WO2019044786A1

WO2019044786A1 - Resin sheet and curable composition for producing same

Info

Publication number: WO2019044786A1
Application number: PCT/JP2018/031625
Authority: WO
Inventors: 浩之神村
Original assignee: 東亞合成株式会社
Priority date: 2017-08-29
Filing date: 2018-08-28
Publication date: 2019-03-07
Also published as: KR20200046024A; CN111032754A; JPWO2019044786A1; KR102595289B1; TW201912691A; JP7120240B2; TWI783031B

Abstract

The problem addressed by the present invention is to provide: a resin sheet having excellent mechanical properties, such as bending properties and the like, impact resistance, and hardness as well as excellent processability that is usable as an OPS resin; and a curable composition capable of producing a resin sheet having these properties. A resin sheet having a flexural modulus of 2.5 GPa or higher in a bending test, a 50% break height of 50 cm or higher in a falling weight test using a 40 g weight with a tip radius of 5 mm, and a pencil hardness of 3H or higher. One made from a cured product of the curable composition is preferred as the resin sheet, and a resin sheet that is a cured product of a composition in which the proportion of ring-opened caprolactone structural units is 0.5-3.0 mol/L relative to the total weight of curable compounds in the composition is more preferred.

Description

Resin sheet and curable composition for producing the same

The present invention relates to a resin sheet and a curable composition for producing the same, and the resin sheet can be preferably used for optics such as a liquid crystal display (LCD) and an organic EL, and the resin sheet for forming a touch panel transparent conductive film It can preferably be used and belongs to these technical fields.
In the present specification, an acryloyl group or a methacryloyl group is represented as (meth) acryloyl group, an acrylate or methacrylate is represented as (meth) acrylate, and acrylic acid or methacrylic acid is represented as (meth) acrylic acid.
Further, in the present specification, the notations of X to Y showing the range of various physical properties and the notations of X to Y etc showing the ratio of each component mean X or more and Y or less.

In recent years, many touch panel integrated liquid crystal display devices or touch panel integrated organic EL display devices have been applied to mobile devices such as smartphones, tablet terminals, and car navigation systems.
Conventionally, as a transparent conductive thin film of a touch panel, a conductive glass in which a thin film of indium tin oxide (hereinafter referred to as "ITO") is formed on glass is well known. Poor in flexibility and processability. Therefore, depending on the application, a transparent conductive sheet based on a polyethylene terephthalate sheet (with a glass transition temperature of about 120 ° C) is used because of its advantages such as excellent flexibility, processability, and impact resistance, and lightweight. ing.

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

Then, what is called OPS (One Plastic Solution) which directly forms touch sensors, such as ITO, in a resin sheet as a material of a cover which is excellent in impact resistance is proposed.
In addition to the performance as a sensor substrate, the resin used for OPS is also required to have the capability of protecting the display device and maintaining the appearance. Therefore, it is necessary to have a flexural modulus, an abrasion resistance, and an impact resistance that can protect the display device.

However, acrylic resin, which has been used as a cover resin in the past, is easily damaged due to lack of impact resistance, and polycarbonate resin is easily scratched due to lack of surface hardness and loses transparency. Had.
As a method of improving the abrasion resistance and impact resistance of acrylic resin and polycarbonate resin, a so-called hard coat treatment method has been proposed in which a coating layer having excellent abrasion resistance etc. is formed on the surface of these resins ( Patent documents 1 and 2).

On the other hand, in recent years, display-related cover resins such as portable terminals are required to have various shapes due to diversification of tastes of users, and processing of three-dimensional shapes having smooth curved surfaces as well as two-dimensional sheet shapes is also required. ing.
However, hard coating on a resin molded into a three-dimensional shape in advance requires dipping or spray coating, and it is difficult to form a smooth hard coat layer, and the designability is reduced. In addition, in the method of cutting or polishing the resin sheet which has been previously subjected to hard coating treatment and three-dimensional processing, the hard coating layer of the polished and cut portion is lost, so the impact resistance and scratch resistance of the cover resin Will decrease. In particular, polycarbonate resin is difficult to process because it is melted by heat when it is processed by a rotary hollow machine.

As a resin sheet which solves the above-mentioned subject, a resin sheet with a glass transition temperature of 200 ° C. or more and a flexural modulus of 3.0 GPa or more, which is produced from a cured product of a photocurable composition containing polyfunctional (meth) acrylate (Patent Document 3).
However, although the said resin sheet has high elastic modulus, since impact resistance is inadequate, it is difficult to use as a cover resin.
In addition, in Patent Document 1, a photocurable composition containing a bismethacrylate having an alicyclic skeleton and a mercapto compound is used, and by adding a mercapto compound, the cured product is given appropriate toughness. However, there is a problem that the pot life of the composition is shortened, and there is also a problem that the surface hardness and the abrasion resistance are also reduced.

As described above, no resin sheet having satisfactory physical properties as a resin for OPS has been found so far, and it is particularly difficult to simultaneously achieve hardness, toughness and impact resistance, and the processability is also insufficient. The

Japanese Patent Application Publication No. 2007-030307 JP, 2015-123721, A JP, 2015-063655, A

The present inventors are a resin sheet which is excellent in mechanical properties such as bending properties, impact resistance and hardness, and processability which can be used as a resin for OPS, and a curing type capable of producing a resin sheet having the physical properties. A thorough study was conducted to find the composition.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the resin sheet which has a specific bending elastic modulus, impact resistance, and hardness was effective, as a result of earnestly examining in order to solve the said subject.
Furthermore, the present inventor has a composition containing an ethylenically unsaturated compound as a curable composition for producing a resin sheet having the above physical properties, and the compound further containing a ring-opened caprolactone unit in a specific ratio in the composition. It has been found that the objects can solve the above-mentioned problems, and the present invention has been completed.

The present invention is a resin having a 50% breaking height of 50 cm or more and a pencil hardness of 3 H or more in a falling weight test using a weight having a bending elastic modulus of 2.5 GPa or more and 40 g and a tip radius of 5 mm in a bending test. It relates to a sheet.
As the resin sheet, one having a total light transmittance of 90% or more at a thickness of 1 mm is further preferable.

As a resin sheet, what consists of hardened | cured material of a curable composition is preferable.
As the curable composition, one containing a ring-opened caprolactone structural unit in a ratio of 0.5 to 3.0 mol / L with respect to the total amount of the curable compound in the composition is preferable.

Furthermore, a composition comprising the following components (A) to (C) as a curable composition, wherein the ring-opened caprolactone unit is 0. 0 to the total amount of the components (A) and (B) in the composition. A resin sheet comprising a cured product of a composition containing 5 to 3.0 mol / L is preferable.
Component (A): Compound having an open ring caprolactone unit and having an ethylenically unsaturated group (B) Component: Compound having an ethylenically unsaturated group other than the component (A) (C) Component: radical polymerization initiator

The component (A) is preferably one containing a compound having a ring-opened caprolactone unit and having two or more (meth) acryloyl groups.

As the component (B), one containing a compound having two or more (B-1) (meth) acryloyl groups is preferable.
Further, as the component (B-1), one containing a (B-1-1) di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms is preferable, and the above-mentioned (B-) is further preferable. 1-1) The components are 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and neopentyl glycol di (meth) Those which are one or more selected from the group consisting of acrylates are preferable.
Further, as the component (B-1), one containing a compound having three or more (meth) acryloyl groups is preferable.

The curable composition preferably contains 20 to 60 mol% of methacryloyl group in 100 mol% of the total amount of ethylenically unsaturated groups contained in the components (A) and (B).
Moreover, that whose (A) and (B) component does not contain the compound which has a urethane bond is preferable.

As (C) component, (C1) thermal radical polymerization initiator or / and (C2) photo radical polymerization initiator are preferable.

The present invention relates to a composition comprising the components (A) to (C), wherein 0.5 to 3 of the ring-opened caprolactone unit is used based on the total amount of the components (A) and (B) in the composition. The present invention also relates to a curable composition for resin sheet production which contains 0 mol / L.

The component (B) preferably contains a compound having two or more (B-1) (meth) acryloyl groups, and the component (B-1) is preferably the component (B-1-1).
Further, as the component (B-1), one containing a compound having three or more (meth) acryloyl groups is preferable.

