KR20220002137A - Urethane(meth)acrylate, active energy-ray curable resin composition, cured product and laminate - Google Patents

Abstract

The purpose of the present invention is to provide urethane (meth)acrylate which provides a cured product with low moisture permeability and an active energy ray-curable resin composition. The present invention comprises: a hydride (a1) of a polymer of a hydrocarbon (a1-1) having an olefinic double bond and a cyclic structure and a compound (a1-2) having an active hydrogen; urethane (meth)acrylate which is a reactant with following (I) and/or (II); (I) (meth)acrylate (a2) having one isocyanate group; and (II) polyisocyanates (a3) and (meth)acrylates having hydroxy groups (a4).

Description

Urethane (meth)acrylate, active energy ray-curable resin composition, cured product, and laminate {URETHANE(METH)ACRYLATE, ACTIVE ENERGY-RAY CURABLE RESIN COMPOSITION, CURED PRODUCT AND LAMINATE}

The present invention relates to a urethane (meth)acrylate, an active energy ray-curable resin composition, a cured product, and a laminate.

The polarizing plate conventionally used for a liquid crystal display device is manufactured by adsorbing an iodine etc. to a polyvinyl alcohol film, and bonding a triacetyl cellulose film (TAC film) to both surfaces of the polarizer made to orientate by extending|stretching etc. Moreover, on the surface of a TAC film, a transparent active energy ray-curable resin composition is apply|coated and hardened, the film (hard-coat layer) of high hardness is formed, and the flaw prevention function is provided. As such a resin composition, the thing using polyfunctional urethane (meth)acrylate etc. is known, for example (patent document 1).

However, since the TAC film has high hygroscopicity (having high moisture permeability), depending on the use environment, humidity may cause it to expand and contract, causing display unevenness or the like.

As a technique for solving moisture permeability, an active energy ray-curable resin composition essentially containing a petroleum resin having a hydroxyl value of 10 mgKOH/g or less and a (meth)acrylate compound is disclosed, but even if the petroleum resin is used, moisture permeability is It was still high (patent document 2).

Japanese Patent Laid-Open No. 9-290491 Japanese Laid-Open Patent Publication No. 2018-135452

The subject of this invention is providing the urethane (meth)acrylate which provides hardened|cured material provided with low moisture permeability, and an active energy ray-curable resin composition.

MEANS TO SOLVE THE PROBLEM When these inventors earnestly examined, the urethane (meth)acrylate which synthesize|combined the hydride of a specific olefin type polymer as a raw material found out that the said subject was solved, and came to complete this invention. That is, this invention relates to the following urethane (meth)acrylates, an active energy ray-curable resin composition, hardened|cured material, and a laminated body.

1. A hydride (a1) of a polymer of a hydrocarbon (a1-1) having an olefinic double bond and a cyclic structure and a compound (a1-2) having an active hydrogen;

Urethane (meth)acrylate which is a reaction product with the following (I) and/or (II).

(I) (meth)acrylate having one isocyanate group (a2)

(II) polyisocyanates (a3) and (meth)acrylates having hydroxyl groups (a4)

2. (a1-1) The urethane (meth)acrylate of Claim 1 in which a component contains dicyclopentadiene and/or styrene.

3. (a1-2) The urethane (meth)acrylate according to 1 or 2, wherein the component contains an unsaturated aliphatic alcohol.

4. (a2) The urethane (meth)acrylate in any one of the preceding paragraphs 1-3 whose component is isocyanatoalkyl (meth)acrylate.

5. The urethane (meth)acrylate according to any one of items 1 to 4, wherein the component (a3) is an alicyclic polyisocyanate.

6. Active energy ray-curable resin composition containing the urethane (meth)acrylate in any one of the preceding paragraphs 1-5.

7. The active energy ray-curable resin composition according to the above 6, further comprising an active energy ray-curable monomer (B) and/or a metal oxide (C).

8. Hardened|cured material of the active-energy-ray-curable resin composition as described in the preceding item 6 or 7.

9. A laminate having the cured product according to the preceding item 8 on at least one side of a base film having a water vapor transmission rate of 200 g/m 2 ·24 h or more.

10. The laminate according to item 9, wherein the moisture permeability is 100 g/m 2 ·24 h or less.

The urethane (meth)acrylate which concerns on this invention provides the hardened|cured material provided with low moisture permeability. Moreover, the said hardened|cured material is excellent also in light resistance, and hardness is also maintained. Since the said hardened|cured material is low moisture permeability, it can apply to uses, such as a barrier film, a polarizing plate, the sealing material of organic electroluminescent element, and a packaging film.

The urethane (meth)acrylate of the present invention contains a hydrocarbon (a1-1) having an olefinic double bond and a cyclic structure (hereinafter referred to as (a1-1) component) and a compound (a1-2) having an active hydrogen ) (hereinafter referred to as (a1-2) component.) A hydride (a1) of a polymer (hereinafter referred to as (a1) component.);

It is a reaction product with the following (I) and/or (II).

(I) (meth)acrylate (a2) having one isocyanate group (hereinafter referred to as (a2) component.)

(II) Polyisocyanate (a3) (hereinafter referred to as (a3) component) and (meth)acrylate (a4) having a hydroxyl group (hereinafter referred to as (a4) component).

The urethane (meth)acrylate of the present invention is, for example, a reaction product of the component (a1) and the component (a2) (hereinafter referred to as urethane (meth)acrylate (A1)).

