the performance varies due to drying. Since the composition described in Patent Document 2 disperses a chain-like metal powder having a large particle size, transparency is lowered. Since the composition described in Patent Document 3 contains a large amount of non-curable dispersant, the strength of the cured film decreases. Since the material described in Patent Document 5 contains high-concentration chargeable inorganic particles, transparency is lowered. The paint described in Patent Document 6 has insufficient long-term storage stability. Patent Document 7 does not disclose any method for producing a composition having antistatic performance. When the transparent conductive film is formed by applying and drying the paint described in Patent Document 8, the organic matrix made of the binder composition is not provided with a cross-linked structure, so it cannot be said that the organic solvent resistance is sufficient.

  Increasing the amount of conductive particles to increase the antistatic performance can be easily conceived, but in that case, the transparency decreases due to the increase in visible light absorption by the cured film, and the UV transmittance decreases. The problems that the curability is lowered, the adhesion to the base material, and the leveling property of the coating liquid are impaired cannot be avoided. On the other hand, when the blending amount of the conductive particles is reduced, sufficient antistatic performance is not exhibited.

The present invention has been made in view of the above-described problems, and can exhibit sufficient antistatic performance even when the amount of conductive particles is small, has excellent curability, and is applied to the surface of various substrates. Antistatic, having a cured film layer obtained by curing a liquid curable composition that can form a coating film having excellent antistatic properties, hardness, and scratch resistance, and having both transparency and surface resistance. It is an object of the present invention to provide an antireflection film laminate having an antistatic function.
It is another object of the present invention to provide an antireflection laminate having excellent scratch resistance and stain resistance.

As a result of earnest research to solve the above-mentioned problems, the present inventor has obtained conductive particles having a specific particle size, compounds having two or more polymerizable unsaturated groups in the molecule, a photopolymerization initiator, and a solvent. It has been found that the above object can be achieved by a laminate having a cured film layer obtained by curing the contained composition, and the present invention has been completed.
Further, by combining a low refractive index film obtained by curing a specific ethylenically unsaturated group-containing fluoropolymer and a curable resin composition containing silica particles, the anti-reflective laminate has scratch resistance and contamination resistance. As a result, the present invention has been completed.

That is, this invention provides the following laminated bodies and the manufacturing method of a laminated body.
[1] at least a substrate;
A cured film layer comprising the following components (A) to (D) and a cured liquid curable composition having a content of the component (A) of 5 to 40% by weight in the total solid components;
A laminate having
[Liquid curable composition]
(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less (B) Compound having two or more polymerizable unsaturated groups in the molecule (C) Photopolymerization initiator (D ) Solvent [2] The laminate according to [1] or [1] above, wherein the component (A) is oxide particles surface-treated with a surface treatment agent.
[3] In the above [2], the surface treatment agent is a compound having two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. The liquid curable composition as described.
-X-C (= Y) -NH- (1)
[Wherein, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

[4] The laminate according to any one of [1] to [3], which is an optical component having an antistatic function.
[5] The laminate according to [4], which is an antireflection film.
[6] The laminate according to any one of [1] to [5], wherein the surface resistance value is 1 × 10 ¹³ Ω / □ or less.
[7] The laminate is an antireflection film in which at least an antistatic layer and a low refractive index layer are laminated on a base material in this order from the side close to the base material,
The laminate according to [5] or [6] above, wherein the cured film layer is an antistatic layer.
[8] The laminate according to [7], wherein a refractive index of the antistatic layer is higher than a refractive index of the low refractive index layer.
[9] The laminate according to any one of [1] to [8], wherein a hard coat layer is further formed on the substrate.
[10] The low refractive index layer is
The following components (G) and (H):
(G) a compound containing one isocyanate group and at least one ethylenically unsaturated group;
A hydroxyl group-containing fluoropolymer,
An ethylenically unsaturated group-containing fluoropolymer obtained by reacting
(H) particles mainly composed of silica,
The laminated body in any one of said [7]-[9] which is a hardened | cured material of curable resin composition containing this.

［式中、Ｒ^１１はフッ素原子、フルオロアルキル基又は−ＯＲ^１２で表される基（Ｒ^１２はアルキル基又はフルオロアルキル基を示す）を示す］

［式中、Ｒ^１３は水素原子又はメチル基を、Ｒ^１４はアルキル基、−(ＣＨ₂)_ｃ−ＯＲ^１５若しくは−ＯＣＯＲ^１５で表される基（Ｒ^１５はアルキル基又はグリシジル基を、ｃ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］

［式中、Ｒ^１６は水素原子又はメチル基を、Ｒ^１７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］ [11] The hydroxyl group-containing fluoropolymer comprises the following structural units (a) 20 to 70 mol%, (b) 10 to 70 mol% and (c) 5 to 70 mol%, and
The laminate according to [11] above, wherein the number average molecular weight in terms of polystyrene measured by gel permeation chromatography is 5,000 to 500,000.
(A) Structural unit represented by the following formula (11) (b) Structural unit represented by the following formula (12) (c) Structural unit represented by the following formula (13)

[Wherein R ¹¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ¹² (R ¹² represents an alkyl group or a fluoroalkyl group)]

[Wherein, R ¹³ represents a hydrogen atom or a methyl group, R ¹⁴ represents an alkyl group, a group represented by — (CH ₂ ) _c —OR ¹⁵ or —OCOR ¹⁵ (R ¹⁵ represents an alkyl group or a glycidyl group, c Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

[Wherein R ¹⁶ represents a hydrogen atom or a methyl group, R ¹⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

［式中、Ｒ^１８及びＲ^１９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］
［１３］前記成分（Ｈ）が、表面にエチレン性不飽和基を有するシリカ粒子である上記［１０］〜［１２］のいずれかに記載の積層体。
［１４］前記成分（Ｈ）が、
下記式（２２）で表されるケイ素化合物及び下記式（２３）で表されるケイ素化合物の加水分解物及び／又は加水分解縮合物からなり、平均粒径が５〜５０ｎｍである多孔質シリカ粒子（Ｈ１）
ＳｉＸ_４ ・・・（２２）
Ｒ^２９ _ｊＳｉＸ_４−ｊ ・・・（２３）
（Ｘはそれぞれ独立に炭素数１〜４のアルコキシ基、ハロゲノ基、イソシアネート基、炭素数２〜４のアルキルオキシカルボニル基又は炭素数１〜４のアルキルアミノ基を示す。Ｒ^２９は炭素数２〜８のアルケニル基、炭素数４〜８のアクリロキシアルキル基又は炭素数５〜８のメタクリロキシアルキル基、ｊは１〜３の整数を示す。尚、式（２２）のＸ及び式（２３）のＸは、同一であっても異なっていてもよい。）
である上記［１０］〜［１３］のいずれかに記載の積層体。 [12] The laminate according to [10] or [11], wherein the hydroxyl group-containing fluoropolymer further contains 0.1 to 10 mol% of the following structural unit (d) derived from an azo group-containing polysiloxane compound. body.
(D) Structural unit represented by the following general formula (14)

[Wherein R ¹⁸ and R ¹⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]
[13] The laminate according to any one of [10] to [12], wherein the component (H) is silica particles having an ethylenically unsaturated group on the surface.
[14] The component (H) is
Porous silica particles comprising a silicon compound represented by the following formula (22) and a hydrolyzate and / or hydrolysis condensate of the silicon compound represented by the following formula (23) and having an average particle diameter of 5 to 50 nm (H1)
SiX ₄ (22)
R ²⁹ _j SiX _4-j (23)
(X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ represents 2 carbon atoms. -8 alkenyl group, C 4-8 acryloxyalkyl group or C 5-8 methacryloxyalkyl group, j represents an integer of 1 to 3. X in formula (22) and formula (23 ) X may be the same or different.)
The laminate according to any one of the above [10] to [13].

[15] The component (H) is
It consists of a silicon compound represented by the following formula (22), a silicon compound represented by the following formula (23) and a hydrolyzate and / or hydrolysis condensate of the silicon compound represented by the following formula (24), and the average Porous silica particles (H2) having a particle size of 5 to 50 nm
SiX ₄ (22)
R ²⁹ _j SiX _4-j (23)
R ³⁰ _k SiX _4-k (24)
(X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ represents 2 carbon atoms. 8 alkenyl group, acryloxy group or methacryloxy alkyl group having a carbon number of 5 to 8, j is ^{.R 30} represents an integer of 1 to 3 fluorine-substituted alkyl having 1 to 12 carbon atoms having 4 to 8 carbon atoms Group k represents an integer of 1 to 3. X in formula (22), X in formula (23) and X in formula (24) may be the same or different.
The laminate according to any one of the above [10] to [13].
[16] When the porous silica particles (H1) have a total of 100 mol% of the silicon compound represented by the formula (22) and the silicon compound represented by the formula (23), the hydrolyzate. And / or the hydrolysis condensate comprises a reaction product of 67 to 99 mol% of a silicon compound represented by the formula (22) and 33 to 1 mol% of a silicon compound represented by the formula (23) [14] The laminated body as described in.
[17] The total of the silicon compound represented by the formula (22), the silicon compound represented by the formula (23) and the silicon compound represented by the formula (24), wherein the porous silica particles (H2) are Is 100 mol%, the hydrolyzate and / or hydrolysis condensate is composed of 60 to 98 mol% of a silicon compound represented by the formula (22) and 1 to 30 silicon compounds represented by the formula (23). The laminate according to [15] above, comprising a reaction product of 1 to 20 mol% of a silicon compound represented by mol% and formula (24).

[18] On the substrate, a liquid curable composition containing the following components (A) to (D) is applied and irradiated with radiation to form a cured film layer obtained by curing the composition. The manufacturing method of the laminated body including the process to do.
[Liquid curable composition]
(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less (B) Two or more polymerizable unsaturated groups in the molecule Compound (C) Photopolymerization initiator (D) Solvent

According to the present invention, a liquid curable composition having excellent curability and capable of forming a coating film (film) having excellent antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. It is possible to provide an antistatic laminate having a cured film obtained by curing the above.
Conventionally, in order to obtain sufficient conductivity using tin-containing indium oxide (ITO), it was necessary to blend expensive tin-containing indium oxide (ITO) particles with a high content (usually about 60% by weight). ADVANTAGE OF THE INVENTION According to this invention, even if content of a tin containing indium oxide (ITO) particle is low, sufficient electroconductivity can be expressed and the laminated body for antistatic which has the cured film excellent in the antistatic performance is obtained. be able to.
In addition, according to the present invention, by using fine tin-containing indium oxide (ITO) particles, it is possible to achieve both a sufficient surface resistance value and transparency of the cured film even if the content is kept low. The laminate of the present invention is useful as an optical component having an antistatic function, particularly as an antireflection film having an antistatic function.
Furthermore, by forming a low refractive index layer having a specific configuration, an antireflection laminate excellent in scratch resistance and stain resistance can be obtained.

