JP6992483B2 - Active energy ray polymerizable adhesive and laminate - Google Patents

Description

The present invention relates to an active energy ray-polymerizable adhesive.

The polarizing plate used in a liquid crystal display or an organic EL display generally has a configuration in which a protective film such as triacetyl cellulose is bonded to both sides of a polyvinyl alcohol polarizing element using an adhesive. As the adhesive, an active energy ray-polymerizable adhesive is often used.

Patent Document 1 discloses an active energy ray-polymerizable adhesive containing an N-substituted amide-based monomer and a monofunctional acrylate having an aromatic ring and a hydroxyl group.

Further, Patent Document 2 discloses an active energy ray adhesive containing an alicyclic epoxy resin, a polyol having a number average molecular weight of 400 or more, and an active energy ray polymerization initiator.

Japanese Unexamined Patent Publication No. 2008-287207 JP-A-2007-224235

However, when the production line is increased in speed in order to increase the productivity of the polarizing plate and the irradiation amount of the active energy ray is lowered accordingly, the conventional active energy ray adhesive has a problem that the peeling strength is lowered. Further, even if the peel strength does not decrease, there is a problem that the peel strength decreases when the display incorporating the polarizing plate is used under the condition of being exposed to water droplets.

The present invention provides an active energy ray-polymerizable adhesive and a polarizing plate in which good peel strength can be obtained with a low irradiation dose and the peel strength does not easily decrease even when used under conditions where water droplets are applied (hereinafter referred to as water resistance). The purpose.

The active energy ray-polymerizable adhesive of the present invention includes a hydroxyl group-containing radically polymerizable monomer (A), a polyfunctional radically polymerizable compound (B) (excluding the hydroxyl group-containing radically polymerizable monomer (A)) and a cationically polymerizable monomer. The compound and the compound (C) represented by the following general formula (1) are included.

General formula (1)

(However, in the formula, X represents a hydroxyl group or a carboxyl group. R ₁ to R ₄ are independently hydrogen atoms, linear or split-chain alkyl groups, alkenyl groups, alcoholic groups, and halogen atoms, respectively. Represents a group selected from among.)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an active energy ray-polymerizable adhesive and a polarizing plate which can obtain good peel strength with a low irradiation amount and have water resistance.

First, the terms used in the present specification will be described. By "active energy ray" is meant an energy ray in the broad sense that can provide the energy required for activation to cause a chemical reaction, including ultraviolet light, visible light, infrared light, electron beam (EB), and radiation. In the active energy ray-polymerizable adhesive of the present invention, the polymerization reaction proceeds by irradiation with the above-mentioned active energy rays to form a cured product such as an adhesive layer.
Further, "(meth) acryloyl" includes "acryloyl and methacryloyl". "(Meta) acrylic acid" includes "acrylic acid and methacrylic acid". "(Meta) acrylate" includes "acrylate and methacrylate". "(Meta) acryloyloxy" includes "acryloyloxy and methacryloyloxy". "(Meta) allyl" includes "allyl and methallyl". The "monomer" is an "ethylenically unsaturated double bond-containing monomer" having a formula of less than 500. The "oligomer" is a compound having a formula or weight average molecular weight of 500 or more and 100,000 or less.
"
The polymerizable component is a general term for monomers and oligomers that polymerize with active energy rays other than the polymerization initiator.

<Active energy ray-polymerizable adhesive>
The active energy ray-polymerizable adhesive of the present invention (hereinafter, also simply referred to as “adhesive”) is a hydroxyl group-containing radical polymerizable monomer (A) and a radical polymerizable compound (B) (however, a hydroxyl group-containing radical polymerizable monomer). (Excluding (A)) and a cationically polymerizable compound, and a compound (C) represented by the following general formula (1).

(In the formula, X represents a hydroxyl group or a carboxyl group. R ₁ to R ₄ are independently from a hydrogen atom, a linear or split chain alkyl group, an alkenyl group, an alcohol group, and a halogen atom, respectively. Represents the group chosen.)

Since the adhesive of the present invention contains the compound (C) represented by the general formula (1) in addition to the radically polymerizable monomer (A) containing a hydroxyl group and the radically polymerizable compound (B), good peeling can be performed with a low irradiation dose. It is strong and water resistant.

The adhesive of the present invention is preferably used for applications such as forming a polarizing plate and for adhering members constituting a display (referred to as a display application). Needless to say, the adhesive can be used for purposes other than display applications.

<Hydroxy group-containing radical polymerizable monomer (A)>
The hydroxyl group-containing radically polymerizable monomer (A) (hereinafter, also referred to as monomer (A)) is a radically polymerizable monomer having a hydroxyl group. The radically polymerizable functional group of the monomer (A) is preferably, for example, a (meth) acryloyl group, a vinyl group or the like.

The monomer (A) having a (meth) acryloyl group is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylate. 4-Hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid 8-hydroxyoctyl, cyclohexanedimethanol mono (meth) acrylic acid ester, (meth) acrylic acid 12-hydroxylauryl, (meth) acrylic Examples thereof include ethyl-α- (hydroxymethyl) acid. Cyclohexanedimethanol mono (meth) acrylate, cyclohexanediethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-a (meth) acryloylxyethyl-2-hydroxyethyl-phthalic acid and the like can be mentioned. Be done.

Examples of the monomer (A) having a vinyl group include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether and the like. ..

Among these, the monomer (A) has 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate in terms of obtaining good peel strength at a low irradiation dose. Hydroxypropyl and 4-hydroxybutyl (meth) acrylate are preferred.

The monomer (A) can be used alone or in combination of two or more.

The monomer (A) preferably contains 5 to 60% by mass in 100% by mass of the polymerizable component, and more preferably 10 to 45% by mass.

