Active energy ray polymerizable resin composition and laminate

Abstract

To provide an active energy-polymerizable composition which is excellent in storage stability, and has high heat resistance and excellent curability, an active energy-polymerizable composition which is applicable to a heating and coating step due to high heat resistance, and has good adhesion, moisture heat resistance and bending resistance even when an ultraviolet absorption base material is used due to excellent curability, and a laminate formed of the active energy-polymerizable composition.SOLUTION: An active energy ray-polymerizable resin composition contains 1-99 mass% of a cationic polymerizable compound (K), 0.01 mass% to 10 mass% of a sulfide compound (S) (excluding thioxanthone compound (T)), and an acid generator (KE).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-polymerizable resin composition and a laminate. [Background technology]

[0002] Active energy ray-polymerizable resin compositions have excellent properties, such as high polymerization rate, excellent workability due to the fact that they can generally be used without solvents, and extremely low energy required for polymerization. Examples of active energy ray-polymerizable resin compositions include radical-based, cationic-based, and combined radical- and cationic-based (hybrid-based) active energy ray-polymerizable resin compositions, and they are used in a wide range of fields, such as adhesives and coating agents.

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

[0004] Aqueous adhesives and active energy ray-polymerizable resin compositions are used to bond a PVA-based polarizer and a protective film, and active energy ray-polymerizable resin compositions are increasingly being used as adhesives in view of the versatility of the substrate used in the protective film, as well as production efficiency and energy saving. In particular, cationic and hybrid active energy ray-polymerizable resin compositions have been investigated in view of water resistance and moist heat resistance (Patent Documents 1 and 2).

[0005] The protective films used in polarizing plates are made of triacetyl cellulose, acrylic, cycloolefin, polyester, or polycarbonate materials. The configuration of the polarizing plate, including the protective film, is selected depending on the type of liquid crystal panel used for LCD displays. In recent years, polarizing plates have also been used as circular polarizing plates for organic EL displays by combining them with retardation films, and various protective films are selected depending on the use of the polarizing plate.

[0006] As described above, various protective films are used as the configuration of polarizing plates, and in the manufacture of polarizing plates, it is necessary to produce polarizing plates of a plurality of configurations on a single production line. Therefore, as a method for ensuring adhesive strength for a wide variety of protective films without replacing the active energy ray-polymerizable resin composition, a method of heating the active energy ray-polymerizable resin composition to erode the protective film and increase adhesive strength is sometimes used.

[0007] However, when a cationic or hybrid active energy ray-polymerizable resin composition is heated and subjected to a long run, the viscosity increases, which may cause problems in application or reduce adhesive strength.

[0008] Furthermore, in circular polarizers for organic EL displays, a film that absorbs ultraviolet rays with wavelengths of 380 nm or less (ultraviolet-absorbing substrate) may be used as a protective film for the polarizer to protect the organic EL elements from ultraviolet rays with wavelengths of 380 nm or less.

[0009] In such a polarizing plate configuration, when a polarizer and a protective film are bonded together using an active energy ray-polymerizable resin composition, even if ultraviolet light is irradiated through the ultraviolet ray-absorbing base material, ultraviolet light having a wavelength in the range in which the active energy ray-polymerizable resin composition undergoes an initiation reaction is absorbed by the ultraviolet ray-absorbing base material, which is likely to cause poor curing and makes it difficult to fully exhibit performance.

[0010] Therefore, for such polarizing plate configurations, a technology has been investigated in which a photoinitiator having an absorption edge at a wavelength longer than 380 nm is used in an active energy ray-polymerizable resin composition used to bond a polarizer and a protective film together (Patent Document 3). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-245925 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-018722 [Patent Document 3] International Publication No. 2011 / 013663 Summary of the Invention [Problem to be solved by the invention]

[0012] However, these conventional active energy ray-polymerizable resin compositions are currently unable to achieve both curability and temperature stability.

