Active energy ray curable adhesive and laminate

Abstract

Provided are: an active energy ray-curable adhesive which, in the production of a laminate comprising a film (F1) comprising a cycloolefin resin having a polar group, is capable of forming a laminate having excellent transparency, little warpage after curing, and excellent adhesiveness; the problem of the present application is solved by an active energy ray-curable adhesive for film bonding used in the production of a laminate provided with a film (F1) comprising a cycloolefin resin having a polar group, and containing 20-95% by mass of a monofunctional monomer (M1) per 100% by mass of the adhesive.

Description

Technical Field

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

[0002] Active energy ray-curable adhesives have a fast polymerization rate and can generally be used without solvents, so they have excellent workability and extremely low energy requirements during polymerization. Examples of active energy ray-curable adhesives include free radical-based, cationic-based, or a combination (mixed system) of free radical-based and cationic-based active energy ray-curable adhesives, which are used in a wide range of applications.

[0003] Polarizing plates used in fields related to liquid crystal displays, etc. are usually manufactured by uniaxially stretching a material obtained by adsorbing iodine or a dye onto polyvinyl alcohol (PVA). This PVA-based polarizing plate shrinks due to heat and moisture, resulting in a reduction in polarization performance. Therefore, a polarizing plate with a protective film attached to the surface of the PVA-based polarizing plate is used as a polarizer.

[0004] In the bonding of a PVA-based polarizing plate and a protective film, an aqueous adhesive or an active energy ray-curable adhesive is used. Among them, from the viewpoints of the versatility of the substrate for the protective film, production efficiency improvement, and energy conservation, the use of active energy ray-curable adhesives is being promoted.

[0005] For active energy ray-curable adhesives, properties such as sufficient adhesiveness in the bonding of a PVA-based polarizing plate and a protective film, heat resistance, moisture resistance, and water resistance for suppressing the reduction of the polarization performance of the PVA-based polarizing plate are required.

[0006] In Patent Document 1, regarding problems such as the bonding strength of a polarizer using a film with a moisture permeability lower than that of triacetyl cellulose such as a norbornene-based resin film as a protective film, a cationic active energy ray-curable adhesive mainly composed of an epoxy resin without an aromatic ring is disclosed.

[0007] In Patent Document 2, as an adhesive that firmly bonds not only to norbornene-based resins but also to acrylic resins and triacetyl cellulose films, a mixed active energy ray-curable adhesive using 2-hydroxybutyl acrylate and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane is disclosed.

[0008] In Patent Document 3, regarding problems of warping, polarization characteristics, and durability, a free radical-based active energy ray-curable adhesive using an acrylic monomer with a specific range of SP values is disclosed.

[0009] On the other hand, a triacetyl cellulose film was previously used as the protective film in a polarizing plate. However, a polarizing plate with a triacetyl cellulose film having a high moisture permeability as the protective film deteriorates under humid heat conditions such as a temperature of 60°C and a relative humidity of 90%RH. Therefore, as a resin film with a low moisture permeability, the use of amorphous polyolefin resins, acrylic resins, etc. has increased (Patent Documents 1, 2, 3).

[0010] In addition, in recent years, it has been possible to further thin the film. As an amorphous polyolefin resin that can easily impart functions such as anti-blocking, anti-glare, and UV cut-off, a copolymer resin of a monomer having a polar group and a cycloolefin monomer, a mixed resin of a polymer having a polar group and a cycloolefin polymer, and a cycloolefin resin having a polar group are used. Patent Document 4 discloses a polarizing plate obtained by laminating an optical film made of a cycloolefin resin having a polar group and a polarizing film made of polyvinyl alcohol with an ultraviolet curable adhesive composed of dipropylene glycol diacrylate and a plurality of epoxy monomers.

[0011] However, for films composed of a copolymer resin of a monomer having a polar group and a cycloolefin monomer, a mixed resin of a polymer having a polar group and a cycloolefin polymer, and a cycloolefin resin having a polar group, conventional adhesives have problems such as high coating film haze, large warpage of the polarizing plate after manufacturing, and low adhesive strength.

[0012] Prior Art Documents

[0013] Patent Documents

[0014] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004-245925

[0015] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2010-018722

[0016] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2013-210513

[0017] Patent Document 4: International Publication No. 2023 / 276304 Summary of the Invention

[0018] Problems to be Solved by the Invention

[0019] An object of the present invention is to provide a radiation curable adhesive that can form a laminate with excellent transparency, small warpage after curing, excellent adhesiveness, and excellent high temperature and high humidity resistance in the manufacture of a laminate including a film (F1) made of a cycloolefin resin having a polar group, and a laminate using the same.

[0020] Means for Solving the Problems

[0021] The inventors of the present invention have conducted intensive research repeatedly to solve the above problems, and as a result, it has been found that the above object can be achieved by the active energy ray-curable composition shown below, thereby completing the present invention.

[0022] The present invention relates to an active energy ray-curable adhesive used for film bonding in the manufacture of a laminate, the laminate including a film (F1) made of a cycloolefin resin having a polar group, and in 100% by mass of the adhesive, 20 to 95% by mass of a monofunctional monomer (M1) is contained.

[0023] In addition, the present invention relates to the above active energy ray-curable adhesive, wherein the monofunctional monomer (M1) includes a monofunctional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group.

[0024] In addition, the present invention relates to the above active energy ray-curable adhesive, wherein the monofunctional monomer (M1) further includes a monofunctional monomer (M1-2) containing a hydroxyl group.

[0025] In addition, the present invention relates to the above active energy ray-curable adhesive, wherein the monofunctional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group includes at least one monofunctional monomer having any one structure selected from the group consisting of an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group, an aromatic ring, and a heterocyclic ring (excluding a heterocyclic ring having an aromatic ring).

[0026] In addition, the present invention relates to the above active energy ray-curable adhesive, which further contains an oligomer (O) having a weight average molecular weight of 1,000 to 60,000.

[0027] In addition, the present invention relates to the above 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).

[0028] In addition, the present invention relates to the above active energy ray-curable adhesive, wherein the oligomer (O) contains urethane acrylate (O-1).

[0029] In addition, the present invention relates to the above active energy ray-curable adhesive, wherein the urethane acrylate (O-1) is a reaction product of a polyol, a polyisocyanate, and a monofunctional monomer (M1-2) containing a hydroxyl group, and the polyol is any one selected from the group consisting of a polyether polyol having an alkylene structure with 4 or more carbon atoms, a polyester polyol having 12 or more carbon atoms in a unit structure, and a polyolefin polyol.

[0030] In addition, the present invention relates to the above-described active energy ray-curable adhesive, which further contains a polyfunctional monomer (M2).

[0031] In addition, the present invention relates to the above-described active energy ray-curable adhesive, which further contains a silane compound (S).

[0032] In addition, the present invention relates to the above-described active energy ray-curable adhesive, wherein, in 100% by mass of the total amount of the adhesive, it contains 10 to 70% by mass of a monofunctional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group, 10 to 70% by mass of a monofunctional monomer (M1-2) containing a hydroxyl group, 1 to 30% by mass of an oligomer (O), 1 to 50% by mass of a polyfunctional monomer (M2), and 1 to 30% by mass of a silane compound (S).

[0033] In addition, the present invention relates to a laminate which sequentially includes a film (F1), an adhesive layer composed of the above-described active energy ray-curable adhesive, and the film (F1) or a film (F2), and the film (F2) is any one selected from the group consisting of a polyvinyl alcohol-based film, a polyacetyl cellulose-based film, a norbornene polymer without a monomer having a polar group, a polypropylene-based film, a polyacrylic acid-based film, a polycarbonate-based film, a polyester-based film, a polyimide-based film, and a glass film.

[0034] Advantages of the Invention

[0035] According to the present invention, it is possible to provide an active energy ray-curable adhesive capable of forming a laminate having excellent transparency, small warpage after curing, and excellent adhesiveness in the manufacture of a laminate including a film (F1) composed of a norbornene-based resin having a polar group, and a laminate using the same. Detailed Embodiments

[0036] The preferred embodiments of the present invention will be described below. In this specification, in the case of being labeled as “(meth)acrylic acid”, unless otherwise specified, it respectively means “acrylic acid or methacrylic acid”. In addition, a monomer means a monomer having an ethylenically unsaturated double bond group, a monofunctional monomer means a monomer having 1 ethylenically unsaturated double bond group, and a polyfunctional monomer means a monomer having 2 or more ethylenically unsaturated double bond groups.

[0037] In addition, sometimes the monofunctional monomer (M1) is simply referred to as compound (M1), the monofunctional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group is simply referred to as compound (M1-1), the monofunctional monomer (M1-2) containing a hydroxyl group is simply referred to as compound (M1-2), the oligomer (O) with a weight-average molecular weight of 1,000 to 60,000 is simply referred to as compound (O), the urethane acrylate (O-1) is simply referred to as compound (O-1), the polyester acrylate (O-2) is simply referred to as compound (O-2), the epoxy acrylate (O-3) is simply referred to as compound (O-3), the polyfunctional monomer (M2) is simply referred to as compound (M2), the silane compound (S) is simply referred to as compound (S), the film (F1) composed of a cycloolefin resin having a polar group is simply referred to as film (F1), and the active energy ray-curable adhesive is simply referred to as adhesive.

