Active energy ray-curable adhesive and laminate

Abstract

To provide an active energy ray-curable adhesive for manufacturing a laminate including a film (F1) comprising a cycloolefin-based resin having a polar group, where the adhesive can form a laminate being excellent in transparency, exhibiting low warping after curing, and having excellent adhesiveness; and a laminate employing the same.SOLUTION: The active energy ray-curable adhesive for film lamination used in manufacturing a laminate including a film (F1) comprising a cycloolefin-based resin having a polar group, the adhesive containing 20 to 95 mass% of a monofunctional monomer (M1) in 100 mass% of the adhesive.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable adhesive and a laminate using the same. [Background technology]

[0002] Active energy ray curable adhesives have excellent properties such as high polymerization speed, excellent workability due to the fact that they can generally be used without solvent, and extremely low energy required for polymerization. Active energy ray curable adhesives include radical, cationic, and combined radical and cationic (hybrid) active energy ray curable adhesives, and are used in a wide range of applications.

[0003] Polarizers used in fields related to liquid crystal displays are usually manufactured by uniaxially stretching polyvinyl alcohol (PVA) to which iodine or dye has been adsorbed. This polyvinyl alcohol-based polarizer shrinks due to heat or moisture, resulting in a decrease in polarization performance. Therefore, a protective film is attached to the surface of the PVA-based polarizer and used as a polarizing plate.

[0004] Water-based adhesives and active energy ray-curable adhesives are used to bond PVA-based polarizers and protective films, and the use of active energy ray-curable adhesives in particular is increasing due to the versatility of the substrates used in the protective films and the benefits of increased efficiency and energy saving in production. Active energy ray-curable adhesives are required to have sufficient adhesion to bond the PVA-based polarizer and protective film together, as well as heat resistance, moisture resistance, water resistance, and other properties to prevent a decrease in the polarizing performance of the PVA-based polarizer.

[0005] Patent Document 1 discloses a cationic active energy ray-curable adhesive whose main component is an epoxy resin that does not contain an aromatic ring, in order to address issues such as the adhesive strength of polarizing plates that use, as a protective film, a film such as a norbornene-based resin film that has lower moisture permeability than triacetyl cellulose.

[0006] Patent Document 2 discloses a hybrid active energy ray-curable adhesive that combines 2-hydroxybutyl acrylate and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane as an adhesive that firmly bonds not only to norbornene-based resins but also to acrylic resin and triacetyl cellulose films.

[0007] Patent Document 3 discloses a radical-based active energy ray-curable adhesive that uses an acrylic monomer having an SP value within a specific range in order to address the issues of warping, polarization characteristics, and durability.

[0008] Meanwhile, triacetyl cellulose film was previously used as a protective film for polarizing plates, but polarizing plates to which triacetyl cellulose film with high moisture permeability is attached as a protective film are prone to deterioration under humid and hot conditions such as a temperature of 60°C and a relative humidity of 90% RH, so there has been an increase in the use of resin films with low moisture permeability, such as amorphous polyolefin resins and acrylic resins (Patent Documents 1, 2, 3).

[0009] In recent years, it has become possible to make films thinner than ever before, and amorphous polyolefin resins that are easy to add functions such as anti-blocking, anti-glare, and UV protection include copolymer resins of monomers with polar groups and cycloolefin monomers, mixed resins of polymers with polar groups and cycloolefin polymers, and cycloolefin resins with polar groups. Patent Document 4 discloses a polarizing plate obtained by bonding an optical film made of a cycloolefin resin having a polar group and a polarizer made of polyvinyl alcohol with an ultraviolet-curable adhesive made of dipropylene glycol diacrylate and multiple epoxy monomers.

[0010] However, when used with films made of copolymer resins of monomers having polar groups and cycloolefin monomers, mixed resins of polymers having polar groups and cycloolefin polymers, or cycloolefin resins having polar groups, conventional adhesives had problems such as high coating haze, significant warping of the polarizing plate after production, and low adhesive strength. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2004-245925 A [Patent Document 2] JP 2010-018722 A [Patent Document 3] JP 2013-210513 A [Patent Document 4] International Publication No. 2023 / 276304 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention aims to provide an active energy ray-curable adhesive capable of forming a laminate having excellent transparency, small warping after curing, excellent adhesion, and excellent resistance to high temperature and high humidity in the production of a laminate including a film (F1) made of a cycloolefin resin having a polar group, and a laminate using the same. [Means for solving the problem]

[0013] As a result of intensive research aimed at solving the above problems, the present inventors have found that the above object can be achieved by the active energy ray-curable composition shown below, and have thus completed the present invention.

[0014] The present invention relates to an adhesive for film lamination used in the production of a laminate comprising a film (F1) made of a cycloolefin resin having a polar group, The present invention relates to an active energy ray-curable adhesive that contains 20 to 95 mass % of a monofunctional monomer (M1) based on 100 mass % of the adhesive.

[0015] The present invention also relates to the active energy ray-curable adhesive, wherein the monofunctional monomer (M1) comprises a monofunctional monomer (M1-1) having 7 or more carbon atoms and containing no hydroxyl group.

[0016] The present invention also relates to the active energy ray-curable adhesive, wherein the monofunctional monomer (M1) further contains a monofunctional monomer (M1-2) containing a hydroxyl group.

[0017] The present invention also relates to the active energy ray-curable adhesive, wherein the monofunctional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group comprises at least one monofunctional monomer having any structure selected from the group consisting of an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group, an aromatic ring, and a heterocycle (excluding those having an aromatic ring).

[0018] The present invention also relates to the active energy ray-curable adhesive, which further contains an oligomer (O) having a weight average molecular weight of 1,000 to 60,000.

[0019] The present invention also relates to the active energy ray-curable adhesive, wherein the oligomer (O) is at least one selected from the group consisting of urethane acrylate (O-1), polyester acrylate (O-2) and epoxy acrylate (O-3).

[0020] The present invention also relates to the active energy ray-curable adhesive, wherein the oligomer (O) contains a urethane acrylate (O-1).

[0021] The present invention also provides a method for producing a urethane acrylate (O-1) which is a reaction product of a polyol, a polyisocyanate, and a monofunctional monomer (M1-2) containing a hydroxyl group, The present invention relates to the active energy ray-curable adhesive, wherein the polyol is any one selected from the group consisting of polyether polyols having an alkylene structure with 4 or more carbon atoms, polyester polyols having a unit structure with 12 or more carbon atoms, and polyolefin polyols.

[0022] The present invention also relates to the active energy ray-curable adhesive further comprising a polyfunctional monomer (M2).

[0023] The present invention also relates to the active energy ray-curable adhesive further comprising a silane compound (S).

[0024] The present invention also relates to the active energy ray-curable adhesive, which contains, based on a total amount (100 mass%) of the adhesive, 10 to 70 mass% of a monofunctional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group, 10 to 70 mass% of a monofunctional monomer (M1-2) that contains a hydroxyl group, 1 to 30 mass% of an oligomer (O), 1 to 50 mass% of a polyfunctional monomer (M2), and 1 to 30 mass% of a silane compound (S).

[0025] The present invention also relates to a laminate comprising, in this order, a film (F1), an adhesive layer made of the active energy ray-curable adhesive, and a film (F1) or a film (F2), wherein the film (F2) is any one selected from the group consisting of a polyvinyl alcohol-based film, a polyacetyl cellulose-based film, a cycloolefin polymer not containing a monomer having a polar group, a polypropylene-based film, a polyacrylic-based film, a polycarbonate-based film, a polyester-based film, a polyimide-based film, and a glass film. Effect of the Invention

[0026] The present invention can provide an active energy ray-curable adhesive capable of forming a laminate having excellent transparency, small warpage after curing, and excellent adhesion in the production of a laminate including a film (F1) made of a cycloolefin resin having a polar group, and a laminate using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] A preferred embodiment of the present invention will be described below. In this specification, when "(meth)acrylic" is used, it means "acrylic or methacrylic" unless otherwise specified. Furthermore, a monomer refers to a monomer having an ethylenically unsaturated double bond group, a monofunctional monomer refers to a monomer having one ethylenically unsaturated double bond group, and a polyfunctional monomer refers to a monomer having two or more ethylenically unsaturated double bond groups.