<Radical polymerizable compound (B)>
The radically polymerizable compound (B) (hereinafter, also referred to as compound (B)) is a compound other than the hydroxyl group-containing radically polymerizable monomer (A). The compound (B) may be one or more selected from the group consisting of a bifunctional radically polymerizable monomer (B1), a trifunctional or higher functional radically polymerizable monomer (B2), and a radically polymerizable oligomer (B3). preferable.

Among the bifunctional radically polymerizable monomers (B1), the monomers having a (meth) acryloyl group include, for example, pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,4-butanediol. Di (meth) acrylate, 2,2-dimethylpropane-1,3-diol di (meth) acrylate, hexanediol di (meth) acrylate, heptanediol di (meth) acrylate, nonanediol di (meth) acrylate, etc. Di (meth) acrylate monomer having no 2-4 alkyleneoxy groups;
Ethyleneoxy-modified pentanediol di (meth) acrylate, propyleneoxy-modified pentanediol di (meth) acrylate, tetramethyleneoxy-modified pentanediol di (meth) acrylate, ethyleneoxy-modified 2,2-dimethylpropane-1,3-dioldi ( Meta) acrylate, propyleneoxy modified 2,2-dimethylpropane-1,3-diol di (meth) acrylate, tetramethyleneoxy modified 2,2-dimethylpropane-1,3-diol di (meth) acrylate, ethyleneoxy-modified hexanediol Di (meth) acrylate, propyleneoxy-modified hexanediol di (meth) acrylate, tetramethyleneoxy-modified hexanediol di (meth) acrylate, ethyleneoxy-modified heptanediol di (meth) acrylate, propyleneoxy-modified heptanediol di (meth) acrylate , A di (meth) acrylate monomer having an alkyleneoxy group such as tetramethyleneoxy-modified heptanediol di (meth) acrylate;
Neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, Di (meth) acrylate monomer having one kind of alkylene glycol such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate;
Ethylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-dipropylene glycol di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate; etc. 2 Di (meth) acrylate monomer having more than one kind of alkyleneoxy;
Examples thereof include ethyleneoxy-modified di (meth) acrylate of isocyanuric acid, propyleneoxy-modified di (meth) acrylate of isocyanuric acid, butyloxy-modified di (meth) acrylate of isocyanuric acid, and butyloxy-modified di (meth) acrylate of isocyanuric acid.

Among the bifunctional radically polymerizable monomers (B1), the monomers having a (meth) acryloyl group include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, and polyethylene glycol. Divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, Examples thereof include 1,4-cyclohexanediol divinyl ether (CHODVE) and 1,4-cyclohexanedimethanol divinyl ether (CHDVE).

Among these, compound (B1) is a diethylene glycol di (meth) acrylate, a dipropylene glycol di (meth) acrylate, or a hexanediol di (meth) acrylate in terms of improving peel strength and water resistance at a low irradiation dose. , Propyleneoxy 2 mol-modified 2,2-dimethylpropane-1, tripropylene glycol di (meth) acrylate and isocyanuric acid ethyleneoxy-modified di (meth) acrylate are preferred.

Among the trifunctional or higher functional radical polymerizable monomers (B2), the monomers having a (meth) acryloyl group are, for example, trimethylol propantri (meth) acrylate, ethyleneoxy-modified trimethylol propanthry (meth) acrylate, and propyleneoxy-modified. Trimethylol propanetri (meth) acrylate, tri (meth) acrylate such as tetramethyleneoxy-modified trimethylolpropanetri (meth) acrylate, propyleneoxy 2 mol-modified 2,2-dimethylpropane-1, ethyleneoxy 3 mol-modified trimethylolpropanetri (Meta) acrylate, propyleneoxy 3 mol modified trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, propyleneoxy 3 mol modified glycerin (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate, isocyanurate propylene Oxy-modified tri (meth) acrylates, isocyanuric acid butyl oxy-modified tri (meth) acrylates and isocyanuric acid butyl oxy-modified tri (meth) acrylates;
Dimethylolpropanetetra (meth) acrylate, ethyleneoxy-modified dimethylolpropanetetra (meth) acrylate, prolenoxy-modified dimethylolpropanetetra (meth) acrylate, tetramethyleneoxy-modified dimethylolpropanetetra (meth) acrylate, ditrimethylolpropanetetra (meth) Examples thereof include meth) acrylate and pentaerythritol tetra (meth) acrylate.

Among the trifunctional or higher functional radical polymerizable monomers (B2), the monomers having a vinyl group include, for example, trimetylolpropanetrivinyl ether, ethyleneoxy-added trimethylolpropanetrivinyl ether (TMPEOTVE), epentaerythritol tetravinyl ether, and ethyleneoxy-added. Examples thereof include pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, and dipentaerythritol hexavinyl ether.

Among these, the compound (B2) is preferably trimethylolpropane triacrylate or isocyanuric acid ethyleneoxy-modified tri (meth) acrylate in terms of achieving both good peel strength and water resistance at a low irradiation dose.

The radically polymerizable oligomer (B3) is a compound having a weight average molecular weight of 500 to 100,000 other than the monomer (A), the bifunctional radically polymerizable monomer (B1), and the trifunctional or higher functional radically polymerizable monomer (B2). .. When the adhesive contains a radically polymerizable oligomer (B3), in addition to good peel strength and water resistance at a low irradiation dose, the peel strength after the heat resistance test is further improved.

The radically polymerizable oligomer (B3) is preferably, for example, a polyurethane-based oligomer, a polyester-based oligomer, or an epoxy-based oligomer. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene having a known weight average molecular weight as a standard substance.