The composition preferably contains 20 to 60 mol% of methacryloyl group in 100 mol% of the total amount of ethylenically unsaturated groups contained in the components (A) and (B).
Moreover, that whose (A) and (B) component does not contain the compound which has a urethane bond is preferable.

As the composition, the cured product has a 50% breaking height of 50 cm or more in a falling weight test using a weight having a flexural modulus of 2.5 GPa or more and 40 g in a bending test and a tip radius of 5 mm, and a pencil hardness Is preferably 3H or more.

As a method for producing a resin sheet using the composition described above, there is a production method in which the composition is poured into a mold composed of a substrate / substrate for providing a substrate / wax, and then heated. preferable.
Moreover, after pouring a composition in the shaping | molding die comprised with the base material / base material for providing base material / wrinkles, the manufacturing method which irradiates an active energy ray from either base material side is preferable.
In this case, heating can be performed after irradiation with active energy rays.
Hereinafter, the present invention will be described in detail.

According to the resin sheet of the present invention, it is excellent in mechanical characteristics such as bending characteristics, impact resistance and hardness, excellent in processability, and can be preferably used as a resin for OPS.
Further, according to the composition of the present invention, the obtained cured product is excellent in mechanical properties such as bending properties described above, impact resistance and hardness, and also excellent in processability.

FIG. 1 is a view showing an example of a mold used for producing a resin sheet using the composition of the present invention. FIG. 2 is a figure which shows two examples about the shape of the resin sheet of this invention.

1. Resin sheet The present invention has a 50% breaking height of 50 cm or more and a pencil hardness of 3 H or more in a falling weight test using a weight having a bending elastic modulus of 2.5 GPa or more and 40 g and a tip radius of 5 mm in a bending test. Relates to a resin sheet.

1-1. Physical Properties of Resin Sheet The resin sheet of the present invention has a flexural modulus of 2.5 GPa or more in a bending test, preferably 3.0 GPa or more, more preferably 2.5 to 10 GPa, particularly preferably 3.0. It is ~ 10 GPa. The resin sheet having the elastic modulus is excellent in rigidity.
The elastic modulus in the bending test in the present invention means a value calculated from the stress of strain 0.1% and 1% in the bending test performed at a distance between supporting points of 30 mm and a bending speed of 0.2 mm / min.

The resin sheet of the present invention has a 50% breaking height of 50 cm or more in a falling weight test using a weight of 40 g and a tip radius of 5 mm, preferably 60 cm or more, more preferably 50 to 500 cm, 60 to 60 cm 500 cm is particularly preferred.
The drop weight test in the present invention means the result of measurement according to JIS K 7211-1.

The resin sheet of the present invention preferably has a pencil hardness of 3H or more and 4H or more, more preferably 3H to 10H, particularly preferably 4H to 10H.
The pencil hardness in the present invention means a value measured by a method according to JIS K-5600.

When the resin sheet is used for optical applications, the total light transmittance is preferably 90% or more, more preferably 91% or more, particularly preferably 90 to 100%, and still more preferably 91 to 100 It is 100%.
In the present invention, the total light transmittance means the result of measurement of a test specimen having a thickness of 1 mm in accordance with JIS K7375.

As a resin sheet, what has processability is preferable. Specifically, as the processability, one having a machinability and abradability is preferable. More specifically, as the machinability, those which can be processed by a rotary cutting machine (NC router) are preferable.
As described above, the conventional acrylic resin and polycarbonate resin have the same pencil hardness as that of the present invention by hard coating treatment, but when cutting or polishing the curved surface of the end portion adopted in smartphones and the like in recent years The hard coat layer is lost, and the abrasion resistance and impact resistance of the processed portion are lost.

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

As a resin sheet, what has heat resistance is preferable. Heat resistance is a physical property that is required when producing a transparent electrode such as ITO using a resin sheet, and achieves low sheet resistance and high transmittance comparable to when forming a film on a glass substrate. In order to achieve this, vacuum deposition at a high temperature of 150.degree. C. or higher is required. If the elastic modulus is insufficient during film formation, the resin sheet itself is distorted, and a film-formed product having a desired shape can not be obtained. In addition, if the change in appearance such as the decrease in transparency or yellowing of the resin sheet is large during film formation, it can not be used as a transparent electrode substrate.
The heat resistance of the resin sheet is preferably such that the elastic modulus at 200 ° C. is 0.1 GPa or more, more preferably 1.0 GPa or more, and particularly preferably 1.0 to 5 GPa.
By setting the elastic modulus at 200 ° C. to 0.1 GPa or more, it is possible to obtain a homogeneous ITO transparent electrode film having a low resistance equivalent to film formation on a glass substrate, and to be a substrate in a vacuum film formation process. Not only the deformation of the resin sheet is suppressed and the appearance after film formation is good, but the film formation of a large area resin film is performed without causing the nonuniformity of ITO film thickness and electric resistance after film formation. Improve productivity.
The elastic modulus in the present invention indicates a storage elastic modulus in a dynamic viscoelasticity spectrum measured in a tension mode at a frequency of 1 Hz, a temperature rising temperature of 2 ° C./min.

1-2. Shape of Resin Sheet As the resin sheet in the present invention, sheets of various shapes and structures can be used.
Examples of the shape of the resin sheet include a square or rectangular flat plate-like body (hereinafter simply referred to as a "plate-like body"), a shape in which four corners of the plate-like body are rounded, and side surfaces of two sides of the plate-like body The curved shape [for example, (a) of FIG. 2], and the shape [for example, (b) of FIG. 2] etc. in which the side of the four sides of the plate-like body is curved are mentioned.

1-3. Manufacturing Method of Resin Sheet The resin sheet in the present invention can be manufactured by various molding methods.
Specific examples include extrusion molding using a thermoplastic resin, injection molding, vacuum molding, compression molding and cast molding, and compression molding and cast molding using a curable composition.

The resin sheet of the present invention is preferably a resin sheet obtained from a cured product of a curable composition, because resin sheets having various shapes can be preferably produced.
The curable composition is a composition containing a curable compound, and examples of the curable compound include radically polymerizable compounds, cationically polymerizable compounds, anionically polymerizable compounds, polyfunctional isocyanates and polyhydric alcohols.
The curable compound is preferably a compound having a ring-opened caprolactone structure. The proportion of the compound having a ring-opened caprolactone structure is preferably a ratio of 0.5 to 3.0 mol / L of the ring-opened caprolactone structural unit with respect to the total amount of the curable compound in the composition.
Examples of the curable composition include a composition containing a radically polymerizable compound and a radically polymerizable initiator, a composition containing a cationically polymerizable compound and a cationic polymerization initiator, and an anionically polymerizable compound and a composition containing an anionic polymerization initiator. And polyaddition polymerizable compositions such as polyfunctional isocyanates and polyhydric alcohols.
As a radically polymerizable compound, the compound which has an ethylenically unsaturated group is mentioned.
As a radically polymerizable initiator, a thermal radical polymerization initiator, an optical radical polymerization initiator, etc. are mentioned.
An epoxy compound, an oxetane compound, vinyl ether etc. are mentioned as a cationically polymerizable compound.
As a photocationic polymerization initiator in a cationic polymerization initiator, a sulfonium salt, an iodonium salt, a diazonium salt etc. are mentioned.
Examples of the anionic polymerizable compound include α-cyanoacrylates, methylene malonates, epoxy compounds, and ε-caprolactone.
Examples of the photoanion polymerization initiator in the anionic polymerization initiator include chromium amine thiocyanate, platinum acetylacetonate, pentacarbonyl metal complex, Schiff base, ferrocene, metallocene and alkylaluminum porphyrin.

In the present invention, a curable composition for producing a resin sheet is preferably a composition containing a radically polymerizable compound and a radically polymerizable initiator.
Furthermore, the curable composition is a composition containing the following components (A) to (C), and the ring-opened caprolactone unit is added to the total amount of the components (A) and (B) in the composition. The composition containing 0.5 to 3.0 mol / L is more preferable.
Component (A): Compound having an open ring caprolactone unit and having an ethylenically unsaturated group (B) Component: Compound having an ethylenically unsaturated group other than the component (A) (C) Component: Radical polymerization initiator The curable composition containing the components (A) to (C) will be described.