[0028] In addition, a monofunctional monomer (M1) is compound (M1), a monofunctional monomer (M1-1) having 7 or more carbon atoms and not containing a hydroxyl group is compound (M1-1), a monofunctional monomer (M1-2) containing a hydroxyl group is compound (M1-2), an oligomer (O) having a weight average molecular weight of 1000 to 60,000 is compound (O), a urethane acrylate (O-1) is compound (O-1), a polyester acrylate (O-2) is compound (O-2), an epoxy acrylate (O-3) is compound (O-3), a polyfunctional monomer (M2) is compound (M2), a silane compound (S) is compound (S), and a film (F1) made of a cycloolefin resin having a polar group is compound (F1). The film (F1) and the active energy ray curing adhesive may be abbreviated to adhesive. In this specification, unless otherwise specified, a numerical range specified using "~" is intended to include the numerical values ​​before and after "~" as the lower and upper limit values ​​of the range. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-equivalent weight average molecular weight and number average molecular weight determined by gel permeation chromatography (GPC) measurement.

[0029] <Monofunctional monomer (M1)> The compound (M1) is a compound having one ethylenically unsaturated double bond group. By including the compound (M1) in the adhesive, an adhesive layer having excellent transparency is obtained, the laminate is less likely to curl after curing, and the crosslink density of the cured adhesive film is not too high, making it easier to adhere to the film (F1).

[0030] Compound (M1) is classified into monofunctional monomer (M1-1) having 7 or more carbon atoms and not containing hydroxyl group, monofunctional monomer (M1-2) containing hydroxyl group, and other monofunctional monomer (M1-3), and can be used without any particular limitation. It is preferable to contain compound (M1-1), and more preferable to use compound (M1-1) and compound (M1-2) in combination. The compound (M1) preferably has a mass average molecular weight of less than 1000, and more preferably less than 500. When the compound (M1) has a mass average molecular weight of less than 1000, the viscosity of the resin composition does not become too high, and it becomes easy to control the film thickness during coating.

[0031] The content of compound (M1) is 20 to 95% by mass in 100% by mass of the adhesive. If the content of compound (M1) is less than 20% by mass, the coating film haze and curling properties are poor, and if it exceeds 95% by mass, curing is insufficient, resulting in poor adhesive strength and moist heat resistance. From the viewpoints of coating haze, curling, adhesion, and resistance to moist heat, the content is preferably 20 to 95% by mass, and more preferably 40 to 80% by mass since the adhesion and resistance to moist heat are particularly excellent.

[0032] <Monofunctional monomer having 7 or more carbon atoms and no hydroxyl group (M1-1)> The compound (M1-1) is a monofunctional monomer having a structure with 7 or more carbon atoms and not containing a hydroxyl group. By including the compound (M1-1), the adhesive can easily erode the film (F1), improving the adhesive strength. In addition, the moisture and heat resistance and curling properties are improved.

[0033] In order to improve adhesive strength, the compound (M1-1) preferably contains a monofunctional monomer having a structure selected from the group consisting of an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group (excluding those containing an epoxy structure in a cycloalkyl group), an aromatic ring, and a heterocyclic structure not containing an aromatic ring. These structures may be used alone or in combination of two or more. In particular, those containing an aliphatic cyclic hydrocarbon group are preferred because they improve the adhesive strength to a wide range of substrates. Furthermore, when the compound (M1-1) contains a hydrophilic structure, the erosion of the film (F1) decreases, so the compound (M1-1) preferably has a structure that does not contain an organic acid, an amino group, or ethylene oxide having two or more repeating units.

[0034] The content of the compound (M1-1) is preferably 10 to 70 mass%, more preferably 10 to 50 mass%, in 100 mass% of the adhesive. When it is 10 mass% or more, the adhesive strength with the film (F1) is further improved, and when it is 70 mass% or less, the adhesive strength is further improved over a wide range of substrates.

[0035] Examples of the compound (M1-1) include n-heptyl (meth)acrylate, 2-methylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 1-methylheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like. (meth)acrylic acid esters containing an aliphatic chain hydrocarbon group having 7 or more carbon atoms, such as acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, 2-propylheptyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isopalmityl (meth)acrylate, cetyl (meth)acrylate, isostearyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate;

[0036] For example, aliphatic cyclic hydrocarbon group-containing (meth)acrylic acid esters having 7 or more carbon atoms, such as trimethylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 4-t-butylcyclohexanol (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalate, and 3-[2-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy]propyl acrylate;

[0037] For example, benzyl (meth)acrylate, ethylene oxide modified phenoxy (meth)acrylate, nonylphenol ethylene oxide modified (meth)acrylate, nonylphenol propylene oxide modified (meth)acrylate, phenoxybenzyl (meth)acrylate, ethoxylated phenoxybenzyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, polyethylene glycol modified o-phenylphenoxy (meth)acrylate, 2-hydroxy-3-phenyl (meth)acrylic acid esters containing aromatic rings having 7 or more carbon atoms, such as paraphenoxypropyl acrylate, paracumylphenol ethylene oxide modified (meth)acrylate, 1-naphthylmethyl (meth)acrylate, 2-naphthyl acrylate, fluorenol (meth)acrylate, 2-oxo-1,2-diphenylethyl (meth)acrylate, 2-anthryl (meth)acrylate, anthrylmethyl (meth)acrylate, and neopentyl glycol-acrylic acid-benzoic acid ester;

[0038] Examples of such heterocycle-containing (meth)acrylic acid esters include (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, propoxylated tetrahydrofurfuryl (meth)acrylate, and 4-hydroxybutyl acrylate glycidyl ether.

[0039] <Hydroxyl-containing monofunctional monomer (M1-2)> The compound (M1-2) is a monofunctional monomer containing a hydroxyl group. By including the compound (M1-2) in the resin composition, hydrogen bonds are formed with hydrophilic functional groups of the substrate, improving the adhesive strength.

[0040] The content of the compound (M1-2) is preferably 10 to 70 mass%, more preferably 10 to 50 mass%, in 100 mass% of the active energy ray-curable adhesive. When it is 10 mass% or more, the adhesive strength is further improved, and when it is 70 mass% or less, the adhesive strength is further improved over a wide range of substrates.

[0041] The compound (M1-2) is not particularly limited as long as it has a hydroxyl group and one ethylenically unsaturated double bond group, and examples thereof include 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 1-hydroxybutyl (meth)acrylate. fatty acid ester-based (meth)acrylic acid esters such as 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, ethyl-α-(hydroxymethyl) (meth)acrylate, and monofunctional (meth)acrylic acid; or hydroxyl-containing aliphatic (meth)acrylic acid esters such as (meth)acrylic acid esters having a hydroxyl group at the end obtained by ring-opening addition of ε-caprolactone lactone to a compound having a hydroxyl-containing ethylenically unsaturated double bond group, and alkylene oxide-added (meth)acrylic acid esters obtained by repeatedly adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to a compound having a hydroxyl-containing ethylenically unsaturated double bond group;

[0042] For example, hydroxyl group-containing aliphatic vinyl ethers such as 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, or alkylene oxide adduct vinyl ethers having hydroxyl groups at the terminals of repeated additions of alkylene oxides such as ethylene oxide and propylene oxide;

[0043] For example, hydroxyl-containing aliphatic (meth)allyl alcohols or (meth)allyl ethers such as (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, or alkylene oxide adduct (meth)allyl ethers having hydroxyl groups at the terminals of repeatedly added alkylene oxides such as ethylene oxide or propylene oxide;

[0044] For example, compounds having an ethylenically unsaturated double bond group having a plurality of hydroxyl groups, such as propenediol, butenediol, heptenediol, octenediol, and glycerol di(meth)acrylate; For example, hydroxyl group-containing (meth)acrylamides such as N-hydroxyethyl(meth)acrylamide (N-hydroxyethylacrylamide and N-hydroxyethylmethacrylamide are collectively referred to as "N-hydroxyethyl(meth)acrylamide", the same applies below), N-hydroxypropyl(meth)acrylamide, N-hydroxybutyl(meth)acrylamide, N-hydroxyhexyl(meth)acrylamide, and N-hydroxyoctyl(meth)acrylamide;

[0045] For example, monomers having a hydroxyl group and an ethenyl group, such as vinyl alcohol, are included, but are not limited thereto. These may be used alone or in combination of two or more kinds.

[0046] As the compound (M1-2), from the viewpoint of adhesion to the substrate, an acrylic acid ester of a diol having 1 to 6 carbon atoms is preferable, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are particularly preferable.

[0047] <Other monofunctional monomers (M1-3)> The other monofunctional monomer refers to a monofunctional monomer other than the above (M1-1) and (M1-2). (M1-3) is not limited in any way as long as it is a compound having an ethylenically unsaturated double bond group. The content of (M1-3) is preferably 0 to 30 mass% in terms of adhesive strength to a wide range of substrates.