[0013]

[0009] Therefore, an object of the present invention is to provide an active energy ray-polymerizable composition having excellent storage stability, high heat resistance, and excellent curability. Another object of the present invention is to provide an active energy ray-polymerizable composition that is adaptable to a hot coating process due to its high heat resistance, and furthermore, has excellent curability and exhibits good adhesion, moist heat resistance, and flex resistance even when an ultraviolet-absorbing substrate is used, and to provide a laminate formed from the active energy ray-polymerizable composition. [Means for solving the problem]

[0014] As a result of extensive research to solve the above problems, the present inventors have found that the above object can be achieved by the active energy ray-polymerizable composition shown below, and have thus completed the present invention.

[0015] [1] An active energy ray-polymerizable resin composition comprising 1 to 99 mass% of a cationically polymerizable compound (K), 0.01 to 10 mass% of a sulfide compound (S) (excluding a thioxanthone compound (T)), and an acid generator (KE). [2] The active energy ray-polymerizable resin composition according to [1], wherein the acid generator (KE) is an iodonium salt-based acid generator (KE1). [3] The active energy ray-polymerizable resin composition according to [1], wherein the acid generator (KE) is a sulfonium salt-based acid generator (KE2). [4] The active energy ray-polymerizable resin composition according to [2], further comprising a thioxanthone compound (T). [5] The active energy ray-polymerizable resin composition according to any one of [1] to [4], further comprising a compound (M) having an α,β-ethylenically unsaturated double bond group. [6] The active energy ray-polymerizable resin composition according to [5], wherein the compound (M) having an α,β-ethylenically unsaturated double bond group has a mass average molecular weight of less than 1000 and contains a compound (Ma1) having a hydroxyl group and an α,β-ethylenically unsaturated double bond group. [7] The active-energy ray-polymerizable resin composition according to [5] or [6], wherein the compound (M) having an α,β-ethylenically unsaturated double bond group includes a compound (Mb) having an α,β-ethylenically unsaturated double bond group having a mass-average molecular weight of 1,000 or more and 60,000 or less. [8] The active energy ray-polymerizable resin composition according to any one of [5] to [7], wherein the compound (M) having an α,β-ethylenically unsaturated double bond group has a mass average molecular weight of less than 1000 and contains a compound (Ma2) having two or more α,β-ethylenically unsaturated double bond groups and at least one of a cycloalkane skeleton and a cycloalkene skeleton. [9] The active energy ray-polymerizable resin composition according to any one of [1] to [8], which is an adhesive.

[10] A laminate obtained by laminating a resin composition layer made of the active energy ray-polymerizable resin composition according to any one of [1] to [9] on one or both sides of a substrate (F).

[11] The laminate according to

[10] , wherein the substrate (F) is a polyacetyl cellulose film, a polynorbornene film, a polypropylene film, a polyacrylic film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, or a polyimide film.

[12] A device comprising a first substrate (F), a resin composition layer made of the active energy ray-polymerizable resin composition according to any one of [4] to [9], and a second substrate (F) in this order; A laminate in which at least one of the substrates (F) is an ultraviolet-absorbing substrate.

[13] The laminate according to claim 12, wherein both the first substrate (F) and the second substrate (F) are ultraviolet-absorbing substrates.

[14] The laminate according to any one of

[10] to

[13] , which is used for an optical element. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide an active energy ray-polymerizable composition having excellent storage stability, high heat resistance, and excellent curability. In addition, due to its high heat resistance, it is also applicable to a hot coating process, and further, due to its excellent curability, it is possible to provide an active energy ray-polymerizable composition having good adhesion, moist heat resistance, and flex resistance even when an ultraviolet absorbing substrate is used, and to provide a laminate formed from the active energy ray-polymerizable composition. DETAILED DESCRIPTION OF THE INVENTION