<Polyurethane oligomer>
The polyurethane-based oligomer is a compound having two or more urethane bonds and ethylenically unsaturated double bonds in the molecule. In the polyurethane-based oligomer, for example, a compound having an isocyanate group at the terminal obtained by reacting a compound having two or more isocyanate groups with a compound having a hydroxyl group is reacted with a (meth) acryloyl group having a hydroxyl group and a vinyl group. Can be obtained. Further, it can be obtained by reacting a compound having a hydroxyl group with a compound having an isocyanate group and a (meth) acrylate group. Examples of the ethylenically unsaturated double bond include a (meth) acryloyl group and a vinyl group.

Compounds having one or more isocyanate groups include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,4-phenylene bismethylene diisocyanate, and 3-isocyanate methyl-3. , 5,5-trimethylcyclohexyl isocyanate, hexamethylene diisocyanate and other aliphatic isocyanates.

Commercially available products of polyurethane-based oligomers include aromatic polyurethane-based oligomers such as EBECRYL210, EBECRYL220 (above, manufactured by Dycel Ornex), CN9782, CN9783 (above, manufactured by SARTOMER), purple light 3000B, and purple light. Examples thereof include aliphatic polyurethane oligomers such as 3700B (above, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8701 (above, manufactured by Daicel Ornex).

<Polyester oligomer>
The polyester-based oligomer is a compound having two or more ester bonds and ethylenically unsaturated double bonds in the molecule. The polyester-based oligomer is an esterification reaction between, for example, a hydroxyl group of a polyester synthesized by polycondensing a polybasic acid and a polyhydric alcohol with a (meth) acrylate having a carboxyl group (for example, (meth) acrylic acid). Can be synthesized with.

The polybasic acid is an aliphatic polybase such as oxalic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, itaconic acid, succinic acid anhydride and maleic anhydride. Alicyclic polybasic acids such as acids, dimer acids and cyclohexanedicarboxylic acids; aromatic polybasic acids such as isophthalic acid, terephthalic acid and biphenyldicarboxylic acid.

The polyhydric alcohol is preferably a relatively low molecular weight polyol having a number average molecular weight (Mn) of about 50 to 500, or a relatively high molecular weight polyol having a number average molecular weight (Mn) of 500 to 30,000.

Glycols having a relatively low molecular weight include, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentane. Diol, 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (additional moles: 10 or less), poly Oxypropylene glycol (additional number of moles 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neo An aliphatic or alicyclic type such as pentylglycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, and dimerdiol. Glycol;

1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'-methylenediphenol, 4, Examples thereof include 4'-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropyridenephenol and the like.

Examples of the polyol having a relatively high amount of substance include polyoxyethylene glycol (with 11 or more moles with ethyleneoxy groups) and polyoxypropylene glycol (with 11 or more moles with propyleneoxy groups).

Examples of commercially available polyester oligomers include aromatic polyester oligomers such as CN296, CN2203, CN2259, and CN2261 (above, manufactured by SARTOMER), CN294, CN2270, CN2271 (above, manufactured by SARTOMER), and the like. Be done.

<Epoxy oligomer>
The epoxy-based oligomer is a compound having a (meth) acryloyl group obtained by reacting an epoxy group of a compound having an epoxy group with a compound having a carboxyl group and / or a hydroxyl group. The epoxy-based oligomer may have an epoxy group, but it is preferably a compound in which all of the epoxy groups are reacted with a carboxyl group or a hydroxyl group to be consumed.
To give an example of a method for synthesizing an epoxy-based oligomer, for example, a bisphenol-type polyepoxy-based oligomer contains a bisphenol A-type diglycidyl ether and a compound having one or more carboxyl groups in a molecule such as (meth) acrylic acid. The reaction can be carried out to synthesize a bisphenol A type epoxy compound. In the epoxy-based oligomer, a small amount of epoxy group may remain.

Examples of commercially available epoxy-based oligomers include aromatic epoxy-based oligomers such as CN104, CN110 (above, manufactured by SARTOMER), EBECRYL600, EBECRYL3701 (above, manufactured by Dycel Ornex); CN111, CN113 (above, SARTOMER). EBECRYL860 (manufactured by Dycel Ornex) and other aliphatic epoxy-based oligomers;

The blending amount of the radically polymerizable oligomer (B3) is preferably about 1 to 30% by mass, more preferably 2 to 15% by mass, based on 100% by mass of the polymerizable component. By using an appropriate amount of the radically polymerizable oligomer (B3) in the adhesive of the present invention, the molecules that have been reacted in advance can enter the crosslinked network after curing and impart cohesive force, so that the adhesive can be adhered after the heat resistance test. Power is improved.

Compound (B) can be used alone or in combination of two or more.

The compound (B) preferably contains 15 to 70% by mass, more preferably 20 to 60% by mass, in 100% by mass of the polymerizable component.

<Compound (C) represented by the general formula (1)>
The compound (C) represented by the general formula (1) (hereinafter referred to as compound (C)) suppresses the curing shrinkage of the adhesive due to irradiation with active energy rays, and makes it difficult to apply a load such as strain to the substrate. , The adhesive layer and the base material are in close contact with each other. As a result, good peel strength can be obtained with a low irradiation amount, and water resistance is improved.

General formula (1)

In the above formula, X represents a hydroxyl group or a carboxyl group. R ₁ to R ₄ each independently represent a group selected from a hydrogen atom, a linear or split-chain alkyl group, an alkenyl group, an alcohol group, and a halogen atom.

The linear or split alkyl group may be, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, a tertiary butyl group, an isobutyl group, a normal pentyl group, an amyl group, an isoamyl group, and the like. Examples thereof include a normal hexyl group, a normal heptyl group, an octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a lauryl group, a cetyl group, a stearyl group, and an isostearyl group.

Examples of the alkenyl group include a vinyl group, an allyl group and a propenyl group, and a group in which the 2-position of a vinyl group such as a 2-methylvinyl group and a 2-ethylvinyl group is substituted with the above alkyl group.