[0038] In this specification, unless otherwise specified, the numerical range determined by "~" includes the range with the values described before and after "~" as the lower limit value and the upper limit value.

[0039] In addition, in this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) refer to the weight-average molecular weight and the number-average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).

[0040] <Monofunctional monomer (M1)>

[0041] Compound (M1) is a compound having one ethylenically unsaturated double bond group. By including compound (M1) in the adhesive, an adhesive layer with excellent transparency can be obtained. After curing, it is not easy to cause curling of the laminate, the crosslinking density of the adhesive cured film will not become too high, and it is easy to be closely adhered to the film (F1).

[0042] Compound (M1) is classified into the monofunctional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group, the monofunctional monomer (M1-2) containing a hydroxyl group, and other monofunctional monomers (M1-3), and is used without particular limitation. It is preferably to contain compound (M1-1), and more preferably to use compound (M1-1) and compound (M1-2) in combination.

[0043] The weight-average molecular weight of compound (M1) is preferably less than 1,000, and more preferably less than 500. When the weight-average molecular weight of compound (M1) is less than 1,000, the viscosity of the resin composition will not become too high, and the film thickness control during coating becomes easy.

[0044] In 100% by mass of the adhesive, the content rate of compound (M1) is 20 to 95% by mass. When the content rate of compound (M1) is less than 20% by mass, the haze and curling property of the coating film are poor. When it exceeds 95% by mass, the curing is insufficient, and the adhesive strength and heat and humidity resistance deteriorate.

[0045] From the aspects of film haze, curling property, adhesion, and heat and humidity resistance, it is preferably 20 to 95% by mass. If it is 40 to 80% by mass, the adhesion and heat and humidity resistance are particularly excellent, so it is more preferred.

[0046] <Mono-functional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group>

[0047] Compound (M1-1) is a mono-functional monomer containing a structure having 7 or more carbon atoms and no hydroxyl group. By including compound (M1-1), the adhesive easily erodes the film (F1), and the adhesion is improved. In addition, the heat and humidity resistance and curling property are improved.

[0048] In order to improve the adhesion, compound (M1-1) preferably includes a mono-functional monomer having a structure selected from the group consisting of an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group (excluding a group having an epoxy structure in the cycloalkyl group), an aromatic ring, and a heterocyclic structure without an aromatic ring.

[0049] These structures can be used alone or in combination of multiple kinds. Especially when an aliphatic cyclic hydrocarbon group is included, the adhesion to a wide range of substrates is improved, so it is preferred.

[0050] In addition, when compound (M1-1) contains a hydrophilic structure, the erosiveness of the film (F1) is reduced, so it is preferably free of organic acids, amino groups, and structures having 2 or more repeating units of ethylene oxide.

[0051] In 100% by mass of the adhesive, the content of compound (M1-1) is preferably 10 to 70% by mass, more preferably 10 to 50% by mass. If it is 10% by mass or more, the adhesion to the film (F1) is further improved. If it is 70% by mass or less, the adhesion to a wide range of substrates is further improved.

[0052] Examples of compound (M1-1) include: for example, (meth)acrylic acid n-heptyl ester, (meth)acrylic acid 2-methylhexyl ester, (meth)acrylic acid n-octyl ester, (meth)acrylic acid isooctyl ester, (meth)acrylic acid 1-methylheptyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid nonyl ester, (meth)acrylic acid isononyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid isodecyl ester, (meth)acrylic acid 2-propylheptyl ester, (meth)acrylic acid lauryl ester, (meth)acrylic acid tridecyl ester, (meth)acrylic acid isopalmitate, (meth)acrylic acid cetyl ester, (meth)acrylic acid isostearyl ester, (meth)acrylic acid stearyl ester, (meth)acrylic acid docosyl ester, etc. (meth)acrylate esters containing an aliphatic chain hydrocarbon group having 7 or more carbon atoms;

[0053] For example, (meth)acrylate esters containing an aliphatic cyclic hydrocarbon group having 7 or more carbon atoms such as trimethylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, dicyclopentyl (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, 3-[2-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy]propyl acrylate, etc.;

[0054] For example, (meth)acrylate esters containing an aromatic ring having 7 or more carbon atoms such as 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-phenylphenoxypropyl acrylate, p-cumylphenol 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, neopentyl glycol-acrylic-benzoic acid ester, etc.;

[0055] For example, (meth)acrylate esters containing a heterocycle having 7 or more carbon atoms such as (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, glycidyl ether of 4-hydroxybutyl acrylate, etc.

[0056] <Mono-functional monomer (M1-2) containing a hydroxyl group>

[0057] Compound (M1-2) is a mono-functional monomer containing a hydroxyl group. By including compound (M1-2) in the resin composition, hydrogen bonds are formed with hydrophilic functional groups of the substrate, etc., and the adhesive force is improved.

[0058] In 100% by mass of the active energy ray-curable adhesive, the content of compound (M1-2) is preferably 10 to 70% by mass, more preferably 10 to 50% by mass. If it is 10% by mass or more, the adhesive force is further improved, and if it is 70% by mass or less, the adhesive force for a wide range of substrates is further improved.

[0059] As the compound (M1-2), there is no particular limitation as long as it is a compound having 1 hydroxyl group and 1 ethylenically unsaturated double bond group. For example, the following can be cited: 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, ethyl-α-(hydroxymethyl) (meth)acrylate, fatty acid ester-based (meth)acrylates such as monofunctional (meth)acrylic acid, or (meth)acrylates having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone to the compound having the above-mentioned ethylenically unsaturated double bond group containing a hydroxyl group, alkylene oxide addition (meth)acrylates obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to the compound having the above-mentioned ethylenically unsaturated double bond group containing a hydroxyl group, etc., aliphatic (meth)acrylates containing a hydroxyl group;

[0060] For example, aliphatic vinyl ethers containing a hydroxyl group 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, glycerol vinyl ether, or alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal formed by repeated addition of alkylene oxides such as ethylene oxide and propylene oxide;

[0061] For example, aliphatic (meth)allyl alcohols or (meth)allyl ethers containing a hydroxyl group 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, glycerol (meth)allyl ether, or alkylene oxide addition (meth)allyl ethers having a hydroxyl group at the terminal formed by repeated addition of alkylene oxides such as ethylene oxide and propylene oxide;

[0062] For example, compounds having an ethylenically unsaturated double bond group containing a plurality of hydroxyl groups such as propylene glycol, butylene glycol, heptylene glycol, octylene glycol, and glycerol di(meth)acrylate;

[0063] For example, (meth)acrylamides containing hydroxyl groups such as N-hydroxyethyl(meth)acrylamide (N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as "N-hydroxyethyl(meth)acrylamide". The same applies hereinafter), N-hydroxypropyl(meth)acrylamide, N-hydroxybutyl(meth)acrylamide, N-hydroxyhexyl(meth)acrylamide, N-hydroxyoctyl(meth)acrylamide;

[0064] For example, monomers having hydroxyl groups and vinyl groups such as vinyl alcohol, etc., but are not particularly limited to these. They can be used alone or in combination of multiple kinds.

[0065] As the compound (M1-2), from the aspect of adhesion to the substrate, acrylates of diols having 1 to 6 carbon atoms are preferred, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are particularly preferred.

[0066] <Other monofunctional monomers (M1-3)>

[0067] Other monofunctional monomers refer to monofunctional monomers other than the above (M1-1) and (M1-2). (M1-3) has no limitation as long as it is a compound having an ethylenically unsaturated double bond group. From the aspect of adhesion to a wide range of substrates, the content of (M1-3) is preferably 0 to 30% by mass.

[0068] <Oligomer (O)>

[0069] The weight average molecular weight of the oligomer (O) is 1000 to 60,000, and it is a compound 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 with a weight average molecular weight of 1000 to 60,000 (O-4). At least one or more oligomers selected from the group consisting of the compound (O-1), the compound (O-2), and the compound (O-3) are preferred and can be used without particular limitation. However, in the case of a compound having an alkoxysilyl group, it is classified as the silane compound (S) described later.

[0070] By using the oligomer (O), it is not easy to cause curling of the adherend after the adhesive is cured. Among them, urethane (meth)acrylate (O-1) is easy to relieve curing shrinkage, so the curling after curing is small, has a urethane bond with a large polarity, so the coating film is not easily damaged and the adhesion is also improved.

[0071] The weight-average molecular weight of the compound (O) is preferably in the range of 5,000 to 50,000. When the weight-average molecular weight of the compound (O) is within this range, the adhesive strength, the haze of the coating film, and the curling property are excellent.

[0072] In 100% by mass of the active energy ray-curable adhesive, the content of the compound (O) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass. If it is 1% by mass or more, the curling after curing is improved. If it is 30% by mass or less, the viscosity does not become too high, and the control of the film thickness during coating becomes easy.