Hereinafter, embodiments of the present invention will be specifically described.
The laminate of the present invention has at least a substrate and a cured film layer formed by curing a liquid curable composition containing the following components (A) to (D).
[Liquid curable composition]
(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less (B) Two or more polymerizable unsaturated groups in the molecule Compound (C) Photopolymerization initiator (D) Solvent

In addition, the antireflection film, which is a preferred embodiment / use of the laminate of the present invention, is formed by laminating at least the antistatic layer and the low refractive index layer composed of the cured film layer in this order from the side closer to the substrate. The low-refractive-index layer is a cured product of a curable resin composition containing the following components (G) and (H).
(G) An ethylenically unsaturated group-containing fluoropolymer obtained by reacting a compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluoropolymer ( H) Silica particles

I. Laminate The most basic configuration of the laminate of the present invention is shown in FIG. The laminated body 1 of this invention has the cured film layer 12 formed by hardening the base material 10 and the said liquid curable composition.
The laminated body of this invention should just have the base material 10 and the cured film layer 12, and may provide a various layer according to the objective. The layer provided according to the purpose will be described later.

Since the laminate 1 of the present invention has a cured film layer 12 having excellent scratch resistance and adhesion, it is particularly useful as a hard coat.
Further, the laminate 1 of the present invention is an antistatic laminate in which a cured film layer 12 having an excellent antistatic function is disposed on a substrate having various shapes such as a film, a plate, or a lens. Useful as a body.

  As an application example of the laminate of the present invention, for example, an antireflection film having an antistatic function (hereinafter referred to as “with antistatic function” for various display panels such as a CRT, a liquid crystal display panel, a plasma display panel, and an electroluminescence display panel. As an antireflection film), and as an antireflection film with an antistatic function, such as a plastic lens, a polarizing film, and a solar battery panel.

(1) Cured film layer The cured film layer provided on the substrate of the laminate of the present invention is referred to as the following liquid curable composition (hereinafter simply referred to as “composition” or “antistatic layer forming composition”). And a function as a conductive film and / or a function as a hard coat can be imparted to the laminate.
Hereinafter, the liquid curable composition (antistatic layer forming composition) used in the present invention will be specifically described.
1. Ingredient (A)
The component (A) used in the present invention is tin-containing indium oxide (hereinafter sometimes simply referred to as “ITO”) particles. A component (A) is an essential component in order to provide electroconductivity (antistatic property) to the cured film obtained by hardening the composition of this invention. Moreover, the primary particle diameter of ITO particle | grains is 20 nm or less, and a secondary particle diameter is 50 nm or less. By setting the particle diameter of the ITO particles as described above, it is possible to ensure conductivity (antistatic property) and at the same time maintain the transparency of the cured film. If the primary particle size and the secondary particle size of ITO particles exceed 20 nm and 50 nm, respectively, the transparency of the resulting cured film may be impaired.
The primary particle size of the ITO particles is preferably 15 nm or less, and the secondary particle size is preferably 40 nm or less.

The primary particle diameter of the ITO particles of the component (A) is a value measured with a transmission electron microscope when the shape is spherical, regardless of the presence or absence of a surface treatment described later, and the shape is elongated like a needle shape. In this case, the short axis is observed with a transmission electron microscope, and the value is obtained as the number average particle diameter.
The secondary particle size of the ITO particles of the component (A) is a value determined by a dynamic light scattering particle size distribution measuring device regardless of the presence or absence of a surface treatment described later.

  As a commercial item as such powder of ITO particle | grains, the Fuji Chemical Co., Ltd. brand name: ITO powder etc. can be mentioned, for example.

  The ITO particles used as the component (A) can be used in a state of being dispersed in a powder or a solvent, but it is preferable to use in a state of being dispersed in a solvent because uniform dispersibility is easily obtained.

  As a commercial item which disperse | distributed ITO particle | grains used as a component (A) to the solvent, the Fuji Chemical Co., Ltd. brand name: Hout form NID-20 etc. can be mentioned, for example.

The ITO particles used as the component (A) may be ITO particles surface-treated with a surface treatment agent or the like in order to improve dispersibility in a solvent.
Here, examples of the surface treatment agent include an alkoxysilane compound, tetrabutoxy titanium, tetrabutoxy zirconium, tetraisopropoxy aluminum, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the alkoxysilane compound include compounds having an unsaturated double bond in the molecule, such as γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and γ-glycid. A group of compounds having an epoxy group in the molecule such as xylpropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, and an amino group in the molecule such as γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane. Compound groups having γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc., compounds having a mercapto group in the molecule, alkyltrisilanes such as methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane Etc. Can do. Among these surface treatment agents, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, etc. are surface-treated ITO particles. From the viewpoint of dispersion stability.

Moreover, as a surface treating agent, what has a functional group which copolymerizes or crosslinks with an organic resin (reactive surface treating agent) is also preferable. As such a surface treatment agent, a compound group having an unsaturated double bond in the molecule, two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or hydrolysis may be used. A compound having a group that forms a silanol group is preferred.
-X-C (= Y) -NH- (1)
[Wherein, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

  The group represented by the formula (1) is preferably a urethane bond [—O—C (═O) —NH—], —O—C (═S) —NH—, and a thiourethane bond [—S—C ( = O) -NH-] is at least one group selected from the group consisting of.

式中、Ｒ^１はメチル基、Ｒ^２は炭素数１〜６のアルキル基、Ｒ^３は水素原子又はメチル基、ｍは１又は２、ｎは１〜５の整数、Ｘは炭素数１〜６の２価のアルキレン基、Ｙは鎖状、環状、分岐状いずれかの炭素数３〜１４の２価の炭化水素基、Ｚは（ｎ＋１）価の鎖状、環状、分岐状いずれかの炭素数２〜１４の２価の炭化水素基である。Ｚ内には、エーテル結合を含んでもよい。 As such a surface treating agent, for example, urethane bond [—O—C (═O) NH—] and / or thiourethane bond [—S—C (═O) NH—] and two or more in the molecule The alkoxysilane compound which has a polymerizable unsaturated group can be mentioned. Specific examples include compounds represented by the following formula (2).

In the formula, R ¹ is a methyl group, R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a methyl group, m is 1 or 2, n is an integer of 1 to 5, and X is 1 to 5 carbon atoms. 6 is a divalent alkylene group having 3 to 14 carbon atoms, Y is a chain, cyclic or branched group, and Z is any one of an (n + 1) -valent chain, cyclic or branched group. A divalent hydrocarbon group having 2 to 14 carbon atoms. Z may contain an ether bond.

The compound represented by the formula (2) can be produced by reacting mercaptoalkoxysilanes, diisocyanates and hydroxyl group-containing polyfunctional (meth) acrylates.
As a preferable production method, for example, an intermediate bonded with a thiourethane bond by reaction of mercaptoalkoxysilanes and diisocyanates is produced, and then a urethane bond is formed by reaction of the remaining isocyanate with a hydroxyl group-containing polyfunctional (meth) acrylate. And a method for producing a product bonded with the above.

  The same product can also be obtained by reacting the remaining isocyanate with mercaptoalkoxysilane after first producing an intermediate bonded with a urethane bond by reaction of diisocyanates with hydroxyl group-containing polyfunctional (meth) acrylates. Although it can be obtained, the addition reaction of mercaptoalkoxysilanes and (meth) acrylic groups occurs at the same time, so that the purity is lowered and a gel-like product may be formed.

  Examples of mercaptoalkoxysilanes used in the production of the compound represented by the formula (2) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltributoxysilane, and γ-mercaptopropyldimethylmethoxy. Examples include silane and γ-mercaptopropylmethyldimethoxysilane. Of these, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane are preferable.

  As a commercial item of mercapto alkoxysilanes, Toray Dow Corning Co., Ltd. brand name: SH6062 can be mentioned, for example.

  Examples of diisocyanates include 1,4-butylene diisocyanate, 1,6-hexylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated bisphenol A diisocyanate, 2,4-toluene diisocyanate, 2,6- And toluene diisocyanate. Among these, 2,4-toluene diisocyanate, isophorone diisocyanate, and hydrogenated xylylene diisocyanate are preferable.

  As a commercial item of a polyisocyanate compound, Mitsui Nisso Urethane Co., Ltd. product name: TDI-80 / 20, TDI-100, MDI-CR100, MDI-CR300, MDI-PH, NDI, Nippon Polyurethane Industry ( Product name: Coronate T, Millionate MT, Millionate MR, HDI, Takeda Pharmaceutical Co., Ltd. Product name: Takenate 600, etc.

  Examples of the hydroxyl group-containing polyfunctional (meth) acrylates include trimethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipenta An example is erythritol penta (meth) acrylate. Of these, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable. These form two or more polymerizable unsaturated groups in the compound represented by formula (2).

  These mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates can be used singly or in combination of two or more.

The preferred blending ratio of mercaptoalkoxysilanes, diisocyanates and hydroxyl group-containing polyfunctional (meth) acrylates in the case of producing the compound represented by formula (2) is preferably a molar ratio of diisocyanates to mercaptoalkoxysilanes. 0.8-1.5, More preferably, it is 1.0-1.2. When this molar ratio is less than 0.8, the storage stability of the composition may be lowered, and when it exceeds 1.5, the dispersibility may be lowered.
The molar ratio of the hydroxyl group-containing (meth) acrylates to the diisocyanates is preferably 1.0 to 1.5, and more preferably 1.0 to 1.2. When this molar ratio is less than 1.0, gelation may occur, and when it exceeds 1.5, the antistatic property may deteriorate.

  The production of the compound represented by the formula (2) is usually preferably carried out in dry air in order to prevent anaerobic polymerization of the acrylic group and to prevent hydrolysis of the alkoxysilane. The reaction temperature is preferably 0 ° C to 100 ° C, more preferably 20 ° C to 80 ° C.

  In the production of the compound represented by the formula (2), a known catalyst may be added by a urethane reaction for the purpose of shortening the production time. Examples of the catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin di (2-ethylhexanoate), and octyltin triacetate. The addition amount of the catalyst is 0.01% by weight to 1% by weight with respect to the total amount with the diisocyanates.

  Moreover, you may add a thermal-polymerization inhibitor at the time of manufacture in order to prevent the thermal polymerization of the compound shown in Formula (2). Examples of the thermal polymerization inhibitor include p-methoxyphenol and hydroquinone. The addition amount of the thermal polymerization inhibitor is preferably 0.01% by weight to 1% by weight with respect to the total with the hydroxyl group-containing polyfunctional (meth) acrylates.

The production of the compound represented by the formula (2) can also be carried out in a solvent. The solvent can be appropriately selected from solvents having a boiling point of 200 ° C. or less without reacting with mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates.
Specific examples of such solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate and amyl acetate, and hydrocarbons such as toluene and xylene.

In the present invention, (A) the surface-treated ITO particles can be produced by hydrolyzing the surface treatment agent in the presence of ITO particles. A preferable production method is (A) a method in which water is added to a mixture of ITO particles, a surface treatment agent, and an organic solvent, and the mixture is hydrolyzed.
In this production method, by hydrolysis of the surface treatment agent, the alkoxy group is once converted into a silanol group (Si—OH), and this silanol group reacts with the metal hydroxide (M—OH) on the ITO particles, It is presumed that the surface treatment agent is fixed on the ITO particles by forming a metalloxane bond (M—O—Si).