[0017] Preferred embodiments of the present invention are described below. In this specification, a numerical range specified using "to" includes the numerical values ​​before and after "to" as the lower and upper limits of the range. A "major component" refers to the component with the highest content. In addition, in this specification, the terms "film" and "sheet" are not distinguished by thickness. In other words, in this specification, the term "sheet" includes thin film-like objects, and the term "film" includes thick sheet-like objects. In this specification, the term "(meth)acrylic" means "acrylic or methacrylic" unless otherwise specified. In addition, "iodonium salt acid generator (KE1)" is referred to as "compound (KE1)", "sulfonium salt acid generator (KE2)" as "compound (KE2)", "compound (M) having an α,β-ethylenically unsaturated double bond group" as "compound (M)", "compound (Ma) having an α,β-ethylenically unsaturated double bond group with a mass average molecular weight of less than 1,000" as "compound (Ma)", "compound (Ma1) having a hydroxyl group and an α,β-ethylenically unsaturated double bond group" as "compound (Ma1)", "compound (Ma2) having a mass average molecular weight of less than 1,000 and having two or more cycloalkane skeletons and / or cycloalkene skeletons and an α,β-ethylenically unsaturated double bond group" as "compound (Ma2 ... "Compound (Mb) having an α,β-ethylenically unsaturated double bond group of 1,000 or more and 60,000 or less" will be referred to as "compound (Mb)", "compound (Mb1) which is a polyurethane oligomer" will be referred to as "compound (Mb1)", "compound (Mb2) which is a polyester oligomer" will be referred to as "compound (Mb2)", "compound (Mb3) which is a polyepoxy oligomer" will be referred to as "compound (Mb3)", "other compound (Mb4) having an α,β-ethylenically unsaturated double bond group of 1,000 or more and 60,000 or less" will be referred to as "compound (Mb4)", "compound (Mc) having an α,β-ethylenically unsaturated double bond group of molecular weight exceeding 60,000" will be referred to as "compound (Mc)", and "active energy ray polymerizable resin composition" will be referred to as "resin composition". Unless otherwise noted, the various components appearing in this specification may be used independently as a single type or as a mixture of two or more types.

[0018] <<Active Energy Ray-Polymerizable Resin Composition>> The active energy ray-polymerizable resin composition of the present invention contains 1 to 99 mass % of a cationically polymerizable compound (K), 0.01 to 10 mass % of a sulfide compound (S) (excluding a thioxanthone compound (T)), and an acid generator (KE). This makes it possible to obtain an active energy ray-polymerizable composition having excellent storage stability, high heat resistance, and excellent curing properties, and the composition can be suitably used as an adhesive, a coating agent, or the like, and has excellent adhesion, moist heat resistance, and flex resistance. Furthermore, depending on the application, the high heat resistance makes it suitable for use in heated coating processes, and furthermore, the excellent curing properties mean that even when an ultraviolet-absorbing substrate is used, the adhesive properties, moist heat resistance, and bending resistance are excellent. Therefore, the film can be used in a variety of applications, such as hard coat films, laminates for optical elements such as polarizing films, or decorative films.

[0019] <Cationic polymerizable compound (K)> The cationic polymerizable compound (K) is contained in an amount of 1 to 99% by mass relative to 100% by mass of the active energy ray-polymerizable resin composition. When the amount is 99% by mass or less, the active energy ray-polymerizable resin composition has high storage stability and high adhesive strength and flex resistance after long-term storage. When the amount is less than 1% by mass, the adhesion and moist heat resistance are insufficient. From the viewpoints of storage stability, adhesion to substrates, and moist heat resistance, the amount is more preferably 5 to 99% by mass, and even more preferably 5 to 50% by mass. Examples of the cationically polymerizable compound (K) include a cationically polymerizable compound (K1) that is an oxirane compound, which is a three-membered cyclic ether compound, a cationically polymerizable compound (K2) that is a cyclic hetero compound other than an oxirane compound, a cyclic hetero compound, or a vinyl ether compound. Among them, from the viewpoints of excellent reactivity with active energy rays and excellent flexibility and adhesive strength of the resin composition layer after curing, cyclic hetero compounds are more preferred, and the cationically polymerizable compound (K1) is particularly preferred.

