JP6519729B2 - Resin sheet and method for manufacturing the same - Google Patents

Description

The present invention relates to a curable composition for producing a resin sheet, and a resin sheet obtained from the composition can be preferably used for optical substrates such as liquid crystal displays (LCDs) and organic ELs, and a resin sheet for forming a touch panel transparent conductive film More preferably, they belong to these technical fields.
In the present specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.

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

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

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

Patent Document 1 discloses a plastic member for forming a transparent conductive film obtained by photocuring a photocurable composition containing a bismethacrylate having an alicyclic skeleton and a mercapto compound.
However, although the mercapto compound is added to provide a cured product with appropriate toughness, there has been a problem that the pot life of the composition is shortened and the stability of the composition is lowered.

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

  As described above, a resin sheet having satisfactory performance for OPS has not been found so far, and the development of a resin composition having an excellent balance between rigidity and toughness has been a major issue.

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

The present inventors diligently studied in order to find a curable composition in which the obtained resin sheet is excellent in rigidity and toughness, specifically, a curable composition excellent in hardness and bending characteristics.
In the present invention, "excellent in rigidity" means excellent in hardness of cured product and elastic modulus in bending test, and "excellent in toughness" means large stress and strain in bending test, that is, It means that the breaking energy is large.

  As a result of intensive studies to solve the above problems, the present inventors have found that a hydrogen bonding compound having one ethylenic unsaturated group, a hydrogen bonding compound having two or more ethylenic unsaturated groups, and the like. It has been found that a composition containing a compound having an ethylenically unsaturated group in a specific ratio can solve the above-mentioned problems, and the present invention has been completed.

The present invention is a composition comprising the following components (A) to (C), wherein the total amount of components (A) to (C) is 100% by weight, 2 to 40% by weight of component (A), B) A cured product of a curable composition for resin sheet production containing 10 to 90% by weight of component B and 0 to 80% by weight of component C ,
The present invention relates to a resin sheet having a thickness of 100 μm to 5 mm of a cured product .
Component (A): a hydrogen bonding compound having a carboxyl group and one ethylenically unsaturated group (B): a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, which is 3 or more (meth) Compound (C) having an acryloyl group : a compound having an ethylenically unsaturated group, which is a compound other than the components (A) and (B)

As the component (A), a compound having a carboxyl group and one ethylenically unsaturated group is used .

As the component (B) has a urethane bond, using a compound having two or more (meth) acryloyl groups, the reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate is good preferred, organic polyisocyanate And a reaction product of hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups is particularly preferable.

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

As a cured product of the composition, one having an elastic modulus of 1 GPa or more and a maximum strain of 2% or more in a bending test is preferable. Moreover, that whose breaking energy in the bending test of hardened | cured material is 2 MJ / m < ³ > or more is preferable.

As a resin sheet which consists of hardened | cured material of a composition, that whose thickness of hardened | cured material is 100 micrometers-5 mm is preferable.
As a method for producing a resin sheet, after the composition described above is poured into a mold composed of a substrate / substrate for providing a substrate / wrinkle, an active energy ray from any substrate side The manufacturing method which irradiates is preferable. Furthermore, the manufacturing method which heats after irradiating an active energy ray is more preferable.
Moreover, as a method for producing a resin sheet, a production method in which the composition described above is poured into a mold composed of a substrate / substrate for providing a substrate / wrinkle, and then heated is preferable.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, the resin sheet obtained becomes excellent in rigidity and toughness, specifically, becomes excellent in hardness and bending characteristics, and particularly in bending characteristics, elastic modulus, maximum stress, maximum strain, It becomes excellent in any physical properties of strain at break and energy at break.

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

The present invention relates to a composition comprising components (A) to (C), wherein 2 to 40% by weight of component (A) is contained in 100% by weight of the total amount of components (A) to (C), (B A cured product of a curable composition for resin sheet production containing 10 to 90% by weight of the component and 0 to 80% by weight of the component (C) ,
The present invention relates to a resin sheet having a thickness of 100 μm to 5 mm of a cured product .
Hereinafter, the details of each component and composition will be described.

1. Component (A) The component (A) is a hydrogen bonding compound having a carboxyl group and one 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 a (meth) acryloyl group and a vinyl group are preferable.