Alternatively, a reaction product of the component (a1), the component (a3), and the component (a4) (hereinafter referred to as urethane (meth)acrylate (A2)), etc. can be mentioned.

First, the urethane (meth)acrylate (A1) (hereinafter also referred to as (A1) component.) will be described.

The component (a1) is a hydride of a polymer of a hydrocarbon (a1-1) having an olefinic double bond and a cyclic structure and a compound (a1-2) having an active hydrogen. (a1) By using a component, hardened|cured material shows low moisture permeability.

Component (a1-1) is a hydrocarbon composed of a carbon atom and a hydrogen atom, and each having at least one olefinic double bond and at least one cyclic structure in the molecule. (a1-1) It does not specifically limit as a component, For example, Cyclobutenes, such as cyclobutene, methylcyclobutene, dimethylcyclobutene, tetramethylcyclobutene, ethylcyclobutene; cyclopentene, such as cyclopentene, methylcyclopentene, dimethylcyclopentene, ethylcyclopentene, ethylmethylcyclopentene, and propylcyclopentene; cyclohexenes such as cyclohexene, methylcyclohexene, dimethylcyclohexene, trimethylcyclohexene, tetramethylcyclohexene, ethylcyclohexene, ethylmethylcyclohexene, methylpropylcyclohexene, isopropylmethylcyclohexene, and butylcyclohexene; cycloheptenes such as cycloheptene, methylcyclopentene, dimethylcyclopentene, ethylcyclopentene, and propylcyclopentene; cyclooctene, such as cyclooctene and methylcyclooctene; cyclobutadiene, such as cyclobutadiene, methylcyclobutadiene, dimethylcyclobutadiene, and ethylcyclobutadiene; cyclopentadiene, such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, ethylcyclopentadiene, and diethylcyclopentadiene; cyclohexadiene, such as cyclohexadiene, methylcyclohexadiene, dimethylcyclohexadiene, trimethylcyclohexadiene, tetramethylcyclohexadiene, pentamethylcyclohexadiene, and methylisopropylcyclohexadiene; cyclooctadiene, such as cyclooctadiene and dimethylcyclooctadiene; Dicyclopentadiene such as dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tetramethyldicyclopentadiene, pentamethyldicyclopentadiene, ethyldicyclopentadiene, and diethyldicyclopentadiene ; dicyclohexadiene, such as dicyclohexadiene, methyldicyclohexadiene, dimethyldicyclohexadiene, trimethyldicyclohexadiene, tetramethyldicyclohexadiene, and pentamethyldicyclohexadiene; styrenes such as styrene, α-methylstyrene, β-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, and 4-ethylstyrene; Indene, such as indene, methyl indene, dimethyl indene, ethyl indene, and butyl indene, etc. are mentioned. These may be individual and may combine 2 or more types. Especially, it is preferable to contain dicyclopentadiene and/or styrene from a reactive point with (a1-2) component.

(a1-2) A component means the compound which has at least 1 active hydrogen in a molecule|numerator. "Active hydrogen" means a hydroxyl group (-OH), a carboxyl group (-COOH), a thiol group (-SH), a sulfo _{group (-SO 3} H), an amino group (-NH ₂ , -NH-), a phosphoric acid group in the molecule (-OP(=O)-(OH) ₂ ) means a hydrogen atom in a functional group, etc., but in the present invention, a compound having a hydroxyl group from the viewpoint of easily reacting with the component (a2) or component (a3) described later , the compound which has a carboxyl group, and the compound which has an amino group are preferable.

As a compound which has a hydroxyl group, For example, Unsaturated aliphatic alcohols, such as allyl alcohol and methallyl alcohol; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( hydroxyalkyl (meth)acrylates such as meth)acrylate; Phenolic compounds, such as a phenol, cresol, bisphenol A, bisphenol F, and a phenol novolak, etc. are mentioned. These may be individual and may combine 2 or more types. In addition, "unsaturated" means having at least one carbon-carbon double bond and/or a carbon-carbon triple bond in a molecule|numerator. (hereinafter the same)

As a compound which has a carboxyl group, For example, unsaturated aliphatic carboxylic acids, such as maleic acid, maleic anhydride, and fumaric acid; and aromatic carboxylic acids such as phthalic acid, isophthalic acid, phthalic anhydride and trimellitic acid. These may be individual and may combine 2 or more types.

As a compound which has an amino group, For example, Unsaturated aliphatic amines, such as allylamine and methallylamine; Aromatic amines, such as aniline, etc. are mentioned. These may be individual and may combine 2 or more types.

Among these compounds, an unsaturated aliphatic alcohol is preferable in terms of reactivity with the component (a1-1).

The ratio of the component (a1-1) and the component (a1-2) used is usually 3/1 to 1/3, preferably 2/1 to 1/2, in terms of molar ratio.

The polymer before the hydrogenation reaction is obtained by making the component (a1-2) coexist and react with the component (a1-1). It does not specifically limit as a reaction method, Various well-known methods are employable. For example, in the presence of a catalyst such as aluminum chloride or boron trifluoride, at about -20 to 60°C, the component (a1-1) and the component (a1-2) are heated for 1 to 6 hours, followed by cationic polymerization ; In an autoclave, the method of heating the component (a1-1) and (a1-2) for 1 to 8 hours at about 150-300 degreeC, and making it thermally polymerize, etc. are mentioned. In the said thermal polymerization, you may add radical generators, such as di-tert- butyl peroxide, as needed.

