CN118255929A - Active energy ray polymerizable resin composition and laminate - Google Patents

Abstract

The present invention provides an active energy line polymerizable resin composition and a laminate, wherein a laminate having excellent adhesion, excellent durability to humidity, and no peeling even when bent repeatedly can be formed. The active energy line polymerizable resin composition disclosed herein comprises: (A) a compound having a hydroxyl group and containing an ethylenically unsaturated double bond group (wherein (B) is excluded), (B) a compound having two or more benzene rings and containing an ethylenically unsaturated double bond group, and (C) all compounds having a weight average molecular weight of 1,000 to 60,000 and having a carbamate structure and two ethylenically unsaturated double bonds, and a silane compound (D) having a reactive functional group and having an alkoxy group on a silicon atom, and a photoacid generator (E).

Description

Active energy ray-polymerizable resin composition and laminate

This application claims priority based on Japanese Patent Application No. 2022-203127 filed on December 20, 2022, and all the contents disclosed therein are incorporated herein by reference.

Technical Field

The present disclosure relates to an active energy ray-polymerizable resin composition and a laminate thereof.

Background technique

Active energy ray-polymerizable resin compositions have excellent properties such as high workability and low energy required for polymerization due to their high polymerization speed and the fact that they can usually be used without a solvent. Types of active energy ray-polymerizable resin compositions include free radical-based, cationic-based, and combinations thereof (mixed-based), and are used in a wide range of fields such as adhesives and coating agents.

Polarizers used in liquid crystal display devices are usually made by uniaxially stretching a polyvinyl alcohol (PVA) film adsorbed with iodine and dyes. Since the PVA-based polarizer shrinks due to heat and moisture, the polarization performance is reduced, so a protective film is attached to the surface and used in the form of a polarizing plate.

In the past, water-based adhesives and active energy ray polymerizable resin compositions were used to bond the PVA-based polarizer to the protective film. Among them, active energy ray polymerizable resin compositions are preferred from the perspectives of versatility of the substrate used in the protective film, efficiency and energy saving in production, etc. The active energy ray polymerizable resin composition for the above-mentioned purpose is required to have sufficient adhesion for bonding the PVA-based polarizer to the protective film, and heat resistance, moisture resistance, and water resistance for suppressing the reduction of the polarization performance of the PVA-based polarizer.

Japanese Patent Application Publication No. 2004-245925 discloses a cationic active energy ray-polymerizable adhesive having an aromatic-free epoxy resin as a main component to address issues such as the bonding strength of polarizing plates using a film (norbornene-based resin film, etc.) having a lower moisture permeability than triacetyl cellulose as a protective film.

In Japanese Patent Publication No. 2010-018722, an active energy ray-polymerizable adhesive using a mixture of 2-hydroxybutyl acrylate and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane is disclosed as an adhesive that can firmly bond not only to a film of a norbornene-based resin but also to films of an acrylic resin, triacetyl cellulose, and the like.

Japanese Patent Application Laid-Open No. 2017-194572 discloses a radical-based active energy ray-polymerizable adhesive using acryloylmorpholine and an alkyl acrylate having 10 to 20 carbon atoms in combination to address issues such as water resistance.

Summary of the invention

[Problems to be solved by the invention]

In the field of organic electroluminescence (EL) displays, polarizing plates ((elliptical) circular polarizing plates, etc.) are sometimes used, which are formed by laminating a phase difference film (λ/4 phase difference film, etc.) on a polarizer. In recent years, the development of bendable organic EL displays is advancing, and protective films thinner than before are gradually used for the purpose of improving the bendability of polarizing plates. However, the thinner the protective film, the more it tends to increase moisture permeability and deteriorate moisture resistance. Bending resistance and moisture resistance are mutually divergent properties. In existing adhesives, it is difficult to take into account both the bending resistance and moisture resistance of polarizing plates.

An object of the present disclosure is to provide an active energy ray-polymerizable resin composition and a laminate using the same, wherein a laminate having excellent adhesiveness, excellent durability against humidity, and no peeling even when repeatedly bent can be formed.

[Technical means to solve the problem]

The present inventors have conducted intensive studies and, as a result, have found that the above-mentioned problems can be solved by the active energy ray-polymerizable composition described below, thereby completing the present invention.

[1] An active energy ray-polymerizable resin composition comprising: all of the following compounds (A), (B) and (C), a silane compound (D) having a reactive functional group and an alkoxy group on a silicon atom, and a photoacid generator (E);

(A) a compound having a hydroxyl group and containing an ethylenically unsaturated double bond group (except (B));

(B) a compound having two or more benzene rings and containing an ethylenically unsaturated double bond group;

(C) A compound having a weight average molecular weight of 1,000 to 60,000 and having a urethane structure and two ethylenically unsaturated double bond groups.

[2] The active energy ray-polymerizable resin composition according to [1], wherein the compound (B) comprises at least one of the following (b1) and (b2),

(b1) a compound having two benzene rings and one ethylenically unsaturated double bond group;

(b2) A compound having three or more benzene rings and containing an ethylenically unsaturated double bond group.

[3] The active energy ray-polymerizable resin composition according to [1] or [2], wherein the compound (D) is a silane compound having an epoxy group and an alkoxy group on a silicon atom.

[4] The active energy ray-polymerizable resin composition according to any one of [1] to [3], further comprising a compound (F) having an alicyclic structure and containing an ethylenically unsaturated double bond group,

The compound (F) includes a compound having two or more aliphatic hydrocarbon monocyclic structures and/or a compound having an aliphatic hydrocarbon polycyclic structure.

[5] An active energy ray-polymerizable resin composition according to [4], wherein the active energy ray-polymerizable resin composition contains 10% to 60% by mass of the compound (A), 5% to 65% by mass of the compound (B), 1% to 20% by mass of the compound (C), 2% to 20% by mass of the compound (D), and 5% to 40% by mass of the compound (F) in 100% by mass of the active energy ray-polymerizable resin composition.

[6] A laminate comprising: a layer comprising the active energy ray-polymerizable resin composition according to any one of [1] to [5], or a layer comprising a cured product of the active energy ray-polymerizable resin composition; and a substrate.

[Effects of the Invention]

According to the present disclosure, an active energy ray-polymerizable resin composition and a laminate using the same can be provided, wherein a laminate having excellent adhesiveness, excellent durability against humidity, and no peeling even when repeatedly bent can be formed.

Detailed ways

Hereinafter, preferred embodiments of the present invention will be described.

Generally, for a thin film formed body, the terms "film", "sheet" and "plate" are used according to the thickness, but there is no clear distinction between them. The "film" used in this specification includes "sheet" and "plate".

In this specification, "(meth)acrylic acid" means "acrylic acid or methacrylic acid" unless otherwise specified.

In the present specification, a compound (A) having a hydroxyl group and containing an ethylenically unsaturated double bond group is sometimes referred to as compound (A), a compound (B) having two or more benzene rings and containing an ethylenically unsaturated double bond group (excluding compounds having a hydroxyl group) is referred to as compound (B), a compound (C) having a carbamate structure and two ethylenically unsaturated double bond groups is referred to as compound (C), and a silane compound (D) having a reactive functional group and an alkoxy group on a silicon atom is referred to as compound (D).