Component (A) is a compound having a hydrogen bond group and one ethylenically unsaturated group.
The hydrogen bonding group in this case includes a carboxyl group, a hydroxyl group, an amido group, a carbamate group imide group and a urea group, preferably a carboxyl group, a hydroxyl group, an amido group and a carbamate group , and a compound having a carboxyl group is used .

Examples of compounds having a carboxyl group include (meth) acrylic acid, polycaprolactone modified products of (meth) acrylic acid, Michael addition type polymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and phthalic anhydride Examples thereof include acid adducts and carboxyl group-containing (meth) acrylates such as adducts of 2-hydroxyethyl (meth) acrylate and succinic anhydride.
Among these compounds, (meth) acrylic acid is preferred.

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

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

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

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

The content ratio of (A) is 2 to 40% by weight in a total of 100% by weight of the components (A), (B) and (C) (hereinafter collectively referred to as "curable component"), Preferably, it is 5 to 40% by weight.
If the blending ratio of (A) is less than 2% by weight, the balance between the rigidity and the toughness is lowered, while if it exceeds 40% by weight, the thermal decomposition becomes remarkable and the heat resistance is lowered.

2. Component (B) The component (B) is a hydrogen bonding compound having a urethane bond and having two or more ethylenically unsaturated groups.
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.
The “hydrogen bonding property” in the component (B) is preferably a compound having a unit having a hydrogen bonding property in the chemical structure, and a urethane bond is preferable as the unit.

As the component (B), a compound having a urethane bond and having two or more (meth) acryloyl groups [hereinafter, referred to as “component (B1)”] is preferable. The component (B1) is a compound usually called urethane (meth) acrylate.
As the component (B1), a reactant of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate [hereinafter referred to as “component (B1-1)”], and a reaction of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate [Hereafter, referred to as "(B1-2) component"] and the like.
The components (B1-1) and (B1-2) will be described below.

2-1. (B1-1) component
The component (B1-1) is a reactant of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate.

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

As the organic polyisocyanate, aliphatic polyisocyanate having no alicyclic group (hereinafter simply referred to as "aliphatic polyisocyanate"), aliphatic polyisocyanate having an alicyclic group (hereinafter "alicyclic polyisocyanate") And polyisocyanates having a heterocyclic ring and aromatic polyisocyanates.
Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate.
Alicyclic polyisocyanates include hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate and isophorone diisocyanate trimer, etc. .
Examples of the polyisocyanate having a heterocyclic ring include hexamethylene diisocyanate trimer and the like.
Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate and 1,5-naphthalene diisocyanate.
In the present invention, as the organic polyisocyanate, aliphatic polyisocyanate is preferable in that the physical properties of the cured product are excellent and yellowing is small.

The hydroxyl group-containing (meth) acrylate is preferably a hydroxyl group-containing mono (meth) acrylate.
As a hydroxyl group-containing mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxy And hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate.

2-2. (B1-2) component
The component (B1-2) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and is a compound referred to as a urethane adduct.
The use of the component (B1-2) as the component (B) is preferable because the crosslink density is increased and the heat resistance is improved, and the toughness is also improved by the combined use with the component (A).

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

In the component (B1-2), a compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter referred to as "hydroxyl group-containing polyfunctional (meth) acrylate") is used as the hydroxyl group-containing (meth) acrylate You can also.
When the reaction product of the organic polyisocyanate and the hydroxyl group-containing polyfunctional (meth) acrylate [hereinafter referred to as “(B1-2-1) component”] is used as the component (B1-2), the crosslink density becomes high, and the heat resistance is increased. It is preferable because it is also excellent in the properties, abrasion resistance and abrasion resistance.
As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used. Specifically, trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, di or tri of ditrimethylolpropane Examples include di-, tri-, tetra- or penta (meth) acrylates of (meth) acrylate and dipentaerythritol.
Among these, a compound having three or more (meth) acryloyl groups and having one hydroxyl group is preferable in that the cured film is excellent in abrasion resistance and abrasion resistance, and specifically, pentaerythritol tritol. Examples include (meth) acrylate, ditrimethylolpropane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.
Among these compounds, pentaerythritol tri (meth) acrylate is more preferable in that warpage of the obtained cured product can be prevented.