Although the said superposition|polymerization can also be performed by non-solvent, it is preferable to carry out in an organic solvent from the point of the calorific value at the time of reaction. The organic solvent is not particularly limited as long as it is inert to these reaction components, and examples thereof include alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; Aromatic hydrocarbons, such as benzene, toluene, and xylene, etc. are mentioned. These may be individual and may combine 2 or more types. Moreover, as the usage-amount of an organic solvent, it is 20 to 95 weight% in reaction density|concentration, It is preferable to adjust so that it may become preferably 40 to 90 weight%.

(a1) component is what hydrogenated the polymer obtained above. As the hydrogenation conditions, usually, the pressure is about 1 to 30 MPa (preferably about 3 to 25 MPa), the temperature is about 50 to 400 ° C (preferably about 100 to 350 ° C), and the time is 10 minutes to 10 It is about an hour (preferably about 20 minutes - about 7 hours). In addition, the above hydrogenation conditions do not exclude those outside the numerical range, and for example, if hydrogenation can be carried out using a catalyst capable of causing a reaction even at a pressure of less than 1 MPa, it may be carried out under those conditions.

Examples of the catalyst used for the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, and rhenium, or metal compounds such as oxides and sulfides thereof. The catalyst may be used while being supported on a carrier such as alumina, silica, silica alumina (diatomaceous earth), carbon, or titania, which is porous and has a large surface area.

The usage-amount of a catalyst is about 0.01 to 10 weight% normally with respect to the said polymer.

Said hydrogenation reaction is implemented in the state which melt|dissolved the said polymer or melt|dissolved in the organic solvent. The organic solvent is not particularly limited as long as it is inert during the hydrogenation reaction and can dissolve the component (a1) of the polymer or reactant of the raw material, for example, oxygen in rings such as tetrahydrofuran and dioxane compounds having atoms; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and 2-ethylhexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; Alcohol, such as isopropyl alcohol, n-butanol, 2-methyl- 2-propanol, cyclohexanol, n-hexanol, and 2-ethylhexanol, etc. are mentioned. These may be individual or may combine 2 or more types. Although it does not specifically limit as the usage-amount of an organic solvent, As a reaction density|concentration, it is 95 weight% or less normally, It is preferable to adjust so that it may become preferably 30 to 90 weight%.

As a physical property of the obtained component (a1), for example, a hydroxyl value is 80-250 mgKOH/g normally, Preferably it is 100-240 mgKOH/g. By setting it as the said range, there exists a tendency for color tone to be favorable and to react easily with (a2) component or (a3) component. In addition, a hydroxyl value is a measured value based on JISK-0070.

Moreover, the softening point of (a1) component is 90-120 degreeC normally, Preferably it is 95-115 degreeC. In addition, a softening point is a measured value based on JISK-5902.

(a2) A component is a (meth)acrylate which has one isocyanate group, and is a component which contributes to the hardness and low moisture permeability of hardened|cured material. (a2) As a component, For example, iso, such as 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-butylisocyanatobutyl (meth)acrylate cyanatoalkyl (meth)acrylate; 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, etc. are mentioned. Moreover, as a commercial item, Showa Denko Co., Ltd. product "Karenz AOI", "Karenz MOI", "Karenz MOI-EG", "Karenz BEI", etc. can be used. These may be individual and may combine 2 or more types. Especially, the point of the reactivity with (a1) component and the low moisture permeability of hardened|cured material to isocyanatoalkyl (meth)acrylate is preferable.

Although it does not specifically limit as the usage-amount of (a2) component, (a2) In the ratio of the number of isocyanate groups in component (NCO _(a2) ), and the number of hydroxyl groups in (a1) component (OH _(a1) ), [ (NCO _(a2)) /(OH _(a1) )] =0.90 to 1.05 are preferable, and 0.95 to 1.00 are more preferable.

(A1) A component is obtained by making a (a1) component and (a2) component react. The conditions are not particularly limited, and for example, usually the temperature is about 50 to 100°C (preferably about 60 to 80°C), and the time is about 0.1 to 6 hours (preferably 0.5 to 2 hours). degree) is.

In addition, manufacture of (A1) component can be performed either in the organic solvent mentioned above, or under no solvent.

Although it does not specifically limit as a physical property of the component (A1) obtained in this way, For example, about 300-10000 are preferable and, as for a weight average molecular weight, about 500-7000 is more preferable. In addition, the weight average molecular weight here is the value measured by the GPC method (polystyrene conversion value by the gel permeation chromatography method). (hereinafter the same)

Next, the urethane (meth)acrylate (A2) of this invention (henceforth (A2) component is also mentioned.) is demonstrated.

(a1) The component is as described in the previous paragraph.

(a3) It does not specifically limit as a component, For example, Aliphatic polyisocyanate, such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, and lysine diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,4-cyclohexanediisocyanate, norbornenemethane diisocyanate, cyclohexane-1,4-diylbis(methylene)diisocyanate, hydrogenation alicyclic polyisocyanates such as xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated dimethyldiphenylmethane diisocyanate, and hydrogenated naphthalene diisocyanate; Aromatic polyisocyanate, such as xylylene diisocyanate, tolylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, dimethyl diphenylmethane diisocyanate, and naphthalene diisocyanate, etc. are mentioned. In addition, these may be individual and may combine 2 or more types. Moreover, as for (a3) component, what has any structure of a nurate body, an adduct body, and a burette body can be used. Especially, the point of the low moisture permeability of hardened|cured material to alicyclic polyisocyanate is preferable, and isophorone diisocyanate, norbornenemethane diisocyanate, and hydrogenated xylylene diisocyanate are more preferable.

