KR20180119161A - A curing composition for producing a resin sheet which imparts a strong cured product - Google Patents

Abstract

A curable composition for the production of a resin sheet excellent in rigidity and toughness and excellent in heat resistance.
(A) is contained in an amount of 40 to 80 wt%, and the component (A) is contained in a total amount of 100 wt% of the component (A), the component (B) % Of the component (B), 60 to 20 wt% of the component (B), and 0 to 40 wt% of the component (C). Component (A): Oligomer or polymer having a weakly basic group having a pKa of -3 to 1 in a conjugated acid (B) Component: Compound having a carboxyl group and an ethylenic unsaturated group Component (C): Component (A) Of the ethylenically unsaturated group-containing compound

Description

A curing composition for producing a resin sheet which imparts a strong cured product

The present invention relates to a curable composition capable of producing a resin sheet or a film in a simple and short time, and more preferably relates to an active energy ray curable composition, and the resin sheet obtained from the composition is suitable for optical applications such as a liquid crystal display (LCD) And can be used for various applications including a substrate for a polarizer and a protective film for a polarizer.

In the present specification, acryloyl group or methacryloyl group is referred to as (meth) acryloyl group, acrylate or methacrylate is referred to as (meth) acrylate, and acrylic acid or methacrylic acid is referred to as .

In the present invention, " resin sheet " means a resin sheet or a resin film.

Recently, many touch panel integrated liquid crystal display devices or touch panel integrated organic EL display devices have been applied to mobile devices such as smart phones, 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 a glass is well known. However, flexibility and workability are inferior because the substrate is glass . For this reason, a transparent conductive sheet based on a polyethylene terephthalate sheet has been used for 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 in order to contribute to the thinness and weight reduction of the touch panel, the improvement of the transmittance and the cost reduction of the member, Glass Solution) has been adopted. However, the OGS type has a problem that if the cover glass is broken, the touch panel can not be operated.

As a material of a cover excellent in impact resistance, so-called OPS (One Plastic Solution) which directly forms a touch sensor such as ITO on a resin sheet has been proposed. However, in the conventional acrylic or polycarbonate-based sheet, since the surface hardness is low, scratches tend to occur and the toughness may be insufficient, so that there is a possibility that the acrylic resin or polycarbonate sheet is broken by an impact force from the outside.

Patent Document 1 discloses a plastic member for forming a transparent conductive film which is obtained by photo-curing a photo-curable composition comprising a bismethacrylate and a mercapto compound having a alicyclic skeleton.

In Patent Document 2, there is proposed a resin composition which is obtained by photo-curing a photo-curable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure, a bifunctional (meth) acrylate having an alicyclic structure, Mu m in thickness.

Japanese Patent Application Laid-Open No. 2002-161113 Japanese Patent Application Laid-Open No. 2007-56180

However, the invention described in Patent Document 1 has a problem that although the toughness is imparted with an appropriate toughness by blending a mercapto compound, the usable time (pot life) of the composition is shortened and the stability of the composition is lowered.

In addition, the invention described in Patent Document 2 has a problem that appearance problems arise in a heating process in a process of forming a transparent conductive film or a metal electrode since the rigidity equivalent to that of glass can not be exhibited. In addition, there are many cases where the toughness is insufficient, so that there is a possibility of breakage due to an impact force from the outside.

As described above, no resin sheet having satisfactory performance for OPS has been found so far, and a curable composition which gives a cured product having excellent performance to a thermoplastic resin with high impact has not been obtained with respect to toughness, Remained.

On the other hand, as a resin sheet for a polarizer protective film in the production of a polarizing plate, a cellulose acetate resin such as triacetyl cellulose and diacetyl cellulose, a cyclic olefin such as acrylic resin, polyethylene terephthalate, polycarbonate and norbornene, And a cyclic polyolefin resin.

These resin sheets have been conventionally used as protective films for various polarizing plates and have excellent rigidity and toughness, but they have been insufficient in applications requiring heat resistance.

The present inventors have found that the obtained resin sheet is excellent in rigidity and toughness, and more specifically, has excellent physical properties such as elastic modulus, maximum stress and breaking deformation in the bending test, and furthermore, in the tensile test, And a breaking deformation. When the composition is used as a protective film for a polarizer, it has been extensively studied in order to find a curable composition having excellent heat resistance in addition to rigidity and toughness.

In the present invention, " excellent in rigidity " means that the hardness of the cured product is high and that the modulus of elasticity in the bending test or tensile test is high, and the term "excellent in toughness" means that in the bending test or the tensile test Means a large stress and deformation, that is, a large breaking energy, and in particular, a large breaking deformation.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted various studies in order to solve the above problems. As a result, they have found out the possibility of achieving both rigidity and robustness of a cured product by using a composition using intermolecular interactions other than covalent bonds, It was found that the effect of acid / base interaction was much higher than that of bonding.

 However, since the durability and heat resistance of the cured product deteriorate in the strong acid / base interaction in which the neutralized salt is formed, it is thought that a rather weak acid / base interaction is preferable, and a polymer containing an acidic carboxylic acid group, The combination of polymers including genital was noted.

Table 1 shows the literature values of " pKa of conjugated acid " which is a measure of the basicity of the functional group.

The inventors of the present invention have examined various combinations of weak base groups having suitable interactions with carboxylic acid group-containing polymers by hinting the values in the table. As a result, it has been found that a weak base group having a conjugated acid having a pKa of -3 to 1 is the best, That is, an excellent balance of affinity and stability, and has completed the present invention.

That is, the present invention relates to a curable composition comprising a component (A), a component (B) and optionally a component (C)

(A), 60 to 20% by weight of the component (B) and 0 to 20% by weight of the component (C) in 100% by weight of the total amount of the component (A) 40% by weight < RTI ID = 0.0 >

To a curable composition for producing a resin sheet.

Component (A): Oligomer or polymer having weakly basic group having conjugated acid having a pKa of -3 to 1

(B): a compound having a carboxyl group and an ethylenic unsaturated group

(C): an ethylenically unsaturated group-containing compound other than the component (A) and the component (B)

Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, it is possible to easily produce a resin sheet that combines rigidity and toughness. Specifically, in the bending test, any physical properties such as elastic modulus, maximum stress and breaking deformation are excellent. Further, , It has excellent physical properties such as elastic modulus, maximum stress and breaking deformation. Further, when used as a polarizer protective film, it has excellent heat resistance in addition to rigidity and toughness.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view showing an example of a molding die used when a resin sheet is produced using the composition of the present invention. FIG.

The present invention relates to a curable composition comprising a component (A), a component (B) and optionally a component (C)

(A), 60 to 20% by weight of the component (B) and 0 to 20% by weight of the component (C) in 100% by weight of the total amount of the component (A) 40% by weight < RTI ID = 0.0 >

Curable composition for producing a resin sheet.

Component (A): Oligomer or polymer having weakly basic group having conjugated acid having a pKa of -3 to 1

(B): a compound having a carboxyl group and an ethylenic unsaturated group

(C): an ethylenically unsaturated group-containing compound other than the component (A) and the component (B)

Hereinafter, the details of each component and composition will be described.

1. Component (A)

(A) is an oligomer or polymer having a weakly basic group having a pKa of a conjugated acid of -3 to 1.

Here, the pKa of the conjugated acid means a value measured by an electrochemical method such as a hydrogen electrode method or a glass electrode method, and when it can not be measured by an electrochemical method, It means the value measured by optical method.

In the case of an oligomer or polymer having an ester group (pKa = -6.5), a ketone group (pKa = -7) and an ether group (pKa = -3.5) in which the pKa of the conjugated acid is not smaller than -3, (Aniline; pKa = 4.6, pyridine; pKa = 5.6, secondary amine (pKa)) having a conjugated acid having a pKa of more than 1, while the basicity is excessively weak, ; pKa = 11), there is a problem that stability and heat resistance are low.