In this specification, unless otherwise specified, a numerical range defined by using “to” includes the lower limit value and the upper limit value described before and after “to”.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are weight average molecular weight (Mw) and number average molecular weight (Mn) calculated in terms of standard polystyrene determined by gel permeation chromatography (GPC).

"Active energy ray-polymerizable resin composition"

The active energy line polymerizable resin composition disclosed herein comprises: a compound (A) having a hydroxyl group and containing an ethylenically unsaturated double bond group, a compound (B) having two or more benzene rings and containing an ethylenically unsaturated double bond group (wherein the compound having a hydroxyl group is excluded), a compound (C) having a carbamate structure and two ethylenically unsaturated double bond groups, a silane compound (D) having a reactive functional group and having an alkoxy group on a silicon atom, and a photoacid generator (E).

The active energy ray-polymerizable resin composition having the above structure can form a laminated body that has excellent durability against humidity and does not peel off even when bent repeatedly, and is suitable for an adhesive.

<Hydroxyl-containing and ethylenically unsaturated double bond group-containing compound (A)>

Compound (A) is a compound having a hydroxyl group and an ethylenically unsaturated double bond group. Compound (A) can form hydrogen bonds with the hydrophilic functional groups of the substrate, etc., which helps to improve the adhesive force. In terms of not making the viscosity of the resin composition too high and making it easy to control the film thickness during coating, the weight average molecular weight (Mw) of compound (A) is preferably less than 1,000, and more preferably 100 to 500.

As compound (A), a compound having one ethylenically unsaturated double bond group is preferred from the viewpoint of adhesive strength.

The content of the compound (A) is preferably 10% to 60% by mass, more preferably 15% to 50% by mass, in 100% by mass of the active energy ray-polymerizable resin composition. When the content of the compound (A) is 10% by mass or more, the adhesive force is further improved, and when it is 60% by mass or less, the balance between the adhesive force and the moisture resistance becomes good.

The compound (A) is not particularly limited as long as it is a compound having a hydroxyl group and an ethylenically unsaturated double bond group, and examples thereof include monofunctional fatty acid esters such as monofunctional (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and ethyl-α-(hydroxymethyl) (meth)acrylate.

Examples of the compound (A) include (meth)acrylates having a hydroxyl group at the terminal obtained by ring-opening addition of ε-caprolactone to the above-mentioned compound containing a hydroxyl group and having an ethylenically unsaturated double bond group, and alkylene oxide-added (meth)acrylates obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to the above-mentioned compound containing a hydroxyl group and having an ethylenically unsaturated double bond group, and other hydroxyl-containing aliphatic (meth)acrylates.

Examples of the compound (A) 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 alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal obtained by repeatedly adding an alkylene oxide such as ethylene oxide and propylene oxide.

Examples of the compound (A) include (meth)allyl alcohol, isopropenyl alcohol, dimethyl (meth)allyl alcohol, hydroxyethyl (meth)allyl ether, hydroxypropyl (meth)allyl ether, hydroxybutyl (meth)allyl ether, hydroxyhexyl (meth)allyl ether, hydroxyoctyl (meth)allyl ether, hydroxydecyl (meth)allyl ether, hydroxydodecyl (meth)allyl ether, hydroxyoctadecyl (meth)allyl ether, glyceryl (meth)allyl ether, and alkylene oxide addition (meth)allyl ethers having a hydroxyl group at the terminal to which an alkylene oxide such as ethylene oxide and propylene oxide is repeatedly added, and other hydroxyl group-containing aliphatic (meth)allyl alcohols or (meth)allyl ethers.

Examples of the compound (A) include compounds having a plurality of hydroxyl groups and an ethylenically unsaturated double bond group, such as propylene glycol, butene glycol, heptene glycol, octenylene glycol, and glycerol di(meth)acrylate.

Examples of the compound (A) include hydroxyl group-containing (meth)acrylamides such as N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N-hydroxybutyl (meth)acrylamide, N-hydroxyhexyl (meth)acrylamide, and N-hydroxyoctyl (meth)acrylamide.

Examples of the compound (A) include monomers having a hydroxyl group and a vinyl group, such as vinyl alcohol.

The compound (A) is not limited to the compounds exemplified above. The compound (A) may be used alone or in combination of two or more.

As compound (A), from the viewpoint of adhesion to the substrate, acrylic acid esters of diols having 1 to 6 carbon atoms are preferred, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are particularly preferred.

<Compound (B) having two or more benzene rings and containing an ethylenically unsaturated double bond group>

Compound (B) is a compound having two or more aromatic groups and ethylenically unsaturated double bond groups. Compound (B) can help improve moisture resistance. In terms of not making the viscosity of the resin composition too high and making it easy to control the film thickness during coating, the weight average molecular weight (Mw) of compound (B) is preferably less than 1,000, more preferably 190 to 900.

Examples of compound (B) include a compound (b1) having two benzene rings and one ethylenically unsaturated double bond group, a compound (b2) having three or more benzene rings and containing an ethylenically unsaturated double bond group, and a compound (b3) having two benzene rings and two ethylenically unsaturated double bond groups. Compound (B) preferably includes at least one of compound (b1) and compound (b2). Compound (b1) has a good balance between moisture resistance and bending properties, and compound (b2) has excellent tape peeling and moisture resistance. Compound (B) more preferably includes compound (b1).

The content of the compound (B) is preferably 5% to 65% by mass, more preferably 10% to 55% by mass, in 100% by mass of the active energy ray-polymerizable resin composition. When the content of the compound (B) is 5% by mass or more, the moisture resistance is further improved, and when it is 65% by mass or less, the balance among adhesion, flexibility, and moisture resistance becomes good.

As compound (b1), there is no particular limitation as long as it is a compound having two benzene rings and one ethylenically unsaturated double bond group, and examples thereof include: phenoxybenzyl (meth)acrylate, ethoxylated phenoxybenzyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, polyethylene glycol-modified o-phenylphenoxy (meth)acrylate, 2-hydroxy-3-phenylphenoxypropyl acrylate, p-pentylphenoxyethyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate, 2-naphthyl acrylate, fluorenol (meth)acrylate, and 2-oxo-1,2-diphenylethyl (meth)acrylate. Naphthyl is a group formed by condensation of two benzene rings and is regarded as a group having two benzene rings.

As compound (b2), there is no particular limitation as long as it is a compound having three or more benzene rings and containing an ethylenically unsaturated double bond group, and examples thereof include: ethoxylated bisphenylfluorene di(meth)acrylate, polyethylene glycol-modified bisphenylfluorene di(meth)acrylate, 2-anthryl (meth)acrylate, and anthracenyl methyl (meth)acrylate, etc. Anthracenyl is a group formed by condensation of three benzene rings and is regarded as a group having three benzene rings.

The compound (b3) is not particularly limited as long as it is a compound having two benzene rings and two ethylenically unsaturated double bond groups, and examples thereof include bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated propoxylated bisphenol A diacrylate, bisphenol F diacrylate, ethoxylated bisphenol F diacrylate, ethoxylated propoxylated bisphenol F diacrylate, and 4,4'-bisacryloxymethylbiphenyl.

