JP6493699B2 - Resin sheet and manufacturing method thereof - Google Patents

Description

The present invention relates to a curable composition for producing a resin sheet, and the resin sheet obtained from the composition can be preferably used for an optical substrate such as a liquid crystal display (LCD) and an organic EL, and is a resin sheet for forming a touch panel transparent conductive film. It 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, a touch panel integrated liquid crystal display device or a touch panel integrated organic EL display device is often 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, but it is possible because the base material is glass. Poor flexibility and workability. Therefore, a transparent conductive sheet based on a polyethylene terephthalate sheet is used depending on applications because of its advantages such as excellent flexibility, workability, impact resistance, and light weight.

  On the other hand, since it is expected to contribute to reducing the thickness and weight of the touch panel, improving the transmittance, and reducing the cost of components, a cover-integrated touch panel that directly forms a touch sensor such as ITO on the cover glass, so-called OGS (One Glass) (Solution) is partially adopted. However, the OGS type has a problem that the touch panel cannot be operated if the cover glass is broken.

  Thus, as a cover material having excellent impact resistance, a so-called OPS (One Plastic Solution) in which a touch sensor such as ITO is directly formed on a resin sheet has been proposed. However, conventional acrylic and polycarbonate sheets are easily scratched because of their low surface hardness, and the toughness may be insufficient and may be broken by an external impact force.

In patent document 1, the plastic member for transparent conductive film formation obtained by photocuring the photocurable composition containing the bismethacrylate which has alicyclic skeleton, and a mercapto compound is disclosed.
However, blending a mercapto compound gives moderate toughness to the cured product, but there is a problem that the pot life of the composition is shortened, and the surface hardness and scratch resistance are also reduced. There was also a problem of doing.

In Patent Document 2, it is obtained by photocuring a photocurable composition containing a polyfunctional urethane (meth) acrylate having an alicyclic structure, a bifunctional (meth) acrylate having an alicyclic structure, and a photopolymerization initiator, A transparent resin molded body having a thickness of 50 to 500 μm is disclosed.
However, since the same rigidity as glass cannot be exhibited, there is a problem that appearance defects occur in the heating step in the transparent conductive film or metal electrode formation process.

  As described above, a resin sheet having satisfactory physical properties as an OPS resin has not been found so far, and it is particularly difficult to achieve both hardness and toughness, and scratch resistance is insufficient.

JP 2002-161113 A JP 2007-56180 A

  The present inventors have conducted intensive studies to find a curable composition in which the obtained resin sheet is excellent in hardness and bending properties.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing di (meth) acrylate having a specific carbon number can solve the above problems, and completes the present invention. It came to.

The present invention is a composition comprising the following components (A) and (B), in which the total amount of the components (A) and (B) is 100% by weight, the component (A) is 5 to 70% by weight, and (B) 95 to 30 wt% viewing including the component,
Component (B) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups is added in a total amount of 100 weights of components (A) and (B). a cured product of including resin sheet for producing curable composition in a proportion of more than 20% by weight in%
The cured product has a thickness of 100 μm to 5 mm .
Component (A): One or more selected from the group consisting of the following components (A1) and (A2)
Component (A1): di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms
Component (A2): Poly (alkylene glycol) di (meth) acrylate, wherein the total number of carbon atoms constituting the polyoxyalkylene group is 4 to 20 (B) Component: an ethylenically unsaturated group A compound other than the component (A)

As the component (A1), 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and neopentyl glycol di (meth) One or more selected from acrylates are preferred.
The component (A2) is preferably at least one selected from polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate.

The component (B) preferably includes a compound having 3 or more (meth) acryloyl groups. Furthermore, in the present invention, (B) as a component, a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate is preferably a compound having three or more (meth) acryloyl group, the compound (A It is intended to include at a ratio of more than 20% by weight) and (B) in the total amount 100% by weight of component.

  As the composition, a composition further containing a photopolymerization initiator (D) and / or a thermal polymerization initiator (E) is preferable.

As a hardened | cured material of a composition, the thing whose pencil hardness is 3H or more is preferable.
As a resin sheet which consists of a hardened | cured material of a composition, the thing whose thickness of hardened | cured material is 100 micrometers-5 mm is preferable.

As a method for producing the resin sheet, after pouring the above-described composition into a molding die composed of a base material / base material for providing a base material / weir, an active energy ray is applied from any base material side. The production method of irradiating is preferable. Furthermore, the manufacturing method which heats after irradiating an active energy ray is more preferable.
Moreover, as a manufacturing method of a resin sheet, the manufacturing method which heats after pouring the above-mentioned composition in the shaping | molding die comprised with the base material / base material for providing a base material / weir is preferable.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, the obtained resin sheet is excellent in hardness and bending properties.
In addition, the resulting resin sheet is excellent in scratch resistance.

FIG. 1 is a diagram showing an example of a mold used when a resin sheet is produced using the composition of the present invention.

This invention is a composition containing (A) and (B) component, Comprising: In the total amount of 100 weight% of (A) and (B) component, (A) component is 5-70 weight%, and ( the B) component 95 to 30 wt% seen including,
Component (B) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups is added in a total amount of 100 weights of components (A) and (B). a cured product of including resin sheet for producing curable composition in a proportion of more than 20% by weight in%
The cured product has a thickness of 100 μm to 5 mm .
Hereinafter, the detail of each component and a composition is demonstrated.

1. (A) component (A) component is 1 or more types chosen from the group which consists of (A1) component and (A2) component.
The component (A1) 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.
Even in the case of a di (meth) acrylate having a linear or branched alkylene group, a compound having 3 or less carbon atoms has insufficient hardness and scratch resistance of the cured product, while the number of carbon atoms is not sufficient. The compound of 21 or more will reduce the rigidity and heat resistance of the cured product.
The divalent linear alkylene group having 4 to 20 carbon atoms in the component (A1) includes 1,4-butylene group, 1,6-hexylene group and 1,9-nonylene group having bonds at both ends. preferable.
Specific examples of the compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate.