As the weak base group of the component (A), various functional groups can be used as far as the pKa of the conjugated acid satisfies the range of -3 to 1. When the carbamate group (pKa = -3) and the amide group (pKa = 0.42) Among them, a carbamate group is particularly preferable.

The concentration of the weakly basic group in the component (A) is preferably 1 to 10 meq / g.

Examples of the compound having a carbamate group include a compound having a urethane bond.

Examples of the compound having an amide group include a polyamide having an aliphatic skeleton generally referred to as nylon.

In the present invention, as the oligomer or polymer, a compound having a molecular weight of 500 to 10,000 is preferable.

In the present invention, the molecular weight means an absolute molecular weight measurable by mass spectrometry, while the molecular weight of a high molecular weight substance means a weight average molecular weight (hereinafter referred to as " Mw ").

In the present invention, Mw means Mw in terms of polystyrene measured by gel permeation chromatography (GPC).

As the component (A), a compound having an ethylenic unsaturated group (hereinafter referred to as a "component (A1)") and a compound having no ethylenic unsaturated group (hereinafter referred to as a "component (A2)") can be used.

Hereinafter, components (A1) and (A2) will be described.

1-1. (A1) Component

The component (A1) is a compound having an ethylenically unsaturated group in the oligomer or polymer.

The number of ethylenically unsaturated groups in one molecule is preferably 2 or more, more preferably 3 or more, and particularly preferably 3 or 4. The concentration of the ethylenic unsaturated group is preferably 0.3 to 10 meq / g.

The fact that the number and concentration of the ethylenic unsaturated groups fall within the above range results in that the resulting cured product has excellent mechanical properties, particularly excellent balance between rigidity and toughness.

Examples of the ethylenic unsaturated group in the component (A1) include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and a (meth) acryloyl group is preferable.

As the component (A1), a compound having a urethane bond and two or more (meth) acryloyl groups [hereinafter referred to as "(A1-1) component") is preferable. The component (A1-1) is a compound generally called urethane (meth) acrylate.

Examples of the component (A1-1) include a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate [hereinafter referred to as "urethane (meth) acrylate" for convenience), an organic polyisocyanate and a hydroxyl group- Acrylate (hereinafter referred to as " urethane adduct ").

1-1-1. Urethane (meth) acrylate

Urethane (meth) acrylate is a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate.

As the polyol which is a raw material of the urethane (meth) acrylate, a diol is preferable and a diol having a low molecular weight diol, a polyester skeleton, a diol having a polyether skeleton and a diol having a polycarbonate skeleton are preferably used.

Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.

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 the dicarboxylic acid or its anhydride include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.

Examples of the diol having a polyether skeleton include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the diol having a polycarbonate skeleton include a reaction product of at least one diol selected from the group consisting of the low molecular weight diol and bisphenol such as bisphenol A and a dialkyl carbonate ester such as ethylene carbonate and dibutyl carbonate have.

Examples of the organic polyisocyanate include aliphatic polyisocyanates having no alicyclic group (hereinafter simply referred to as "aliphatic polyisocyanate"), aliphatic polyisocyanates having alicyclic groups (hereinafter referred to as "alicyclic polyisocyanate"), heterocyclic rings And aromatic polyisocyanates, and the like.

Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate .

Examples of the polyisocyanate having a heterocyclic ring include hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, p-phenylenediisocyanate and 1,5-naphthalene diisocyanate.

The organic polyisocyanate preferably used in the present invention is a polyisocyanate having an aliphatic polyisocyanate and a heterocyclic ring because of excellent physical properties of the cured product and low yellowing.

As the hydroxyl group-containing (meth) acrylate, a hydroxyl group-containing mono (meth) acrylate is preferable. Examples of the hydroxyl group-containing mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, , Hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylate and hydroxy octyl (meth) acrylate, and the like.

1-1-2. Urethane duct

Urethane ducts are reactants of organic polyisocyanates and hydroxyl group-containing (meth) acrylates.

The use of a urethane adhesive as the component (A) is preferable because it enhances the crosslinking density and improves the heat resistance, as well as the toughness by the combined use with the component (B).

Examples of the organic polyisocyanate and hydroxyl group-containing (meth) acrylate in the urethane acrylate include the above-mentioned compounds.

(Hereinafter referred to as " hydroxyl group-containing polyfunctional (meth) acrylate ") as the hydroxyl group-containing (meth) acrylate may be used in the urethane- .

As a urethane duct, the use of a reaction product of an organic polyisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate (hereinafter referred to as "urethane adduct P1") has a high crosslinking density and excellent heat resistance, abrasion resistance and scratch resistance Is preferable.

As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, and specific examples thereof include trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, ditrimethylolpropane Di (meth) acrylate of dipentaerythritol, di (tri), tetra (penta) or penta (meth) acrylate of dipentaerythritol.

Of these, compounds having three or more (meth) acryloyl groups and having one hydroxyl group are preferable from the viewpoint of excellent abrasion resistance and scratch resistance, and specific examples thereof include pentaerythritol tri (meth) acrylate, di Trimethylolpropane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Of these compounds, pentaerythritol tri (meth) acrylate is more preferable because it can prevent the warp of the resulting cured product.

In the production of the urethane adduct P1, the hydroxyl group-containing polyfunctional (meth) acrylate as a raw material is a mixture containing a hydroxyl group-containing polyfunctional (meth) acrylate and a polyfunctional (meth) acrylate not having a hydroxyl group, As the urethane duct P1, those produced using the mixture may also be used.

Specific examples thereof include a mixture of trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate, a mixture of ditrimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) And mixtures of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The reactant obtained from the mixture is a mixture of components (A) and (C).

As a preferred compound of the urethane duct, there can be mentioned a reaction product of an organic polyisocyanate having at least three isocyanate groups and a hydroxyl group-containing mono (meth) acrylate [hereinafter referred to as "urethane adduct P2"].

Examples of the hydroxyl group-containing mono (meth) acrylate in the urethane adduct P2 include the same compounds as the above-mentioned compounds.

Examples of the organic polyisocyanate having three or more isocyanate groups include the above hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Preferable examples of the urethane adduct P2 include an addition reaction product of hexamethylene diisocyanate trimer and hydroxybutyl acrylate.

1-1-3. Preferred (A1-1) component

As the component (A1-1), a urethane adduct is preferable. As the urethane adduct, a compound having three or more (meth) acryloyl groups as a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) More preferred are compounds having three or four (meth) acryloyl groups. The compound has rigidity and high toughness due to the proper crosslinking density of the cured product.

Examples of the urethane adduct having three or more (meth) acryloyl groups include the above-mentioned urethane adduct P1 and urethane adduct P2, and urethane adducts having three or four (meth) acryloyl groups A urethane duct P2 can be mentioned.

1-1-4. (A1-1) < / RTI >

(A1-1) component, the addition reaction of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate in a urethane (meth) acrylate, an addition reaction of an organic polyisocyanate and a hydroxyl group (Meth) acrylate.

This addition reaction may be non-catalytic, but in order to proceed the reaction efficiently, a tin catalyst such as dibutyltin dilaurate, an amine catalyst such as triethylamine, a metal complex system such as zinc complex or iron complex Catalyst or the like may be added.

1-2. (A2) Component

The component (A2) is an oligomer or polymer having a weakly basic group whose conjugated acid has a pKa of -3 to 1, and is a compound having no ethylenic unsaturated group.

Examples of the component (A2) include urethane and polyamide, and polyurethane is preferably used.

Examples of the polyurethane include an addition reaction product of a polyol and a polyisocyanate.

As the polyol and the polyisocyanate in the polyurethane raw material, the same compounds as described above can be mentioned.

As the polyol, a diol having a polyester skeleton, a diol having a polyether skeleton and a diol having a polycarbonate skeleton are preferable.

As the polyisocyanate, aliphatic diisocyanate and alicyclic diisocyanate are preferable.

Examples of the polyamides include aliphatic polyamides having an alkylene group having 10 or more carbon atoms such as polyamide (nylon 11) ring-opening polycondensation of undecane lactam and ring-opened polycondensation of lauryl lactam (nylon 12).