[0048] <Oligomer (O)> The oligomer (O) is a compound having a weight average molecular weight of 1000 to 60,000 and containing an ethylenically unsaturated double bond group. The oligomer (O) is classified into urethane (meth)acrylate (O-1), polyester (meth)acrylate (O-2), epoxy (meth)acrylate (O-3), and other compounds having an ethylenically unsaturated double bond group having a weight average molecular weight of 1000 to 60,000 (O-4). At least one oligomer selected from the group consisting of the compounds (O-1), (O-2), and (O-3) is preferred, and can be used without any particular restrictions. However, in the case of a compound having an alkoxysilyl group, it is classified into the silane compound (S) described later.

[0049] By using oligomer (O), the laminate is less likely to curl after the adhesive hardens. Among them, urethane (meth)acrylate (O-1) is particularly effective in reducing cure shrinkage, resulting in less curling after curing, and since it has a urethane bond with high polarity, the coating film is less likely to break and the adhesive strength is improved.

[0050] The weight average molecular weight of the compound (O) is preferably in the range of 5000 to 50,000. When the weight average molecular weight of the compound (O) is in this range, the adhesive strength, coating film haze, and curling properties are excellent.

[0051] The content of the compound (O) is preferably 1 to 30 mass%, more preferably 2 to 20 mass%, in 100 mass% of the active energy ray-curable adhesive. If it is 1 mass% or more, curling after curing is improved, and if it is 30 mass% or less, the viscosity does not become too high, making it easy to control the film thickness during coating.

[0052] Examples of the urethane (meth)acrylate (O-1) include a compound obtained by reacting a polyisocyanate with a compound (M1-2), a compound obtained by reacting a urethane prepolymer having isocyanate groups at its terminals, obtained by reacting a polyisocyanate with a polyol, with the compound (M1-2), and a compound obtained by reacting a urethane prepolymer having isocyanate groups at its terminals, obtained by reacting a polyisocyanate with a polyol, with a compound having two or more amino groups, with the compound (M1-2).

[0053] Compound (O-1) is preferably a reaction product of polyisocyanate, polyol, and compound (M1-2), and more preferably a compound obtained by reacting them in a molar ratio of 2:1:2. By reacting them in the above ratio, a structure having acrylate groups at both ends of one molecule is theoretically obtained, so that flexibility and crosslinking density are well balanced, the laminate after curing has little curl, and the adhesion to the substrate is good.

[0054] Examples of the polyisocyanate include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

[0055] More specifically, examples of aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4 ... ,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and the like.

[0056] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0057] 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-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

[0058] Examples of alicyclic polyisocyanates include 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 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(isocyanatemethyl)cyclohexane.

[0059] Also usable are 2-methylpentane-2,4-diol adducts of some of the above polyisocyanates, trimers having an isocyanurate ring, etc. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, and modified products of these polyisocyanates, etc. As the modified polyisocyanate, a modified product having any one of a carbodiimide group, a uretdione group, a uretoimine group, a biuret group reacted with water, and an isocyanurate group, or two or more of these groups, can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

[0060] From the viewpoint of preventing curling, the compound having an isocyanate group is preferably an aliphatic diisocyanate or alicyclic diisocyanate compound. In addition, examples of polyols 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 each of these can be used without any particular limitation.

[0061] More specifically, examples of low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition mole number of 10 or less), polyoxypropanediol, ... aliphatic or alicyclic diols such as propylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, and dimer diol; 1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene Examples of the aromatic diols include aromatic diols such as 1,4-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-, M- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, and addition type bisphenols obtained by adding alkylene oxide to bisphenol.

[0062] Examples of the raw material bisphenol for the addition type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide. More specifically, examples of high molecular weight polyols include polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, polyester polyols, polyamide polyols, polycarbonate polyols, polyurethane polyols, polybutadiene polyols, and polyolefin polyols. The polyester polyol is a polyester obtained by polycondensing a polybasic acid and a polyhydric alcohol in a ratio in which a hydroxyl group remains at the molecular end used in the synthesis of the polyester (meth)acrylate (O-2) described later, and the polybasic acid and the polyhydric alcohol can be the same as those used in the synthesis of the polyester (meth)acrylate (O-2). Polycarbonate polyols can be obtained by reacting the above-mentioned low molecular weight diols with carbonates or phosgene.

[0063] Examples of commercially available polyester polyols include the Vylon series manufactured by Toyobo Co., Ltd., the Kuraray Polyol P series manufactured by Kuraray Co., Ltd., and the Kyowapol series manufactured by Kyowa Hakko Chemical Co., Ltd. As a commercially available product of the polyamide polyol, TPAE617 manufactured by Fuji Chemical Industry Co., Ltd., etc. can be used. Examples of commercially available polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals Corporation, Kuraray Polyol PMHC series and Kuraray Polyol C series manufactured by Kuraray Co., Ltd.

[0064] Commercially available examples of the polyurethane polyol include the Vylon UR series manufactured by Toyobo Co., Ltd., and 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, Inc. In addition, 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.

[0065] The polyol is preferably a high molecular weight polyether diol or a high molecular weight polyester diol from the viewpoint of adhesion.

[0066] Specific examples of amines having an amino group include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 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;

[0067] Alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; Aromatic diamines such as phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and 4,4'-bis-(sec-butyl)diphenylmethane; Silylamines having a monofunctional silylamino group, such as trimethylsilyldimethylamine; Silylamines having bifunctional silylamino groups, such as 1,1,3,3-tetramethyldisilazane, can be used.

[0068] The urethane (meth)acrylate (O-1) is preferably a reaction product of a polyol, a polyisocyanate, and an acrylic acid ester having a hydroxyl group. The polyol is preferably a polyether polyol having an alkylene structure with 4 or more carbon atoms, a polyester polyol having 12 or more carbon atoms in the unit structure, a polybutadiene polyol, or a polyolefin polyol, and particularly preferably a polyether polyol made of a polyol with 4 or more carbon atoms, or a polyester polyol having 12 or more carbon atoms in the unit structure.

[0069] The polyester (meth)acrylate (O-2) is a compound obtained by esterifying the terminal hydroxyl group of a polyester obtained by polycondensing a polybasic acid and a polyhydric alcohol in a ratio such that a hydroxyl group remains at the molecular end with an ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule, such as (meth)acrylic acid or maleic acid, or a compound obtained by esterifying the terminal carboxyl group of a polyester obtained by polycondensing a polybasic acid and a polyhydric alcohol in a ratio such that a carboxyl group remains at the molecular end with the aforementioned compound (M1-2), such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. In addition, polyester (meth)acrylates obtained from acid anhydrides, glycidyl (meth)acrylate, and compounds having at least one hydroxyl group can also be used as the polyester (meth)acrylate (O-2).

[0070] The polybasic acid may be aliphatic, alicyclic, or aromatic, and may be used without any particular limitation.Specific examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, and maleic anhydride, and these aliphatic dicarboxylic acids and their anhydrides may be used. Also usable are anhydride derivatives such as succinic anhydride derivatives (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl succinic anhydride, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc.), and maleic anhydride derivatives (2-methyl maleic anhydride, 2,3-dimethyl maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, 2,3-dichloro maleic anhydride, phenyl maleic anhydride, 2,3-diphenyl maleic anhydride, etc.).

[0071] More specifically, examples of alicyclic polybasic acids include alicyclic dicarboxylic acids such as dimer acid, cyclopropane-1α,2α-dicarboxylic acid, cyclopropane-1α,2β-dicarboxylic acid, cyclopropane-1β,2α-dicarboxylic acid, cyclobutane- 1,2-dicarboxylic acid, cyclobutane-1α,2β-dicarboxylic acid, cyclobutane-1α,3β-dicarboxylic acid, cyclobutane-1α,3α-dicarboxylic acid, (1R)-cyclopentane-1β,2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β,2β)-cyclopentane-1,3-dicarboxylic acid, (1β,3β)-cyclopentane-1,3-dicarboxylic acid, (1S,2S)-1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydrote Examples of the alicyclic dicarboxylic acids include saturated alicyclic dicarboxylic acids such as tetrahydrophthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, and tetrahydrophthalic acid, and unsaturated alicyclic dicarboxylic acids having one or two unsaturated double bonds in the ring, such as 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,3-dicarboxylic acid, and 2,5-hexadiene-1α,4α-dicarboxylic acid. These alicyclic dicarboxylic acids and their anhydrides can be used.

[0072] In addition, hydrogenated phthalic anhydride derivatives such as derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride) and derivatives of tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) can also be used as alicyclic dicarboxylic acid anhydrides.

