JP5088163B2 - Curable composition, cured film thereof and laminate - Google Patents

Abstract

A curing composition, a cured film formed by curing the composition, and a laminate having the cured film are provided to increase refractivity and reflectivity and to improve scratch resistance and antistatic property. A curing composition comprises (A) a particle having a polymerizable unsaturated group, comprising an oxide of at least one element selected from the group consisting of Zn, In, Sn and Sb as a main component and having a median diameter of 65-85 nm; (B) a compound having at least polymerizable unsaturated group, at least one alkylene oxide chain and at least two aromatic rings; and (C) a compound having at least one polymerizable unsaturated group other than (A) and (B).

Description

  The present invention relates to a curable composition, a cured film obtained by curing the curable composition, and a laminate. More specifically, the present invention relates to a curable composition, a cured film, and a laminate that provide a cured film having a high refractive index and an antistatic property.

  In recent years, plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. As a protective coating material and anti-reflection coating material for preventing scratches (abrasion) on various substrate surfaces and preventing contamination, it has excellent coating properties, and the surface of each substrate has hardness, There is a demand for a curable composition capable of forming a cured film having excellent scratch resistance, abrasion resistance, surface slipperiness, low curling properties, adhesion, transparency, chemical resistance, and coating film appearance. ing.

  Furthermore, in the curable composition that gives a cured film having antistatic properties, conductive particles are included, but it has stable antistatic performance, transparency, reflectance and scratch resistance. There was a problem that the cured film shown below could not be formed.

JP 2004-331909 A JP 200531282 A JP-A-2005-146110

  The present invention has been made in view of the above-described problems, and provides a curable composition that provides a cured film having stable antistatic performance and excellent scratch resistance, and further having a high refractive index and a high reflectance. Objective.

  In order to achieve the above-mentioned object, the present inventors have conducted intensive research, can achieve a certain surface resistance value by controlling the particle size of conductive particles having a polymerizable unsaturated group, and polymerization. By using a compound having an EO-modified bisphenol A skeleton having a polymerizable unsaturated group as a part of the binder resin, a curable composition that gives a cured film having a high refractive index and excellent scratch resistance is obtained. As a result, the present invention was completed.

［式（Ｂ−１）中、Ｒ^１及びＲ^２はそれぞれ炭素数２〜４の２価の炭化水素基、Ｒ^３は単結合又は芳香環を有していてもよい炭素数１〜２０の２価の炭化水素基、Ｒ^５及びＲ^６は水素原子又はメチル基、Ｒ^１４及びＲ^１５はそれぞれ水素原子又は（メタ）アクリロイル基を示し、ｑ個あるＲ^１４とｐ個あるＲ^１５のうち少なくとも１個は（メタ）アクリロイル基である。ｍ及びｎはそれぞれ１〜３０、ｐは１〜４、ｑは０〜４の数を示す。］
３．前記成分（Ｂ）の化合物が、下記一般式（Ｂ−２）で示される構造を有する上記１又は２に記載の硬化性組成物。

［式（Ｂ−２）中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^１１、Ｒ^１２はそれぞれ、水素原子、メチル基、フェニル基を示し、Ｒ^１３は水素原子又は（メタ）アクリロイル基を示し、ｍはそれぞれ独立に１〜３０の数を示す。］
４．前記成分（Ａ）の酸化物粒子が、アンチモン含有酸化スズ、スズ含有酸化インジウム、フッ素含有酸化スズ、アルミニウム含有酸化亜鉛からなる群から選択される上記１〜３のいずれかに記載の硬化性組成物。
５．前記成分（Ａ）の酸化物粒子が、アンチモン含有酸化スズである上記４に記載の硬化性組成物。
６．前記成分（Ａ）の有する重合性不飽和基が、下記式（４）に示す構造を含む基である上記１〜５のいずれかに記載の硬化性組成物。

［式（４）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］
７．さらに、（Ｄ）活性エネルギー線の照射により活性種を発生する化合物を含有する上記１〜６のいずれかに記載の硬化性組成物。
８．さらに、（Ｅ）有機溶剤を含む上記１〜７のいずれかに記載の硬化性組成物。
９．前記成分（Ｃ）が有する重合性不飽和基が（メタ）アクリロイル基である上記１〜８のいずれかに記載の硬化性組成物。
１０．上記１〜９のいずれかに記載の硬化性組成物を硬化させてなる硬化膜。
１１．基材上に上記１０に記載の硬化膜を有する積層体。 That is, the present invention provides the following curable composition, cured film and laminate.
1. The following components (A) to (D):
(A) an oxide of at least one element selected from the group consisting of zinc, indium, tin, and antimony having a polymerizable unsaturated group and a median diameter in the range of 65 to 85 nm as a main component Particles (B) one or more polymerizable unsaturated groups, one or more alkylene oxide chains and two or more aromatic rings (C) one or more other than components (A) and (B) A curable composition containing a compound having a polymerizable unsaturated group.
2. 2. The curable composition according to 1 above, wherein the component (B) compound has a structure represented by the following general formula (B-1).