[0073] Examples of the urethane (meth)acrylate (O-1) include a compound obtained by reacting a polyisocyanate with the compound (M1-2), a compound obtained by reacting a urethane prepolymer having terminal isocyanate groups, which is obtained by reacting a polyisocyanate with a polyol, with the compound (M1-2), or a compound obtained by reacting a urethane prepolymer having terminal isocyanate groups, which is obtained by reacting a polyisocyanate with a polyol, with a compound having two or more amino groups, and then reacting the resulting urethane prepolymer having terminal isocyanate groups with the compound (M1-2).

[0074] The compound (O-1) is preferably a reaction product of a polyisocyanate, a polyol, and the compound (M1-2), more preferably a compound obtained by reacting at a molar ratio of 2:1:2, respectively. This is because, by reacting at the above ratio, theoretically, a structure having acrylate groups at both ends of one molecule is formed, so the balance between flexibility and crosslink density is good, the curling of the cured laminate is small, and the substrate adhesion becomes good.

[0075] Examples of the polyisocyanate include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and the like.

[0076] More specifically, examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, benzidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4''-triphenylmethane triisocyanate, and the like.

[0077] Examples of the aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

[0078] Examples of the araliphatic polyisocyanates include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylbenzene dimethylene diisocyanate, 1,3-tetramethylbenzene dimethylene diisocyanate, etc.

[0079] Examples of the alicyclic polyisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (alias: 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), 1,4-bis(isocyanatomethyl)cyclohexane, etc.

[0080] In addition, 2-methylpentane-2,4-diol adducts of a part of the above polyisocyanates, trimers having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (alias: PAPI), naphthalene diisocyanate, and their polyisocyanate modified products, etc. can be used. It should be noted that as the polyisocyanate modified product, any group of carbodiimide group, uretdione group, uretonimine group, biuret group that reacts with water, isocyanurate group, or a modified product having two or more of these groups can be used. The reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

[0081] From the viewpoint of curling, the compound having an isocyanate group is preferably an aliphatic diisocyanate or an alicyclic diisocyanate compound.

[0082] In addition, examples of the polyol include low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500 and high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000, and they can be used without particular limitation respectively.

[0083] As low molecular weight polyols, more specifically, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-bis(hydroxymethyl)heptane, 2-butyl-2-ethyl-1,3-propanediol, polyethylene glycol (with an addition mole number of 10 or less), polypropylene glycol (with an addition mole number of 10 or less), propylene glycol, 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, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol and other aliphatic or alicyclic diols;

[0084] 1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediphenol, 4,4'-(2-norbornene)diphenol, 4,4'-dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene, 4,4'-isopropylidenediphenol, addition-type bisphenols obtained by adding an alkylene oxide to bisphenol and other aromatic diols.

[0085] As the bisphenol which is the raw material for the addition-type bisphenol, bisphenol A, bisphenol F, etc. can be cited, and as the raw material alkylene oxide, ethylene oxide, propylene oxide, etc. can be cited.

[0086] As high molecular weight polyols, more specifically, for example, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester polyols, polyamide polyols, polycarbonate polyols and polyurethane polyols, polybutadiene polyols, polyolefin polyols. The polyester polyol is a polyester obtained by polycondensing a polybasic acid and a polyol with a ratio of hydroxyl groups remaining at the molecular ends used in the synthesis of the following polyester (meth)acrylate (O-2), and the polybasic acid and the polyol can be the same substances as those used in the synthesis of the polyester (meth)acrylate (O-2).

[0087] The polycarbonate polyol is obtained by the reaction of the above low molecular weight diol with a carbonate or phosgene.

[0088] As commercially available products of the above polyester polyols, for example, the VYLON series manufactured by Toyobo Co., Ltd., the KURARAY polyol P series manufactured by Kuraray Co., Ltd., and the KYOWAPOLE series manufactured by Kyowa Hakko Chemical Co., Ltd. can be cited.

[0089] As commercially available products of the above polyamide polyols, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. etc. can be used.

[0090] Examples of commercially available products of the above polycarbonate polyols include OXYMER N112 manufactured by PERSTORP, PCDL series manufactured by Asahi Kasei Chemicals Corporation, KURARAY polyol PMHC series manufactured by KURARAY Co., Ltd., KURARAY polyol C series, etc.

[0091] Examples of commercially available products of the above polyurethane polyols include VYLON UR series manufactured by Toyobo Co., Ltd., TAKELEC E158 (hydroxyl value = 20, acid value < 3), TAKELEC E551T (hydroxyl value = 30, acid value < 3), and TAKELEC Y2789 (hydroxyl value = 10, acid value < 2) manufactured by Mitsui Chemicals Polyurethanes, Inc., etc.

[0092] 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.

[0093] From the viewpoint of adhesion, the polyol is preferably a high molecular weight polyether diol or a high molecular weight polyester diol.

[0094] In addition, as amines having an amino group, more specifically, for example, aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethyl ethylenediamine, hexamethylenediamine 2-hydroxyethyl ethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-hydroxyethyl ethylene)diamine, (di-hydroxyethylpropylene)diamine, (2-hydroxypropyl ethylene)diamine, (di-hydroxypropyl ethylene)diamine, piperazine;

[0095] alicyclic polyamines such as isophoronediamine, dicyclohexylmethane-4,4'-diamine;

[0096] aromatic diamines such as phenylenediamine, xylylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis(sec-butyl)diphenylmethane;

[0097] silylamines having a monofunctional silyl amino group such as trimethylsilyldimethylamine, silylamines having a difunctional silyl amino group such as 1,1,3,3-tetramethyldisilazane.

[0098] The urethane (meth)acrylate (O-1) is preferably a reaction product of a polyol, a polyisocyanate, and an acrylate having a hydroxyl group. As the polyol, a polyether polyol having an alkylene structure with 4 or more carbon atoms, a polyester polyol having a unit structure with 12 or more carbon atoms, a polybutadiene polyol, or a polyolefin polyol is preferably used. In particular, a polyether polyol composed of a polyol having 4 or more carbon atoms and a polyester polyol having a unit structure with 12 or more carbon atoms are preferably used.

[0099] 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 polyol at a ratio of leaving a hydroxyl group at the molecular end with a compound having an ethylenically unsaturated double bond group having 1 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 polyol at a ratio of leaving a carboxyl group at the molecular end with the aforementioned compound (M1-2) such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

[0100] In addition, a polyester (meth)acrylate obtained from an acid anhydride, glycidyl (meth)acrylate, and a compound having at least 1 hydroxyl group can also be used as the polyester (meth)acrylate (O-2).

[0101] Examples of the above polybasic acids include aliphatic, alicyclic, and aromatic types, and they can be used without particular limitation respectively. More specifically, 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, maleic anhydride, etc. These aliphatic dicarboxylic acids and their anhydrides can be used. In addition, derivatives of succinic anhydride (methylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, butylsuccinic anhydride, isobutylsuccinic anhydride, hexylsuccinic anhydride, octylsuccinic anhydride, dodecenylsuccinic anhydride, phenylsuccinic anhydride, etc.), derivatives of glutaric anhydride (glutaric anhydride, 3-allylglutaric anhydride, 2,4-dimethylglutaric anhydride, 2,4-diethylglutaric anhydride, butylglutaric anhydride, hexylglutaric anhydride, etc.), derivatives of maleic anhydride (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, 2,3-dichloromaleic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, etc.) and other acid anhydride derivatives can also be used.

[0102] As alicyclic polybasic acids, more specifically, for example, as alicyclic dicarboxylic acids, examples include dimer acid, cyclopropane-α,2α-dicarboxylic acid, cyclopropane-α,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, cumane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid and other saturated alicyclic dicarboxylic acids, 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, 2,5-hexadiene-1α,4α-dicarboxylic acid and other unsaturated alicyclic dicarboxylic acids having one or two unsaturated double bonds in the ring. These alicyclic dicarboxylic acids and their anhydrides can be used.

[0103] In addition, derivatives of hexahydrophthalic anhydride ((3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), 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.) and other hydrogenated phthalic anhydride derivatives can also be used as alicyclic dicarboxylic anhydrides.

[0104] As aromatic polybasic acids, more specifically, for example, as aromatic dicarboxylic acids, examples thereof include phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethyl terephthalic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindane dicarboxylic acid, 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (-)-1,3-acenaphthene dicarboxylic acid, 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, 3,9-perylene dicarboxylic acid and other aromatic dicarboxylic acids, phthalic anhydride, 4-methylphthalic anhydride and other aromatic dicarboxylic anhydrides. These aromatic dicarboxylic acids and their anhydrides can be used.

[0105] Furthermore, acid anhydrides such as chlorendic anhydride, endic anhydride, biphenyl dicarboxylic anhydride, nadic anhydride, methylene-norbornene anhydride, methyl-methylene-norbornene anhydride, 1,2-cyclohexane dicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, octahydro-1,3-dioxo-4,5-isobenzofurandicarboxylic anhydride can be used as polybasic acids.

