TWI815797B - Thermal curable composition - Google Patents

Abstract

An object of the present invention is to provide a thermal curable composition that can make a cured product having no problems in deformation and coloration, and excellent mechanical properties such as hardness and flexural properties. A thermal curable composition of the present invention includes component (A), component (B), and component (D), and optionally component (C), wherein the content of component (A) is 20 to 60 wt %, the content of component (B) is 80 to 40 wt %, the content of component (A) is 0 to 40 wt %, with respect to 100 weight % of a total content of component (A), component (B) and component (C), and the content of metacrylate group is 20 to 60 mol % with respect to 100 mol % of a total content of ethylenically unsaturated groups included in component (A) , component (B) and component (C), component (A): a compound having isocyanurate ring and two or more (meth)acrylate groups; component (B): a compound having two or more (meth)acrylate groups and other than component (A); component (C): a compound having one ethylenically unsaturated group; and component (D): a thermal polymerization initiator.

Description

thermosetting composition

The present invention relates to a thermosetting composition, which is particularly suitable for use in the production of resin sheets. The obtained resin sheets are suitable for use in optical substrates such as liquid crystal displays (LCDs) and organic ELs, and are more suitable for use in transparent conductive films of touch panels. The present invention belongs to these technical fields as a resin sheet for forming. In addition, in this specification, an acryl group or a methacryloyl group is expressed as (meth)acrylyl group, and an acrylate or methacrylate is expressed as (meth)acrylate.

In recent years, most mobile devices such as smartphones, tablets, and car navigation systems have gradually adopted touch panel-integrated liquid crystal display devices or touch panel-integrated organic EL display devices. Conventionally, conductive glass in which an indium tin oxide (hereinafter referred to as "ITO") thin film is formed on glass has been widely known as a transparent conductive film for a touch panel. However, since the base material is glass, flexibility and workability are poor. Therefore, from the viewpoint of advantages such as excellent flexibility, workability, impact resistance, and lightweight, a polyethylene terephthalate sheet can be used as a transparent conductive sheet as a base material depending on the application.

On the other hand, from the viewpoint of being expected to contribute to thinner and lighter touch panels, improvement in light transmittance, and reduction in component costs, in some cases, touch sensing such as ITO can be directly formed on the glass cover. The cover plate of the tester is integrated with the touch panel, the so-called OGS (One Glass Solution). However, if the glass cover of the OGS type panel is broken, there will be a problem that the touch panel cannot be operated.

Therefore, as a cover material with excellent impact resistance, some literature proposes a touch sensor such as ITO that is directly formed on a resin sheet, a so-called OPS (One Plastic Solution). However, conventional acrylic resin or polycarbonate resin sheets have low surface hardness and are therefore easily scratched. In addition, they may have insufficient toughness and may be broken due to impact force from the outside.

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

Patent Document 2 discloses a transparent resin molded article with a thickness of 50 to 500 μm, which is made of a polyfunctional urethane (meth)acrylate having an alicyclic structure and a bifunctional (meth)acrylate having an alicyclic structure. It is obtained by photocuring a photocurable composition of base) acrylate and photopolymerization initiator. Prior art documents Patent documents

[Patent Document 1] Japanese Patent Application Laid-Open No. 2002-161113 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-56180

Problems to be Solved by the Invention However, although the plastic member described in Patent Document 1 imparts moderate toughness to the cured product by blending a mercapto compound, there is a problem that the pot life of the composition is shortened, and Problems with reduced surface hardness or scratch resistance. In addition, the transparent resin molded article described in Patent Document 2 cannot exhibit the same rigidity as glass, so there is a problem of poor appearance during the heating step in the process of forming a transparent conductive film or a metal electrode. As mentioned above, it has not been found that resin sheets have satisfactory physical properties as a resin for OPS. In particular, it is difficult to balance hardness and strength, and scratch resistance is also insufficient.

When manufacturing a resin sheet, a photocurable composition as described above may be used, or a thermosetting composition may be used. The composition can be used according to its purpose or characteristics. The advantage of thermosetting compositions is that they can be produced with simple equipment, and multiple sheets can be produced simultaneously with one heating device. However, when conventional thermosetting compositions are used, there may be problems due to heating. Problems with deformation or coloration of the resin sheet. In addition, even when a photocurable composition as described above is applied to a thermosetting composition, the same problem occurs.

The inventors of the present invention sought to find a thermosetting composition in which the resulting cured product has no problems with deformation or coloration and has excellent mechanical properties such as hardness and bending characteristics. Especially when used in the production of resin sheets, it is difficult to It is studied and examined that it has excellent surface physical properties such as cracking, impact resistance, surface hardness and scratch resistance. means to solve problems

The inventors of the present invention conducted intensive research in order to solve the above-mentioned problems, and found that a composition including di(meth)acrylate having a trimeric isocyanate ring and other multifunctional (meth)acrylates can solve the above-mentioned problems, and completed the present invention. .

The present invention relates to a thermosetting composition, which contains the following (A) component, (B) component and (D) component, and any of the following (C) components. When the total amount of (A) to (C) components is 100 In weight %, it contains 20 to 60 weight % of (A) component, 80 to 40 weight % of (B) component and 0 to 40 weight % of (C) component, and is contained in (A) to (C) components. The total amount of ethylenically unsaturated groups (100 mol%) includes 20 to 60 mol% of methacrylic groups. (A) Component: A compound having an isocyanate ring and two or more (meth)acrylyl groups. (B) Component: a compound having two or more (meth)acrylyl groups and a compound other than (A) component. (C) Component: A compound having one ethylenically unsaturated group. (D) Ingredient: thermal polymerization initiator. You can also change the description as follows. The thermosetting composition of the present invention contains the above-mentioned component (A), (B) and (D), and may also contain the above-mentioned component (C). When it contains the (C) component, (A) to ( C) The total amount of component 100% includes (A) component 20 to 60 wt%, (B) component 80 to 40 wt% and (C) component exceeding 0 to 40 wt%, and (A) ~ The total amount of ethylenically unsaturated groups contained in the component (C) is 100 mol%, including 20 to 60 mol% of methacrylic groups. When the component (C) is not included, in (A) ) component and (B) component include 20 to 60 wt% of (A) component and 80 to 40 wt% of (B) component in 100 wt% of the total amount of (A) component and (B) component. The total amount of ethylenically unsaturated groups of 100 mol% includes 20 to 60 mol% of methacrylic groups.

The component (A) is preferably a compound having a trimeric isocyanate ring and having two (meth)acrylyl groups or/and a compound having a trimeric isocyanate ring and having three (meth)acrylyl groups.

The component (B) preferably contains di(meth)acrylate (B-1) having a linear alkylene group having 4 to 20 carbon atoms. In addition, 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. One or more types of di(meth)acrylate is preferred. In addition, component (B) preferably further contains a compound having three or more (meth)acrylyl groups.