Although it does not specifically limit as the usage-amount of (a3) component, (a3) In the ratio of the number of isocyanate groups (NCO _(a3) ) in the component, and the number of hydroxyl groups (OH _(a1) ) in (a1) component, [ (NCO _(a3) )/(OH _(a1) )] =0.90 to 1.05 are preferable, and 0.95 to 1.00 are more preferable.

(a4) As a component, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acryl aliphatic mono(meth)acrylates having a hydroxyl group such as a rate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate; Alicyclic mono(meth)acrylate which has hydroxyl groups, such as 4-hydroxycyclohexyl (meth)acrylate and 5-hydroxycyclooctyl (meth)acrylate; Mono (meth) acrylate having a hydroxyl group and an ether chain, such as 2-hydroxy-3-phenyloxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate ; erythritol (meth)acrylates such as erythritol di(meth)acrylate and erythritol tri(meth)acrylate; pentaerythritol (meth)acrylates such as pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, and pentaerythritol tri(meth)acrylate; Dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( dipentaerythritol (meth)acrylates such as meth)acrylate; Tripentaerythritol (such as tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate) Meth) acrylates, etc. are mentioned. These may be individual and may combine 2 or more types. Especially, from the point of the reactivity with an isocyanate group and the low moisture permeability of hardened|cured material, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, penta Erythritol (meth)acrylates are preferable, and 2-hydroxyethyl acrylate is more preferable.

In addition, as said (a4) component, you may use the mixture containing the poly(meth)acrylate which does not contain a hydroxyl group. It does not specifically limit as poly(meth)acrylate which does not contain a hydroxyl group, For example, erythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth) ) acrylate, and tripentaerythritol octa (meth)acrylate. As content of the poly(meth)acrylate which does not contain a hydroxyl group, it is 60 weight% or less with respect to 100 weight% of (a4) component.

(a4) As a commercial item of the component, "Aronix M305", "Aronix M306", "Aronix M400", "Aronix M402", "Aronix M403", "Aronix M404", " Aronix M405', 『Aronix M406』 (manufactured by Toa Synthesis Co., Ltd.), 『KAYARAD DPHA』 (manufactured by Nippon Kayaku Co., Ltd.), 『A-9550』, 『A-DPH』 (Shin-Nakamura Chemical Co., Ltd.) ), "Viscoat #300", "Viscoat #802" (manufactured by Osaka Organic Chemical Co., Ltd.), "Miramer M500" (manufactured by MIWON Specialty Chemical Co, Ltd.), and the like.

Although it does not specifically limit as the usage-amount of component (a4), From the point of the low moisture permeability of hardened|cured material, (a1) component and the prepolymer which is a reaction product of (a3) (hereinafter also referred to as (a') component.) Number of isocyanate groups _{(NCO (a '))} and, (a4) at a ratio of the number of hydroxyl groups _{(OH (a4))} in the _{component, [(NCO (a')} ) / (OH (a4))] = 0.90 ~ 1.05 are preferred and 0.95 to 1.00 are more preferable.

The component (A2) can be produced by various known methods, for example, the component (a1) and the component (a3) are reacted to produce a prepolymer (a′), followed by the component (a′) and (a4) It is obtained by making a component react. The reaction conditions are not particularly limited, and for example, usually the temperature is about 50 to 100°C (preferably about 60 to 80°C), and the time is about 0.1 to 6 hours (preferably 0.5 to 2 hours). degree) is.

In addition, manufacture of (A2) component can be performed either in the organic solvent mentioned above, or under no solvent.

Although it does not specifically limit as a physical property of the component (A2) obtained in this way, For example, about 500-20000 are preferable and, as for a weight average molecular weight, about 1000-12000 are more preferable.

The active energy ray-curable resin composition of this invention contains the said urethane (meth)acrylate ((A1) component and/or (A2) component).

The active energy ray-curable resin composition of the present invention may further contain an active energy ray-curable monomer (B) (hereinafter, referred to as (B) component.) and/or a metal oxide (C).

The component (B) is not particularly limited as long as it is a curable monomer other than the above urethane (meth)acrylate, and for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acryl rate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl ( Meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, Tri n-decyl (meth) acrylate, n-lauryl (meth) acrylate, n-myristyl (meth) acrylate, n-palmityl (meth) acrylate, n-stearyl (meth) acrylate, aliphatic (meth)acrylates such as isostearyl (meth)acrylate;

Cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, norbornanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy alicyclic (meth)acrylates such as ethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and tricyclodecanedimethyloldi(meth)acrylate;

aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, and nonylphenoxypolyethylene glycol (meth)acrylate;

Methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-ethoxyethoxyethyl (meth) (meth)acrylates having an alkoxyalkyl group such as acrylate;

monoalkylene glycol (meth)acrylates such as ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate;

Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri polyalkylene glycol (meth)acrylates such as propylene glycol di(meth)acrylate;

alkoxy polyalkylene glycol (meth)acrylates such as methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, and methoxydipropylene glycol (meth)acrylate;

(meth)acrylamides, such as (meth)acrylamide, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, and (meth)acryloylmorpholine;

(meth)acrylates having an epoxy group such as glycidyl (meth)acrylate;

dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate;

Pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate or a mixture thereof pentaerythritol (meth) acrylates;

Dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( dipentaerythritol (meth)acrylates of meth)acrylate, dipentaerythritol hexa(meth)acrylate, or a mixture thereof;

Tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa ( tripentaerythritol (meth)acrylates of meth)acrylate or a mixture thereof;

Trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. are mentioned.