  The compounding amount of the surface treatment agent is preferably 0.1 to 50 parts by weight, and more preferably 1 to 35 parts by weight with respect to 100 parts by weight of (A) ITO particles. If the surface treatment agent is less than 0.1 parts by weight, the cured film may have insufficient wear resistance, and if it exceeds 50 parts by weight, the antistatic performance may be insufficient.

  The amount of water is preferably 0.5 to 1.5 equivalents based on the total alkoxy equivalents in the surface treatment agent, and 0.5 to 5.0 weights per 100 parts by weight of the surface treatment agent. It is preferable to add a part. The water used is preferably ion exchange water or distilled water.

  The hydrolysis reaction can be carried out in the presence of an organic solvent by heating and stirring at a temperature of 0 ° C. to the boiling point of the component, usually 30 to 100 ° C. for 1 to 24 hours. As the organic solvent, when (A) ITO particles dispersed in an organic solvent in advance are used, it can be carried out as they are, but an organic solvent may be added separately.

In addition, when performing a hydrolysis, in order to accelerate | stimulate reaction, you may add an acid or a base as a catalyst.
Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, methanesulfonic acid, toluenesulfonic acid, phthalic acid, malic acid, tartaric acid, malonic acid, formic acid, oxalic acid, methacrylic acid, acrylic acid, and itaconic acid. And organic salts such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride.
Examples of the base include amines such as aqueous ammonia, triethylamine, tributylamine, and triethanolamine. A preferable catalyst is an acid, and an organic acid is more preferable. The addition amount of these catalysts is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight, with respect to 100 parts by weight of the alkoxysilane compound.

By adding a dehydrating agent at the end of the hydrolysis reaction, (A) the hydrolyzate of the surface treatment agent can be more effectively fixed on the ITO particles.
Examples of the dehydrating agent include organic carboxylic acid orthoesters and ketals. Specifically, for example, orthoformate methyl ester, orthoformate ethyl ester, orthoacetic acid methyl ester, orthoacetic acid ethyl ester, etc., acetone dimethyl ketal, diethyl ketone dimethyl, etc. Examples include ketal, acetophenone dimethyl ketal, cyclohexanone dimethyl ketal, cyclohexanone diethyl ketal, and benzophenone dimethyl ketal. Among them, preferred are organic carboxylic acid orthoesters, and more preferred are orthoformate methyl ester and orthoformate ethyl ester.

  These dehydrating agents can be added in an amount of not less than 10 moles and not more than 10 moles, preferably not less than 1 mole and not more than 3 moles of the water content contained in the composition. If it is less than the equivalent mole, the storage stability may not be sufficiently improved. These dehydrating agents are preferably added after the preparation of the composition. This promotes the storage stability of the composition and the formation of chemical bonds between the silanol groups in the hydrolyzate of the surface treatment agent and (A) ITO particles.

Since the (A) ITO particles surface-treated with such a surface treatment agent have extremely good dispersibility in a solvent, the surface treatment agent is chemically bonded via a siloxy group (Si—O—). (A) It is estimated that it is fixed to the surface of the ITO particles.
In the present invention, the (A) ITO particles surface-treated with the reactive surface treatment agent are particularly referred to as reactive particles (RA).

  The blending amount of component (A) is not particularly limited, but is preferably 5 to 40% by weight, more preferably 7 to 35% by weight, based on 100% by weight of the total solid content of the composition of the present invention. The same applies to the case where the component (A) is surface-treated. When the blending amount is less than 5% by weight, the antistatic property may be inferior, and when it exceeds 40 parts by weight, the film forming property of the coating film may be inferior. Here, the compounding quantity of a component (A) says the compounding quantity as the solid content, and does not contain a dispersion medium.

2. Ingredient (B)
Component (B) used in the present invention is a compound having two or more polymerizable unsaturated groups in the molecule, and imparts film formability and transparency to a cured film obtained by curing the composition of the present invention. It is an ingredient to do. By using such a component (B), a cured product having excellent scratch resistance and organic solvent resistance can be obtained.

Specific examples of the component (B) include (meth) acrylic esters and vinyl compounds.
(Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane diyldimethanol Di (meth) acrylates, poly (meth) acrylates of ethylene oxide or propylene oxide adducts of starting alcohols in the production of these compounds, oligoesters having two or more (meth) acryloyl groups in the molecule (meta ) Acrylates, oligoether (meth) acrylates, oligourethane (meth) acrylates, oligoepoxy (meth) acrylates, and the like.
Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra ( (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecanediyldimethanol di (meth) acrylate are preferred. These (B) components may be used individually by 1 type, and may use 2 or more types together.

  The amount of component (B) is preferably 55 to 94% by weight, more preferably 60 to 92% by weight, based on 100% by weight of the total solid content of the composition of the present invention. If the amount of component (B) is less than 55% by weight, the resulting cured product may have poor transparency, and if it exceeds 94% by weight, the antistatic property may be inferior.

3. Ingredient (C)
Component (C) is a photopolymerization initiator, and is added to increase the curing rate when the composition of the present invention is cured by irradiation with radiation.
In the present invention, radiation means visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, α rays, β rays, γ rays, and the like.

  The amount of component (C) is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on 100% by weight of the total solid content of the composition of the present invention. A component (C) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the component (C) include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Oxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4-trimethylpentylphosphine oxide and the like.

4). Ingredient (D)
Component (D) used in the present invention is a solvent and is a component for adjusting the fluidity of the composition of the present invention.

  The solvent which is the component (D) in the composition of the present invention is preferably added so that the concentration of the total solid content of the composition is 0.5 to 75% by weight. That is, (D) The amount of the solvent added is preferably in the range of 33.3 to 19,900 parts by weight when the total solid content of the composition of the present invention is 100 parts by weight. The reason for this is that (D) when the amount of the solvent added is less than 33.3 parts by weight, the viscosity of the composition may increase and the coatability may decrease, while when it exceeds 19,900 parts by weight, This is because the thickness of the cured product is too thin and sufficient hardness may not be exhibited.

  Although the kind of solvent is not specifically limited, Usually, a solvent having a boiling point of 200 ° C. or less at normal pressure is preferable. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides and the like are used. These can be used alone or in combination of two or more.

  Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, and phenethyl alcohol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ethers include dibutyl ether, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), and the like. Examples of the esters include ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate, and ethyl acetoacetate. Examples of hydrocarbons include toluene and xylene. Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  In the case where the ITO particles of component (A) are dispersed in a dispersion medium, the dispersion medium may be used as it is as the solvent of component (D), or only a solvent different from the dispersion medium is used. You may use, Furthermore, you may use a dispersion medium and another solvent together as a solvent of a component (D).

5. Compound having other polymerizable unsaturated group The composition of the present invention requires a compound having other polymerizable unsaturated group (component (E)) as a component other than components (A) to (D). It can be blended according to. Here, the component (E) is a compound having one polymerizable unsaturated group in the molecule.
Specific examples of the component (E) include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate and other alicyclic structure-containing (meth) acrylate, 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 ( Acrylate), propyl (meth) acrylate, isopropyl (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 Relate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) ) Acrylate, 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, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, Examples thereof include hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and a compound represented by the following formula (3).
_{^{CH 2 -C (R 4) -COO}} (R 5 O) p -Ph-R 6 Formula (3)
(Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, Ph represents a phenylene group, and p represents a number of 0 to 12, preferably 1 to 8.)

  As a commercial item of an ingredient (E), Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, the product made 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 L -A, SA, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (above, manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (above And Hitachi Chemical Co., Ltd.).

6). Non-conductive particles In the present invention, the non-conductive particles or the non-conductive particles and the alkoxysilane compound are reacted in an organic solvent as long as the liquid curable composition does not cause problems such as separation and gelation. You may use together the particle | grains obtained.

By using the non-conductive particles together with the ITO particles as the component (A), the antistatic function, that is, the scratch resistance while maintaining a value of 10 ¹³ Ω / □ or less as the surface resistance when a cured film is formed. Can be improved.

  Specific examples of such non-conductive particles include oxide particles such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and cerium oxide, or a group consisting of silicon, aluminum, zirconium, titanium, and cerium. Examples thereof include oxide particles containing two or more selected elements.

  The primary particle size of the non-conductive particles is preferably 0.1 μm or less, more preferably 0.001 to 0.05 μm, as a value obtained by observation with a transmission electron microscope. When it exceeds 0.1 μm, sedimentation may occur in the composition or the smoothness of the coating film may be lowered.

  When mix | blending nonelectroconductive particle | grains with the composition of this invention, you may mix, after hydrolyzing a nonelectroconductive particle and an alkoxysilane compound in an organic solvent. This treatment improves the dispersion stability of the non-conductive particles. The hydrolysis treatment of the non-conductive particles and the alkoxysilane compound in the organic solvent can be performed in the same manner as the method for treating the oxide particles as the component (A) described above.

As a commercial product of non-conductive particles, for example, as silicon oxide particles (for example, silica particles), colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA- ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. it can. Further, as powder silica, product names manufactured by Nippon Aerosil Co., Ltd .: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product names: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd. Trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade names: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd.
In addition, as an aqueous dispersion of aluminum oxide (alumina), manufactured by Nissan Chemical Industries, Ltd. Trade name: Alumina Sol-100, -200, -520; As a dispersion of zirconium oxide, manufactured by Sumitomo Osaka Cement Co., Ltd. ( (Toluene, methyl ethyl ketone-dispersed zirconia sol); As cerium oxide aqueous dispersion, manufactured by Taki Chemical Co., Ltd. Product name: Niedal; As powders and solvent dispersions of alumina, zirconium oxide, titanium oxide, etc. Product name: Nanotech etc. can be mentioned.

  The blending ratio of the non-conductive particles is preferably 0.1 to 35% by weight, more preferably 1 to 30% by weight in 100% by weight of the total solid content of the composition of the present invention.

7). Additives In the composition of the present invention, other additives such as antioxidants, ultraviolet absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants and the like are blended as necessary. be able to. As antioxidant, Ciba Specialty Chemicals Co., Ltd. product name: Irganox 1010, 1035, 1076, 1222, etc. As UV absorber, Ciba Specialty Chemicals Co., Ltd. product name: Tinuvin P234, 320, 326, 327, 328, 213, 329, manufactured by Sipro Kasei Co., Ltd., trade name: Seasorb 102, 103, 501, 202, 712, etc., as light stabilizers, manufactured by Ciba Specialty Chemicals Co., Ltd., trade names: Tinuvin 292, 144, 622LD, Sankyo Co., Ltd. product name: Sanol LS770, LS440, Sumitomo Chemical Co., Ltd. product name: Sumisorb TM-061.

  The viscosity of the composition of the present invention thus obtained is usually 1 to 20,000 mPa · s, preferably 1 to 1,000 mPa · s at 25 ° C.

  As described above, the solid content excluding the solvent (D) of the composition of the present invention is preferably in the range of 0.5 to 75% by weight. If the solid content is less than 0.5% by weight, the resulting cured product has a too thin film thickness and may not exhibit sufficient hardness. If it exceeds 75% by weight, the viscosity of the composition increases. The applicability may decrease.