[In Formula (B-1), R ¹ and R ² are each a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ³ is a C 1-20 which may have a single bond or an aromatic ring. A divalent hydrocarbon group, R ⁵ and R ⁶ are a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁵ are each a hydrogen atom or a (meth) acryloyl group, and q of R ¹⁴ and p of R ¹⁵ At least one is a (meth) acryloyl group. m and n are each 1 to 30, p is 1 to 4, and q is 0 to 4. ]
3. The curable composition according to 1 or 2 above, wherein the compound of the component (B) has a structure represented by the following general formula (B-2).

[In Formula (B-2), R ⁴ represents a hydrogen atom or a methyl group, R ¹¹ and R ¹² represent a hydrogen atom, a methyl group, and a phenyl group, respectively, and R ¹³ represents a hydrogen atom or a (meth) acryloyl group. M represents a number of 1 to 30 independently. ]
4). The curable composition according to any one of 1 to 3 above, wherein the oxide particles of the component (A) are selected from the group consisting of antimony-containing tin oxide, tin-containing indium oxide, fluorine-containing tin oxide, and aluminum-containing zinc oxide. object.
5. 5. The curable composition according to 4 above, wherein the component (A) oxide particles are antimony-containing tin oxide.
6). The curable composition according to any one of 1 to 5 above, wherein the polymerizable unsaturated group of the component (A) is a group containing a structure represented by the following formula (4).

[In Formula (4), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
7). Furthermore, (D) The curable composition in any one of said 1-6 containing the compound which generate | occur | produces active species by irradiation of an active energy ray.
8). Furthermore, (E) The curable composition in any one of said 1-7 containing an organic solvent.
9. The curable composition in any one of said 1-8 whose polymerizable unsaturated group which the said component (C) has is a (meth) acryloyl group.
10. The cured film formed by hardening | curing the curable composition in any one of said 1-9.
11. A laminate having the cured film described in 10 above on a substrate.

The curable composition of the present invention can provide a cured film having stable antistatic performance, high refractive index and high reflectance, and excellent scratch resistance.
The cured film of the present invention can be used as an antistatic layer, a high refractive index layer, and a hard coat layer of an antireflection laminate.

I. Curable composition The curable composition of this invention (henceforth the composition of this invention) may contain the following component (A)-(F). Among these, components (A) to (C) are essential components, and components (D) to (F) are optional components that are added as necessary.
(A) an oxide of at least one element selected from the group consisting of zinc, indium, tin, and antimony having a polymerizable unsaturated group and a median diameter in the range of 65 to 85 nm as a main component Particles (B) one or more polymerizable unsaturated groups, one or more alkylene oxide chains and two or more aromatic rings (C) one or more other than the above components (A) and (B) Compound (D) having a polymerizable unsaturated group Compound (E) Organic solvent (F) additive that generates active species upon irradiation with active energy rays

(1) Hereinafter, each component will be described.
(A) an oxide of at least one element selected from the group consisting of zinc, indium, tin, and antimony having a polymerizable unsaturated group and a median diameter in the range of 65 to 85 nm as a main component The particle component (A) is a particle having a polymerizable unsaturated group and having a specific median diameter and having an oxide of a specific element as a main component (hereinafter referred to as “reactive particle”).
The reactive particles include particles (Aa) mainly composed of an oxide of at least one element selected from the group consisting of zinc, indium, tin, and antimony, and a polymerizable unsaturated group and hydrolyzable silyl in the molecule. It can be obtained by reacting an organic compound (Ab) having a group.
By blending the component (A), it reacts with the polymerizable unsaturated group of the components (B) and (C) described below, and by polymerization, the hardness of the resulting cured film can be further increased, Curing shrinkage (warpage) can be reduced.

(1) Particles mainly composed of oxide (Aa) (hereinafter referred to as “oxide particles”)
Examples of the oxide particles (Aa) include particles of zinc oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and the like. Among these, particles of antimony oxide are preferable from the viewpoint of high hardness. These may be used alone or in combination of two or more. Furthermore, the oxide particles (Aa) are preferably used as a powder or solvent-dispersed sol. When used as a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
Examples of oxide particles (Aa) that can impart excellent antistatic properties include antimony-containing tin oxide, tin-containing indium oxide, fluorine-containing tin oxide, and aluminum-containing zinc oxide.

The median diameter of the reactive particles needs to be in the range of 65 to 85 nm, and preferably in the range of 70 to 80 nm. If the median diameter of the particles is less than 65 nm, the surface resistance may increase or the scratch resistance may decrease. If it exceeds 85 nm, the transparency may be impaired or the reflectance may be reduced.
Here, the median diameter means a diameter in which the large side and the small side are equal when the powder is divided into two from a certain particle diameter.
The median diameter of the antimony-containing tin oxide particles dispersed in the obtained dispersion can be measured under the following conditions.
Equipment: Dynamic light scattering type particle size distribution measuring device manufactured by HORIBA, Ltd. Measurement conditions: Temperature 25 ° C
Sample Analytical condition of measurement data as sample solution: Particle size standard Volume standard
Dispersed particles ATO particles Refractive index 2.05
Dispersion medium Methanol Refractive index 1.329
The median diameter is controlled by the dispersion time. That is, the median diameter can be increased by shortening the dispersion time, and the median diameter can be decreased by increasing the dispersion time.