The component (A2) may be used alone, but is preferably used in combination with the component (A1).

The combined use ratio in this case is preferably less than 50% by weight, more preferably 2 to 40% by weight, based on 100% of the total amount of the components (A1) and (A2).

By incorporating the components (A1) and (A2) in such proportions, fracture deformation of the cured product can be improved and toughness can be improved.

2. Component (B)

The component (B) of the present invention is a compound having a carboxyl group and an ethylenic unsaturated group.

Examples of the ethylenic unsaturated group in the component (B) include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and a (meth) acryloyl group is preferable.

As the component (B), various compounds can be used. Examples of the component (B) include a modified product of (meth) acrylic acid, polycaprolactone of (meth) acrylic acid, a Michael addition type oligomer of (meth) acrylic acid, a 2-hydroxyethyl (Meth) acrylate, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and the like, such as adducts of anhydrides and phthalic anhydrides, adducts of 2-hydroxyethyl (meth) acrylate and succinic anhydride.

Among these compounds, (meth) acrylic acid and maleic anhydride are preferable, and (meth) acrylic acid is more preferable.

The content of the component (A) and the content of the component (B) are such that the content of the component (A) is 40 to 80% by weight and the content of the component (B) Is 60 to 20% by weight, preferably 50 to 70% by weight of the component (A) and 30 to 50% by weight of the component (B).

When the proportion of the component (A) is less than 40% by weight or the proportion of the component (B) is more than 60% by weight, the toughness is lowered and the proportion of the component (A) exceeds 80% ) Component is less than 20% by weight, the rigidity is lowered.

3. Component (C)

The present invention essentially includes the above components (A) and (B), but may contain an ethylenically unsaturated group-containing compound other than the above components (A) and (B) as the component (C).

Examples of the ethylenic unsaturated group in the component (C) include a (meth) acryloyl group, a vinyl group and a vinyl ether group, and a (meth) acryloyl group is preferable. However, when maleic anhydride is used as the component (B), a styryl group can be preferably used.

Examples of the compound having one ethylenically unsaturated group in the component (C) include a compound having one (meth) acryloyl group [hereinafter referred to as "monofunctional (meth) acrylate").

Specific examples of the monofunctional (meth) acrylate include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i Acrylates such as butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylates such as 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, allyl ) (Meth) acrylate, p-cumylphenol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (Meth) acrylate, p-cumylphenyl (meth) acrylate, 2- (2-hydroxyethyl) (Meth) acryloyloxyethylhexahydrophthalimide, N- (meth) acryloyloxyethyltetrahydrophthalimide, and the like can be given .

In the component (C), as the compound having two or more ethylenic unsaturated groups, a compound having two (meth) acryloyl groups [hereinafter referred to as "bifunctional (meth) acrylate" (Meth) acryloyl group is hereinafter referred to as " X functional (meth) acrylate ", di (meth) acrylate and bisphenol A di (meth) acrylate of a bisphenol A alkylene oxide adduct Bifunctional (meth) acrylates having an aromatic skeleton such as methacrylate;

Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di 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, Bifunctional (meth) acrylates having an aliphatic skeleton such as 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate;

Hydroxypivalic neopentyl glycol di (meth) acrylate;

Bifunctional (meth) acrylates having an alicyclic skeleton such as dimethyloltricyclodecane di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate and spiroglycol di (meth) acrylate;

 And the like.

Examples of the alkylene oxide adducts described above include ethylene oxide adducts and propylene oxide adducts.

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

As the component (C), only one kind may be used, or two or more kinds may be used in combination.

(Meth) acrylate and hexanediol di (meth) acrylate among the above-mentioned compounds as the component (C) for the reason that rigidity and heat resistance can be imparted. (Meth) acrylate having an alicyclic skeleton such as acrylate, isobornyl (meth) acrylate and the like, and alicyclic dicarboxylic acids such as dimethyloltricyclodecanedi (meth) acrylate, cyclohexanedimethanol di And bifunctional (meth) acrylates having an alicyclic skeleton such as spiroglycol di (meth) acrylate.

(C) is 0 to 40% by weight, preferably 0 to 30% by weight, based on 100% by weight of the total amount of the components (A), (B) and (C). If the proportion of the component (C) exceeds 40% by weight, balance between toughness and rigidity is lowered.

4. Curable composition for manufacturing a resin sheet

The present invention relates to a curable composition for the production of a resin sheet, which comprises the component (A) and the component (B) as essential components and optionally contains the component (C).

The composition may be produced by a conventional method, for example, by mixing the component (A) and the component (B), and optionally the component (C) and other components with stirring.

The viscosity of the composition may be appropriately set according to the purpose, and is preferably from 50 to 10,000 mPa · s.

In the present invention, the term "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 component (A) and the component (B) as essential components and optionally the component (C), but various components may be blended depending on the purpose.

Specific examples of the other components include a photopolymerization initiator (hereinafter referred to as "component (D)"), a thermal polymerization initiator (hereinafter referred to as "component (E)"), an organic solvent, a plasticizer, A light resistance improver, a compound having two or more mercapto groups [hereinafter referred to as "polyfunctional mercaptan"], and an isocyanate compound.

Hereinafter, these components will be described. The later-described components may be used alone or in combination of two or more.

4-1. Other ingredients

4-1-1. (D) Component

Component (D) is a photopolymerization initiator.

Component (D) is a component to be blended when ultraviolet rays and visible rays are used as active energy rays. When an electron beam is used, it is not always necessary to blend it, but it may be blended in a small amount as needed to improve the curability.

Specific examples of the component (D) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1-phenylpropan-1-one, 1- [4- (2- hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- ] Phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) 1- (4-morpholin-4-ylphenyl) butan-1-one, 2-dimethylamino-2- Aromatic ketone compounds such as Deca Optomer N-1414 (manufactured by ADEKA Corporation), phenylglyoxylic acid methyl ester, ethyl anthraquinone, and phenanthrenequinone;

Benzophenone, 4-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzo Phenanone, 4,4'-bis (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzo Benzophenone-based compounds such as phenone and 4-methoxy-4'-dimethylaminobenzophenone;

Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;

Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl- -9H-thioxanthon-2-yl] oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;

Acridine-based compounds such as acridone and 10-butyl-2-chloroacridone;

1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3- Oxalic acid esters such as ethyl ethanone-1- (O-acetyl oxime);

A dimer of 2- (o-chlorophenyl) -4,5-diphenylimidazole, a dimer of 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole, (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- methoxyphenyl) (P-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer; And acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

As the component (D), a photopolymerization initiator having a molecular weight of 350 or more may be used in addition to the above. When the photopolymerization initiator having a molecular weight of 350 or more is used in the production of a transparent conductive film, the resin sheet obtained by the decomposed product after irradiation does not cause discoloration, and when the decomposed product is used for the production of a transparent conductive film, It is possible to achieve a high vacuum in a short period of time and to prevent the film quality of the conductor layer from lowering and making it difficult to reduce the resistance.

Specific examples of the component (D) include a polymer of hydroxy ketone, and examples thereof include compounds represented by the following formula (1). This compound is also preferable in view of excellent compatibility with the components (A) to (C).

[Chemical Formula 1]

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, and n represents a number of 2 to 5. In addition, n means the average number of repeats of the unit.

As the alkyl group for R ² , a lower alkyl group such as methyl group, ethyl group and propyl group is preferable.

Specific examples of the compound represented by the formula (1) include oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone.

This compound is commercially available, for example, ESACURE KIP 150 (manufactured by Lamberti) is known. ESACURE KIP 150 is a compound represented by the 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) n + 30.1)].

Examples of the compound other than the above include 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, oxyphenylacetic acid and the like.

This compound is commercially available, and Irgacure 754 (manufactured 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.

(D) is preferably 0.01 to 0.01 part by weight based on 100 parts by weight of the total of the components (A) and (B) or the components (A) to (C) To 10 parts by weight, more preferably 0.1 to 5 parts by weight.