8). Method for preparing antistatic layer forming composition The liquid curable composition of the present invention comprises the above components (A) to (D), and, if necessary, the above-mentioned compounds having other polymerizable unsaturated groups, non-conductive. It can be obtained by adding and mixing conductive particles and other additives.

9. Forming Method of Cured Film Layer The cured film layer of the laminate of the present invention is obtained by applying the above-mentioned antistatic layer forming composition to the substrate and drying it, and then irradiating with radiation to cure the composition. Obtainable.
If the surface resistance of the obtained cured film layer is 1 × 10 ¹³ Ω / □ or less, sufficient antistatic performance can be exhibited. Usually, it is 1 × 10 ¹² Ω / □ or less, preferably 1 × 10 ¹⁰ Ω. / □ or less, more preferably 1 × 10 ⁸ Ω / □ or less. When the surface resistance exceeds 1 × 10 ¹³ Ω / □, the antistatic performance is not sufficient, and dust may be easily attached or the attached dust may not be easily removed.
The surface resistance of the laminate (antireflection film with antistatic function) of the present invention when a low refractive index layer or the like to be described later is formed on a cured film layer having a surface resistance value in the above range is usually 1 × 10 ¹³ Ω / □ or less, preferably 1 × 10 ¹⁰ Ω / □ or less, more preferably 1 × 10 ⁸ Ω / □ or less.

  Although there is no restriction | limiting in particular as a coating method of the composition for antistatic layer formation, For example, well-known methods, such as roll coating, spray coating, flow coating, dipping, screen printing, inkjet printing, are applicable.

The radiation source used for curing the composition for forming an antistatic layer is not particularly limited as long as it can be cured in a short time after the composition is applied.
Examples of the visible ray source include direct sunlight, lamps, fluorescent lamps, and lasers. Examples of the ultraviolet ray source include mercury lamps, halide lamps, and lasers, and electron beam source. For example, a method using thermoelectrons generated from a commercially available tungsten filament, a cold cathode method in which a metal is generated through a high voltage pulse, and a secondary electron generated by collision of ionized gaseous molecules with a metal electrode. Secondary electron system using
Examples of the source of α rays, β rays, and γ rays include fission materials such as ⁶⁰ Co. For the γ rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations may be irradiated alone or in combination of two or more, or one or more kinds of radiation may be irradiated after a certain period of time.

The film thickness of the cured film layer is preferably 0.05 to 30 μm. It is relatively thick, preferably 2 to 15 μm, in applications that place importance on scratch resistance on the outermost surface such as touch panels and CRTs. On the other hand, when used as an antistatic film for an optical film, the thickness is preferably 0.05 to 10 μm.
Moreover, when using for an optical film, transparency is required and it is preferable that a total light transmittance is 85% or more.

(2) Substrate The substrate used for the laminate of the present invention is not particularly limited, such as metal, ceramics, glass, plastic, wood, slate, etc., and may be appropriately selected according to the purpose of use. As a material having high productivity and capable of exhibiting industrial utility, it is preferably applied to, for example, a film or a fiber-like substrate. Particularly preferred materials are plastic film and plastic plate. Examples of such plastics include polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, diallyl carbonate of diethylene glycol (CR-39), ABS resin, AS resin. , Polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene resin), and the like.

In addition, since the tin-containing indium oxide (ITO) particles of the component (A) are unevenly distributed on the substrate side and higher conductivity (antistatic property) is obtained, the substrate on which the composition for forming an antistatic layer is applied. Is preferably a base material such as polyester or polyethylene terephthalate (PET) in which the surface to which the composition for forming an antistatic layer is applied is subjected to an easy adhesion treatment.
Examples of such easy adhesion treatment include treatment such as corona discharge treatment and easy adhesion layer coating treatment.
As a preferable commercially available base material subjected to easy adhesion treatment, polyester film A4300 (manufactured by Toyobo Co., Ltd.) and the like can be mentioned.

  The thickness of the base material should be appropriately set according to the purpose and is not particularly limited, but is usually in the range of 30 to 5000 μm, preferably 50 to 2000 μm.

II. Next, the configuration of each layer when the laminate of the present invention is used as an antireflection film having an antistatic function will be described with reference to FIGS. 2A to 2I.
When providing an optical article with an antireflection function, a method of forming a low refractive index layer or a multilayer structure of a low refractive index layer and a high refractive index layer is formed on a substrate or a substrate that has been hard-coated. It is known that this method is effective.
FIG. 2A shows a first embodiment when the laminate of the present invention is used as an antireflection film with an antistatic function. In the antireflection film 2 with an antistatic function, an antistatic layer 12, which is a cured film layer obtained by curing the liquid curable composition, is formed on a substrate 10, and the low refractive index layer 18 is further formed thereon. Formed. In the first embodiment, the antistatic layer 12 has both an antistatic function and a function as a hard coat layer. In the first embodiment, the refractive index of the antistatic layer 12 needs to be higher than the refractive index of the low refractive index layer 18.

  As another form, the antistatic layer 12 of the antireflection film 2 of the present invention can also function as a hard coat layer, but a hard coat layer can be provided separately. In this case, the hard coat layer 11 is provided between the antistatic layer 12 and the low refractive index layer 18. In this case, the refractive index of the hard coat layer 11 must be higher than the refractive index of the low refractive index layer 18. These aspects are shown in FIG. 2C.

  FIG. 2D shows a second embodiment when the laminate of the present invention is used as an antireflection film with an antistatic function. In the second embodiment, the antireflection film 2 with the antistatic function is formed by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on the base material 10, and further thereon. The high refractive index layer 16 and the low refractive index layer 18 are formed in this order. In the second form, the antistatic layer 12 may have both an antistatic function, a function as a hard coat, and a function as a medium refractive index layer. In the second embodiment, in order for the antistatic layer 12 to function as a middle refractive index layer, the refractive index of the antistatic layer 12 is lower than the refractive index of the high refractive index layer 16 and the low refractive index layer 18 It must be higher than the refractive index.

  In the second form, a form in which a hard coat layer is separately provided is also possible as in the first form. The hard coat layer 11 can be provided between the antistatic layer 12 and the high refractive index layer 16. These forms are shown in FIG. 2F.

  FIG. 2G shows a third embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function. In the third embodiment, the antireflection film 2 with an antistatic function is obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on a substrate 10, and further The intermediate refractive index layer 14, the high refractive index layer 16, and the low refractive index layer 18 are formed in this order. In the third embodiment, the antistatic layer 12 has both an antistatic function and a function as a hard coat.

  In the third embodiment, a hard coat layer can be separately provided as in the first embodiment. The hard coat layer 11 can be provided between the antistatic layer 12 and the medium refractive index layer 14. These configurations are shown in FIG. 2I.

The layers other than the antistatic layer and the substrate provided in the first to third embodiments of the antireflection film with an antistatic function will be described.
(2) Low Refractive Index Layer The low refractive index layer is a layer having a thickness of 0.05 to 0.20 μm and a refractive index of 1.30 to 1.45. In addition, the refractive index in this invention means the refractive index of 589 nm in 25 degreeC.
The material used for the low refractive index layer is not particularly limited as long as the desired properties can be obtained. And cured products such as epoxy group-containing compounds and fluorine-containing epoxy group-containing compounds. Moreover, in order to raise the intensity | strength of a low refractive index layer, a silica fine particle etc. can also be mix | blended.
In the preferable aspect which uses the laminated body of this invention as an antireflection film, a low refractive index layer is formed using the curable resin composition containing the component (E) and (F) mentioned later.

(3) High Refractive Index Layer The high refractive index layer has a thickness in the range of 0.05 to 0.20 μm and a refractive index in the range of 1.55 to 2.20.
In order to form a high refractive index layer, high refractive index inorganic particles, for example, metal oxide particles can be blended.

Specific examples of the metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, zinc oxide (ZnO) particles, antimony-containing ZnO, Al-containing ZnO particles ZrO ₂ particles, and TiO ₂ particles. And silica-coated TiO ₂ particles, Al ₂ O ₃ / ZrO ₂ -coated TiO ₂ particles, and CeO ₂ particles. Antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, Al-containing ZnO particles, and Al ₂ O ₃ / ZrO ₂ -coated TiO ₂ particles are preferable. These metal oxide particles can be used singly or in combination of two or more.
Further, the high refractive index layer can have a function of a hard coat layer.

(4) Medium Refractive Index Layer When combining three or more refractive index layers, the refractive index is 1.50 to 1.90, which is higher than the low refractive index layer and lower than the high refractive index layer. A layer having a refractive index is represented as a middle refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.80, more preferably 1.50 to 1.75. The middle refractive index layer has a thickness in the range of 0.05 to 0.20 μm.
In order to form the middle refractive index layer, inorganic particles having a high refractive index, for example, metal oxide particles can be blended.

Specific examples of metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, ZnO particles, antimony-containing ZnO, Al-containing ZnO particles, ZrO ₂ particles, TiO ₂ particles, silica coating TiO ₂ particles, Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles, CeO ₂ particles and the like can be mentioned. Antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, Al-containing ZnO particles, and ZrO ₂ particles are preferable. These metal oxide particles can be used singly or in combination of two or more.

  The reflectance can be lowered by combining the low refractive index layer and the high refractive index layer, and the reflectance can be lowered by combining the low refractive index layer, the high refractive index layer, and the middle refractive index layer. In addition to being able to reduce color glare.

(5) Hard coat layer As a specific example of the hard coat layer, it is preferable that the hard coat layer is composed of a material such as SiO ₂ , an epoxy resin, an acrylic resin, or a melamine resin. Moreover, you may mix | blend a silica particle with these resin.
The hard coat layer has the effect of increasing the mechanical strength of the laminate. The thickness of the hard coat layer is
Usually, it is in the range of 0.5-50 μm, preferably 1-30 μm. Alternatively, the refractive index of the docoat layer is usually in the range of 1.45 to 1.70, preferably 1.45 to 1.60.

(6) Substrate The material of the substrate when the laminate of the present invention is used as an antireflection film needs to be transparent, for example, polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, Examples include polystyrene, polyester, polyolefin, triacetyl cellulose resin, diallyl carbonate (CR-39) of diethylene glycol, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and cyclized polyolefin resin (for example, norbornene resin). Can do.
In addition, as described above, since the tin-containing indium oxide (ITO) particles of the component (A) are unevenly distributed on the substrate side and higher conductivity (anti-static property) is obtained, the group subjected to the easy adhesion treatment A material is preferred. Examples of such easy adhesion treatment include treatment such as corona discharge treatment and easy adhesion layer coating treatment.
As a preferable commercially available base material subjected to easy adhesion treatment, polyester film A4300 (manufactured by Toyobo Co., Ltd.) and the like can be mentioned.

  Although the thickness of a base material is not specifically limited, Usually, 30-300 micrometers, Preferably it is the range of 50-200 micrometers.

(7) Other layers In the production of the laminate of the present invention, in order to further impart other requirements such as non-glare effect, light selective absorption effect, weather resistance, durability, transferability, etc., for example, Adding a layer containing light-scattering particles of 1 μm or more, adding a layer containing a dye, adding a layer containing an ultraviolet absorber, adding an adhesive layer, adding an adhesive layer and a release layer Further, these function-imparting components can be added as one component of the antistatic layer forming composition and / or the low refractive index layer forming composition used in the present invention.