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

The proportion of component (D) is preferably 0.1 to 5 parts by weight of component (D) based on 100 parts by weight of the total amount of components (A) to (C).

The physical properties of the cured product of the composition are preferably a bending elastic modulus of 2.5 GPa or more during a bending test, and the total light transmittance is preferably 90% or more.

The composition of the present invention is preferably a thermosetting composition for producing resin sheets. In addition, the thickness of the cured product of the obtained resin sheet is preferably 100 μm to 5 mm.

The manufacturing method of the resin sheet is preferably a method of pouring the thermosetting composition of the present invention into a mold composed of a base material, a base material for forming a weir, and the base material in this order and then heating the mold. The present invention will be described in detail below. Invention effect

According to the composition of the present invention, the obtained cured product has no problems of deformation or coloration. In addition, it has excellent mechanical properties such as hardness and bending characteristics. Even when used in the production of resin sheets, it is not easy to break, has excellent impact resistance, surface hardness and Excellent surface properties such as scratch resistance.

The present invention relates to a thermosetting composition, which is a composition containing components (A) to (D), and contains 20 to 20% of the component (A) in 100% by weight of the total amount of the components (A) to (C). 60% by weight, 80 to 40% by weight of component (B) and 0 to 40% by weight of component (C), and the total amount of ethylenically unsaturated groups contained in components (A) to (C) is 100 mol% , containing 20 to 60 mol% of methacrylic groups. The details of each ingredient and composition are described below.

1. Component (A) Component (A) is a compound having an isocyanate ring and two or more (meth)acrylyl groups. Various compounds can be used as the component (A) as long as it is a compound having an isocyanate ring and two or more (meth)acrylyl groups. The component (A) is preferably a compound having an isocyanate ring and two (meth)acrylyl groups or/and a compound having three (meth)acrylyl groups. Specific examples include di(meth)acrylate of an oxyalkylene isocyanate adduct, tri(meth)acrylate of an oxyalkylene isocyanate adduct, and cyclotriisocyanate. Di(meth)acrylate of oxyalkane and ε-caprolactone adduct, tri(meth)acrylate of ethylene glycol triisocyanade and ε-caprolactone adduct, etc. Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide, with ethylene oxide being preferred. The molar number of addition of alkylene oxide is preferably 1 to 3 moles per molecule. In addition, the addition molar number of ε-caprolactone is preferably 1 to 3 moles per molecule.

(A) Component may use only 1 type of the said compound, or may use 2 or more types together.

The component (A) is commercially available, and examples thereof include the following products. ･Diacrylate ester of 3 molar adduct of ethylene oxide triisocyanurate: ARONIX M-215 manufactured by Toagosei Co., Ltd. ･Triacrylic acid ester of 3 molar adduct of ethylene oxide trimeric isocyanate Esters: A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., FANCRYL FA-731A manufactured by Hitachi Chemical Co., Ltd. ･Di- and tri(meth)acrylates of ethylene oxide triisocyanate 3-mol adduct Mixture: ARONIX M-315 manufactured by Toagosei Co., Ltd. Triacrylate of an adduct of 3 moles of ethylene oxide tripolyisocyanate and 1 mole of ε-caprolactone: Examples include Shin Nakamura Chemical Industry Co., Ltd. Co., Ltd. A-9300-1CL, etc. ･Triacrylate of the adduct of 3 moles of ethylene oxide tripolyisocyanate and 3 moles of ε-caprolactone: ARONIX M-327 manufactured by Toagosei Co., Ltd.

The content ratio of component (A) is 20 to 60 wt% of the total amount of components (A) to (C), preferably 30 to 55 wt%. When the content of component (A) is less than 20% by weight, the rupture strain and 50% impact damage height are low, and the resin sheet becomes brittle. If it exceeds 60% by weight, the surface hardness such as pencil hardness or scratch resistance decreases.

2. Component (B) Component (B) is a compound having two or more (meth)acrylyl groups and is a compound other than component (A). Examples of the component (B) include compounds having two (meth)acrylyl groups [hereinafter referred to as "bifunctional (meth)acrylate"] and compounds having three or more (meth)acrylyl groups [hereinafter referred to as "bifunctional (meth)acrylate"] It is called "trifunctional or higher (meth)acrylate"] etc.

2-1.2 Functional (meth)acrylate Bifunctional (meth)acrylate includes di(meth)acrylate having an alkylene group and polyalkylene glycol di(meth)acrylate.

Suitable examples of the di(meth)acrylate having an alkylene group are di(meth)acrylates having a linear or branched alkylene group having 4 to 20 carbon atoms [hereinafter referred to as "(B-1) ) ingredient"] is better. 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 have excellent hardness and scratch resistance of the cured product compared to di(meth)acrylates having a linear or branched alkylene group with a carbon number of 3 or less. , compared to the case of compounds with a carbon number of 21 or more, the rigidity or heat resistance of the cured product is superior. 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-butylene group having bonds at both ends. Shen Renji is better. Specific examples of this compound include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate. Acrylic etc.

The bivalent 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. ), 2-methyl-1,3-propylene group, and isobutylene group with a degree of polymerization of 5 or less are preferred. Specific examples of this compound include neopentyl glycol di(meth)acrylate, which is most suitably used.

(B-1) Component, among these compounds, is selected from 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9 - One or more types of the group consisting of nonanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate is preferred. (B-1) Component, among these compounds, further selected from the group consisting of 1,6-hexanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate More than one of them is preferred.

The polyalkylene glycol di(meth)acrylate is preferably a di(meth)acrylate whose total carbon number constituting the polyoxyalkylene group is 4 to 20. Specific examples of polyalkylene glycol di(meth)acrylate include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. ) 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 Meth)acrylate, polybutylene glycol di(meth)acrylate and poly(1-methylbutylene glycol) di(meth)acrylate, etc.

Polyalkylene glycol di(meth)acrylate, among these compounds, is selected from the group consisting of polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate and polybutylene glycol di(meth)acrylate. One or more types of the group consisting of (meth)acrylates is preferred. Polyalkylene glycol di(meth)acrylate, among these compounds, further selected from the group consisting of polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate. One or more types are preferred.

Examples of bifunctional (meth)acrylates other than those mentioned above include di(meth)acrylates of bisphenol A alkylene oxide adducts and bifunctional bifunctional (meth)acrylates with aromatic skeletons such as bisphenol A di(meth)acrylates. (Meth)acrylate; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate and other 2-functional (meth)acrylate with aliphatic skeleton ) acrylate; hydroxypivalate neopentyl glycol di(meth)acrylate; dimethyloltricyclodecane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate and spiro Bifunctional (meth)acrylate having an alicyclic skeleton such as cyclodiol di(meth)acrylate; In addition, among the above, alkylene oxide adducts include ethylene oxide adducts and Propylene oxide adduct, etc.

