JPWO2018030339A1 - Thermosetting composition - Google Patents

Abstract

The resulting cured product provides a thermosetting composition which is free from deformation and coloring problems and is also excellent in mechanical properties such as hardness and bending properties. The thermosetting composition of the present invention comprises (A) component, (B) component and (D) component, and optionally (C) component, and the total amount of (A) to (C) component is 100% by weight. 20 to 60% by weight of (A) component, 80 to 40% by weight of (B) component and 0 to 40% by weight of (C) component, and contained in (A) to (C) component 20 to 60 mol% of methacryloyl groups are contained in 100 mol% of the total amount of ethylenic unsaturated groups. Component (A): Compound having an isocyanurate ring and having two or more (meth) acryloyl groups (B) Component: a compound having two or more (meth) acryloyl groups, which is a compound other than the component (A) Component (C): Compound having one ethylenically unsaturated group (D) Component: Thermal polymerization initiator

Description

The present invention relates to a thermosetting composition, and in particular, can be preferably used for resin sheet production, and the obtained resin sheet can be preferably used for optical substrates such as liquid crystal displays (LCDs) and organic EL, etc. The resin sheet for film formation can be preferably used and belongs to these technical fields.
In the present specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.

In recent years, many touch panel integrated liquid crystal display devices or touch panel integrated organic EL display devices have been applied to mobile devices such as smartphones, tablet terminals, and car navigation systems.
Conventionally, as a transparent conductive thin film of a touch panel, a conductive glass in which a thin film of indium tin oxide (hereinafter referred to as "ITO") is formed on glass is well known. Poor in flexibility and processability. Therefore, depending on the application, a transparent conductive sheet based on a polyethylene terephthalate sheet is used because of its advantages such as excellent flexibility, processability, impact resistance, and light weight.

  On the other hand, a cover-integrated touch panel in which a touch sensor such as ITO is directly formed on a cover glass, so-called OGS (One Glass), from the viewpoint of contributing to reduction in thickness and weight of touch panel, improvement in transmittance and cost reduction of members. Solution) is adopted. However, the OGS type has a problem that the touch panel can not be operated if the cover glass is broken.

  Then, what is called OPS (One Plastic Solution) which directly forms touch sensors, such as ITO, in a resin sheet as a material of a cover which is excellent in impact resistance is proposed. However, conventional acrylic resin and polycarbonate resin sheets are low in surface hardness, so they are easily damaged, and toughness may be insufficient, and they may be broken by external impact force.

  Patent Document 1 discloses a plastic member for forming a transparent conductive film obtained by photocuring a photocurable composition containing a bismethacrylate having an alicyclic skeleton and a mercapto compound.

  In Patent Document 2, it is obtained by photocuring a photocurable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure, a bifunctional (meth) acrylate having an alicyclic structure, and a photopolymerization initiator. A transparent resin molding having a thickness of 50 to 500 μm is disclosed.

JP, 2002-161113, A JP 2007-56180 A

However, although the plastic member described in Patent Document 1 imparts appropriate toughness to the cured product by blending a mercapto compound, there is a problem that the pot life of the composition becomes short. And there is also a problem that the surface hardness and the abrasion resistance also decrease.
In addition, since the same rigidity as that of the transparent resin molded body and glass described in Patent Document 2 can not be expressed, there is a problem that appearance defects occur in the heating step in the transparent conductive film and metal electrode forming process.
As described above, a resin sheet having satisfactory physical properties as a resin for OPS has not been found so far, and it is particularly difficult to simultaneously achieve hardness and toughness, and the scratch resistance was also insufficient.

In resin sheet production, although there are cases of using the above-mentioned photocurable composition and thermosetting compositions, they are used properly depending on the purpose and characteristics.
As a feature of the thermosetting composition, it can be manufactured by a simple device, and it is possible to manufacture a plurality of sheets simultaneously by one heating device, but when a conventional thermosetting composition is used, heating is possible. There is a problem that the resin sheet obtained by this method is deformed or coloring occurs.
In addition, when the photocurable composition as described above is applied to a thermosetting composition, it has the same problem.

  The present inventors are hard to be cracked when the resulting cured product is used in the production of a thermosetting composition, particularly a resin sheet, which has no problems of deformation or coloring and is also excellent in mechanical properties such as hardness and bending properties. In order to find a thermosetting composition which is excellent in impact resistance and excellent in surface physical properties such as surface hardness and scratch resistance, earnest studies were conducted.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a di (meth) acrylate having an isocyanurate ring and other polyfunctional (meth) acrylates can solve the above problems. The present invention has been completed.

The present invention comprises the following components (A), (B) and (D), and optionally the following (C) components,
20 to 60% by weight of component (A), 80 to 40% by weight of component (B) and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C) And it is related with the thermosetting composition which contains 20-60 mol% of methacryloyl groups in 100 mol% of total amounts of the ethylenically unsaturated group contained in (A)-(C) component.
Component (A): a compound having an isocyanurate ring and having two or more (meth) acryloyl groups (B): a compound having two or more (meth) acryloyl groups, which is a compound other than the component (A) Component (C): Compound having one ethylenically unsaturated group Component (D): Thermal polymerization initiator Also, it may be rephrased as follows.
The thermosetting composition of the present invention may include the component (A), the component (B) and the component (D), and may include the component (C).
When the component (C) is contained, 20 to 60% by weight of the component (A), 80 to 40% by weight of the component (B) in 100% by weight of the total amount of the components (A) to (C) And 20 to 60 mol% of methacryloyl group in 100 mol% of the total amount of ethylenically unsaturated groups contained in components (A) to (C). ,
When the component (C) is not contained, 20 to 60 wt% of the component (A) and 80 to 40 wt% of the component (B) are contained in 100 wt% of the total amount of the component (A) and the component (B). And 20-60 mol% of methacryloyl groups are contained in 100 mol% of the total amount of the ethylenically unsaturated group contained in (A) component and (B) component.

  The component (A) is preferably a compound having an isocyanurate ring and having two (meth) acryloyl groups or / and an isocyanurate ring and having three (meth) acryloyl groups.

As the component (B), one containing a di (meth) acrylate (B-1) having a linear alkylene group having 4 to 20 carbon atoms is preferable.
Furthermore, as the component (B-1), 1 is selected from 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate More than species are preferred.
Moreover, as (B) component, what further contains the compound which has a 3 or more (meth) acryloyl group is preferable.

  It is preferable that the components (A) to (C) do not contain a compound having a urethane bond.