[0020] As the cationically polymerizable compound (K), it is preferable to use at least one of the cationically polymerizable compound (K1) and the cationically polymerizable compound (K2) as the main component. The content of the cationically polymerizable compound (K1) and the cationically polymerizable compound (K2) in 100% by mass of the cationically polymerizable compound (K) is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass, from the viewpoint of adhesion to the substrate. When both the cationically polymerizable compound (K1) and the cationically polymerizable compound (K2) are contained, the total content thereof is preferably within the above range.

[0021] [Cationically polymerizable compound (K1)] The cationically polymerizable compound (K1) is an oxirane compound that is a three-membered cyclic ether compound, and is not particularly limited as long as it is a compound in which a group formed by removing one or more hydrogen atoms from a compound having a three-membered cyclic ether group is bonded to another chemical structure. Examples of the cationic polymerizable compound (K1) include aliphatic cyclic ether groups such as oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloromethyl)oxirane, (bromomethyl)oxirane, and oxiranylacetonitrile; and examples thereof include 3,4-oxiranecyclohexylmethyl 3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl 3,4-oxirane-6-methylcyclohexanecarboxylate, ethylenebis(3,4-oxiranecyclohexanecarboxylate), bis(3,4-oxiranecyclohexylmethyl)adipate, and bis(3,4-oxirane-6-methylcyclohexylmethyl). Examples of three-membered cyclic ether groups bonded to an alicyclic ring include adipate, diethylene glycol bis(3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis(3,4-oxiranecyclohexyl methyl ether), 2,3,14,15-dioxirane-7,11,18,21-tetraoxatrispiro-[5.2.2.5.2.2]heneicosane (a compound that can also be named 3,4-oxiranecyclohexanespiro-2',6'-dioxanespiro-3'',5''-dioxanespiro-3''',4'''-oxiranecyclohexane), 4-(3,4-oxiranecyclohexyl)-2,6-dioxa-8,9-oxiranespiro[5.5]undecane, 4-vinylcyclohexene dioxide, bis-2,3-oxiranecyclopentyl ether, and dicyclopentadiene dioxide.

[0022] The oxirane equivalent of the cationically polymerizable compound (K1) is usually 30 to 3000 g / eq, preferably 50 to 1500 g / eq, and more preferably 80 to 500 g / eq. An oxirane equivalent of 30 g / eq or more is preferred because the resin composition layer after curing has excellent flexibility and high adhesive strength. On the other hand, an oxirane equivalent of 3000 g / eq or less provides better compatibility with other components. A range of 80 to 500 g / eq is preferred because it provides a good balance.

[0023] Furthermore, the cationically polymerizable compound (K1) can be classified into cationically polymerizable compounds (K11) that are oxirane compounds without an alkoxysilyl group and cationically polymerizable compounds (K12) that are oxirane compounds with an alkoxysilyl group. The cationically polymerizable compound (K11) that is an oxirane compound without an alkoxysilyl group can be further classified into cationically polymerizable compounds (K111) that are oxirane compounds with an aromatic ring and cationically polymerizable compounds (K112) that are oxirane compounds without an aromatic ring. The oxirane compounds without an aromatic ring can be further classified into cationically polymerizable compounds (K1121) that do not contain an alicyclic structure at the oxirane moiety and cationically polymerizable compounds (K1122) that contain an alicyclic structure at the oxirane moiety. When the main component of the composition of the present invention is a cationically polymerizable compound (K), it is preferable to contain a cationically polymerizable compound (K111) which is an oxirane compound having an aromatic ring, in order to improve adhesive strength.