  In addition, as an aqueous dispersion of zinc antimonate powder, Celnax manufactured by Nissan Chemical Industries, Ltd .; as a powder and solvent dispersion of tin oxide, indium oxide, zinc oxide, etc., Nanotech manufactured by CI Kasei Co., Ltd .; antimony Examples of the water-dispersed sol of doped tin oxide include SN-100D manufactured by Ishihara Sangyo Co., Ltd .; examples of the ITO powder include products manufactured by Mitsubishi Materials Corporation.

The oxide particles (Aa) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indeterminate shape, and preferably a spherical shape. The specific surface area of the oxide particles (Aa) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These oxide particles (Aa) can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, the use of an organic solvent-dispersed sol of an oxide is preferable in applications where the cured product requires excellent transparency.

(2) Organic compound (Ab)
The organic compound (Ab) used in the present invention is a compound having a polymerizable unsaturated group, and is preferably an organic compound containing a group represented by the following formula (4).

［式（４）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］

[In Formula (4), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]

  Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least 1 of these is included. Moreover, it is preferable that this organic compound (Eb) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

(I) Polymerizable unsaturated group Although there is no restriction | limiting in particular as a polymerizable unsaturated group contained in an organic compound (Eb), For example, an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, an ethynyl Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (4) The group [—UC— (V) —NH—] represented by the formula (4) contained in the organic compound is specifically represented by [—O—C ( = O) -NH-], [-O-C (= S) -NH-], [-S-C (= O) -NH-], [-NH-C (= O) -NH-], Six types of [—NH—C (═S) —NH—] and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [-UC (= V) -NH-] represented by the formula (4) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion and heat resistance to adjacent layers such as materials and high refractive index layers.

(Iii) Silanol group or group that generates a silanol group by hydrolysis The organic compound (Eb) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. A compound having a group bonded thereto, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the oxide particles (Aa) by a condensation reaction that occurs following a condensation reaction or hydrolysis.

(Iv) Preferred Embodiment As a preferred specific example of the organic compound (Ab), for example, a compound represented by the following formula (11) can be mentioned.

In the formula (11), R ⁶ and R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ⁶ O) _j R ⁷ _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ⁸ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ⁹ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ¹⁰ is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by the formula (11) include compounds represented by the following formulas (12) and (13).

［式（１２）及び式（１３）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

[In the formulas (12) and (13), “Acryl” represents an acryloyl group. ]

  For the synthesis of the organic compound (Ab) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent.

(3) Preparation of reactive particles (A) An organic compound (Eb) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with the metal oxide particles (Aa), hydrolyzed, and combined. . The ratio of the organic polymer component, ie, hydrolyzable silane hydrolyzate and condensate, in the resulting reactive particles (E) is usually the weight loss% when the dry powder is completely burned in air. The constant value can be obtained, for example, by thermogravimetric analysis from room temperature to usually 800 ° C. in air.

  The amount of the organic compound (Ab) bound to the oxide particles (Aa) is preferably 100% by weight of the reactive particles (A) (the total of the metal oxide particles (Aa) and the organic compound (Ab)), It is 0.01% by weight or more, more preferably 0.1% by weight or more, and particularly preferably 1% by weight or more. When the amount of the organic compound (Ab) bound to the metal oxide particles (Aa) is less than 0.01% by weight, the dispersibility of the reactive particles (A) in the composition is not sufficient, and the resulting curing is obtained. The transparency and scratch resistance of the object may not be sufficient. Moreover, the compounding ratio of the metal oxide particles (Aa) in the raw material during the production of the reactive particles (A) is preferably 5 to 99% by weight, and more preferably 10 to 98% by weight. The content of the oxide particles (Aa) constituting the reactive particles (A) is preferably 65 to 95% by weight of the reactive particles (A).

The amount of component (A) in the composition of the present invention is preferably 50 to 90% by weight when the total amount of the composition excluding the organic solvent is 100% by weight, and 65 to 85% by weight. More preferably, it is particularly preferably in the range of 75 to 80% by weight. When the blending amount of the component (A) is less than 50% by weight, a high reflectance may not be obtained when a cured film is obtained, and when it exceeds 90% by weight, the film formability may be insufficient. is there.
In addition, content of the reactive particle (A) means solid content, and when the reactive particle (A) is used in the form of a solvent-dispersed sol, the content does not include the amount of solvent.