  The proportion of the component (D) is preferably such that it contains 0.1 to 5 parts by weight of the component (D) with respect to 100 parts by weight of the total amount of the components (A) to (C).

  As the physical properties of the cured product of the composition, those having a flexural modulus of 2.5 GPa or more in a bending test are preferable, and those having a total light transmittance of 90% or more are preferable.

The composition of the present invention is preferably used as a thermosetting composition for resin sheet production.
Furthermore, as for the obtained resin sheet, as thickness of hardened | cured material, what is 100 micrometers-5 mm is preferable.

As a method for producing a resin sheet, there is a method in which the thermosetting composition of the present invention is poured into a mold composed of a base material, a base material for providing wrinkles, and a base material in this order, and then heated. preferable.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, the obtained cured product has no problem of deformation or coloring, is further excellent in mechanical characteristics such as hardness and bending characteristics, and is not easily broken when used in resin sheet production. It is excellent in impact resistance, and excellent in surface physical properties such as surface hardness and scratch resistance.

FIG. 1 is a view showing an example of a mold used for producing a resin sheet using the composition of the present invention.

The present invention relates to a composition comprising components (A) to (D),
20 to 60% by weight of component (A), 80 to 40% by weight of component (B) and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C) And it is related with the thermosetting composition which contains 20-60 mol% of methacryloyl groups in 100 mol% of total amounts of the ethylenically unsaturated group contained in (A)-(C) component.
Hereinafter, the details of each component and composition will be described.

1. Component (A) Component (A) is a compound having an isocyanurate ring and having two or more (meth) acryloyl groups.
As the component (A), various compounds can be used as long as they are compounds having an isocyanurate ring and two or more (meth) acryloyl groups.
The component (A) is preferably a compound having an isocyanurate ring and having two (meth) acryloyl groups or / and a compound having three (meth) acryloyl groups.
As a specific example, di (meth) acrylate of isocyanuric acid alkylene oxide adduct, tri (meth) acrylate of isocyanuric acid alkylene oxide adduct, di (meth) acrylate of ε-caprolactone adduct to isocyanuric acid alkylene oxide adduct, The tri (meth) acrylate etc. of the (epsilon) -caprolactone adduct to the isocyanuric acid alkylene oxide adduct can be mentioned.
Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide, and ethylene oxide is preferable. The addition mole number of the alkylene oxide is preferably 1 to 3 moles in one molecule.
In addition, the addition mole number of ε-caprolactone is preferably 1 to 3 moles in one molecule.

  As the component (A), only one type of the above-described compounds may be used, or two or more types may be used in combination.

The component (A) is commercially available and includes, for example, the following products.
· Diacrylate of ethylene oxide trioxide adduct of isocyanurate: Toho Gosei Co., Ltd. Alonics M-215
Triacrylate of 3-mole adduct of isocyanuric acid ethylene oxide: A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., Funcryl FA-731A manufactured by Hitachi Chemical Co., Ltd.
· Mixture of di- and tri (meth) acrylates of isocyanuric acid ethylene oxide 3 molar adduct: Toonago Co., Ltd. Alonics M-315
-Triacrylate of 1 mol adduct of? -Caprolactone to 3 mol adduct of isocyanuric acid ethylene oxide: A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd. and the like.
· Triacrylate of ε-caprolactone 3 mol adduct to isocyanurate ethylene oxide 3 mol adduct: Toonago Kaisha, Ltd. Alonics M-327

The content ratio of the component (A) is 20 to 60% by weight, preferably 30 to 55% by weight, of the component (A) in 100% by weight of the total amount of the components (A) to (C).
When the content ratio of the component (A) is less than 20% by weight, the breaking strain and the 50% impact fracture height are low, the resin sheet becomes brittle, and when it exceeds 60% by weight, surface hardness such as pencil hardness The abrasion resistance is reduced.

2. Component (B) The component (B) is a compound having two or more (meth) acryloyl groups, and is a compound other than the component (A).
As the component (B), a compound having two (meth) acryloyl groups [hereinafter referred to as “bifunctional (meth) acrylate”] and a compound having three or more (meth) acryloyl groups [hereinafter, “3 And the like) and the like.

As the 2-1.2 functional (meth) acrylate bifunctional (meth) acrylate, di (meth) acrylate having an alkylene group and polyalkylene glycol di (meth) acrylate can be mentioned.

Preferred examples of the di (meth) acrylate having an alkylene group include di (meth) acrylates having a linear or branched alkylene group having 4 to 20 carbon atoms (hereinafter referred to as "(B-1) component") preferable.
The component (B-1) is a di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms. In the present invention, an alkylene group means a divalent substituent obtained by removing two hydrogen atoms from an alkane.
These di (meth) acrylates are superior in hardness and abrasion resistance of the cured product to di (meth) acrylates having a linear or branched alkylene group having 3 or less carbon atoms, and the carbon number is It becomes the thing excellent in the rigidity and heat resistance of hardened | cured material with respect to 21 or more compounds.
The divalent linear alkylene group having 4 to 20 carbon atoms in the component (B-1) is a 1,4-butylene group, a 1,6-hexylene group or a 1,9-nonylene group having a bond at both ends Groups are preferred.
As a specific example of the said compound, a 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, 9- nonanediol di (meth) acrylate etc. can be mentioned.

The divalent branched alkylene group having 4 to 20 carbon atoms in the component (B-1) is a neopentylene group (2,2-dimethyl-1,3-propylene group) having a bond at both ends, and 2-methyl. A 1,3-propylene group and an isobutylene group having a degree of polymerization of 5 or less are preferable.
Specific examples of the compound include neopentyl glycol di (meth) acrylate, which is most preferably used.

Among these compounds, as component (B-1), 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and One or more selected from the group consisting of neopentyl glycol di (meth) acrylate is preferable.
Among these compounds, as the component (B-1), one or more selected from the group consisting of 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are further selected. preferable.

The polyalkylene glycol di (meth) acrylate is preferably a di (meth) acrylate having a total of 4 to 20 carbon atoms constituting a polyoxyalkylene group.
Specific examples of polyalkylene glycol di (meth) acrylates include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and poly (1-methylbutylene glycol) di Examples include (meth) acrylates and the like.

Among these compounds, one or more selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate as the polyalkylene glycol di (meth) acrylate preferable.
Among these compounds, the polyalkylene glycol di (meth) acrylate is more preferably at least one selected from the group consisting of polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate.