[0073] More specifically, examples of aromatic polybasic acids include aromatic dicarboxylic acids such as o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2,2'-biphenyl dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindane dicarboxylic acid, 1,2-azulenedicarboxylic acid, and 1,3-azulenedicarboxylic acid. Examples of aromatic dicarboxylic acids that can be used include 1,4-anthracene dicarboxylic acid, 1,5-anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracene dicarboxylic acid, 1,2-phenanthrene dicarboxylic acid, 4,5-phenanthrene dicarboxylic acid, and 3,9-perylene dicarboxylic acid; and aromatic dicarboxylic anhydrides such as phthalic anhydride and 4-methylphthalic anhydride. These aromatic dicarboxylic acids and their anhydrides can be used.

[0074] Furthermore, acid anhydrides such as chlorendic anhydride, HET acid anhydride, biphenyl dicarboxylic anhydride, himic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 1,2-cyclohexane dicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, and octahydro-1,3-dioxo-4,5-isobenzofurandicarboxylic anhydride can also be used as polybasic acids.

[0075] In addition, examples of polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500, and relatively high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000, each of which can be used without any particular limitation.

[0076] More specifically, examples of relatively low molecular weight polyols include ethylene glycol. aliphatic or alicyclic diols such as propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, and dimer diol;

[0077] Examples of the aromatic diols include 1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-, M- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, and addition type bisphenols obtained by adding alkylene oxide to bisphenol.

[0078] Examples of the raw material bisphenol for the addition type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide. More specifically, the relatively high molecular weight polyols include, for example, high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. High molecular weight polycarbonate polyols can be obtained by reacting the above-mentioned relatively low molecular weight diols with carbonate esters or phosgene.

[0079] Examples of commercially available high molecular weight polyester polyols include the Vylon series manufactured by Toyobo Co., Ltd., the Kuraray Polyol P series manufactured by Kuraray Co., Ltd., and the Kyowapol series manufactured by Kyowa Hakko Chemical Co., Ltd. As a commercially available product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Chemical Industry Co., Ltd., etc. can be used. Examples of commercially available high molecular weight polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals Corporation, Kuraray Polyol PMHC series and Kuraray Polyol C series manufactured by Kuraray Co., Ltd.

[0080] Commercially available high molecular weight polyurethane polyols include, for example, the Vylon UR series manufactured by Toyobo Co., Ltd., and 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), all manufactured by Mitsui Chemicals Polyurethanes. In addition, 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 that can be used as the high molecular weight polyol.

[0081] Epoxy acrylate (O-3) is a compound obtained by reacting an epoxy group in an epoxy compound having two or more epoxy groups with a carboxyl group in a carboxyl group-containing (meth)acrylate compound in an approximately equivalent amount. Alternatively, an epoxy group in an epoxy compound having two or more epoxy groups is reacted with an equivalent amount of a carboxyl group in a polybasic acid. The compound is obtained by reacting in a ratio of less than 1:1, leaving epoxy groups, and reacting the carboxyl groups in the carboxyl group-containing (meth)acrylate compound in an approximately equal amount to the remaining epoxy groups. In either case, by keeping the balance between the "carboxyl groups" and the "epoxy groups" in the entire reaction system within ±10%, it is preferable that the carboxyl groups or epoxy groups are less likely to remain in the adhesive of the present invention, and the storage stability of the adhesive is improved.

[0082] The epoxy compound containing two or more epoxy groups is not particularly limited as long as it is a compound containing two epoxy groups. Specific examples of the epoxy compound include cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexyl ether, and the like. Sandiol diglycidyl ether, bisphenol A epichlorohydrin type epoxy resin, bisphenol F epichlorohydrin type epoxy resin, biphenol epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin epichlorohydrin adduct, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenolfluorene diglycidyl ether, biscresolfluorene diglycidyl ether, bisphenoxyethanolfluorene diglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-diglycidylaniline, N,N-diglycidyltoluidine, and epoxy compounds having excellent flexibility as disclosed in JP-A Nos. 2004-156024, 2004-315595, and 2004-323777.

[0083] Among these, epoxy resins containing bisphenol A, bisphenol F, biphenyl, or a fluorene skeleton are preferred because the finally obtained epoxy (meth)acrylate (O-3) has a high refractive index. In the present invention, the epoxy compounds containing two or more epoxy groups may be used alone or in combination.

[0084] Examples of the carboxyl group-containing (meth)acrylate compound that can be used in the production of the epoxy (meth)acrylate (O-3) include (meth)acrylic acid, crotonic acid, dibasic acid (maleic acid, fumaric acid, itaconic acid, phthalic acid, succinic acid, etc.) half-esterified with a hydroxyl group-containing acrylate compound, dibasic acid anhydride half-esterified with a hydroxyl group-containing acrylate compound, itaconic anhydride half-esterified with an alkyl alcohol, and compounds to which several moles of ε-caprolactone have been added. Examples of the polybasic acid that can be used in the production of the epoxy (meth)acrylate (O-3) include the polybasic acids exemplified for use in the production of the polyester (meth)acrylate (O-2).

[0085] <Polyfunctional Monomer (M2)> Compound (M2) is a compound having two or more ethylenically unsaturated double bond groups. By including compound (M2), the crosslink density of the cured film of the adhesive is improved, the cured film is less likely to be destroyed, and the adhesive strength is improved. Compound (M2) is preferably included in an amount of 1 to 50 mass%, and more preferably 1 to 30 mass%, based on 100 mass% of the active energy ray-curable adhesive. Within this range, the crosslink density of the cured film of the adhesive is appropriate, the cured film is less likely to be destroyed, and peeling from the substrate interface is prevented. Since peeling is less likely to occur, adhesive strength is improved. The weight average molecular weight of the compound (M2) is preferably less than 1000, and more preferably less than 500. When the weight average molecular weight of the compound (M2) is less than 1000, the viscosity of the resin composition does not become too high, and it becomes easy to control the film thickness during coating.

[0086] Examples of the compound (M2) include 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-dimethylpropyldiol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, and 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, bisphenol A ethoxy-modified di(meth)acrylate, bisphenol F ethoxy-modified di(meth)acrylate, difunctional (meth)acrylic acid esters such as ethylene glycol modified bisphenylfluorenedi(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, sorbitol di(meth)acrylate, and ethoxy isocyanurate modified diacrylate;

[0087] For example, trifunctional (meth)acrylic acid esters such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, sorbitol tri(meth)acrylate, 1,1,1-trishydroxymethylethane tri(meth)acrylate, and tris(2-acryloyloxyethyl) isocyanurate;

[0088] For example, tetrafunctional (meth)acrylic acid esters such as pentaerythritol tetra(meth)acrylate, 2,2-bis(hydroxymethyl)1,3-propanediol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate can be mentioned.

[0089] The compound (M2) is preferably a bifunctional or trifunctional (meth)acrylate having an alkylene group having 7 to 20 carbon atoms, an alicyclic structure, or a heterocyclic structure, since it has excellent adhesion to the substrate (F1), and 1,9-nonanediol diacrylate, dimethylol dicyclopentane di(meth)acrylate, and tris(2-acryloyloxyethyl) isocyanurate are preferred. The compound (M2) can be used alone or in combination of two or more kinds.

[0090] <Silane Compound (S)> The silane compound (S) can be used without any particular limitation as long as it is a compound having an alkoxysilyl structure. The active energy ray curable adhesive of the present invention improves its moist heat resistance by containing the silane compound (S). The silane compound (S) is preferable because it has excellent adhesive strength and moist heat resistance when it has a reactive functional group. Among them, the reactive functional group of the compound (S) is more preferably an epoxy group or an isocyanato group.

[0091] Examples of the silane compound (S) include silane compounds having a methacryloxy group, two alkyl groups, and two alkoxy groups, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropylmethyldiethoxysilane; Acryloxy groups and alkyl groups such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-acryloxypropylmethyldimethoxysilane silane compounds having two alkyl and two alkoxy groups; Silane compounds having three (meth)acryloxyalkyl groups and three alkoxy groups, such as γ-methacryloxymethyltrimethoxysilane and γ-acryloxymethyltrimethoxysilane; Alkoxysilanes having a vinyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, and vinyltris(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; Examples of the silane compound include a silane compound having an isocyanato group and an alkoxy group, such as 3-isocyanatepropyltriethoxysilane. The silane compounds can be used alone or in combination of two or more kinds.

[0092] Among the above silane compounds, silane compounds containing an epoxy group or an isocyanato group are preferred because they improve moisture resistance and adhesion to hydrophilic substrates, and silane compounds containing an epoxy group are more preferred.