These (B) components may be individual and may combine 2 or more types. Among them, pentaerythritol (meth) acrylates, dipentaerythritol (meth) acrylates, and tripentaerythritol (meth) acrylates are preferable from the viewpoint of hardness of the cured product, and dipentaerythritol (meth) ) acrylates are more preferable.

When component (B) is used as a component of an active energy ray-curable resin composition, as the content, from the point of low moisture permeability of hardened|cured material, it is solid content weight ratio of (A1) component, (A2) component, and (B) component It is normally 1-80 weight% in 100 weight% of total, Preferably it is 1-50 weight%.

(C) The component is not specifically limited, For example, silica, alumina, zirconium oxide, titanium oxide, antimony oxide, a tin oxide, indium oxide, zinc oxide, etc. are mentioned. In addition, as (C)component, you may use what was doped with aluminum, phosphorus, fluorine, etc. These may be individual and may combine 2 or more types.

In addition, commercially available products include 『TOL-ST』, 『MEK-ST-40』, 『MEK-ST-L』, 『MEK-ST-ZL』, 『MEK-ST-UP』, 『MIBK-ST』, "CHO-ST-M", "EAC-ST", "PMA-ST" (above, manufactured by Nissan Chemical Co., Ltd.), etc. are mentioned.

Moreover, (C) component may use the metal oxide which has an organic functional group on the surface. An "organic functional group" is a group which has at least a carbon atom, For example, a methacryloyl group, an acryloyl group, a vinyl group, an epoxy group, an isocyanate group, a urethane group, an organosiloxane group, etc. are mentioned.

As a commercial item of the metal oxide which has an organic functional group on the surface, "MEK-EC-2130Y", "MEK-AC2140Z", "MEK-AC-4130Y", "PGM-AC2140Y", "PGM-AC3140Y" , 『PGM-AC4130Y』, 『MIBK-SD』, 『MIBK-SD-L』 (manufactured by Nissan Chemical Co., Ltd.), 『NANOBYK-3603』, 『NANOBYK-3610』, 『NANOBYK-3650』, 『NANOBYK- 3652] (manufactured by Bik Chemie Japan Co., Ltd.), "ALMIBK30WT%-H06", "SIRMIBK15ET%-H24", "SIRMIBK15ET%-H83", (manufactured by CIK Nanotech Co., Ltd.), "ELECOM-V#8802" , "ELECOM-V#8803", "ELECOM-V#8804" (manufactured by Nikki Catalyst Chemical Co., Ltd.), and the like.

(C) Although it does not specifically limit as an average primary particle diameter of component, From the point of transparency of hardened|cured material, about 4-200 nm is preferable, and about 7-50 nm is more preferable. In addition, it does not specifically limit as a measuring method of an average primary particle diameter, For example, a light scattering method etc. are mentioned.

When the component (C) is used as a component of the active energy ray-curable resin composition, the content thereof is, from the viewpoint of flexibility of the cured product, the urethane (meth)acrylate of the present invention and the component (C) in a solid content weight ratio. It is usually 1-70 weight% in 100 weight% of total, Preferably it is 1-50 weight%.

The active energy ray-curable resin composition of the present invention may further contain an organic solvent.

It does not specifically limit as an organic solvent, For example, benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, aromatic hydrocarbons such as decalin and aromatic naphtha; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, and n-decane; alicyclic hydrocarbons such as cyclohexane; Ethyl acetate, propyl acetate, n-butyl acetate, s-butyl acetate, t-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-methoxyethyl acetate, 2-butoxyethyl acetate, acetate 3- esters such as methoxybutyl, 1-methoxypropyl acetate, and methyl benzoate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methylcyclohexanone; carbonates such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; acyclic ethers such as diisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran, 1,3-dioxolane, and 1,4-dioxane; monohydroxy ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; Alcohol, such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutanol, s-butanol, and t-butanol, etc. are mentioned. Moreover, when using an organic solvent as a component of an active energy ray-curable resin composition, as the content, 0.5 to 80 weight% is preferable.

The active energy ray-curable resin composition of this invention contains a photoinitiator further. In addition, when preparing an active-energy-ray-curable resin composition, a photoinitiator may be mix|blended, and may mix|blend just before coating to a base film.

It does not specifically limit as a photoinitiator, For example, Photoinitiators, such as a benzoin compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, a thioxanthone compound, an oxime ester compound, an amine and a quinone Photosensitizers, such as these, etc. are mentioned, More specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy -1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2 -morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2) ,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 1,2-octanedione 1-[4-(phenyl thio)-2-(o-benzoyloxime)], eta Non 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyl oxime) etc. are mentioned. These may be individual and may combine 2 or more types. Moreover, as content of a photoinitiator, 0.5-20 weight part is preferable with respect to a total of 100 weight part of the urethane (meth)acrylate of this invention, (B) component, and (C) component, 2-10 weight part is more desirable.

The active energy ray-curable resin composition of the present invention further contains additives such as a surface conditioning agent, a surfactant, a UV absorber, an antioxidant, a light stabilizer, a silane coupling agent, colloidal silica, an antifoaming agent, a wetting agent, a rust preventive agent, and a leveling agent You can do it.

The active energy ray-curable resin composition of this invention is obtained by mixing the said urethane (meth)acrylate, (B) component and (C) component, a photoinitiator, and an organic solvent as needed, and the said additive. The mixing means and mixing order are not specifically limited.