As bifunctional (meth) acrylates other than the above, difunctional (meth) acrylates having an aromatic skeleton such as di (meth) acrylate of bisphenol A alkylene oxide adduct and bisphenol A di (meth) acrylate;
A bifunctional (meth) acrylate having an aliphatic skeleton such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate;
Hydroxypivalate neopentyl glycol di (meth) acrylate;
Bifunctional (meth) acrylates having an alicyclic skeleton such as dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate and spiroglycol di (meth) acrylate;
In the above, examples of the alkylene oxide adduct include ethylene oxide adduct and propylene oxide adduct.

As a bifunctional (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, etc. are mentioned besides the above-mentioned compound.
Hereinafter, these compounds will be described.

2-1-1. Polyester (meth) acrylate As polyester (meth) acrylate, the dehydration condensation product of polyester diol and (meth) acrylic acid, etc. are mentioned.
Here, as polyester diol, the reaction product of diol and dicarboxylic acid or its anhydride, etc. are mentioned.
As a diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neo And low molecular weight diols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and alkylene oxide adducts of these compounds.
Examples of dicarboxylic acids or their anhydrides include dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, and compounds thereof Anhydrides and the like.

2-1-2. Epoxy (meth) acrylate epoxy (meth) acrylate is a compound in which (meth) acrylic acid is addition-reacted to an epoxy resin. As an epoxy resin, an aromatic epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

  Specific examples of the aromatic epoxy resin include diglycidyl ethers having a benzene skeleton such as resorcinol diglycidyl ether and hydroquinone diglycidyl ether; diphenols of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof. Bisphenol type diglycidyl ethers such as glycidyl ether; novolac type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin; glycidyl phthalimide; and o-phthalic acid diglycidyl ester.

Specific examples of aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. Of diglycidyl ethers of polyalkylene glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and adducts thereof with alkylene oxide; diglycidyl ethers of hydrogenated bisphenol A and adducts of alkylene oxides thereof; and diglycidyl esters of tetrahydrophthalic acid Etc.
In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

2-1-3. Polyether (meth) acrylate Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) diacrylates, such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) And the like.

2-2.3 Functional or More (Meth) Acrylate Trifunctional or More (Meth) Acrylate: trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, ditrimethylol propane tri or tetra (meth) acrylate And polyol poly (meth) acrylates such as dipentaerythritol tri, tetra, penta or hexa (meth) acrylates; and tri (meth) acrylates of trimethylolpropane alkylene oxide adducts, tri or tetra of pentaerythritol alkylene oxide adducts (Meth) acrylate, tri or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, and dipentaerythritol alkylene oxide adduct , Tetra, poly (meth) acrylate of penta or hexa (meth) polyol alkylene oxide adducts such as acrylate.
In the poly (meth) acrylate of the polyol alkylene oxide adduct, ethylene oxide and propylene oxide are preferable as the alkylene oxide.

2-3. As a preferable aspect (B) component, only 1 type of the above-mentioned compound may be used, or 2 or more types may be used together.
As the component (B), one containing the above-mentioned component (B-1) is preferable, and further, as the component (B-1), 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di- One or more selected from the group consisting of (meth) acrylate and 1,9-nonanediol di (meth) acrylate is preferred.
In this case, the content of the component (B-1) is preferably 30 to 70% by weight of the component (B-1) in 100% by weight of the total amount of the component (B).
Moreover, that in which (B) component contains the compound which has a 3 or more (meth) acryloyl group is preferable.
In this case, the content ratio of the compound having three or more (meth) acryloyl groups is 30 to 70 compounds having three or more (meth) acryloyl groups in 100% by weight of the total amount of the component (B). Weight percent is preferred.

2-4. Content ratio As the content ratio of the component (B), the total amount of the components (A) to (C) is 100 to 40% by weight, preferably 45 to 75% by weight of the component (B). is there.
When the content ratio of the component (B) is less than 40% by weight, surface hardness such as pencil hardness and scratch resistance decrease, and when it exceeds 80% by weight, the breaking strain and the 50% impact fracture height are low. , The resin sheet becomes brittle.
Furthermore, as a preferable content rate of (B-1) component, it is 30 to 70 weight% in 100 weight% of the total amount of (B) component.

3. Component (C) Component (C) is a compound having one ethylenically unsaturated group. The component (C) is a component to be blended for the purpose of adjusting the viscosity of the composition and various physical properties of the cured product according to the purpose.
Examples of the ethylenically unsaturated group in the component (C) include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and the (meth) acryloyl group is preferable.

Examples of the component (C) include compounds having one (meth) acryloyl group [hereinafter, referred to as "monofunctional (meth) acrylate"] and the like.
Specific examples of monofunctional (meth) acrylates include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 1- Adamantyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate О-phenylphenol ethylene oxide adduct (1 to 4 moles adduct) (meth) acrylate, p-cumylphenol ethylene oxide adduct (1 to 4 moles adduct) (meth) acrylate, phenyl (meth) acrylate, о-phenylphenyl (meth) acrylate, p-cumylphenyl (meth) acrylate and the like.

The monofunctional (meth) acrylate may be a compound having various functional groups.
Examples of compounds having a carboxyl group include (meth) acrylic acid, polycaprolactone modified products of (meth) acrylic acid, Michael addition type polymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and phthalic anhydride Examples thereof include acid adducts and carboxyl group-containing (meth) acrylates such as adducts of 2-hydroxyethyl (meth) acrylate and succinic anhydride.

Examples of the compound having a hydroxyl group include (meth) acrylates having a hydroxyl group.
As the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxy And hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate.

Examples of the compound having an amide group include N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and (meth) acrylamide compounds.
Specific examples of (meth) acrylamide compounds include N-alkyls such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-t-butyl (meth) acrylamide Acrylamide;
N, N-dialkylacrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide;
N-alkoxyalkyls such as N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide And (meth) acryloyl morpholine and the like.

  Examples of the compound having a carbamate group include (meth) acrylates having an oxazolidone group, and specific examples thereof include 2- (2-oxo-3-oxazolidinyl) ethyl acrylate and the like.

  Examples of compounds having an imide group include compounds having a maleimide group. Examples of the compound having a maleimide group include (meth) acrylates having a hexahydrophthalimide group and (meth) acrylates having a tetrahydrophthalimide group. Specific examples of the (meth) acrylate having a hexahydrophthalimide group include N- (meth) acryloyloxyethyl hexahydrophthalimide and the like. Examples of (meth) acrylates having a tetrahydrophthalimide group include N- (meth) acryloyloxyethyl tetrahydrophthalimide and the like.