2. A curable composition for producing a curable composition resin sheet for producing a resin sheet is a composition comprising the following components (A) to (C), which comprises the components (A) and (B) in the composition: Preferred is a composition containing 0.5 to 3.0 mol / L of ring-opened caprolactone units with respect to the total amount.
Component (A): Compound having an open ring caprolactone unit and having an ethylenically unsaturated group (B) Component: Compound having an ethylenically unsaturated group other than the component (A) (C) Component: polymerization initiator Details of the components (A) to (C), the other components and the composition will be described.

2-1. Component (A) Component (A) is a compound having a ring-opened caprolactone unit and having an ethylenically unsaturated group.
Examples of the ethylenically unsaturated group in the component (A) include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and the (meth) acryloyl group is preferable.

As the component (A), a compound having two or more ethylenic unsaturated groups is preferable, and a compound having two or more (meth) acryloyl groups is more preferable.
Examples of such compounds include poly (meth) acrylates of polyol ε-caprolactone adducts obtained by esterifying compounds obtained by adding ε-caprolactone to polyols with (meth) acrylic acid, and ε-caprolactones to polyol alkylene oxide adducts Preference is given to poly (meth) acrylates of ε-caprolactone adducts to polyol alkylene oxide adducts, in which the added compounds are esterified with (meth) acrylic acid.
Specific examples of the polyol in the compound include polyols having an aliphatic skeleton such as ethylene glycol, butylene glycol, hexanediol, nonanediol and neopentyl glycol;
Polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, polybutylene glycol, poly (1-methylbutylene glycol);
Hydroxypivalate neopentyl glycol;
Diols having an alicyclic skeleton such as dimethylol tricyclodecane, cyclohexane dimethanol and spiro glycol;
Trivalent or higher polyols such as glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol; and isocyanurate.
In the above, examples of the alkylene oxide adduct include ethylene oxide adduct and propylene oxide adduct.

More specific examples of the component (A) include di-, tri- or tetra (meth) acrylates of ε-caprolactone adduct of pentaerythritol, poly (meth) acrylates of ε-caprolactone adduct of dipentaerythritol, isocyanuric acid Examples thereof include di- or tri (meth) acrylates of ε-caprolactone adducts to alkylene oxide adducts, and di (meth) acrylates of ε-caprolactone adducts of neopentyl glycol hydroxypivalate.
Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide and propylene oxide, and ethylene oxide is preferable. The addition mole number of the alkylene oxide is preferably 1 to 3 moles in one molecule.
The addition mole number of ε-caprolactone is preferably 1 to 7 moles in one molecule.

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

The component (A) is commercially available and includes, for example, the following products.
Triacrylate of 1 mol adduct of ε-caprolactone to 3 mol adduct of isocyanuric acid ethylene oxide: A-93001 CL manufactured by Shin-Nakamura Chemical Co., Ltd. and the like.
· Triacrylate of ε-caprolactone 3 mol adduct to isocyanurate ethylene oxide 3 mol adduct: Tritonate of Toagosei Co., Ltd. Alonics M-327
· Poly (meth) acrylate of ε-caprolactone adduct of dipentaerythritol: Nippon Gunsan Co., Ltd. KYARAD DPCA-20, DPCA-30, DPCA-60 (dipentaerythritol with ε-caprolactone in 2 moles, 3 Compound starting from a compound obtained by adding mol and 6 mol)
· Di (meth) acrylate of ε-caprolactone 2 molar adduct of hydroxypivalate neopentyl glycol: KYARAD HX-220 manufactured by Nippon Explosives Co., Ltd.
-Di (meth) acrylate of ε-caprolactone 4 molar adduct of hydroxypivalate neopentyl glycol: KYARAD HX-620 manufactured by Nippon Explosives Co., Ltd.

The content of the component (A) is preferably 20 to 60% by weight, more preferably 30 to 55% by weight, of the component (A) in 100% by weight of the total amount of the components (A) and (B). .
By setting the content ratio of the component (A) to 20% by weight or more, the breaking strain and the 50% impact fracture height are high, and the resin sheet can be toughened, and by being 60% by weight or less, the pencil hardness etc. Surface hardness and scratch resistance can be high.

2-2. Component (B) The component (B) is a compound having an ethylenically unsaturated group 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, with a (meth) acryloyl group being preferred.
As the component (B), a compound having two or more ethylenic unsaturated groups [hereinafter referred to as "polyfunctional unsaturated compound"] and a compound having one ethylenic unsaturated group [hereinafter, "(B-2) And the like.
Each of the compounds is specifically described below.

2-2-1. Multifunctional Unsaturated Compound As the polyfunctional unsaturated compound, a compound having (B-1) two or more (meth) acryloyl groups [hereinafter, referred to as “component (B-1)”] is preferable.
As component (B-1), di (meth) acrylate having an aromatic skeleton such as di (meth) acrylate of bisphenol A alkylene oxide adduct and bisphenol A di (meth) acrylate;
Ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylates having an aliphatic skeleton such as di (meth) acrylates and neopentyl glycol di (meth) acrylates;
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene 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, poly (1-methylbutylene glycol) di (meth) acrylate, etc. Polyalkylene glycol di (meth) acrylate;
Hydroxypivalate neopentyl glycol di (meth) acrylate;
Examples thereof include di (meth) acrylates having an alicyclic skeleton such as dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate and spiroglycol di (meth) acrylate.
Other examples of the component (B-1) include di- or tri (meth) acrylate of glycerin, di- or tri (meth) acrylate of trimethylolpropane, di-, tri- or tetra (meth) acrylate of pentaerythritol, di-trimethylol Polyfunctional di-, tri- or tetra (meth) acrylates of propane; and polyfunctional (meth) acrylates of polyols such as di-, tri-, tetra- or hexa (meth) acrylates of dipentaerythritol;
Di or tri (meth) acrylate of glycerol alkylene oxide adduct, di, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, di, tri or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct Polyfunctional (meth) acrylate of a polyol alkylene oxide adduct such as di-, tri-, tetra-, penta- or hexa (meth) acrylate of pentaerythritol alkylene oxide adduct; and di- or tri- (meth) acrylate of alkylene oxide adduct of isocyanuric acid And polyfunctional (meth) acrylates having an isocyanurate ring.
In the above, examples of the alkylene oxide adduct include ethylene oxide adduct and propylene oxide adduct.

As the component (B-1), urethane (meth) acrylates, polyester (meth) acrylates, epoxy (meth) acrylates, polyether (meth) acrylates and the like can be mentioned besides the above.

As urethane (meth) acrylate, urethane (meth) acrylate which is a compound which has a urethane bond and has two or more (meth) acryloyl groups can be used preferably. Examples of the urethane (meth) acrylate include a polyol, a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate.

Examples of polyester (meth) acrylates include dehydrated condensates of polyester diols and (meth) acrylic acid. Here, as polyester diol, the reaction product of diol and dicarboxylic acid or its anhydride, etc. are mentioned.

Epoxy (meth) acrylate is a compound obtained by addition reaction of (meth) acrylic acid to an epoxy resin. As an epoxy resin, an aromatic epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

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

Specific examples of aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. Diglycidyl ethers of polyalkylene glycols; neoglycidyl glycol, diglycidyl ethers of dibromo neopentyl glycol and its alkylene oxide adducts; diglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; Can be mentioned.
In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

Polyether (meth) acrylate oligomers include polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate .

◆ Preferred (B-1) Component (B-1) Component is a bifunctional (meth) acrylate having an alkylene group-containing di (meth) acrylate and a polyalkylene glycol di (meth) acrylate and an isocyanurate ring Those containing one or more compounds selected from polyfunctional (meth) acrylates are preferred.

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

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

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

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

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

2-2-2. Component (B-2) As the component (B-2) (compound having one ethylenically unsaturated group), a compound having one (meth) acryloyl group [hereinafter referred to as “monofunctional (meth) acrylate” Etc. can be mentioned.

The monofunctional (meth) acrylate is a radically polymerizable compound having one (meth) acryloyl group, and specific examples thereof 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-meth Syethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxy Ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, ol-phenylphenol ethylene oxide (EO) modified (EO 1 to 4 moles modified) (meth) acrylate, p-cumylphenol EO modified (EO 1 to 4 moles modified) ( Examples thereof include meta) acrylates, phenyl (meth) acrylates, and --phenylphenyl (meth) acrylates and p-cumylphenyl (meth) acrylates.