The alkoxy group includes, for example, a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, a secondary butoxy group, a tertiary butoxy group, an amyloxy group, an isoamyloxy group, a normal heptyloxy group, an octyloxy group and an iso. Examples thereof include an octyloxy group, a nonyloxy group, an isononyloxy group, a decyloxy group, an isodecyloxy group, a lauryloxy group, a cetyloxy group, a stearyloxy group, and an isostearyloxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The compounds of the above general formula (1) in which X is a hydroxyl group and R ₁ to R ₄ have a linear or demarcated alkyl group are, for example, catechol, 3-methylcatechol, 4-methylcatechol, 3,4-dimethylcatechol, 3 , 5-dimethyl catechol, 4,5-dimethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 3-propyl catechol, 4-propyl catechol, 3-isopropyl catechol, 4-isopropyl catechol, 3-butyl catechol, 4- Butyl catechol, 3-isobutyl catechol, 4-isobutyl catechol, 3-secondary butyl catechol, 4-secondary butyl catechol, 3-tertiary butyl catechol, 4-territory butyl catechol, 3-territory butyl-5-methyl catechol, Examples thereof include alkyl catechols such as 3-methyl-5-tertiary butyl catechol, 3-territory butyl-6-methyl catechol, and 3,5-ditercious butyl catechol.

Examples of the compound in the general formula (1) in which X is a hydroxyl group and R ₁ to R ₄ have an alkenyl group include alkenyl catechols such as 3-vinyl catechol, 4-vinyl catechol, 3-propenyl catechol, and 4-propenyl catechol. Be done.

The compound (C) in the general formula (1) in which X is a hydroxyl group and R ₁ to R ₄ have an alkoxy group is, for example, 3-methoxycatechol, 4-methoxycatechol, 3-tertiary butyl-5-methoxycatechol, 4 , 6-Ditercious butyl-5-methoxycatechol and other alkoxycatechols.

The compound (C) in the general formula (1) in which X is a hydroxyl group and R ₁ to R ₄ have a halogen atom is, for example, 3-fluorocatechol, 4-fluorocatechol, 3-chlorocatechol, 4-chlorocatechol, 3-. Examples thereof include halogenated catechols such as bromocatechol, 4-bromocatechol, 3-iodocatechol, and 4-iodocatechol.

The compound (C) in the general formula (1) in which X is a carboxyl group and R ₁ to R ₄ have a linear or demarcated alkyl group is salicylic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 6 -Salicylic acid such as methylsalicylic acid, 3,5-ditersial butyl salicylic acid and the like can be mentioned.

Examples of the compound (C) in which X in the general formula (1) has a carboxyl group and R ₁ to R ₄ have an alkenyl group include salicylic acids such as 3-vinylsalicylic acid, 4-vinylsalicylic acid, and 5-vinylsalicylic acid.

Examples of the compound (C) in which X in the general formula (1) has a carboxyl group and R ₁ to R ₄ have an alkoxy group include salicylic acids such as 3-methoxysalicylic acid, 4-methoxysalicylic acid, and 5-methoxysalicylic acid.

The compound (C) in which X in the general formula (1) has a carboxyl group and R ₁ to R ₄ have a halogen atom is 3-chlorosalicylic acid, 4-chlorosalicylic acid, 3-fluorosalicylic acid, 3-fluoro-5-chlorosalicylic acid. Such as salicylic acid.

Compound (C) can be used alone or in combination of two or more.

Among these, compound (C) has 3,4-dimethylcatechol, 3,5-dimethylcatechol, 4-ethylcatechol, 3 from the viewpoint that good peel strength can be obtained at a lower irradiation dose and water resistance is further improved. -Propylcatechol, 4-propylcatechol, 3-tersary butyl catechol, 4-tersary butyl catechol, 3-tersary butyl-5-methylcatechol, 3-methyl-5-tersary butyl catechol, 3-tershal butyl -6-methylcatechol and 3,5-diterishary butylcatechol are more preferred.

When the compound (C) is blended with an adhesive, the radical polymerization rate of the monomer (A) and the compound (B) is slowed down when irradiated with active energy rays, and the curing shrinkage of the adhesive layer is suppressed, so that the adhesive is adhesive to the substrate. Water resistance is improved by increasing the adhesiveness.

The compound (C) preferably contains 0.01 to 5% by mass, more preferably 0.05 to 3% by mass in the adhesive. Adhesion and water resistance are further improved when the compound (C) is contained in an appropriate amount.

<Cation-polymerizable compound (D)>
The adhesive of the present invention can further contain a cationically polymerizable compound (D) (hereinafter referred to as compound (D)).
The cationically polymerizable functional group of the compound (D) is preferably, for example, an epoxy group, an oxetanyl group, a vinyl ether group, a cyclic carbonate or the like. The compound (D) is a compound other than the monomer (A), the compound (B) and the compound (C).

The cationically polymerizable compound (D) is one or more selected from the group consisting of a cationically polymerizable oligomer and a cationically polymerizable monomer. The cationically polymerizable monomer is a compound having a formula or weight average molecular weight (Mw) of less than 2000, and the cationically polymerizable oligomer is a compound having an Mw of 2000 or more.

As the cationically polymerizable monomer having an epoxy group, for example, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, an epoxy group-containing silane coupling agent, or the like is preferable.

The aromatic epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A propyleneoxy adduct diglycidyl ether, and phenol-novolac epoxy. , Cresol novolac epoxy, biphenyl type epoxy, resorcin diglycidyl ether, phenyl glycidyl ether, phenol ethylene oxyglycidyl ether, t-butyl phenyl glycidyl ether and the like.