(B) Compound having one or more polymerizable unsaturated groups, one or more alkylene oxide chains, and two or more aromatic rings. Component (B) is not only a compound having a high refractive index but also oxide particles. It has a property that it is easy to adhere to air and hardly adheres to air, and the resulting cured film can have a higher refractive index.
Conventionally, it has been considered that when a compound having a bisphenol skeleton is modified with alkylene oxide (AO), the flexibility of the compound increases, and the hardness of the resulting cured film decreases. However, the present inventors have found that in combination with antimony-containing tin oxide (ATO), the hardness of the cured film such as scratch resistance is not lowered.

The compound of component (B) preferably has a structure represented by the following general formula (B-1).

In formula (B-1), R ¹ and R ² are each a divalent hydrocarbon group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group .
R ³ is a C1-C20 divalent hydrocarbon group which may have a single bond or an aromatic ring. Examples of the divalent hydrocarbon group include methylene, isopropylidene, methylphenylmethylidene and the like. preferable.
R ⁵ and R ⁶ represent a hydrogen atom or a methyl group.
R ¹⁴ and R ¹⁵ each represent a hydrogen atom or a (meth) acryloyl group, and at least one of q R ¹⁴ and p R ¹⁵ is a (meth) acryloyl group.
m and n each represent a number of 1 to 30, preferably 1 to 10.
p shows the number of 1-4, Preferably it is 1-2.
q shows the number of 0-4, Preferably it is 1-2.

式（Ｂ−２）中、Ｒ^４はそれぞれ水素原子又はメチル基を示す。
Ｒ^１１、Ｒ^１２はそれぞれ、水素原子、メチル基、フェニル基を示す。
Ｒ^１３は、水素原子、または（メタ）アクリロイル基を示す。
ｍは１〜３０の数を示し、好ましくは１〜１０である。 The compound of component (B) more preferably has a structure represented by the following general formula (B-2).

In formula (B-2), R ⁴ represents a hydrogen atom or a methyl group, respectively.
R ¹¹ and R ¹² each represent a hydrogen atom, a methyl group, or a phenyl group.
R ¹³ represents a hydrogen atom or a (meth) acryloyl group.
m shows the number of 1-30, Preferably it is 1-10.

(1) Polymerizable unsaturated group The polymerizable unsaturated group possessed by component (B) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl group. A cinnamoyl group, a maleate group and an acrylamide group can be mentioned as preferred examples.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with the components (A) and (C) by an active radical species.

(2) Production method of compound of component (B) In the case of compound of component (B) and alkylene oxide is ethylene oxide (EO), it can be produced as follows.
Bisphenol and oxirane are reacted under basic conditions to prepare an EO adduct of bisphenol. Bisphenol EO adduct diacrylate can be prepared by reacting EO adduct of bisphenol with acrylic acid using p-toluenesulfonic acid as a catalyst.

(3) Specific Examples Specific examples of the compound of component (B) include ethylene oxide (hereinafter referred to as “EO”) adduct di (meth) acrylate of bisphenol A, propylene oxide of bisphenol A (hereinafter referred to as “PO”). PO adduct di (meth) acrylate, EO adduct di (meth) acrylate of bisphenol F, PO adduct di (meth) acrylate of bisphenol F, etc., EO adduct di (meth) acrylate of bisphenol A, etc. preferable.
Examples of commercially available compounds of component (B) include Biscoat 700 (bisphenol A, EO adduct diacrylate; manufactured by Osaka Organic Chemical Co., Ltd.), Light Ester BP-2EM (EO adduct dimethacrylate of bisphenol A). , Light acrylate BP-4EA (EO adduct diacrylate of bisphenol A), light acrylate BP-4PA (PO adduct diacrylate of bisphenol A); manufactured by Kyoeisha Chemical Co., Ltd., Aronix M-208 (EO addition of bisphenol F) Product diacrylate), Aronix M-210, Aronix 211B (EO adduct diacrylate of bisphenol A); manufactured by Toagosei Co., Ltd., SR-349, SR-601, SR-602 (EO adduct diacrylate of bisphenol A) ), SR-348, SR- 80, SR-9036 (EO adduct dimethacrylate of bisphenol A) KAYARAD R-551, R-712 (EO adduct diacrylate of bisphenol A) ,; Nippon Kayaku Co., Ltd., NK ESTER
ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-3 (EO adduct diacrylate of bisphenol A), NK ESTER
BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N (EO adduct dimethacrylate of bisphenol A); Shin-Nakamura Chemical Co., Ltd., etc. are mentioned.

  The compounding amount of the component (B) in the composition of the present invention is usually 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 100% by weight based on the total amount of the composition excluding the organic solvent. Is in the range of 4-6% by weight. If the content of the component (B) is less than 1% by weight, the reflectivity may decrease, and if it exceeds 15% by weight, the curability may be insufficient.

(C) Compound having one or more polymerizable unsaturated groups other than components (A) and (B) A compound having one or more polymerizable unsaturated groups is obtained by curing the composition of the present invention. It is used to enhance the scratch resistance of the cured film and the antireflection film using the cured film.

  The compound is not particularly limited as long as it is a compound containing at least one polymerizable unsaturated group in the molecule. As the polymerizable unsaturated group, a (meth) acryloyl group is preferable.