  The laminate of the present invention can prevent or contaminate, for example, a plastic optical component, a touch panel, a film-type liquid crystal element, a plastic casing, a plastic container, a flooring material as a building interior material, a wall material, and artificial marble. It can be suitably used as a hard coating material for preventing; an adhesive for various substrates, a sealing material; a binder material for printing ink, and the like.

Only one of these layers may be formed, or two or more different layers may be formed.
The film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm, the film thickness of the hard coat layer is usually 1 to 20 μm, and the film thickness of the antistatic layer is usually 0.05 to 30 μm.
In this invention, the manufacturing method of a layer can be manufactured by well-known methods, such as application | coating and hardening, vapor deposition, sputtering.

III. Low Refractive Index Layer In order to use the laminate of the present invention as an antireflection film, it is necessary to form a low refractive index layer on at least the cured film layer. The low refractive index layer formed in the laminate of the present invention is a curable resin composition (hereinafter referred to as “low refractive index layer” containing (G) an ethylenically unsaturated group-containing fluoropolymer and (H) silica particles. It is preferably a cured product composed of “formation composition”.
Hereinafter, components (G) and (H) will be described.

1. Ingredient (G)
The ethylenically unsaturated group-containing fluoropolymer (G) used in the composition for forming a low refractive index layer comprises a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing polymer. It is obtained by reacting with a fluoropolymer.

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

Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
As examples of diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylisocyanate), and 1,3-bis (isocyanatomethyl) 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, etc. can be obtained.

(2) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
(A) A structural unit represented by the following formula (11).
(B) A structural unit represented by the following formula (12).
(C) A structural unit represented by the following formula (13).

［式中、Ｒ^１１はフッ素原子、フルオロアルキル基又は−ＯＲ^１２で表される基（Ｒ^１２はアルキル基又はフルオロアルキル基を示す）を示す］

[Wherein R ¹¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ¹² (R ¹² represents an alkyl group or a fluoroalkyl group)]

［式中、Ｒ^１３は水素原子又はメチル基を、Ｒ^１４はアルキル基、−(ＣＨ₂)_ｃ−ＯＲ^１５若しくは−ＯＣＯＲ^１５で表される基（Ｒ^１５はアルキル基又はグリシジル基を、ｃ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］

[Wherein, R ¹³ represents a hydrogen atom or a methyl group, R ¹⁴ represents an alkyl group, a group represented by — (CH ₂ ) _c —OR ¹⁵ or —OCOR ¹⁵ (R ¹⁵ represents an alkyl group or a glycidyl group, c Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

［式中、Ｒ^１６は水素原子又はメチル基を、Ｒ^１７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］

[Wherein R ¹⁶ represents a hydrogen atom or a methyl group, R ¹⁷ 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 (11), examples of the fluoroalkyl group of R ¹¹ and R ¹² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group. A C1-C6 fluoroalkyl group is mentioned. The alkyl group R ^12, 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), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether) ) Class of single species or a combination of two or more species.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and a combination of these is more preferable.

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

(Ii) Structural unit (b)
In the formula (12), examples of the alkyl group represented by R ¹³ or R ¹⁴ 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, and R ¹⁵ Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

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

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

(Iii) Structural unit (c)
In the formula (13), as the hydroxyalkyl group of R ¹⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group , 6-hydroxyhexyl group and the like.

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.
In addition to the above, the hydroxyl group-containing vinyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, and polypropylene. Glycol (meth) acrylate or the like can be used.

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

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

［式中、Ｒ^１８及びＲ^１９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 (14).

[Wherein R ¹⁸ and R ¹⁹ 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 (14), the alkyl group of R ¹⁸ or R ^{19 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 (14). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following formula (15).

［式中、Ｒ^２０〜Ｒ^２３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、Ｒ^２４〜Ｒ^２７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、ｄ、ｅ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。］

[Wherein R ^{20 to} R ²³ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ^{24 to} R ²⁷ may be the same or different, and represent a hydrogen atom or an alkyl group. D and e 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 (15) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

［式中、Ｒ^２０〜Ｒ^２３、Ｒ^２４〜Ｒ^２７、ｄ、ｅ、ｓ、ｔ及びｙは、上記式（１５）と同じである。］ (E) A structural unit represented by the following formula (16).

[Wherein, R ^{20 to} R ²³ , R ^{24 to} R ²⁷ , d, e, s, t, and y are the same as those in the above formula (15). ]

In the formulas (15) and (16), examples of the alkyl group represented by R ^{20 to} R ²³ 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 ^{24 to} R ²⁷ 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 (15) is particularly preferably a compound represented by the following formula (17).

［式中、ｙ及びｚは、上記式（１５）と同じである。］

[Wherein y and z are the same as those in the above formula (15). ]

In addition, it is preferable that the content rate of a structural unit (d) shall be 0.1-10 mol part, when the sum total of structural unit (a)-(c) is 100 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.
For these reasons, the content of the structural unit (d) is more preferably 0.1 to 5 parts by mole, and still more preferably 0.1 to 3 parts by mole. 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).

［式中、Ｒ^２５は乳化作用を有する基を示す］ (F) A structural unit represented by the following formula (18).

[Wherein R ²⁵ represents a group having an emulsifying action]

In the formula (18), the group having an emulsifying action of R ²⁵ 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.

［式中、ｇは１〜２０の数、ｆは０〜４の数、ｕは３〜５０の数を示す］ Examples of the group having such an emulsifying action include a group represented by the following formula (19).

[Wherein, g is a number from 1 to 20, f is a number from 0 to 4, and u is a number from 3 to 50]

  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (20).

［式中、ｇ、ｆ及びｕは、上記式（１９）と同様である］

[Wherein g, f and u are the same as in the above formula (19)]

In addition, when the sum total of structural unit (a)-(c) is 100 mol part, it is preferable that the content rate of a structural unit (f) shall be 0.1-5 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%, the curable resin composition This is because the adhesiveness of the film does not increase excessively, handling becomes easy, and moisture resistance does not decrease even when used as a coating material.
For such reasons, the content of the structural unit (f) is more preferably 0.1 to 3 mol parts, and further preferably 0.2 to 3 mol parts.

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

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

The addition amount of the component (G) in the curable resin composition is not particularly limited, but is usually 1 to 95% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 1% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. This is because if it exceeds 95% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.
For this reason, the amount of component (G) added is more preferably 2 to 90% by weight, and even more preferably 3 to 85% by weight.

2. Ingredient (H)
(1) Particles mainly composed of silica The composition for forming a low refractive index layer used in the present invention can contain particles mainly composed of silica, and is a cured product of the composition for forming a low refractive index layer. It is possible to improve the scratch resistance, particularly the steel wool resistance. As the particles mainly composed of silica, particles mainly composed of silica having a number average particle diameter of 1 to 100 nm are preferable. The particle size is measured with a transmission electron microscope. The particle size of the component (H) is preferably 5 to 80 nm, and more preferably 10 to 60 nm.
As these particles containing silica as a main component, known particles can be used, and the shape is not particularly limited. As long as it is spherical, it is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core-shell type particles, or the like. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a solid content of 10 to 40% by weight is preferred.

  The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

  As a commercial item of the particle | grains which have a silica as a main component, as a colloidal silica, for example, Nissan Chemical Industries Ltd. brand name: Methanol silica sol, IPA-ST, MEK-ST, MEK-ST-S, MEK-ST- L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL etc. can be mentioned.

Moreover, what carried out surface treatments, such as chemical modification, on the colloidal silica surface can be used, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or one containing a hydrolyzate thereof. Can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. 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.

(2) Preferred embodiment (silica particles having an ethylenically unsaturated group on the surface)
The silica particles used in the present invention preferably have an ethylenically unsaturated group (hereinafter referred to as “reactive silica particles”). The method for producing reactive silica particles is not particularly limited. For example, the reactive silica particles can be obtained by reacting the silica particles having a number average particle size of 10 to 100 nm with a reactive surface treatment agent.

  Here, examples of the surface treatment agent include an alkoxysilane compound, tetrabutoxy titanium, tetrabutoxy zirconium, tetraisopropoxy aluminum, and the like. These can be used alone or in combination of two or more.

式中、Ｒ^２６はメチル基、Ｒ^２７は炭素数１〜６のアルキル基、Ｒ^２８は水素原子又はメチル基、ａは１又は２、ｂは１〜５の整数、Ａは炭素数１〜６の２価のアルキレン基、Ｂは鎖状、環状、分岐状いずれかの炭素数３〜１４の２価の炭化水素基、Ｚは（ｂ＋１）価の鎖状、環状、分岐状いずれかの炭素数２〜１４の２価の炭化水素基である。Ｚ内には、エーテル結合を含んでもよい。
シリカ粒子がエチレン性不飽和基を有していることにより、ＵＶ硬化系アクリルモノマーと共架橋化することができ、耐擦傷性が向上する。 Specific examples of the surface treatment agent include compounds having an unsaturated double bond in the molecule such as γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and the following general formula ( 21).

In the formula, R ²⁶ is a methyl group, R ²⁷ is an alkyl group having 1 to 6 carbon atoms, R ²⁸ is a hydrogen atom or a methyl group, a is 1 or 2, b is an integer of 1 to 5, and A is 1 to 5 carbon atoms. 6 divalent alkylene group, B is a chain, cyclic or branched divalent hydrocarbon group having 3 to 14 carbon atoms, Z is a (b + 1) valent chain, cyclic or branched group A divalent hydrocarbon group having 2 to 14 carbon atoms. Z may contain an ether bond.
When the silica particles have an ethylenically unsaturated group, they can be co-crosslinked with the UV curable acrylic monomer, and the scratch resistance is improved.

(3) Preferred embodiment (porous silica particles)
As silica particles used in the composition for forming a low refractive index layer, porous silica particles are preferable.
As the porous silica particles, it is more preferable to use the first porous silica particles (H1) or the second porous silica particles (H2). The first porous silica particles (H1) are obtained by hydrolysis and / or hydrolysis condensation of a silicon compound represented by the following formula (22) and a silicon compound represented by the following formula (23). That is, it can be obtained by hydrolysis and / or hydrolysis condensation of the silicon compound represented by the formula (22) and hydrolysis and / or hydrolysis condensation of the silicon compound represented by the formula (23). The silicon compound represented by the formula (22) and the silicon compound represented by the formula (23) may be mixed and simultaneously hydrolyzed and / or hydrolyzed and condensed, or the silicon represented by the formula (22) The compound may be hydrolyzed and / or hydrolyzed and condensed, and then further hydrolyzed and / or hydrolyzed and condensed by adding the silicon compound represented by the formula (23). The second porous silica particles (H2) are a silicon compound represented by the following formula (22), a silicon compound represented by the following formula (23), and a hydrolysis of the silicon compound represented by the following formula (24). And / or obtained by hydrolysis condensation. That is, the silicon compound represented by formula (22) is hydrolyzed and / or hydrolyzed and condensed, and the silicon compound represented by formula (23) is hydrolyzed and / or hydrolyzed and condensed, and formula (24) Is obtained by hydrolysis and / or hydrolysis condensation. The silicon compound represented by formula (22), the silicon compound represented by formula (23) and the silicon compound represented by formula (24) may be mixed and simultaneously hydrolyzed and / or hydrolyzed and condensed. Then, the silicon compound represented by the formula (22) is hydrolyzed and / or hydrolyzed and condensed, and then the silicon compound represented by the formula (23) and the silicon compound represented by the formula (24) are added. Hydrolysis and / or hydrolysis condensation may be performed.
SiX ₄ (22)
R ²⁹ _j SiX _4-j (23)
R ³⁰ _k SiX _4-k (24)

In the formulas (22), (23) and (24), X is each independently an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, a carboxyl group, an alkyloxycarbonyl group having 2 to 4 carbon atoms or a carbon number. 1 to 4 alkylamino groups, preferably an alkoxy group and a halogeno group, more preferably an alkoxy group. In the formulas (22), (23) and (24), Xs may be the same or different.
Examples of the compound represented by the formula (22) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrachlorosilane.