Bifunctional (meth)acrylates include, in addition to the aforementioned compounds, polyester (meth)acrylates, epoxy (meth)acrylates, polyether (meth)acrylates, and the like. These compounds are described below.

2-1-1. Polyester (meth)acrylate Examples of polyester (meth)acrylate include dehydration condensates of polyester diol and (meth)acrylic acid. Examples of the polyester diol include reaction products of diol and dicarboxylic acid or anhydride thereof. Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, and tetramethylene glycol. Low molecular weight glycols such as methyl glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc. As well as alkylene oxide adducts of these compounds. Examples of the dicarboxylic acid or its anhydride include phthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and metaphenyl Dicarboxylic acids such as tricarboxylic acid, and anhydrides of these compounds, etc.

2-1-2. Epoxy (meth)acrylate Epoxy (meth)acrylate is a compound that causes an addition reaction between epoxy resin and (meth)acrylic acid. Epoxy resins include aromatic epoxy resins, aliphatic epoxy resins, and the like.

Aromatic epoxy resins, specifically, include benzene-skeletal diepoxypropyl ethers such as resorcin diglycidyl ether and hydroquinone diglycidyl ether; bisphenol A and bisphenol F , bisphenol type diglycidyl ether such as bisphenol S, bisphenol fluorene or the diglycidyl ether of its alkylene oxide adduct; phenol novolac type epoxy resin and cresol novolac type epoxy resin, etc. Phenolic epoxy resin; epoxypropyl phthalimide; and diepoxypropyl phthalate, etc.

Aliphatic epoxy resins, specifically, include diepoxypropyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; polyethylene glycol Diglycidyl ether of polyalkylene glycol such as alcohol and polypropylene glycol; Diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and their alkylene oxide adducts. base ether; diepoxypropyl ether of hydrogenated bisphenol A and its alkylene oxide adduct; and diepoxypropyl tetrahydrophthalate, etc. Among the above, preferred alkylene oxides for the alkylene oxide adduct are ethylene oxide, propylene oxide, and the like.

2-1-3. Polyether (meth)acrylate Polyether (meth)acrylate oligomers include polyalkylene glycol di(meth)acrylate, including polyethylene glycol di(meth)acrylate. Acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, etc.

2-2.3 or more functional (meth)acrylates. Examples of 3 or more functional (meth)acrylates include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri- or tetra(meth)acrylate, Polyol poly(meth)acrylates such as ditrimethylolpropane tri or tetra(meth)acrylate, and dineopenterythritol tri, tetra, penta or hexa(meth)acrylate; and trihydroxyl Tri(meth)acrylate of methylpropane alkylene oxide adduct, tri- or tetra(meth)acrylate of neopentyl erythritol alkylene oxide adduct, ditrimethylolpropane alkylene oxide adduct polyol alkylene oxide adducts such as tri- or tetra-(meth)acrylate and tri-, tetra-, penta- or hexa-(meth)acrylate of dineopenterythritol alkylene oxide adduct. (meth)acrylate, etc. Among the poly(meth)acrylates of the above polyol alkylene oxide adducts, the alkylene oxides are preferably ethylene oxide and propylene oxide.

2-3. Appropriate aspect As component (B), only one type of the aforementioned compounds may be used, or two or more types may be used in combination. The component (B) preferably contains the aforementioned component (B-1). In addition, the component (B-1) is selected from the group consisting of 1,4-butanediol di(meth)acrylate and 1,6-hexanediol. One or more types of the group consisting of alcohol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate is preferred. In this case, the content ratio of component (B-1) is preferably such that 30 to 70% by weight of component (B-1) is contained in 100% by weight of the total amount of component (B). In addition, component (B) preferably contains a compound having three or more (meth)acrylyl groups. In this case, the content ratio of the compound having three or more (meth)acrylyl groups is such that the compound having three or more (meth)acrylyl groups is included in 100% by weight of the total amount of component (B) 30 to 70% by weight is preferred.

2-4. Content ratio The content ratio of component (B) is 40 to 80 wt% of the total amount of components (A) to (C), preferably 45 to 75 wt%. When the content of component (B) is less than 40% by weight, surface hardness such as pencil hardness or scratch resistance decreases. If it exceeds 80% by weight, the fracture strain and 50% impact damage height are low, and the resin sheet becomes brittle. In addition, a suitable content ratio of component (B-1) is 30 to 70% by weight based on 100% by weight of the total amount of component (B).

3. Component (C) Component (C) is a compound having one ethylenically unsaturated group. The component (C) is a component blended to adjust the viscosity of the composition or to adjust the physical properties of the cured product according to the purpose. Examples of the ethylenically unsaturated group in component (C) include (meth)acrylyl group, vinyl group, vinyl ether group, etc., with (meth)acrylyl group being preferred.

Examples of the component (C) include compounds having one (meth)acrylyl group [hereinafter referred to as "monofunctional (meth)acrylate"] and the like. Specific examples of monofunctional (meth)acrylates include iso(meth)acrylate. Ester, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, (methyl) 1-Adamantyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ( tert-butyl methacrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-Methoxyethyl acrylate, tetrahydrofuranmethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylamineethyl (meth)acrylate, di(meth)acrylate Ethylamine ethyl ester, benzyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, O-phenylphenol ethylene oxide adduct (1 to 4 molar adduct) (meth)acrylate, p-cumylphenol ethylene oxide adduct (1 to 4 molar adduct) ) (meth)acrylate, phenyl (meth)acrylate, o-phenylphenyl (meth)acrylate, and p-cumylphenyl (meth)acrylate, etc.

Monofunctional (meth)acrylates can be compounds having various functional groups. Examples of the compound having a carboxyl group include (meth)acrylic acid, polycaprolactone denatured product of (meth)acrylic acid, Michael addition type polymer of (meth)acrylic acid, and 2-hydroxy(meth)acrylic acid. Carboxyl group-containing (meth)acrylates such as the adduct of ethyl ester and phthalic anhydride, and the adduct of 2-hydroxyethyl (meth)acrylate and succinic anhydride.

Examples of the compound having a hydroxyl group include (meth)acrylate having a hydroxyl group. Examples of (meth)acrylates having hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxypentyl (meth)acrylate. ester, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, and hydroxyalkyl (meth)acrylate.

Examples of compounds having a amide group include N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, and (meth)acrylamide-based compounds. Specific examples of the (meth)acrylamide-based compound include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-isopropyl(meth)acrylamide. N-alkylacrylamides such as amines and N-tert-butyl(meth)acrylamide; N,N-dimethyl(meth)acrylamide and N,N-diethyl(methyl)acrylamide ) acrylamide and other N,N-dialkyl acrylamide; N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl N-alkoxyalkyl (methyl) groups such as (meth)acrylamide and N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, etc. Acrylamide; and (meth)acrylamide, etc.