<Compound having a urethane structure and two ethylenically unsaturated double bond groups (C)>

Compound (C) is a compound having a weight average molecular weight (Mw) of 1,000 to 60,000 and having a carbamate structure and two ethylenically unsaturated double bond groups, and is generally referred to as a carbamate acrylate. Compound (C) has a carbamate bond with high polarity and a weight average molecular weight (Mw) of 1,000 to 60,000, which contributes to the toughness of the coating film, good substrate adhesion, and improved bending resistance. From the perspective of compatibility and bending resistance of the coating film after polymerization, the weight average molecular weight (Mw) of compound (C) is particularly preferably 5,000 to 50,000.

The content of the compound (C) is preferably 1% to 20% by mass, more preferably 2% to 10% by mass, in 100% by mass of the active energy ray-polymerizable resin composition. If the content of the compound (C) is 1% by mass or more, the bending resistance is further improved, and if it is 20% by mass or less, the viscosity does not become too high, and the film thickness during coating can be easily controlled.

Examples of the compound (C) include a compound obtained by reacting a compound having two or more isocyanate groups with the compound (A), or a compound obtained by reacting a terminal isocyanate group-containing urethane prepolymer obtained by reacting a compound having two or more isocyanate groups with a polyol, and the compound (A); a compound obtained by reacting a terminal isocyanate group-containing urethane prepolymer obtained by reacting a compound having two or more isocyanate groups with a polyol and a compound having two or more amino groups, and the compound (A); and the like.

As compound (C), a compound obtained by reacting a compound having two or more isocyanate groups, a polyol, and compound (A) at a molar ratio of 2:1:2 is preferred. By reacting at the above ratio, compound (C) theoretically has a structure having acrylate groups at both ends of one molecule. In the above case, the balance between flexibility and crosslinking density is good, and substrate adhesion and toughness are excellent, so bending resistance becomes good.

Examples of the compound having two or more isocyanate groups include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, and 4,4′,4″-triphenylmethane triisocyanate.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include ω,ω′-diisocyanate-1,3-dimethylbenzene, ω,ω′-diisocyanate-1,4-dimethylbenzene, ω,ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylene diisocyanate, and 1,3-tetramethylxylene diisocyanate.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI (isophorone diisocyanate)), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), and 1,4-bis(isocyanate methyl)cyclohexane.

It is also possible to use the 2-methylpentane-2,4-diol adduct of a part of the polyisocyanate or a trimer with an isocyanurate ring. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and polyisocyanate modifications thereof can be used. As polyisocyanate modifications, it is possible to use a modified product having a carbodiimide group, a uretdione group, a uretonimine group, a biuret group reacting with water, and one or more isocyanurate groups. The reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

As the compound having an isocyanate group, an aliphatic diisocyanate compound or an alicyclic diisocyanate compound is preferred from the viewpoint of bending resistance.

Examples of the polyol include low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500 and high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000, and any of them can be used without particular limitation.

Examples of low molecular weight polyols include ethylene glycol and propylene glycol. aliphatic or alicyclic diols such as 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadienyl dimethanol, and dimer diol;

Aromatic diols such as 1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediphenol, 4,4'-(2-norbornylene)diphenol, 4,4'-dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxybenzene or p-dihydroxybenzene, 4,4'-isopropylidenephenol, and addition-type bisphenols obtained by adding alkylene oxide to p-bisphenol.

Examples of the raw material bisphenol of the addition type bisphenol include bisphenol A and bisphenol F. Examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.

Examples of high molecular weight polyols include polyether polyols, polyester polyols, polyamide polyols, polycarbonate polyols, and polyurethane polyols. Polycarbonate polyols are obtained by reacting the low molecular weight diols with carbonate or phosgene.

Examples of commercially available polyester polyols include Vylon series manufactured by Toyobo Co., Ltd., Kuraray Polyol P series manufactured by Kuraray Co., Ltd., and Kyowa Paul series manufactured by Kyowa Hakko Chemical Co., Ltd.

As a commercial item of polyamide polyol, TPAE617 etc. manufactured by Fuji Chemical Industries, Ltd. are mentioned, for example.

Examples of commercially available polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray Polyol PMHC series and Kuraray Polyol C series manufactured by Kuraray Corporation, and the like.

Commercially available products of polyurethane polyols include, for example, Vylon UR series manufactured by Toyobo Co., Ltd., Takelac E158 (hydroxyl value = 20, acid value <3), Takelac E551T (hydroxyl value = 30, acid value <3), and Takelac Y2789 (hydroxyl value = 10, acid value <2) manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.

Polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly(β-methyl-γ-valerolactone) diol, and polyvalerolactone diol are also included in the high molecular weight polyols.

As the polyol, from the viewpoint of adhesion, a high molecular weight polyether diol or a high molecular weight polyester diol is preferred.

Examples of the amines having an amino group include:

Aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-2-hydroxyethylethylene)diamine, (di-2-hydroxyethylpropylene)diamine, (2-hydroxypropylethylene)diamine, (di-2-hydroxypropylethylene)diamine, and piperazine;

Alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine;

Aromatic diamines such as phenylenediamine, xylylenediamine, 2,4-tolylene diamine, 2,6-tolylene diamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and 4,4'-bis-(sec-butyl)diphenylmethane, etc.

<Compound having an alicyclic structure and containing an ethylenically unsaturated double bond group (F)>

The resin composition of the present disclosure preferably further contains a compound (F) having an alicyclic structure and containing an ethylenically unsaturated double bond group (hereinafter referred to as compound (F)).

Compound (F) is preferably a compound (f1) having a structure in which two or more monocyclic aliphatic hydrocarbon rings are linked via an alkyl group, an ether bond, an ester bond, etc. (hereinafter referred to as compound (f1)); a compound (f2) having an aliphatic polycyclic structure having a bridging structure such as a norbornane skeleton, a norbornene skeleton, and an adamantane skeleton (hereinafter referred to as compound (f2)). Among them, compound (f2) is more preferred because of its excellent adhesion and moisture resistance.

Examples of the compound (f1) include hydrogenated bisphenol A diacrylate and ethylene oxide (EO)-modified hydrogenated bisphenol A diacrylate.

As compound (f2), it is sufficient as long as it has one or more structures among a norbornene skeleton, a norbornane skeleton, and an adamantane skeleton, and one or more ethylenically unsaturated double bonds, and examples thereof include: dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, dihydroxymethyldicyclopentane di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, isobornyl (meth)acrylate, 3-hydroxy-1-adamantane (meth)acrylate. The present invention relates to a kind of alkyl esters, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate, 1,3-adamantyl glycol di(meth)acrylate, 1,3,5-adamantyl tri(meth)acrylate, 3-hydroxy-1,5-adamantyl di(meth)acrylate, and 3,5-dihydroxy-1-adamantyl (meth)acrylate. Among them, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, and dihydroxymethyldicyclopentane di(meth)acrylate are preferred from the viewpoint of excellent adhesiveness.

Furthermore, compounds having one or more structures of a norbornene skeleton, a norbornane skeleton, and an adamantane skeleton, and one or more ethylenically unsaturated double bonds are also included in the compound (f2) even if they have a hydroxyl group.

The content of the compound (F) is preferably 5% by mass to 40% by mass in 100% by mass of the active energy ray-polymerizable resin composition. The above range is preferred because the adhesive force is more excellent.