In the formula (23), R ²⁹ is an alkenyl group having 2 to 8 carbon atoms, an acryloxyalkyl group having 4 to 8 carbon atoms or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably a vinyl group, an allyl group, An acryloxyethyl group, an acryloxypropyl group, an acryloxybutyl group, a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxybutyl group.
In formula (23), j is an integer of 1-3, Preferably it is 1-2.
Examples of the compound represented by the formula (23) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.
By using the compound represented by the formula (23), the porous silica particles can contain an ethylenically unsaturated group. By containing an ethylenically unsaturated group, the scratch resistance of the antireflection film of the present invention having a cured film obtained by curing the curable composition is improved.

In the formula (24), R ³⁰ is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, preferably a fluorine-substituted alkyl group having 3 to 12 carbon atoms, more preferably a fluorine-substituted alkyl group having 3 to 10 carbon atoms. It is.
In formula (24), k is an integer of 1-3, Preferably it is 1-2.
Examples of the compound represented by the formula (24) include 3,3,3-trifluoropropyltrimethoxysilane, 2-perfluorohexylmethyltrimethoxysilane, 2-perfluorohexylethyltrimethoxysilane, and 2-par. Examples include fluorooctylethyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, and 3,3-di (trifluoromethyl) -3-fluoropropyltriethoxysilane.
By using the compound represented by the formula (24), the porous silica particles can contain a fluorine-containing alkyl group. By including a fluorine-containing alkyl group, the stain resistance of the cured film obtained by curing the curable composition can be improved.
In addition, you may use 2 or more types of silicon compounds represented by Formula (22), the silicon compound represented by Formula (23), and the silicon compound represented by Formula (24), respectively.

In the first porous silica particles (H1), when the total of the silicon compound represented by the formula (22) and the silicon compound represented by the formula (23) is 100 mol%, the first porous silica particles (H1) are represented by the formula (22). The silicon compound represented by the formula (23) is preferably hydrolyzed at a ratio of 67 to 99/1 to 33 (mol%), more preferably 70 to 98/2 to 30 (mol%). And / or hydrolytic condensation.
In the second porous silica particles (H2), the total of the silicon compound represented by the formula (22), the silicon compound represented by the formula (23) and the silicon compound represented by (24) is 100 mol%. The silicon compound represented by the formula (22) / the silicon compound represented by the formula (23) / the silicon compound represented by the formula (24) is preferably 60 to 98/1 to 30/1. The hydrolysis and / or hydrolysis condensation is carried out at a ratio of 20 (mol%), more preferably 65 to 96/2 to 20/2 to 15 (mol%).

The first and second porous silica particles (H1) and (H2) used in the present invention have an average particle diameter of 5 to 50 nm, preferably 5 to 45 nm, more preferably 5 to 40 nm. is there. An average particle diameter is a number average particle diameter, and is measured with a transmission electron microscope observation image. “Porous” means that the specific surface area is 50 to 1000 m ² / g, preferably 50 to 800 m ² / g, more preferably 100 to 800 m ² / g. The specific surface area is measured by the BET method.
When the average particle size is within the above range, scattering of the obtained coating film in the visible light region can be suppressed. Moreover, by making it porous, a density falls and the refractive index of the film | membrane containing such a porous silica particle becomes low.

The porous silica particles (H) are obtained by the production method described below.
The first or second porous silica particles (H1) and (H2) are at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and half ethers of diols. In the presence, the silicon compound represented by the formula (22) and the silicon compound represented by the formula (23), or the silicon compound represented by the formula (22), respectively, represented by the formula (23). The silicon compound and the silicon compound represented by the formula (24) can be produced by hydrolysis and / or hydrolysis condensation.

As the basic compound, for example, an amine compound is used. Specific examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane. , Diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutyla Down, it can be mentioned trimethylamine, triethylamine, tripropylamine, tributylamine and the like. Preferably, ammonia, ethanolamine, tetramethylamine hydroxide and the like are used.
These basic compounds may be used alone or in combination of two or more.

The acid amide, diol or diol half ether is preferably compatible with water and alcohol.
As the acid amide, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like are used, and preferably N, N-dimethylformamide and N, N-dimethylacetamide are used.

As the diol, for example, ethylene glycol, propylene glycol, 1,2-butanediol and the like are used, and preferably ethylene glycol and propylene glycol are used. As the diol half ether, for example, ethylene glycol monomethyl ether or propylene glycol monomethyl ether is used.
The porous silica particles used in the present invention can be made porous by coexisting acid amide, diol or half ether of diol during synthesis.

The total concentration of the silicon compound of the formula (22) and the silicon compound of the formula (23) or the silicon compound of the formulas (22) to (24) in the reaction solution is usually 0.5 to 10% by weight in terms of complete hydrolysis condensate. , Preferably 1 to 8% by weight. Here, “in terms of complete hydrolysis condensate” is a theoretical value calculated on the assumption that the silicon compound has been completely hydrolyzed and condensed, and the silicon compound of formula (22) and the silicon compound or formula of (23) This corresponds to the weight when X of the silicon compound of (22) to (24) is substituted with 1/2 mole of oxygen atom of X. By making the concentration of the silicon compound at the time of particle synthesis in the above range, coarsening of the particles can be prevented and particles having an average particle diameter of 5 to 50 nm can be obtained.
The silicon compound of the formula (22) and the silicon compound of the formula (23), or the silicon compound of the formula (22), the silicon compound of the formula (23) and the silicon compound of the formula (24) are mixed at the same time for hydrolysis and / or In the presence of at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols and half ethers of diols, The silicon compound represented is hydrolyzed and / or hydrolyzed and condensed, and then the silicon compound represented by the formula (23), or the silicon compound represented by the formula (23) and the formula (24), respectively. Further, the silicon compound may be added to cause hydrolysis and / or hydrolysis condensation.

The reaction temperature of hydrolysis and / or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of the alcohol and acid amide to be used. The reaction time depends on the silicon compound represented by the formula (22), the silicon compound represented by the formula (23), the kind of the silicon compound represented by the formula (24), the reaction rate, the kind and amount of the base, and the like. The optimum value is of a changing nature and is not limited.
By adding an organic solvent to the obtained hydrolysis and / or hydrolysis condensation reaction liquid, and further removing unnecessary components by a method such as distillation or liquid-liquid extraction as necessary, the porous silica particles are converted into an organic solvent. A dispersed dispersion can be obtained.

  The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium.

  The blending amount of the porous silica particles (H) in the resin composition is usually 5 to 99% by weight, preferably 10 to 98% by weight, and preferably 15 to 97% by weight with respect to the total amount of the composition other than the organic solvent. Further preferred. If it is less than 5% by weight, the hardness of the cured film may be insufficient, and if it exceeds 99% by weight, sufficient film strength may not be obtained. In addition, the quantity of particle | grains means solid content and when particle | grains are used with the form of a solvent dispersion liquid, the quantity of a solvent is not included in the compounding quantity.

(4) Arbitrary addition component The following component can be added to the composition for low refractive index layers used by this invention as needed.

(I) Polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group If necessary, the product contains a polyfunctional (meth) acrylate compound containing at least two or more (meth) acryloyl groups and / or a fluorine-containing (meth) containing at least one (meth) acryloyl group. An acrylate compound can also be added.

(1) Polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups About this compound, any compound containing at least two (meth) acryloyl groups in the molecule is particularly limited. Is not to be done. Examples of such include neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone Modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, “U-15HA” Product name, include alone or in a combination of two or more of Shin-Nakamura Chemical Co., Ltd.), and the like.
Of these, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) Acrylate is particularly preferred.

(2) Fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group The compound may be a fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group. There is no particular limitation. Examples of such include perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

The amount of component (I) to be added is not particularly limited, but is usually 0 to 90% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount exceeds 90% by weight, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained.
For this reason, the amount of component (I) added is more preferably 80% by weight or less, and still more preferably 60% by weight or less.

(J) Compound that generates active species by irradiation of active energy rays or heat In the present invention, a compound that generates active species by irradiation of active energy rays or heat can also be added. A compound that generates active species upon irradiation with active energy rays or heat is used to cure the curable resin composition.

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

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

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

(Ii) Addition amount The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.01% by weight, 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% by weight, the refractive index of the cured film increases and the antireflection effect may be lowered.
For this reason, the amount of the photopolymerization initiator added is more preferably 0.05 to 15% by weight, more preferably 0.1 to 15% by weight, based on the total amount of the composition other than the organic solvent. More preferably.

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

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

(Ii) Addition amount The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.01% by weight, 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% by weight, the refractive index of the cured film increases and the antireflection effect may be lowered.
For this reason, it is more preferable that the amount of the thermal polymerization initiator added is 0.05 to 15% by weight based on the total amount of the composition other than the organic solvent. More preferably, the value of

(K) Organic solvent It is preferable to add an organic solvent to the curable resin composition. Thus, by adding an organic solvent, a thin antireflection film can be formed uniformly. As such an organic solvent, an alcohol solvent having 1 to 8 carbon atoms, a ketone solvent having 3 to 10 carbon atoms, and an ester solvent having 3 to 10 carbon atoms can be preferably used, such as methyl isobutyl ketone, methyl ethyl ketone, methyl amyl Ketones, methanol, ethanol, t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol monopropyl ether and the like are particularly preferable examples. These organic solvents can be used singly or in combination of two or more.

  The addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by weight with respect to 100 parts by weight of the composition other than the organic solvent. This is because when the addition amount is less than 100 parts by weight, it may be difficult to adjust the viscosity of the curable resin composition. On the other hand, when the addition amount exceeds 100,000 parts by weight, the curable resin may be difficult to adjust. This is because the storage stability of the composition may decrease, or the viscosity may decrease excessively, making handling difficult.

Additives In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, and a plasticizer, as long as the objects and effects of the present invention are not impaired. Further, additives such as ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the component (H), pigments, dyes, and the like can be further contained.