In the production of the component (B1-2-1), the raw material hydroxyl group-containing polyfunctional (meth) acrylate is usually a mixture containing a hydroxyl group-containing polyfunctional (meth) acrylate and a polyfunctional (meth) acrylate having no hydroxyl group. However, as the (B1-2-1) component, one produced using the mixture can also be used.
Specifically, a mixture of trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate, a mixture of ditrimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol pentamer A mixture of (meth) acrylate and dipentaerythritol hexa (meth) acrylate may, for example, be mentioned.
The reactant obtained from the mixture is a mixture of the (B) component and the (C) component.

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

Furthermore, as the component (B1-2), a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups is more preferable. The said compound becomes what has high toughness while maintaining rigidity by the moderate crosslinking density of hardened | cured material.
Examples of the compound include the (B1-2-1) component and the (B1-2-2) component described above.

2-3. Method for producing component (B1)
Component (B1) is, in component (B1-1), the addition reaction of a polyol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate, and in component (B1-2), organic polyisocyanate and hydroxyl group-containing (meth) acrylate Manufactured by the addition reaction of
Although this addition reaction can be carried out without using a catalyst, a tin-based catalyst such as dibutyltin dilaurate, an amine-based catalyst such as triethylamine, or the like may be added to efficiently promote the reaction.

The content ratio of (B) is 10 to 90% by weight, preferably 15 to 70% by weight, in the total 100% by weight of the curable component.
If the content of (B) is less than 10% by weight or more than 90% by weight, the balance between stiffness and toughness will be reduced.

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

  Examples of the compound having one ethylenic unsaturated group in the specific example of the component (C) include compounds having one (meth) acryloyl group [hereinafter referred to as “monofunctional (meth) acrylate”] and the like. .

  Specific examples of monofunctional (meth) acrylates include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 1- Adamantyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate О-phenylphenol EO modified (n = 1 to 4) (meth) acrylate, p-cumylphenol EO modified (n = 1 to 4) (meth) acrylate, phenyl (meth) acrylate, о-phenylphenyl (meth) ) Acrylate, p-cumylphenyl (meth) acrylate and the like.

In the specific example of the component (C), a compound having two or more ethylenic unsaturated groups is a compound having two (meth) acryloyl groups [hereinafter referred to as “bifunctional (meth) acrylate”. Hereinafter, the compound which has three or more (meth) acryloyl groups is described similarly to "(circle) functional (meth) acrylate." And difunctional (meth) acrylates 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, 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 Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, polybutylene glycol di (meth) acrylate, poly (1-methyl butylene glycol) di (meth) acrylate, 1 6- hexanediol di (meth) acrylate, 1,9-difunctional (meth) acrylates having an aliphatic skeleton such nonanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate;
Hydroxypivalate neopentyl glycol di (meth) acrylate;
Bifunctional (meth) acrylates having an alicyclic skeleton such as dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate and spiroglycol di (meth) acrylate;
In the above, examples of the alkylene oxide adduct include ethylene oxide adduct and propylene oxide adduct.

  As the component (C), an oligomer can also be used, and specific examples include polyester (meth) acrylate and epoxy (meth) aclay.

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

  Among the compounds described above, the component (C) is monofunctional (meth) having an alicyclic skeleton such as trifunctional or higher functional (meth) acrylate or isobornyl (meth) acrylate because it can impart rigidity and heat resistance. Preferred are acrylates and difunctional (meth) acrylates having an alicyclic skeleton such as dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate and spiroglycol di (meth) acrylate.

The content ratio of (C) is 0 to 80% by weight, preferably 10 to 70% by weight, in the total 100% by weight of the curable component.
When the content ratio of (C) exceeds 80% by weight, the toughness is lowered.

4. The curable composition for resin sheet manufacture TECHNICAL FIELD This invention relates to the curable composition for resin sheet manufacture which has said (A)-(C) component as an essential component.
The composition may be produced according to a conventional method. For example, the components (A) to (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.