[0106] In addition, as polyhydric alcohols, lower molecular weight polyhydric alcohols having a number average molecular weight (Mn) of about 50 to 500 and higher molecular weight polyhydric alcohols having a number average molecular weight (Mn) of 500 to 30,000 can be used without particular limitation, respectively.

[0107] More specifically, examples of the lower molecular weight polyhydric alcohols include aliphatic or alicyclic diols such as ethylene glycol, 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'-bis(hydroxymethyl)heptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition mole number is 10 or less), polyoxypropylene glycol (addition mole number is 10 or less), propylene glycol, 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, dimer diol;

[0108] Aromatic diols such as 1,3-bis(2-hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediphenol, 4,4'-(2-norbornanyl)diphenol, 4,4'-dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene, 4,4'-isopropylidenediphenol, addition-type bisphenols obtained by adding an alkylene oxide to a bisphenol, etc.

[0109] Examples of the bisphenol as a raw material 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.

[0110] As higher molecular weight polyols, more specifically, for example, high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols and high molecular weight polyurethane polyols can be cited. The high molecular weight polycarbonate polyol is obtained by the reaction of the above lower molecular weight diol with a carbonate or phosgene.

[0111] Examples of commercially available products of the above 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 KYOWAPOLE series manufactured by Kyowa Hakko Chemical Co., Ltd.

[0112] As a commercially available product of the above high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. etc. can be used.

[0113] Examples of commercially available products of the above high molecular weight polycarbonate polyols include OXYMER N112 manufactured by PERSTORP AB, the PCDL series manufactured by Asahi Kasei Chemicals Corporation, the KURARAY polyol PMHC series and the KURARAY polyol C series manufactured by KURARAY Co., Ltd. etc.

[0114] Examples of commercially available products of the above polyurethane polyols include the VYLON UR series manufactured by Toyobo Co., Ltd., TAKELEC E158 (hydroxyl value = 20, acid value < 3), TAKELEC E551T (hydroxyl value = 30, acid value < 3) and TAKELEC Y2789 (hydroxyl value = 10, acid value < 2) manufactured by Mitsui Chemicals Polyurethanes, Inc. etc.

[0115] In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly(β-methyl-γ-valerolactone) diol, polyvalerolactone diol, etc. are also included in the high molecular weight polyols that can be used as the above high molecular weight polyols.

[0116] Epoxy acrylate (O-3) is a compound obtained by reacting the carboxyl group in a carboxyl group-containing (meth)acrylate compound with the epoxy group in an epoxy compound having two or more epoxy groups in approximately equal amounts. Alternatively, it is a compound obtained by reacting the carboxyl group in a polybasic acid with the epoxy group in an epoxy compound having two or more epoxy groups in a proportion less than the equivalent amount, leaving residual epoxy groups, and then reacting the carboxyl group in the carboxyl group-containing (meth)acrylate compound with the remaining epoxy groups in an approximately equal amount. In either case, by making the balance between "carboxyl group" and "epoxy group" in the entire reaction system within ±10% of equivalence, the carboxyl group or epoxy group is less likely to remain in the adhesive of the present invention, and the storage stability of the adhesive becomes good, so it is preferred.

[0117] As the epoxy compound having two or more epoxy groups, any compound containing two epoxy groups may be used, and there is no particular limitation. Specifically, for example, cresol novolak type epoxy compounds, phenol novolak type epoxy compounds, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A-epichlorohydrin type epoxy resin, bisphenol F-epichlorohydrin type epoxy resin, biphenol-epichlorohydrin type epoxy resin, polyglycidyl ether of glycerol-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 type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenyl sulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorene diglycidyl ether, biscresol fluorene diglycidyl ether, bisphenoxyethanol fluorene diglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-diglycidylaniline, N,N-diglycidyltoluidine, and epoxy compounds with excellent flexibility disclosed in JP-A-2004-156024, JP-A-2004-315595, and JP-A-2004-323777, etc.

[0118] Among them, epoxy resins containing bisphenol A, bisphenol F, biphenyl, and fluorene skeletons are preferred because the refractive index of the finally obtained epoxy (meth)acrylate (O-3) becomes high.

[0119] In the present invention, the epoxy compound having two or more epoxy groups can be used alone or in combination of multiple kinds.

[0120] As a carboxyl group-containing (meth)acrylate compound that can be used in the production of epoxy (meth)acrylate (O-3), examples include substances obtained by semi-esterifying (meth)acrylic acid, crotonic acid, or dibasic acids (such as maleic acid, fumaric acid, itaconic acid, phthalic acid, succinic acid, etc.) with a hydroxyl group-containing acrylate compound, substances obtained by semi-esterifying a dibasic acid anhydride with a hydroxyl group-containing acrylate compound, substances obtained by semi-esterifying itaconic anhydride with an alkyl alcohol, and substances obtained by adding several moles of ε-caprolactone to these compounds. The polybasic acids that can be used in the production of epoxy (meth)acrylate (O-3) can be the polybasic acids exemplified as those used in the production of polyester (meth)acrylate (O-2).

[0121] <Polyfunctional monomer (M2)>

[0122] Compound (M2) is a compound having two or more ethylenically unsaturated double bond groups. By including compound (M2), the crosslinking density of the adhesive cured film is increased, the destruction of the cured film is less likely to occur, and the adhesive strength is increased. In 100% by mass of the active energy ray-curable adhesive, compound (M2) is preferably contained in an amount of 1 to 50% by mass, more preferably 1 to 30% by mass. If it is within this range, the crosslinking density of the adhesive cured film is appropriate, the destruction of the cured film is less likely to occur, and peeling from the substrate interface is less likely to occur, so the adhesive strength is increased. The weight average molecular weight of compound (M2) is preferably less than 1000, more preferably less than 500. When the weight average molecular weight of compound (M2) is less than 1000, the viscosity of the resin composition does not become too high, and the control of the film thickness during coating becomes easy.

[0123] Examples of compound (M2) include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-dimethylpropyl glycol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, and 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, bisphenol A ethoxylated di(meth)acrylate, bisphenol F ethoxylated di(meth)acrylate, ethylene glycol-modified bisphenol fluorene di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, sorbitol di(meth)acrylate, isocyanuric acid ethoxylated diacrylate, etc., bifunctional (meth)acrylate esters;

[0124] For example, trifunctional (meth)acrylate compounds such as tris(2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, sorbitol triacrylate, 1,1,1-trimethylol ethane triacrylate, and isocyanuric acid tris(2-acryloyloxyethyl) ester;

[0125] For example, tetrafunctional (meth)acrylate compounds such as pentaerythritol tetraacrylate, 2,2-bis(hydroxymethyl)-1,3-propanediol tetraacrylate, sorbitol tetraacrylate, and bis-trimethylolpropane tetraacrylate.

[0126] Regarding the compound (M2), since bifunctional or trifunctional (meth)acrylate having any one of an alkylene group having 7 to 20 carbon atoms, an alicyclic structure, and a heterocyclic structure has excellent adhesion to the substrate (F1), it is preferred, and 1,9-nonanediol diacrylate, dimethylol dicyclopentane di(meth)acrylate, and isocyanuric acid tris(2-acryloyloxyethyl) ester are preferred. The compound (M2) can be used alone or in combination of two or more.

[0127] <Silane compound (S)>

[0128] The silane compound (S) can be used without particular limitation as long as it is a compound having an alkoxysilyl group structure. The active energy ray-curable adhesive of the present invention has improved heat and humidity resistance by containing the silane compound (S). If the silane compound (S) has a reactive functional group, the adhesive strength and heat and humidity resistance are excellent, and thus it is preferred. Among them, the reactive functional group of the compound (S) is more preferably an epoxy group or an isocyanate group.

[0129] Examples of the silane compound (S) include: silane compounds having a methacryloyloxy group, an alkyl group, and two alkoxy groups such as γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltributoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxysilane;

[0130] Silane compounds having an acryloyloxy group, an alkyl group, and two alkoxy groups such as γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane;

[0131] Silane compounds having a (meth)acryloyloxyalkyl group and three alkoxy groups such as γ-methacryloyloxymethyltrimethoxysilane and γ-acryloyloxymethyltrimethoxysilane;

[0132] Alkoxysilanes having vinyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinyltris(2-methoxyethoxy)silane;

[0133] Silane compounds having mercapto and alkoxy groups such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, 10-mercapto decyltrimethoxysilane;

[0134] Silane compounds having epoxy and alkoxy groups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane;

[0135] Silane compounds having isocyanate and alkoxy groups such as 3-isocyanatopropyltriethoxysilane.

[0136] The silane compounds can be used alone or in combination of two or more.

[0137] Among the above silane compounds, in order to improve the moisture resistance and the adhesiveness to hydrophilic substrates, silane compounds containing epoxy groups or isocyanate groups are preferred, and silane compounds containing epoxy groups are more preferred.