As the divalent branched alkylene group having 4 to 20 carbon atoms in the component (A1), a neopentyl group (2-methyl-2methyl-1,3-propylene group) having a bond at both ends, 2-methyl- A 1,3-propylene group and an isobutylene group having a polymerization degree of 5 or less are preferred.
Specific examples of the compound include neopentyl glycol di (meth) acrylate, and are most preferably used.

Among these compounds, (A1) component is 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and neopentyl. One or more selected from glycol di (meth) acrylate is preferred.
Among these compounds, the component (A1) is more preferably at least one selected from 1,6-hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate.

The component (A2) is a polyalkylene glycol di (meth) acrylate, and is a di (meth) acrylate having a total of 4 to 20 carbon atoms constituting the polyoxyalkylene group.
Even in the case of polyalkylene glycol di (meth) acrylate, a compound having a total of 3 or less carbon atoms constituting the polyoxyalkylene group has insufficient hardness and scratch resistance of the cured product, whereas carbon A compound having a number of 21 or more decreases the rigidity and heat resistance of the cured product.
As an example of the total number of carbon atoms constituting the polyoxyalkylene group in component (A2) being 4 to 20, the number of repeating oxyethylene units is 2 to 6, and the number of repeating oxypropylene units is 2 to 6. Examples thereof include 2 to 5 polyoxypropylene groups, oxybutylene groups, and polyoxybutylene groups having 2 to 4 repeating oxybutylene units. The oxypropylene units, -OCH ₂ CH ₂ CH ₂ - and -OCH ₂ CH (CH ₃₎ - either _{good, -OCH 2 CH (CH 3)} - are preferred.

  Specific examples of the component (A2) 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 (meth) acrylate Etc.

Among these compounds, the component (A2) is preferably at least one selected from polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) acrylate.
Among these compounds, the component (A2) is more preferably one or more selected from polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate.

  As the component (A), only one of the above-described components (A1) and (A2) may be used, or two or more may be used in combination.

2. Component (B) The component (B) is a compound having an ethylenically unsaturated group, and is a compound other than the component (A).
Examples of the ethylenically unsaturated group in component (B) include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and a (meth) acryloyl group is preferred.

The component (B) includes a compound having one ethylenically unsaturated group [hereinafter referred to as “monofunctional unsaturated compound”] and a compound having two or more ethylenically unsaturated groups [hereinafter referred to as “polyfunctional unsaturated group”. Compound ”and the like.
Hereinafter, each compound will be specifically described.

2-1. Monofunctional unsaturated compound Examples of the monofunctional unsaturated compound include compounds having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”).

  Specific examples of the monofunctional (meth) acrylate 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 ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Rate, 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 mol adduct) (meth) acrylate, p-cumylphenol ethylene oxide adduct (1 to 4 mol adduct) (meth) acrylate, phenyl (meth) acrylate, о-Phenylphenyl (meth) acrylate, p-cumylphenyl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxyethyl tetrahydrophthalimi Etc. The.

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

Examples of the compound having a hydroxyl group include (meth) acrylate 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-alkyl such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nt-butyl (meth) acrylamide. Acrylamide;
N, N-dialkylacrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide;
N-alkoxyalkyl such as N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide ( And (meth) acryloylmorpholine.

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

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

2-2. Polyfunctional unsaturated compound As the polyfunctional unsaturated compound, a compound having two (meth) acryloyl groups [hereinafter referred to as "bifunctional (meth) acrylate". Hereinafter, a compound having three or more (meth) acryloyl groups is represented in the same manner as “◯ functional (meth) acrylate”. ] Is a bifunctional (meth) acrylate 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 other than the component (A) such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate;
Hydroxypivalate neopentyl glycol di (meth) acrylate;
A bifunctional (meth) acrylate having an alicyclic skeleton such as dimethylol tricyclodecane di (meth) acrylate, cyclohexanedimethanol 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.

Examples of the polyfunctional (meth) acrylate include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and polyether (meth) acrylate other than the above.
Hereinafter, these compounds will be described.

2-2-1. As the urethane (meth) acrylate polyfunctional (meth) acrylate, urethane (meth) acrylate [hereinafter referred to as “component (B1)”], which is a compound having a urethane bond and having two or more (meth) acryloyl groups. preferable.
Component (B1) includes a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “(B1-1) component”), and a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate. [Hereinafter referred to as “component (B1-2)”] and the like.
Hereinafter, the component (B1-1) and the component (B1-2) will be described.

1) Component (B1-1)
The component (B1-1) is a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate.

As the polyol in the component (B1-1), a diol is preferable.
As the diol, a low molecular weight diol, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferable.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and the like.
Examples of the diol having a polyester skeleton include an esterification reaction product of a diol component such as the low molecular weight diol or polycaprolactone diol and an acid component such as dicarboxylic acid or an anhydride thereof.
Examples of the dicarboxylic acid or anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polyetramethylene glycol.
Examples of the polycarbonate diol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.

Examples of organic polyisocyanates include aliphatic polyisocyanates having no alicyclic groups (hereinafter simply referred to as “aliphatic polyisocyanates”), aliphatic polyisocyanates having alicyclic groups (hereinafter referred to as “alicyclic polyisocyanates”). And polyisocyanates having aromatic rings and aromatic polyisocyanates.
Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic polyisocyanate include hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and isophorone diisocyanate trimer. It is done.
Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.
In the present invention, the organic polyisocyanate is preferably an aliphatic polyisocyanate from the viewpoints of excellent physical properties of the cured product and little yellowing.

As the hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing mono (meth) acrylate is preferable.
Examples of the hydroxyl group-containing mono (meth) acrylate include 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.

2) Component (B1-2)
The component (B1-2) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and is a compound called a urethane adduct.
As the component (B), it is preferable to use the component (B1-2) because the crosslinking density is increased and the heat resistance is improved.