The resin composition of the present disclosure may also contain other compounds (M) having ethylenically unsaturated double bonds. Examples of the compound (M) include a compound (m1) having an alkanediol in the main chain and two ethylenically unsaturated double bonds, a compound (m2) having three ethylenically unsaturated double bonds, and other compounds (m3) having ethylenically unsaturated double bonds.

Examples of the compound (m1) include difunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-dimethylpropyl glycol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 2,2-diethyl-1,3-propylene glycol di(meth)acrylate, and 2,5-dimethyl-2,5-hexanediol di(meth)acrylate.

Examples of the compound (m2) include trifunctional (meth)acrylates such as 1,2,3-propanetriol tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, 1,1,1-trihydroxymethylethane tri(meth)acrylate, and tri(2-acryloyloxyethyl) isocyanurate.

Examples of the compound (m3) include:

Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-hexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate;

(Meth)acrylates having a cycloalkane skeleton or a cycloolefin skeleton, such as cyclohexyl (meth)acrylate, 1-methyl-1-cyclopentyl (meth)acrylate, and 2-(meth)acryloyloxyethyl hexahydrophthalate;

(meth)acrylates having one aromatic ring and one acryloyl group, such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenol ethylene oxide-modified (meth)acrylate, nonylphenol ethylene oxide-modified (meth)acrylate, nonylphenol propylene oxide-modified (meth)acrylate, and phthalic acid monohydroxyethyl (meth)acrylate;

Tetrafunctional or higher-functional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, 2,2-bis(hydroxymethyl)1,3-propylene glycol tetra(meth)acrylate, and di-2,2-bis(hydroxymethyl)1,3-propylene glycol polyoxyl hepta(meth)acrylate.

The compound (M) can be used alone or in combination of two or more.

The compound (M) preferably contains the compound (m1) and/or the compound (m2). It is more preferred that the compound (M) contains both the compound (m1) and the compound (m2) because unreacted substances are less likely to remain and the adhesiveness and water resistance are excellent.

The content of the compound (m1) is preferably 0 to 60% by mass, more preferably 5 to 50% by mass, in 100% by mass of the active energy ray-polymerizable resin composition. When the content of the compound (m1) is 60% by mass or less, the adhesiveness and water resistance are particularly excellent.

The content of the compound (m2) is preferably 0 to 50% by mass, more preferably 5 to 40% by mass, in 100% by mass of the active energy ray-polymerizable resin composition. When the content of the compound (m2) is 50% by mass or less, the adhesiveness and water resistance are particularly excellent.

The total content of the compound (m1) and the compound (m2) is preferably 0 to 60% by mass, more preferably 5 to 50% by mass, in 100% by mass of the active energy ray-polymerizable resin composition. When the total content is 60% by mass or less, the adhesiveness and water resistance are particularly excellent.

<Silane compound (D) having a reactive functional group and an alkoxy group on a silicon atom>

Compound (D) is a compound having two reaction sites, a reactive functional group and an alkoxysilyl site. At the alkoxysilyl site, alcohol is separated by hydrolysis, and then a siloxane bond is formed by dehydration condensation, and the hardening is performed by repeating the above process. It is believed that part of the alkoxysilyl site is cross-linked with the hydroxyl group of compound (A) and the hydroxyl group of the substrate when the substrate has a hydroxyl group.

Examples of the reactive functional group include (meth)acryloyloxy, vinyl, mercapto, epoxy, and isocyanate groups. When the reactive functional group is (meth)acryloyloxy, vinyl, or mercapto, it can crosslink with the ethylenically unsaturated double bond groups possessed by compound (A), compound (B), compound (C), compound (F), and compound (M). When the reactive functional group is an epoxy or isocyanate group, it can crosslink with the hydroxyl group of compound (A) and the hydroxyl group of the substrate when the substrate has a hydroxyl group.

The resin composition of the present disclosure shows excellent moisture resistance by including compound (D). It is inferred that the reason is that the reactive functional group of compound (D) is cross-linked with the hydroxyl and ethylenic unsaturated double bond groups contained in the constituents of the resin composition, and the cross-linking density of the adhesive coating becomes higher. In addition, in the case where the substrate has a hydroxyl group, in addition to the cross-linking of the constituents of the compound (D) and the resin composition, the hydroxyl group of the alkoxysilane group part and the substrate is also cross-linked, thereby improving adhesion and moisture resistance. Wherein, in the case where the reactive functional group of compound (D) is an epoxy group or an isocyanate group that can be cross-linked with a hydroxyl group, the effect of improving adhesion and moisture resistance further becomes higher.

Examples of the silane compound (D) include:

Silane compounds having a methacryloxy group, an alkyl group, and two or more alkoxy groups, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropylmethyldiethoxysilane;

Silane compounds having an acryloxy group, an alkyl group, and two or more alkoxy groups, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-acryloxypropylmethyldimethoxysilane;

Silane compounds having a (meth)acryloyloxyalkyl group and three alkoxy groups, such as γ-methacryloyloxymethyltrimethoxysilane and γ-acryloyloxymethyltrimethoxysilane;

Alkoxysilanes having a vinyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, and vinyltri(2-methoxyethoxy)silane;

Silane compounds having a mercapto group and an alkoxy group, such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, and 10-mercaptodecyltrimethoxysilane;

Silane compounds having an epoxy group and an alkoxy group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane;

Silane compounds having an isocyanate group and an alkoxy group, such as 3-isocyanatepropyltriethoxysilane, and the like.

The silane compounds may be used alone or in combination of two or more.

Among the silane compounds, a silane compound containing an epoxy group or an isocyanate group is preferred because it improves moisture resistance and adhesion to a hydrophilic substrate, and a silane compound containing an epoxy group is more preferred.

The content of the compound (D) is preferably 2% to 20% by mass, more preferably 5% to 20% by mass, in 100% by mass of the active energy ray-polymerizable resin composition. When the content of the compound (D) is 2% by mass or more, the moisture resistance is further improved, and when it is 20% by mass or less, the balance between the adhesive force and the moisture resistance is good.

＜Photoacid generator (E)＞

The photoacid generator (E) can generate an acid by irradiation with active energy rays such as visible light, ultraviolet light, X-rays, or electron beams, and catalytically act to initiate the polymerization reaction of the silane compound and the cationic polymerizable compound. Examples of the photoacid generator include: sulfonium salt acid generators (e1); iodonium salt acid generators (e2); diazonium salt acid generators; ammonium salt acid generators; phosphonium salt acid generators and other onium salt acid generators.

Among them, from the viewpoint of providing an active energy ray-polymerizable resin composition having excellent photodecomposition efficiency and further excellent curability, sulfonium salt acid generators (e1) and iodonium salt acid generators (e2) are preferred.

From the viewpoint of curability of the active energy ray-polymerizable resin composition, the content of the photoacid generator (E) is preferably 0.1% by mass or more in 100% by mass of the active energy ray-polymerizable resin composition.

From the viewpoint of moist heat resistance, the content of the photo-acid generator (E) is preferably 20% by mass or more, more preferably 0.5% by mass to 10% by mass.

Examples of the sulfonium salt acid generator (e1) include triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, and triarylsulfonium tetrakis(pentafluorophenyl)borate.