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

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

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

Examples of (meth) acrylates having a maleimide group having a substitution site in the unsaturated bond include (meth) acrylates having a hexahydrophthalimide group and (meth) acrylates having a tetrahydrophthalimide group. Specific examples of the (meth) acrylate having a hexahydrophthalimide group include N- (meth) acryloyloxyethyl hexahydrophthalimide and the like. Examples of (meth) acrylates having a tetrahydrophthalimide group include N- (meth) acryloyloxyethyl tetrahydrophthalimide and the like.

Examples of the component (B-2) other than monofunctional (meth) acrylates include radically polymerizable vinyl compounds such as aromatic vinyl compounds, maleimide compounds, (meth) acrylamide compounds and N-vinyl compounds.

Examples of the aromatic vinyl compound include styrene, alkyl styrene and halogenated styrene.
Specific examples of alkylstyrenes include methylstyrene, ethylstyrene and propylstyrene.
Specific examples of the halogenated styrene include fluorostyrene, chlorostyrene and bromostyrene.
Among the above-described compounds, styrene is preferred as the aromatic vinyl compound.

Examples of the maleimide compound include N-phenyl maleimide, maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-cyclohexyl maleimide, and N-polyethylene glycol polyol ether maleimide.

Specific examples of (meth) acrylamide compounds include N-alkyls such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and Nt-butyl (meth) acrylamide. Acrylamide;
N, N-dialkyl acrylamides such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide;
N-alkoxyalkyl compounds such as N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide And (meth) acryloyl morpholine and the like.

Examples of compounds having an amido group include N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and the like.

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

2-2-4. Content ratio The content ratio of the component (B) is preferably 40 to 80% by weight, more preferably 45 to 75% by weight in 100% by weight of the total amount of the components (A) and (B). It is.
When the content ratio of the component (B) is 40% by weight or more, the surface hardness such as pencil hardness and the scratch resistance can be excellent, and when it is 80% by weight or less, the strain at break and 50% impact It is excellent in breaking height and can make the resin sheet tough.
Further, a preferable content of the component (B-1-1) is 30 to 70% by weight in 100% by weight of the total amount of the component (B).
As a content rate of a monofunctional unsaturated compound, 0 to 40 weight% of a monofunctional unsaturated compound is preferable in 100 weight% of the total amount of (A) and (B) component, More preferably, it is 0 to 20 weight% It is.
By setting the content ratio of the monofunctional unsaturated compound to 40% by weight or less, since the unreacted component remains in the resin sheet after curing, it is prevented that the resin sheet is plasticized and the bending elastic modulus is lowered. be able to.

2-3. Component (C) Component (C) is a radical polymerization initiator.
When the composition is used as a thermosetting composition, a thermal polymerization initiator (C-1) [hereinafter referred to as "component (C-1)"] is blended to form an active energy ray curable composition. When used as a substance, a photopolymerization initiator (C-2) [hereinafter referred to as "component (C-2)"] is blended.
The components (C-1) and (C-2) will be described below.

2-3-1. When the component (C-1) is used as a thermosetting composition, the component (C-1) (thermal polymerization initiator) can be blended.
As the component (C-1), various compounds can be used, and organic peroxides and azo initiators are preferable. Furthermore, among these, organic peroxides are more preferable because they are excellent in the polymerization initiator efficiency, can reduce the outgas derived from the polymerization initiator decomposition product, and are further excellent in the impact resistance of the composition.

Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1 1,1-Bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2 , 2-Bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-Bis (t-butylperoxy) cyclododecane, dilauroyl peroxide, t-hexylperoxyisopropyl monocarbonate, t-butyl Peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy Urate, t-butylperoxypivalate, t-hexylperoxypivalate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t- Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butyl) Peroxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α'-bis (t-butylperoxyisophthalate) Peroxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2, -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, and t-butyl hydroperoxide Peroxide etc. are mentioned.

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. Also, it is possible to carry out a redox reaction by combining an organic peroxide with a reducing agent.

The content ratio of the component (C-1) is preferably 0.1 to 5 parts by weight of the component (C-1) with respect to 100 parts by weight of the total amount of the components (A) and (B).
By setting the ratio of the component (C-1) to 0.1 parts by weight or more, the entire resin sheet can be uniformly cured, and by setting the ratio to 5 parts by weight or less, low-molecular-weight polymerization initiator decomposition products remaining Outgassing can be reduced.

2-3-2. Component (C-2) The component (C-2) is a photopolymerization initiator.
The component (C-2) is a component to be blended when ultraviolet light and visible light are used as active energy rays. When using an electron beam, although it is not necessary to mix | blend necessarily, in order to improve hardenability, it can also be mix | blended in small quantities as needed.

Specific examples of the component (C-2) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4 -1- (methyl vinyl)] 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-morpholinopropane- -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4 Aromatic ketone compounds such as -ylphenyl) butan-1-one, adecadecamer N-1414 (manufactured by ADEKA Co., Ltd.), phenylglyoxylic acid methyl ester, ethyl anthraquinone, phenanthrenequinone and the like;
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 systems such as (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone Compound;
Bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, ethyl (2,4,6-trimethyl benzoyl) phenyl phosphinate and bis (2,6- An acyl phosphine oxide compound such as dimethoxy benzoyl) -2,4,4-trimethylpentyl phosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy-2 Thioxanthone compounds such as -hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone and 10-butyl-2-chloroacridone;
1- [4- (phenylthio)]-1,2-octanedione-2- (O-benzoyloxime) and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Oxime esters such as ethanone-1- (O-acetyl oxime);
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 And acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

As the component (C-2), it is also possible to use a photopolymerization initiator having a molecular weight of 350 or more besides the above. The photopolymerization initiator having a molecular weight of 350 or more does not cause coloration of the resin sheet obtained by the decomposition product after light irradiation, and when the composition is used for producing a transparent conductive film, the decomposition product is vacuum of the transparent conductor layer 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 being lowered and it becomes difficult to reduce the resistance.

Specific examples of the component (C-2) include polymers of hydroxyketones, and examples thereof include compounds represented by the following formula (1). The said compound is also preferable at the point which is excellent in compatibility with (A) and (B) component.

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, and n represents an integer of 2 to 5. In addition, n means the repetition number of the said unit.
As the alkyl group, R ² is preferably a lower alkyl group such as a methyl group, an ethyl group and a propyl group.

Specific examples of the compound represented by the formula (1) include oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone and the like.
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 number of 2 to 3, and [(204.3 × n + 16.0) Or 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.

The compounding ratio of the component (C-2) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). It is.
By setting the compounding ratio to 0.01 parts by weight or more, the composition can be cured with an appropriate amount of ultraviolet light or visible light amount, productivity can be improved, and by setting it to 10 parts by weight or less, curing It is possible to have excellent weather resistance and transparency of the object.
Further, the components (C-1) and (C-2) may be used in combination and heat curing may be carried out for the purpose of further improving the reaction rate after photocuring.

2-4. Method for Producing Composition and Physical Properties The present invention relates to a composition comprising the components (A) to (C), wherein the ring-opened caprolactone unit is used relative to the total amount of the components (A) and (B) in the composition. And a curable composition for producing a resin sheet containing 0.5 to 3.0 mol / L.
When the ring-opened caprolactone unit is less than 0.5 mol / L, the impact resistance is reduced, and the 50% breaking height in the falling weight test using a weight of 40 g and R 5 mm becomes 50 cm or less, 3.0 If it exceeds mol / L, the modulus of elasticity of the resin becomes 2.5 GPa or less, and the rigidity required to protect the display required for OPS is insufficient. As the ring-opened caprolactone unit, 0.5 to 3.0 mol / L is preferable.
The ring-opened caprolactone unit with respect to the total amount of the components (A) and (B) in the composition means a mole of a structure in which ε-caprolactone is opened with respect to 1 L of total volume of the composition.
More specifically, the molar concentration of the ring-opened caprolactone unit is contained in the composition from the content ratio of the component (A) contained in the composition and the number of moles of the ring-opened caprolactone unit in 1 mol of the component (A). The number of moles of ring-opened caprolactone units is calculated, and this value is divided by the volume of the composition (mol / L). The volume of the composition is calculated from the specific gravity of the composition.
The composition may be produced according to a conventional method. For example, the components (A), (B) and (C) and, if necessary, other components can be mixed by stirring.

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

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

As the components (A) and (B) which are curable components in the present invention, the above-mentioned compounds can be appropriately combined and used. In the case of a thermosetting composition, in particular, a compound having a urethane bond It is preferable not to contain In the composition containing a compound having a urethane bond, for example, urethane (meth) acrylate, the cured product is colored.