[0138] In 100% by mass of the active energy ray curable adhesive, the content of the silane compound is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass. If it is 1% by mass or more, the moisture resistance is further improved, and if it is 30% by mass or less, the balance between the adhesive force and the moisture resistance is good.

[0139] <Free radical polymerization initiator (E)>

[0140] In the active energy ray curable adhesive of the present invention, it is further preferred to contain a free radical polymerization initiator (E). By using the free radical polymerization initiator (E), the free radical polymerization reaction can be promoted.

[0141] As the radical polymerization initiator (E), it can be arbitrarily selected and used from known radical polymerization initiators. 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-oxanthrone, camphorquinone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc. As commercially available products, for example, Irgacure-184, 907, 651, 1700, 1800, 819, 369, 261, Darocure-TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide manufactured by BASF), OMnirad819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide manufactured by IGM Resins B.V), Darocure-1173 (manufactured by Merck), Esacure-KIP150, TZT (manufactured by Japanese Siberhegner), Kayacure BMS, Kayacure DMBI (manufactured by Japanese Kayaku), etc. can be cited.

[0142] From the viewpoint of having photo-bleaching property, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred.

[0143] The content rate of the radical initiator (E) is preferably 0.01 to 20% by mass in 100% by mass of the active energy ray-curable adhesive.

[0144] <Photoacid generator (G)>

[0145] The acid generator (G) generates an acid by irradiating active energy rays such as visible light, ultraviolet rays, X-rays or electron beams, and catalytically acts to initiate the polymerization reaction of a silane compound or a cationic polymerizable compound. As the acid generator, for example, sulfonium salt-based acid generators, iodonium salt-based acid generators, diazonium salt-based acid generators, ammonium salt-based acid generators, phosphonium salt-based acid generators and other onium salt-based acid generators can be cited.

[0146] Among them, from the viewpoint of being able to obtain an active energy ray-curable adhesive with excellent photo-decomposition efficiency and more excellent curability, sulfonium salt-based acid generators and iodonium salt-based acid generators are preferred.

[0147] From the viewpoint of the curability of the active energy ray-curable adhesive, in 100% by mass of the active energy ray-curable adhesive, the content rate of the acid generator (G) is preferably 0.1% by mass or more. On the other hand, from the viewpoint of the heat and humidity resistance, it is preferably 20% by mass or less, and more preferably 0.5 to 10% by mass.

[0148] Examples of the sulfonium salt-based acid generator include triaryl sulfonium hexafluorophosphate, triaryl sulfonium hexafluoroantimonate, triaryl sulfonium tetrakis(pentafluorophenyl)borate, etc.

[0149] Examples of commercially available products of the sulfonium salt-based acid generator include triaryl sulfonium hexafluorophosphate (CPI-110P, manufactured by San-Apro), UVACURE1590 (manufactured by Daicel-Cytec), etc.

[0150] Examples of the iodonium salt-based acid generator include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate, (4-methylphenyl)(4-isopropylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakis(pentafluoro)borate, etc.

[0151] Examples of commercially available products of the iodonium salt-based acid generator include bis(4-tert-butylphenyl)iodonium hexafluorophosphate (WPI-170, manufactured by Wako Pure Chemical Industries, Ltd.), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), IK-1 (manufactured by San-Apro), (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate (OMnicat250, IGM resins), etc.

[0152] <Active energy ray sensitizer (H)>

[0153] In addition, 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. Examples of the sensitizer (H) include thioxanthone compounds, anthracene compounds, naphthalene compounds, aminobenzoate compounds, carbazole compounds, perylene, phenothiazine, eosin, etc.

[0154] Examples of the sensitizer (H) include thioxanthone-based compounds such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-hydroxythioxanthone, 2-acetoxythioxanthone, 2-propoxythioxanthone, etc.;

[0155] Anthracene-based compounds such as 9,10-dimethoxyanthracene, 9,10-ethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, etc.;

[0156] Naphthalene compounds such as 1,4 - dimethoxynaphthalene, 1,4 - diethoxynaphthalene, 1,4 - dipropoxynaphthalene, 1,4 - dibutoxynaphthalene, etc.

[0157] <Other components>

[0158] In the active energy ray - curable adhesive of the present invention, as long as it is within the range not impairing the effects of the present invention, in addition to the above - mentioned components, additives can also be appropriately blended. For example, from the viewpoints of reducing the polymerization - curing shrinkage rate, reducing the thermal expansion rate, improving the dimensional stability, improving the elastic modulus, adjusting the viscosity, improving the thermal conductivity, improving the strength, improving the toughness, improving the coloring, etc., organic or inorganic fillers can be blended. As such fillers, polymers, ceramics, metals, metal oxides, metal salts, dye pigments, etc. can be used, and the shape is not particularly limited to particulate, fibrous, etc. It should be noted that when blending the above - mentioned polymers, softening agents, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy - imparting agents, dispersion stabilizers, fluidity - imparting agents, defoaming agents, etc. can be dissolved, semi - dissolved or micro - dispersed in the active energy ray - curable adhesive not as fillers but as polymer blends or polymer alloys.

[0159] The active energy ray - curable adhesive of the present invention preferably contains substantially no water and organic solvents in terms of drying equipment and drying energy. However, when the radical initiator (E), photo - acid generator (F) and sensitizer (G) are poorly soluble in the compound (M1) or become highly viscous, a small amount of water or organic solvent may be included to dissolve the radical initiator (E), photo - acid generator (F) and sensitizer (G). The content of water or organic solvent in the active energy ray - curable adhesive is within 5% by mass. The organic solvents that can be used are not particularly limited. Specifically, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, other hydrocarbon - based solvents, etc. and water can be further added to adjust the viscosity of the active energy ray - curable adhesive, and the active energy ray - curable adhesive can also be heated to reduce the viscosity.

[0160] <Film>

[0161] The film is preferably a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, and isotropy, for example. Regarding the film, there is a film (F1) composed of a cycloolefin - based resin having a polar group and a film (F2) other than that. The polar group refers to a polar functional group or atomic group. For example, carboxyl group, hydroxyl group, amino group, carbonyl group, ester bond, ether bond, amide group, carbonate group, urethane group, imide group, cyano group, or a structure directly bonded by a halogen atom having a higher electronegativity than carbon atom, etc. are exemplified, and there is no limitation as long as it is a functional group having a larger polarity than the olefin structure.

[0162] The film (F1) is not limited as long as it has a polar structure and a norbornene structure in the monomer structure of the resin. Examples of the film (F1) include a resin containing a norbornene monomer having a polar group as a structural unit, a copolymer resin of a norbornene monomer having no polar group and a monomer having a polar group but no norbornene, or a mixed resin of a norbornene polymer having no polar group and a resin composed of a monomer having a polar group but no norbornene, etc., and they may also be mixed resins. The film (F1) preferably contains a resin containing a norbornene monomer having a polar group as a structural unit.

[0163] The norbornene resin having a polar group may be a copolymer resin of a norbornene monomer having a polar group and other monomers. Examples of other monomers include a norbornene monomer having no polar group, a monomer having a polar group but no norbornene skeleton, an olefin other than norbornene, etc. In addition, a mixed resin of a norbornene resin having a polar group and other resins may also be used.

[0164] The norbornene monomer having a polar group is represented by the general formula (a-1) or (a-2).

[0165] General formula (a-1)

[0166]

[0167] In the general formula (a-1), at least one of R 1 ~R 4 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 from 0 to 2. Among them, R 1 and R 2 do not simultaneously represent hydrogen atoms, and R 3 and R 4 do not simultaneously represent hydrogen atoms.

[0168] The hydrocarbon group having 1 to 30 carbon atoms may further have a linking group containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Examples of such a linking group include divalent polar groups such as a carbonyl group, an imino group, an ether bond, a silyl ether bond, and a thioether bond.

[0169] In the general formula (a-1), examples of the polar group represented by R 1 ~R 4 include a carboxyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide group, and a cyano group.

[0170] General formula (a-2)

[0171]

[0172] In general formula (a-2), R 5 represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an alkylsilyl group having an alkyl group with 1 to 5 carbon atoms. R 6 represents a polar group. Specifically, it represents a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide 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 from 0 to 2.

[0173] The cycloolefin monomer having no polar group is represented by general formula (a-3).

[0174] General formula (a-3)

[0175]

[0176] 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. p represents an integer from 0 to 2.

[0177] Examples of the monomer having a polar group include (meth)acrylate monomers having 1 to 20 carbon atoms such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate having an ester bond;

[0178] vinyl ether monomers having an ether bond such as 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether;

[0179] vinyl ester monomers having an ester bond such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate;

[0180] vinyl amide monomers having an amide bond such as vinyl formamide, vinyl acetamide, and vinyl pyrrolidone;

[0181] olefin compounds having a polar group, and the like.