Examples of commercially available products of the sulfonium salt acid generator (e1) include triarylsulfonium hexafluorophosphate (CPI-110P, manufactured by San-apro) and UVACURE 1590 (manufactured by Daicel-Cytec).

Examples of the iodonium salt acid generator (e2) include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, (4-methylphenyl)(4-isopropylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and diphenyliodonium tetrakis(pentafluoro)borate.

Examples of commercially available iodonium salt acid generators (e2) include bis(4-tert-butylphenyl)iodonium hexafluorophosphate (WPI-170, manufactured by Wako Pure Chemical Industries, Ltd.), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), IK-1 (manufactured by San-apro Co., Ltd.), and (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate (Omnicat 250, IGM resins).

＜Radical polymerization initiator (G)＞

The active energy ray-polymerizable resin composition of the present disclosure preferably further contains a radical polymerization initiator (G). By using the radical polymerization initiator (G), the radical polymerization reaction can be accelerated.

As the radical polymerization initiator (G), an existing one can be used. Specific examples include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4-xanthone, camphorquinone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Examples of commercially available products include Irgacure-184, 907, 651, 1700, 1800, 819, 369, and 261, DAROCUR-TPO (manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), Omnirad 819 (manufactured by IGM Resins B.V., bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), DAROCUR-1173 (manufactured by Merck), Esacure KIP150 and TZT (manufactured by Nihon Siber Hegner), and Kayacure BMS and Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.).

From the viewpoint of having photo bleaching properties, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are preferred.

The content of the radical polymerization initiator (G) is preferably 0.01% by mass to 20% by mass in 100% by mass of the active energy ray-polymerizable resin composition.

＜Active energy ray sensitizer (H)＞

In order to improve the reactivity of the photoacid generator (E), an active energy ray sensitizer (H) may be used in combination. Examples of the sensitizer (H) include thioxanthone compounds, anthracene compounds, naphthalene compounds, aminobenzoate compounds, carbazole compounds, perylene, phenothiazine, and rose Bengal.

Examples of the sensitizer (H) include:

Thioxanthone compounds such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-hydroxythioxanthone, 2-acetoxythioxanthone, and 2-propoxythioxanthone;

Anthracene compounds such as 9,10-dimethoxyanthracene, 9,10-ethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene; naphthalene compounds such as 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, and 1,4-dibutoxynaphthalene.

＜Other ingredients＞

In addition to the above-mentioned components, one or more additives may be appropriately blended into the active energy ray-polymerizable resin composition of the present disclosure within a range that does not impair the effects of the present invention.

For example, from the perspectives of reducing the shrinkage rate of polymerization curing, reducing the thermal expansion coefficient, improving dimensional stability, improving elastic modulus, adjusting viscosity, improving thermal conductivity, improving strength, improving toughness, and improving coloring, an organic or inorganic filler can be prepared as an additive. As a filler, polymers, ceramics, metals, metal oxides, metal salts, and dyes and pigments can be used, and there is no particular limitation on the shape, which is particulate and fibrous. In addition, the polymer can be dissolved, semi-dissolved, or micro-dispersed in the active energy line polymerizable resin composition instead of a filler, as a softness imparting agent, plasticizer, flame retardant, storage stabilizer, antioxidant, ultraviolet absorber, thixotropy imparting agent, dispersion stabilizer, fluidity imparting agent, defoamer, polymer blend, and polymer alloy.

In terms of drying equipment and drying energy, the active energy line polymerizable resin composition of the present disclosure is preferably substantially free of water and organic solvent. However, in the case where the photoacid generator (E) or the free radical polymerization initiator (G) is poorly soluble or has high viscosity in the compound (A), the compound (B), the compound (D), the compound (F) and the compound (M), a small amount of water or an organic solvent can be used to dissolve the photoacid generator (E) or the free radical polymerization initiator (G). The content of water or organic solvent in the active energy line polymerizable resin composition is preferably 0% by mass to 5% by mass.

The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents.

The viscosity of the active energy ray-polymerizable resin composition may be adjusted by adding water to the organic solvent, or the viscosity may be reduced by heating the active energy ray-polymerizable resin composition.

"Layered"

The laminate disclosed herein includes: a layer containing an active energy line polymerizable resin composition, or a layer containing a cured product of the active energy line polymerizable resin composition (hereinafter, also referred to as a resin composition layer or a cured product layer); and a substrate. The active energy line polymerizable resin composition can be applied to one or both sides of the substrate. When the active energy line polymerizable resin composition is used as an adhesive, the substrate may be multiple. When the active energy line polymerizable resin composition is used as a coating agent, the substrate may be single or multiple.

The laminated body of the present disclosure can be obtained as follows.

The active energy ray-polymerizable resin composition of the present disclosure is applied to one surface of a first transparent film (first film-like substrate), and a second transparent film (second film-like substrate) is laminated on the formed coating to obtain a three-layer laminate.

Furthermore, the active energy ray-polymerizable resin composition of the present disclosure may be applied to one or both sides of the three-layer laminate, and a transparent film, glass, or a transparent resin molded body may be laminated on the formed coating to form a multilayer structure.

In addition, it is needless to say that the laminated body of the present invention is not limited to the above-mentioned laminated structure.

The film thickness of the resin composition layer is not particularly limited and can be appropriately adjusted according to the intended use. To facilitate coating, water and/or an organic solvent may be added to the resin composition to adjust the viscosity.

When the film thickness of the resin composition layer is 0.1 μm to 6 μm, the viscosity of the resin composition is preferably 1 mPa·s to 1500 mPa·s, more preferably 10 mPa·s to 1300 mPa·s, and further preferably 20 mPa·s to 1000 mPa·s. If the viscosity is 1500 mPa·s or less, a 0.1 μm to 6 μm thin film coating with excellent optical properties such as transmittance can be performed. If the viscosity is 1 mPa·s or more, the film thickness of the resin composition layer can be easily controlled.

When the film thickness of the resin composition layer is 6 μm to 300 μm, the viscosity of the resin composition is preferably 1500 mPa·s to 100,000 mPa·s, and more preferably 3,000 mPa·s to 50,000 mPa·s.

＜Application method＞

The coating of the active energy ray-polymerizable resin composition disclosed herein can be carried out using existing devices or methods such as a Meyer bar, an applicator, a brush, a sprayer, a roller, a gravure coater, a die coater, a microgravure coater, a lip coater, a comma coater, a curtain coater, a knife coater, a reverse coater, and a spin coater.

＜Base material＞

The substrate may be a film substrate, a glass plate, or a paper product, etc., without any particular limitation. When the active energy ray polymerizable resin composition disclosed herein is used as an adhesive for bonding two or more substrates, a substrate that is easily permeable to the active energy ray is required in order to irradiate the active energy ray and polymerize. In the case described above, it is preferred that at least one substrate is a transparent substrate such as a transparent film or a transparent glass plate. Alternatively, as one of the substrates, a substrate that is difficult for the active energy ray to penetrate, such as wood, a metal plate, a plastic plate, or a paper product, may be used, and as the other substrate, a transparent substrate such as a transparent film or a transparent glass plate may be used, and the active energy ray may be irradiated from the transparent substrate side to perform polymerization and curing.

As the substrate, a film substrate is preferred. Examples of the film substrate include cellophane, various transparent plastic films, and synthetic paper, and various transparent plastic films are preferred. The film substrate may be a single-layer structure or a laminated structure.