[0093] The content of the silane compound is preferably 1 to 30 mass%, and more preferably 5 to 20 mass%, in 100 mass% of the active energy ray-curable adhesive. If it is 1 mass% or more, moisture resistance is further improved, and if it is 30 mass% or less, a good balance between adhesive strength and moisture resistance is achieved.

[0094] <Radical polymerization initiator (E)> The active energy ray-curable adhesive of the present invention preferably further contains a radical polymerization initiator (E). By using the radical polymerization initiator (E), the radical polymerization reaction can be promoted.

[0095] The radical polymerization initiator (E) can be arbitrarily selected from known initiators and used. Specific examples thereof include, for example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-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 (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF), OMnirad819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by IGM Resins B.V.), Darocur-1173 (manufactured by Merck), and Ezacure. -KIP150, TZT (manufactured by Nippon SiberHegner Co., Ltd.), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.), etc. 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred because of its photobleaching properties.

[0096] The content of the radical initiator (E) is preferably from 0.01 to 20% by mass in 100% by mass of the active energy ray-curable adhesive.

[0097] <Photoacid generator (G)> The acid generator (G) generates an acid when exposed to active energy rays such as visible light, ultraviolet light, X-rays, or electron beams, and acts catalytically to initiate a polymerization reaction of a silane compound and a cationic polymerizable compound. Examples of the acid generator include onium salt acid generators such as sulfonium salt acid generators, iodonium salt acid generators, diazonium salt acid generators, ammonium salt acid generators, and phosphonium salt acid generators.

[0098] Among these, from the viewpoint of obtaining an active energy ray-curable adhesive having excellent photodecomposition efficiency and excellent curing properties, sulfonium salt-based acid generators and iodonium salt-based acid generators are preferred.

[0099] From the viewpoint of the curability of the active energy ray-curable adhesive, the content of the acid generator (G) is preferably 0.1 mass% or more in 100 mass% of the active energy ray-curable adhesive, while from the viewpoint of the moist heat resistance, the content is preferably 20 mass% or less, and more preferably 0.5 to 10 mass%.

[0100] Examples of sulfonium salt acid generators include triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, and triarylsulfonium tetrakis(pentafluorophenyl)borate.

[0101] Examples of commercially available sulfonium salt acid generators include triarylsulfonium hexafluorophosphate (CPI-110P, manufactured by San-Apro) and UVACURE 1590 (manufactured by Daicel-Cytec).

[0102] Iodonium salt acid generators include bis(4-tertiarybutylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate, (4-methylphenyl)( 4-isopropylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakis(pentafluoro)borate, etc.

[0103] Commercially available iodonium salt acid generators include, for example, bis(4-tertiarybutylphenyl)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.), (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate, and Examples include OMnicat250, IGM resins.

[0104] <Active energy ray sensitizer (H)> In order to improve the reactivity of the radical initiator (E) and the acid generator (G), an active energy ray sensitizer (H) may be used in combination. The sensitizer (H) may be, for example, a thioxanthone compound, an anthracene compound, a naphthalene compound, an aminobenzoate compound, a carbazole compound, or the like. compounds, perylene, phenothiazine, rose bengal, etc.

[0105] 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; Examples of the anthracene compounds include 9,10-dimethoxyanthracene, 9,10-ethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene; and naphthalene compounds such as 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, and 1,4-dibutoxynaphthalene.

[0106] <Other ingredients> In addition to the above-mentioned components, additives can be appropriately blended into the active energy ray curable adhesive of the present invention, as long as the effect of the present invention is not impaired. For example, organic or inorganic fillers can be blended from the viewpoints of reducing polymerization curing shrinkage, reducing thermal expansion, improving dimensional stability, improving elastic modulus, adjusting viscosity, improving thermal conductivity, improving strength, improving toughness, improving coloring, etc. As such fillers, polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, etc. can be used, and the shape is not particularly limited to particles, fibers, etc. When blending the above polymers, it is also possible to dissolve, semi-dissolve, or micro-disperse softeners, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy-imparting agents, dispersion stabilizers, fluidity-imparting agents, defoamers, etc., in the active energy ray curable adhesive as polymer blends or polymer alloys rather than as fillers.

[0107] The active energy ray-curable adhesive of the present invention is preferably substantially free of water or organic solvents in terms of drying equipment and drying energy. However, in cases where the radical initiator (E), photoacid generator (F), and sensitizer (G) are poorly soluble in the compound (M1) or have a high viscosity, In this case, a small amount of water is required to dissolve the radical initiator (E), the photoacid generator (F), and the sensitizer (G). The content of water or organic solvent in the active energy ray curable adhesive is within 5 mass%. The organic solvent that can be used is not particularly limited, but specifically, organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents, or water can be further added to adjust the viscosity of the active energy ray curable adhesive, or the viscosity can be reduced by heating the active energy ray curable adhesive.

[0108] <Film> The film is preferably a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc. The film may be a film (F1) made of a cycloolefin resin having a polar group, or a film (F2) made of other than the polar group. The polar group refers to a functional group or atomic group having polarity. Examples include a carboxyl group, a hydroxyl group, an amino group, a carbonyl group, an ester bond, an ether bond, an amide group, a carbonate group, a carbamate group, an imide group, a cyano group, or a structure in which a halogen atom having a higher electronegativity than a carbon atom is directly bonded, but there is no limitation as long as the functional group has a higher polarity than the olefin structure.

[0109] The film (F1) is not limited as long as the monomer structure constituting the resin has a polar structure and a cycloolefin structure. For example, the film (F1) may be a resin containing a cycloolefin monomer having a polar group as a constituent unit, or a copolymer resin of a cycloolefin monomer having no polar group and a monomer having a polar group without containing a cycloolefin, or a mixed resin of a cycloolefin polymer having no polar group and a monomer having a polar group without containing a cycloolefin, or the like, and may be a mixed resin of these. The film (F1) is preferably a resin containing a cycloolefin monomer having a polar group as a constituent unit.

[0110] The cycloolefin resin having a polar group may be a copolymer resin of a cycloolefin monomer having a polar group and another monomer. Examples of the other monomer include a cycloolefin monomer having no polar group, a monomer having a polar group without including a cycloolefin skeleton, and an olefin other than a cycloolefin. A mixed resin of a cycloolefin resin having a polar group and another resin may also be used.

[0111] The cycloolefin monomer having a polar group is represented by the general formula (a-1) or (a-2).

[0112] General formula (a-1) JPEG2025085581000001.jpg5589In general formula (a-1), R 1 ~R 4 At least one of R represents a polar group, and the others each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. p represents an integer of 0 to 2. 1 and R 2 does not simultaneously represent a hydrogen atom, and R 3 and R 4 does not simultaneously represent a hydrogen atom.

[0113] The hydrocarbon group having 1 to 30 carbon atoms may further have a linking group containing, for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Examples of such linking groups include divalent polar groups such as a carbonyl group, an imino group, an ether bond, a silyl ether bond, and a thioether bond.

[0114] In general formula (a-1), R 1 ~R 4 Examples of the polar group represented by the formula include a carboxy group, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amido group, and a cyano group.

[0115] General formula (a-2) JPEG2025085581000002.jpg5581In general formula (a-2), R 5 R represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group having 1 to 5 carbon atoms. 6 represents a polar group, specifically, a carboxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amido group, a cyano group, or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). p represents an integer of 0 to 2.

[0116] The cycloolefin monomer having no polar group is represented by the general formula (a-3). General formula (a-3) JPEG2025085581000003.jpg5790 In general formula (a-3), R 7 ~R 10 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and p represents an integer of 0 to 2.

[0117] Examples of the monomer having a polar group include (meth)acrylate monomers such as alkyl (meth)acrylates having 1 to 20 carbon atoms, such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate, each having an ester bond; Vinyl ether monomers having an ether bond, such as 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether; Vinyl ester monomers having an ester bond, such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Vinyl amide monomers having an amide bond, such as vinyl formamide, vinyl acetamide, and vinyl pyrrolidone; Examples of the compound include olefin compounds having a polar group.

[0118] Examples of the film (F2) include polyolefin-based films such as polyvinyl alcohol film, polytriacetyl cellulose film, polypropylene, polyethylene, cycloolefin polymers not containing a monomer unit having a polar group, and ethylene-vinyl acetate copolymer; polyester-based films such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate-based films, polyarylate-based films, polyacrylic-based films, polyphenylene sulfide-based films, polystyrene-based films, polyvinyl-based films, polyamide-based films, polyimide-based films, and polyoxirane-based films.