  Examples of the compound having one (meth) acryloyl group include acryloylmorpholine, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Aliphatic structure-containing (meth) acrylates such as pentenyl (meth) acrylate and cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propylene (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, tetrahydro Furyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy Ethylene glycol (meth) acrylate, 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, di Ethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl Examples thereof include vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and a compound represented by the following formula (15).

_{^{CH 2 = C (R 26)}} -COO (R 27 O) d -Ph-R 28 (15)
Wherein R ²⁶ represents a hydrogen atom or a methyl group, R ²⁷ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ²⁸ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, Ph represents a phenylene group, and d represents a number of 0 to 12, preferably 1 to 8.)

  As these commercial products, Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, manufactured by Toagosei Co., Ltd.); -MTA, # 192, # 193 (Osaka Organic Chemical Co., Ltd.); NK Ester AMP-10G, AMP-20G, AMP-60G (above, Shin-Nakamura Chemical Co., Ltd.); Light acrylate LA, S-A, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (hidden, Hitachi Chemical) Kogyo Co., Ltd.).

  Examples of the compound having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, and tricyclo Decanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene Oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether at both ends (meth) acrylic acid Adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, Polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate DOO, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, can be exemplified ditrimethylolpropane tetra (meth) acrylate. Examples of commercially available products of these polyfunctional monomers include SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, Viscoat 360, Viscoat GPT, Biscoat 400, Biscoat 3000, Viscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-604, R-684, PET- 30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, D -0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (above, Japan) Kayaku Co., Ltd.), M-220, M-233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M- 6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, Shinichi) Sakai Chemical Co., Ltd.), lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa High Polymer Co., Ltd.) and the like.

  In addition, among these, the compound which contains at least 3 or more (meth) acryloyl groups in a molecule | numerator is more preferable for the composition of this invention. The three or more compounds can be selected from the tri (meth) acrylate compounds exemplified above, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds, and the like. Of these, pentaerythritol hydroxytriacrylate and trimethylolpropane triacrylate are particularly preferred. Each of the above compounds can be used alone or in combination of two or more.

  The amount of component (C) in the composition of the present invention is not particularly limited, but is usually 1 to 15% by weight, preferably 100% by weight, based on the total amount of the composition other than the organic solvent. Is in the range of 5-14 wt%, more preferably 11-13 wt%. If the amount of component (C) is less than 1% by weight, scratch resistance of the resulting cured coating film may not be obtained. On the other hand, if it exceeds 15% by weight, the refractive index may decrease. There is.

(D) Compound that generates active species upon irradiation with active energy rays In the composition of the present invention, a compound that generates active species upon irradiation with active energy rays (hereinafter sometimes referred to as “component (D)”). Add. Such a compound is used for efficiently curing the curable composition.

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

  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-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, 1-hydride Xylcyclohexyl 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-benzoyl -4'-methyldiphenyl sulfide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzyl, or BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, Combination of a dye sensitizer can be mentioned.

  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, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropane-1-o , 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer Etc.

  The amount of component (D) in the composition of the present invention is not particularly limited, but is preferably 0 to 15% by weight when the total amount of the composition excluding the organic solvent is 100% by weight. 2 to 8% by weight is more preferable, and 3 to 6% by weight is particularly preferable. If it exceeds 15% by weight, the hardness may decrease.

(E) Organic solvent The composition of the present invention may contain an organic solvent. By containing the organic solvent, a thin antireflection film can be formed uniformly. Such organic solvents include acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone and other ketones, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and other esters, propylene glycol monomethyl ether, methanol, ethanol , Sec-butanol, t-butanol, alcohols such as 2-propanol and isopropanol, aromatics such as benzene, toluene and chlorobenzene, and aliphatics such as hexane and cyclohexane, alone or in combination of two or more. It is done. Among these, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol, ethanol, sec-butanol , T-butanol, 2-propanol, isopropanol and the like are preferable, and methyl isobutyl ketone, methyl amyl ketone, and t-butanol are used alone or in combination of two or more.

  As the organic solvent, only the dispersion medium of the reactive particles of the component (A) described above may be used, or another organic solvent may be used in combination.

  The blending amount of the organic solvent is not particularly limited, but is preferably 10 to 100,000 parts by weight with respect to 100 parts by weight of the total composition excluding the organic solvent. This is because when the amount of the organic solvent is less than 10 parts by weight, it may be difficult to adjust the viscosity of the curable composition. On the other hand, when the amount exceeds 100,000 parts by weight, the curable composition is used. This is because the storage stability of the resin may decrease, or the viscosity may decrease excessively, making handling difficult.

(F) Additive The composition of the present invention includes a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surfactant as long as the objects and effects of the present invention are not impaired. It is also preferable to further contain additives such as a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, a pigment, and a dye.

(2) Preparation method of the composition of the present invention The composition of the present invention comprises a composition containing the components (A) to (D) and, if necessary, the components (E) to (F). It can also be prepared by adding and mixing 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.