As an example of compounds other than monofunctional (meth) acrylate in (C) component, an aromatic vinyl compound etc. are mentioned.
Examples of the aromatic vinyl compound include styrene, alkyl styrene and halogenated styrene.
Specific examples of alkylstyrenes include methylstyrene, ethylstyrene and propylstyrene.
Specific examples of the halogenated styrene include fluorostyrene, chlorostyrene and bromostyrene.
Among the above-mentioned compounds, styrene is preferred as the aromatic vinyl compound.

  As the component (C), only one type of the above-described compounds may be used, or two or more types may be used in combination.

The content ratio of the component (C) is 0 to 40% by weight, preferably 0 to 20% by weight, of the component (C) in 100% by weight of the total amount of the components (A) to (C).
If the content ratio of the component (C) exceeds 40% by weight, unreacted components remain in the resin sheet after curing, thereby plasticizing the resin sheet and lowering the flexural modulus.

4. Component (D) Component (D) is a thermal polymerization initiator.
As the component (D), various compounds can be used, and organic peroxides and azo initiators are preferable. Furthermore, among these, organic peroxides are more preferable because they are excellent in the polymerization initiator efficiency, can reduce the outgas derived from the polymerization initiator decomposition product, and are further excellent in the impact resistance of the composition.

  Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2 , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, dilauroyl peroxide, t-hexylperoxyisopropyl monocarbonate, t-butyl Peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxira Rate, t-butylperoxypivalate, t-hexylperoxypivalate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t- Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butyl) Peroxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α'-bis (t-butyl) Peroxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5- (T-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne -3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide Etc.

Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Alternatively, the organic peroxide can be converted to a redox reaction by combining with a reducing agent.

The content ratio of the component (D) is preferably 0.1 to 5 parts by weight of the component (D) with respect to 100 parts by weight of the total amount of the components (A) to (C).
By setting the ratio of the component (D) to 0.1 parts by weight or more, the entire resin sheet can be uniformly cured, and by setting the ratio to 5 parts by weight or less, the low molecular weight decomposition product of the low molecular weight polymerization initiator is derived. Outgassing can be reduced.

5. Thermosetting composition The present invention comprises the component (A), the component (B) and the component (D), and optionally the component (C),
20 to 60% by weight of component (A), 80 to 40% by weight of component (B) and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C) And it is related with the thermosetting composition which contains 20-60 mol% of methacryloyl groups in 100 mol% of total amounts of the ethylenically unsaturated group contained in (A)-(C) component.

  As the components (A) to (C) which are curable components which are cured by heating in the present invention, the above-mentioned compounds can be appropriately combined and used, but preferably they do not contain a compound having a urethane bond. In the composition containing a compound having a urethane bond, for example, urethane (meth) acrylate, the cured product is colored.

The composition of the present invention needs to contain 20 to 60 mol% of methacryloyl group in the total amount of 100 mol% of the ethylenically unsaturated groups contained in the components (A) to (C), and preferably 30 60 mol%.
If the proportion of methacryloyl groups is less than 20 mol%, the distortion of the resin sheet after thermosetting will increase, and if it exceeds 60 mol%, the coloring before and after the heat resistance test will be large.
The proportion of methacryloyl group in the present invention means mol% obtained by dividing the number of moles of all methacryloyl groups in the components (A) to (C) by the number of moles of all ethylenically unsaturated groups and multiplying by 100. The compound having two or more (meth) acryloyl groups is often a mixture of compounds having different numbers of (meth) acryloyl groups in commercial products, so the proportion of (meth) acryloyl groups is incorrect. There may be. In this case, the (meth) acryloyl group equivalent of the raw material compound is measured in advance by using an iodine value or the like, and calculation is performed based on this value.

  The composition may be produced according to a conventional method. For example, the components (A), (B) and (D), and, if necessary, the components (C) and other components are stirred and mixed. Can be manufactured.

The viscosity of the composition may be appropriately set according to the purpose, and is preferably 50 to 10,000 mPa · s.
In the present invention, viscosity means a value measured at 25 ° C. using an E-type viscometer.

The composition of the present invention contains the above components (A), (B) and (D) as essential components, but depending on the purpose, it is necessary to blend various components such as component (C). Can.
As other components, specifically, an organic solvent, a plasticizer, a polymerization inhibitor or / and an antioxidant, a light resistance improver, and a compound having two or more mercapto groups [hereinafter, "polyfunctional mercaptan" Can be mentioned.
Hereinafter, these components will be described. The components to be described later may be used alone or in combination of two or more.

5-1. Other ingredients
1) Organic solvent The composition of the present invention can be blended with an organic solvent for the purpose of improving the coatability to a substrate.
However, when using the resin sheet obtained for a transparent conductive film use, what does not contain an organic solvent is preferable.

Specific examples of the organic solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxy Ethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1 -Methoxy-2-propanol, 1-ethoxy-2-propanol and propylene glycol monomethyl Alcohol solvents such as ether;
Ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-butoxyethyl) ether;
Acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di-n-propyl ketone, diisobutyl ketone, phohone, isophorone, cyclopentanone, cyclohexanone and methylcyclohexanone etc. Ketone solvents;
Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate, cellosolve acetate; and N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2 And aprotic polar solvents such as pyrrolidone and γ-butyrolactone.

  The proportion of the organic solvent may be set appropriately, but preferably 90% by weight or less in the composition, and more preferably 80% by weight or less.

2) Plasticizer A plasticizer can be added for the purpose of imparting flexibility to a cured product and improving brittleness.
Specific examples of the plasticizer include phthalic acid dialkyl esters such as dioctyl phthalate and diisononyl phthalate, adipic acid dialkyl esters such as dioctyl adipate, sebacic acid esters, azelaic acid esters, phosphoric acid esters such as tricresyl phosphate, and polypropylene Examples include liquid polyether polyols such as glycol, polycaprolactone diol, and liquid polyester polyols such as 3-methylpentanediol adipate. In addition, soft acrylic polymers having a number average molecular weight of 10,000 or less can be mentioned.
The proportion of these plasticizers may be set appropriately, but is preferably 30 parts by weight or less with respect to 100 parts by weight in total of the components (A) to (C) (hereinafter referred to as "curable components"), More preferably, it is 20 parts by weight or less.
By setting the content to 30 parts by weight or less, it is possible to obtain excellent strength and heat resistance.