[0182] Examples of the film (F2) include polyolefin-based films such as a polyvinyl alcohol film, a polytriacetyl cellulose film, polypropylene, polyethylene, a cycloolefin polymer containing no monomer unit having a polar group, and an ethylene-vinyl acetate copolymer; polyester-based films such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate-based films, polyarylate-based films, polyacrylic acid-based films, polyphenylene sulfide-based films, polystyrene-based films, polyethylene-based films, polyamide-based films, polyimide-based films, and polyethylene oxide-based films.

[0183] The thickness of the film can be appropriately determined. Generally, from the viewpoints of workability such as strength and processability, and thin layer properties, etc., it is preferably 1 to 100 μM, more preferably 5 to 50 μM.

[0184] <Laminated body>

[0185] The laminated body of the present invention is preferably used as an optical laminated body, and more preferably as a laminated body for optical elements. The laminated structure of the laminated body of the present invention sequentially includes a film (F1), an adhesive layer composed of the active energy ray curable adhesive of the present invention, and a film (F1) or a film (F2). A laminated body formed by overlapping three or more substrates such as film (F1) / adhesive layer / film (F2) / adhesive layer / film (F2) is preferred.

[0186] When the laminated body of the present invention is used for optical element applications, it is preferable to use a transparent film or an optical film. An optical film is a film obtained by coating a transparent film with a coating liquid having an optical function to impart an optical function. Optical functions include phase difference, light diffusion, light condensation, refraction, scattering, haze (HAZE), etc. Examples of optical films include hard coat films, antistatic coating films, antiglare coating films, polarizing films, phase difference films, elliptically polarized films, antireflection films, light diffusion films, brightness enhancement films, prism films (also called prism sheets), and light guide films (also called light guide plates). These can be used alone or in combination of two or more according to the application.

[0187] The laminated body of the present invention can also be used as a polarizing plate film. In this case, the laminated body is preferably a laminated body such as film (F1) / adhesive layer / polyvinyl alcohol-based polarizing film (film (F2)) / adhesive layer / film (F2). For film (F1) and film (F2), it is preferable to use a transparent film or an optical film.

[0188] The laminated body can be obtained as follows. A film is formed by coating an active energy ray curable adhesive on one surface of a transparent film as a film-like substrate, and another transparent film is laminated on the formed film. Then, an active energy ray curable adhesive is coated on one surface or both surfaces of the laminated body, and further laminated on another transparent film, glass, or transparent molded body, thereby obtaining a laminated body.

[0189] There is no particular limitation on the film thickness of the adhesive layer formed by the active energy ray curable adhesive of the present invention, and it can be appropriately adjusted according to the use purpose.

[0190] When the film 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, when coated on a substrate, a thin film coating of 0.1 to 6 μM can be performed, and optical properties such as transmittance are also excellent. On the other hand, if the viscosity is 1 MPa·s or more, the control of the film thickness of the adhesive layer becomes easy, so it is preferred.

[0191] In addition, when the film thickness of the adhesive layer is 6 to 300 μM, the viscosity is preferably 1,000 to 100,000 MPa·s, more preferably 3,000 to 50,000 MPa·s.

[0192] <Coating method>

[0193] The coating method of the active energy ray-curable adhesive of the present invention can utilize known coating methods such as a Mayer rod, a coater, a brush, a sprayer, a roller, a gravure coater, a die coater, a microgravure coater, a lip coater, a bevel wheel coater, a curtain coater, a knife coater, a reverse roll coater, a spin coater, etc.

[0194] 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 required. The active energy ray polymerization reaction is carried out by irradiating active energy rays during or at the time of lamination of the resin composition, and further after lamination, but it is preferably carried out by irradiating active energy rays after lamination to carry out the polymerization reaction.

[0195] <Active energy rays>

[0196] The active energy ray-curable adhesive of the present invention is coated on a substrate, and the formed film is irradiated with active energy rays to carry out polymerization curing. As the irradiation light source of the active energy rays, the light in the wavelength region of 150 to 550 nM is mainly used, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a gallium lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, an LED lamp, a xenon lamp, etc. In addition, a semiconductor laser, an electron beam, etc. can also be used as the active energy rays.

[0197] The irradiation intensity of ultraviolet rays is preferably 10 to 3000 mW / cm² 2 . If the irradiation intensity satisfies the above range, rapid curing becomes easy, and the deterioration of the substrate can be suppressed to a minimum. The cumulative irradiation amount expressed in the form of the product of the irradiation intensity and the irradiation time is preferably 50 to 20,000 MJ / cm² 2 . If the cumulative irradiation amount satisfies the above cumulative irradiation amount, short-time curing becomes easy and the productivity is further improved.

[0198] The polarizing plate (polarizing film) using the active energy ray-curable adhesive can be obtained more specifically as follows.

[0199] The polarizing plate (polarizing film) using the active energy ray-curable adhesive is preferably produced by any one of the following methods (I) to (III), etc., but is not particularly limited.

[0200] (I) A photo-curable adhesive is coated on one surface of a protective film as the first transparent film to form a first polymerizable adhesive layer.

[0201] A photo-curable adhesive is coated on one surface of a second protective film as the transparent film to form a second photo-curable adhesive layer.

[0202] Then, the first photo-curable adhesive layer surface and the second photo-curable adhesive layer surface are simultaneously or sequentially overlapped on each surface of the polyvinyl alcohol-based polarizing plate, and then photo-energy rays are irradiated to polymerize and cure the first photo-curable adhesive layer and the second photo-curable adhesive layer, thereby manufacturing.

[0203] (II) A photo-curable adhesive is coated on one surface of the polyvinyl alcohol-based polarizing plate to form a first photo-curable adhesive layer, and the surface of the formed first photo-curable adhesive layer is covered with a first protective film as the transparent film. Then, a photo-curable adhesive is coated on the other surface of the polyvinyl alcohol-based polarizing plate to form a second photo-curable adhesive layer, and the surface of the formed second photo-curable adhesive layer is covered with a second protective film. Photo-energy rays are irradiated to polymerize and cure the first photo-curable adhesive layer and the second photo-curable adhesive layer, thereby manufacturing.

[0204] (III) A photo-curable adhesive is accumulated at the end where the protective film as the first transparent film is overlapped with the polyvinyl alcohol-based polarizing plate and at the end of the second protective film that is overlapped with the surface of the polyvinyl alcohol-based polarizing plate that does not have the first protective film. Then, it is passed between rollers to spread the adhesive between the layers. Then, photo-energy rays are irradiated to polymerize and cure the photo-curable adhesive, thereby manufacturing.

[0205] Examples

[0206] Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. In addition, in the following examples and comparative examples, "parts" and "%" represent "parts by mass" and "mass%", respectively, and "RH" represents relative humidity.

[0207] In addition, the compounding amounts in the table are parts by mass, and the values other than the solvent are converted values of non-volatile components. In addition, the blank in the table indicates non-compounding.

[0208] <Method for measuring weight-average molecular weight>

[0209] "Weight-average molecular weight" is a value measured using the gel permeation chromatography "HLC-8220GPC" manufactured by Tosoh Corporation. Separation columns: Four "TSK-GEL SUPER H5000", "TSK-GEL SUPER H4000", "TSK-GEL SUPER H3000", and "TSK-GEL SUPER H2000" manufactured by Tosoh Corporation are connected in series. Tetrahydrofuran at a temperature of 40°C is used as the mobile phase, and the weight-average molecular weight in terms of polystyrene is measured at a flow rate of 0.6 Ml / minute.

[0210] <Method for Measuring Hydroxyl Value>

[0211] The measurement of the hydroxyl value is as described below. Precisely weigh approximately 1 g of the sample into a conical flask with a stopper, add 100 Ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1) mixture and dissolve it. Then, precisely add 5 Ml of an acetylating agent (a solution prepared by dissolving 25 g of acetic anhydride in pyridine to make a 100 Ml solution), and stir for about 1 hour. Add phenolphthalein test solution as an indicator and continue stirring for 30 seconds. Thereafter, titrate with 0.1 N alcoholic potassium hydroxide solution until the solution turns light pink, and calculate the hydroxyl value using the following formula. The hydroxyl value is the value in the dry state of the resin (unit: MgKOH / g).

[0212] Hydroxyl value (Mg KOH / g) = [{(b - a) × F × 28.25} / S] / (non-volatile component concentration / 100) + D

[0213] Where, S: Sampling amount of the sample (g),

[0214] a: Consumption of 0.1 N alcoholic potassium hydroxide solution (Ml),

[0215] b: Consumption of 0.1 N alcoholic potassium hydroxide solution in the blank experiment (Ml),

[0216] F: Valence of 0.1 N alcoholic potassium hydroxide solution,

[0217] D: Acid value (Mg KOH / g).

[0218] The materials used in the examples and comparative examples are as described below.