  In the component (B1-2), examples of the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate include the compounds described above.

In the component (B1-2), a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter referred to as “hydroxyl group-containing polyfunctional (meth) acrylate”) is used as the hydroxyl group-containing (meth) acrylate. You can also.
As the component (B1-2), the use of the organic polyisocyanate and the hydroxyl group-containing polyfunctional (meth) acrylate (hereinafter referred to as “(B1-2-1) component”) increases the crosslink density and is heat resistant. In addition to improving the properties, it is preferable because it is excellent in hardness, abrasion resistance and scratch resistance.
As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, specifically, trimethylolpropane di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, ditrimethylolpropane di- or tri- Examples include (meth) acrylate and dipentaerythritol di, tri, tetra, or penta (meth) acrylate.
Among these, a compound having three or more (meth) acryloyl groups and one hydroxyl group is preferable in that the cured film is excellent in hardness, abrasion resistance and scratch resistance. Examples include erythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
Among these compounds, pentaerythritol tri (meth) acrylate is more preferable because it can prevent warpage of the resulting cured product.

In the production of the component (B1-2-1), the raw material hydroxyl group-containing polyfunctional (meth) acrylate is usually a mixture containing a hydroxyl group-containing polyfunctional (meth) acrylate and a polyfunctional (meth) acrylate having no hydroxyl group. However, what was manufactured using the said mixture can also be used as (B1-2-1) component.
Specifically, a mixture of trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate, a mixture of ditrimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol penta And a mixture of (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Another preferred compound of the component (B1-2) is a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing mono (meth) acrylate [hereinafter referred to as “(B1-2-2) component”. ].
Examples of the hydroxyl group-containing mono (meth) acrylate in the component (B1-2-2) include the same compounds as those described above.
Examples of the organic polyisocyanate having three or more isocyanate groups include the aforementioned hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.
Preferable examples of the component (B1-2-2) include addition reaction products of hexamethylene diisocyanate trimer and hydroxybutyl acrylate.

Further, the component (B1-2) is more preferably a compound which is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate and has three or more (meth) acryloyl groups. The said compound maintains a rigidity with high toughness simultaneously with the crosslinking density of hardened | cured material.
Examples of the compound include the components (B1-2-1) and (B1-2-2) described above.

3) Production method of component (B1)
Component (B1) is an addition reaction of polyol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate in component (B1-1), and organic polyisocyanate and hydroxyl group-containing (meth) acrylate in component (B1-2) It is produced by the addition reaction of
Although this addition reaction can be performed without a catalyst, a tin-based catalyst such as dibutyltin dilaurate, an amine-based catalyst such as triethylamine, or the like may be added in order to advance the reaction efficiently.

2-2-2. Polyester (meth) acrylate Polyester (meth) acrylate includes a dehydration condensate of polyester diol and (meth) acrylic acid.
Here, examples of the polyester diol include a reaction product of a diol and a dicarboxylic acid or an anhydride thereof.
Diols include 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 Examples thereof include low molecular weight diols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and 1,6-hexanediol, and alkylene oxide adducts thereof.
Examples of the dicarboxylic acid or its anhydride include orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, and these An anhydride etc. are mentioned.

2-2-3. Epoxy (meth) acrylate Epoxy (meth) acrylate is a compound obtained by adding (meth) acrylic acid to an epoxy resin. Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

  Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether, hydroquinone diglycidyl ether; diglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or alkylene oxide adducts thereof; phenol novolac type epoxy resin and Examples thereof include novolak type epoxy resins such as cresol novolac type epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.

Specific examples of the aliphatic epoxy resin 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. Diglycidyl ethers of polyalkylene glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; diglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; tetrahydrophthalic acid diglycidyl esters, etc. Is mentioned.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.

2-2-3. Polyether (meth) acrylate Polyether (meth) acrylate oligomers include polyalkylene glycol (meth) diacrylates, including polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meta). ) Acrylate and the like.

2-3. As the general component (B), only one of the above-described compounds may be used, or two or more may be used in combination.

As the component (B), among the above-mentioned compounds, a trifunctional or higher functional (meth) acrylate is preferable, and an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate are more preferable because of excellent rigidity and heat resistance of the cured product. And a compound having 3 or more (meth) acryloyl groups.
When (B) component contains trifunctional or higher functional (meth) acrylate, it is preferable to contain 20% by weight or more in component (B). Further, the trifunctional or higher functional (meth) acrylate preferably contains 20% by weight or more in 100% by weight of the total amount of the components (A) and (B).
The monofunctional (meth) acrylate is a monofunctional (meth) acrylate having an alicyclic skeleton such as isobornyl (meth) acrylate, and the bifunctional (meth) acrylate is dimethylol tricyclodecanedi (meth). Bifunctional (meth) acrylates having an alicyclic skeleton such as acrylate, cyclohexanedimethanol di (meth) acrylate and spiroglycol di (meth) acrylate are preferred.

3. The curable composition for producing a resin sheet The present invention is a composition containing the components (A) and (B), and the components (A) and (B) (hereinafter collectively referred to as “curable components”). It is related with the curable composition for resin sheet manufacture which contains 5-70 weight% of (A) component and 95-30 weight% of (B) component in the total amount of 100 weight%.
When the content ratio of the component (A) is less than 5% by weight or the content ratio of the component (B) exceeds 95% by weight, the scratch resistance of the cured product becomes insufficient. On the other hand, when the content ratio of the component (A) exceeds 70% by weight or the content ratio of the component (B) is less than 30%, rigidity and heat resistance are insufficient.
As a content rate of (A) and (B) component, 10 to 50 weight% and 90 to 50 weight% are respectively preferable with respect to a total of 100 weight% of a sclerosing | hardenable component.

  As a manufacturing method of a composition, what is necessary is just to follow a conventional method, for example, it can manufacture by stirring and mixing (A) and (B) component and another component as needed.