By setting the blending ratio to 0.01% by weight or more, the composition can be cured by an appropriate amount of ultraviolet ray or visible light, thereby improving the productivity. On the other hand, when the amount is 10 parts by weight or less, the cured product can be excellent in weather resistance and transparency.

4-1-2. (E) Component

When the composition is used as a thermosetting composition, component (E) (thermal polymerization initiator) may be blended.

As the component (E), various compounds can be used, and organic peroxides and azo-based 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, , T-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Hexane, hexane, 2,2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, Propyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxypivalate, t- Butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxide (t-butyl peroxyphenyl) (Benzoyl peroxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butyl Butyl peroxybenzoate, di-t-butyl peroxyisophthalate,?,? '- bis (t-butylperoxy) Butylperoxy) diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumylperoxide, di- Dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilylperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, and the like.

Specific examples of the azo based compound include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoyl azo) isobutyronitrile, 2-phenylazo-4-methoxy- , 4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane and the like.

These may be used alone or in combination of two or more. The organic peroxide may be combined with a reducing agent to form a redox reaction.

The use ratio of the component (E) is preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the curable component.

In the case of using the thermal polymerization initiator alone, it may be carried out according to the usual radical thermal polymerization method. In some cases, thermal curing may be carried out in combination with the photo polymerization initiator, for the purpose of further improving the reaction rate after photo- .

4-1-3. Organic solvent

The composition of the present invention can be mixed with an organic solvent for the purpose of improving the coating property on the substrate. However, when the obtained resin sheet is used for a transparent conductive film application, it is preferable not to include an organic solvent.

Specific examples of the organic solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene and cyclohexane;

Butanol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropanol Butoxyethanol, 2-butoxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene Alcohol solvents such as glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and propylene glycol monomethyl ether;

(2-methoxyethyl) ether, bis (2-ethoxyethyl) ether and bis (2-ethoxyethyl) ether, such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis Ethyl) ether;

But are not limited to, acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, di- , Ketone solvents such as cyclohexanone and methylcyclohexanone;

Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol monomethyl ether acetate and cellosolve acetate;

And aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and? -Butyrolactone.

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

4-1-4. Plasticizer

A plasticizer may be added for the purpose of imparting flexibility to the cured product and improving the ease of breakage.

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 esters, azelaic acid esters, phosphoric acid tricresyl phosphate Liquid polyether polyols such as esters and polypropylene glycols, liquid polyester polyols such as polycaprolactone diols and 3-methylpentanediol adipate, and the like. Further, a soft acrylic polymer having a number average molecular weight of 10,000 or less and the like can be given.

The blending ratio of these plasticizers is appropriately set, 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 curing components.

When the amount is 30 parts by weight or less, strength and heat resistance can be excellent.

4-1-5. Polymerization inhibitor and / or antioxidant

In the composition of the present invention, a polymerization inhibitor and / or an antioxidant may be added in order to improve the storage stability.

As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol and various phenol-based antioxidants are preferable, but a sulfur secondary antioxidant, Etc. may be added.

The total mixing 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 curable components.

4-1-6. Light resistance improver

To the composition of the present invention, a light resistance improving agent such as an ultraviolet absorber or a light stabilizer may be added.

Examples of the ultraviolet absorber include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- (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;

Dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxy- 4-methoxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone , 2,3 ', 4,4'-tetrahydroxybenzophenone, or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

Examples of the light stabilizer include N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformylhexamethylenediamine, bis (3,5-ditertiarybutyl-4-hydroxybenzyl) -2-n-butyl malonate, bis (1,2,2,6,6- Pentamethyl-4-piperidinyl) sebacate, and other low molecular weight hindered amine compounds; (2,2,6,6-tetramethyl-4-piperidyl) -N, N'-diformyl hexamethylenediamine, bis (1,2,2,6,6-penta Methyl-4-piperidinyl) sebacate, and other hindered amine light stabilizers such as the high molecular weight hindered amine compounds.

The blending ratio of the light resistance improver is preferably 0 to 5 parts by weight, more preferably 0 to 1 part by weight, based on 100 parts by weight of the total amount of the curable components.

4-1-7. Polyfunctional mercaptan

The polyfunctional mercaptan can be blended as needed for the purpose of preventing curing shrinkage of the cured composition and for imparting toughness.

As the polyfunctional mercaptan, various compounds can be used as long as they are compounds having two or more mercapto groups.

For example, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, and the like.

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, based on 100 parts by weight of the curable component. By setting the ratio to 20 parts by weight or less, deterioration of the heat resistance and rigidity of the resulting cured product can be prevented.

4-1-8. Isocyanate compound

In the case of using a hardly adhesive base material such as polyvinyl alcohol, an isocyanate compound may be added as means for improving the adhesion with a base material.

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

Examples of the compound having one isocyanate group having two ethylenically unsaturated groups include 1,1-bis [(meth) acryloyloxymethyl] ethyl (meth) acrylate as an example of a compound in which these two groups are connected by a saturated, saturated hydrocarbon skeleton. Isocyanate and the like.

Examples of the compound having two or more isocyanate groups include tolylene diisocyanate, phenylenediisocyanate, chlorophenylenediisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, norbornene diisocyanate, But are not limited to, diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, phthalene diisocyanate, dimethyldiphenyl diisocyanate, dianiline diisocyanate, tetramethyl xylylene isocyanate, trimethyl hexamethylene Diisocyanate, lysine diisocyanate, and the like. Further, an adduct-based isocyanate compound in which these isocyanate compounds are added to polyfunctional alcohols such as trimethylolpropane , Isocyanurate compounds of these isocyanate compounds, biuret-type compounds, allophanate-type compounds, and the like, and further known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols and the like An isocyanate compound of urethane prepolymer type which is subjected to addition reaction.

4-1-9. Other components than the above

In addition to the above-mentioned other components, a release agent, a filler, a soluble polymer and the like may be added to the composition of the present invention.

The releasing agent is compounded for the purpose of facilitating release from the substrate. As the release agent, various surfactants can be used as long as they can be released from the substrate and the compounded liquid and the cured product are not cloudy. For example, anionic surfactants such as alkylbenzenesulfonic acids and the like, cationic surfactants such as alkylammonium salts, nonionic surfactants such as polyoxyethylene alkyl ethers, amphoteric surfactants such as alkylcarboxybetaines, And a surfactant containing silicon.

The filler is blended for the purpose of improving the mechanical properties of the resulting resin sheet. As the filler, both an inorganic compound and an organic compound can be used. Examples of the inorganic compound include silica and alumina. As the organic compound, a polymer can be used. When the resin sheet obtained from the composition of the present invention is used for optical use, it is preferable that the filler does not lower the optical properties.

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 is soluble in the composition. In the present invention, a polymer which is not dissolved in the composition is referred to as a filler and is distinguished.

The mixing 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 curing component.

4-2. Physical Properties of Cured Products

As the physical properties of the cured product of the composition of the present invention, it is preferable that the cured product has a modulus of elasticity of 0.5 GPa or more in the tensile test and a fracture strain of 5% or more.

The cured product having such a modulus of elasticity is excellent in rigidity, and having the maximum strain is tough.

The elastic modulus is more preferably 0.8 GPa or more, and the breaking strain is more preferably 8% or more. The modulus of elasticity is preferably 10 GPa or less, and more preferably 8 GPa or less. The breaking strain is preferably 2,000% or less, more preferably 1,000% or less.

In the present invention, the elastic modulus in the tensile test is a tensile test in which a short-shaped test piece having a length of 50 mm or more is fixed at 20 mm between jigs at a tensile speed of 40 mm / And a stress of 2%.

Further, the breaking deformation in the present invention means a value calculated from the distance between the jigs in the same test and the initial value (20 mm).

The glass transition temperature (hereinafter referred to as " Tg ") of the cured product of the composition is preferably 50 to 250 ° C, more preferably 80 to 200 ° C. The resin sheet obtained by setting the Tg to 50 DEG C or higher is excellent in rigidity and heat resistance, and when it is 250 DEG C or less, toughness can be maintained.