The cured product of the present invention is obtained by curing the active energy ray-curable resin composition.

The hardened|cured material of this invention is not specifically limited, For example, it is obtained by coating the said active energy ray-curable resin composition to a base film, and irradiating an active energy ray.

As a base film, in order that the obtained laminated body may show low moisture permeability, it is preferable to use a thing with a water vapor transmission rate of 200 g/m<2>*24h or more. In addition, water vapor transmission rate is the value measured by the cup method in the environment of the relative humidity of a temperature of 40 degreeC and 90% of humidity based on JISZ0208. (hereinafter the same)

As said base film, For example, Cellulose ester-type films, such as a diacetyl cellulose film, a triacetyl cellulose film, an acetylpropyl cellulose film, and an acetylbutyl cellulose film; Polyvinyl alcohol-type films, such as a polyvinyl alcohol film and an ethylene vinyl alcohol film; Cellophane, a polyamide film, a polylactic acid film, etc. are mentioned. In addition, the thing of light peeling and heavy peeling can be used for a base film, and the thing of an unprocessed thing and plasma-processed thing can be used.

Moreover, in order to peel easily with the layer of hardened|cured material to the said base film, you may perform a peeling process. The peeling treatment is not particularly necessary when peeling is easy, but in order to peel more easily, a melamine resin, a silicone resin, a fluororesin, a cellulose derivative, a urea resin, a polyolefin resin, or a paraffin resin can be laminated as a release layer. These base films may be independent and may combine 2 or more types.

It does not specifically limit as thickness of the said base film, Usually, it is about 12-500 micrometers, Preferably it is 25-200 micrometers.

It does not specifically limit as a coating method, For example, an applicator, a bar coater, a roll coater, a knife coater, a gravure coater, a spray coater, a comma coater, a lip coater, gravure printing, screen printing etc. are mentioned. The coating amount of an active energy ray hardening type coating agent composition is not specifically limited, either, Usually, it coats so that the film thickness of the hardened|cured material after irradiation may be set to about 1-50 micrometers.

After coating, although you may irradiate an active energy ray, in order to harden partially, you may heat-dry a coating film. Moreover, when making it heat-drying, it is preferable to make it dry for 20 second - 10 minutes at the temperature of about 40-100 degreeC.

It does not specifically limit as an active energy ray, For example, light rays, such as an ultraviolet-ray, infrared rays, and visible light, an electron beam, X-ray, alpha-ray, β-ray, gamma-ray, a neutron beam, etc. are mentioned. In this invention, a light ray is preferable and an ultraviolet-ray is more preferable.

It does not specifically limit as a light source of an ultraviolet-ray, For example, a xenon lamp, a high-pressure mercury-vapor lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a chemical lamp, an electrodeless lamp, an LED lamp, etc. are mentioned. Moreover, the accumulated irradiation amount and conveying speed of an ultraviolet-ray are not specifically limited, either, An integrated irradiation amount is 100-3000 mJ/cm<2> normally, and a conveyance speed is about 5-50 m/min normally. Moreover, after irradiating an ultraviolet-ray, you may heat as needed in order to make it harden completely.

The laminate of this invention has the layer of the said hardened|cured material. The base film to be used, the curing method, and the like are the same as described above.

As a physical property of the obtained laminated body, a water vapor transmission rate is 100 g/m<2>*24 h or less, Preferably it is 80 g/m<2>*24 h or less, More preferably, it is 70 g/m<2>*24 h or less.

Example

Hereinafter, although an Example is given and this invention is further demonstrated concretely, this invention is not limited. In addition, "part" and "%" are both based on weight, unless otherwise stated.

<Production of cyclopentadiene/allyl alcohol polymer>

In an autoclave for 1 liter, 280 parts of dicyclopentadiene, 120 parts of allyl alcohol, and 150 parts of toluene as a solvent were charged in the proportions shown in Table 1, and after nitrogen substitution, the temperature was kept at 250°C, and the reaction was performed for 6 hours. . Next, the obtained alcohol-modified dicyclopentadiene polymer solution was taken out, toluene, unreacted substances, and low-boiling components were distilled off under reduced pressure at 240°C and 1.0 kPa for 30 minutes, softening point 100°C, color tone 12G, hydroxyl value 240 mg/KOH of a dicyclopentadiene/allyl alcohol polymer (hereinafter referred to as DCPDA resin) was obtained.

manufacturing example

In the autoclave, 500 parts of DCPDA resin and 7 parts of nickel/diatomaceous earth catalyst (nickel loading amount 50 weight%) were thrown in, it heat-retained at 280 degreeC, and hydrogenated by 20 Mpa of hydrogen pressures for 5 hours. Next, the reaction solution is taken out, dissolved in 500 parts of toluene, the catalyst is removed by filtration, and then toluene is distilled off under reduced pressure at 200°C and 2.7 kPa for 30 minutes, softening point 105°C, color tone 150 Hazen, hydroxyl value 100 450 parts of hydride of DCPDA resin of mg/KOH was obtained.

manufacturing example

In the autoclave, 500 parts of DCPDA resin and 7 parts of nickel/diatomaceous earth catalyst (nickel loading amount 50 weight%) were thrown in, it heat-retained at 250 degreeC, and hydrogenated by 20 MPa of hydrogen pressures for 5 hours. Next, the reaction solution is taken out, dissolved in 500 parts of toluene, the catalyst is removed by filtration, and then toluene is distilled off under reduced pressure at 200°C and 2.7 kPa for 30 minutes, softening point 105°C, color tone 200 Hazen, hydroxyl value 200 450 parts of hydride of DCPDA resin of mg/KOH was obtained.