Examples of compounds having a urethane group include oxazolidinone-based (meth)acrylate, etc., specific examples thereof include 2-(2-oxo-3- Azolidinyl)ethyl acrylate, etc.

Examples of the compound having an amide imine group include compounds having a maleimide group. Examples of the compound having a maleimide group include (meth)acrylate having a hexahydrophthalimide group, (meth)acrylate having a tetrahydrophthalimide group, and the like. Specific examples of the (meth)acrylate having a hexahydrophthaloimide group include N-(meth)acryloxyethyl hexahydrophthaloimide and the like. Examples of the (meth)acrylate having a tetrahydrophthaloimide group include N-(meth)acryloxyethyl tetrahydrophthaloimide and the like.

Examples of compounds other than the monofunctional (meth)acrylate in the component (C) include aromatic vinyl compounds and the like. Examples of aromatic vinyl compounds include styrene, alkyl styrene, halogenated styrene, and the like. Specific examples of alkyl styrene include methyl styrene, ethyl styrene, propyl styrene, and the like. Specific examples of halogenated styrene include fluorostyrene, chlorostyrene, bromostyrene, and the like. Among the aromatic vinyl compounds mentioned above, styrene is preferred.

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

The content ratio of component (C) is 0 to 40 wt%, preferably 0 to 20 wt%, based on 100 wt% of the total amount of components (A) to (C). If the content ratio of component (C) exceeds 40% by weight, unreacted components will remain in the cured resin sheet, thereby plasticizing the resin sheet and reducing the bending elastic modulus.

4. (D) Component (D) is a thermal polymerization initiator. Various compounds can be used as component (D), and organic peroxides and azo initiators are preferred. Among them, organic peroxides are preferred because they are excellent in polymerization initiator efficiency, can reduce fugitive gas from decomposition products of the polymerization initiator, and even have excellent impact resistance of the composition.

Specific examples of organic peroxides include 1,1-bis(tertiary butylperoxy)2-methylcyclohexane and 1,1-bis(tertiary hexylperoxy)-3,3,5- Trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy) ) cyclododecane, dilauryl peroxide, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethyl Hexanoate, tert-butylperoxylaurate, tert-butylperoxypivalate, tert-hexylperoxypivalate, 2,5-dimethyl-2,5-di(m- Toluyl peroxy)hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy 2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2, 5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxyacetate, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroxyperoxybenzoate, n-butyl-4,4-bis(tert-butylperoxy)valerate, di-tert-butylperoxyisophthalate, α,α'-bis (Third-butylperoxy)dicumylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylperoxy Cumene oxide, di-tert-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, diisopropyl Benzene hydroperoxide, tert-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide , and third-butyl hydroperoxide, etc.

Specific examples of the azo compound include 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminomethyl azo)isobutyronitrile, and 2-phenylazo- 4-methoxy-2,4-dimethylvaleronitrile, azobis-tertiary octane, azobis-tertiary butane, etc. These may be used individually, or 2 or more types may be used together. In addition, organic peroxides can also perform redox reactions by combining with reducing agents.

The content ratio of component (D) is preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the total amount of components (A) to (C). By setting the proportion of component (D) at 0.1 parts by weight or more, the entire resin sheet can be uniformly hardened, and by setting it at 5 parts by weight or less, the emission of residual low-molecular-weight polymerization initiator decomposition products can be reduced. gas.

5. Thermosetting composition The present invention relates to a thermosetting composition, which contains the aforementioned (A) component, (B) component and (D) component, and any of the aforementioned (C) components, in (A) to ( The total amount of component C (100% by weight) includes 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). ) component contains 20 to 60 mol% of methacrylic groups based on 100 mol% of the total amount of ethylenically unsaturated groups contained in the component.

The above-mentioned components (A) to (C) of the curable component hardened by heating in the present invention can be used in appropriate combinations of the above-mentioned compounds, and it is preferable that they do not contain compounds having a urethane bond. For compounds having urethane bonds, such as compositions containing urethane (meth)acrylate, the cured product will be colored.

The composition of the present invention must contain 20 to 60 mol% of methacrylic groups based on 100 mol% of the total amount of ethylenically unsaturated groups contained in components (A) to (C), preferably 30 mol%. ~60 mol%. If the proportion of methacryl groups is less than 20 mol%, the resin sheet will be seriously deformed after thermal hardening. If it exceeds 60 mol%, the coloring before and after the heat resistance test will be serious. The ratio of the methacryl group in the present invention means the total number of moles of methacryl groups in components (A) to (C) divided by the total number of moles of ethylenically unsaturated groups multiplied by 100. Ear%. In addition, among commercially available compounds with two or more (meth)acrylyl groups, there are many mixtures of compounds with different numbers of (meth)acrylyl groups, so there are (meth)acrylyl groups. The ratio of hydroxyl groups is incorrect. In this case, the (meth)acrylyl group equivalent of the raw material compound is measured in advance based on the iodine value, etc., and the calculation is performed based on this value.

The composition can be produced by a common method. For example, the composition can be produced by stirring and mixing (A) component, (B) component, and (D) component, and if necessary, (C) component and other components.

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

The composition of the present invention contains the above-mentioned (A) component, (B) component and (D) component as essential components, but various components such as (C) component may be blended depending on the purpose. Specific examples of other components include organic solvents, plasticizers, polymerization inhibitors or/and antioxidants, light resistance improving agents, and compounds with two or more mercapto groups [hereinafter referred to as "polyfunctional thiols"], etc. These ingredients are explained below. In addition, only one type of the components mentioned below may be used, or two or more types may be used in combination.

5-1. Other components 1) Organic solvent The composition of the present invention may be blended with an organic solvent in order to improve the coating properties on the substrate. However, when the obtained resin sheet is used as a transparent conductive film, it is preferable that it does not contain an organic solvent.

Specific examples of organic solvents include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene, and cyclohexane; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2 -Butanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2 -Isoamyloxyethanol, 2-hexoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furanmethyl alcohol, tetrahydrofuranmethyl alcohol, diethylene glycol, diethylene glycol monomethyl ether , alcohol-based solvents such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and propylene glycol monomethyl ether; tetrahydrofuran, two alkane, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether and bis(2- Ether solvents such as butoxyethyl ether; acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl amyl ketone, Ketone solvents such as di-n-propyl ketone, diisobutyl ketone, phorone, isophorone, cyclopentanone, cyclohexanone and methylcyclohexanone; ethyl acetate, butyl acetate, isobutyl acetate ester, methylglycol acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, etc.; and N,N-dimethylformamide, N,N-dimethylacetamide, Aprotic polar solvents such as dimethylsulfoxide, N-methyl-2-pyrrolidone, and γ-butyrolactone.

The proportion of the organic solvent can be appropriately set, and it is preferably 90% by weight or less in the composition, preferably 80% by weight or less.