(5) Preparation method of composition for forming low refractive index layer The curable resin composition used in the present invention is the above (G) ethylenically unsaturated group-containing fluoropolymer and the above (H) component, or necessary. Depending on the above, the components (I), (J), (K) organic solvent, and additives can be added and mixed at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

(6) Curing method of the composition for forming a low refractive index layer The curing conditions for the composition for forming a low refractive index layer are not particularly limited. For example, when an active energy ray is used, the exposure amount is set to 0. A value in the range of 01 to 10 J / cm ² is 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 0.1 to 5 J / cm ² , and more preferably set to a value in the range of 0.3 to 3 J / cm ^2. .

When the composition for forming a low refractive index layer is heated and cured, it is preferably heated at a temperature in the range of 30 to 200 ° C. for 0.5 to 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 1 to 120 minutes, and further to heat at a temperature in the range of 80 to 150 ° C. for 1 to 60 minutes. preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts and% respectively represent parts by weight and% by weight unless otherwise specified.

Production Example 1: Production of Liquid Curable Composition 1 In a container shielded from ultraviolet rays, tin-containing indium oxide dispersion (Hout Form NID-20, manufactured by Fuji Chemical Co., Ltd., dispersion solvent isopropyl alcohol, tin-containing indium oxide 20 wt. %, Average primary particle size 13 nm, hereinafter may be referred to as ITO particle-1) 50 parts, dipentaerythritol hexaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) 86 parts, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts of 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, isopropyl alcohol 141.8 And 51.3 parts of propylene glycol monomethyl ether by stirring at 50 ° C. for 2 hours To obtain a liquid curable composition 1 single solution. 2 g of this composition was weighed on an aluminum pan, dried on a hot plate at 170 ° C. for 1 hour, and weighed to determine the solid content, which was 30% by weight. In addition, 2 g of this composition was weighed in a magnetic crucible, pre-dried on a hot plate at 80 ° C. for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour. When determined, it was 10% by weight.

Production Examples 2 and 3: Production of liquid curable compositions 2 and 3 Liquid curable compositions 2 and 3 shown in Table 1 were obtained by the same operation method.
In Table 1, the blending amount of the ITO particles and the dispersant represents only the solid content in the added dispersion, and the dispersion medium is included in the blending amount of the solvent.

The contents of the abbreviations in Table 1 are shown below.
ITO particle-1: Hout form NID-20 manufactured by Fuji Chemical Co., Ltd. (primary particle size: 13 nm, secondary particle size: 25 nm IPA dispersion)
Dispersant 1: Dispersant contained in Hout Foam NID-20 manufactured by Fuji Chemical Co., Ltd. ITO particle-2: Nanotech manufactured by CI Kasei Co., Ltd. (primary particle size: 25 nm, secondary particle size: 80 nm EtOH dispersion)
Dispersant 2: Dispersant included in Nanotech, manufactured by CI Kasei Co., Ltd. PGME: Propylene glycol monomethyl ether IPA: Isopropanol EtOH: Ethanol

Production Example 4: Preparation of Specified Organic Compound (Aa) In a dry air, a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate is stirred at 50 ° C. for 1 hour with 222 parts of isophorone diisocyanate. After dropping, the mixture was stirred with heating at 70 ° C. for 3 hours. NK ester A-TMM-3LM-N (60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Among these, the reaction is concerned with pentaerythritol having a hydroxyl group. 549 parts were added dropwise at 30 ° C. over 1 hour, and the mixture was heated and stirred at 60 ° C. for 10 hours to obtain an organic compound having a polymerizable unsaturated group (specific organic compound (Aa)). . When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having both urethane bonds was formed. As described above, this composition contains 773 parts in total of the compounds represented by the following formula (25) and the following formula (26), and 220 parts of pentaerythritol tetraacrylate that was not involved in the reaction. .

（式中、Ａｃｒｙｌは、アクリロイル基を示す。）

(In the formula, Acryl represents an acryloyl group.)

Production Example 5: Preparation of polyfunctional acrylate To a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer, NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (Only the pentaerythritol triacrylate having a hydroxyl group is involved in the reaction.) After dropwise addition of 93 parts at 10 ° C. for 1 hour, the mixture was stirred at 60 ° C. for 6 hours, did.
About the product in this reaction liquid, when the amount of residual isocyanate was measured by FT-IR similarly to manufacture example 4, it was 0.1 weight% or less, and it confirmed that reaction was performed substantially quantitatively. . Moreover, it confirmed that a urethane bond and an acryloyl group (polymerizable unsaturated group) were included in the molecule | numerator.
As described above, this composition contains 75 parts of the compound (B-1) represented by the following formula (27), and 37 parts of pentaerythritol tetraacrylate not involved in the reaction.

（式中、Ａｃｒｙｌは、アクリロイル基を示す。）

(In the formula, Acryl represents an acryloyl group.)

Production Example 6: Production of reactive silica particle sol to which an organic compound having a polymerizable unsaturated group is bonded. Silica particle sol (methyl ethyl ketone silica sol, MEK-ST-L manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 0.05 μm) , Silica concentration 30%) 143 g (43 g as silica particles), 2.8 g of a solution containing the specific organic compound (Aa) produced in Production Example 4, 0.1 g of distilled water, and 0.01 g of p-hydroquinone monomethyl ether are mixed. The mixture was heated and stirred at 65 ° C. Four hours later, 1.0 g of orthoformate methyl ester was added, and the mixture was further heated for 1 hour to obtain a reactive silica particle sol having a solid content of 31%.

Production Example 7: Production of hydroxyl-containing fluorine-containing polymer A stainless steel autoclave with an internal volume of 1.5 L with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then 465 g of ethyl acetate, 138.5 g of perfluoro (propyl vinyl ether), 37 of ethyl vinyl ether 37 0.5 g, 46.0 g of hydroxyethyl vinyl ether, 180.0 g of “ADEKA rear soap ER-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) as a nonionic reactive emulsifier, and “VPS-1001” (Japanese) as an azo group-containing polydimethylsiloxane After adding 9.0 g of Koyo Pure Chemical Industries Ltd. and 1.5 g of lauroyl peroxide and cooling to −50 ° C. with dry ice-methanol, oxygen in the system was again removed with nitrogen gas.
Next, 86.0 g of hexafluoropropylene was added, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 2.9 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 2.0 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 30.0%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer.

Production Example 8: Production of ethylenically unsaturated group-containing fluorine-containing polymer Hydroxyl-containing fluorine-containing polymer obtained in Production Example 7 in a 1-liter separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer 70.0 g of the polymer, 0.01 g of 2,6-di-t-butylmethylphenol and 520 g of MIBK as a polymerization inhibitor were charged, and the hydroxyl group-containing fluoropolymer was dissolved in MIBK at 20 ° C., and the solution was transparent and uniform. Stirring was continued until Next, 22 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.2 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 65 ° C. And stirring for 5 hours to obtain a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer. 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%.

Production Example 9: Preparation of Composition 1 for Forming Low Refractive Index Layer 20 g of reactive silica particle sol obtained in Production Example 6 (6.2 g as reactive particles), ethylenically unsaturated group obtained in Production Example 8 -Containing fluoropolymer 101.0 g (15.2 g as an ethylenically unsaturated group-containing fluoropolymer), 1.7 g of dipentaerythritol pentaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2- 1.2 g of morpholinopropan-1-one (C-2), 0.4 g of the compound represented by the formula (27) obtained in Production Example 5, organic copolymer-containing special silicon (Floren AC-901, Kyoeisha Chemical Co., Ltd.) Ltd.) 0.1 g and methyl isobutyl ketone 505.6 g were added and stirred at room temperature for 1 hour to obtain a composition 1 for forming a low refractive index layer. The solid content was determined in the same manner as in Production Example 1 and found to be 4% by weight.

Production Example 10: Synthesis of Porous Silica Particles In a quartz separable flask, 22.24 g of tetraethoxysilane, 841.97 g of methanol, and 30.00 g of propylene glycol were added and mixed uniformly, and then a 1% aqueous solution of ammonia 101 was added. 0.000 g was added. Then, the solution was allowed to react at 40 ° C. for 8 hours with stirring, and 0.92 g of vinyltrimethoxysilane and 1.54 g of methacryloxypropyltrimethoxysilane (SZ-6030 manufactured by Toray Dow Corning Silicone Co., Ltd.) were added. And reacted at 40 ° C. for 1 hour. Subsequently, 2.33 g of 2-perfluorohexylethyltrimethoxysilane (GE Toshiba Silicone Co., Ltd. product TSL8257) was added and reacted at 40 ° C. for 1 hour. After cooling the reaction solution to room temperature, 1000.00 g of methyl isobutyl ketone and 1000.00 g of a 0.1% aqueous solution of oxalic acid were added, and the mixture was stirred and allowed to stand. The upper layer separated into two layers was separated and concentrated with a rotary evaporator until the solid content concentration became 5% to obtain a porous silica particle solution.
After adding 10 g of ethanol to 1 g of the porous silica particle solution obtained above and mixing, 1 drop was dropped on a carbon grid for a transmission electron microscope and then dried at room temperature for 24 hours. When observation was performed using an electron microscope JEM-2010F and the particle size of the porous silica particles was measured, the average particle size was 20 nm.
10 g of the porous silica particle solution was placed in an aluminum dish and dried on a hot plate at 150 ° C. for 1 hour to obtain a powder sample of porous silica particles 1. When the BET specific surface area of the obtained porous silica particle powder was measured using AUTOSORB-1 manufactured by Quantachrome Instruments, the specific surface area was 200 m ² / g.

Production Example 11: Preparation of Composition 2 for Forming Low Refractive Index Layer 56 g of MIBK solution of the ethylenically unsaturated group-containing fluoropolymer obtained in Production Example 8 (8. as ethylenically unsaturated group-containing fluoropolymer). 5 g), 1750 g of porous silica particle dispersion obtained in Production Example 10 (87.5 g as porous silica particles), 2-methyl-1- [4- (methylthio) phenyl] -2 as a photopolymerization initiator -4 g of morpholinopropan-1-one and 700 g of MIBK were charged into a glass separable flask equipped with a stirrer and stirred at 23 ° C for 1 hour to obtain a composition 2 for forming a low refractive index layer. The solid content was determined in the same manner as in Production Example 1 and found to be 4% by weight.

Example 1
Production of Antireflection Laminate 1 The liquid curable composition 1 obtained in Production Example 1 was subjected to surface easy adhesion treatment using wire bar coater # 20, polyester film A4300 (manufactured by Toyobo Co., Ltd.) The film was coated on a film having a thickness of 188 μm and dried in an oven at 80 ° C. for 3 minutes. Subsequently, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp in the atmosphere to produce a film having an antistatic hard coat layer. When the film thickness of the antistatic hard coat layer was measured with a stylus type surface shape measuring instrument, it was 3 μm. On this film with an antistatic hard coat, the composition 1 for forming a low refractive index layer obtained in Production Example 9 was applied using a wire bar coater # 3, and the conditions of 80 ° C. for 1 minute in an oven were applied. And dried. Next, under a nitrogen atmosphere, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp, and a low refractive index layer was formed to produce the antireflection laminate 1. The film thickness of the low refractive index layer was calculated from the reflectance of the obtained antireflection laminate 1 and found to be 0.1 μm.