Further, Tg in the present invention means a temperature at which the tensile loss coefficient tan? In the dynamic viscoelasticity spectrum measured at the frequency of 1 Hz, the temperature rising temperature of 2 占 폚 / min and the tensile mode becomes the maximum.

4-3. Film thickness

The film thickness of the resin sheet may be suitably set according to the purpose.

In particular, when it is used for glass substitute use, preferably OPS application, it is preferably 100 탆 to 5 mm, more preferably 200 탆 to 3 mm.

When it is used as a polarizer protective layer, it is preferably 10 μm to 2 mm, more preferably 20 μm to 200 μm.

5. Manufacturing method of resin sheet

As the method for producing the resin sheet using the composition of the present invention, various methods can be adopted.

In the technical field of the resin sheet related to the present invention, a case where the film thickness is relatively large is referred to as a sheet, and a case where the film thickness is comparatively small is often referred to as a film.

As described above, the " resin sheet " in the present invention means a resin sheet or a resin film.

Specifically, when an active energy ray-curable composition is used as the composition, for example, the following four production methods can be mentioned.

1) Preparation method 1-1

A method of coating a composition on a substrate and irradiating an active energy ray to cure the composition

2) Preparation method 1-2

A method in which a composition is coated on a base material and the base material is bonded to another base material and then the active energy ray is irradiated to cure the composition

3) Preparation method 1-3

A method of pouring a composition into a substrate having a space portion and irradiating an active energy ray to cure the composition

4) Preparation method 1-4

A method in which a composition is poured into a substrate having a space and is then cemented with another substrate, and then the active energy ray is irradiated to cure the composition

In the case of these production methods, it is also possible to heat after irradiation with active energy rays.

When the resin sheet obtained from the composition of the present invention is used for glass substitution, the aforementioned production method 1-4 is preferable.

When the resin sheet obtained from the composition of the present invention is used as a polarizer protective film, the aforementioned production methods 1-1 and 1-2 are 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

A method of coating a composition on a substrate and curing the composition by heating

6) Recipe 2-2

A method in which a composition is coated on a base material and is then cemented with another base material and then heated to cure the composition

7) Manufacturing method 2-3

A method of flowing the composition onto a substrate having a space and curing the composition by heating

8) Preparation method 2-4

A method in which a composition is poured into a substrate having a space portion and is then cemented with another substrate and then heated to cure the composition

When the resin sheet obtained from the composition of the present invention is used for glass substitution, 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 aforementioned production methods 2-1 and 2-2 are preferable.

As the polymerization method, both a batch method and a continuous method can be employed.

Examples of the continuous method include a method in which the composition is coated or poured into a base material, and the base material on the belt is continuously supplied.

As another example of the continuous type, there is a method called continuous casting method in addition to the above. That is, two consecutive mirror-surface stainless steel belts are arranged vertically on the caterpillar, the composition is poured between the belt and the belt, and polymerization is continuously carried out between the belt and the belt while slowly moving the belt, And a manufacturing method.

For glass substitute applications, a batch formula is preferred.

5-1. materials

As the substrate, a peelable substrate and a substrate having no releasability (hereinafter, referred to as " non-formed substrate ") can be used.

Examples of the peelable substrate include a metal, a glass, a polymer film subjected to a release treatment, and a surface untreated polymer film having peelability (hereinafter collectively referred to as a " release material ").

For the purpose of facilitating the release of the cured product, the substrate surface may be subjected to a release treatment. As the mold-releasing treatment furnace, for example, silicon or the like may be used to coat or treat the surface of the base material.

Examples of the release-treated polymer film and the surface-untreated polymer film having releasability include a silicone-treated polyethylene terephthalate film, a surface untreated polyethylene terephthalate film, a surface untreated cycloolefin polymer film, and a surface untreated OPP film (polypropylene) have.

For the resin sheet obtained from the composition of the present invention, it is preferable to use a substrate having a surface roughness Ra (center line averaged roughness) of 0.15 탆 or less in order to lower the haze or impart surface smoothness. More preferable. The haze is preferably 3.0% or less.

Specific examples of the substrate include glass, polyethylene terephthalate film, cycloolefin polymer film, OPP film (oriented polypropylene), cellulose acetate resin such as polyvinyl alcohol, triacetylcellulose and diacetylcellulose, acrylic resin, polyester , A cyclic polyolefin resin having as a monomer a cyclic olefin such as polycarbonate, polyarylate, polyethersulfone or norbornene.

In the present invention, the surface roughness Ra means that the roughness of the film surface is measured and the average roughness is calculated.

Examples of the non-forming substrate include various plastics other than the above, and examples thereof include cellulose acetate resins such as polyvinyl alcohol, triacetylcellulose and diacetylcellulose, acrylic resins, polyesters, polycarbonates, polyarylates, And cyclic polyolefin resins in which cyclic olefins such as norbornene are used as monomers.

When the composition of the present invention is used as a polarizer protective material, a polyvinyl alcohol film, that is, a polarizer film obtained by impregnating iodine or dye with impregnation is used as a substrate.

In applications where the base material and the cured layer are provided in an integrated state without peeling the resin sheet or film as a polymer of the curable composition from the base material, for the purpose of improving the adhesiveness of both layers, Chemical treatment can be carried out on the substrate surface.

As a substrate having a space portion, a substrate having a concave portion can be mentioned. And a hole having a predetermined shape in the form of a desired film thickness is formed on the template material to form a concave portion.

In this case, after the composition is poured into the substrate having the concave portion, another substrate may be superimposed on the substrate having the concave portion.

Another example of the base material having a space portion is a base material in which a weir (spacer) is formed on a mold material so that the cured product has a desired film thickness (hereinafter referred to as a " molding die & . In this case, another substrate may be overlapped on the bank.

As an example of the forming mold, FIG. 1 will be described.

(A1-1) and (a1-2) in FIG. 1 are examples of two sheets (1) of (1) (1) of FIG. 1: (a1-1) ((3)) of one sheet of weft (FIG. 1: (2) 'of (2-1) And is an example of a molding die constituted.

1 (a2) of FIG. 1 is a plan view of a substrate (FIG. 1: (a2) (3)) for forming two sheets (1) As shown in Fig.

As shown in Fig. 1, a base material for forming a dam is a base material having a shape having a hole portion (3-1 in Fig. 1: (a1-1)) for injecting a composition into an upper portion (Fig. 1: (a1-1) (3)) and a shape not having a cavity (Fig. 1: (a1-1) It is preferable to have a shape having a hollow portion for the opening. As a substrate for forming the dam, various materials can be used, and examples thereof include silicone rubber and the like.

Specific examples of (a1-1) and (a1-2) in Fig. 1 include a mold composed of two glass sheets as a base material, two films subjected to release treatment, and a base material for forming one sheet .

1 ((a1-1) (2)) is laminated on a glass (Fig. 1 (a1-1) : (3) of (a1-1)] is used as a superposition (spacer). (2) 'of FIG. 1: (a1-2)] is superimposed on the film and a glass (1) of FIG. 1 (a1-2) .

A concrete example of (a2) in Fig. 1 is a case where glass or metal subjected to the release treatment is used as the base material ((1) and (1) 'of Fig. 1 (a2)], and since the releasability of the cured product is excellent, Two films subjected to the release treatment in (a1-1) or (a1-2) in Fig. 1 are unnecessary.

Further, when the cured product of the composition itself is excellent in releasability, it is also possible to use glass as the substrate ((1) and (1) 'in FIG. 1: (a2) Examples in which the cured product of the composition itself is excellent in releasability include an example in which a release agent is blended in the composition.

5-2. Pretreatment of the composition

In coating or injecting the composition of the present invention, the composition is preferably prepared by mixing the resulting resin film with a raw material component so as to prevent the formation of defects such as the prevention of foreign matter contamination or the occurrence of defects such as voids, , And purified.