[0119] The thickness of the film can be appropriately determined, but generally, from the viewpoints of strength, workability such as handleability, thin layer property, and the like, it is preferably 1 to 100 μM, more preferably 5 to 50 μM.

[0120] <Laminate> The laminate of the present invention is preferably used as an optical laminate, more preferably as a laminate for optical elements. The laminate of the present invention has a lamination structure including a film (F1), an adhesive layer made of the active energy ray-curable adhesive of the present invention, a film (F1) or a film (F2), A laminate in which three or more substrates are laminated, such as film (F1) / adhesive layer / film (F2) / adhesive layer / film (F2), is preferred.

[0121] When the laminate of the present invention is used for an optical element, it is preferable to use a transparent film or an optical film. The optical film is a film to which an optical function is imparted by applying a coating liquid having an optical function to a transparent film. The optical function is retardation, light diffusion, light collection, refraction, scattering, haze, etc. Examples of the optical film include a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a light diffusion film, a brightness improvement film, a prism film (also called a prism sheet), and a light guide film (also called a light guide plate). These can be used alone or in combination of two or more types depending on the application.

[0122] The laminate of the present invention can also be used as a polarizing plate film. In this case, the laminate is preferably a laminate such as film (F1) / adhesive layer / polyvinyl alcohol polarizer (film (F2)) / adhesive layer / film (F2), and the films (F1) and (F2) are preferably transparent films or optical films.

[0123] The laminate can be obtained as follows: A coating is formed by applying an active energy ray-curable adhesive to one side of a transparent film, which is a film-like substrate, and then laminating another transparent film onto the coating, and further applying an active energy ray-curable adhesive to one or both sides of this laminate, and then laminating it on another transparent film, glass, or a transparent molded body to obtain a laminate.

[0124] The thickness of the adhesive layer formed from the active energy ray-curable adhesive of the present invention is not particularly limited, and can be appropriately adjusted depending on the application.

[0125] When the thickness of the adhesive layer is 0.1 to 6 μM, the viscosity is preferably 1 to 1000 MPa·s, and more preferably 10 to 500 MPa·s. If the viscosity is 1000 MPa·s or less, a thin film of 0.1 to 6 μM can be formed when the adhesive layer is applied to a substrate, and optical properties such as transmittance are also excellent. On the other hand, a viscosity of 1 MPa·s or more is preferable because it makes it easier to control the thickness of the adhesive layer.

[0126] When the adhesive layer has a thickness of 6 to 300 μM, the viscosity is preferably 1000 to 100,000 MPa·s, and more preferably 3,000 to 50,000 MPa·s.

[0127] <Coating method> The active energy ray-curable adhesive of the present invention can be applied by any known application method, such as with a Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, microgravure coater, lip coater, comma coater, curtain coater, knife coater, reverse coater, or spin coater.

[0128] In the laminate, in order to bond the resin composition to the substrate, a polymerization reaction of the resin composition by irradiation with active energy rays is necessary. The active energy ray polymerization reaction proceeds by irradiating with active energy rays when the resin composition is applied or when laminating, or after lamination, but it is preferable to proceed with the polymerization reaction by irradiating with active energy rays after lamination.

[0129] <Active energy rays> The active energy ray curable adhesive of the present invention is applied to a substrate, and the formed coating is polymerized and cured by irradiating the coating with active energy rays. These mainly use light in the 0 to 550 nM wavelength range, and examples of such light 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, LED lamps, xenon lamps, etc. In addition, semiconductor lasers, electron beams, etc. can also be used as active energy rays.

[0130] The UV irradiation intensity is 10 to 3000MW / cM. 2 When the irradiation intensity satisfies the above range, rapid curing is facilitated and deterioration of the substrate can be minimized. The integrated irradiation amount, which is expressed as the product of the irradiation intensity and the irradiation time, is preferably 50 to 20,000 MJ / cM. 2 When the accumulated irradiation amount satisfies the above-mentioned accumulated irradiation amount, curing in a short time becomes easy, and productivity is further improved.

[0131] More specifically, a polarizing plate (polarizing film) using an active energy ray-curable adhesive can be obtained as follows.

[0132] A polarizing plate (polarizing film) using an active energy ray-curable adhesive is preferably produced by, for example, any one of the following methods (I) to (III).

[0133] (I) applying an active energy ray curable adhesive to one surface of a protective film, which is a first transparent film, to form a first polymerizable adhesive layer; An active energy ray-curable adhesive is applied to one surface of a second protective film, which is a transparent film, to form a second active energy ray-curable adhesive layer; Next, a first active energy ray curable adhesive was applied to each surface of the polyvinyl alcohol-based polarizer. a method for producing the laminated ...

[0134] (II) A method for producing a polarizer by coating one surface of a polyvinyl alcohol-based polarizer with an active energy ray-curable adhesive to form a first active energy ray-curable adhesive layer, covering the surface of the first active energy ray-curable adhesive layer formed with a first protective film which is a transparent film, coating the other surface of the polyvinyl alcohol-based polarizer with an active energy ray-curable adhesive to form a second active energy ray-curable adhesive layer, covering the surface of the second active energy ray-curable adhesive layer formed with a second protective film, irradiating with active energy rays, and polymerizing and curing the first active energy ray-curable adhesive layer and the second active energy ray-curable adhesive layer,

[0135] (III) A protective film, which is a first transparent film, and a polyvinyl alcohol-based polarizer are laminated. An active energy ray curable adhesive is dropped onto the end of the first protective film and onto the end of the second protective film that is placed on the side of the polyvinyl alcohol polarizer where the first protective film is not present, and then the layer is passed between rolls to spread the adhesive between the layers. Next, the active energy ray is irradiated to polymerize and cure the active energy ray curable adhesive, but the method is not particularly limited. EXAMPLES

[0136] Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, "parts" and "%" respectively represent "parts by mass" and "% by mass", and "RH" represents relative humidity. The blend amounts in the table are in parts by mass, and amounts other than the solvent are calculated as non-volatile contents. Note that blanks in the table indicate that no blend was made.

[0137] <Method for measuring weight average molecular weight> The weight average molecular weight is measured by gel permeation chromatography (TOSOH CORPORATION) HLC-8220GPC" and separation columns: Tosoh Corporation's "TSK-GEL SUPER H5000" and "TSK-GEL SUPER H40 The weight average molecular weight in terms of polystyrene was measured using four columns of "TSK-GEL SUPER H2000," "TSK-GEL SUPER H3000," and "TSK-GEL SUPER H2000" connected in series, using tetrahydrofuran at a temperature of 40°C as the mobile phase, and a flow rate of 0.6 mL / min.

[0138] <Method for measuring hydroxyl value> The hydroxyl value was measured as follows. Approximately 1 g of sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and 100 mL of a toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1) mixture was added to dissolve it. Then, exactly 5 mL of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to a volume of 100 mL) was added and stirred for approximately 1 hour. Phenolphthalein test solution was added as an indicator, and stirring was continued for 30 seconds. After that, the solution was titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color, and the hydroxyl value was calculated by the following formula. The hydroxyl value was the value in the dry state of the resin (unit: MgKOH / g). Hydroxyl value (MgKOH / g) = [{(ba) × F × 28.25} / S] / (non-volatile matter concentration / 100) + D Where S is the amount of sample taken (g) a: Consumption of 0.1N alcoholic potassium hydroxide solution (Ml) b: Consumption of 0.1N alcoholic potassium hydroxide solution in the blank experiment (Ml) F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (MgKOH / g)

[0139] The materials used in the examples and comparative examples are as follows.

[0140] <Monofunctional monomer (M1)> Monofunctional monomers (M1-1) that have 7 or more carbon atoms and do not contain hydroxyl groups LA: Lauryl acrylate IBXA: Isobornyl acrylate BzA: benzyl acrylate MEDOLMA: (2-methyl-1,3-dioxolan-4-yl)methyl acrylate M5300: ω-carboxy-polycaprolactone (n≒2) monoacrylate

[0141] Monofunctional monomer containing a hydroxyl group (M1-2) 4HBA: 4-hydroxybutyl acrylate CHDMMA: Cyclohexanedimethanol monoacrylate Other monofunctional monomers (M1-3) THFA: Tetrahydrofurfuryl acrylate

[0142] <Polyfunctional Monomer (M2)> 1,9NDDA: 1,9-nonanediol diacrylate DCPDA: dicyclopentyl dimethylene diacrylate INANTA: Isocyanuric acid EO modified triacrylate DPGDA: Dipropylene glycol diacrylate

[0143] <Oligomer (O)> Polyurethane acrylate (O-1): <Production of urethane acrylate 1> In a five-necked separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 200.0 parts of polypropylene glycol (Sanyo Chemical Industries, Ltd.: Sannix PP-1000, hydroxyl value 112 MgKOH / g) and 49 parts of isophorone diisocyanate were added. The mixture was charged with 0.5 parts of 4-hydroxybutyl acrylate and heated to 60°C while introducing dry air. 0.05 parts of dibutyltin dilaurate was added to the mixture and allowed to react for 2 hours. Separately, 5.2 parts of 4-hydroxybutyl acrylate and 0.05 parts of hydroquinone monomethyl ether were charged into a dropping funnel and dropped into the separable flask over 1 hour. After the dropping was completed, stirring was continued at 80°C for 3 hours, and then the reaction was terminated by confirming that there was no absorption peak of the isocyanato group in the infrared absorption spectrum, and urethane acrylate 1 was obtained. Its weight average molecular weight was 15,000.