In the laminate, a polymerization reaction of the resin composition based on active energy ray irradiation is required during bonding. The irradiation time of the active energy ray can be any time after the resin composition is applied and the film is formed, and can be any time before the substrate is laminated on the film, during the process of laminating the substrate on the film, or after the substrate is laminated on the film. Preferably, it is after the substrate is laminated on the film.

＜Active Energy Ray＞

Examples of active energy rays include ultraviolet rays and electron beams, and ultraviolet rays are preferred.

As the irradiation light source, a light source that mainly emits light in the wavelength range of 150nm to 550nm is preferred, and examples thereof include: low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, gallium lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, light-emitting diode (LED) lamps, xenon lamps, and semiconductor lasers.

The ultraviolet irradiation intensity is preferably 10 mW/cm ² to 3000 mW/cm ² , and the cumulative irradiation dose, which is the product of the irradiation intensity and the irradiation time, is preferably 50 mJ/cm ² to 20,000 mJ/cm ² in terms of facilitating rapid curing and suppressing degradation of the substrate.

<Laminate for optical element>

The laminated body of the present disclosure is suitable for optical applications, particularly for optical element applications.

As the optical laminate, for example, a sheet-like laminate formed by laminating a plurality of layers such as transparent film/adhesive layer/transparent film and transparent film/adhesive layer/transparent film/adhesive layer/transparent film is preferred. At least one transparent film may be replaced with glass or an optical member (optical molded body, etc.).

As a transparent film that can be used as an optical film, a plastic film having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropy is preferred, and a thermoplastic resin film is more preferred. Examples thereof include: polyvinyl alcohol film; polytriacetyl cellulose film; polyolefin films such as polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer; polyester films such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate films, polynorbornene films, polyarylate films, polyacrylic acid films, polyphenylene sulfide films, polystyrene films, polyethylene films, polyamide films, polyimide films, and polyoxypropylene films.

The transparent film may be used alone or in combination of two or more. For example, a polycycloolefin film may be used on one side of the laminate, and a polyacrylic acid film may be used on the other side.

The thickness of the transparent film can be appropriately determined, and is usually about 1 μm to 500 μm, preferably 1 μm to 300 μm, more preferably 5 μm to 200 μm, and even more preferably 5 μm to 150 μm from the viewpoints of strength, workability such as handleability, and thinness.

Furthermore, when transparent films are provided on both sides of an optical film such as a polarizing film, the materials of the transparent films on both sides may be the same or different.

In the laminate for optical elements, an optical film can be used as a substrate. The optical film can be, for example, a film formed by applying a coating liquid having an optical function on the transparent film. As optical functions, light transmission, light diffusion, light focusing, refraction, light scattering, and haze can be listed. As optical films, for example, hard coatings, antistatic coatings, anti-glare coatings, polarizing films (linear polarizing films and (elliptical) circular polarizing films, etc.), phase difference films, anti-reflection films, light diffusion films, brightness enhancement films, prism films, and light guide films can be listed. These can be used alone or in combination of two or more according to the purpose.

The polarizing film (also called polarizing plate) can be a sheet-like optical film with a multilayer structure formed by laminating a protective film such as a polytriacetyl cellulose film (also called a TAC film), a polycycloolefin film (such as a polynorbornene film), a polyacrylic film, a polycarbonate film, and a polyester film on one or both sides of a polyvinyl alcohol-based polarizer via an adhesive.

The active energy ray-polymerizable resin composition disclosed in the present invention is suitable as the adhesive.

The multi-layer optical film using the active energy ray-polymerizable resin composition disclosed herein as an adhesive can be further adhered to glass plates of liquid crystal display devices, plasma display panels (PDP) modules, touch screen modules, and organic EL modules, or transparent films such as the various plastic films described above, via the active energy ray-polymerizable resin composition disclosed herein.

The method for producing a polarizing film using the active energy ray-polymerizable resin composition of the present disclosure as an adhesive is not particularly limited, and for example, the following (Method I) to (Method III) are preferred.

(Method I)

An active energy ray polymerizable adhesive is applied to one side of the first protective film (first transparent film) to form a first polymerizable adhesive layer. An active energy ray polymerizable adhesive is applied to one side of the second protective film (second transparent film) to form a second polymerizable adhesive layer. The order of these steps is not particularly limited and they may be performed simultaneously.

Then, the first polymerizable adhesive layer formed on the first protective film is overlapped on one side of the polyvinyl alcohol-based polarizer. The second polymerizable adhesive layer formed on the second protective film is overlapped on the other side of the polyvinyl alcohol-based polarizer. The order of these steps is not particularly limited, and they can also be implemented simultaneously.

Then, active energy rays are irradiated to polymerize and cure the first polymerizable adhesive layer and the second polymerizable adhesive layer.

(Method II)

On one side of the polyvinyl alcohol polarizer, an active energy line polymerizable adhesive is applied to form a first polymerizable adhesive layer, and its surface is covered with a first protective film (first transparent film). On the other side of the polyvinyl alcohol polarizer, an active energy line polymerizable adhesive is applied to form a second polymerizable adhesive layer, and its surface is covered with a second protective film (second transparent film). The order of these steps is not particularly limited, and they can also be implemented simultaneously.

Then, active energy rays are irradiated to polymerize and cure the first polymerizable adhesive layer and the second polymerizable adhesive layer.

(Method III)

A first protective film (first transparent film) is overlapped on one side of the polyvinyl alcohol-based polarizer. A second protective film (second transparent film) is overlapped on the other side of the polyvinyl alcohol-based polarizer. The order of these steps is not particularly limited and they can be implemented simultaneously.

Then, an active energy ray polymerizable adhesive is dripped onto the end of the laminate of the polyvinyl alcohol-based polarizer and the first protective film. An active energy ray polymerizable adhesive is dripped onto the end of the laminate of the polyvinyl alcohol-based polarizer and the second protective film. The order of these steps is not particularly limited, and they may be performed simultaneously.

Next, the obtained temporary laminate is passed between a pair of rollers to spread the adhesive between the layers.

Then, active energy rays are irradiated to polymerize and cure the active energy ray-polymerizable adhesive.

[Example]

Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. In addition, in the following examples and comparative examples, "parts" and "%" as units of the amount of preparation respectively represent "parts by mass" and "% by mass", and "RH" refers to relative humidity. In addition, in the table, the unit of the amount of preparation is "parts by mass", and the amount of the ingredients other than the solvent is the non-volatile component conversion value. The blank column in the table means no preparation.

<Method for measuring weight average molecular weight (Mw)>

The "weight average molecular weight (Mw)" is a weight average molecular weight (Mw) in terms of standard polystyrene obtained by measuring using a gel permeation chromatograph "HLC-8220GPC" manufactured by Tosoh Co., Ltd. As a separation column, four "TSK-GELSUPER H5000", "TSK-GELSUPER H4000", "TSK-GEL SUPER H3000", and "TSK-GEL SUPER H2000" manufactured by Tosoh Co., Ltd. were connected in series, tetrahydrofuran at a temperature of 40°C was used as the mobile phase, and the measurement was performed at a flow rate of 0.6 ml/min.