3) Polymerization Inhibitor or / and Antioxidant In the composition of the present invention, a polymerization inhibitor or / and an antioxidant can be added in order to improve the storage stability.
As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable, but sulfur secondary antioxidants, phosphorus secondary Next antioxidants and the like can also be added.
The total blending ratio of the polymerization inhibitor and / or the antioxidant is preferably 3 parts by weight or less, more preferably 0.5 parts by weight or less, based on 100 parts by weight of the total of the curable components.

4) Light Resistance Improver A light resistance improver such as an ultraviolet light absorber or a light stabilizer may be added to the composition of the present invention.
Examples of UV absorbers include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole. Benzotriazole compounds such as 2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole;
Triazine compounds such as 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine;
2,4-Dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4,4 ' -Trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3', 4,4'-tetrahydroxybenzophenone, or 2, 2 And benzophenone compounds such as dihydroxy-4,4'-dimethoxybenzophenone and the like.
As a light stabilizer, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformyl hexamethylene diamine, bis (1,2,6,6) -) Pentamethyl-4-piperidyl) -2- (3,5-ditert-butyl-4-hydroxybenzyl) -2-n-butyl malonate, bis (1,2,2,6,6-pentamethyl-4-) Low molecular weight hindered amine compounds such as piperidinyl) sebacate; N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformyl hexamethylene diamine, bis (1,2 And hindered amine light stabilizers such as high molecular weight hindered amine compounds such as 2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
The compounding ratio of the light resistance improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 parts by weight with respect to 100 parts by weight of the total amount of the curable components.

5) Multifunctional mercaptan The polyfunctional mercaptan can be blended as necessary for the purpose of preventing the cure shrinkage of the cured product of the composition and for the purpose of imparting toughness.
As polyfunctional mercaptan, various compounds can be used as long as they are compounds having two or more mercapto groups.
For example, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate and the like can be mentioned.
The proportion of the polyfunctional mercaptan is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less with respect to 100 parts by weight of the curable component. By setting this ratio to 20 parts by weight or less, it is possible to prevent a decrease in the heat resistance and the rigidity of the obtained cured product.

6) Other components besides the above In addition to the above-mentioned other components , a mold release agent, a filler, a soluble polymer, etc. can be blended with the composition of the present invention.
The release agent is blended in order to facilitate release of the resulting resin sheet from the substrate. As the mold release agent, various surfactants can be used if they can be released from the substrate and the compounded liquid and the cured product are not turbid. For example, anionic surfactants such as alkyl benzene sulfonic acid, cationic surfactants such as alkyl ammonium salt, nonionic surfactants such as polyoxyethylene alkyl ether, amphoteric surfactants such as alkyl carboxy betaine, and further fluorine or silicon And surfactants contained therein.
The filler is blended for the purpose of improving the mechanical properties of the obtained resin sheet. Both inorganic and organic compounds can be used as the filler. Examples of the inorganic compound include silica and alumina. A polymer can be used as the organic compound. As a filler, when the resin sheet obtained from the composition of this invention is used for an optical use, what does not reduce an optical physical property is preferable.
The soluble polymer is blended for the purpose of improving the mechanical properties of the resulting resin sheet. By soluble polymer is meant a polymer that dissolves in the composition. In the present invention, polymers which do not dissolve in the composition are referred to as fillers for distinction.
The blending ratio of these other compounds is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the curable component.

5-2. Cured product physical properties The composition of the present invention exhibits an effect of causing no deformation in the cured product after heat curing.
As the evaluation method of the said physical property, the method of evaluating by the average value of in-plane phase difference is preferable.
As an average value of the in-plane phase difference of hardened | cured material of this invention, 10 nm or less is preferable, More preferably, it is 8 or less.
In the present invention, the in-plane retardation means a phase difference generated in the X direction and the Y direction by birefringence generated when linearly polarized light is made incident on a resin sheet.

The physical properties of the cured product of the composition according to the present invention are preferably those having a flexural modulus of 2.5 GPa or more in a bending test, and more preferably 3.0 GPa or more. The cured product of the composition having the elastic modulus is excellent in rigidity.
The elastic modulus in the bending test in the present invention means a value calculated from the stress of strain 0.1% and 1% in the bending test performed at a distance between supporting points of 30 mm and a bending speed of 0.2 mm / min.

When the cured product of the composition of the present invention is used for optical applications, the total light transmittance is preferably 90% or more, more preferably 91% or more.
In the present invention, the total light transmittance means the result of measurement of a test specimen having a thickness of 1 mm in accordance with JIS K7375.

Furthermore, as a physical property of the hardened | cured material of the composition in this invention, that whose pencil hardness is 3H or more is preferable.
In addition, the pencil hardness in this invention means the value measured by the method according to JISK-5600.

5-3. Thickness When the composition of the present invention is used for a resin sheet, the thickness of the resin sheet may be appropriately set according to the purpose.
In particular, when used for glass substitute applications such as OPS, 100 μm to 5 mm is preferable, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm.

6. Applications The compositions of the present invention can be used for various applications, in particular preferably as moldings.
Examples of the molding material include a resin sheet and three-dimensional modeling by an inkjet method, and the like, and can be preferably used for a resin sheet.
Hereinafter, the resin sheet will be described.

6-1. Method of Producing Resin Sheet As a method of producing a resin sheet using the composition of the present invention, various methods can be adopted, and the following four production methods can be mentioned, for example.
1) Manufacturing method 1
Method of applying a composition to a substrate and heating to cure the composition
2) Manufacturing method 2
A method of coating a composition on a substrate and laminating it with another substrate, followed by heating to cure the composition
3) Production method 3
Method of pouring a composition into a substrate having a space and heating to cure the composition
4) Production method 4
Method of pouring a composition on a substrate having a space portion and bonding it to another substrate and heating to cure the composition In the case of using a resin sheet obtained from the composition of the present invention in a glass substitute application And the said manufacturing method 4 is preferable.
As a polymerization system, either a batch system or a continuous system can be adopted.
As an example of a continuous type, the method of continuously supplying a belt-like base material etc. is mentioned as a coating or pouring base material, and a composition.

As another example of the continuous system, a method called continuous cast method is mentioned besides the above. That is, two continuous belts of mirror-surface stainless steel are arranged up and down like a caterpillar, the composition is poured between the belt and the belt, and polymerization is continuously performed between the belt and belt while moving the belt slowly. The method etc. of manufacturing a sheet are mentioned.
For glass substitute applications, batchwise is preferred.