manufacturing example

500 parts of a styrene/allyl alcohol polymer (manufactured by Sigma-Aldrich, softening point 102.5° C., number average molecular weight 950) (hereinafter referred to as STA resin), and 7 parts of a nickel/diatomaceous earth catalyst (nickel loading: 50 wt%) in an autoclave, It heat-retained at 250 degreeC, and hydrogenated by the hydrogen pressure of 20 Mpa for 5 hours. Next, the reaction solution is taken out, dissolved in 500 parts of toluene, the catalyst is removed by filtration, and then toluene is distilled off under reduced pressure at 200°C and 2.7 kPa for 30 minutes, softening point 100°C, color tone 120 Hazen, hydroxyl value 100 450 parts of hydride of STA resin of mg/KOH was obtained.

Preparation Example 1

In a three-neck flask equipped with a stirrer, a thermometer, and a reflux cooling tube, 40 parts of the hydride of DCPDA resin obtained in Production Example A, 40 parts of toluene, 8.1 parts of 2-isocyanatoethyl acrylate, 0.02 parts of tin octylate, hydro 0.05 part of quinone monomethyl ether was added, and it reacted at 80 degreeC until residual isocyanate group became 0.1 % or less, and the solution of the urethane (meth)acrylate (A-1) of 55% of solid content concentration was obtained.

Preparation 2

In manufacture example 1, it carried out similarly by changing 2-isocyanatoethyl acrylate into 4.2 parts, and the solution of the urethane (meth)acrylate (A-2) of 52% of solid content concentration was obtained.

Preparation 3

In the same three-necked flask as in Production Example 1, 40 parts of the hydride of DCPDA resin obtained in Production Example B, 40 parts of toluene, 16.1 parts of 2-isocyanatoethyl acrylate, 0.02 parts of tin octylate, and hydroquinone monomethyl ether 0.05 part was added, and it reacted at 80 degreeC until residual isocyanate group became 0.1 % or less, and the solution of the urethane (meth)acrylate (A-3) of 58% of solid content concentration was obtained.

Preparation 4

To the same three-necked flask as in Production Example 1, 40 parts of the hydride of DCPDA resin obtained in Production Example A, 41 parts of toluene, 13.8 parts of hydrogenated xylylene diisocyanate, and 0.02 parts of tin octylate were added and reacted at 80°C for 2 hours. . Thereafter, 8.5 parts of 2-hydroxyethyl acrylate (HEA), 0.01 parts of tin octylate, and 0.07 parts of hydroquinone monomethyl ether are added, and the reaction is carried out until the residual isocyanate group becomes 0.1% or less, and the solid content concentration is 60%. A solution of urethane (meth)acrylate (A-4) was obtained.

Preparation 5

To a three-necked flask similar to Production Example 1, 40 parts of the hydride of DCPDA resin obtained in Production Example A, 43 parts of toluene, 15.8 parts of isophorone diisocyanate, and 0.02 parts of tin octylate were added, and reacted at 80°C for 2 hours. Thereafter, 8.5 parts of 2-hydroxyethyl acrylate (HEA), 0.01 parts of tin octylate, and 0.07 parts of hydroquinone monomethyl ether are added, and the reaction is carried out until the residual isocyanate group becomes 0.1% or less, and the solid content concentration is 60%. A solution of urethane (meth)acrylate (A-5) was obtained.

Preparation 6

To the same three-necked flask as in Production Example 1, 40 parts of the hydride of DCPDA resin obtained in Production Example A, 57.1 parts of toluene, 13.8 parts of hydrogenated xylylene diisocyanate, and 0.01 parts of tin octylate were added, and reacted at 80°C for 2 hours. . Then, 33.2 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: "Aronix M-305", manufactured by Toa Synthesis Co., Ltd.) (PETA), 0.03 parts of tin octylate, 0.07 parts of hydroquinone monomethyl ether was added, it reacted until the residual isocyanate group became 0.1 % or less, and the solution of the urethane (meth)acrylate (A-6) of 60% of solid content concentration was obtained.

Preparation 7

In Production Example 1, the same procedure was performed by changing from the hydride of DCPDA resin in Production Example A to the hydride of the STA resin obtained in Production Example C, and urethane (meth)acrylate (A-7) having a solid content concentration of 55% A solution was obtained.

Comparative Preparation Example 1

In manufacture example 1, it carried out similarly by changing into DCPDA resin (polymer which is not hydrogenated), and the solution of the urethane (meth)acrylate (A-8) of 55% of solid content concentration was obtained.

Example 1

100 parts of the solution of (A-1) obtained in Production Example 1 (solid weight: 55 parts), 1-hydroxycyclohexylphenyl ketone (photoinitiator, trade name: 『Omnirad184』, manufactured by IGM Resins BV) 1.5 parts, 0.2 parts of a silicone surface conditioning agent (additive, brand name: "BYK-UV3570", manufactured by BYK) and 13.5 parts of methyl ethyl ketone were blended and stirred until dissolved to prepare an active energy ray-curable resin composition.

Examples 2 to 6, Comparative Examples 1 to 2

100 parts of solutions of (A) component shown in Table 1 were mix|blended, and the active energy ray hardening-type resin composition was prepared, respectively. In Comparative Example 2, 60 parts of the hydride of DCPDA resin obtained in Production Example A was used.