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

The composition of the present invention contains the components (A) to (C) as essential components, but various components can be blended depending on the purpose.
As other components, specifically, a photopolymerization initiator [hereinafter referred to as “component (D)”], a thermal polymerization initiator [hereinafter referred to as “component (E)”], an organic solvent, a plasticizer, polymerization inhibition And / or an antioxidant, a light resistance improver, and a compound having two or more mercapto groups [hereinafter referred to as "polyfunctional mercaptan"] and the like 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.

4-1. Other ingredients
1) Component (D) The component (D) is a photopolymerization initiator.
The component (D) is a component to be blended when ultraviolet light and visible light are used as active energy rays. When using an electron beam as an active energy ray, it is not necessary to mix | blend, but in order to improve curability, it can also be mix | blended in a small amount as needed.

As component (D), benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] Propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) )] Phenyl] -2-morpholinopropan-1-one, 2 Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 -Aromatic ketone compounds such as adekaoptomer N-1414 (manufactured by ADEKA Co., Ltd.), phenylglyoxylic acid methyl ester, ethyl anthraquinone, phenanthrene quinone, etc .;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis ( Benzophenone compounds such as diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone ;
Bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, ethyl- (2,4,6-trimethyl benzoyl) phenyl phosphinate and bis (2, Acyl phosphine oxide compounds such as 6-dimethoxybenzoyl) -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]- Thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone and 10-butyl-2-chloroacridone;
1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Oxime esters such as -1- (O-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-Triarylimidazoles 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 (D), 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.

As the component (D), various compounds having a molecular weight of 350 or more and capable of initiating polymerization by light such as ultraviolet light and visible light can be used.
Specific examples of the component (D) 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)-(C) component.

In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, and n represents 2 to 5 numbers.
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 2 to 3 and [(204.3 × n + 16.0) or It is a compound having a molecular weight of (204.3 × n + 30.1)].

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

The compounding ratio of the component (D) 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 curable components.
By setting the compounding ratio of the component (D) to 0.01% by weight or more, the composition can be cured with an appropriate amount of ultraviolet light or visible light amount, and productivity can be improved. By doing this, the weather resistance and the transparency of the cured product can be made excellent.

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

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

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

The use ratio of the component (E) is preferably 10 parts by weight or less based on 100 parts by weight of the total of the curable components.
When the thermal polymerization initiator is used alone, it may be carried out according to the conventional means of radical thermal polymerization, and in some cases, it may be used in combination with a photopolymerization initiator and heat cured for the purpose of further improving the reaction rate after photocuring. Curing can also be performed.

3) 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;
Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone and the like can be mentioned.

  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.

4) Plasticizer A plasticizer can be added for the purpose of imparting flexibility to the cured product and improving the 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, and liquid polyester polyols such as polycaprolactone diol and 3-methylpentanediol adipate. In addition, soft acrylic polymers having a number average molecular weight of 10,000 or less can be mentioned.
The blending ratio of these plasticizers may be set appropriately, but is 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 curable components.
By setting the content to 30 parts by weight or less, it is possible to obtain excellent strength and heat resistance.

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

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

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

4-2. Physical properties of the cured product As the physical properties of the cured product of the composition according to the present invention, those having an elastic modulus of 1 GPa or more and a maximum strain of 2% or more in a bending test are preferable. The cured product of the composition having the elastic modulus is excellent in rigidity, and the one having the maximum strain is tough.
The elastic modulus is preferably 2 GPa or more, more preferably 3 GPa or more.
The maximum strain is preferably 3% or more, more preferably 4% or more.
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.
Further, the maximum strain in the present invention means a strain at which the stress shows the maximum value in the same test.

Furthermore, as a cured product of the composition, one having a breaking energy of 2 MJ / m ³ or more in a bending test is preferable. If the cured product of the composition has the breaking energy, it becomes tough.
The breaking energy is preferably 3 MJ / m ³ or more, more preferably 4 MJ / m ³ or more.
Incidentally, the breaking energy in the bending test in the present invention means a value calculated from the area of the stress-strain curve in the bending test performed at a distance between supporting points of 30 mm and a bending speed of 0.2 mm / min.