The aliphatic epoxy compound is preferably an aliphatic monoalcohol, an aliphatic polyalcohol, and a glycidyl ether as an alkylene oxy adduct thereof.
The aliphatic epoxy compounds include, for example, 2-ethyl-hexyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerin. Examples thereof include triglycidyl ether, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, polypropylene glycol and the like.

The alicyclic epoxy compound is, for example, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9 diepoxylimonene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-. (3,4-Epoxy Cyclohexyl-5,5-Spiro-3,4-Epoxy) Cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6- Methylcyclohexylmethyl) adipate and the like can be mentioned.

Examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxy. Examples thereof include silane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane and the like.

The cationically polymerizable monomer having an epoxy group has an epoxy equivalent of about 30 to 3000 g / eq, preferably 50 to 1500 g / eq. When the epoxy equivalent is about 30 to 3000 g / eq, it is easy to obtain an appropriate peel strength.

Cationic polymerizable monomers having an oxetanyl group include, for example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and di (1-ethyl-3-oxetanyl). ) Methyl Ether, 3-Ethyl-3- (Phenoxymethyl) Oxetane, 3-Ethyl-3- (2-Ethyl-Hexyloxymethyl) Oxetane, Phenolenovolac Oxetane, 3-Ethyl-{(3-Triethoxysilyl) Propoxy) methyl} oxetane and the like.

The cationically polymerizable monomer having a vinyl ether group includes, for example, n-amyl vinyl ether, i-amyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethyl-hexyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether, oleyl vinyl ether and the like. Alkyl vinyl ether;
Ring structure-containing vinyl ethers such as cyclohexyl vinyl ether, 2-methylcyclohexylvinyl ether, cyclohexylmethylvinyl ether, and benzyl vinyl ether;
Glycerol monovinyl ether, 1,4-butanjiol monovinyl ether, 1,4-butanjiol divinyl ether, 1,6-hexanedio-ludivinyl ether, neopentyl glycol divinyl ether, pentaerythritol-ludivinyl ether, pentaerythritol Tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, 1,4-dihydroxycyclohexanemonovinyl ether, 1,4-dihydroxycyclohexanedivinyl ether, 1,4-dihydroxymethylcyclohexanemonovinyl ether, 1,4-dihydroxy Hydroxide-containing vinyl ethers such as methylcyclohexanedivinyl ethers;
Ethyleneoxy group-containing vinyl ethers such as triethylene glycol divinyl ether and diethylene glycol monobutyl monovinyl ether;
Other vinyl ethers such as glycidyl vinyl ethers and ethylene glycol vinyl ether methacrylates may be mentioned.

Examples of the cyclic carbonate compound include ethylene carbonate and propylene carbonate.

The cationically polymerizable oligomer is a compound having a weight average molecular weight of 2000 to 100,000. The cationically polymerizable oligomer may have a predetermined molecular weight and an epoxy group, and its molecular structure is not limited. However, a structure in which the acrylic polymer has a cationically polymerizable functional group is preferable. The method for synthesizing the cationically polymerizable oligomer is, for example, a method for synthesizing a cationically polymerizable oligomer having a desired polymerizable functional group by polymerizing a (meth) acrylate having an epoxy group, a (meth) acrylate having an oxetanyl group, or the like. Alternatively, a method of synthesizing an acrylic polymer and then further reacting with a cationically polymerizable functional group-containing compound to synthesize a cationically polymerizable oligomer can be mentioned. Here, the cationically polymerizable functional group is preferably an epoxy group or an oxetanyl group from the viewpoint of being excellent in cationically polymerizable.

Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate.

The (meth) acrylate having an oxetanyl group is, for example, 3-oxetanylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, 3-butyl-. Examples thereof include 3-oxetanylmethyl (meth) acrylate and 3-hexyl-3-oxetanylmethyl (meth) acrylate.

The cationically polymerizable compound (D) is preferably contained in the adhesive in an amount of 0.1 to 30% by mass, more preferably 1 to 25% by mass.

When the active energy ray is an electron beam, the adhesive of the present invention can be cured without blending an active energy ray polymerization initiator. On the other hand, when the active energy ray is other than the electron beam, it is preferable to add an active energy ray polymerization initiator to the adhesive.

Examples of the active energy ray polymerization initiator include a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator.
As the radical polymerization initiator, a known radical polymerization initiator can be used. Examples of commercially available products include Irgacure-184, 907, 651, 1700, 1800, 819, 369, 261, DAROCUR-TPO (above, manufactured by BASF), DaroCure-1173 (manufactured by Merck), Ezacure-KIP150, TZT (manufactured by Nippon Kayaku Co., Ltd.), Kayacure BMS, Kayacure DMBI, (all manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

As the cationic polymerization initiator, a known cationic polymerization initiator can be used. Examples of commercially available products include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec) and CPI-110P (manufactured by San-Apro), IRGACURE250 (manufactured by BASF), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), and Rp. Examples thereof include iodonium salts such as 2074 (manufactured by Rhodia Japan).

As the anionic polymerization initiator, a known anionic polymerization initiator can be used. Examples of commercially available products include WPBG-165, WPBG-018, WPBG-172, WPBG-140, WPBG-166, WPBG-027, WPBG-082, WPBG-167, WPBG-168, WPBG-266 (or more, Wako Pure Chemical Industries, Ltd.) and the like.

The active energy ray polymerization initiator preferably contains 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, in 100% by mass of the adhesive.

The adhesive of the present invention further comprises a photosensitizer, an amine-based catalyst, a phosphorus-based catalyst, a filler, an antistatic agent, an antioxidant, an antioxidant, a tackifier, an anti-blocking agent, and a defoaming agent, if necessary. It can contain agents, plasticizers, silane coupling agents, titanium coupling agents and the like.