6-1-1. As a base material , any of a peelable base material and a base material having no releasability (hereinafter, referred to as "non-releasing base material") can be used.
Examples of the releasable substrate include metal, glass, a film subjected to mold release treatment, and a surface untreated film having releasability (hereinafter collectively referred to as "mold release material").
Examples of the release material include silicone-treated polyethylene terephthalate film, surface-untreated polyethylene terephthalate film, surface-untreated cycloolefin polymer film, and surface-untreated OPP film (polypropylene).

In order to give low haze or to impart surface smoothness to a resin sheet obtained from the composition of the present invention, the surface roughness (center line average roughness) Ra is 0.15 μm or less as a peelable substrate. It is preferable to use the substrate of the above, and a substrate of 0.001 to 0.100 .mu.m is more preferable. Furthermore, 3.0% or less is preferable as a haze.
Specific examples of the substrate include glass, surface untreated polyethylene terephthalate film, surface untreated OPP film (polypropylene) and the like.
In the present invention, the surface roughness Ra means a value obtained by measuring the surface roughness of the film and calculating the average roughness.

  Examples of non-releasing base materials include various plastics other than the above, and cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, polyesters, polycarbonates, polyarylates, polyether sulfones, norbornenes, etc. Cyclic polyolefin resin as a monomer.

As a base material which has a space part, a base material which has a crevice is mentioned. What formed the hole of the predetermined shape made into the target film thickness to a mold release material, and formed the recessed part is mentioned.
In this case, after the composition is poured into a substrate having a recess, another substrate can be overlaid on the substrate having the recess.
As another example of the base material having a space portion, one having a mold (spacer) provided on the mold release material so that the cured product has a desired film thickness (hereinafter referred to as "mold") may also be mentioned. . Again, another substrate can be overlaid on the crucible.
As the mold release material in this case, glass and glass subjected to mold release treatment are preferable.

As an example of a mold, FIG. 1 will be described.
In (a1-1) and (a1-2) of FIG. 1, two sheets of base materials [(1) of (a1-1) and (a1-2) of (1) ′] of FIG. A substrate having excellent releasability [FIG. 1: (2) of (a1-1) and (2) ′ of (a1-2)] and a substrate for providing one sheet of wedge (FIG. 1: (a1-) It is an example of the shaping | molding die comprised from (3) of 1).
FIG. 1 (a2) shows two substrates [FIG. 1: (a2) (1) and (1) ′)], and a substrate for providing one crucible [FIG. 1: (a2) It is an example of the shaping | molding die comprised from (3).

  As shown in FIG. 1, the base material [(1) (a1-1) (3)] for forming a weir preferably has a shape having a cavity for injecting the composition on the top [FIG. 1: (3-1) of (a1-1). As a base material for providing the said wrinkles, various materials can be used and silicone rubber etc. can be mentioned.

As a specific example of (a1-1) and (a1-2) of FIG. 1, it is comprised from the base material for providing two glass as a base material, two sheets of the film by which the mold release process was carried out, and one sheet of wrinkles. Molds that can be used.
For laminating a release-treated film [FIG. 1: (2) of (a1-1)] on a glass [FIG. 1: (1) of (a1-1)], and providing a crease thereon The base material (FIG. 1: (3) of (a1-1)) is used as an overlapping weir (spacer). Furthermore, a release-treated film [FIG. 1: (2) ′ of (a1-2)] is overlaid, and a glass [FIG. 1: (1) ′ of (a1-2)] is overlaid thereon. It is a mold.

As a specific example of (a2) of FIG. 1, it is a case where the glass and metal by which the mold release process was carried out are used as a base material [FIG. Because of the excellent releasability of the film, the two release-treated films in (a1-1) and (a1-2) of FIG. 1 are unnecessary.
In addition, when the cured product of the composition itself is excellent in releasability, glass can also be used as a base material (FIG. 1: (1) and (1) ′ of (a2)). As an example in which the cured product of the composition itself is excellent in releasability, an example in which a release agent is blended in the composition can be mentioned.

6-1-2. Pretreatment of Composition In coating or injection of the composition of the present invention, the composition obtained is a resin sheet obtained which prevents contamination of foreign matter, generation of defects such as voids, and has excellent optical properties. In order to achieve this, it is preferable to use the purified one after stirring and mixing the raw material components.
As a method of purifying the composition, a method of filtering the composition is simple and preferred. As a method of filtration, pressure filtration etc. are mentioned.
The filtration accuracy is preferably 10 μm or less, more preferably 5 μm or less. The smaller the filtration accuracy, the better. The lower limit is preferably 0.1 μm from the viewpoint of suppression of clogging of the filter, suppression of filter replacement frequency, and productivity.

In the production of the resin sheet, in order to prevent the inclusion of air bubbles in the cured product, it is preferable to carry out a defoaming treatment after blending the respective components.
The defoaming method may, for example, be stationary, vacuum pressure reduction, centrifugal separation, cyclone (autorotation / revolution mixer), gas-liquid separation membrane, ultrasonic wave, pressure vibration, defoaming by a multi-screw extruder, or the like.

6-1-3. Coating or Injection In the case of coating the composition on a substrate, it may be appropriately set according to the purpose, and a conventionally known bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll Examples of the method include coating using a coater, a die coater, a lip coater, a gravure coater, and a microgravure coater.
In the case of injecting the composition into a substrate having a space portion, a method of injecting the composition into an injection device such as a syringe or an injection device may be mentioned.

The film thickness in this case may be appropriately set in accordance with the intended film thickness of the resin sheet.
In particular, when used for glass replacement applications, preferably OPS applications, 100 μm to 5 mm is preferable, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm.

6-1-4. As a heating method in the case of using a thermosetting composition as a heating composition, a method of immersing in heat and a heat medium bath such as oil, a method of using a heat press, a method of holding in a temperature controlled thermostatic chamber, etc. It can be mentioned.
Conditions such as the heating temperature in the case of heating may be appropriately set according to the composition to be used, the substrate, the purpose and the like. As heating temperature, 40-250 degreeC is preferable. The heating time may be appropriately set according to the composition to be used, the desired resin sheet, etc., and may be 3 hours or more. The upper limit of the heating time is preferably 24 hours or less in consideration of economy.
Moreover, heating temperature can also be changed according to the objective. For example, when using the thermal-polymerization initiator from which decomposition temperature differs, and the case where the hardening distortion of the resin sheet obtained is eliminated, etc. are mentioned.
As a specific temperature, for example, a method of polymerizing at relatively low temperature of about 40 to 80 ° C. for several minutes to several hours and then polymerizing at relatively high temperature of 100 ° C. or more for several hours can be mentioned. According to the said heating method, the hardening distortion of the resin sheet obtained can be eliminated and the resin sheet which is excellent in various mechanical physical properties, such as a fracture distortion, can be obtained.