[0219] <Mono-functional monomer (M1)>

[0220] · Mono-functional monomer (M1-1) having 7 or more carbon atoms and no hydroxyl group

[0221] LA: Lauryl acrylate

[0222] IBXA: Isobornyl acrylate

[0223] BzA: Benzyl acrylate

[0224] MEDOLMA: Methyl (2-methyl-1,3-dioxolan-4-yl)methyl acrylate M5300: ω-carboxy-polycaprolactone (n≈2) monoacrylate

[0225] · Monofunctional monomer (M1-2) containing a hydroxyl group

[0226] 4HBA: 4-Hydroxybutyl acrylate

[0227] CHDMMA: Cyclohexanedimethanol monoacrylate

[0228] · Other monofunctional monomers (M1-3)

[0229] THFA: Tetrahydrofurfuryl acrylate

[0230] <Polyfunctional monomer (M2)>

[0231] 1,9NDDA: 1,9-Nonanediol diacrylate

[0232] DCPDA: Dicyclopentyl dimethylene diacrylate

[0233] INANTA: EO-modified triacrylate isocyanurate

[0234] DPGDA: Dipropylene glycol diacrylate

[0235] <Oligomer (O)>

[0236] · Urethane acrylate (O-1):

[0237] <Manufacture of urethane acrylate 1>

[0238] In a five-neck separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer, and a dropping funnel, 200.0 parts of polypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd.: SANNIX PP-1000, hydroxyl value 112 MgKOH / g) and 49.5 parts of isophorone diisocyanate were added, and the temperature was raised to 60 °C while introducing dry air. 0.05 part of dibutyltin dilaurate was added thereto, and the reaction was carried out for 2 hours. Separately, 5.2 parts of 4-hydroxybutyl acrylate and 0.05 part of hydroquinone monomethyl ether were placed in the dropping funnel and added dropwise to the separable flask over 1 hour. After completion of the dropwise addition, stirring was continued at 80 °C for 3 hours, and then the absence of an absorption peak of the isocyanate group was confirmed by infrared absorption spectroscopy to terminate the reaction, obtaining urethane acrylate 1. Its weight average molecular weight was 15,000.

[0239] <Manufacture of urethane acrylate 2>

[0240] In a five-neck separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer, and a dropping funnel, 222.2 parts of polytetramethylene glycol (manufactured by Hodogaya Chemical Co., Ltd.: PTG2000, hydroxyl value 56 MgKOH / g) and 28.0 parts of isophorone diisocyanate were added, and the temperature was raised to 60 °C while introducing dry air. 0.05 part of dibutyltin dilaurate was added thereto, and the reaction was carried out for 1 hour. Separately, 3.7 parts of 4-hydroxybutyl acrylate and 0.05 part of hydroquinone monomethyl ether were placed in the dropping funnel, and the mixture was added dropwise to the separable flask over 1 hour. After the addition was completed, stirring was continued at 80 °C for 3 hours, and then the absence of an absorption peak of isocyanate groups was confirmed by infrared absorption spectroscopy to end the reaction, obtaining urethane acrylate 2. Its weight-average molecular weight was 22,000.

[0241] <Production of urethane acrylate 3>

[0242] In a five-neck 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 part of zinc oxide were added. Under normal pressure, while introducing dry air, the condensed water formed was distilled off at 210 °C, and esterification was carried out simultaneously. After confirming that the acid value became 2 MgKOH / g, the pressure was reduced, the temperature inside the flask was raised to 260 °C, and the reaction for removing ethylene glycol was carried out for 10 hours. The OH value was 8.9 MgKOH / g. Then, 3.4 parts of isophorone diisocyanate were added to 250 parts of the obtained polyester diol, dry air was introduced, and the temperature was raised to 60 °C at the same time. 0.05 part of dibutyltin dilaurate was added thereto, and the reaction was carried out for 1 hour. Separately, 1.7 parts of 4-hydroxybutyl acrylate and 0.05 part of hydroquinone monomethyl ether were placed in the dropping funnel, and the mixture was added dropwise to the separable flask over 1 hour. After the addition was completed, stirring was continued at 80 °C for 3 hours, and then the absence of an absorption peak of isocyanate groups was confirmed by infrared absorption spectroscopy to end the reaction, obtaining urethane acrylate 3. Its weight-average molecular weight was 49,000.

[0243] <Production of urethane acrylate 4>

[0244] In a five-neck 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 part of zinc oxide were charged. Under atmospheric pressure, while passing dry air and distilling off the generated condensation water at 210 °C, esterification was carried out. After confirming that the acid value became 2 MgKOH / g, the pressure was reduced, the temperature inside the flask was raised to 260 °C, and the glycol removal reaction was carried out for 10 hours. The OH value was 7.2 MgKOH / g. Then, 3.5 parts of isophorone diisocyanate were added to 250 parts of the obtained polyester diol, dry air was introduced, and the temperature was raised to 60 °C at the same time. 0.05 part of dibutyltin dilaurate was added thereto, and the reaction was carried out for 1 hour. Separately, 2.4 parts of 4-hydroxybutyl acrylate and 0.05 part of hydroquinone monomethyl ether were charged into a dropping funnel, and the mixture was added dropwise to the separable flask over 1 hour. After the dropping was completed, stirring was continued at 80 °C for 3 hours, and then the absence of an absorption peak of the isocyanate group was confirmed by infrared absorption spectroscopy to end the reaction, obtaining urethane acrylate 4. Its weight-average molecular weight was 34,000.

[0245] <Production of urethane acrylate 5>

[0246] In a five-neck separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer, and a dropping funnel, 250 parts of polybutadiene having hydroxyl groups introduced at both ends (manufactured by Nippon Soda Co., Ltd.: GI-1000, hydroxyl value 67 MgKOH / g, number-average molecular weight 1500) and 47.8 parts of isophorone diisocyanate were added, and the temperature was raised to 60 °C while introducing dry air. 0.05 part of dibutyltin dilaurate was added thereto, and the reaction was carried out for 1 hour. Separately, 13.2 parts of 4-hydroxybutyl acrylate and 0.05 part of hydroquinone monomethyl ether were charged into a dropping funnel, and the mixture was added dropwise to the separable flask over 1 hour. After the dropping was completed, stirring was continued at 80 °C for 3 hours, and then the absence of an absorption peak of the isocyanate group was confirmed by infrared absorption spectroscopy to end the reaction, obtaining urethane acrylate 5. Its weight-average molecular weight was 8,200.

[0247] · Polyester acrylate (O-2):

[0248] <Production of polyester acrylate 1>

[0249] In a five-neck 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 part of zinc oxide were added. Under normal pressure, while introducing dry air, the condensed water generated was distilled off at 210 °C, and esterification was carried out simultaneously to obtain a polyester dicarboxylic acid with an acid value of 22.8 MgKOH / g. Next, with respect to 250 g of the obtained polyester dicarboxylic acid, 21.0 parts of glycidyl acrylate 4-hydroxybutyl ether, 0.01 part of tetrabutylammonium borate, and 0.05 part of hydroquinone monomethyl ether were added, 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 5400.

[0250] · Epoxy acrylate (O-3)

[0251] <Manufacture of epoxy acrylate 1>

[0252] In a five-neck separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, 250.0 parts of bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical Corporation: JER4005P, epoxy equivalent 1075), 34.0 parts of acrylic acid, 0.05 part of hydroquinone monomethyl ether, and 20 parts of MEK were charged and dissolved while introducing dry air and heating to 60 °C. 0.5 part of tetrabutylammonium borate was added thereto, and the temperature was raised to 100 °C and reacted for 8 hours to obtain epoxy acrylate 1. The weight-average molecular weight of epoxy acrylate 1 was 2500.

[0253] · Acrylic acid acrylate (O-4)

[0254] XMAP RC100C (acrylic acid acrylate manufactured by Kaneka Corporation, Mw = 25000)

[0255] <Silane compound (S)>

[0256] KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0257] KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0258] KBM-5103: 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0259] KBE-9007: 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0260] TEMS: Tetramethoxysilane

[0261] <Free Radical Initiator (E)>

[0262] TPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (OMnirad TPO manufactured by IGM resins BV)

[0263] <Photoacid generator (G)>

[0264] CPI-110P: Triarylsulfonium-PF manufactured by San-Apro 6 Salt-type photoacid generator

[0265] OMnicat250: 4-isobutylphenyl (4-methylphenyl) iodonium hexafluorophosphate (manufactured by IGM resins BV)

[0266] <Active Energy Ray Sensitizer (H)>

[0267] ITX: 2-isopropylthioxanthone

[0268] DBA: 9,10-Dibutoxyanthracene

[0269] <Film (F1) Composed of Cycloolefin Resin Having a Polar Group>

[0270] Use of 8-methyl-8-methoxycarbonyl tetracyclo[4.4.0.1 2,5 .1 7,10 ]A film composed of a resin obtained by polymerizing 3-dodecene (in the general formula (2), p is 1, R5 is a carbon atom, and R6 is a methoxycarbonyl group).

[0271] [Example 1]

[0272] 14 parts of IBXA as a monofunctional monomer (M1), 30 parts of BzA, 40 parts of MEDOLMA, 10 parts of M5300, 3 parts of TPO as a free radical polymerization initiator (E), and 3 parts of ITX as an active energy ray sensitizer (H) are put into a light-shielded 300 ml glass bottle, and after being fully stirred with a disperser, the mixture is fully degassed to obtain an active energy ray-curable adhesive.