What is necessary is just to set the viscosity of a composition suitably according to the objective, and 50-10,000 mPa * s is preferable.
In the present invention, the viscosity means a value measured at 25 ° C. using an E-type viscometer.

  The composition of the present invention can be used as an active energy ray-curable composition and a thermosetting composition.

The composition of the present invention comprises the components (A) and (B) as essential components, but various components can be blended depending on the purpose.
As other components, specifically, a photopolymerization initiator (hereinafter referred to as “component (C)”), a thermal polymerization initiator (hereinafter referred to as “component (D)”), an organic solvent, a plasticizer, a polymerization Inhibitors and / or antioxidants, light resistance improvers, and compounds having two or more mercapto groups (hereinafter referred to as “polyfunctional mercaptan”) and the like can be mentioned.
Hereinafter, these components will be described. In addition, the component mentioned later may be used only 1 type, and may use 2 or more types together.

3-1. Other ingredients
1) Component (C) The component (C) is a photopolymerization initiator.
(C) A component is a component mix | blended when an ultraviolet-ray and visible light are used as an active energy ray. When an electron beam is used as the active energy ray, it is not always necessary to add it, but a small amount can be added as necessary in order to improve curability.

Component (C) includes benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] Propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) )] Phenyl] -2-morpholinopropan-1-one, 2 Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 -Aromatic ketone compounds such as ON, Adekaoptomer N-1414 (manufactured by ADEKA), phenylglyoxylic acid methyl ester, ethyl anthraquinone, phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis ( Benzophenone compounds such as diethylamino) benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone ;
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2, Acylphosphine oxide compounds such as 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy]- Thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone, 10-butyl-2-chloroacridone;
1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Oxime esters such as -1- (O-acetyloxime);
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 2,4,5-triarylimidazole such as 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Dimer; and acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

  As the component (C), in addition to the above, a photopolymerization initiator having a molecular weight of 350 or more can be used. The photopolymerization initiator having a molecular weight of 350 or more does not cause coloring of the resin sheet obtained by the decomposed product after light irradiation, and the decomposed product is a vacuum of the transparent conductor layer when used for the production of a transparent conductive film. Since no outgas is generated at the time of film formation, a high vacuum can be reached in a short time, and it is possible to prevent the film quality of the conductor layer from deteriorating and becoming difficult to reduce resistance.

As the component (C), various compounds can be used as long as they have a molecular weight of 350 or more and can be polymerized by light such as ultraviolet rays and visible rays.
Specific examples of the component (C) include hydroxyketone polymers, and examples include compounds represented by the following formula (1). The said compound is also preferable at the point which is excellent in compatibility with (A)-(C) component.

In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, and n represents a 2 to 5 number.
R ² is preferably a lower alkyl group such as a methyl group, an ethyl group and a propyl group as the alkyl group.

Specific examples of the compound represented by the formula (1) include oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone.
The compound is commercially available, and for example, ESACURE KIP 150 (manufactured by Lamberti) is known. ESACURE KIP 150 is a compound represented by the above formula (1), wherein R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, n is a 2-3 number, and [(204.3 × n + 16.0) or It is a compound having a molecular weight of (204.3 × n + 30.1)].

Examples of compounds other than the above include 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid.
The said compound is marketed and Irgacure 754 (made by BASF) is known. Irgacure 754 is a mixture of oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester.

(C) As a compounding ratio of a component, 0.01-10 weight part is preferable with respect to 100 weight part of total amounts of a sclerosing | hardenable component, More preferably, it is 0.1-5 weight part.
By setting the blending ratio of the component (C) to 0.01% by weight or more, the composition can be cured with an appropriate amount of ultraviolet light or visible light, and the productivity can be improved. By doing, it can be made the thing excellent in the weather resistance and transparency of hardened | cured material.

2) When the component composition (D) is used as a thermosetting composition, the component (D) (thermal polymerization initiator) can be blended.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.

  Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, dilauroyl peroxide, t-hexylperoxyisopropyl monocarbonate, t-butyl Peroxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyla Rate, t-butylperoxypivalate, t-hexylperoxypivalate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t- Butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 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 Di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexin-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, 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. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

(D) As a usage rate of a component, 10 weight part or less is preferable with respect to 100 weight part of sclerosing | hardenable component total amount.
When the thermal polymerization initiator is used alone, it may be carried out in accordance with conventional means of normal radical thermal polymerization. In some cases, the thermal polymerization initiator is used in combination with a photopolymerization initiator and photocured for the purpose of further improving the reaction rate. Curing can also be performed.

3) Organic solvent The composition of this invention can mix | blend an organic solvent for the objective of improving the coating property to a base material.
However, when using the obtained resin sheet 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, phorone, isophorone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc. Ketone solvents;
Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate, cellosolve acetate;
Examples include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and γ-butyrolactone.

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

4) A plasticizer can be added for the purpose of imparting flexibility to the cured plasticizer and improving brittleness.
Specific examples of the plasticizer include dialkyl phthalates such as dioctyl phthalate and diisononyl phthalate, dialkyl esters of adipic acid such as dioctyl adipate, phosphate esters such as sebacic acid ester, azelaic acid ester and tricresyl phosphate, polypropylene Examples thereof include liquid polyether polyols such as glycol, liquid polyester polyols such as polycaprolactone diol and 3-methylpentanediol adipate. Moreover, a soft acrylic polymer having a number average molecular weight of 10,000 or less can be used.
The blending ratio of these plasticizers may be set as appropriate, but is preferably 30 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the total of the curable components.
By setting it to 30 parts by weight or less, the strength and heat resistance can be improved.

5) Polymerization inhibitor or / and antioxidant To the composition of the present invention, a polymerization inhibitor or / and an antioxidant can be added in order to improve storage stability.
As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable. A secondary antioxidant or the like can also be added.
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 with respect to 100 parts by weight of the total amount of the curable components.