The composition of the present invention preferably contains 20 to 60 mol% of methacryloyl group in the total amount of 100 mol% of the ethylenically unsaturated groups contained in the components (A) and (B), more preferably It is 30 to 60 mol%.
The distortion of the resin sheet after curing can be reduced by setting the ratio of methacryloyl groups to 20 mol% or more, and the coloring before and after the heat resistance test can be suppressed by setting the ratio to 60 mol% or less.
The proportion of methacryloyl group in the present invention means mol% obtained by dividing the number of moles of all methacryloyl groups in the components (A) and (B) by the number of moles of all ethylenically unsaturated groups and multiplying by 100. The compound having two or more (meth) acryloyl groups is often a mixture of compounds having different numbers of (meth) acryloyl groups in commercial products, so the proportion of (meth) acryloyl groups is incorrect. There may be. In this case, the (meth)
The acryloyl group equivalent is measured and calculated based on this value.

2-5. Other Components The composition of the present invention contains the components (A), (B) and (C), but various components can be blended depending on the purpose.
As other components, specifically, an organic solvent, a plasticizer, a polymerization inhibitor or / and an antioxidant, a light resistance improver, a compound having two or more mercapto groups [hereinafter referred to as "polyfunctional mercaptan" ], And an isocyanate compound etc. can be mentioned.
Hereinafter, these components will be described. The components to be described later may be used alone or in combination of two or more.

2-5-1. Organic solvent The composition of the present invention can be blended with an organic solvent for the purpose of improving the coatability to a substrate. However, when using the resin sheet obtained for a transparent conductive film use, what does not contain an organic solvent is preferable.

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

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

2-5-2. A plasticizer can be added for the purpose of imparting flexibility to the cured plasticizer and improving brittleness.
Specific examples of the plasticizer include phthalic acid dialkyl esters such as dioctyl phthalate and diisononyl phthalate, adipic acid dialkyl esters such as dioctyl adipate, sebacic acid esters, azelaic acid esters, phosphoric acid esters such as tricresyl phosphate, and polypropylene Examples include liquid polyether polyols such as glycol, polycaprolactone diol, and liquid polyester polyols such as 3-methylpentanediol adipate. In addition, soft acrylic polymers having a number average molecular weight of 10,000 or less can be mentioned.

The proportions of these plasticizers may be suitably set, but preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the total of the component (A).
By setting the content to 30 parts by weight or less, it is possible to obtain excellent strength and heat resistance.

2-5-3. Polymerization Inhibitor and / or Antioxidant A polymerization inhibitor or / and an antioxidant can be added to the composition of the present invention in order to improve the storage stability.
As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and various phenolic antioxidants are preferable, but sulfur secondary antioxidants, phosphorus secondary Next antioxidants and the like can also be added.
The total blending ratio of the polymerization inhibitor and / or the antioxidant is preferably 3 parts by weight or less, more preferably 0.5 parts by weight or less, based on 100 parts by weight of the total amount of the component (A).

2-5-4. The composition of the light resistance improver present invention, the light resistance improving agent such as an ultraviolet absorber or a light stabilizer may be added.
Examples of UV absorbers include 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, and 2- (2′-hydroxy-3′-5′-di-t-butylphenyl) benzotriazole. Benzotriazole compounds such as 2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole;
Triazine compounds such as 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -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 Mention may be made of benzophenone compounds such as'-dihydroxy-4,4'-dimethoxybenzophenone and the like.
As a light stabilizer, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformyl hexamethylene diamine, bis (1,2,6,6) -Pentamethyl-4-piperidyl) -2- (3,5-ditertiarybutyl-4-hydroxybenzyl) -2-n-butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ) Low molecular weight hindered amine compounds such as sebacate; N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformylhexamethylene diamine, bis (1,2,2,2) Mention may be made of hindered amine light stabilizers such as high molecular weight hindered amine compounds such as 6,6 pentamethyl-4-piperidinyl) sebacate.

The compounding ratio of the light resistance improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 parts by weight with respect to 100 parts by weight of the total amount of the component (A).

2-5-5. Multifunctional mercaptan The polyfunctional mercaptan can be blended as necessary for the purpose of preventing the cure shrinkage of the cured product of the composition and for the purpose of imparting toughness.
As polyfunctional mercaptan, various compounds can be used as long as they are compounds having two or more mercapto groups.

For example, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate and the like can be mentioned.

The proportion of the polyfunctional mercaptan is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less with respect to 100 parts by weight of the component (A). By setting this ratio to 20 parts by weight or less, it is possible to prevent a decrease in the heat resistance and the rigidity of the obtained cured product.

2-5-6. When using a poorly adhesive substrate such as an isocyanate compound polyvinyl alcohol, an isocyanate compound can be added as a means for improving the adhesion to the substrate.

Examples of the compound having one ethylenically unsaturated group and one isocyanate group include (meth) acryloyloxyalkyl isocyanates such as 2- (meth) acryloyloxyethyl isocyanate and the like, and these two groups are oxyalkylene Examples of compounds linked by a skeleton include (meth) acryloyloxyalkoxyalkyl isocyanates such as 2- (meth) acryloyloxyethoxyethyl isocyanate and compounds in which these two groups are linked by an aromatic hydrocarbon skeleton Examples include 2- (meth) acryloyloxyphenyl isocyanate and the like.

As a compound having two ethylenically unsaturated groups and one isocyanate group, examples of compounds in which these two groups are linked by a branched saturated hydrocarbon skeleton include 1,1-bis [( And (meth) acryloyloxymethyl] ethyl isocyanate and the like.
As a compound having two or more isocyanate groups, tolylene diisocyanate, phenylene diisocyanate, chlorophenylene diisocyanate, cyclohexane diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, norbornene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, phthalene diisocyanate, dimethyl diphenyl diisocyanate, dianiline diisocyanate, tetramethyl xylylene isocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, etc. Methylol propa Adduct-type isocyanate compounds added to polyfunctional alcohols such as cyanide, isocyanurate compounds of these isocyanate compounds, burette-type compounds, allophanate-type compounds, etc., and further, known polyether polyols, polyester polyols, acrylic polyols, polybutadienes Examples thereof include urethane prepolymer type isocyanate compounds in which a polyol, a polyisoprene polyol and the like are subjected to an addition reaction.

2-5-7. Other components besides the above In addition to the above-mentioned other components , a mold release agent, a filler, a soluble polymer and the like can be blended into the composition of the present invention.
The release agent is blended in order to facilitate release of the resulting resin sheet from the substrate. As the mold release agent, various surfactants can be used if they can be released from the substrate and the compounded liquid and the cured product are not turbid. For example, anionic surfactants such as alkyl benzene sulfonic acid, cationic surfactants such as alkyl ammonium salt, nonionic surfactants such as polyoxyethylene alkyl ether, amphoteric surfactants such as alkyl carboxy betaine, and further fluorine or silicon And surfactants contained therein.
The filler is blended for the purpose of improving the mechanical properties of the obtained resin sheet. Both inorganic and organic compounds can be used as the filler. Examples of the inorganic compound include silica and alumina. A polymer can be used as the organic compound. As a filler, when the resin sheet obtained from the composition of this invention is used for an optical use, what does not reduce an optical physical property is preferable.
The soluble polymer is blended for the purpose of improving the mechanical properties of the resulting resin sheet. By soluble polymer is meant a polymer that dissolves in the composition. In the present invention, polymers which do not dissolve in the composition are referred to as fillers for distinction.
The compounding ratio of these other compounds is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the component (A).

2-5-8. Cured product physical properties The cured product of the composition of the present invention preferably satisfies the physical properties of the resin sheet described above.
That is, the 50% breaking height is 50 cm or more, and the pencil hardness is 3 H or more in a falling weight test using a weight having a bending elastic modulus of 2.5 GPa or more and 40 g and a tip radius of 5 mm in a bending test. Physical properties are also in the above-mentioned range.

When the resin sheet is used for optical applications, the total light transmittance is preferably 90% or more, more preferably 91% or more.
In addition, although there is an example using phase separation etc. as a resin sheet which has impact resistance, transparency fell. On the other hand, the resin sheet obtained from the composition of the present invention is also excellent in transparency.