As a method of purifying the composition, a method of filtering the composition is simple and preferable. Examples of the filtration method include pressure filtration and the like.

The filtration accuracy is preferably 10 占 퐉 or less, and more preferably 5 占 퐉 or less. The smaller the filtration accuracy, the better. However, if the filter is too small, the filter tends to clog the eyes, the frequency of replacement of the filter increases, and the productivity decreases. Therefore, the lower limit is preferably 0.1 mu m.

At the time of production of the resin sheet, in order to prevent the cured product from containing bubbles, it is preferable to carry out defoaming treatment after blending each component. Examples of the degassing treatment include a degassing process using a vacuum, a vacuum decompression, a centrifugal separation, a cyclone (rotation / revolution mixer), a gas-liquid separation membrane, an ultrasonic wave, a pressure oscillation and a multiaxial extruder.

5-3. Coating or injection

The coating method for coating a composition on a substrate may be suitably set according to the purpose and may be suitably selected in accordance with the purpose and may be suitably selected from among conventionally known bar coater, And a method of coating with a microgravure coater or the like.

When a composition is injected into a substrate having a space portion, the composition may be injected by injecting it into an injection device such as a syringe or an injection device.

The film thickness in this case may be suitably set in accordance with the intended film thickness of the resin sheet.

In particular, when it is used for glass substitute use, preferably OPS application, it is preferably 100 μm to 5 mm, more preferably 200 μm to 3 mm, and particularly preferably 300 μm to 2 mm.

When it is used as a polarizer protective layer, it is preferably 10 μm to 2 mm, more preferably 20 μm to 200 μm.

5-4. Active energy ray irradiation

Examples of the active energy ray when the active energy ray-curable composition is used as the composition include ultraviolet rays, visible rays, electron rays and X-rays, and ultraviolet rays and visible rays are preferred Do. Examples of the ultraviolet irradiator include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a black light lamp, a UV non-electrode lamp and an LED.

The irradiation conditions such as the dose and the irradiation intensity in the active energy beam irradiation may be suitably set in accordance with the composition, substrate and purpose of use.

In this case, the active energy ray can be irradiated and then heated. The heating method may be the same as the latter method. Stabilization by rearrangement of molecular chains, progress of polymerization reaction, coupling reaction of free radicals, and the like occur by heat treatment and improvement of heat resistance and optical properties can be expected.

The heating temperature is preferably 50 ° C to 200 ° C, more preferably 100 ° C to 150 ° C. If the heating temperature is low, the effect of the heat treatment is low. If the heating temperature is excessively high, the toughness may decrease due to a crosslinking reaction or the like. The heating time is preferably 1 hour to 1 day, more preferably 2 hours to 10 hours. If the heating time is short, the effect of the heat treatment is low. If the heating time is excessively long, the toughness may decrease due to the crosslinking reaction or the like.

5-5. heating

Examples of the heating method in the case of using the thermosetting composition as the composition include a method of immersing in a heat bath such as heat and oil, a method of using a hot press, and a method of being kept in a warm room-type thermostat.

The conditions such as the heating temperature in the case of heating may be suitably set according to the composition to be used, the substrate and the purpose. The heating temperature is preferably 40 ° C to 250 ° C. The heating time may be suitably set according to the composition to be used and the intended resin sheet, and may be 3 hours or more. The upper limit of the heating time is preferably 24 hours or less in consideration of economical efficiency.

It is also possible to change the heating temperature according to the purpose. For example, a thermal polymerization initiator having a different decomposition temperature is used. Examples of the specific temperature include a method of polymerizing at a relatively low temperature of about 40 to 80 캜 for several hours and then polymerizing at a relatively high temperature of 100 캜 or more for several hours.

6. Use of resin sheet

The resin sheet made of the composition of the present invention can be preferably used particularly as an optical sheet.

The optical sheet formed from the composition of the present invention can be used in various optical applications. More specifically, a liquid crystal display device such as a polarizer protective film of a polarizing plate for a liquid crystal display, a protective film of a circular polarizing plate for an organic EL, a supporting film for a prism sheet and a light guide film, a sheet used for a touch panel- A base sheet of a film (for example, a hard coat sheet, an edible sheet, a transparent conductive sheet) and a sheet having a surface shape (for example, a sheet having a Mosse type antireflective sheet or a textured structure for a solar cell) (Weather-resistant) sheet for outdoor use, a film for LED illumination or organic EL lighting, and a transparent heat-resistant sheet for flexible electronics.

The optical sheet formed from the composition of the present invention is excellent in heat resistance and therefore can be preferably used for producing a transparent conductive sheet. A composition for use in this application is preferably a solventless composition that does not contain an organic solvent because it can suppress the generation of outgassing during the vacuum deposition of the transparent conductive material layer.

The optical sheet of the present invention can also be used as a transparent conductive sheet base material for OPS because the thick film has excellent heat resistance, flexibility, flexibility and high strength. In this case, the optical sheet having the film thickness of 0.5 mm or more and 1.5 mm or less The sheet can be more preferably used.

The transparent conductive sheet can be produced by a conventional method.

Examples of the metal oxide that forms the transparent conductor layer include indium oxide, tin oxide, zinc oxide, titanium oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, Complex oxides and the like. Of these, indium-tin composite oxides and indium-zinc composite oxides are preferable from the viewpoints of environmental stability and circuit processability.

The transparent conductor layer can be formed by a conventional method, and the optical sheet of the present invention can be used to form the transparent conductor layer by a sputtering method using a vacuum deposition apparatus using the metal oxide.

More specifically, the metal oxide is used as a target material and subjected to dehydration and degassing, followed by evacuation to make a vacuum. After the optical sheet is heated to a predetermined temperature, a transparent conductor layer And the like.

The polarizing plate of the present invention is preferably a polarizing plate in which a sheet-like cured product of the composition of the present invention is directly formed as a protective film on at least one side of a polarizer, and at least one side of a polarizer formed of a polyvinyl alcohol- Is a polarizing plate directly formed with a sheet-like cured product of the composition of the present invention.

The method for producing the polarizing plate of the present invention is not particularly limited, but it is possible to use a polarizing plate made of a polyvinyl alcohol-based resin after coating the composition of the present invention on at least one surface thereof, Method.

As the polarizer, various materials can be used as long as they have a function of selectively transmitting linearly polarized light in one direction from natural light.

For example, there are a iodine-based polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol-based film, a dye-based polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based film, a dichroic dye is coated, A coating type polarizer and the like. These iodine-based polarizing films, dye-based polarizing films and coated polarizers have a function of selectively transmitting linearly polarized light in one direction from natural light and absorbing linearly polarized light in the other direction, and are called absorption-type polarizers. Of these polarizers, it is preferable to use an absorptive polarizer excellent in visibility. The thickness of the absorptive polarizer is preferably from 5 to 40 mu m.

When a protective film is provided on both surfaces of the polarizer, it is most preferable to have the protective film of the present invention on both surfaces. However, if necessary, a sheet-like cured product of the composition of the present invention is used as a protective film on one side and a protective film (hereinafter referred to as another protective film) other than the sheet- May be used.

Other protective films include, for example, cellulose acetate resin films such as triacetylcellulose and diacetylcellulose, acrylic resin films, polyester resin films, cyclic polyolefin resin films using cyclic olefins such as norbornene as monomers, and the like . When these are used as a protective film on the display side, a film having a retardation may be used.

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In the following, " part " means weight part and "% " means weight%.

1. Examples 1 to 7, Comparative Examples 1 to 4

1) Preparation of composition

The components shown in Tables 1 to 3 were compounded in the indicated ratios and mixed (1,800 rpm x 4 minutes) using a rotary mixer (ARE-250 manufactured by Shinki Co., Ltd.) (2,000 rpm x 1 minute).

The abbreviations in Tables 1 to 6 mean the following.