6) Light resistance improver A light resistance improver such as an ultraviolet absorber or a light stabilizer may be added to the composition of the present invention.
Examples of the ultraviolet absorber include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 Benzotriazole compounds such as'-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 Examples include benzophenone compounds such as'-dihydroxy-4,4'-dimethoxybenzophenone.
Examples of the light stabilizer include N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N′-diformylhexamethylenediamine, bis (1,2,6,6). -) Pentamethyl-4-piperidyl) -2- (3,5-ditertiarybutyl-4-hydroxybenzyl) -2-n-butylmalonate, 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′-diformylhexamethylenediamine, bis (1,2 Hindered amine light stabilizers such as high molecular weight hindered amine compounds such as 2,6,6-pentamethyl-4-piperidinyl) sebacate.
The blending ratio of the light fastness improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable component.

7) Polyfunctional mercaptan Polyfunctional mercaptan can be blended as needed for the purpose of preventing curing shrinkage of the composition cured product and imparting toughness.
As the 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 making this ratio 20 parts by weight or less, it is possible to prevent the heat resistance and rigidity of the obtained cured product from being lowered.

8) Other components other than the above In addition to the above-described other components , a release agent, a filler, a soluble polymer, and the like can be blended in the composition of the present invention.
The mold release agent is blended for the purpose of facilitating mold release from the base material. As the mold release agent, various surfactants can be used as long as they can be released from the base material and the mixed solution and the cured product are not turbid. For example, anionic surfactants such as alkylbenzene sulfonic acid, cationic surfactants such as alkyl ammonium salts, nonionic surfactants such as polyoxyethylene alkyl ether, amphoteric surfactants such as alkylcarboxybetaine, and fluorine and silicon And surfactants to be included.
The filler is blended for the purpose of improving the mechanical properties of the resulting resin sheet. As the filler, both inorganic compounds and organic compounds can be used. Examples of the inorganic compound include silica and alumina. A polymer can be used as the organic compound. As the filler, when the resin sheet obtained from the composition of the present invention is used as an optical application, a filler that does not deteriorate optical properties is preferable.
A soluble polymer is mix | blended in order to improve the mechanical property of the resin sheet obtained. The soluble polymer means a polymer that dissolves in the composition. In the present invention, a polymer that does not dissolve in the composition is referred to as a filler 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 with respect to 100 parts by weight of the curable component.

3-2. Cured material properties As a physical property of the cured product of the composition in the present invention, the pencil hardness is 3H or more.
The pencil hardness is preferably 5 or more, more preferably 7 or more.
In addition, the pencil hardness in this invention means the value measured by the method according to JIS K-5600.

Moreover, as a physical property of the hardened | cured material of the composition in this invention, that whose elasticity modulus in a bending test is 1 GPa or more and whose maximum distortion is 2% or more is preferable. What the cured | curing material of a composition has the said elasticity modulus becomes excellent in rigidity, and what has the said maximum distortion becomes toughness.
The elastic modulus in the bending test in the present invention means a value calculated from a stress of 0.1% and 1% in a bending test performed at a distance between supporting points of 30 mm and a bending speed of 0.2 mm / min.
Moreover, the maximum strain in the present invention means a strain in which the stress shows a maximum value in the same test.

As a glass transition temperature (henceforth "Tg") of the hardened | cured material of a composition, 0-250 degreeC is preferable, More preferably, it is 20-230 degreeC. By setting Tg to 0 ° C. or higher, the resulting resin sheet is excellent in rigidity and heat resistance, and by setting it to 250 ° C. or lower, toughness can be maintained.
In the present invention, Tg means a temperature at which the tensile loss coefficient tan δ in the dynamic viscoelastic spectrum measured in the tensile mode is 1 Hz, the temperature rise temperature is 2 ° C./min, and the maximum.

3-3. The film thickness of the resin sheet may be set as appropriate according to the purpose, but is in the range of 100 μm to 5 mm .
When using for glass substitute uses, such as OPS especially, 100 micrometers-5 mm are preferable, More preferably, they are 200 micrometers-3 mm, Especially preferably, they are 300 micrometers-2 mm.

4). Manufacturing method of resin sheet As a manufacturing method of the resin sheet using the composition of the present invention, various methods can be adopted.
Specifically, when using an active energy ray hardening-type composition as a composition, the following four manufacturing methods are mentioned, for example.
1) Manufacturing method 1-1
A method of curing a composition by applying the composition to a substrate and irradiating with active energy rays
2) Manufacturing method 1-2
A method of curing a composition by applying an active energy ray after applying the composition to a substrate and bonding it to another substrate
3) Manufacturing method 1-3
Method of pouring a composition into a substrate having a space and curing the composition by irradiation with active energy rays
4) Manufacturing method 1-4
The composition is poured into a base material having a space and bonded to another base material, and then the composition is cured by irradiating with active energy rays. In the case of these production methods, heating may be performed after irradiating active energy rays. it can.
When the resin sheet obtained from the composition of the present invention is used for glass replacement, the above production method 1-4 is preferable.

When using a thermosetting composition as a composition, the following four manufacturing methods are mentioned, for example.
5) Manufacturing method 2-1
Method of applying composition to substrate and heating to cure the composition
6) Manufacturing method 2-2
A method in which a composition is applied to a substrate and bonded to another substrate, and then heated to cure the composition.
7) Manufacturing method 2-3
A method of pouring a composition into a substrate having a space and curing the composition by heating
8) Manufacturing method 2-4
A method in which a composition is poured into a base material having a space and pasted with another base material, and then the composition is heated to harden the composition. When the resin sheet obtained from the composition of the present invention is used in a glass substitute application The above production method 2-4 is preferable.
As the polymerization method, either a batch method or a continuous method can be adopted.
Examples of the continuous type include a method of continuously supplying a belt-like base material as a base material to which the composition is applied or poured.

As another example of the continuous type, there is a method called a continuous casting method in addition to the above. That is, two continuous mirror surface stainless steel belts are arranged in a caterpillar shape, and the composition is poured between the belts. Polymerization is performed continuously between the belts while slowly moving the belts. Examples include a method for producing a sheet.
In the glass substitute application, the batch type is preferable.