The adhesive of the present invention preferably has a viscosity at 25 ° C. of 1 to 2000 mPa · s, more preferably 10 to 1500 mPa · s, and even more preferably 20 to 1000 mPa · s. If the viscosity is adjusted to an appropriate range, a smooth film can be easily formed by coating. The viscosity is a value measured at 10 rotations / minute with a 1 ° 34'x R24 rotor using an E-type cone rotor viscometer, and is a value 1 minute after the start of rotation.

The laminate of the present invention comprises a first substrate, an adhesive layer which is a cured product of an active energy ray-polymerizable adhesive, and a second substrate.

To form the adhesive layer, the second base material is bonded onto the adhesive layer formed by coating on the first base material. Irradiation of the active energy ray is performed at an arbitrary timing. For example, the active energy rays can be irradiated at the time of applying the adhesive, at the time of laminating, and further after laminating. Among these, it is preferable to irradiate the active energy ray after laminating the second base material to cure. Therefore, it is preferable that at least one of the first base material and the second base material does not inhibit the curing reaction by the active energy ray. Further, the first base material and the second base material may be the same material.

As the first base material and the second base material, it is preferable to use a film-like base material. Examples of the film-like substrate include cellophane, plastic film, metal foil, paper and the like. Among these, plastic is preferable, and transparent plastic is more preferable. As the film-like substrate, a single layer or a multilayer structure in which a plurality of substrates are laminated can be used. A plate-shaped substrate can be used in addition to the film substrate.

The plastic film is a polyolefin film such as a polyvinyl alcohol film, polypropylene, polyethylene, polycycloolefin, and an ethylene-vinyl acetate copolymer; a polyester film such as polyethylene terephthalate and polybutylene terephthalate; a polycarbonate film, a polynorbornene film. Examples thereof include a film, a polyarylate film, a polyacrylic film, a polyphenylene sulfide film, a polystyrene film, a polyvinyl film, a polyamide film, a polyimide film, a polytriacetyl cellulose film, and a polyoxylan film.

The composition of the laminate is such that if a transparent plastic or a transparent glass plate is used for the first base material, a base material that is difficult for active energy rays to pass through as the second base material, for example, wood, a metal plate, a plastic plate, etc. A processed paper product or the like may be used.

The thickness of the base material is usually about 5 to 50,000 μm.

For coating, a known coating device can be used. Examples thereof include a Meyer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a micro gravure coater, a lip coater, a comma coater, a curtain coater, a knife coater, a reverse coater, a spin coater and the like.

The thickness of the adhesive layer is preferably 0.1 to 6 μm, more preferably 0.1 to 3 μm. When the thickness of the adhesive layer is within the above range, the adhesive strength is further improved.

The active energy ray preferably has a wavelength or light including ultraviolet rays, and more preferably a wavelength of 150 to 550 nm. Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, an LED lamp, a xenon lamp, and a metal halide lamp. ..

The irradiation intensity of the active energy ray is preferably 10 to 500 mW / cm ² . The integrated irradiation amount expressed as the product of the irradiation intensity and the irradiation time is preferably 10 to 5000 mJ / cm ² , more preferably 30 to 4000 mJ / cm ² .

Examples of the embodiment of the laminated body include a sheet shape obtained by laminating a plurality of transparent films such as a transparent film / adhesive layer / transparent film or a transparent film / adhesive layer / transparent film / adhesive layer / transparent film. Multilayer film is preferred. In another embodiment, a sheet-like multilayer film such as a transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film is bonded to another optical member such as glass or an optical sheet. The configuration is also preferable. These laminates are irradiated with the active energy ray-polymerizable adhesive from one side or both sides of the base material to cure the adhesive layer.

The laminate of the present invention is preferably used for optical purposes, and more preferably used as a polarizing plate.

The optical application is an application used for a liquid crystal display device, a PDP module, a touch panel module, an organic EL module, and the like. The laminated body used for such a purpose is called an optical laminated body. The optical laminate uses an optical film on at least one of a first substrate and a second substrate. The optical film is, for example, a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film (also called a polarizing plate), a retardation film, an elliptical polarizing film, an antireflection film, a light diffusing film, a brightness improving film, and a prism film. (Also referred to as a prism sheet), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like can be mentioned.

In the polarizing plate, the first base material is a polarizing element, and a protective film is used as the second base material. Further, the polarizing plate may be provided with a third substrate via an adhesive layer on the opposite surface of the first substrate on the second substrate side. A protective film is used as the third substrate.

As the splitter, for example, a polyvinyl alcohol film or the like is preferable. The thickness of the stator is usually about 2 to 200 μm.

The protective film is, for example, a polytriacetyl cellulose-based protective film (hereinafter referred to as “TAC film”) which is a polyacetyl cellulose-based film, a polycycloolefin-based film which is a polynorbornene-based film, a polyacrylic film, a polycarbonate-based film, and the like. Examples include polyester films. The thickness of the protective film is usually about 5 to 200 μm.

An example of a method for manufacturing a polarizing plate will be described.

(1) An active energy ray-polymerizable adhesive is applied to one surface of a protective film, which is a first transparent film, to form a first adhesive layer, and one of the protective films, which is a second transparent film. An active energy ray-polymerizable adhesive is applied to the surface of the surface to form a second adhesive layer.

Next, each surface of the polyvinyl alcohol-based polarizing element is superposed simultaneously or sequentially with respect to the first adhesive layer and the second adhesive layer surface. Next, a method of producing by irradiating with active energy rays and curing the first adhesive layer and the second adhesive layer.

(2) An active energy ray-polymerizable adhesive is applied to one surface of a polyvinyl alcohol-based polarizing element to form a first adhesive layer, and the surface of the formed first adhesive layer is a transparent film. Cover with a first protective film. Next, an active energy ray hard-polymerizable adhesive is applied to the other surface of the polyvinyl alcohol-based polarizing element to form a second adhesive layer, and the surface of the formed second adhesive layer is covered with a second protective film. Cover with. Next, a method of producing by irradiating with active energy rays and curing the first adhesive layer and the second adhesive layer.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, "part" is "mass part", and "%" represents "mass%". The blending amount in the table is a part by mass.