(A) Component

OT-1000: An addition reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate (urethane adduct having 6 acryloyl groups per molecule (hereinafter referred to as "adduct") and pentaerythritol tetraacrylate 62: 38 (weight ratio)] (manufactured by Dow Corning Toray Co., Ltd., hereinafter referred to as "PETeA"), Aronix OT-1000

In Example 1 and Comparative Example 1, 30 parts of OT-1000 was used, and in Example 2, 15 parts of OT-1000 was used. In Table 1, an adduct corresponding to component (B) contained in OT-1000 and PETeA corresponding to component (C) are separately described.

HBUA: an addition reaction product of hexamethylene diisocyanate trimer and hydroxybutyl acrylate (urethane adduct having three acryloyl groups in one molecule)

MB-111: 60/40 mixture of polyurethane syrup polyurethane manufactured by Negami Kogyo Co., Ltd. and isobornyl acrylate (IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd.). Weight average molecular weight 65,000, number average molecular weight 33,000

In Tables 3 and 4, polyurethane corresponding to component (A) contained in MB-111 is described as PU, isobornyl acrylate corresponding to component (C) contained in HBUA is divided into IBXA .

Component (B)

AA: Acrylic acid, manufactured by Donga Synthetic Chemical Co., Ltd.

· MAA: methacrylic acid, manufactured by Mitsubishi Rayon Co., Ltd.

(C) Component

M-309: trimethylolpropane triacrylate, Aronix M-309 (trade name, manufactured by Donga Chemical Co., Ltd.)

HDDA: 1,6-hexanediol diacrylate, Viscot # 230 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

(D) Component

DC-1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one, DAROCURE 1173 manufactured by BASF Japan

Molding molds shown in (a1-1) and (a1-2) in Fig. 1 were used as molds for producing resin sheets. (3) 'was used as a substrate for forming the dam.

Two glass plates (100 mm x 100 mm, thickness 1 mm), two release-treated polyethylene terephthalate (PET) films (100 mm x 100 mm, Serafil MFA manufactured by Toray Co., Ltd.) and one sheet of flexible vinyl chloride A mold (thickness 1.0 mm) was prepared.

(A1-1): (2) in Fig. 1) was superimposed on a glass plate ((a1-1): (1) in Fig. 1), and a flexible vinyl chloride mold (a1-1): (3) ') were stacked to form a dam (spacer). (A1-2): (2) 'in FIG. 1) was laminated while taking care not to allow air bubbles to enter the composition, and a glass plate [ (A1-2): (1) 'in Fig. 1), and the whole was fixed with a clip to form a mold.

The obtained mold was irradiated with ultraviolet rays to cure the composition.

The ultraviolet ray irradiation conditions were as follows: Conveyor type ultraviolet ray irradiation apparatus (trade name: US5-X0602; Metal halide lamp 80 W / cm. (Hereinafter referred to as " X0602 "), and passed through 20 times under conditions of roughness of about 140 mW / cm 2, transporting speed of 5 m / min, and cumulative light quantity of about 400 mJ / cm 2. The irradiation surface was changed for each irradiation.

After irradiating with ultraviolet rays, the glass was removed from the molding die, and the releasable PET film was peeled off to take out the cured product to obtain a resin sheet.

The resulting resin sheet was evaluated for bending hardness, bending properties and tensile properties according to the following methods. The results are shown in Tables 2 and 3.

3) Evaluation method

(1) Plastic hardness

(0 to 300 mN / 10 sec → 5 sec → 300 to 0 mN / 10 sec) using a Vickers indenter using a micro hardness meter (Fisher Scope H100CS manufactured by Fisher Instruments) And the hardness (HUpl value) was obtained.

(2) Bending characteristics

The resin sheet was cut into a size of 60 (mm) in length × 10 (mm) in length by a laser cutter, and dirt was removed with methanol as a test piece.

The bending test was carried out using 5566A manufactured by In-Strong Co., at a point-to-point distance of 30 mm, a bending speed of 5.0 mm / sec, and 23 占 폚. The flexural modulus (GPa) was calculated from the stresses of 0.1% and 1% strain. The measurement was repeated 5 times and the average value was shown. In the rupture deformation in the table, those which were not destroyed by the bending test were described as " - ".

In addition, the non-destructive rate in the table means the number of samples which were not destroyed in the bending test / the total number of samples.

(3) Tensile properties

The tensile test was carried out only for the samples having a nondestructive rate of 100% in the bending test.

The test was carried out at 23 DEG C with a jig distance of 20 mm and a tensile speed of 40 mm / min using a monolithic test piece of the same size as that of the bending test, using Instrong 5566A. The deformation was calculated as the initial length of 20 mm assuming that the number of jigs was increased.

The tensile modulus was calculated from the stresses of 1% and 2% strain. The measurement was repeated 5 times and the average value was shown.

(4) Viscoelastic spectrum

A viscoelasticity measuring device DMS6100 manufactured by Seiko Instruments Inc. was used and measured at a frequency of 1 HZ and a heating rate of 2 占 폚 / min in a tensile mode.

The tan? Max temperature was recorded as a reference of the glass transition temperature.

4) General

From the results shown in Tables 2 and 3, it can be seen that the resin sheet obtained from the compositions of Examples 1 to 7 of the present invention had a high hardness, a high elastic modulus and a maximum stress in the bending test, It was not destroyed at all.

The tensile test was also carried out on Examples 2 to 7 since it was not destroyed in the bending test and thus the evaluation of toughness was impossible. As a result, as shown in Table 3, the resin sheets obtained from the compositions of Examples 2 to 7 had excellent results even in the tensile test.

On the other hand, the resin sheet obtained from the composition of Comparative Example 1 which did not contain the component (B) had 100% destruction (non-breaking rate of 0%) in the bending test. In the resin sheet obtained from the composition of Comparative Example 2 in which the ratio of the component (B) was less than the lower limit of the present invention, 40% of the test pieces were broken (non-breaking ratio: 60%). In the resin sheet obtained from the composition of Comparative Example 3 which does not contain the component (B), 80% of the test pieces were broken in the bending test (non-breaking rate: 20%). The resin sheet obtained from the composition of Comparative Example 4 in which the ratio of the component (B) exceeds the upper limit of the present invention was 100% broken in the bending test (non-breaking rate: 0%).

2. Examples 8 to 10 and Comparative Example 5

1) Preparation and evaluation of composition and resin sheet

A resin sheet was prepared and evaluated in the same manner as in Examples 1 to 7 except that the cured product obtained after ultraviolet irradiation was subjected to heat treatment in a nitrogen stream at 120 캜 for 5 hours. Table 4 shows the composition and evaluation results.

As a comparative example 4, a polycarbonate (Yuferon NF-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a typical toughness thermoplastic resin, Hereinafter abbreviated as " EUP "), and evaluated in the same manner as in Examples 1 to 7. The evaluation results are shown in Table 4.

2) General

From the results of Table 4, it can be seen that the resin sheet obtained from the composition of Example 8 of the present invention had a high hardness, an excellent bend test result, no break at the bend test, and excellent tensile test results.

The resin sheet of Example 8 in which the heat treatment was not performed was compared with the resin sheet of Example 8 in which the heat treatment was performed and the resin sheet of Example 8 in which the heat treatment was performed showed the stiffness ) Was further improved.

The resin sheets obtained from the compositions of Examples 9 and 10 containing PU (polyurethane) as the component (A) were also excellent in the results of the bending test and in the bending test, The tensile test results were also excellent.

The resin sheet obtained from the composition of Example 9 was obtained in the same manner as in Example 8 except that Example 9 containing polyurethane as the component (A) was compared with Example 8 containing no PU (polyurethane) as the component (A) The breaking deformation of the tensile test was improved.

The resin sheet obtained from the compositions of Examples 8 to 10 had higher rigidity (plasticity hardness, tensile elastic modulus, and maximum stress) and higher fracture deformation than the polycarbonate (EUP), which is a typical toughness thermoplastic resin of Comparative Example 5, I can see that it is in.

3. Examples 11 to 12, Comparative Example 6 (Example having a thickness of 100 占 퐉)

1) Preparation and evaluation of composition and resin sheet

Using the composition of the present invention, a comparatively thin resin sheet was produced and evaluated.