4-1. As the base material , any of a peelable base material and a base material having no releasability (hereinafter referred to as “non-releasable base material”) can be used.
Examples of the peelable substrate include metal, glass, a release-treated film, and a surface untreated film having peelability (hereinafter, collectively referred to as “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 make the resin sheet obtained from the composition of the present invention have a low haze or provide surface smoothness, the surface roughness (centerline average roughness) Ra is 0.15 μm or less as a peelable substrate. It is preferable to use a base material of 0.001 to 0.100 μm. Furthermore, the haze is preferably 3.0% or less.
Specific examples of the substrate include glass, untreated surface polyethylene terephthalate film, untreated surface 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 an average roughness.

  Examples of the non-releasable substrate include various plastics other than the above, cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resin, polyester, polycarbonate, polyarylate, polyethersulfone, norbornene and the like And cyclic polyolefin resins having a cyclic olefin as a monomer.

As a base material which has a space part, the base material which has a recessed part is mentioned. An example is one in which a hole having a predetermined shape with a desired film thickness is formed in the release material, and a recess is formed.
In this case, after pouring the composition into the substrate having a recess, another substrate can be stacked on the substrate having the recess.
As another example of the base material having a space portion, a material provided with a weir (spacer) on the mold release material so that the cured product has a desired film thickness (hereinafter referred to as “molding die”), and the like can also be mentioned. . In this case, another base material can be stacked on the weir.
As the release material in this case, glass and glass subjected to release treatment are preferable.

FIG. 1 will be described as an example of the mold.
(A1-1) and (a1-2) in FIG. 1 show two substrates [FIG. 1: (1) in (a1-1) and (1) ′ in (a1-2)] Base material excellent in releasability [FIG. 1: (2) of (a1-1) and (2) ′ of (a1-2)] and base material for providing one weir [FIG. 1: (a1- This is an example of a mold composed of (1) (3)].
(A2) in FIG. 1 shows two substrates [FIG. 1: (1) and (1) ′ in (a2)] and a substrate for providing one weir [FIG. 1: (a2)] (3)].

  As shown in FIG. 1, the base material for providing the weir [FIG. 1: (3) in (a1-1)] preferably has a shape having a hole for injecting the composition at the top [FIG. 1: (3-1) of (a1-1)]. As a base material for providing the weir, various materials can be used, and silicone rubber can be exemplified.

As a specific example of (a1-1) and (a1-2) in FIG. 1, it is composed of two substrates as a substrate, two release-treated films, and a substrate for providing one weir. Molds that can be used.
On top of the glass (Fig. 1: (a1-1) (1)), the release-treated film [Fig. 1: (a1-1) (2)] is stacked, and a weir is provided on it. The base material (FIG. 1: (a1-1) (3)) is used as a stack weir (spacer). Furthermore, a film (FIG. 1: (2) ′ of (a1-2)) which has been subjected to release treatment is overlaid thereon, and glass [FIG. 1: (1) ′ of (a1-2)] is overlaid thereon. Use a mold.

A specific example of (a2) in FIG. 1 is a case of using a release-treated glass or metal as a base material [(1) and (1) ′ in FIG. 1: (a2)], and a cured product. Therefore, it is not necessary to use the two release processed films in (a1-1) and (a1-2) of FIG.
Further, when the cured product of the composition itself is excellent in releasability, glass can also be used as a substrate [(1) and (1) ′ in FIG. 1: (a2)]. An example in which the cured product of the composition is excellent in releasability includes an example in which a release agent is blended with the composition.

4-2. Pre-treatment of the composition Upon application or injection of the composition of the present invention, as the composition, the obtained resin film can be prevented from introducing foreign substances, preventing defects such as voids, or having excellent optical properties. Therefore, it is preferable to use a purified product after stirring and mixing the raw material components.
As a method for purifying the composition, a method of filtering the composition is simple and preferable. Examples of the filtration method include pressure filtration.
The filtration accuracy is preferably 10 μm or less, more preferably 5 μm or less. The lower the filtration accuracy, the better. However, if the filter accuracy is too small, the filter is likely to be clogged, and the filter replacement frequency increases and the productivity is lowered. Therefore, the lower limit is preferably 0.1 μm.

In the production of the resin sheet, it is preferable to carry out defoaming treatment after blending each component in order to prevent bubbles from being contained in the cured product.
Examples of the defoaming treatment include standing, vacuum decompression, centrifugation, cyclone (automatic / revolving mixer), gas-liquid separation membrane, ultrasonic wave, pressure vibration, and defoaming with a multi-screw extruder.

4-3. As a coating method when the composition is applied to the coating or injection base material, it may be appropriately set according to the purpose, and conventionally known bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll. Examples of the coating method include a coater, a die coater, a lip coater, a gravure coater, and a micro gravure coater.
In the case of injecting the composition into the substrate having the space, a method of injecting the composition into an injection device such as a syringe or an injection device can be used.

What is necessary is just to set suitably as a film thickness in this case according to the target film thickness of an above described resin sheet.
In particular, when used for glass replacement, preferably OPS, the thickness is preferably 100 μm to 5 mm, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm.

4-4. In the case of using the active energy ray-curable composition as the active energy ray irradiation composition, examples of the active energy ray include ultraviolet rays, visible rays, electron beams, and X-rays, and the cured product can have a film thickness. In this respect, ultraviolet rays and visible rays are preferable.
Examples of the ultraviolet irradiation device include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a black light lamp, a UV electrodeless lamp, and an LED.
What is necessary is just to set suitably irradiation conditions, such as a dose and irradiation intensity in active energy ray irradiation, according to the composition to be used, a base material, a purpose, etc.
In this case, it can heat after irradiating an active energy ray. Examples of the heating method include the same methods as described later.