2) Plasticizer: In order to impart softness to the hardened material and improve its brittleness, a plasticizer can be added. Specific examples of plasticizers include dialkyl phthalates such as dioctyl phthalate and diisononyl phthalate, dialkyl adipates such as dioctyl adipate, and secretic acid esters. , phosphate esters such as azalea acid ester and tricresyl phosphate, liquid polyether polyols such as polypropylene glycol, polycaprolactone diol, and liquid 3-methylpentanediol adipate, etc. Polyester polyols, etc. Also included are soft acrylic polymers having a number average molecular weight of 10,000 or less. The blending ratio of these plasticizers can be set appropriately. The total of the components (A) to (C) (hereinafter, "hardening component") is preferably 30 parts by weight or less per 100 parts by weight, more preferably 20 parts by weight or less. By setting the content to 30 parts by weight or less, strength and heat resistance can be improved.

3) Polymerization inhibitor and/or antioxidant In order to improve storage stability, a polymerization inhibitor or/and antioxidant may be added to the composition of the present invention. Polymerization inhibitors are preferably hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants. However, sulfur-based secondary antioxidants can also be added. Oxidants, phosphorus secondary antioxidants, etc. The total blending ratio of these polymerization inhibitors and/or antioxidants 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 amount of curable components.

4) Light resistance improving agent In the composition of the present invention, a light resistance improving agent such as an ultraviolet absorber or a light stabilizer may be added. Examples of ultraviolet absorbers include 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzo Triazole, and benzotriazole compounds such as 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole; 2,4-bis(2,4- Dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-tri Wait three Compounds; 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' - Benzophenone compounds such as tetrahydroxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone wait. Photostabilizers include N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-dimethylylhexamethylenediamine, bis (1,2,6,6-)pentamethyl-4-piperidinyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate, Low molecular weight hindered amine compounds such as bis(1,2,2,6,6-pentamethyl-4-piperidinyl)mylinate; N,N'-bis(2,2,6,6-tetrakis) Methyl-4-piperidyl)-N,N'-dimethylhexamethylenediamine, bis(1,2,2,6,6-pentamethyl-4-piperidyl)lipidin Hindered amine-based light stabilizers such as high molecular weight hindered amine compounds such as acid esters. The blending ratio of the light resistance improving agent is preferably 0 to 5 parts by weight, more preferably 0 to 1 part by weight relative to 100 parts by weight of the total amount of curable components.

5) Polyfunctional thiol Polyfunctional thiol can be blended as necessary to prevent hardening shrinkage of the cured product of the composition or to impart strength and toughness. As long as the polyfunctional thiol is a compound having two or more mercapto groups, various compounds can be used. Examples thereof include neopentyl erythritol tetrathioglycolate, neopentyl erythritol tetrathiopropionate, and the like. The ratio of the polyfunctional thiol is preferably 20 parts by weight or less based on 100 parts by weight of the curable component, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less. By making this ratio 20 parts by weight or less, it is possible to prevent the resulting cured product from being reduced in heat resistance or rigidity.

6) Other components other than the above In the composition of the present invention, in addition to the other components mentioned above, a release agent, a filler, a soluble polymer, etc. may also be blended. The release agent is blended in order to facilitate the release of the obtained resin sheet from the base material. As the release agent, various surfactants can be used as long as they can be released from the base material and do not cloud the mixed liquid and hardened product. Examples include anionic surfactants such as alkylbenzenesulfonic acid, cationic surfactants such as alkyl ammonium salts, nonionic surfactants such as polyoxyethylene alkyl ethers, and amphoteric surfactants such as alkylcarboxybetaine. , or even surfactants containing fluorine or silicon. Fillers are blended in order to improve the mechanical properties of the resulting resin sheet. Either an inorganic compound or an organic compound can be used as a filler. Examples of inorganic compounds include silica and alumina. Polymers can be used as organic compounds. When the resin sheet obtained from the composition of the present invention is used for optical purposes, it is preferable that the filler does not reduce the optical properties. The soluble polymer is blended in order to improve the mechanical properties of the obtained resin sheet. Soluble polymer means a polymer that is dissolved in the composition. In the present invention, polymers that are insoluble in the composition are called fillers for distinction. The blending ratio of these other compounds is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less based on 100 parts by weight of the curable component.

5-2. Physical properties of cured product The composition of the present invention exhibits the effect of preventing deformation of the cured product after thermal curing. The method of evaluating this physical property is preferably a method of evaluating the average value of the in-plane phase differences. The average value of the in-plane retardation of the hardened material of the present invention is preferably 10 nm or less, and more preferably 8 nm or less. In the present invention, the in-plane phase difference means a phase difference that occurs in the X direction and the Y direction due to birefringence generated when linearly polarized light is incident on the resin sheet.

Regarding the physical properties of the hardened product of the composition of the present invention, the bending elastic modulus during a bending test is preferably 2.5 GPa or more, and more preferably 3.0 GPa or more. When the cured product of the composition has this elastic modulus, it has excellent rigidity. In addition, the elastic modulus during a bending test in the present invention means calculated from the stress when the deformation is 0.1% and 1% in a bending test conducted with a distance between fulcrums of 30 mm and a bending speed of 0.2 mm/minute. value.

In addition, when the cured product of the composition of the present invention is used for optical purposes, the total light transmittance is preferably 90% or more, and more preferably 91% or more. In addition, in the present invention, the total light transmittance means the result of measuring a test body with a thickness of 1 mm in accordance with JIS K7375.

In addition, the physical properties of the cured product of the composition in the present invention are preferably such that the pencil hardness is 3H or more. In addition, the pencil hardness in this invention means the value measured based on the method of JIS K-5600.

5-3. Film thickness When the composition of the present invention is used in a resin sheet, the film thickness of the resin sheet may be appropriately set according to the purpose. Especially when used for glass replacement applications such as OPS, 100 μm to 5 mm is preferred, 200 μm to 3 mm is more preferred, and 300 μm to 2 mm is particularly preferred.

6. Applications The composition of the present invention can be used for various purposes, and is particularly suitable for use as forming materials. Examples of molding materials include resin sheets and three-dimensional molding using inkjet methods, and resin sheets are suitably used. The resin sheet will be described below.

6-1. Manufacturing method of resin sheet Various methods can be used to manufacture the resin sheet using the composition of the present invention, and examples thereof include the following four manufacturing methods. 1) Preparation method 1: Apply the composition to the base material and heat to harden the composition 2) Preparation method 2: Apply the composition to the base material and bond it to other base materials, then heat to harden the composition 3) Preparation method 3: Pour the composition into a base material with a space and heat to harden the composition. 4) Preparation method 4: Pour the composition into a base material with a space and bond it to other base materials, then heat to harden the composition. When the resin sheet obtained from the composition of the present invention is used as a substitute for glass, the above-mentioned production method 4 is preferred. The polymerization method can be either a batch method or a continuous method. Examples of the continuous method include a method of coating or pouring the composition onto a base material and continuously supplying the strip-shaped base material.