(3) Curing conditions for the composition of the present invention The composition of the present invention can be cured by heat and / or radiation (light). When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Moreover, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited, and for gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

As conditions for curing by heating, it is preferable to heat at a temperature within a range of 30 to 200 ° C. for 1 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 2 to 120 minutes, and further to heat at a temperature in the range of 80 to 150 ° C. for 5 to 60 minutes. preferable.
As for the subsequent irradiation conditions, it is preferable to set the exposure amount to a value within the range of 0.01 to 10 J / cm ² .
This is because when the exposure dose is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure dose exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.
Moreover, such a reason, the exposure amount is more preferably within a range of 0.1~5J / cm ^2, further preferably a value within the range of 0.3~3J / cm ² .

II. Cured film and laminate The cured film of the present invention comprises a cured product obtained by curing the composition of the present invention. Since the cured film of the present invention has a high refractive index and antistatic properties, it is useful as a high refractive index antistatic layer.
The laminate of the present invention comprises a layer comprising the cured film of the present invention. The layer made of the cured film of the present invention is a layer having a function of a high refractive index layer and / or an antistatic layer. Furthermore, when the laminated body of this invention is an antireflection film, a low refractive index layer, a hard-coat layer, and / or a base material other than the said layer can be included.
FIG. 1 shows a cross-sectional view of such an antireflection film. As shown in FIG. 1, a hard coat layer 3, a high refractive index layer 4, and a low refractive index layer 5 are laminated on a substrate 2.
At this time, instead of the hard coat layer 3, the high refractive index layer 4 may be formed directly on the substrate 2. Further, an intermediate refractive index layer 6 may be provided between the hard coat layer 3 and the high refractive index layer 4 (not shown).

(1) Low Refractive Index Layer The curable composition for forming the low refractive index layer is not particularly limited, and known low refractive index layer forming materials can be used.

The refractive index of the low refractive index layer (refractive index of Na-D line, measurement temperature 25 ° C.) is preferably 1.50 or less. This is because when the refractive index of the low refractive index film exceeds 1.50, the antireflection effect may be significantly reduced. Therefore, the refractive index of the low refractive index film is more preferably 1.48 or less, and further preferably 1.45 or less.
When a plurality of low refractive index films are provided, at least one of them should have a refractive index value within the above-mentioned range. It may be a value exceeding 50.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 200 nm, for example. This is because when the thickness of the low refractive index layer is less than 50 nm, the antireflection effect may not be sufficiently obtained. On the other hand, when the thickness exceeds 200 nm, optical interference occurs and antireflection is caused. This is because the effect may be reduced.
Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and further preferably 70 to 150 nm.

(2) High refractive index layer A high refractive index layer is comprised from the cured film obtained by hardening | curing the composition of this invention. Since the high refractive index layer also has antistatic properties, it improves the dustproof properties of the laminate.
Since the composition and the like of the composition of the present invention are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the high refractive index layer will be described below.
The refractive index of the high refractive index layer is preferably 1.57 or more, more preferably 1.58 or more, and particularly preferably 1.59 or more. If the refractive index of the high refractive index layer is less than 1.57, good antireflection properties may not be obtained.
Further, the difference from the refractive index of the low refractive index layer is preferably 0.16 or more, more preferably 0.17 or more. If the difference in refractive index between the high refractive index layer and the low refractive index layer is less than 0.16, the antireflection effect may not be obtained.

The thickness of the high refractive index layer is not particularly limited, but is preferably 50 to 30,000 nm, for example. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, the antireflection effect and adhesion to the substrate may be reduced when combined with the low refractive index layer, while the thickness is If the thickness exceeds 30,000 nm, optical interference may occur, and the antireflection effect may be reduced.
Therefore, the thickness of the high refractive index layer is more preferably 50 to 1,000 nm, and further preferably 60 to 500 nm.
In order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness of the plurality of high refractive index layers is set to 50 to 30,000 nm. Good.
In addition, when providing a hard-coat layer between a high refractive index layer and a base material, the thickness of a high refractive index layer can be 50-300 nm.

(3) Hard coat layer The constituent material of the hard coat layer used in the antireflection film of the present invention is not particularly limited. Examples of such a material include one kind of siloxane resin, acrylic resin, melamine resin, epoxy resin, or a combination of two or more kinds.

  Moreover, although it does not restrict | limit especially also about the thickness of a hard-coat layer, it is preferable to set it as 1-100 micrometers, and it is more preferable to set it as 3-30 micrometers. The reason for this is that if the thickness of the hard coat layer is less than 1 μm, the hardness as the hard coat may be reduced. This is because it may be deformed.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples. “%” And “parts” mean “% by weight” and “parts by weight” unless otherwise specified.