[0273] [Examples 2 to 45, Comparative Examples 1 to 3]

[0274] As shown in Tables 1 to 3, an active energy ray-curable adhesive was obtained in the same manner as in Example 1 except that the composition and the blending amount (parts by mass) were changed.

[0275] 《Evaluation of laminated bodies》

[0276] The obtained energy ray-curable adhesive was used to fabricate the following laminate X1, and the laminate was evaluated by the following method. The results are shown in Tables 1 to 3.

[0277] <Fabrication of Laminate X1 (Polarizing Plate)>

[0278] As the film (F1), a film with a thickness of 40 μM made of a norbornene resin having polar groups but not containing an ultraviolet absorber was used. As the film (F2), a triacetyl cellulose film (hereinafter referred to as TAC) with a thickness of 50 μM containing an ultraviolet absorber was used. On one surface of the films (F1) and (F2), corona treatment was performed at a discharge amount of 300 W·Min / M 2 Then, within 1 hour, the energy ray-curable adhesives shown in Tables 1 to 3 were coated on the corona-treated surfaces of the respective films using a wire bar coater so that the thickness became 2 μM, forming a coating film. A polyvinyl alcohol-based (hereinafter simply referred to as PVA) polarizing plate (film (F2)) was sandwiched between the energy ray-curable adhesive layers formed on the aforementioned films (F1) and (F2), obtaining a laminate composed of a norbornene resin film having polar groups / adhesive layer / PVA polarizing plate / adhesive layer / TAC (i.e., film (F1) / adhesive layer / film (F2) / adhesive layer / film (F2)). The periphery of this laminate was fixed to a tin plate with transparent tape in such a manner that TAC was in contact with the tin plate.

[0279] The laminate was irradiated with ultraviolet rays having a maximum illuminance of 300 mW / cm 2 and an accumulated light amount of 300 MJ / cm 2 from the film (F1) side using an energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba Corporation), fabricating the laminate X1 (polarizing plate).

[0280] <Fabrication of Laminate X2>

[0281] As the film (F1), a film with a thickness of 40 μM made of a norbornene resin having polar groups but not containing an ultraviolet absorber was used. As the film (F2), a polyester film (hereinafter referred to as PET) with a thickness of 60 μM containing an ultraviolet absorber was used. On one surface of the films (F1) and (F2), corona treatment was performed at a discharge amount of 300 W·Min / M 2 Then, within 1 hour, the energy ray-curable adhesives shown in Tables 1 to 3 were coated on the corona-treated surface of the film (F1) using a wire bar coater so that the thickness became 10 μM, forming a coating film. The film (F1) was laminated with the film (F2), obtaining a laminate composed of a norbornene resin film having polar groups / adhesive layer / PET (i.e., film (F1) / adhesive layer / film (F2)). The periphery of this laminate was fixed to a tin plate with transparent tape in such a manner that PET was in contact with the tin plate.

[0282] Irradiate from the side of the film (F1) with an active energy ray irradiating device (high-pressure mercury lamp manufactured by Toshiba Corporation) at a maximum illuminance of 300 mW / cm² 2 and a cumulative light quantity of 300 MJ / cm² 2 of ultraviolet rays to form a laminate X2.

[0283] <Adhesion of laminate X1>

[0284] Cut the obtained laminate X1 (polarizing plate) into a size of 25 mm × 150 mm with a cutter to be used as a measurement sample. Stick a double-sided adhesive tape (DF8712S manufactured by TOYOCHEM Co., Ltd.) on the surface of the transparent film (1) of the sample, and use a laminator to laminate it on a metal plate to obtain a laminate of the polarizing plate and the metal plate. Use the obtained laminate as a laminate for measuring adhesion. In the polarizing plate, a peeling trigger is preset between the film (F1) and the polarizer. Peel the measurement laminate at a speed of 300 mm / minute at an angle of 90° under the conditions of 23°C and 50% RH as the peeling force. At this time, measure the peeling force between the PVA polarizer and the film (F1).

[0285] <Adhesion of laminate X2>

[0286] Cut the obtained laminate X2 into a size of 25 mm × 150 mm with a cutter to be used as a measurement sample. Stick a double-sided adhesive tape (DF8712S manufactured by TOYOCHEM Co., Ltd.) on the surface of the transparent film (1) of the sample, and use a laminator to laminate it on a metal plate to obtain a laminate of the laminate X2 and the metal plate. Use the obtained laminate as a laminate for measuring adhesion. In the laminate X2, a peeling trigger is preset between the film (F1) and the PET. Peel the measurement laminate at a speed of 300 mm / minute at an angle of 90° under the conditions of 23°C and 50% RH as the peeling force. At this time, measure the peeling force between the film (F1) and the PET.

[0287] Evaluate the peeling forces of the laminate X1 and the laminate X2 as adhesion in four grades.

[0288] [Evaluation criteria]

[0289] ◎: The peeling force is 2.0 (N / 25 mm) or more, which is very excellent

[0290] ○: The peeling force is 1.5 (N / 25 mm) or more and less than 2.0 (N / 25 mm), which is excellent

[0291] △: The peeling force is 1.0 (N / 25 mm) or more and less than 1.5 (N / 25 mm), which is practical

[0292] ×: The peeling force is less than 1.0 (N / 25MM) and it is not practical.

[0293] <Humidity and Heat Test>

[0294] The laminate X1 was exposed for 1000 hours under the conditions of a temperature of 60°C - 90% RH. After the exposure, the end of the laminate X1 was observed with a microscope, and the shrinkage amplitude of the PVA polarizer was measured. The measured shrinkage amplitude was evaluated in 4 grades.

[0295] ◎: The shrinkage amplitude is 0 μM or more and less than 300 μM, which is very excellent.

[0296] ○: The shrinkage amplitude is 300 μM or more and less than 600 μM, which is excellent.

[0297] △: The shrinkage amplitude is 600 μM or more and less than 1000 μM, which is practical.

[0298] ×: The shrinkage amplitude is 1000 μM or more and it is not practical.

[0299] <Haze Value Evaluation>

[0300] Under the environment of 23°C and 50% RH, using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name "SH7000"), the haze value was measured according to JIS K 7136. The measured haze value was evaluated in 4 grades.

[0301] [Evaluation Criteria]

[0302] ◎: 0 or more to less than 0.3, which is very excellent.

[0303] ○: 0.3 or more and less than 0.6, which is excellent.

[0304] △: 0.6 or more and less than 0.9, which is practical.

[0305] ×: 0.9 or more and it is not practical.

[0306] <Curling Evaluation>

[0307] In such a way that the long sides of the laminate X1 and the laminate X2 become the extending direction, it was cut into a size of 50MM × 150MM with a cutter as a measurement sample. The convex surface was placed downward on a horizontal plane, and the distances from 4 places at the end of the sample to the horizontal plane were measured. The measured values were evaluated in 4 grades.

[0308] ◎: 0 MM or more and less than 10 MM, which is very excellent.

[0309] ○: 10 MM or more and less than 20 MM, which is excellent.

[0310] △: 20 MM or more and less than 30 MM, which is practical.

[0311] ×: Over 30MM, not practical

[0312] [Table 1]

[0313]

[0314] [Table 2]

[0315]

[0316] [Table 3]

[0317]

[0318] As shown in Tables 1 to 3, it can be confirmed that the active energy ray-curable adhesive of the present invention has excellent adhesiveness, and has high moisture resistance and excellent haze and curling properties.

Claims

1. An active energy ray-curable adhesive, which is an adhesive for film lamination used in the production of a laminate, the laminate comprising a film F1 composed of a cycloolefin resin having a polar group, The monofunctional monomer M1 is contained in 100% by mass of the adhesive in an amount of 20 to 95% by mass.

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

3. The active energy ray-curable adhesive according to claim 2, wherein The monofunctional monomer M1 further includes 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 contains 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 heterocyclic ring, and the heterocyclic ring does not include a heterocyclic ring 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. 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. The active energy ray-curable adhesive according to claim 5, wherein Oligomer O comprises urethane acrylate O-1.

8. The active energy ray-curable adhesive according to claim 7, wherein Urethane acrylate O-1 is a reaction product of a polyol, a polyisocyanate and a hydroxyl-containing monofunctional monomer M1-2. The polyol is any one selected from the group consisting of a polyether polyol having an alkylene structure having 4 or more carbon atoms, a polyester polyol having 12 or more carbon atoms in a unit structure, and a polyolefin polyol. 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, wherein In the total amount 100 mass % of the adhesive, 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 are contained.

12. A laminate comprising, in this order, a film F1, an adhesive layer comprising the active energy ray-curable adhesive according to any one of claims 1 to 11, and the film F1 or the film F2, The film F2 is any one selected from the group consisting of polyvinyl alcohol films, polyacetyl cellulose films, cycloolefin polymers not containing a monomer having a polar group, polypropylene films, polyacrylic acid films, polycarbonate films, polyester films, polyimide films, and glass films.

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