The compositions were prepared in the same manner as in Examples 1 to 7.

The obtained composition was applied to a cycloolefin polymer film (manufactured by Nippon Zeon Co., Ltd.) having a thickness of 100 mu m as a substrate. Product Name: ZEONOR ZF14. (Hereinafter referred to as " Zeonor ZF ") was used, a coating film having a thickness of about 100 mu m was formed by using an applicator, and Zeonor ZF was covered with caution so that bubbles would not enter the coating film.

The laminate was irradiated with ultraviolet rays to cure the composition.

The ultraviolet irradiation condition was X0602, and passed five times under conditions of roughness of 240 mW / cm 2, transporting speed of 5 m / min, and cumulative light quantity of about 680 mJ / cm 2.

After irradiating ultraviolet rays, Zeonor ZF was removed from the laminate and the cured product was taken out.

The resultant cured product was heat-treated in a nitrogen stream at 120 DEG C for 5 hours to obtain a resin sheet.

Using the obtained resin sheet, viscoelastic spectrum measurement and tensile test were carried out.

The viscoelastic spectral measurement was carried out in the same manner as described above.

The tensile test was carried out using a dumbbell type test piece with a No. 6 dumbbell tread and a tensile speed of 40 mm / min at 23 ° C using an Instrong 5566A. The deformation was calculated as the initial length of 20 mm, assuming that the width of the specimen was 4 mm wide and 20 mm long. The tensile modulus was calculated from the stresses of 1% and 2% strain. Repeated 5 times, the average value was shown.

The composition of the mixture and the evaluation results are shown in Table 5.

As Comparative Example 6, Zeonor ZF, which is a representative optical film, was used and evaluated in the same manner as described above. The evaluation results are shown in Table 5. In Table 5, Zeonor ZF is denoted as " ZEO ".

2) General

From the results shown in Table 5, the resin sheets of Examples 11 and 12 having a thickness of about 100 占 퐉 had high Tg, excellent heat resistance, and excellent tensile test results.

Further, since the resin sheets of Examples 11 and 12 were strong resins, they were able to be hit by a footplate without breaking.

Further, it was found that the resin sheets of Examples 11 and 12 are films excellent in rigidity, toughness and heat resistance as compared with the cycloolefin polymer (Zeonor ZF) which is a typical optical film of Comparative Example 6.

4. Example 13 (Evaluation as Polarizer Protective Film)

A polyvinyl alcohol film having a thickness of 80 탆 was swelled in a water bath at 30 캜 and then dyed in an aqueous iodine solution of 5% by weight (weight ratio: iodine / potassium iodide = 1/10). Subsequently, it was immersed in an aqueous solution containing 3% by weight of boric acid and 2% by weight of potassium iodide, uniaxially stretched to 5.5 times in an aqueous solution containing 4% by weight of boric acid at 55 ° C and 3% by weight of potassium iodide , And immersed in an aqueous 5 wt% potassium iodide solution. Thereafter, the resultant was dried in an oven at 70 캜 for 1 minute to obtain a polarizer having a thickness of 30 탆.

1.2% by weight of Duranate TPA-100 (1,6-hexamethylene diisocyanate triallyl monomer) manufactured by Asahi Chemical Industry Co., Ltd.) as an isocyanate compound was added to the composition of Example 12 as a polarizer protective film , One side of the polarizer was coated and ultraviolet cured in the same manner as in Examples 11 to 12 and a polarizer protective film was formed on the other side of the polarizer in the same manner.

 Further, any surface of the polarizer was subjected to corona treatment in advance.

As to the adhesiveness between the cured product and the polarizer, the presence or absence of peeling at the end when cut into a size of 50 mm x 50 mm using a pencil was observed, and as a result, the cured product and the polarizer were integrated and no peeling was observed. The polarizing plate was allowed to stand for 120 hours in a constant temperature and humidity bath at 60 DEG C and 90% RH, and the presence or absence of discoloration of iodine was examined. As a result, discoloration of iodine was not observed.

From the above results, it was found that when the composition of the present invention is used as a protective film, a polarizing plate having excellent humidity resistance and adhesion can be obtained.

As is clear from the results of the above examples, the resin composition of the present invention can easily obtain a resin sheet having both rigidity and toughness, and can be used for applications including optical sheets or films .

Industrial availability

The composition of the present invention can be suitably used for producing a resin sheet, and the obtained resin sheet can be used for various purposes, and can be preferably used particularly as an optical sheet or a film. The optical sheet can be preferably used for producing a transparent conductive sheet, and can be more preferably used for producing a transparent conductive sheet for a touch panel, and can be preferably used for a protective film for a polarizer.

Claims (22)

(A), (B) and optionally (C)
(A), 60 to 20% by weight of the component (B) and 0 to 20% by weight of the component (C) in 100% by weight of the total amount of the component (A) 40% by weight < RTI ID = 0.0 >
Curable composition for manufacturing a resin sheet.
Component (A): Oligomer or polymer having weakly basic group having conjugated acid having a pKa of -3 to 1
(B): a compound having a carboxyl group and an ethylenic unsaturated group
(C): an ethylenically unsaturated group-containing compound other than the component (A) and the component (B) The method according to claim 1,
Wherein the weak base group of the component (A) is a group selected from the group consisting of a carbamate group and an amide group. 3. The method according to claim 1 or 2,
Wherein the component (A) is an oligomer or polymer having a molecular weight of 500 to 10,000. 4. The method according to any one of claims 1 to 3,
Wherein the component (A) comprises (A1) an oligomer or polymer comprising an ethylenically unsaturated group. 5. The method of claim 4,
Wherein the component (A1) is a compound having a urethane bond and two or more (meth) acryloyl groups. 6. The method of claim 5,
Wherein the component (A1) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate. The method according to claim 6,
Wherein the component (A1) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate and has at least three (meth) acryloyl groups. 8. The method of claim 7,
Wherein the component (A1) is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate and has 3 or 4 (meth) acryloyl groups. 9. The method according to any one of claims 4 to 8,
Wherein the component (A) comprises an oligomer or polymer having no (A1) component and (A2) an ethylenically unsaturated group and the component (A2) is contained in an amount of 0% by weight in a total amount of 100% By weight and less than 50% by weight based on the total weight of the curable composition. 10. The method of claim 9,
Wherein the component (A2) is a polyurethane. 11. The method according to any one of claims 1 to 10,
Wherein the component (B) is (meth) acrylic acid. 12. The method according to any one of claims 1 to 11,
The curable composition for producing a resin sheet further comprising a photopolymerization initiator. 12. The method according to any one of claims 1 to 11,
The curable composition for producing a resin sheet further comprising a thermal polymerization initiator. 14. The method according to any one of claims 1 to 13,
Wherein the cured product has a modulus of elasticity of 0.5 GPa or more in the tensile test and a fracture strain of 5% or more. A resin sheet comprising a cured product of the composition according to any one of claims 1 to 14. The composition according to any one of claims 1 to 12 is poured into a mold having a substrate, a substrate for forming a weir and a substrate in at least the following order, and then the resin ≪ / RTI > 17. The method of claim 16,
Irradiating an active energy ray, and heating the resin sheet. A method for producing a resin sheet, which comprises applying the composition according to any one of claims 1 to 12 to a substrate and then irradiating an active energy ray. 19. The method of claim 18,
Irradiating an active energy ray, and heating the resin sheet. A method for producing a resin sheet for heating after flowing the composition according to any one of claims 1 to 11 and 13 into a mold having at least a substrate, a substrate for forming a weir and a substrate in this order . A polarizing plate in which a sheet-like cured product of the composition according to any one of claims 1 to 12 is directly formed on at least one side of a polarizer formed of a polyvinyl alcohol-based resin as a protective film. A method for producing a polarizing plate, comprising applying a composition according to any one of claims 1 to 12 on at least one surface of a polarizer formed of a polyvinyl alcohol-based resin, and then irradiating an active energy ray from any of the substrates.

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