Other examples of the continuous type include a method called a continuous casting method in addition to the above. That is to say, two continuous mirror-finished stainless steel belts are placed side by side in a crawler-like shape, the composition is poured between the belts, and the steel belts are slowly moved while polymerization is performed between the continuous belts. And the method of manufacturing the resin sheet, etc. In terms of glass replacement applications, the batch type is preferred.

6-1-1. Base material As the base material, either a releasable base material or a base material without mold releasability (hereinafter referred to as "non-release base material") can be used. Peelable base materials include metal, glass, release-treated films, and releasable surface-untreated films (hereinafter collectively referred to as "release materials"). Release materials include silicone-treated polyethylene terephthalate film, surface-untreated polyethylene terephthalate film, surface-untreated cyclic olefin polymer film, and surface-untreated OPP film (polypropylene )wait.

In order to make the resin sheet obtained from the composition of the present invention low in haze or impart surface smoothness to the resin sheet, a peelable base material having a surface roughness (center line average roughness) Ra of 0.15 μm or less is used. Preferably, a substrate of 0.001 to 0.100 μm is preferred. In addition, the haze is preferably 3.0% or less. Specific examples of the base material include glass, surface-untreated polyethylene terephthalate film, surface-untreated OPP film (polypropylene), and the like. In addition, in the present invention, the surface roughness Ra means measuring the unevenness of the film surface and calculating the average roughness.

Non-releasing base materials include various plastics other than those mentioned above, such as cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose, and diethyl cellulose, acrylic resins, polyesters, and polycarbonates. , polyarylate, polyether ester, drop Cyclic polyolefin resins using cyclic olefins as monomers such as olefins, etc.

Examples of the base material having a space part include a base material having a recessed part. Examples include a mold release material that has a hole set to a target film thickness and a predetermined shape to form a recessed portion. In this case, after pouring the composition into the base material having the recessed portion, other base materials can be laminated on the base material having the recessed portion. Other examples of the base material having a space include a mold release material provided with a spacer so that the cured product has a target film thickness (hereinafter referred to as a "forming mold"). In this case, other base materials can also be laminated on the weir. In this case, the release material is preferably glass or release-treated glass.

An example of a molding die will be described with reference to FIG. 1 . (a1-1) and (a1-2) in Figure 1 are composed of two pieces of base material [Figure 1: (1) of (a1-1) and (1)' of (a1-2)], two pieces of demolding A base material with excellent properties [Figure 1: (2) of (a1-1) and (2)' of (a1-2)] and a piece of base material used to set the weir [Figure 1: (a1-1) ( 3)] Example of a forming mold composed of. Figure 1(a2) is composed of two pieces of base material [(1) and (1)' of Figure 1(a2)], and one piece of base material used to set the weir [(3) of Figure 1(a2) ] Example of a forming mold composed of.

The base material for setting up the weir [Figure 1: (3) of (a1-1)] preferably has a shape in which the upper part has a hole portion for injecting the composition, as shown in Figure 1 [Figure 1: (3-1) of (a1-1)]. The base material used for setting the weir can include various materials, polysilicone rubber, etc.

Specific examples of (a1-1) and (a1-2) in Figure 1 include a molding consisting of two sheets of glass as base materials, two sheets of films subjected to release treatment, and one base material for providing a weir. mold. Laminate the release-treated film [(2) of Figure 1: (a1-1)] on the glass [(1) of Figure 1: (a1-1)], and laminate it to form the base of the weir. The material [Figure 1: (3) of (a1-1)] is used to make a weir (spacer). Further, the release-treated film [(2)' of Figure 1: (a1-2)] is laminated thereon, and glass [(1)' of Figure 1: (a1-2)] is laminated thereon, And made into a forming mold.

A specific example of (a2) in Figure 1, for example, when release-treated glass or metal is used as the base material [(1) and (1)' of Figure 1: (a2)], the cured product has excellent release properties. , therefore there is no need for the two release-treated films in (a1-1) or (a1-2) of Figure 1 . In addition, when the cured product of the composition itself has excellent mold releasability, glass may be used as the base material [(1) and (1)' in Figure 1: (a2)]. An example in which the cured product of the composition itself has excellent mold releasability includes blending a mold release agent into the composition.

6-1-2. Pretreatment of the composition When applying or injecting the composition of the present invention, in order to prevent foreign matter from being mixed into the resin sheet obtained, to prevent the occurrence of defects such as voids, or to produce a product with excellent optical properties, The composition is preferably one in which the raw material components are stirred and mixed and then refined. As for the purification method of the composition, the method of filtering the composition is simple and suitable. Examples of filtration methods include pressure filtration and the like. The filtration precision is preferably below 10 μm, preferably below 5 μm. The smaller the filtration precision, the better. From the viewpoint of suppressing filter clogging, reducing filter replacement frequency, and productivity, the lower limit is preferably 0.1 μm.

When producing a resin sheet, in order to prevent bubbles from being contained in the cured product, it is preferable to blend each component and then perform a defoaming treatment. Examples of defoaming treatment methods include degassing by standing, vacuum reduction, centrifugal separation, cyclone (rotation, revolution mixer), gas-liquid separation membrane, ultrasonic wave, pressure vibration, and multi-axis extruder.

6-1-3. When coating or injecting a coating composition onto a base material, the coating method can be appropriately set according to the purpose. Examples of the coating composition include rod coaters, spreaders, scrapers, and conventionally known methods. Coating methods include blade coaters, comma blade coaters, reverse roll coaters, die coaters, lip coaters, gravure coaters and micro-gravure coaters. When the composition is injected into a base material having a space, a method in which the composition is put into an injection machine or injection device such as a syringe and then injected is included.

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

6-1-4. Heating: When a thermosetting composition is used as the composition, the heating method includes a method of immersing in a heat medium bath such as heat or oil, a method of using hot calendaring, and a method of maintaining a temperature-controlled constant temperature. Methods in the tank, etc. During heating, conditions such as heating temperature may be appropriately set according to the composition, base material, purpose, etc. used. The heating temperature is preferably 40 to 250°C. The heating time can be set appropriately according to the composition used, the target resin sheet, etc., and an example is 3 hours or more. Considering economy, the upper limit of heating time is preferably less than 24 hours. In addition, the heating temperature can be changed according to the purpose. Examples include the case of using thermal polymerization initiators with different decomposition temperatures, the case of solving the hardening deformation of the obtained resin sheet, and the like. Specific examples of the temperature include a method of polymerizing at a relatively low temperature of about 40 to 80° C. for several minutes to several hours, and then polymerizing at a relatively high temperature of 100° C. or higher for several hours. According to this heating method, the hardening deformation of the obtained resin sheet can be resolved, and a resin sheet excellent in various mechanical properties such as rupture strain can be obtained.