[0144] <Production of urethane acrylate 2> In a 5-necked separable flask equipped with a stirrer, reflux condenser, gas inlet, thermometer, and dropping funnel, 222.2 parts of polytetramethylene glycol (PTG2000 manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value 56.MgKOH / g) and 28.0 parts of isophorone diisocyanate were charged, and the temperature was raised to 60°C while introducing dry air. 0.05 parts of dibutyltin dilaurate were added thereto, and the mixture was reacted for 1 hour. Separately, 3.7 parts of 4-hydroxybutyl acrylate and 0.05 parts of hydroquinone monomethyl ether were charged in a dropping funnel, and the mixture was dropped into the separable flask over 1 hour. After the dropping was completed, stirring was continued at 80°C for 3 hours, and the reaction was terminated by confirming that there was no absorption peak of the isocyanato group in the infrared absorption spectrum, and urethane acrylate 2 was obtained. Its weight average molecular weight was 22,000.

[0145] <Production of urethane acrylate 3> In a 5-necked separable flask equipped with a stirrer, a distillation tube, a gas inlet tube, and a thermometer, 125.0 parts of neopentyl glycol, 146.1 parts of adipic acid, and 0.01 parts of zinc oxide were charged, and esterification was carried out while distilling off the generated condensation water at 210°C under normal pressure and while passing dry air. After confirming that the acid value was 2MgKOH / g, the pressure was reduced and the temperature in the flask was raised to 260°C and deglycolization reaction was carried out over 10 hours. The OH value was 8.9MgKOH / g. Next, 3.4 parts of isophorone diisocyanate was charged to 250 parts of the obtained polyester diol, and the temperature was raised to 60°C while introducing dry air. 0.05 parts of dibutyltin dilaurate was added thereto and reacted for 1 hour. Separately, 1.7 parts of 4-hydroxybutyl acrylate and 0.05 parts of hydroquinone monomethyl ether were charged into a dropping funnel and dropped into a separable flask over 1 hour. After the dropping was completed, stirring was continued at 80°C for 3 hours, and then the reaction was terminated by confirming that there was no absorption peak of an isocyanato group in the infrared absorption spectrum, and urethane acrylate 3 was obtained. The weight average molecular weight was 49,000.

[0146] <Production of urethane acrylate 4> In a five-necked separable flask equipped with a stirrer, a distillation tube, a gas inlet tube, and a thermometer, 118.2 parts of 1,6-hexanediol, 188.2 parts of azelaic acid, and 0.01 parts of zinc oxide were charged, and esterification was carried out while distilling off the generated condensation water at 210 ° C. under normal pressure while passing dry air. After confirming that the acid value was 2 MgKOH / g, the pressure was reduced and the temperature in the flask was raised to 260 ° C., and a deglycolization reaction was carried out over 10 hours. The OH value was 7.2 MgKOH / g. Next, 3.5 parts of isophorone diisocyanate was charged for 250 parts of the obtained polyester diol, and the temperature was raised to 60 ° C. while introducing dry air. 0.05 parts of dibutyltin dilaurate was added thereto and reacted for 1 hour. Separately, 2.4 parts of 4-hydroxybutyl acrylate and 0.05 parts of hydroquinone monomethyl ether were charged into a dropping funnel and dropped into a separable flask over 1 hour. After the dropping was completed, stirring was continued at 80°C for 3 hours, and then the reaction was terminated by confirming that there was no absorption peak of an isocyanato group in the infrared absorption spectrum, and urethane acrylate 4 was obtained. The weight average molecular weight was 34,000.

[0147] <Production of Urethane Acrylate 5> A 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel. In the flask, 250 parts of polybutadiene with hydroxyl groups at both ends (GI-1000, manufactured by Nippon Soda Co., Ltd., hydroxyl value 67 MgKOH / g, number average molecular weight 1500) and 47.8 parts of isophorone diisocyanate were charged, 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 allowed to proceed for 1 hour. Separately, 13.2 parts of 4-hydroxybutyl acrylate and 0.05 parts of hydroquinone monomethyl ether were charged in a dropping funnel, and the mixture was dropped into a separable flask over 1 hour. After the dropwise addition, stirring was continued for 3 hours at 80°C, and the reaction was terminated by confirming that there was no absorption peak of the isocyanato group in the infrared absorption spectrum, and urethane acrylate 5 was obtained. Its weight average molecular weight was 8,200.

[0148] Polyester acrylate (O-2): <Production of Polyester Acrylate 1> In a five-necked separable flask equipped with a stirrer, a distillation tube, a gas inlet tube, and a thermometer, 104.1 parts of neopentyl glycol, 153.4 parts of adipic acid, and 0.01 parts of zinc oxide were charged, and esterification was carried out at 210°C under normal pressure while passing dry air through the flask and distilling off the generated condensation water, to obtain a polyester dicarboxylic acid having an acid value of 22.8 MgKOH / g. Next, 21.0 parts of 4-hydroxybutyl acrylate glycidyl ether, 0.01 parts of tetrabutylammonium borate, and 0.05 parts of hydroquinone monomethyl ether were added to 250 g of the obtained polyester dicarboxylic acid, and an addition reaction was carried out at 100°C until the acid value became 1 MgKOH / g or less, to obtain polyester acrylate 1. The weight average molecular weight of polyester acrylate 1 was 5,400.

[0149] Epoxy acrylate (O-3) <Production of Epoxy Acrylate 1> In a five-necked separable flask equipped with a stirrer, reflux condenser, gas inlet, and thermometer, 250.0 parts of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation: JER4005P, epoxy equivalent 1075), 34.0 parts of acrylic acid, 0.05 parts of hydroquinone monomethyl ether, and 20 parts of MEK were charged and dissolved by heating to 60°C while introducing dry air. 0.5 parts of tetrabutylammonium borate was added thereto, and the mixture was heated to 100°C and reacted for 8 hours to obtain epoxy acrylate 1. The weight average molecular weight of epoxy acrylate 1 was 2500.

[0150] Acrylic acrylate (O-4) XMAP RC100C (Kaneka Corporation acrylic acrylate, Mw=25000)

[0151] <Silane Compound (S)> KBM-403: 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (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

[0152] <Radical initiator (E)> TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (OMnirad TPO manufactured by IGM resins BV)

[0153] <Photoacid generator (G)> CPI-110P: San-Apro Triarylsulfonium PF 6 Salt-type photoacid generator OMnicat250: 4-isobutylphenyl (4-methylphenyl) 1700785408029_3 Hexafluorophosphate (IGM resins BV)

[0154] <Active energy ray sensitizer (H)> ITX: 2-isopropylthioxanthone DBA: 9,10-dibutoxyanthracene

[0155] <Film made of cycloolefin resin having polar group (F1)> 8-Methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 A film made of a resin obtained by polymerizing ]-3-dodecene (p in the general formula (2) is 1, R5 is a carbon atom, and R6 is a methoxycarbonyl group) was used. [Example 1] 14 parts of IBXA, 30 parts of BzA, 40 parts of MEDOLMA, 10 parts of M5300 as monofunctional monomers (M1), 3 parts of TPO as radical polymerization initiator (E), and 3 parts of ITX as active energy ray sensitizer (H) were charged into a light-shielded 300 ml glass bottle, thoroughly stirred with a disperser, and then thoroughly degassed to obtain an active energy ray-curable adhesive.

[0156] [Examples 2 to 45, Comparative Examples 1 to 3] As shown in Tables 1 to 3, except that the compositions and blending amounts (parts by mass) were changed, the same procedure as in Example 1 was followed to obtain active energy ray-curable adhesives.

[0157] Evaluation of the laminate The obtained active energy ray-curable adhesive was used to produce the following laminate X1, which was then evaluated by the following methods. The results are shown in Tables 1 to 3.