Example 2
Production of antireflection laminate 2 Antireflection layer 2 was produced in the same manner as in Example 1 except that composition 2 for forming a low refractive index layer obtained in Production Example 11 was used instead of composition 1 for forming a low refractive index layer. The laminated body 2 was produced. When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0.1 μm.

Example 3
Production of antireflection laminate 3 An antireflection laminate 3 was produced in the same manner as in Example 1 except that the liquid curable composition 2 obtained in Production Example 2 was used instead of the liquid curable composition 1. . When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0.1 μm.

Example 4
Production of antireflection laminate 4 Antireflection treatment was conducted in the same manner as in Example 3 except that the composition 2 for forming a low refractive index layer obtained in Production Example 11 was used instead of the composition 1 for forming a low refractive index layer. The laminated body 4 was produced.

Comparative Example 1
Production of Antireflection Laminate 5 Example 1 except that the liquid curable composition 3 obtained in Production Example 3 was applied on the substrate using the wire bar coater # 40 instead of the liquid resin composition 1. In the same manner as described above, an antireflection laminate 5 was produced. When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0.1 μm.

Comparative Example 2
Production of antireflection laminate 6 Antireflection treatment was conducted in the same manner as in Comparative Example 1 except that the composition 2 for forming a low refractive index layer obtained in Production Example 11 was used instead of the composition 1 for forming a low refractive index layer. The laminated body 6 was produced. When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0.1 μm.

Evaluation Example The following characteristics were evaluated for the antireflection laminates 1 to 6 obtained in Examples 1 to 4 and Comparative Examples 1 to 2.

(A) Total light transmittance and haze The total light transmittance (%) and haze (%) of a cured film film were measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). did. The obtained results are shown in Table 2.

(C) Surface resistance The surface resistance (Ω / □) of the cured film film was measured using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.). Used and measured under the condition of an applied voltage of 100V. The obtained results are shown in Table 2.

(D) Reflectance The reflectance of the obtained antireflection laminate is measured with a spectral reflectance measuring device (instant multi-photometry system, MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) in the wavelength range of 400 to 800 nm. Was measured and evaluated. Table 2 shows the reflectance at a wavelength of 550 nm.

(E) Scratch resistance test 1 (steel wool resistance)
The steel wool resistance test of the antireflection laminate was performed 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 according to the following criteria. The obtained results are shown in Table 2.
◯: Almost no peeling or scratching of the cured film is observed.
(Triangle | delta): A thin crack is recognized by the cured film.
X: Peeling occurred in a part of the cured film, or streak scratches occurred on the surface of the cured film.

(F) Scratch resistance test 2 (cloth abrasion resistance)
The cloth rubbing resistance test of the antireflection laminate was carried out by the following method. That is, a non-woven fabric (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded 20 times under the condition of a load of 1000 g. By rubbing repeatedly, the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The obtained results are shown in Table 2.
◯: Almost no peeling or scratching of the cured film is observed.
(Triangle | delta): A thin crack is recognized by the cured film.
X: Peeling occurred in a part of the cured film, or streak scratches occurred on the surface of the cured film.

(G) Chemical resistance test (ethanol resistance test)
The ethanol resistance test of the cured film was performed by the following method. That is, a non-woven fabric impregnated with ethanol (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded with 500 g. Under the above conditions, rubbing was repeated 20 times, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The obtained results are shown in Table 2.
◯: Almost no peeling or scratching of the cured film is observed.
(Triangle | delta): A thin crack is recognized by the cured film.
X: Peeling occurred in a part of the cured film, or streak scratches occurred on the surface of the cured film.

  From the results of Table 2, Example 1 using particles (ITO particles-1) mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less. -4 show that the total light transmittance is high, the haze is low, the surface resistance is low, and the scratch resistance and chemical resistance are also excellent.

According to the present invention, it is possible to provide an antistatic laminate having a cured film excellent in curability and having a cured film excellent in antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. it can.
The laminate of the present invention mainly includes, for example, a protective film for a touch panel, a transfer foil, a hard coat for an optical disk, a window film for an automobile, an antistatic protective film for a lens, a surface protective film of a high-design container such as a cosmetic container, etc. Anti-reflection with antistatic function for various display panels such as CRT, liquid crystal display panel, plasma display panel, electroluminescence display panel, etc. as a hard coat for the purpose of preventing scratches on the product surface and preventing dust adhesion due to static electricity As a film | membrane, it can utilize as an antireflection film with an antistatic function, such as a plastic lens, a polarizing film, a solar cell panel.
The laminated body of the present invention can be used to prevent or damage (scratch) or contaminate, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic housings, plastic containers, flooring materials as building interior materials, wall materials, and artificial marble. It can be suitably used as a hard coating material for preventing; an adhesive for various substrates, a sealing material; a binder material for printing ink, and the like.

It is a schematic diagram which shows the basic composition of the laminated body of this invention. It is a schematic diagram which shows the 1st form of the antireflection film with an antistatic function of this invention. It is a schematic diagram which shows another form of the 1st form of the antireflection film with an antistatic function of this invention. It is a schematic diagram which shows the 2nd form of the antireflection film with an antistatic function of this invention. It is a schematic diagram which shows another form of the 2nd form of the antireflection film with an antistatic function of this invention. It is a schematic diagram which shows the 3rd form of the antireflection film with an antistatic function of this invention. It is a schematic diagram which shows another form of the 3rd form of the antireflection film with an antistatic function of this invention.

Explanation of symbols

1: Laminated body 2: Antireflection film with antistatic function 10: Base material 11: Hard coat layer 12: Cured film layer or antistatic layer 14: Medium refractive index layer 16: High refractive index layer 18: Low refractive index layer

Claims (17)

At least a substrate;
A cured film layer obtained by curing a liquid curable composition containing the following components (A) to (D), and the content of the component (A) being 5 to 40% by weight in all components excluding the solvent; ,
A laminate having
[Liquid curable composition]
(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less (B) Compound having two or more polymerizable unsaturated groups in the molecule (C) Photopolymerization initiator (D )solvent   The laminate according to claim 1, wherein the component (A) is an oxide particle surface-treated with a surface treatment agent. The laminate according to claim 2, wherein the surface treatment agent is a compound having two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. .
-X-C (= Y) -NH- (1)
[Wherein, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]   It is an antireflection film, The layered product according to any one of claims 1 to 3. The laminate according to any one of claims 1 to 4, wherein the surface resistance value is 1 x 10 ¹³ Ω / □ or less. The laminate is an antireflection film in which at least an antistatic layer and a low refractive index layer are laminated on a substrate in this order from the side close to the substrate,
The laminate according to claim 4 or 5, wherein the cured film layer is an antistatic layer.   The laminate according to claim 6, wherein a refractive index of the antistatic layer is higher than a refractive index of the low refractive index layer.   Furthermore, the laminated body of any one of Claims 1-7 in which the hard-coat layer is formed on the base material. The low refractive index layer is
The following components (G) and (H):
(G) a compound containing one isocyanate group and at least one ethylenically unsaturated group, and an ethylenically unsaturated group-containing fluoropolymer obtained by reacting a hydroxyl group-containing fluoropolymer,
(H) particles mainly composed of silica,
The laminate according to any one of claims 6 to 8, which is a cured product of a curable resin composition containing. The hydroxyl group-containing fluorine-containing polymer has (a) 20 to 70 mol%, (b) 10 to 70 mol% and (c) when the total of the following structural units (a) to (c) is 100 mol%. 5) to 70 mol%, and
The laminate according to claim 9, which has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography.
(A) Structural unit represented by the following formula (11) (b) Structural unit represented by the following formula (12) (c) Structural unit represented by the following formula (13)

[Wherein R ¹¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ¹² (R ¹² represents an alkyl group or a fluoroalkyl group)]

[Wherein, R ¹³ represents a hydrogen atom or a methyl group, R ¹⁴ represents an alkyl group, a group represented by — (CH ₂ ) _c —OR ¹⁵ or —OCOR ¹⁵ (R ¹⁵ represents an alkyl group or a glycidyl group, c Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

[Wherein R ¹⁶ represents a hydrogen atom or a methyl group, R ¹⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1] When the hydroxyl group-containing fluoropolymer is 100 mol parts of the structural units (a) to (c), the following structural units (d) 0.1 to 10 derived from an azo group-containing polysiloxane compound are further included. The laminated body of Claim 9 or 10 containing a molar part.
(D) Structural unit represented by the following general formula (14)

[Wherein R ¹⁸ and R ¹⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]   The laminate according to any one of claims 9 to 11, wherein the component (H) is silica particles having an ethylenically unsaturated group on the surface. The component (H) is
Porous silica particles comprising a silicon compound represented by the following formula (22) and a hydrolyzate and / or hydrolysis condensate of the silicon compound represented by the following formula (23) and having an average particle diameter of 5 to 50 nm (H1)
SiX ₄ (22)
R ²⁹ _j SiX _4-j (23)
(X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ represents 2 carbon atoms. -8 alkenyl group, C 4-8 acryloxyalkyl group or C 5-8 methacryloxyalkyl group, j represents an integer of 1 to 3. X in formula (22) and formula (23 ) X may be the same or different.)
The laminate according to any one of claims 9 to 12. The component (H) is
It consists of a silicon compound represented by the following formula (22), a silicon compound represented by the following formula (23) and a hydrolyzate and / or hydrolysis condensate of the silicon compound represented by the following formula (24), and the average Porous silica particles (H2) having a particle size of 5 to 50 nm
SiX ₄ (22)
R ²⁹ _j SiX _4-j (23)
R ³⁰ _k SiX _4-k (24)
(X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ represents 2 carbon atoms. 8 alkenyl group, acryloxy group or methacryloxy alkyl group having a carbon number of 5 to 8, j is ^{.R 30} represents an integer of 1 to 3 fluorine-substituted alkyl having 1 to 12 carbon atoms having 4 to 8 carbon atoms Group k represents an integer of 1 to 3. X in formula (22), X in formula (23) and X in formula (24) may be the same or different.
The laminate according to any one of claims 9 to 12.   When the porous silica particles (H1) have a total of 100 mol% of the silicon compound represented by the formula (22) and the silicon compound represented by the formula (23), the hydrolyzate and / or The laminate according to claim 13, wherein the hydrolysis condensate comprises a reaction product of 67 to 99 mol% of a silicon compound represented by the formula (22) and 33 to 1 mol% of a silicon compound represented by the formula (23). body.   The porous silica particles (H2) are 100 mol in total of the silicon compound represented by the formula (22), the silicon compound represented by the formula (23) and the silicon compound represented by the formula (24). %, The hydrolyzate and / or hydrolysis condensate is 60 to 98 mol% of the silicon compound represented by the formula (22), 1 to 30 mol% of the silicon compound represented by the formula (23) and The laminated body of Claim 14 which consists of a reaction material of 1-20 mol% of silicon compounds represented by Formula (24). The process of forming the cured film layer obtained by hardening | curing this composition by apply | coating the liquid curable composition containing the following component (A)-(D) on a base material, and irradiating a radiation. The manufacturing method of the laminated body containing.
[Liquid curable composition]
(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less (B) Compound having two or more polymerizable unsaturated groups in the molecule (C) Photopolymerization initiator (D )solvent

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