The resin sheet obtained from the composition of the present invention is excellent in processability. Specifically, as the processability, one having a machinability and abradability is preferable. More specifically, the machinability can be processed by a rotary cutting machine (NC router).
As described above, the conventional acrylic resin and polycarbonate resin have the same pencil hardness as that of the present invention by hard coating treatment, but when cutting or polishing the curved surface of the end portion adopted in smartphones and the like in recent years Although the hard coat layer is lost and the scratch resistance and impact resistance of the processed portion are lost, the resin sheet obtained from the composition of the present invention does not have such a problem.

3. Method of Producing Resin Sheet As a method of producing a resin sheet using the composition of the present invention, various methods can be adopted.
In the technical field of the resin sheet according to the present invention, a relatively thick film is often referred to as a sheet, and a relatively thin film is often referred to as a film.
As described above, in the present invention, "resin sheet" means a resin sheet or a resin film.

Specifically, in the case of using a thermosetting composition as the composition, the following four production methods can be mentioned, for example.
1) Manufacturing method 1-1
Method of applying a composition to a substrate and heating to cure the composition
2) Manufacturing method 1-2
A method of coating a composition on a substrate and laminating it with another substrate, followed by heating to cure the composition
3) Manufacturing method 1-3
Method of pouring a composition into a substrate having a space and heating to cure the composition
4) Manufacturing method 1-4
Method of pouring a composition on a substrate having a space portion and bonding it to another substrate and heating to cure the composition In the case of using a resin sheet obtained from the composition of the present invention in a glass substitute application And the above-mentioned production method 1-4 is preferable.
In the case of using a resin sheet obtained from the composition of the present invention as a polarizer protective film, the above-mentioned production methods 1-1 and 1-2 are preferable.

In the case of using an active energy ray-curable composition as the composition, for example, the following four production methods can be mentioned.
5) Manufacturing method 2-1
Method of applying a composition to a substrate and irradiating the active energy ray to cure the composition
6) Manufacturing method 2-2
A method of applying a composition to a substrate and laminating it with another substrate, and then irradiating active energy rays to cure the composition
7) Manufacturing method 2-3
Method of pouring a composition into a substrate having a space and irradiating the active energy ray to cure the composition
8) Manufacturing method 2-4
Method of pouring a composition into a base material having a space and bonding it to another base material, and then irradiating the active energy ray to cure the composition In the case of these manufacturing methods, heating may also be performed after the active energy ray is irradiated it can.
When the resin sheet obtained from the composition of the present invention is used for glass substitute applications, the above-mentioned production method 2-4 is preferable.
When the resin sheet obtained from the composition of the present invention is used as a polarizer protective film, the above-mentioned production methods 2-1 and 2-2 are preferable.

As a polymerization system, either a batch system or a continuous system can be adopted.
As an example of a continuous type, the method of continuously supplying a belt-like base material etc. is mentioned as a coating or pouring base material, and a composition.
As another example of the continuous system, a method called continuous cast method is mentioned besides the above. That is, two continuous belts of mirror-surface stainless steel are arranged up and down like a caterpillar, the composition is poured between the belt and the belt, and polymerization is continuously performed between the belt and belt while moving the belt slowly. The sheet can be produced by a method for producing the sheet.
For glass substitute applications, batchwise is preferred.

3-1. As a base material , any of a peelable base material and a base material having no releasability (hereinafter, referred to as "non-releasing base material") can be used.
Examples of the releasable substrate include metals, glass, polymer films subjected to release treatment, and surface untreated polymer films having releasability (hereinafter collectively referred to as “release materials”).
The substrate surface can also be subjected to release treatment in order to facilitate release of the cured product. As the release treatment, for example, silicone or the like may be used to coat or treat the surface of the substrate.
The release-treated polymer film and the surface untreated polymer film having releasability include silicone treated polyethylene terephthalate film, surface untreated polyethylene terephthalate film, surface untreated cycloolefin polymer film, surface untreated OPP film (polypropylene), etc. Can be mentioned.

In order to give low haze or impart surface smoothness to a resin sheet obtained from the composition of the present invention, a substrate having a surface roughness (center line average roughness) Ra of 0.15 μm or less is used Is preferred, and a substrate of 0.001 to 0.100 μm is more preferred. Furthermore, 3.0% or less is preferable as a haze.

Specific examples of the substrate include glass, polyethylene terephthalate film or cycloolefin polymer film, OPP film (oriented polypropylene), polyvinyl alcohol, cellulose acetate resin such as triacetyl cellulose and diacetyl cellulose, acrylic resin, polyester, polycarbonate, poly A cyclic polyolefin resin etc. which use cyclic olefins, such as arylate, polyether sulfone and norbornene, as a monomer are mentioned.
In the present invention, the surface roughness Ra means a value obtained by measuring the surface roughness of the film and calculating the average roughness.

Examples of non-releasing base materials include various plastics other than the above, and cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, polyesters, polycarbonates, polyarylates, polyether sulfones, norbornenes, etc. Cyclic polyolefin resin as a monomer.
When the composition of the present invention is used as a polarizer protective material, a polyvinyl alcohol film impregnated with iodine or a dye and then stretched, that is, a polarizer film is a substrate.
For the purpose of improving the adhesion of both layers in the case of practical use in a state in which the substrate and the cured layer are integrated without peeling the resin sheet or film which is a polymer of the curable composition from the substrate. Physical and chemical treatments, including corona discharge treatment, can be applied to the substrate surface.

As a base material which has a space part, a base material which has a crevice is mentioned. What formed the hole of the predetermined shape made into the target film thickness in a formwork material, and formed the recessed part is mentioned.
In this case, after the composition is poured into a substrate having a recess, another substrate can be overlaid on the substrate having the recess.
As another example of the base material having the space portion, a mold material provided with a weir (spacer) such that the cured product has a desired film thickness (hereinafter referred to as a "mold") and the like are also mentioned. Be Again, another substrate can be overlaid on the crucible.
As described above, various shapes can be adopted as the shape of the resin sheet in the present invention, and resin sheets with different shapes can be manufactured by changing the shape of the mold used.

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

As a base material for providing a weir, as shown in FIG. 1, the one having a shape having pores (FIG. 1: (3-1) (3-1)) for injecting the composition to the upper part [FIG. Figure 1: (3-1) of (a1-1) and those without a cavity [Figure 1: (3) 'of (a1-1)] and the like, and the composition is injected into the upper part It is preferable to have a shape having a void portion for the purpose. As a base material for providing the said wrinkles, various materials can be used and silicone rubber etc. can be mentioned.

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

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

The mold of FIG. 1 is an example of a mold for manufacturing a flat plate-like resin sheet, and resin sheets of various shapes can be manufactured by changing the structure of the mold of FIG. 1.
For example, a curved resin sheet can be manufactured by using a mold having a curved structure in the mold of FIG. 1, and using an R-shaped mold having four sides curved in the mold of FIG. Thus, it is possible to manufacture an R-shaped resin sheet in which four sides are curved.

3-2. Pretreatment of Composition In coating or injection of the composition of the present invention, the composition obtained is a resin sheet obtained which prevents contamination of foreign matter, generation of defects such as voids, and has excellent optical properties. In order to achieve this, it is preferable to use the purified one after stirring and mixing the raw material components.
As a method of purifying the composition, a method of filtering the composition is simple and preferred. As a method of filtration, pressure filtration etc. are mentioned.
The filtration accuracy is preferably 10 μm or less, more preferably 5 μm or less. The smaller the filtration accuracy, the better. The filter suppresses clogging, suppresses the replacement frequency of the filter, and the lower limit is preferably 0.1 μm from the viewpoint of productivity.

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

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

The film thickness in this case may be appropriately set in accordance with the intended film thickness of the resin sheet.
In particular, when used for glass replacement applications, preferably OPS applications, it is preferably 100 μm to 5 mm, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm.
When used as a polarizer protective layer, it is preferably 10 μm to 2 mm, more preferably 20 μm to 200 μm.

3-4. As a heating method in the case of using a thermosetting composition as a heating composition, a method of immersing in heat and a heat medium bath such as oil, a method of using a heat press, a method of holding in a temperature controlled thermostatic chamber, etc. It can be mentioned.
Conditions such as the heating temperature in the case of heating may be appropriately set according to the composition to be used, the substrate, the purpose and the like. The heating temperature is preferably 40 to 250.degree. The heating time may be appropriately set according to the composition to be used, the desired resin sheet, etc., and may be 3 hours or more. The upper limit of the heating time is preferably 24 hours or less in consideration of economy.