<Method for measuring hydroxyl value>

Accurately measure about 1g of the sample in a co-corked conical flask, add 100ml of a toluene/ethanol mixture (volume ratio: toluene/ethanol = 2/1) and dissolve it. Furthermore, accurately add 5ml of an acetylating agent (use pyridine to dissolve 25g of acetic anhydride to make a solution with a volume of 100ml), and stir for about 1 hour. Add phenolphthalein test solution as an indicator and stir for 30 seconds. Then, titrate with 0.1N alcoholic potassium hydroxide solution until the solution appears light red, and use the following formula to calculate the hydroxyl value. The hydroxyl value is set to the value of the resin in the dry state (unit: mgKOH/g).

Hydroxyl value (mgKOH/g) = [{(b-a)×F×28.25}/S]/(non-volatile content concentration/100)+D

Each abbreviation in the above formula represents the following parameter.

S: Sample collection amount (g)

a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)

b: Consumption of 0.1N alcoholic potassium hydroxide solution in blank experiment (ml)

F: Titer of 0.1N alcoholic potassium hydroxide solution

D: Acid value (mgKOH/g)

The materials used in Examples and Comparative Examples are as follows.

<Hydroxyl-containing and ethylenically unsaturated double bond group-containing compound (A)>

4HBA: 4-Hydroxybutyl acrylate

CHDMMA: Cyclohexanedimethanol monoacrylate

<Compound (B) having two or more benzene rings and containing an ethylenically unsaturated double bond group>

[Compound (b1) having two benzene rings and one ethylenically unsaturated double bond group]

POBA: Phenoxybenzyl acrylate

PPEA: o-phenylphenoxyethyl acrylate

NMTA: 1-Naphthalene Methanol Acrylate

[Compound (b2) having three or more benzene rings and containing an ethylenically unsaturated double bond group]

BPEFDA: Bisphenylfluoreneethoxy modified diacrylate

[Compound (b3) having two benzene rings and two ethylenically unsaturated double bond groups]

BisAEODA: Bisphenol A ethoxy modified diacrylate

<Compound having a urethane structure and two ethylenically unsaturated double bond groups (C)>

C1: Urethane acrylate 1 prepared by the following method

C2: Urethane acrylate 2 prepared by the following method

<Production of urethane acrylate 1>

In a 5-necked separable flask including a stirrer, a reflux cooling tube, a gas introduction tube, a thermometer, and a dropping funnel, 81.6 parts of polytetramethylene glycol (manufactured by Hodogaya Chemical Co., Ltd.: PTG850, hydroxyl value of 127.1 mgKOH/g) and 41.4 parts of isophorone diisocyanate were placed, and the temperature was raised to 60°C while introducing dry air. 0.05 parts of dibutyltin dilaurate were added thereto, and the reaction was carried out for 1 hour. In addition, 27.0 parts of 4-hydroxybutyl acrylate and 0.15 parts of hydroquinone monomethyl ether were placed in the dropping funnel, and the mixture was dropped into the separable flask over a period of 1 hour. After the addition was completed, stirring was continued at 80°C for 3 hours. The reaction was terminated at the moment when the absence of the absorption peak of the isocyanate group was confirmed in the infrared absorption spectrum, and urethane acrylate 1 was obtained. Its weight average molecular weight (Mw) is 4,000.

<Production of urethane acrylate 2>

In a 5-necked separable flask including a stirrer, a reflux cooling tube, a gas introduction tube, a thermometer, and a dropping funnel, 113.4 parts of a compound obtained by adding 2 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl acrylate (Placcel FA2D manufactured by Daicel Chemical, hydroxyl value 163.0 mgKOH/g), 36.6 parts of isophorone diisocyanate, and 0.15 parts of hydroquinone monomethyl ether were placed, and the temperature was raised to 60°C while introducing dry air. 0.04 parts of dibutyltin dilaurate was added thereto, the temperature was raised, and the reaction was carried out at about 80°C for 3 hours. The reaction was terminated at the moment when the absorption peak of the isocyanate group was confirmed to be absent in the infrared absorption spectrum, and urethane acrylate 2 was obtained. Its weight average molecular weight (Mw) was 1,300.

<Compound having an alicyclic structure and containing an ethylenically unsaturated double bond group (F)>

[Compound (f1) in which two or more monocyclic aliphatic hydrocarbon rings are linked]

HBPEDA: EO modified hydrogenated bisphenol A diacrylate

[Aliphatic polycyclic compound having a bridged structure (f2)]

IBXA: Isobornyl acrylate

DCPTEA: Dicyclopentenyl acrylate

<Other compounds having an ethylenically unsaturated double bond group (M)>

[Compound (m1) having an alkanediol group and two ethylenically unsaturated double bond groups in the main chain]

TPGDA: Tripropylene glycol diacrylate

[Compound having three ethylenically unsaturated double bonds (m2)]

INATA: Isocyanuric acid EO modified triacrylate

[Other compounds having ethylenically unsaturated double bond groups (m3)]

PEA: Phenoxyethyl acrylate

LA: Lauryl acrylate

＜Silane compound (D)＞

KBM-403: 3-Glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBM-5103: 3-Acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

KBE-9007: 3-isocyanatepropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

TEMS: Tetramethoxysilane

＜Photoacid generator (E)＞

[Sulfonium salt acid generator (e1)]

CPI-110P: Made by San-apro, a triarylsulfonium-PF6 salt type photoacid generator

[Iodine salt acid generator (e2)]

Omnicat 250: 4-isobutylphenyl (4-methylphenyl) hexafluorophosphate (manufactured by IGM resins B.V.)

＜Radical polymerization initiator (G)＞

TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by IGM resins B.V., Omnirad TPO)

＜Active energy ray sensitizer (H)＞

2-ITX: 2-isopropylthioxanthone

UVS-1331: 9,10-Dibutoxyanthracene

[Example 1]

In a light-shielded 300 ml glass bottle, 30 parts of 4HBA as a compound (A) having a hydroxyl group and containing an ethylenically unsaturated double bond group, 36 parts of POBA as a compound (B) having two or more benzene rings and containing an ethylenically unsaturated double bond group, 10 parts of urethane acrylate 1 as a compound (C) having a urethane structure and two ethylenically unsaturated double bond groups, 10 parts of IBXA as a compound (F) having an alicyclic structure and containing an ethylenically unsaturated double bond group, 10 parts of KBM-403 as a silane compound (D), 2 parts of CPI-110P as a photoacid generator (E), and 2 parts of TPO as a radical polymerization initiator (G) were placed. After being sufficiently stirred with a disperser, the mixture was sufficiently degassed to obtain an active energy ray-polymerizable resin composition (active energy ray-polymerizable adhesive).

[Example 2 to Example 50, Comparative Example 1 to Comparative Example 8]

An active energy ray-polymerizable resin composition (active energy ray-polymerizable adhesive) was obtained in the same manner as in Example 1 except that the blending composition and blending amount (parts by mass) were changed as shown in Tables 1 to 4.

[Evaluation of Laminated Body]

The following laminate X1 was prepared using the obtained active energy ray-polymerizable resin composition, and was evaluated by the following method. The results are shown in Tables 1 to 4.