The glass transition temperature (hereinafter referred to as “Tg”) of the cured product of the composition is preferably 0 to 250 ° C., more preferably 20 to 230 ° C. By setting the Tg to 0 ° C. or higher, the resin sheet obtained becomes excellent in rigidity and heat resistance, and by setting the temperature to 250 ° C. or lower, toughness can be maintained.
In the present invention, Tg means a temperature at which the tensile loss coefficient tan δ in the dynamic viscoelasticity spectrum measured at a frequency of 1 Hz, a temperature rising temperature of 2 ° C./min, and in a tensile mode is maximum.

4-3. The film thickness of the film thickness 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.

5. 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.
Specifically, in the case of using an active energy ray-curable composition as the composition, the following four production methods can be mentioned, for example.
1) Manufacturing method 1-1
A method of applying a composition to a substrate and irradiating the active energy ray to cure the composition
2) Manufacturing method 1-2
A method of applying a composition to a substrate and laminating it with another substrate, followed by active energy ray irradiation to cure the composition
3) Manufacturing method 1-3
Method of pouring a composition into a substrate having a space portion and irradiating the active energy ray to cure the composition
4) Manufacturing method 1-4
Method of pouring a composition on a base material having a space portion and bonding it to another base material and then irradiating active energy ray to cure the composition In the case of these manufacturing methods, heating may also be performed after active energy ray irradiation. it can.
In the case where the resin sheet obtained from the composition of the present invention is used for a glass substitute application, the above-mentioned production method 1-4 is preferable.

When a thermosetting composition is used 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 heating to cure the composition
6) Manufacturing method 2-2
A method of coating a composition on a substrate and laminating it with another substrate, followed by heating to cure the composition
7) Manufacturing method 2-3
Method of pouring a composition into a substrate having a space and heating to cure the composition
8) Manufacturing method 2-4
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 The above-mentioned preparation method 2-4 is preferable.

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

5-1. As a base material , any of a peelable base material and a base material having no releasability (hereinafter, referred to as "non-releasing base material") can be used.
Examples of the releasable substrate include metal, glass, a film subjected to mold release treatment, and a surface untreated film having releasability (hereinafter collectively referred to as "mold release material").
Examples of the release material include silicone-treated polyethylene terephthalate film, surface-untreated polyethylene terephthalate film, surface-untreated cycloolefin polymer film, and surface-untreated OPP film (polypropylene).

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

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

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

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

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

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

As a specific example of (a2) of FIG. 1, it is a case where the glass and metal by which the mold release process was carried out are used as a base material [FIG. 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.

5-2. In the production of the pretreated resin sheet of the composition, in order to prevent the inclusion of air bubbles in the cured product, it is preferable to carry out a defoaming treatment after blending the respective components.
The defoaming method may, for example, be stationary, vacuum pressure reduction, centrifugal separation, cyclone (autorotation / revolution mixer), gas-liquid separation membrane, ultrasonic wave, pressure vibration, defoaming by a multi-screw extruder, or the like.

5-3. Coating or Injection In the case of coating the composition on a substrate, it may be appropriately set according to the purpose, and a conventionally known bar coater, applicator, doctor blade, knife coater, comma coater, reverse roll Examples of the method include coating using a coater, a die coater, a lip coater, a gravure coater, and a microgravure coater.
In the case of injecting the composition into a substrate having a space portion, a method of injecting the composition into an injection device such as a syringe or an injection device may be mentioned.

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

5-4. 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.

5-5. As a heating method in the case of using a thermosetting composition as a heating composition, a method of immersing in heat and a heat medium bath such as oil, a method of using a heat press, a method of holding in a temperature controlled thermostatic chamber, etc. It can be mentioned.
Conditions such as the heating temperature in the case of heating may be appropriately set according to the composition to be used, the substrate, the purpose and the like. As heating temperature, 40-250 degreeC is preferable. The heating time may be appropriately set according to the composition to be used, the desired resin sheet, etc., and may be 3 hours or more. The upper limit of the heating time is preferably 24 hours or less in consideration of economy.
Moreover, heating temperature can also be changed according to the objective. For example, 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.

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

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

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

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

1. Examples 1 to 4, Reference Examples 1 to 3, Comparative Examples 1 to 6
1) Production of Composition The components (A) to (D) shown in Tables 1 to 3 below are blended in the proportions shown on Tables 1 to 3 below, and further, a rotation / revolution mixer [manufactured by Shinky Co., Ltd. Awatori] Neritaro ARE-250] was used and mixed (1800 rpm × 4 minutes) and defoamed (2000 rpm × 1 minute).