6-2. Use of resin sheet The resin sheet produced from the composition of the present invention is particularly suitable for use as an optical sheet. Optical sheets formed from the composition of the present invention can be used in various optical applications. More specifically, sheets used in liquid crystal display devices such as polarizing plate protective films, supporting films for polarizing plates, and light guide films, or touch panel integrated liquid crystal display devices, and various functional films (such as hard films, etc.) can be exemplified. Coated sheets, decorative sheets, transparent conductive sheets) and sheets with surface shapes (such as moth-eye anti-reflective sheets or sheets with texture structures for solar cells), base sheets for outdoor use such as solar cells Light-resistant (weather-resistant) sheets, films for LED lighting and organic EL lighting, transparent heat-resistant sheets for flexible electronic components, etc.

The optical sheet formed from the composition of the present invention has excellent heat resistance and is therefore suitable for use in the production of transparent conductive sheets. The composition used for this purpose is preferably a solvent-free composition that does not contain an organic solvent, from the viewpoint of suppressing the generation of fugitive gas during vacuum film formation of the transparent conductive layer. In addition, the optical sheet of the present invention has excellent heat resistance even if it is a thick film, is flexible, and has high strength. Therefore, it can also be used as a transparent conductive sheet base material for OPS. In this case, it is more suitable Use optical sheets with a film thickness of 0.5 mm or more and 1.5 mm or less.

The transparent conductive sheet may be manufactured according to a common method. Examples of metal oxides that form the transparent conductor layer include indium oxide, tin oxide, zinc oxide, titanium oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. , titanium-niobium composite oxide, etc. Among these, indium-tin composite oxide and indium-zinc composite oxide are preferred from the viewpoint of environmental stability or circuit processability. The method of forming the transparent conductor layer may be any ordinary method, and examples thereof include a method of forming the transparent conductor layer by a sputtering method using the optical sheet of the present invention, the aforementioned metal oxide, and a vacuum film forming apparatus. More specifically, the above-mentioned metal oxide is used as a target material, and after dehydration and degassing, exhaust is generated to create a vacuum, and the optical sheet reaches a predetermined temperature, and then a sputtering device is used to form a transparent conductor layer on the optical sheet. methods etc. Example

Examples and comparative examples are disclosed below to explain the present invention more specifically. In addition, the following "part" means parts by weight, and "%" means % by weight.

1. Examples 1 to 3, Comparative Examples 1 to 3 1) Preparation of thermosetting composition The components (A), (B) and (D) shown in the following Table 1 and Table 2 were prepared according to the following Table 1 and the ratio shown in Table 2. After stirring and mixing, defoaming under vacuum. In addition, in the following description, the ratio of the methacryl group in 100 mol% of the total amount of ethylenically unsaturated groups is expressed as "methacryl group ratio".

[Table 1]

[Table 2]

In addition, the abbreviations in Table 1 and Table 2 mean the following items. (A) Component･M-315: Di- and triacrylates of ethylene oxide triisocyanate adduct, ARONIX M-315 manufactured by Toagosei Co., Ltd. (B) Component･NDDA: 1,9-nonen Alkane diacrylate, VISCOAT #260 manufactured by Osaka Organic Chemical Industry Co., Ltd. ･NDDMA: 1,9-nonane dimethacrylate, NOD-N manufactured by Shin Nakamura Chemical Industry Co., Ltd. ･TMP-MA: Trimethylol Trimethylolpropane trimethacrylate, manufactured by Kyeisha Chemical Co., Ltd., "Light Ester TMP･M-309: Trimethylolpropane triacrylate, ARONIX M-309 (D) made by Toa Gosei Co., Ltd. Ingredients･ BPO: tert-butyl peroxy-2-ethylhexanoate, Perbutyl O manufactured by NOF Co., Ltd.

2) Production of resin sheet: The molding die shown in (a2) of Fig. 1 was used as a molding die for producing the resin sheet. Use two glass plates [80mm×80mm, thickness 3mm] and one polysilicone plate (thickness 1.0mm). In addition, a glass plate subjected to a mold release treatment using a polysiloxane compound is used. A spacer is produced by laminating a polysilicone plate [Fig. 1 (a2): (3)] on a glass plate [Fig. 1 (a2): (1)]. Further, a glass plate is laminated thereon [(a2): (1)' in Fig. 1] to prepare a forming mold.

The composition obtained above was injected with a syringe into the hollow portion of the polysilicone plate of the molding die [(a2) in Fig. 1: (3-1)]. The forming mold was placed in a drying furnace, heated at 60°C for 0.5 hours, and then heated to 120°C over 6 hours (heating rate: 10°C/time) to harden the composition. After cooling to room temperature, the glass is removed from the mold and demoulded to obtain a resin sheet.

3) Evaluation method For the obtained resin sheet, the average in-plane phase difference, yellowness index, bending elastic modulus, total light transmittance, drop weight test, and pencil hardness were evaluated according to the following method. The results are shown in Table 1 and Table 2.

(1) Average of in-plane phase difference The obtained resin sheet was used to measure the in-plane phase difference with a polarization measurement system (KAMAIRI manufactured by Photron Corporation), and the phase difference in the central part minus 5 mm from the edge was measured and the average value was obtained. .

(2) Yellowness index: Y.I. According to JIS K7375, the yellowness index (Y.I.) of a resin sheet with a thickness of 1 mm before and after heating in the air at 230° C. for 4 hours was measured.

(3) Bending elastic modulus: Cut out 5 test pieces of length 40 (mm) 25℃, 50%RH) and conduct a 3-point bending test. The average value of 5 test pieces was determined as the bending elastic modulus (GPa). In addition, it was observed that failure occurred at a strain of 1.2 times or more of the maximum stress strain, and the failure mode was regarded as ductile failure, and the following cases were regarded as brittle failure.

(4) Total light transmittance According to JIS K7375, the total light transmittance of a resin sheet with a thickness of 1 mm was measured.

(5) Drop weight test (50% impact damage height) A test piece of length 60 (mm) × width 60 (mm) was cut out from the obtained resin sheet, and the obtained resin sheet was placed on the On a metal ring with a diameter of 50 mm, a conical hammer with a tip diameter of 5 mm and a weight of 40 g is dropped from a predetermined height to the center of the resin molded body, and the height at which the probability of damage is 50% or more is recorded. The number of tests at each height is set to 10. (6) Pencil hardness: The surface hardness of the obtained resin sheet was measured based on JIS K-5600.

2. Comparative Examples 4 to 9 1) Production of photocurable composition: (A) and (B) components shown in Table 3 and Table 4 below, and the photopolymerization initiator 2-hydroxy- as other components 2-Methyl-1-phenyl-propan-1-one [Darocur 1173 manufactured by BASF Japan Co., Ltd., hereinafter referred to as "DC1173"] was blended according to the ratio shown in Table 3 and Table 4 below, and after stirring and mixing , defoaming under vacuum.