6-2. Applications of Resin Sheet The resin sheet produced from the composition of the present invention can be preferably used particularly as an optical sheet.
Optical sheets formed from the compositions of the present invention can be used in a variety of optical applications. More specifically, a sheet used for a liquid crystal display device such as a polarizer protective film of a polarizing plate, a support film for a prism sheet, and a light guide film or a touch panel integrated liquid crystal display device, various functional films (for example, hard coat Base sheet of sheet, decoration sheet, transparent conductive sheet) and sheet with surface shape (for example, moth-eye type anti-reflection sheet or sheet with texture structure for solar cell), light resistance for outdoor use such as solar cell (weather resistance) Applications include sheets, films for LED illumination and organic EL illumination, and transparent heat-resistant sheets for flexible electronics.

Since the optical sheet formed from the composition of the present invention is excellent in heat resistance, it can be preferably used for the production of a transparent conductive sheet. As a composition used for this use, the non-solvent type composition which does not contain an organic solvent is preferable at the point which can suppress outgas generation | occurrence | production at the time of vacuum film-forming of a transparent conductive material layer.
Furthermore, since the optical sheet of the present invention is excellent in heat resistance and has flexibility and high strength even if it is a thick film, it can also be used as a transparent conductive sheet substrate for OPS. In the case, an optical sheet having a thickness of 0.5 mm or more and 1.5 mm or less can be more preferably used.

The method for producing the transparent conductive sheet may be in accordance with a conventional method.
As metal oxides for forming the transparent conductor layer, indium oxide, tin oxide, zinc oxide, titanium oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite Oxide, titanium-niobium complex oxide, etc. may be mentioned. Among these, indium-tin complex oxide and indium-zinc complex oxide are preferable from the viewpoint of environmental stability and circuit processability.
As a method of forming a transparent conductor layer, it may be in accordance with a usual method, and is formed by sputtering using a vacuum film forming apparatus using the metal oxide and using the optical sheet of the present invention Etc.
More specifically, after the metal oxide is used as a target material, dehydration and degassing are performed, the gas is evacuated and vacuumed, and the optical sheet is brought to a predetermined temperature, and then a sputtering apparatus is used on the optical sheet. The method of forming a transparent conductor layer etc. are mentioned.

Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples.
Also, in the following, "parts" means parts by weight, and "%" means% by weight.

1. Examples 1 to 3 and Comparative Examples 1 to 3
1) Production of thermosetting composition The components (A), (B) and (D) shown in the following Tables 1 and 2 are blended in the proportions shown in the following Tables 1 and 2 and stirred and mixed, then under vacuum. Degassed at.
In addition, in a postscript, the ratio of the methacryloyl group in 100 mol% of total amounts of an ethylenically unsaturated group is represented as a "methacryl ratio."

The abbreviations in Table 1 and Table 2 mean the following.
(A) Component M-315: Di- and tri-acrylate of ethylene oxide adduct of isocyanuric acid, Toho Gosei Co., Ltd. Alonics M-315
(B) Component · NDDA: 1, 9-nonane diacrylate, biscoat # 260 manufactured by Osaka Organic Chemical Industry Co., Ltd.
-NDDMA: 1, 9-nonane dimethacrylate, NON-N manufactured by Shin-Nakamura Chemical Co., Ltd.
TMP-MA: trimethylolpropane trimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd., "light ester TMP"
M-309: trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd. Alonics M-309
(D) Component BPO: t-butylperoxy-2-ethylhexanoate, perbutyl O made by NOF Corporation

2) Production of resin sheet The mold shown in (a2) of FIG. 1 was used as a mold for producing a resin sheet.
Two glass plates [80 mm × 80 mm, thickness 3 mm] and one silicone plate (thickness 1.0 mm) were used. In addition, the glass plate used what carried out the mold release process by the silicone type compound.
A silicone plate [(a2): (3) in FIG. 1] was placed on a glass plate [(a2): (1) in FIG. 1] to form a spacer. Furthermore, a glass plate [(a2): (1) ′] in FIG.

The composition obtained above was injected by a syringe from the cavity ((a2): (3-1) in FIG. 1) of the silicone plate of the mold.
The mold was placed in a drying furnace, heated at 60 ° C. for 0.5 hours, and then heated to 120 ° C. (heating rate: 10 ° C./hour) over 6 hours to cure the composition.
After cooling to room temperature, the glass was removed from the mold and then demolded to obtain a resin sheet.

3) Evaluation method About the obtained resin sheet, the average of in-plane phase difference, yellow index, a bending elastic modulus, a total light transmittance, a falling weight test, and pencil hardness were evaluated according to the following method. The results are shown in Tables 1 and 2.

(1) Using the resin sheet obtained by averaging the in-plane retardations, the in-plane retardation is measured with a polarization measurement system (KAMAIRI manufactured by Photoron Corporation), and the retardation of the central portion excluding 5 mm from the end is It measured and calculated the average value.

(2) Yellow index: Y. I.
The yellow index (Y.I.) of the resin sheet before and after heating in air at 230 ° C. for 4 hours was measured at a thickness of 1 mm in accordance with JIS K7375.

(3) Five test pieces of length 40 (mm) x width 10 (mm) are cut out from a resin sheet having a bending elastic modulus of 80 mm x 80 mm and a thickness of 1 mm, and Instron 5566A (distance between supporting points 30 mm, 0.2 mm) / Sec, 25 [deg.] C., 50% RH)) was carried out. The average value of five test pieces was taken as the flexural modulus (GPa).
In the case of fracture at a strain of 1.2 times or more at which the yield is observed and the stress is maximum, the fracture mode is a ductile fracture, and in the case of less than that, it is a brittle fracture.

(4) Total light transmittance The total light transmittance of a resin sheet having a thickness of 1 mm was measured in accordance with JIS K7375.

(5) Drop weight test (50% impact fracture height)
From the obtained resin sheet, a test piece of length 60 (mm) × width 60 (mm) is cut out, and the obtained resin sheet is disposed on a metal ring having a diameter of 50 mm according to JIS K 7211-1. A conical weight having a tip diameter of 5 mm and having a weight of 40 g was dropped from a predetermined height to the center of the resin molded body, and the height at which the probability of breakage was 50% or more was recorded. The number of tests at each height was ten.
(6) Pencil hardness In accordance with JIS K-5600, the hardness of the surface of the obtained resin sheet was measured.