Production Example 1: Preparation of antimony particle dispersion Antimony-containing tin oxide particles (manufactured by Ishihara Techno Co., Ltd., trade name: SN-100P, primary particle size 10-30 nm), dispersant (Adeka Corporation, trade name: ADEKA) Pluronic TR-701) and methanol were mixed in a blending amount of 29.1 / 0.9 / 70 (weight ratio) (total solid content 30%, total inorganic content 29.1%).
Using an SC mill manufactured by Mitsui Mining Co., Ltd., treatment was performed for 1 hour under the following conditions to obtain a particle dispersion solution having a median diameter of 59 nm.
Equipment: Mitsui Mining Co., Ltd. SC mill frequency: 60 Hz (equivalent to 3600 rpm)
Casing capacity: 59ml
Liquid volume: 500g
Dispersed bead filling amount: Glass beads (manufactured by TOSHINRIKO, BZ-01)
(Bead diameter 0.1 mm) 40 g Volume filling rate 27%

The median diameter of the antimony-containing tin oxide particles dispersed in the obtained dispersion was measured under the following conditions.
Equipment: Dynamic light scattering type particle size distribution measuring device manufactured by HORIBA, Ltd. Measurement conditions: Temperature 25 ° C
Sample Analytical condition of measurement data as sample solution: Particle size standard Volume standard
Dispersed particles ATO particles Refractive index 2.05
Dispersion medium Methanol Refractive index 1.329

Production Example 2 Production of Organic Compound (Ab) Having Polymerizable Unsaturation Group 50 parts of isophorone diisocyanate is stirred with 50 parts of a solution comprising 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air. After dropwise addition at 1 ° C over 1 hour, the mixture was heated and stirred 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. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the residual isocyanate content 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 a urethane bond was formed.

Production Example 3: Preparation of Reactive Particle Dispersion A 98.6 parts of the antimony particle dispersion produced in Production Example 1, 1.2 parts of the composition produced in Production Example 2, 0.02 part of ion-exchanged water, and p -After stirring a liquid mixture of 0.01 parts of hydroxyphenyl monomethyl ether at 60 ° C. for 4 hours, 0.20 parts of methyl orthoformate is added, and further heated and stirred at the same temperature for 1 hour to obtain a reactive particle dispersion. A was obtained. 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to obtain a solid content of 31%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 96%.

Production Example 4: Preparation of Reactive Particle Dispersion B Reactive particle dispersion B was prepared according to Production Examples 1 to 3 except that the median diameter of the antimony particle dispersion in Production Example 1 was 70 nm.

Production Example 5: Preparation of Reactive Particle Dispersion C Reactive particle dispersion C was prepared in accordance with Production Examples 1 to 3 except that the median diameter of the antimony particle dispersion in Production Example 1 was 78 nm.

Production Example 6: Preparation of Reactive Particle Dispersion D Reactive particle dispersion D was prepared according to Production Examples 1 to 3 except that the median diameter of the antimony particle dispersion in Production Example 1 was 89 nm.

Example 1
(1) Preparation of High Refractive Index Antistatic Curing Composition Each component shown in Table 1 was added to a container shielded from ultraviolet rays and stirred at room temperature for 1 hour to obtain a uniform composition.

(2) Production of a laminate having a hard coat and a high refractive index antistatic layer A hard coat material (manufactured by JSR Corporation, trade name: Z7501) was prepared using a coater equipped with a wire bar (# 12). Coating was performed on a polyethylene terephthalate (PET) film (PET A4300 manufactured by Toyobo Co., Ltd.) as a material. Then, it dried for 3 minutes at 80 degreeC in oven, and formed the coating film. Subsequently, the coating film was ultraviolet-cured under a light irradiation condition of 900 mJ / cm ² using a high-pressure mercury lamp in the atmosphere. Furthermore, the composition prepared in the above (1) was applied onto the hard coat layer cured film using a coater equipped with a wire bar (# 3). Then, it dried for 2 minutes at 80 degreeC in oven, and formed the coating film. Subsequently, the coating film was UV-cured under a light irradiation condition of 600 mJ / cm ² using a high-pressure mercury lamp in the atmosphere to prepare a laminate.

(3) Production of Laminate Having Hard Coat, High Refractive Index Antistatic Layer and Low Refractive Index Layer Low refractive index using a coater equipped with a wire bar (# 12) on the laminate produced according to (2) above. A material (trade name: TU2157, manufactured by JSR Corporation) was applied. At that time, a material having a low refractive index diluted with methyl isobutyl ketone to a solid content of 3.6% was used. Then, it dried for 2 minutes at 80 degreeC in oven, and formed the coating film. Next, the coating film was UV-cured under a light irradiation condition of 600 mJ / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere to prepare a laminate.

(4) Evaluation of Laminate Having Hard Coat and High Refractive Index Antistatic Layer The laminate produced according to the above (2) was measured for transparency (haze), surface resistance, and reflectance.
The haze was measured according to ASTM D1003 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.).
The surface resistance (Ω / □) was measured using a High Resistance Meter 4339B manufactured by Agilent Technology at an applied voltage of 100V.
The reflectance was measured by attaching a large integrating sphere device (manufactured by JASCO Corporation, trade name: ILV-471) to a spectrophotometer (trade name: V-570, manufactured by JASCO Corporation).
The results are shown in Table 1.