4-5. As a heating method in the case of using a thermosetting composition as a heating composition, there are a method of immersing in a heat medium bath such as heat and oil, a method using a heat press, a method of holding in a temperature-controlled thermostat, and the like. Can be mentioned.
What is necessary is just to set conditions, such as heating temperature in the case of heating suitably, according to the composition to be used, a base material, the objective, etc. As heating temperature, 40-250 degreeC is preferable. What is necessary is just to set a heat time suitably according to the composition to be used, the target resin sheet, etc., and 3 hours or more are mentioned. The upper limit of the heating time is preferably 24 hours or less in consideration of economy.
Also, the heating temperature can be changed according to the purpose. For example, the case where the thermal-polymerization initiator from which decomposition temperature differs is used. Specific examples of the temperature include a method of polymerizing at a relatively low temperature of about 40 to 80 ° C. for several hours and then polymerizing at a relatively high temperature of 100 ° C. or higher for several hours.

5. Use of Resin Sheet The resin sheet produced from the composition of the present invention can be preferably used as an optical sheet.
The optical sheet formed from the composition of the present invention can be used for various optical applications. More specifically, sheets used for liquid crystal display devices such as polarizer protective films for polarizing plates, prism sheet support films and light guide films, and touch panel integrated liquid crystal display devices, various functional films (for example, hard coats) Sheets, decorative sheets, transparent conductive sheets) and base sheets with surface shapes (for example, moth-eye type antireflection sheets and sheets with a texture structure for solar cells), light resistance for outdoor use such as solar cells (weather resistance) ) Sheets, films for LED lighting / organic EL lighting, transparent heat-resistant sheets for flexible electronics, and the like.

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. The composition used in this application is preferably a solventless composition that does not contain an organic solvent in that outgassing during the vacuum deposition of the transparent conductive layer can be suppressed.
Furthermore, since the optical sheet of the present invention is excellent in heat resistance even if it is a thick film, it has flexibility and high strength, it can also be used as a transparent conductive sheet substrate for OPS. In this case, an optical sheet having a film thickness of 0.5 mm or more and 1.5 mm or less can be used more preferably.

The manufacturing method of a transparent conductive sheet should just follow a conventional method.
The metal oxide forming the transparent conductor layer is indium oxide, tin oxide, zinc oxide, titanium oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite. Examples thereof include oxides and titanium-niobium composite oxides. Of these, indium-tin composite oxide and indium-zinc composite oxide are preferable from the viewpoints of environmental stability and circuit processability.
As a method of forming the transparent conductor layer, a conventional method may be followed, and a method of forming by sputtering using a vacuum film forming apparatus using the metal oxide, using the optical sheet of the present invention. Etc.
More specifically, the metal oxide is used as a target material, dehydrated and degassed, and then evacuated and vacuumed, the optical sheet is brought to a predetermined temperature, and then sputtered onto the optical sheet. Examples include a method of forming a transparent conductor layer.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “part” means part by weight, and “%” means% by weight.

1. Examples 1 to 6 and Comparative Examples 1 to 3
1) Manufacture of the composition The components (A) to (C) shown in the following Table 1 and Table 2 are blended in the proportions shown in the following Table 1 and Table 2, and a rotation / revolution mixer [Awatori made by Shinky Co., Ltd. Neritaro ARE-250] was used and mixed (1800 rpm × 4 minutes) and defoamed (2000 rpm × 1 minute).

In addition, the symbol in Table 1 and Table 2 means the following.
(A) Component ○ (A1) Component: Linear alkylene diacrylate / HDDA: 1,6-hexanediol diacrylate, Biscoat # 230 manufactured by Osaka Organic Chemical Industry Co., Ltd.
-NDDA: 1,9-nonanediol diacrylate, Kyoeisha Chemical Co., Ltd. light acrylate 1.9ND-A
○ (A2) component: polyoxyalkylene diacrylate, M-220: tripropylene glycol diacrylate, Aronix M-220 manufactured by Toagosei Co., Ltd.
M-240: polyethylene glycol (n≈4) diacrylate, Aronix M-240 manufactured by Toagosei Co., Ltd.
(B) component * M-309: trimethylol propane triacrylate, ARONIX M-309 manufactured by Toagosei Co., Ltd.
UAd: addition reaction product of isophorone diisocyanate and pentaerythritol triacrylate (urethane adduct having 6 acryloyl groups in one molecule)
DPHA-4EO: Hexaacrylate of 4 mol of dipentaerythritol ethylene oxide adduct OT-1000: Addition reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate (referred to as “adduct”) and pentaerythritol tetraacrylate (referred to as “PETeA”) ) [62:38 (weight ratio)], Aronix OT-1000 manufactured by Toagosei Co., Ltd.
DCPA: dimethylol tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd., light acrylate DCP-A
Component (C) DC-1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, DAROCURE 1173 manufactured by BASF Japan Ltd.

2) Manufacture of resin sheet As molds for manufacturing a resin sheet, the molds shown in (a1-1) and (a1-2) of Fig. 1 were used.
Two glass plates [100 mm × 180 mm, thickness 2 mm], two release-treated polyethylene terephthalate (PET) films [100 mm × 180 mm, Toray Co., Ltd. therapy MFA] and one silicone plate (thickness 1 0.0 mm) was used.
A release-treated PET film [(a1-1): (2) in FIG. 1] is superimposed on a glass plate [(a1-1): (1) in FIG. 1], and a silicone plate [FIG. (A1-1) :( 3)] was used as a stack weir (spacer). Further, a release-treated PET film [(a1-2): (2) ′ in FIG. 1] is overlaid thereon, and a glass plate ((a1-2): (1) ′ in FIG. 1) is overlaid thereon. The type.

The composition obtained above was injected from a hole portion of the silicone plate of the molded plate [(a1-1) :( 3-1) in FIG. 1] with a syringe.
Visible light LED was irradiated with respect to the obtained shaping | molding die from one surface by the side of a glass plate, and the composition was hardened. Irradiation conditions are as follows.
○ UV-LED
It irradiated for 60 minutes only from the one glass plate side of a shaping | molding die with the LED irradiation apparatus (Optical intensity | strength of 3.6 nm, 3.6 mW / cm < ² >).