The abbreviations in Tables 1 to 3 mean the following.
(A) Component ACMO: Acryloyl morpholine, KJ Chemicals Ltd. MAA: methacrylic acid, Mitsubishi Rayon KK AA: acrylic acid, Toagosei Co., Ltd. NVF: N-vinylformamide, Tokyo Kasei Co., Ltd. Made in Industry Co., Ltd.
(B) Component · HBUA: Addition reaction product of hexamethylene diisocyanate trimer and hydroxybutyl acrylate (urethane adduct having 3 acryloyl groups in 1 molecule)
· OT-1000: mixture of addition product of pentaerythritol triacrylate and hexamethylene diisocyanate (referred to as "adduct") and pentaerythritol tetraacrylate (referred to as "PETeA") [62: 38 (weight ratio)], Toago synthesis (strain Aronix OT-1000
* In Examples 6 and 7 and Comparative Examples 4 to 6, 50 parts of OT-1000 was used. In Table 3, the adduct corresponding to the component (B) contained in OT-1000 and the PETeA corresponding to the component (C) are separately described.
(C) Component DCPA: Dimethylol tricyclodecane diacrylate, light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.
IB-X: Isobornyl methacrylate, light ester IB-X manufactured by Kyoeisha Chemical Co., Ltd.
M-309: Trimethylolpropane triacrylate, Tooni Gosei Co., Ltd. Alonitsukas M-309
MA: methyl acrylate, manufactured by Toagosei Co., Ltd. MMA: methyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd.
(D) Component DC-1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, DAROCUR 1173 manufactured by BASF Japan Ltd.

2) Production of Resin Sheet As a mold for producing a resin sheet, the molds shown in (a1-1) and (a1-2) of FIG. 1 were used.
Two glass plates [100 mm x 180 mm, thickness 2 mm], two mold-release-treated polyethylene terephthalate (PET) films [100 mm x 180 mm, Toray Industries, Ltd. Therapel MFA] and one silicone rubber plate (thickness 1.0 mm) was used.
A release-treated PET film [(a1-1 of FIG. 1: (2))] is laminated on a glass plate [(a1-1): (1) of FIG. 1], and a silicone rubber plate [ (A1-1): (3) in FIG. 1 were overlapped to form a weir (spacer). Furthermore, a release-treated PET film [(a1-2): (2) 'in FIG. 1] is laminated, and a glass plate [(a1-2): (1)'] in FIG. It was a type.

The composition obtained above was injected using a syringe from the cavity ((a1-1) in FIG. 1: (3-1)) of the silicone rubber plate of the molded plate.
With respect to the obtained molding die, high-pressure mercury lamps (Examples 1 to 5 and Comparative Examples 1 to 3) or visible light LEDs (Examples 6 and 7 and Comparative Example 4) are separately provided on both sides of the glass plate side. 6) was irradiated to cure the composition. The irradiation conditions are as follows.
○ High-pressure mercury lamp I-Graphics Co., Ltd. product UV irradiation device [high-pressure mercury lamp, irradiation intensity 100 mW / cm ² (measured value of UV POWER PUCK manufactured by Fusion UV Systems Japan Ltd.) of 365 nm] One glass plate side was irradiated for 5 minutes, and the other glass plate side was further irradiated for 5 minutes, and ultraviolet rays were irradiated for a total of 10 minutes.
○ UV-LED
It was irradiated for 60 minutes only from the one glass plate side of a shaping | molding die by Opcord Co., Ltd. product LED irradiation apparatus (The irradiation intensity | strength 3.6 mW / cm < ² > of 365 nm).

After cooling, the glass was removed from the mold, and the release-treated PET film was peeled off to take out the cured product. The cured product was heat-treated at 150 ° C. for 6 hours in a nitrogen stream to obtain a resin sheet.
The plastic hardness, the pencil hardness and the bending characteristics of the obtained resin sheet were evaluated according to the following method. The results are shown in Tables 1 to 3.