<Manufacturing of Laminated Body X1 (Polarizing Plate)>

As the first transparent film (1), a polytriacetylcellulose (TAC) film containing an ultraviolet absorber having a thickness of 40 μm was prepared, and as the second transparent film (2), a TAC film not containing an ultraviolet absorber having a thickness of 20 μm was prepared. The surface of one side of the transparent film (1) and the transparent film (2) was corona treated at a discharge amount of 300 W·min/m ^2. Within 1 hour after the corona treatment, the active energy line polymerizable resin composition (active energy line polymerizable adhesive) shown in Tables 1 to 4 was applied to the corona treated surface of each film using a wire bar coater in a manner to a thickness of 2 μm to form a coating.

A polyvinyl alcohol (PVA) polarizer is sandwiched between a first active energy line polymerizable adhesive layer formed on a first transparent film (1) and a second active energy line polymerizable adhesive layer formed on a second transparent film (2), to obtain a rectangular laminated body in a plan view comprising the first transparent film (1)/first adhesive layer/PVA polarizer/second adhesive layer/second transparent film (2). The four sides of the laminated body are fixed to a tin plate using a cellophane tape in such a way that the first transparent film (1) is in contact with the tin plate.

Using an active energy ray irradiation device (manufactured by Toshiba Corporation, high pressure mercury lamp), ultraviolet rays were irradiated from the second transparent film (2) side at a maximum illuminance of 300 mW/ ^cm2 and a cumulative light quantity of 300 mJ/ ^cm2 to produce a laminate X1 (polarizing plate).

＜Adhesion＞

From the obtained laminate X1 (polarizing plate), a sample for measurement of 25 mm × 150 mm in size is cut out using a cutter. A double-sided adhesive tape (manufactured by Toyochem, DF8712S) is attached to the surface of the second transparent film (2) of the sample, and it is bonded to a metal plate using a laminator to obtain a laminate of the polarizing plate and the metal plate. A peeling start is pre-set between the second transparent film (2) and the polarizer. Under the conditions of 23°C and 50% RH, the second transparent film (2) is torn off from the laminate at a speed of 300 mm/min and at an angle of 90°. The peeling force between the PVA polarizer and the second transparent film (2) is measured as the bonding force, and is evaluated in four stages.

[Evaluation criteria]

◎: No peeling or polarizing plate damage, very excellent

○: Can be peeled without damaging the polarizing plate, peeling force is 2.0N/25mm or more, excellent

△: The peeling force is 1.0N/25mm or more and less than 2.0N/25mm, which is practical

×: Peel force is less than 1.0N/25mm, not practical

＜Tape peeling＞

From the laminate X1 (polarizing plate), a sample for measurement of 50 mm × 50 mm in size is cut out using a cutter. A double-sided adhesive tape (manufactured by Toyochem, DF8712S) is affixed to the surface of the second transparent film (2) of the sample, and it is affixed to a glass plate using a laminator to obtain a laminate of the polarizing plate and the glass plate. After the corners of the laminate are firmly attached to the glass plate using cellophane tape, the ends of the tape are grasped and torn off at a speed of more than 100 mm/s. As the cellophane tape, a tape with a width of 25 mm and an adhesion strength of 5N±0.5N per 25 mm of width is used. The test is performed a total of 10 times, and the peeling between the PVA polarizer and the second transparent film (2) is evaluated in four stages.

[Evaluation criteria]

◎: No peeling in all 10 times, very excellent

○: Peeling was observed 1 to 2 times out of 10 times, excellent

△: Peeling was observed 3 to 4 times out of 10 times, so it is practical

×: Peeling was observed 5 or more times out of 10 times, not practical

＜Pressing processability＞

The produced polarizing plate was punched out from the first protective film (1) side using a 100 mm x 100 mm blade manufactured by Dumbbell Co. The inter-film peeling distance at the edge of the punched polarizing plate was measured with a ruler and evaluated in the following four stages.

◎: 0mm, very good

○: More than 0 mm and less than 1 mm, excellent

△: More than 1mm and less than 3mm, practical

×: 3mm or more, not practical

＜Humidity resistance test＞

The laminate X1 was exposed to the conditions of a temperature of 25° C. and 90% RH for 1000 hours. After the exposure, the adhesive strength, tape peeling, and punchability were evaluated in the same manner as in the initial stage.

＜Bending resistance＞

A sample with a size of 120 mm in width and 200 mm in length was cut out from the laminate X1 (polarizing plate). A bending tester (manufactured by Yuasa System Equipment Co., Ltd.) was used to set the conditions so that the inner diameter (diameter) when bent was 2 mm, and 180° bending and opening was set as 1 cycle, and 300,000 cycles of the test were performed. The device was stopped every 100,000 cycles to confirm the appearance of the sample, and the bendability was evaluated from the following viewpoints.

Appearance: The presence or absence of bubbles in the laminate and the presence or absence of appearance defects such as floating or peeling of the cured layer were visually evaluated according to the following criteria.

[Evaluation criteria]

◎: No appearance defects after 300,000 cycles, very excellent

○: No appearance defects after 200,000 cycles, appearance defects after 300,000 cycles, excellent

△: No appearance defects after 100,000 cycles, appearance defects after 200,000 cycles, practical

×: Appearance is defective after 100,000 cycles, not practical

[table 3]

[Table 4]

As shown in Tables 1 to 4, it was confirmed that the active energy ray-polymerizable resin composition of the present disclosure has excellent adhesiveness, high moisture resistance, and excellent bending resistance.

Claims (6)

1. An active energy ray-polymerizable resin composition comprising: all of the following compounds (A), (B) and (C), a silane compound (D) having a reactive functional group and an alkoxy group on a silicon atom, and a photoacid generator (E), (A) a compound having a hydroxyl group and containing an ethylenically unsaturated double bond group, wherein (B) is excluded from the compound (A); (B) a compound having two or more benzene rings and containing an ethylenically unsaturated double bond group; (C) A compound having a weight average molecular weight of 1,000 to 60,000 and having a urethane structure and two ethylenically unsaturated double bond groups. 2. The active energy ray-polymerizable resin composition according to claim 1, wherein the compound (B) comprises at least one of the following (b1) and (b2), (b1) a compound having two benzene rings and one ethylenically unsaturated double bond group; (b2) A compound having three or more benzene rings and containing an ethylenically unsaturated double bond group. 3 . The active energy ray-polymerizable resin composition according to claim 1 , wherein the compound (D) comprises a silane compound having an epoxy group and an alkoxy group on a silicon atom. 4. The active energy ray-polymerizable resin composition according to claim 1, further comprising a compound (F) having an alicyclic structure and containing an ethylenically unsaturated double bond group, The compound (F) includes a compound having two or more aliphatic hydrocarbon monocyclic structures and/or a compound having an aliphatic hydrocarbon polycyclic structure. 5. The active energy ray-polymerizable resin composition according to claim 4, wherein 10% to 60% by mass of the compound (A), 5% to 65% by mass of the compound (B), 1% to 20% by mass of the compound (C), 2% to 20% by mass of the compound (D), and 5% to 40% by mass of the compound (F) are contained in 100% by mass of the active energy ray-polymerizable resin composition. 6 . A laminate comprising: a layer comprising the active energy ray-polymerizable resin composition according to claim 1 , or a layer comprising a cured product of the active energy ray-polymerizable resin composition; and a substrate.