After allowing to cool, the glass was removed from the mold, the release-treated PET film was peeled off, and the cured product was taken out. The cured product was heat-treated at 150 ° C. for 6 hours in a nitrogen stream to obtain a resin sheet.
About the obtained resin sheet, according to the following method, plastic hardness, pencil hardness, and a bending characteristic were evaluated. The results are shown in Tables 1 and 2.

3) Evaluation method
(1) Using a plastic hardness micro-hardness meter (Fischer Scope H100CS manufactured by Fischer Instruments Co., Ltd.), using a Vickers indenter and measuring with a predetermined indentation condition (0 to 300 mN / 10 sec → 5 sec holding → 300 to 0 mN / 10 sec) The plastic hardness (HUpl value) was determined.

(2) Pencil hardness Measured according to JIS K-5600.

(3) Bending characteristics A test piece in which a resin sheet was cut into a size of length 50 (mm) × width 10 (mm) × thickness 1 (mm) and the cut surface was smoothed with sandpaper was used. The bending test was performed using an Instron 5566A at a fulcrum distance of 30 mm, a bending speed of 0.2 mm / min, and 23 ° C. The flexural modulus (GPa) was calculated from a strain of 0.1% and a stress of 1%.

2. In the compositions of General Examples 1 to 6 , the obtained resin sheets were excellent in both hardness and bending properties.
In contrast, the compositions of Comparative Examples 1 to 3 were compositions that did not contain the component (A), but were unable to achieve both hardness and bending characteristics.

  The composition of this invention can be preferably used for manufacture of a resin sheet, and the obtained resin sheet can be used for various uses 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 touch panels.

Claims (13)

A composition comprising the following components (A) and (B):
The total amount of 100 wt% of (A) and component (B), (A) component 5 to 70% by weight, and (B) 95 to 30 wt% viewing including the component,
Component (B) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups is added in a total amount of 100 weights of components (A) and (B) %, Comprising a cured product of a curable composition for producing a resin sheet contained in a proportion of 20% by weight or more ,
The resin sheet whose thickness of hardened | cured material is 100 micrometers-5 mm .
Component (A): One or more selected from the group consisting of the following components (A1) and (A2)
Component (A1): di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms
Component (A2): poly (alkylene glycol) di (meth) acrylate, wherein the total number of carbon atoms constituting the polyoxyalkylene group is 4 to 20, component (B): an ethylenically unsaturated group A compound other than the component (A) (A1) component is 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate resin sheet according to claim 1 is at least one selected from the. The resin sheet according to claim 1 or 2, wherein the component (A2) is at least one selected from polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) acrylate. G. The component (B) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups other than a compound having three or more (meth) acryloyl groups. resin sheet according to any one of claims 1 to 3, including. The resin sheet for producing curable composition further, (C) component: a resin sheet according to any one of claims 1 to 4 which contains a photopolymerization initiator. The resin sheet for producing curable composition further, (D) component: a resin sheet according to any one of claims 1 to 5, including a thermal polymerization initiator. Resin sheet according to any one of claims 1 to 6 pencil hardness of the cured product is not less than 3H. The following curable composition for producing a resin sheet was poured into a molding die composed of a base material / base material for providing a base material / weir and a thickness of the cured product of 100 μm to 5 mm . Then, the manufacturing method of the resin sheet which irradiates an active energy ray from either base material side.

A curable composition for producing a resin sheet: a composition containing the following components (A), (B) and (C),
In a total amount of 100% by weight of the components (A) and (B), the component (A) is included in an amount of 5 to 70% by weight, and the component (B) is included in an amount of 95 to 30% by weight.
Component (B) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups is added in a total amount of 100 weights of components (A) and (B). % Curable composition for producing a resin sheet in a proportion of 20% by weight or more.
Component (A): One or more selected from the group consisting of the following components (A1) and (A2)
Component (A1): di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms
Component (A2): a poly (alkylene glycol) di (meth) acrylate, wherein the total number of carbon atoms constituting the polyoxyalkylene group is 4 to 20
Component (B): a compound having an ethylenically unsaturated group, which is a compound other than component (A)
Component (C): photopolymerization initiator In the curable composition for producing a resin sheet, the component (A1) is 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth). The method for producing a resin sheet according to claim 8, wherein the resin sheet is one or more selected from acrylate and neopentyl glycol di (meth) acrylate. The method for producing a resin sheet according to claim 8 or 9, wherein the curable composition for producing a resin sheet further comprises (D) component: a thermal polymerization initiator . The manufacturing method of the resin sheet of any one of Claims 8-10 heated after irradiating an active energy ray. The following curable composition for producing a resin sheet was poured into a molding die composed of a base material / base material for providing a base material / weir and a thickness of the cured product of 100 μm to 5 mm . Then, the manufacturing method of the resin sheet heated.

A curable composition for producing a resin sheet: a composition containing the following components (A), (B) and (D),
In a total amount of 100% by weight of the components (A) and (B), the component (A) is included in an amount of 5 to 70% by weight, and the component (B) is included in an amount of 95 to 30% by weight.
Component (B) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups is added in a total amount of 100 weights of components (A) and (B). % Curable composition for producing a resin sheet in a proportion of 20% by weight or more.
Component (A): One or more selected from the group consisting of the following components (A1) and (A2)
Component (A1): di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms
Component (A2): a poly (alkylene glycol) di (meth) acrylate, wherein the total number of carbon atoms constituting the polyoxyalkylene group is 4 to 20
Component (B): a compound having an ethylenically unsaturated group, which is a compound other than component (A)
Component (D): thermal polymerization initiator In the curable composition for producing a resin sheet, the component (A1) is 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth). The method for producing a resin sheet according to claim 12, wherein the resin sheet is one or more selected from acrylate and neopentyl glycol di (meth) acrylate.

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