Moreover, heating temperature can also be changed according to the objective. For example, the case where the thermal polymerization initiator from which decomposition temperature differs is used, etc. are mentioned. As a specific temperature, for example, a method of polymerizing at relatively low temperature of about 40 to 80 ° C. for several hours and then polymerizing at relatively high temperature of 100 ° C. or more for several hours can be mentioned.

3-5. As an active energy ray in the case of using an active energy ray-curable composition as an active energy ray irradiation composition, an ultraviolet ray, a visible ray, an electron beam, an X ray, etc. may be mentioned, and a cured product can be made into a film thickness. In terms of ultraviolet light and visible light are preferred. Examples of the ultraviolet irradiation device include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, black light lamps, UV electrodeless lamps, LEDs and the like.
Irradiation conditions such as dose and irradiation intensity in active energy ray irradiation may be appropriately set according to the composition to be used, the substrate, the purpose and the like.

In this case, heating can be performed after irradiation with active energy rays. As the method of the said heating, the method similar to a postscript is mentioned. The heat treatment causes stabilization by molecular chain rearrangement, the progress of polymerization reaction, coupling reaction of frozen radicals, and the like, and improvement of heat resistance and optical properties can be expected.
The heating temperature is preferably 50 to 250 ° C., and more preferably 100 to 200 ° C. If the heating temperature is low, the effect of the heat treatment is low, and if it is too high, the toughness may be reduced due to a crosslinking reaction or the like. The heating time is preferably 1 hour to 1 day, and more preferably 2 to 10 hours. If the heating time is short, the effect of the heat treatment is low, and if it is too long, the toughness may be reduced due to a crosslinking reaction or the like.

Moreover, resin sheets of various shapes can be manufactured by using active energy ray curing and thermal curing in combination.
As a specific example, first, a flat plate-like resin sheet (hereinafter referred to as “semi-cured sheet”) having plasticity that deforms by applying a force without causing the composition to be completely cured by active energy ray irradiation. Manufacture).
Using a semi-hardened sheet, it is bent by mechanical means, or is inserted into a form having a specific shape and deformed to form a desired shape.
The semi-cured sheet molded into the desired shape is heated and completely cured.

4. Applications of Resin Sheet The resin sheet of the present invention can be preferably used particularly as an optical sheet.
Optical sheets formed from the compositions of the present invention can be used in a variety of optical applications. More specifically, it is used for liquid crystal displays such as a polarizer protective film of a polarizing plate for liquid crystal display, a protective film of a circularly polarized plate for organic EL, a support film for prism sheet and a light guide film, and a touch panel integrated liquid crystal display Sheets, various functional films (for example, hard coat sheets, decorative sheets, transparent conductive sheets) and sheets with surface shapes (for example, moth-eye type anti-reflection sheets and sheets with a texture structure for solar cells) Sheets, outdoor light-resistant (weatherproof) sheets such as solar cells, films for LED lighting or organic EL lighting, transparent heat-resistant sheets for flexible electronics, transparent heaters for antifogging of surveillance cameras, etc. Housings for mobile phones etc. Body, car instrument panel cover, sunroof, mirror cover, photo mass Include applications such wearable display devices.

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

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

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

1. Examples 1 to 4 and Comparative Examples 1 to 4
1) Production of UV curable composition After blending the components (A), (B) and (C) shown in the following Tables 1 and 2 in the proportions shown in the following Tables 1 and 2, stirring and mixing, Degassed under vacuum.
In the following description, the molar concentration of the ring-opened caprolactone unit (the structure in which ε-caprolactone is open) in the component (A) is referred to as “CL unit”, and the total amount of ethylenically unsaturated groups is 100 mol. The proportion of methacryloyl groups in% is expressed as "methacryl ratio".
The molar concentration of the CL unit is the number of moles of the ring-opened caprolactone unit contained in the composition from the content ratio of the component (A) contained in the composition and the number of moles of the ring-opened caprolactone unit in 1 mol of the component (A) It was calculated and this value was divided by the composition volume to obtain a value (mol / L). The composition volume was obtained by dividing the composition weight by the specific gravity of the composition.

A specific calculation method of the CL unit will be described based on the first embodiment.
In Example 1, 30 g of the following DPCA-30 is blended.
DPCA-30: poly (meth) acrylate of ε-caprolactone 3 molar adduct of dipentaerythritol (molecular weight: 921)
DPCA-30 has 3 mol of ring-opened caprolactone units in 1 mol of molecule.
Example 1 had a specific weight of 100.5 g and a specific gravity of 1.1, and the CL unit was calculated by the following equation.
The CL units were calculated similarly for the other compositions.
[[30 (g) / 921 (g / mol)] x 3] / [100.5 (g) / 1.1 (g / cm ³ ) / 1000 (cm ³ / L)] = 1.07 (mol / L)

The abbreviations in Table 1 and Table 2 mean the following.
(A) Component · DPCA-30: poly (meth) acrylate of ε-caprolactone 3 mol adduct of dipentaerythritol (molecular weight: 921), manufactured by Nippon Gunsan Co., Ltd. KAYARAD DPCA-30
DPCA-60: poly (meth) acrylate of 6-mole adduct of ε-caprolactone of dipentaerythritol (molecular weight: 1263), manufactured by Nippon Explosives Co., Ltd. KAYARAD DPCA-60
M-327: triacrylate (molecular weight 757) of 3 mol adduct of ε-caprolactone to 3 mol adduct of ethylene oxide isocyanurate (molecular weight 757), manufactured by Toagosei Co., Ltd. Alonics M-327
(B) Component · NDDA: 1,9-nonanediol diacrylate (molecular weight: 268), Osaka Organic Chemical Industry Co., Ltd. Biscoat # 260
HDDA: 1,6-hexanediol diacrylate (molecular weight: 226), Osaka Organic Chemical Industry Co., Ltd. Biscoat # 230
-NPG-MA: neopentyl glycol dimethacrylate (molecular weight 240), NPG manufactured by Shin-Nakamura Chemical Co., Ltd.
TMP-MA: trimethylolpropane trimethacrylate (molecular weight 338), light ester TMP manufactured by Kyoeisha Chemical Co., Ltd.
M-309: A mixture of trimethylolpropane triacrylate (molecular weight: 290), Toagosei Co., Ltd. Alonics M-305
St: Styrene (molecular weight 104), NS Styrene Monomer Co., Ltd. M-225: Polypropylene glycol (repeating unit: about 7) diacrylate (molecular weight 533), Toagosei Co., Ltd. Alonics M-225
M-321: Diacrylate of trimethylolpropane propylene oxide adduct (molecular weight: 645), Toagosei Co., Ltd. Alonics M-321
OT-1000: mixture of pentaerythritol triacrylate and hexamethylene diisocyanate (urethane adduct having 6 acryloyl groups in one molecule) and pentaerythritol tetraacrylate [62: 38 (weight ratio)] (average) Molecular weight 608), Toho Gosei Co., Ltd. Alonics OT-1000
(C) Component DC: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (molecular weight: 164) [Darocure 1173 manufactured by BASF Japan Ltd.]

2) Production of resin sheet The mold shown in (a2) of FIG. 1 was used as a mold for producing a resin sheet.
Two glass plates [80 mm × 80 mm, thickness 3 mm] and one silicone plate (thickness 1.0 mm) were used. In addition, the glass plate used what carried out the mold release process by the silicone type compound.
A silicone plate [(a2): (3) in FIG. 1] was placed on a glass plate [(a2): (1) in FIG. 1] to form a spacer. Furthermore, a glass plate [(a2): (1) ′] in FIG.
The composition obtained above was injected by a syringe from the cavity ((a2): (3-1) in FIG. 1) of the silicone plate of the mold.
With respect to the obtained mold, an illuminance 130 mW / cm ² (UV-A, Fusion UV Systems Japan) is used from one surface on the side of the glass plate using an ultraviolet irradiation apparatus (high pressure mercury lamp) manufactured by IGRAPHICS CO., LTD. It exposed 20 times by 5 m / min of conveyor speeds as UV POWER PUCK by Corporation. At this time, the irradiated surface was reversed every exposure.
After cooling, the glass was removed from the mold, and the obtained cured product was heated at 150 ° C. for 16 hours to obtain a resin sheet.