(Laminate)

On a triacetyl cellulose film (trade name: 『FT TD60ULP』, manufactured by Fuji Film Co., Ltd., moisture permeability: 500 g/m 2 ·24 h, thickness: 60 µm), each active energy ray-curable resin composition was applied to It applied with a #16 bar coater so that it might become 6 micrometers, and it dried at 80 degreeC for 1 minute. Next, using a high-pressure mercury lamp (product name: "UBT-080-7A/BM", manufactured by Multiply Co., Ltd.), an integrated irradiation amount of 600 mJ/cm 2 was irradiated to obtain a laminate.

(water vapor permeability)

Each laminate was measured according to the moisture permeability test method (cup method) of JIS Z 0208. The number of grams of water vapor passing in 24 hours per 1 m 2 of area of the laminate in an atmosphere of a temperature of 40°C and a humidity of 90% was measured. The smaller the number of grams, the better.

(pencil hardness)

According to JISK5600-5-4, the hardness of the hardened|cured material in each laminated body was measured by the pencil scraping test with a load of 500g. 6B or more was considered favorable.

(Lightfastness)

With an ultraviolet auto fade meter (trade name: "ultraviolet auto fade meter U48AU", manufactured by Suga Test Instruments Co., Ltd.), each laminate was exposed to light with a carbon arc lamp for 50 hours. The yellow index value of the laminated body after exposure was measured by the transmission method of the color-difference meter (brand name: ZE6000 Nippon Denshoku Industries Co., Ltd. product). If the measured value was less than 3, it was set as "(circle)", and when it was 3 or more, it was set as "x".

(A-1) The active energy ray-curable resin composition obtained by mix|blending an active energy ray-curable monomer and/or a metal oxide with a component was evaluated similarly. It will be described in detail below.

Example 7

50 parts (solid weight: 27.5 parts) of the solution of (A-1) obtained in Production Example 1, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: "Aronix M402", Toa Synthesis Co., Ltd.) 27.5 parts, 1-hydroxycyclohexylphenyl ketone (photoinitiator, trade name: 『Omnirad184』, manufactured by IGM Resins BV) 1.5 parts, silicone-based surface conditioner (additive, trade name: 『BYK-UV3570』, BYK company make) 0.2 part and 13.5 parts of methyl ethyl ketone were mix|blended, and it stirred until it melt|dissolved, and the active energy ray hardening type resin composition was prepared.

Example 8

50 parts of the solution of (A-1) obtained in Production Example 1 (solid content weight: 27.5 parts), silica (trade name: "MIBK-SD", solid content concentration: 30%, particle diameter: 10-15 nm, Nissan Chemical Co., Ltd. Manufactured) 91.6 parts (solid weight: 27.5 parts), 1-hydroxycyclohexylphenyl ketone (photoinitiator, trade name: 『Omnirad184』, manufactured by IGM Resins BV) 1.5 parts, silicone-based surface conditioner (additive, trade name: 『Tegorad2011』 ', Evonik INTERNATIONAL BV Co., Ltd.) 0.2 part and 13.5 parts of methyl ethyl ketone were mix|blended, and it stirred until it melt|dissolved, and the active energy ray hardening type resin composition was prepared.

Comparative Example 3

In Example 7, the hydride of the DCPDA resin obtained in Production Example A was changed to 27.5 parts, and an active energy ray-curable resin composition was prepared.

The water vapor transmission rate, pencil hardness, and light resistance of the active energy ray-curable resin compositions of Examples 7 and 8 and Comparative Example 3 were measured in the same manner as above. A result is shown in Table 2.

The abbreviation in Table 2 shows the following compounds.

DPHA: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: 『Aronix M402』, manufactured by Toa Synthesis Co., Ltd.)

Si: Silica (trade name: 『MIBK-SD』, solid content concentration: 30%, particle size: 10 to 15 nm, manufactured by Nissan Chemical Co., Ltd.)

Claims (10)

A hydride (a1) of a polymer of a hydrocarbon (a1-1) having an olefinic double bond and a cyclic structure and a compound (a1-2) having an active hydrogen;
Urethane (meth)acrylate which is a reaction product with the following (I) and/or (II).
(I) (meth)acrylate having one isocyanate group (a2)
(II) polyisocyanates (a3) and (meth)acrylates having hydroxyl groups (a4) The method of claim 1,
(a1-1) Urethane (meth)acrylate in which a component contains dicyclopentadiene and/or styrene. 3. The method according to claim 1 or 2,
(a1-2) Urethane (meth)acrylate in which a component contains an unsaturated aliphatic alcohol. 4. The method according to any one of claims 1 to 3,
(a2) Urethane (meth)acrylate whose component is isocyanatoalkyl (meth)acrylate. 5. The method according to any one of claims 1 to 4,
(a3) Urethane (meth)acrylate whose component is alicyclic polyisocyanate. The active energy ray-curable resin composition containing the urethane (meth)acrylate in any one of Claims 1-5. 7. The method of claim 6,
Furthermore, the active energy ray-curable resin composition containing an active energy ray-curable monomer (B) and/or a metal oxide (C). Hardened|cured material of the active-energy-ray-curable resin composition of Claim 6 or 7. The laminate which has the hardened|cured material of Claim 8 on at least single side|surface of the base film whose water vapor transmission rate is 200 g/m<2>*24 h or more. 10. The method of claim 9,
A laminate having a moisture permeability of 100 g/m 2 ·24 h or less.