(5) Evaluation of laminate having hard coat, high-refractive index antistatic layer and low-refractive index layer The laminate prepared according to (3) above was measured for scratch resistance (steel wool resistance) by the following method. did.
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 at 233 g / cm ^2. The film was repeatedly rubbed 10 times under the above conditions, and the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated according to the following criteria. The results are shown in Table 1.
○: Slight thin scratches are observed on the cured film.
X: A streak is recognized on the entire surface of the cured film.

Example 2 and Comparative Examples 1 to 4
A composition was prepared in the same manner as in Example 1 except that the composition described in Table 1 was used, and a laminate was prepared and evaluated. The results are shown in Table 1.

The components in Table 1 are as follows.
Reactive particles A: Production Example 3, median diameter 59 nm
Reactive particle B: Production example 4, median diameter 70 nm
Reactive particles C: Production Example 5, median diameter 78 nm
Reactive particles D: Production Example 6, median diameter 89 nm
Biscoat 700: Osaka Organic Chemical Co., Ltd., Bisphenol A, EO adduct diacrylate PETA: Shin-Nakamura Chemical Co., Ltd., Tetramethylol Methane Triacrylate Irg. 907: manufactured by Ciba Specialty Chemicals Co., Ltd., 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one

From the results of Table 1, in Examples 1 and 2 in which the median diameter of the reactive particles is 70 nm and 78 nm and the compound of the component (B) is included, the surface resistance is as low as 10 ⁹ Ω / cm ² and the highest reflection It can be seen that the rate is high and the scratch resistance is also excellent. On the other hand, in Comparative Example 1 where the median diameter of the reactive particles is as small as 59 nm, it can be seen that the surface resistance is high and the scratch resistance is poor. Conversely, in Comparative Example 2 where the median diameter of the reactive particles is as large as 89 nm, it can be seen that the haze is high and the maximum reflectance is low. Moreover, it turns out that the maximum reflectance becomes low in Comparative Examples 3 and 4 which do not contain the compound of the component (B).

The curable composition of the present invention is useful for producing a cured film having a high refractive index and excellent antistatic properties and scratch resistance.
The cured film of the present invention is useful as a coating film that requires antistatic properties and scratch resistance, and as a high-refractive index antistatic layer of an antireflection film.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Base material 3 Hard coat layer 4 High refractive index antistatic layer 5 Low refractive index layer

Claims (11)

The following components (A) to ( C ):
(A) Oxide particles (Aa) mainly composed of an oxide of at least one element selected from the group consisting of zinc, indium, tin, and antimony, and at least acryloyl group and (meth) acryloyl group in the molecule A reactive particle obtained by reacting one, a hydrolyzable silyl group, and an organic compound (Ab) containing a group represented by the following formula (4), wherein the median diameter is in the range of 65 to 85 nm. Some reactive particles

[In Formula (4), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
(B) Compound having one or more polymerizable unsaturated groups, one or more alkylene oxide chains and two or more aromatic rings (C) One or more polymerizations other than the components (A) and (B) A curable composition containing a compound having a polymerizable unsaturated group. The curable composition of Claim 1 in which the compound of the said component (B) has a structure shown by the following general formula (B-1).

[In Formula (B-1), R ¹ and R ² are each a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ³ is a C 1-20 which may have a single bond or an aromatic ring. A divalent hydrocarbon group, R ⁵ and R ⁶ are a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁵ are each a hydrogen atom or a (meth) acryloyl group, and q of R ¹⁴ and p of R ¹⁵ At least one is a (meth) acryloyl group. m and n are each 1 to 30, p is 1 to 4, and q is 0 to 4. ] The curable composition of Claim 1 or 2 in which the compound of the said component (B) has a structure shown by the following general formula (B-2).

[In Formula (B-2), R ⁴ represents a hydrogen atom or a methyl group, R ¹¹ and R ¹² represent a hydrogen atom, a methyl group, and a phenyl group, respectively, and R ¹³ represents a hydrogen atom or a (meth) acryloyl group. M represents a number of 1 to 30 independently. ] The oxide particle (Aa) of the component (A) is selected from the group consisting of antimony-containing tin oxide, tin-containing indium oxide, fluorine-containing tin oxide, and aluminum-containing zinc oxide. The curable composition according to 1. The curable composition according to claim 4, wherein the oxide particles (Aa) of the component (A) are antimony-containing tin oxide. The curable composition according to any one of claims 1 to 5, wherein the reactive particle of the component (A) has a median diameter in a range of 70 to 78 nm.   Furthermore, (D) The curable composition of any one of Claims 1-6 containing the compound which generate | occur | produces active species by irradiation of an active energy ray.   Furthermore, (E) The curable composition of any one of Claims 1-7 containing an organic solvent.   The curable composition according to any one of claims 1 to 8, wherein the polymerizable unsaturated group of the component (C) is a (meth) acryloyl group.   A cured film obtained by curing the curable composition according to claim 1. The laminated body which has a cured film of Claim 10 on a base material.

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