[0158] <Manufacture of Laminate X1 (Polarizing Plate)> A 40 μM thick film made of a cycloolefin resin with a polar group that does not contain a UV absorbent was used as film (F1), and a 50 μM thick triacetyl cellulose film (hereafter abbreviated as TAC) containing a UV absorbent was used as film (F2). One side of films (F1) and (F2) were heated at 300 W·Min / M. 2 A corona treatment was performed with a discharge amount of 10 ... Active energy ray irradiation equipment (Toshiba high pressure mercury lamp) with maximum illumination of 300MW / cM 2 , Accumulated light output 300MJ / cM 2 The film (F1) side was irradiated with ultraviolet light to prepare a laminate X1 (polarizing plate).

[0159] <Manufacture of laminate X2> As the film (F1), a cycloolefin resin film having a polar group and not containing an ultraviolet absorbing agent, having a thickness of 40 μM, was used, and as the film (F2), a polyester film (hereinafter abbreviated as PET) containing an ultraviolet absorbing agent, having a thickness of 60 μM was used. 1) 300W·Min / M on one side of (F2) 2 Within one hour thereafter, the active energy ray curable adhesive shown in Tables 1 to 3 was applied to the corona treated surface of the film (F1) using a wire bar coater to a thickness of 10 μM to form a coating. The film (F1) and the film (F2) were laminated together to form a film of cycloolefin resin film having a polar group / adhesive layer / PET [film (F1) / adhesive layer / film]. The four sides of this laminate were fixed with cellophane tape so that the PET was in contact with the tin plate, and the laminate was fixed to the tin plate. Active energy ray irradiation equipment (Toshiba high pressure mercury lamp) with maximum illumination of 300MW / cM 2 , Accumulated light output 300MJ / cM 2 The film (F1) side was irradiated with ultraviolet light of 1000 nm to prepare a laminate X2.

[0160] <Laminate X1 adhesive strength> The obtained laminate X1 (polarizing plate) was cut into a size of 25 mm x 150 mm using a cutter to obtain a measurement sample. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to the surface of the transparent film (1) of the sample, and the sample was attached to a metal plate using a laminator to obtain a laminate of a polarizing plate and a metal plate. The obtained laminate was used as a laminate for measuring adhesive strength. A peeling trigger was provided in advance between the film (F1) and the polarizer in the polarizing plate, and the measurement laminate was peeled off at an angle of 90° at a speed of 300 mm / min under conditions of 23°C and 50% RH, and the peeling strength was measured. At this time, the peeling strength between the PVA polarizer and the film (F1) was measured.

[0161] <Laminated body X2 adhesive strength> The obtained laminate X2 was cut into a size of 25 mm x 150 mm using a cutter to obtain a measurement sample. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to the surface of the transparent film (1) of the sample, and the sample was attached to a metal plate using a laminator to obtain a laminate of the laminate X2 and the metal plate. The obtained laminate was used as a laminate for measuring adhesive strength. A peeling trigger was provided in advance between the film (F1) and the PET of the laminate X2, and the laminate for measurement was peeled at an angle of 90° at a speed of 300 mm / min under conditions of 23°C and 50% RH, to obtain the peeling strength. At this time, the peeling strength between the film (F1) and the PET was measured. The peel strength between the laminate X1 and the laminate X2 was evaluated as adhesive strength on a four-level scale. [Evaluation Criteria] ◎: Peel strength is 2.0 (N / 25MM) or more, very good ○: Peel strength is 1.5 (N / 25MM) or more and less than 2.0 (N / 25MM), excellent △: Peel strength is 1.0 (N / 25MM) or more, less than 1.5 (N / 25MM), usable ×: Peel strength is less than 1.0 (N / 25MM), not practical

[0162] <Damp heat test> The laminate X1 was exposed for 1000 hours under the conditions of a temperature of 60°C and 90% RH. After the exposure, the end of the laminate X1 was observed under a microscope to measure the shrinkage width of the PVA polarizer. The measured shrinkage width was evaluated on a 4-point scale. ◎: Contraction amplitude is 0μM or more and less than 300μM, very excellent ○: Contraction amplitude is 300μM or more and less than 600μM, excellent △: Contraction range is 600μM or more and less than 1000μM, usable ×: Contraction width is 1000μM or more, not practical

[0163] <Evaluation of haze value> The haze value of the laminate X2 was measured in an environment of 23° C. and 50% RH using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SH7000") in accordance with JIS K 7136. The measured haze value was evaluated on a four-point scale. [Evaluation Criteria] ◎: 0 or more to less than 0.3, very excellent ○: 0.3 or more, less than 0.6, excellent △: 0.6 or more, less than 0.9, usable ×: 0.9 or more, not practical

[0164] <Curling Evaluation>

[0165] The laminates X1 and X2 were cut into samples of 50 mm x 150 mm using a cutter so that the long sides of the laminates were in the stretching direction, and used as measurement samples. The samples were placed on a horizontal plane with the convex side facing down, and the distances from the horizontal plane to the four ends of the samples were measured. The measured values ​​were evaluated on a four-point scale. ◎: 0mm or more, less than 10mm, very good ○: 10mm or more, less than 20mm, excellent △: 20mm or more, less than 30mm, usable ×: Over 30mm, not practical

[0166] [Table 1]

[0167] [Table 2]

[0168] [Table 3]

[0169] As shown in Tables 1 to 3, it was confirmed that the active energy ray-curable adhesive of the present invention has excellent adhesiveness, high moisture resistance, and excellent haze and curl properties.

Claims

1. An adhesive for film lamination used in the production of a laminate comprising a film (F1) made of a cycloolefin resin having a polar group, An active energy ray-curable adhesive comprising, based on 100 mass % of the adhesive, 20 to 95 mass % of a monofunctional monomer (M1).

2. 2. The active energy ray-curable adhesive according to claim 1, wherein the monofunctional monomer (M1) comprises a monofunctional monomer (M1-1) having 7 or more carbon atoms and not containing a hydroxyl group.

3. 3. The active energy ray-curable adhesive according to claim 2, wherein the monofunctional monomer (M1) further comprises a monofunctional monomer (M1-2) containing a hydroxyl group.

4. The active energy ray-curable adhesive according to claim 2, wherein the monofunctional monomer (M1-1) having 7 or more carbon atoms and not containing a hydroxyl group comprises at least one monofunctional monomer having any structure selected from the group consisting of an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group, an aromatic ring, and a heterocycle (excluding those having an aromatic ring).

5. The active energy ray-curable adhesive according to claim 3, further comprising an oligomer (O) having a weight average molecular weight of 1,000 to 60,000.

6. 6. The active energy ray-curable adhesive according to claim 5, wherein the oligomer (O) is at least one selected from the group consisting of urethane acrylate (O-1), polyester acrylate (O-2) and epoxy acrylate (O-3).

7. 6. The active energy ray-curable adhesive according to claim 5, wherein the oligomer (O) contains a urethane acrylate (O-1).

8. The urethane acrylate (O-1) is a reaction product of a polyol, a polyisocyanate, and a monofunctional monomer (M1-2) containing a hydroxyl group, 8. The active energy ray-curable adhesive according to claim 7, wherein the polyol is any one selected from the group consisting of polyether polyols having an alkylene structure with 4 or more carbon atoms, polyester polyols having a unit structure with 12 or more carbon atoms, and polyolefin polyols.

9. The active energy ray-curable adhesive according to claim 5 , further comprising a polyfunctional monomer (M2).

10. The active energy ray-curable adhesive according to claim 9, further comprising a silane compound (S).

11. The active energy ray-curable adhesive according to claim 10, comprising, based on a total amount of 100 mass%, 10 to 70 mass% of a monofunctional monomer (M1-1) having 7 or more carbon atoms and not containing a hydroxyl group, 10 to 70 mass% of a monofunctional monomer (M1-2) containing a hydroxyl group, 1 to 30 mass% of an oligomer (O), 1 to 50 mass% of a polyfunctional monomer (M2), and 1 to 30 mass% of a silane compound (S).

12. The adhesive layer is made of the active energy ray-curable adhesive according to any one of claims 1 to 11, and the film (F1) or the film (F2) is provided in this order, and the film (F2) is a polyvinyl alcohol-based film, a polyacetyl cellulose-based film, a cycloolefin polymer not containing a monomer having a polar group, a polypropylene-based film, a polyacrylic-based film, a polycarbonate-based film, a polyester-based film, or a combination thereof. The laminate is any one selected from the group consisting of a polyimide film, a polyimide-based film, and a glass film.