3) Evaluation method
(1) Using a Vickers indenter, using a plastic hardness microhardness tester (Fisher Scope H100CS manufactured by Fisher Instruments), it is measured under predetermined indentation conditions (0 to 300 mN / 10 sec → 5 sec holding → 300 to 0 mN / 10 sec) The plastic hardness (HUpl value) was determined.

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

(3) Bending Properties A resin sheet was cut into a size of length 50 (mm) × width 10 (mm) × thickness 1 (mm), and a test piece in which the cut surface was smoothed with sandpaper was used. The bending test was performed using Instron 5566A at a distance between supporting points of 30 mm, a bending speed of 0.2 mm / min, and 23 ° C. Flexural modulus (GPa) was calculated from strains of strain 0.1% and 1%. The breaking energy (MJ / m ³ ) was calculated from the area of the stress-strain curve.

2. In the compositions of General Examples 1 to 4, the resin sheets obtained were excellent in both hardness and bending characteristics.
On the other hand, the compositions of Comparative Examples 1 to 6 are compositions not containing the component (A), but although excellent in hardness, those with insufficient maximum strain, breaking strain and breaking energy in bending characteristics In particular, the decrease in breaking energy was large.

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

Claims (10)

It is a composition containing the following components (A) to (C), and in a total amount of 100% by weight of the components (A) to (C), 2 to 40% by weight of the component (A) and the component (B) It consists of a cured product of a curable composition for resin sheet production containing 10 to 90% by weight and 0 to 80% by weight of the component (C) ,
The resin sheet whose thickness of hardened | cured material is 100 micrometers-5 mm .
Component (A): a hydrogen bonding compound having a carboxyl group and one ethylenically unsaturated group (B): a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, which is 3 or more (meth) Compound (C) having an acryloyl group : a compound having an ethylenically unsaturated group, which is a compound other than the components (A) and (B) The resin sheet for producing curable composition further, (D) component: a resin sheet of claim 1 comprising a photopolymerization initiator. The resin sheet for producing curable composition further, (E) component: the resin sheet according to claim 1 or claim 2 including a thermal polymerization initiator. Elastic modulus than 1GPa in bending test of the cured product, the resin sheet according to any one of claims 1 to 3 maximum strain is 2% or more. Resin sheet according to any one of claims 1 to 4 break energy in bending test of the cured product is 2MJ / m ³ or more. The following curable composition for resin sheet production was cast in a mold composed of a substrate / substrate for providing a substrate / wrinkle and having a thickness of 100 μm to 5 mm of a cured product . After that, the manufacturing method of the resin sheet which irradiates an active energy ray from either base material side.

○ A curable composition for producing a resin sheet: A composition containing the following components (A) to (C), and the component (A) is contained in a total amount of 100% by weight of the components (A) to (C): The curable composition for resin sheet manufacture containing -40 weight%, 10-90 weight% of (B) components, and 0-80 weight% of (C) components.
Component (A): a hydrogen bonding compound having a carboxyl group and one ethylenically unsaturated group
Component (B): a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups
Component (C): a compound having an ethylenically unsaturated group, which is a compound other than the components (A) and (B) The method for producing a resin sheet according to claim 6, wherein the curable composition for producing a resin sheet further comprises (D) component: a photopolymerization initiator. The method for producing a resin sheet according to claim 7, wherein the curable composition for producing a resin sheet further comprises (E) component: a thermal polymerization initiator. The method for producing a resin sheet according to any one of claims 6 to 8 , wherein heating is carried out after irradiation with an active energy ray. The following curable composition for resin sheet production was cast in a mold composed of a substrate / substrate for providing a substrate / wrinkle and having a thickness of 100 μm to 5 mm of a cured product . After, the manufacturing method of the resin sheet heated.

○ A curable composition for producing a resin sheet: A composition containing the following components (A) to (C) and (E) and containing 100% by weight of the total amount of the components (A) to (C): The curable composition for resin sheet manufacture which contains 2 to 40 weight% of A components, 10 to 90 weight% of (B) components, and 0 to 80 weight% of (C) components.
Component (A): a hydrogen bonding compound having a carboxyl group and one ethylenically unsaturated group
Component (B): a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and a compound having three or more (meth) acryloyl groups
Component (C): a compound having an ethylenically unsaturated group, which is a compound other than the components (A) and (B)
Component (E): thermal polymerization initiator

Images