2. Comparative Examples 4 to 9
1) Preparation of photocurable composition (A) and (B) shown in Tables 3 and 4 below and 2-hydroxy-2-methyl-1-phenyl-propane-1 as a photopolymerization initiator of other components -On [Darocur 1173, manufactured by BASF Japan Ltd.]. Hereinafter, it is called "DC1173." ] Were mix | blended in the ratio shown to following Table 3 and Table 4, and after stirring and mixing, it degas | defoamed under a vacuum.

The abbreviations in Table 3 and Table 4 mean the following except for those defined above.
(B) Component · DCP-A: dimethylol tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd., light acrylate DCP-A
· HBUA: adduct of hexamethylene diisocyanate trimer with hydroxybutyl acrylate

2) Production of resin sheet The mold shown in (a2) of FIG. 1 was used as a mold for producing a resin sheet.
The composition obtained above was injected by a syringe from the cavity ((a2): (3-1) in FIG. 1) of the silicone plate of the mold.
With respect to the obtained mold, an illuminance 130 mW / cm ² (UV-A, Fusion UV Systems Japan) is used from one surface on the side of the glass plate using an ultraviolet irradiation apparatus (high pressure mercury lamp) manufactured by Igraphics Co. It exposed 20 times by 5 m / min of conveyor speeds as UV POWER PUCK by Corporation. At this time, the irradiated surface was reversed every exposure.
After cooling, the glass was removed from the mold, and the obtained cured product was heated at 150 ° C. for 16 hours to obtain a resin sheet.
3) Evaluation method About the obtained resin sheet, the average of in-plane phase difference, yellow index, flexural modulus, total light transmittance, falling weight test and pencil hardness were evaluated according to the same method as above. The results are shown in Tables 3 and 4.

3. Comparative Examples 10 and 11
1) Evaluation of commercially available resin sheet Commercially available polymethyl methacrylate (Acrilyat L, manufactured by Mitsubishi Rayon Co., Ltd.). Hereinafter, it is referred to as "PMMA"] and polycarbonate [Iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.]. Hereinafter, using “PC”, the average in-plane retardation, yellow index, flexural modulus, total light transmittance, falling weight test and pencil hardness were evaluated according to the same method as described above. The results are shown in Table 5.

4. The compositions of General Examples 1 to 3 are excellent in any of the in-plane retardation average, yellow index, flexural modulus, drop weight test, total light transmittance and hardness of the resin sheet obtained. The
On the other hand, a thermosetting composition containing the components (A), (B) and (D) but containing no methacrylate (methacrylic ratio less than 20% by mole) of Comparative Examples 1 to 3 In the composition, the average of the in-plane retardation increases, that is, the resin sheet is deformed.
The compositions of Comparative Examples 4 to 6 which contain the components (A) and (B) but do not further contain methacrylate (the methacryl ratio is less than 20 mol%) are photocurable compositions. Since the average of the phase difference is increased, the initial Y. I. The value of has risen. Although the composition of Comparative Example 7 which is a photocurable composition containing the components (A) and (B) and having a methacryl ratio satisfying the range of the present invention, the average of the in-plane retardation decreases and the initial stage And Y. after the heating test. I. The value of has risen.
Further, the compositions of Comparative Examples 8 and 9 which contain (A) and which do not further contain a methacrylate (methacrylic ratio less than 20 mol%) of the photocurable composition have an increase in average of in-plane retardation. Y. after initial and heating test. I. The value of has risen. In particular, the composition of Comparative Example 9 containing a urethane acrylate has Y.1 after initial and heat test. I. The increase in the value was remarkable.
Moreover, in Comparative Example 10 related to commercially available PMMA, the result of the drop weight test was lowered. Further, in Comparative Example 11 relating to commercially available PC, the average of the in-plane retardation significantly increases.

The composition of the present invention can be used for various applications, and in particular, can be preferably used for producing a resin sheet.
The obtained resin sheet can be used for various applications, and can be preferably used as an optical sheet. The said optical sheet can be preferably used for manufacture of a transparent conductive sheet, and can be preferably used by manufacture of the transparent conductive sheet for touchscreens.

Claims (13)

Containing the following components (A), (B) and (D), and optionally the following (C) components,
20 to 60% by weight of component (A), 80 to 40% by weight of component (B) and 0 to 40% by weight of component (C) in 100% by weight of the total amount of components (A) to (C) And a thermosetting composition comprising 20 to 60 mol% of methacryloyl group in 100 mol% of the total amount of ethylenically unsaturated groups contained in the components (A) to (C).
Component (A): a compound having an isocyanurate ring and having two or more (meth) acryloyl groups (B): a compound having two or more (meth) acryloyl groups, which is a compound other than the component (A) Component (C): Compound having one ethylenically unsaturated group Component (D): Thermal polymerization initiator   The component (A) is a compound having an isocyanurate ring and having two (meth) acryloyl groups or / and a compound having an isocyanurate ring and having three (meth) acryloyl groups. The thermosetting composition as described.   The thermosetting composition according to claim 1 or 2, wherein the component (B) contains a di (meth) acrylate (B-1) having a linear alkylene group having 4 to 20 carbon atoms.   The component (B-1) is selected from the group consisting of 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate The thermosetting composition according to claim 3, which is one or more kinds.   The thermosetting composition according to any one of claims 1 to 4, wherein the component (B) contains a compound having three or more (meth) acryloyl groups.   The thermosetting composition according to any one of claims 1 to 5, wherein the components (A) to (C) do not contain a compound having a urethane bond.   The thermosetting composition according to any one of claims 1 to 6, which contains 0.1 to 5 parts by weight of the component (D) relative to 100 parts by weight of the total amount of the components (A) to (C). object.   The thermosetting composition according to any one of claims 1 to 7, which has a flexural modulus of 2.5 GPa or more in a flexural test of the cured product.   The thermosetting composition according to any one of claims 1 to 8, wherein the total light transmittance of the cured product is 90% or more.   The thermosetting composition for resin sheet manufacture containing the composition of any one of Claims 1-9.   The resin sheet which consists of hardened | cured material of the composition of Claim 10.   The resin sheet according to claim 10, wherein the cured product has a thickness of 100 μm to 5 mm.   The method for producing a resin sheet according to claim 10, wherein the composition according to claim 10 is poured into a mold composed of a base material, a base material for providing wrinkles, and a base material in order.

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