[Example 1] <Production example of active energy ray-polymerizable adhesive>
60 parts of 4-hydroxybutyl acrylate (4-HBA manufactured by Osaka Organic Chemical Industry Co., Ltd.) as monomer (A) and neopentyl glycol diacrylate (light acrylate NP-A Kyoeisha) as compound (B) in a light-shielded glass bottle with a capacity of 300 mL. 19 parts of Chemical Co., Ltd., 1 part of 4-ethyl-catechol (manufactured by Wako Pure Chemical Industries, Ltd.) as compound (C), 12 parts of UV3000B (polyurethane-based oligomer manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as radically polymerizable oligomer (B3). , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBE-303, manufactured by Shinetsu Chemical Co., Ltd.) as a cationically polymerizable compound (D), 3 parts, and Irgacure 184 (manufactured by BASF), 3 parts as a radical polymerization initiator. Two parts of CPI-110P (manufactured by San-Apro) were added as a cationic polymerization initiator, and the mixture was sufficiently stirred and defoamed to obtain an active energy ray-polymerizable adhesive.

[Examples 2 to 32, Comparative Example 1]
By carrying out in the same manner as in Example 1 except that the raw materials of Example 1 and the blending amounts thereof were changed as shown in Table 1, the active energy ray-polymerizable properties of Examples 2 to 32 and Comparative Example 1, respectively. Obtained an adhesive.

Hereinafter, the materials used in the examples and their abbreviations are shown.
<Monomer (A)>
4-HBA: 4-Hydroxybutyl Acrylate HPA: 2-Hydroxypropyl Acrylate HEMA: Hydroxyethyl Methacrylate HEA: 2-Hydroxyethyl Acrylate

<Radical polymerizable compounds (B1) (B2)>
NPA: Neopentyl Glycol Diacrylate M200: Hexanediol Diacrylate M220: Tripropylene Glycol Diacrylate M300: Trimethylol Propylene Triacrylate M410: Ditrimethylol Propane Tetraacrylate

<Compound (C)>
3-Methoxy-catechol 4-t-butyl-catechol 4-ethyl-catechol 3-methyl-salicylic acid

<Radical polymerizable oligomer (B3)>
UV3000B: Polyester-based acrylate oligomer, CN2271 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., CN296 manufactured by Daicel Ornex Co., Ltd .: Polyester-based acrylate oligomer, EBECRYL860 manufactured by Daicel Ornex Co., Ltd.

<Cation-polymerizable compound (D)>
EX-211: Neopentyl glycol diglycidyl ether EX-201: 1,3-bis (oxylanylmethoxy) benzene KBE-303: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane KBM-403: 3- Glycydoxypropyltrimethoxysilane

<Active energy ray polymerization initiator>
Irgacure 184: α-hydroxyalkylphenone skeleton, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, BASF CPI-110P: sulfonium salt system, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate , Made by San Appro

The following laminate was prepared using the obtained active energy ray-polymerizable adhesive.

<Manufacturing example of laminated body A>
As the transparent film, an acrylic film having a thickness of 50 μm (manufactured by HBD-022 Mitsubishi Rayon Corporation) and a polynorbornene film having a thickness of 100 μm (manufactured by Zeon Corporation, which does not contain an ultraviolet absorber) were used. Corona treatment was performed on one surface of the two transparent films at a discharge rate of 300 W / min / m ² . Within 1 hour thereafter, the above-mentioned active energy ray-polymerizable adhesive was applied onto the corona-treated surface of the acrylic film using a wire bar coater so as to have a thickness of 4 μm to form an adhesive layer. The polynorbornene-based film was laminated on the adhesive layer, and fixed to the tin plate with cellophane tape on all sides so that the acrylic film was in contact with the tin plate.

The laminated body A (500 mJ / cm ² ) is irradiated with ultraviolet rays having a maximum illuminance of 500 mW / cm ² and an integrated light amount of 500 mJ / cm ² from the polynorbornene film side with an active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba). Created.

The same procedure as above was performed except that the transport speed of the active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba) was adjusted and the irradiation conditions were changed to a maximum illuminance of 500 mW / cm ² and an integrated light intensity of 150 mJ / cm ² . / Cm ² ) was prepared.

<Manufacturing example of laminated body B (polarizing plate)>
As the first transparent film, a polytriacetyl cellulose-based film containing an ultraviolet absorber manufactured by Fuji Film Co., Ltd .: trade name "Fujitac: 80 μm" (thickness 80 μm) is used, and as a second transparent film, ultraviolet rays manufactured by Nippon Zeon Co., Ltd. are used. A polynorbornene-based film (thickness 100 μm) containing no absorbent was used. The surfaces of one side of the first and second transparent films were subjected to corona treatment with a discharge amount of 300 W · min / m ² , respectively, and within 1 hour thereafter, the active energy ray-polymerizable adhesive was applied to the corona treatment of each film. An adhesive layer was formed on the surface by coating with a wire bar coater so as to have a thickness of 4 μm. A polyvinyl alcohol-based polarizing element is sandwiched between the adhesive layer formed on the first and second transparent films, and the laminate is composed of the first transparent film / adhesive layer / PVA-based polarizing element / adhesive layer / second transparent film. I got a body. The four sides of this laminated body were fixed with cellophane tape so that the first transparent film was in contact with the tin plate, and fixed to the tin plate.

The laminated body B (500 mJ / cm ² ) is irradiated with ultraviolet rays having a maximum illuminance of 500 mW / cm ² and an integrated light amount of 500 mJ / cm ² from the second transparent film side with an active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba Corporation). Created.