[0024] More specific examples of the aromatic ring substituent include phenyl, phenylene, tolyl, tolylene, benzyl, benzylidene, benzylidine, xylyl, xylylene, phthalylidene, isophthalylidene, terephthalylidene, phenethylidene, phenethylidine, styryl, styrylidene, as-pseudocumyl, v-pseudocumyl, s-pseudocumyl, mesityl, cumenyl, α-cumyl, hydrocinnamyl, cinnamyl, cinnamylidene, cinnamylidine, duryl, durylene, thymyl, and carvacryl. Examples of substituents include cuminyl, cuminidene, neophyl, xenyl, benzhydryl, benzhydrylidene, trityl, etc., and these include aromatic rings in which a group in the form of a benzene derivative such as benzene, toluene, xylene, styrene, hemimellitene, pseudocumene, mesitylene, cumene, planing, isodurene, durene, cymene, or melitene, from which one or more hydrogen atoms have been removed, can be bonded to another chemical structure.

[0025] Other cycloalkenes include, for example, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, and cyclooctadiene;

[0026] For example, there is mentioned [4n+2]annulene, which has a carbon number other than that of benzene and has three or more carbon atoms constituting the ring.

[0027] For example, aromatic polycyclic compounds such as biphenyl and triphenylmethane;

[0028] For example, carbo-condensed bicyclic compounds such as pentalene, indene, indane, ninhydrin, naphthalene, tetralin, decalin, sapotalene, cadalene, eudalene, naphthol, menadiol, gossypol, naphthoquinone, lawsone, juglone, menadione, plumbagin, phthiocol, echinochrome A, alkannin, shikonin, acetonaphthone, naphthoic acid, naphthoyl, naphthalic acid, naphthalate, acetomenaphthone, naphthionic acid, naphthionate, naphthionyl, dansyl, croceic acid, flavian acid, chromotropic acid, neocuperone, azulene, chamazulene, guaiazulene, heptalene, octalene, and purpurogallin:

[0029] For example, as-indacene, s-indacene, as-hydroindacene, s-hydroindacene, biphenylene, acenaphthylene, acenaphthene, acenaphthoquinone, fluorene, phenalene, perinaphthene, phenanthrene, phenanthryl, phenanthryllium, phenanthridene, phenanthrylene, phenanthrol, morphol, phenanthrone, phenanthraquinone, pymanthrene, retene, anthracene, anthryl, anthrylium, anthrylidene, anthrylene, anthrol, and anthranol. , anthrarobin, anthralin, dithranol, anthroyl, anthrone, bianthrone, anthraquinone, anthraquinonyl, anthraquinonylene, alizarin, quinizarin, anthrarphine, chrysadine, anthragallol, purpurin, flavopurpurin, anthrapurpurin, quinalizarin, tectoquinone, chrysophanol, chrysophanic acid, emodin, rhein, kermesic acid, carminic acid, dianthrimide, anthrimide, chrysanmic acid, colchicine, and other carbon-condensed tricyclic compounds;

[0030] For example, carbon-fused tetracyclic compounds such as trindane, trindane, fluoranthene, acephenanthrylene, acephenanthrene, aceanthrylene, aceanthrene, triphenylene, pyrene, chrysene, tetraphen, tetracene, naphthacene, rubrene, tetracycline, chlortetracycline, oxytetracycline, pleiadene, and benzanthrone;

[0031] For example, carbon-fused five-ring compounds such as picene, perylene, pentaphene, pentacene, tetraphenylene, cholanthrylene, and cholanthrene;

[0032] Examples of aromatic rings include those in which a group formed by removing one or more hydrogen atoms from a cyclic compound, such as a condensed carbon ring compound having six or more rings, such as corannulene, fluminene, anthanthrene, zethrene, hexahelicene, hexaphene, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyranthrene, octaphene, octacene, terrylene, naphthacenonaphthacene, nonaphene, nonacene, violanthrene, violanthrone, isoviolanthrone, isoviolanthrone, ovalene, decphene, decacene, decacyclene, pentacenopentacene, quaterrylene, and hexacenohexacene, can be bonded to another chemical structure.