[table 3]

[Table 4]

In addition, the abbreviations in Table 3 and Table 4 mean the following items in addition to the items defined above. (B) Ingredients ･DCP-A: Dimethylol tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd., Light Acrylate DCP-A ･HBUA: Hexamethylene diisocyanate terpolymer and hydroxybutane Adducts of acrylic acid esters

2) Production of resin sheet: The molding die shown in (a2) of Fig. 1 was used as a molding die for producing the resin sheet. The composition obtained above was injected with a syringe into the hollow portion of the polysilicone plate of the molding die [(a2) in Fig. 1: (3-1)]. For the obtained molding die, an ultraviolet irradiation device (high-pressure mercury lamp) manufactured by EYE GRAPHICS Co., Ltd. was used from the glass plate side, and the illumination intensity was set to 130 mW/cm2 (UV-A, UV POWER manufactured by Fusion UV Systems Japan Co., Ltd. PUCK), exposed 20 times at a conveyor belt speed of 5m/min. At this time, the irradiation surface is reversed for each exposure. After cooling, the glass was removed from the mold, and the obtained hardened material was heated at 150° C. for 16 hours to obtain a resin sheet. 3) Evaluation method For the obtained resin sheet, the average in-plane phase difference, yellow index, bending elastic modulus, total light transmittance, drop weight test, and pencil hardness were evaluated in the same manner as above. These results are shown in Table 3 and Table 4.

3. Comparative Examples 10 and 11 1) Evaluation of commercially available resin sheets Commercially available polymethylmethacrylate [ACRYLITE L manufactured by Mitsubishi Rayon Co., Ltd., hereinafter referred to as "PMMA"] and polycarbonate [Mitsubishi Gas Iupilon NF-2000 manufactured by Chemical Co., Ltd., hereinafter referred to as "PC"], the average in-plane phase difference, yellow index, bending elastic modulus, total light transmittance, drop weight test and pencil hardness were evaluated in the same manner as above . These results are shown in Table 5.

[table 5]

4. Summary The resin sheets obtained from the compositions of Examples 1 to 3 were excellent in the average in-plane phase difference, yellowness index, bending elastic modulus, drop weight test, total light transmittance, and hardness. In contrast, the compositions of Comparative Examples 1 to 3 are thermosetting compositions containing components (A), (B), and (D), but do not contain methacrylate (methacryl group ratio is less than 20 Mol%), the average increase in the in-plane phase difference, that is, the deformation of the resin sheet. In addition, although the compositions of Comparative Examples 4 to 6 contain components (A) and (B), they are photocurable compositions and further do not contain methacrylate (methacrylyl group ratio is less than 20 mol%). ), the average increase in the in-plane phase difference, and the initial Y.I. value increases. Although the composition of Comparative Example 7 contains components (A) and (B), and the methacryl group ratio satisfies the range of the present invention, it is a photocurable composition, and the average in-plane retardation decreases after the initial and heating tests. The Y.I. value increases. In addition, the compositions of Comparative Examples 8 and 9 do not contain (A), are photocurable compositions, and further do not contain methacrylate (methacryl group ratio is less than 20 mol%), and the in-plane phase difference The average rise in Y.I. value rises initially and after the heating test. In particular, the Y.I. value of the composition of Comparative Example 9 containing urethane acrylate increased significantly initially and after the heating test. In addition, Comparative Example 10 is about commercially available PMMA, and the results of the drop weight test were lowered. In addition, Comparative Example 11 is about a commercially available PC, and the average in-plane retardation is significantly increased. Industrial availability

The composition of the present invention can be used in various applications, and is particularly suitable for use in the production of resin sheets. The obtained resin sheet can be used for various purposes and is suitably used as an optical sheet. The optical sheet is suitable for use in the manufacture of transparent conductive sheets, and is more suitable for use in the manufacture of transparent conductive sheets for touch panels.

(1)‧‧‧Substrate (1)'‧‧‧Substrate (2)‧‧‧Substrate with excellent releasability (2)'‧‧‧Substrate with excellent releasability (3)‧‧‧ The base material (3-1) for providing the weir has a hole for injecting the composition

FIG. 1 shows an example of a molding die used when producing a resin sheet using the composition of the present invention.

(1)‧‧‧Substrate

(1)'‧‧‧Substrate

(2)‧‧‧Substrate with excellent mold release properties

(2)'‧‧‧Substrate with excellent mold release properties

(3)‧‧‧The base material used to set up the weir

(3-1)‧‧‧Has a hole for injecting the composition

Claims (13)

A thermosetting composition containing the following (A) component, (B) component and (D) component, and optionally the following (C) component; when the total amount of (A) ~ (C) components is 100% by weight contains 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), and the ethylenic content of components (A) to (C) is not The total amount of saturated groups (100 mol%) includes 20 to 60 mol% of methacrylic groups; (A) Component: a compound with a trimeric isocyanate ring and two or more (meth)acrylyl groups; ( B) Component: a compound having two or more (meth)acrylyl groups and is a compound other than component (A), and it is a bisulfide containing a linear or branched alkylene group having 4 to 20 carbon atoms. (Meth)acrylate (B-1) compound; (C) component: a compound having one ethylenically unsaturated group; (D) component: thermal polymerization initiator. Such as the thermosetting composition of claim 1, wherein the aforementioned component (A) is a compound having a trimeric isocyanate ring and having two (meth)acrylyl groups or/and a compound having a trimeric isocyanate ring and having three (meth)acrylyl groups. base) acrylyl compound. The thermosetting composition of claim 1, wherein the component (B) includes di(meth)acrylate (B-1) having a linear alkylene group having 4 to 20 carbon atoms. The thermosetting composition of claim 1, wherein the component (B-1) is selected from the group consisting of 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. )acrylate, 1,9-nonanediol di(meth)acrylate and One or more types of the group consisting of neopentyl glycol di(meth)acrylate. The thermosetting composition of claim 1, wherein the component (B) contains a compound having three or more (meth)acrylyl groups. The thermosetting composition of claim 1, wherein the aforementioned components (A) to (C) do not contain compounds having urethane bonds. For example, the thermosetting composition of claim 1 contains 0.1 to 5 parts by weight of component (D) based on 100 parts by weight of the total amount of components (A) ~ (C). For example, according to the thermosetting composition of claim 1, the bending elastic modulus of the hardened material during the bending test is 2.5 GPa or more. For example, according to the thermosetting composition of claim 1, the total light transmittance of the cured product is above 90%. A thermosetting composition for producing resin sheets, including the composition according to any one of claims 1 to 9. A resin sheet composed of a hardened product of the composition of claim 10. For example, the thickness of the hardened resin sheet of claim 11 is 100 μm~5mm. A method of manufacturing a resin sheet is to pour the composition according to claim 10 into a mold and then heat it, and the mold is composed of a base material, a base material for forming a weir, and the base material in this order.