3) Evaluation method About the obtained resin sheet, a bending elastic modulus, a drop weight test, pencil hardness, a total light transmittance, and processability were evaluated according to the following method. The results are shown in Tables 1 and 2.

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

(2) Drop weight test (50% impact fracture height)
From the obtained resin sheet, a test piece of length 60 (mm) × width 60 (mm) is cut out, and the obtained resin sheet is disposed on a metal ring of 50 mm in diameter in accordance with JIS K 721-1. A conical weight having a tip diameter of 5 mm and having a weight of 40 g was dropped from a predetermined height to the center of the resin molded body, and the height at which the probability of breakage was 50% or more was recorded. The number of tests at each height was ten.

(3) Pencil Hardness The hardness of the surface of the obtained resin sheet was measured in accordance with JIS K-5600.

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

(5) Processability The appearance of the plate after processing the obtained resin sheet into 130 mm × 92 mm at 10,000 rotations using an NC router (HSM 3500A manufactured by Japan Precision Machinery Co., Ltd.) was confirmed. The obtained results were evaluated on the following three levels.
A: There are no cracks or cracks.
B: There is a crack of 1 mm or less near the processing point.
C: There is a crack of 1 mm or more in the vicinity of the damaged or processed portion of the entire sheet.

2. Examples 5 to 8
1) Preparation of Thermosetting Composition In the UV curable compositions of Examples 1 to 4, 0.5 part of DC of the photopolymerization initiator was added to t-butylperoxy-2-ethylhexanoate [NOF (stock Thermosetting composition was prepared in the same manner except that it was replaced by 0.5 parts of perbutyl O).

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

The composition obtained above was injected by a syringe from the cavity ((a2): (3-1) in FIG. 1) of the silicone plate of the mold.
The mold was placed in a drying furnace, heated at 60 ° C. for 0.5 hours, and then heated to 120 ° C. (heating rate: 10 ° C./hour) over 6 hours to cure the composition.
After cooling to room temperature, the glass was removed from the mold and then demolded to obtain a resin sheet.
The resulting resin sheet was used to evaluate the flexural modulus, drop weight test, pencil hardness, total light transmittance and processability according to the same method as described above. The results were similar to those of Examples 1 to 4.

3. Comparative Example 5 and 6
1) Evaluation of commercially available resin sheet Commercially available polymethyl methacrylate (Acrilyat L, manufactured by Mitsubishi Rayon Co., Ltd.). Hereinafter, it is referred to as "PMMA"] and polycarbonate [Iupilon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.]. The flexural modulus, falling weight test, pencil hardness, total light transmittance and processability were evaluated according to the same method as described above using “PC” hereinafter. The results are shown in Table 3.

4. The compositions of General Examples 1 to 4 were such that the resulting resin sheet was excellent in all of the flexural modulus, the drop weight test, the hardness, the total light transmittance and the processability.
On the other hand, in the compositions of Comparative Examples 1 to 4 in which the ring-opened caprolactone unit not containing the component (A) is less than 0.5 mol / L, the resulting resin sheet has problems in terms of flexural modulus and hardness. Although none was found, the drop weight test (impact resistance) was all lowered. In particular, the resin sheet obtained from the composition of Comparative Example 1 did not have processability.
Moreover, in Comparative Example 5 related to commercially available PMMA, the result of the falling weight test was lowered. Further, in Comparative Example 6 relating to commercially available PC, the hardness was lowered, and further, it had no processability.

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

Claims

A resin sheet having a 50% breaking height of 50 cm or more and a pencil hardness of 3 H or more in a falling weight test using a weight having a bending elastic modulus of 2.5 GPa or more and 40 g and a tip radius of 5 mm in a bending test.
The resin sheet according to claim 1, further having a total light transmittance of 90% or more at a thickness of 1 mm.
The resin sheet according to claim 1 or 2, which comprises a cured product of a curable composition.
The resin sheet according to claim 3, wherein the curable composition comprises the ring-opened caprolactone structural unit in a ratio of 0.5 to 3.0 mol / L with respect to the total amount of the curable compound in the composition.
The curable composition is
Component (A): a compound having a ring-opened caprolactone unit and having an ethylenically unsaturated group,
Component (B): a compound having an ethylenically unsaturated group other than the component (A),
Component (C): a composition containing a radical polymerization initiator,
The ring-opened caprolactone unit is contained in the ratio which will be 0.5-3.0 mol / L with respect to the total amount of the said (A) component in the composition, and the said (B) component. Resin sheet.
The resin sheet according to claim 5, wherein the component (A) has a ring-opened caprolactone unit and contains a compound having two or more (meth) acryloyl groups.
The resin sheet according to claim 5 or 6, wherein the component (B) contains a compound having two or more components (B-1) and (meth) acryloyl groups.
The resin sheet according to claim 7, wherein the component (B-1) comprises a component (B-1-1): a di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms.
The component (B-1-1) is 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and neopentyl glycol The resin sheet according to claim 8, which is at least one selected from the group consisting of di (meth) acrylates.
The resin sheet according to any one of claims 7 to 9, wherein the component (B-1) contains a compound having three or more (meth) acryloyl groups.
11. The methacryloyl group is contained in an amount of 20 to 60 mol% in 100 mol% of the total amount of the ethylenically unsaturated groups contained in the component (A) and the component (B). The resin sheet as described in a term.
The resin sheet according to any one of claims 5 to 11, wherein the component (A) and the component (B) do not contain a compound having a urethane bond.
The resin sheet according to any one of claims 5 to 12, wherein the component (C) comprises a component (C1): thermal radical polymerization initiator.
The resin sheet according to any one of claims 5 to 13, wherein the component (C) comprises a component (C2): radical photopolymerization initiator.
Component (A): a compound having a ring-opened caprolactone unit and having an ethylenically unsaturated group,
Component (B): a compound having an ethylenically unsaturated group other than the component (A),
Component (C): a composition containing a radical polymerization initiator,
A curable composition for producing a resin sheet, comprising a ring-opened caprolactone unit in a ratio of 0.5 to 3.0 mol / L based on the total amount of the component (A) and the component (B) in the composition.
The curable composition for resin sheet manufacture according to claim 15, wherein the component (A) has a ring-opened caprolactone unit and contains a compound having two or more (meth) acryloyl groups.
The curable composition for resin sheet manufacture according to claim 15 or 16, wherein the component (B) contains a compound having two or more components (B-1): (meth) acryloyl groups.
The resin sheet according to claim 17, wherein the component (B-1) comprises a component (B-1-1): a di (meth) acrylate having a linear or branched alkylene group having 4 to 20 carbon atoms. Curable composition.
The component (B-1-1) is 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and neopentyl glycol 19. The curable composition for resin sheet production according to claim 18, which is at least one selected from the group consisting of di (meth) acrylates.
The resin sheet according to any one of claims 17 to 19, wherein the component (B-1) contains a compound having a component (B-1-2): three or more (meth) acryloyl groups. Curable composition.
The methacryloyl group is contained in an amount of 20 to 60 mol% in 100 mol% of the total amount of the ethylenically unsaturated groups contained in the (A) component and the (B) component. The curable composition for resin sheet manufacture as described in a term.
The curable composition for producing a resin sheet according to any one of claims 15 to 21, wherein the component (A) and the component (B) do not contain a compound having a urethane bond.
The curable composition for resin sheet production according to any one of claims 15 to 22, wherein the component (C) comprises a component (C1): thermal radical polymerization initiator.
The curable composition for producing a resin sheet according to any one of claims 15 to 23, wherein the component (C) contains a radical photopolymerization initiator (C2).
The cured product has a 50% breaking height of 50 to 500 cm and a pencil hardness of 3 H to 10 H in a falling weight test using a weight with a bending elastic modulus of 2.5 to 10 GPa and 40 g in a bending test and a tip radius of 5 mm. The curable composition for producing a resin sheet according to any one of claims 15 to 24, which is
A method for producing a resin sheet, which comprises heating the composition after pouring the composition according to claim 23 into a substrate / substrate for providing a substrate / wafer.
Resin which irradiates an active energy ray from any substrate side after pouring the composition according to claim 24 into a mold composed of a substrate / substrate for providing a substrate / wrinkle Sheet manufacturing method.
The method for producing a resin sheet according to claim 27, wherein the resin sheet is heated after being irradiated with active energy rays.