The same procedure as above was performed except that the transport speed of the active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba) was adjusted and the irradiation conditions were changed to a maximum illuminance of 500 mW / cm ² and an integrated light intensity of 150 mJ / cm ² . / Cm ² ) was prepared.

The peel strength, water resistance and heat resistance of the laminates A and B prepared at an integrated light intensity of 500 mJ / cm ² were evaluated. Only the peel strength was evaluated for the laminates A and B prepared with the integrated light intensity of 150 mJ / cm ² . The results are shown in Tables 1 to 4.

《Peeling strength》
The peel strength was measured according to JIS K6 854-4 Adhesive-Peeling Adhesive Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained laminate B was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to one side of the sample and adhered onto a metal plate using a laminator. The laminating body for measurement is provided with a peeling kick in advance between the transparent films, and the laminating body for measurement is placed at a speed of 300 mm / min and 90 ° under the conditions of 23 ° C. and a relative humidity of 50%. The peel strength was measured at the angle of. As for the peeling strength, the acrylic film HBD-022 was peeled off in the case of the laminated body A, and the first transparent film / adhesive layer / PVA-based polarizing element was peeled off in the case of the laminated body B, and the peeling strength was measured. This peel strength was evaluated on a 4-point scale. If the evaluation criteria are ⊚, ◯, and Δ, there is no problem in practical use.
◎: Cannot be peeled off or destroys the base material (extremely good)
◯: Peeling strength is 2.0 (N / 25 mm) or more (good)
Δ: Peeling strength is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) (usable)
×: Peeling strength is less than 1.0 (N / 25 mm) (cannot be used)

"water resistant"
After completely submerging the laminate in a mayonnaise bottle containing ion-exchanged water at 60 ° C and storing it for 24 hours, the laminate was taken out of the water and wiped off with water, and then 24 hours under the conditions of 23 ° C and 50% relative humidity. I kept it. The peel strength of this laminated body was measured according to JIS K6 854-4 in the same manner as the peel strength. The water resistance was evaluated on a 4-point scale based on this peel strength. If the evaluation is ◎, ○, △, there is no problem in practical use.
⊚: Peeling strength is 1.5 (N / 25 mm) or more (extremely good)
◯: Peeling strength is 1.0 (N / 25 mm) or more and less than 1.5 (N / 25 mm) (good)
Δ: Peeling strength is 0.5 (N / 25 mm) or more and less than 1.0 (N / 25 mm) (usable)
×: Peeling strength is less than 0.5 (N / 25 mm) (cannot be used)

"Heat-resistant"
The laminate was stored in a constant temperature bath at 80 ° C. for 200 hours, and the peel strength was measured according to JIS K6 854-4 in the same manner as the above peel strength. The heat resistance was evaluated on a 4-point scale based on this peel strength. If the evaluation is ◎, ○, △, there is no problem in practical use.
◎: Cannot be peeled off or destroys the base material (extremely good)
◯: Peeling strength is 2.0 (N / 25 mm) or more (good)
Δ: Peeling strength is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) (usable)
×: Peeling strength is less than 1.0 (N / 25 mm) (cannot be used)

From the results of Tables 1 to 4, in Examples 1 to 32, good peel strength was obtained with a low irradiation amount, and water resistance was good.

Claims (6)

A hydroxyl group-containing radically polymerizable monomer (A), a bifunctional or higher functional radically polymerizable compound (B) (excluding the hydroxyl group-containing radically polymerizable monomer (A)), and a compound represented by the following general formula (1) ( C) An active energy ray-polymerizable adhesive containing (however, excluding the hydroxyl group- containing radical polymerizable monomer (A) ) and satisfying the following (1) to (3) .
(1) The hydroxyl group-containing radically polymerizable monomer (A) is contained in an amount of 5 to 81% by mass, and the bifunctional or higher functional radical polymerizable compound (B) is contained in an amount of 16 to 91% by mass in 100% by mass of the polymerizable component.
(2) The total of (A) and (B) is 68% by mass or more in 100% by mass of the polymerizable component.
(3) The active energy ray-polymerizable adhesive is 100% by mass, and the compound (C) is contained in an amount of 0.01 to 5% by mass.
General formula (1)

(In the formula, X represents a hydroxyl group or a carboxyl group. R1 to R4 are independently selected from a hydrogen atom, a linear or split chain alkyl group, an alkenyl group, an alcohol group, and a halogen atom, respectively. Represents a group.) The radically polymerizable compound (B) is a bifunctional radically polymerizable monomer (B1), a trifunctional or higher functional radically polymerizable monomer (B2), and a radically polymerizable oligomer having a weight average molecular weight of 500 to 100,000 (B3). The active energy ray polymerization according to claim 1, which is one or more selected from the group consisting of (excluding the bifunctional radically polymerizable monomer (B1) and the trifunctional or higher functional radical polymerizable monomer (B2)). Sex adhesive. The active energy ray-polymerizable adhesive according to claim 1 or 2, further comprising a cationically polymerizable compound (D). The cationically polymerizable compound (D) is selected from the group consisting of a cationically polymerizable oligomer (with a weight average molecular weight of 2,000 or more) and a cationically polymerizable monomer (with a formula or weight average molecular weight of less than 2,000) . The active energy ray-polymerizable adhesive according to claim 3, which is one or more. The active energy ray-polymerizable according to any one of claims 1 to 4, wherein the compound (C) represented by the general formula (1) is contained in an active energy ray-polymerizable adhesive in an amount of 0.01 to 5% by mass. glue. A laminate comprising a first base material, an adhesive layer which is a cured product of the active energy ray-polymerizable adhesive according to any one of claims 1 to 5, and a second base material.