[0033] As the cationically polymerizable compound (K111), which is an oxirane compound having an aromatic ring, particularly preferred are glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, 1,3-phenylenebis(methylene)bis(7-oxabicyclo[4.1.0]heptane-3-carboxylate), and 1,3-bis{(7-oxabicyclo[4.1.0]heptane-3-ylmethoxy)methyl}benzene, which have excellent heat resistance and adhesive strength.

[0034] Examples of the cationically polymerizable compound (K2), which is a cyclic hetero compound other than an oxirane compound, include a compound having an oxetanyl group, which is a four-membered ring ether, a five- or more-membered ring ether compound, and a compound having two or more oxygen or hetero groups other than oxygen.

[0035] Examples of compounds having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, di(1-ethyl-3-oxetanyl)methyl ether, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac oxetane, and 3-ethyl-{(3-triethoxysilylpropoxy)methyl}oxetane.

[0036] The cationic polymerizable compound (K2) which is a cyclic hetero compound other than an oxirane compound includes a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, a fluorine-containing cyclic compound, etc. The cyclic ester compound is preferably a lactone. The cyclic formal compound is preferably a compound selected from dioxolanes, dioxanes, and trioxanes.

[0037] The cationically polymerizable compound (K12), which is an oxirane compound having an alkoxysilyl group, is not limited as long as it is a compound having an alkoxysilyl group and an oxirane structure, and examples thereof include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, polysiloxane having an oxirane structure and an alkoxysilyl group on the side chain, and a polymer of 3-methacryloxypropyltriethoxysilane and glycidyl methacrylate.

[0038] From the viewpoints of the stability of the alkoxysilyl group of the cationic polymerizable compound (K12), which is an oxirane compound having an alkoxysilyl group, solubility with other components, and reactivity, the compound preferably has 2 or more but less than 13 carbon atoms. Methoxy (having 1 carbon atom) has poor storage stability, while solubility and reactivity are poor with carbon atoms of 13 or more. The desired alkoxysilyl moiety can be obtained by an exchange reaction between an oxirane compound having a highly reactive methoxysilyl group and any alcohol.

[0039] The cationic polymerizable compound (K12), which is an oxirane compound having an alkoxysilyl group, further improves substrate adhesion and moist heat resistance, and therefore is preferably contained in an amount of 0.1 to 20 mass% relative to 100 mass% of the active energy ray-polymerizable resin composition. When the amount is 0.1 mass% or more, moist heat resistance is further improved, and when the amount is 20 mass% or less, adhesion is further improved.

[0040] <Acid Generator (KE)> The active energy ray-polymerizable resin composition of the present invention contains an acid generator (KE). The acid generator (KE) generates an acid when irradiated with active energy rays such as visible light, ultraviolet light, X-rays, or electron beams, and acts as a catalyst to initiate the polymerization reaction of the cationically polymerizable compound (K). Examples of the acid generator include onium salt-based acid generators such as iodonium salt-based acid generators (KE1), sulfonium salt-based acid generators (KE2), diazonium salt-based acid generators, ammonium salt-based acid generators, and phosphonium salt-based acid generators. Among these, from the viewpoint of obtaining an active energy ray-polymerizable resin composition having excellent photodecomposition efficiency and excellent curability, an iodonium salt-based acid generator (KE1) or a sulfonium salt-based acid generator (KE1) is preferred. From the viewpoint of storage stability at high temperatures, the sulfonium salt acid generator (KE2) is preferred. Furthermore, when the acid generator (KE) is an iodonium salt-based acid generator (KE1), it is preferable to further contain a thioxanthone compound (T) from the viewpoint of utilizing ultraviolet light of around 420 nm due to the sensitizing effect of the thioxanthone compound (T). The iodonium salt acid generator (KE1) reacts with ultraviolet light of around 420 nm due to its high photodecomposition efficiency combined with the sensitizing effect of the thioxanthone compound (T). Therefore, even when an ultraviolet-absorbing substrate is used as the substrate, an active energy ray-polymerizable resin composition having excellent adhesive strength, moist heat resistance, and flex resistance can be obtained.

[0041] The content of the acid generator (KE) is preferably 0.1% by mass or more relative to 100% by mass of the active energy ray-polymerizable resin composition from the viewpoint of the curability of the active energy ray-polymerizable resin composition, while from the viewpoint of moist heat resistance, it is preferably 20% by mass or less, and more preferably 0.5 to 10% by mass.

[0042] [Iodonium salt-based acid generator (KE1)] Examples of iodonium salt acid generators (KE1) include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and diphenyliodonium tetrakis(pentafluoro)borate.

[0043] Commercially available iodonium salt acid generators (KE1) include bis(4-tert-butylphenyl)iodonium hexafluorophosphate (WPI-170, manufactured by Wako Pure Chemical Industries, Ltd.), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), IK-1 (manufactured by San-Apro Co., Ltd.), and (4-methylphenyl)[4(2-methylpropyl)phenyl]iodonium hexafluorophosphate (Omnicat 250, manufactured by IGM resins).

[0044] The content of the iodonium salt acid generator (KE1) is preferably 0.2% by mass or more in 100% by mass of the active energy ray-polymerizable resin composition from the viewpoints of polymerizability, adhesiveness, and moist heat resistance, while from the viewpoint of the storage stability of the active energy ray-polymerizable resin composition, it is preferably 10% by mass or less, and more preferably 1 to 5% by mass.

[0045] [Sulfonium salt acid generator (KE2)] Examples of sulfonium salt acid generators (KE2) include triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, and triarylsulfonium tetrakis(pentafluorophenyl)borate.

[0046] Commercially available sulfonium salt acid generators (KE2) include, for example, triarylsulfonium hexafluorophosphate (CPI-110P, manufactured by San-Apro) and UVACURE 1590 (manufactured by Daicel-Cytec).

[0047] The content of the sulfonium salt acid generator (KE2) is preferably 0.1% by mass or more relative to 100% by mass of the active energy ray-polymerizable resin composition from the viewpoint of curability of the active energy ray-polymerizable resin composition, while from the viewpoint of moist heat resistance, it is preferably 20% by mass or less, and more preferably 0.5 to 10% by mass.

[0048] <Thioxanthone compounds (T)> The thioxanthone compound (T) is not limited as long as it has a thioxanthone structure. When the acid generator (KE) is an iodonium salt-based acid generator (KE1), it is preferable to further contain a thioxanthone compound (T). The combination of the iodonium salt-based acid generator (KE1) and the thioxanthone compound (T) not only provides excellent storage stability and high heat resistance suitable for use in a heated coating process, but also allows a cationic reaction to proceed using light in the vicinity of 420 nm, even when the substrate is an ultraviolet-absorbing substrate, thereby providing an active-energy ray-polymerizable resin composition with excellent curability.

[0049] Examples of the thioxanthone compound (T) include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-hydroxythioxanthone, 2-acetoxythioxanthone, and 2-propoxythioxanthone.

[0050] The optimum amounts of the iodonium salt acid generator (KE1) and the thioxanthone compound (T) are affected by their concentrations relative to 100% by mass of the entire active energy ray-polymerizable resin composition, regardless of the blending amount of the cationically polymerizable compound (K). From the viewpoints of polymerizability, adhesiveness, and moist heat resistance, the amount of the thioxanthone compound (T) is preferably 0.2% by mass or more relative to 100% by mass of the entire active energy ray-polymerizable resin composition, whereas if the polymerizability is too high, the adhesive strength decreases, so the amount is preferably 10% by mass or less. When the compounding ratio of the iodonium salt acid generator (KE1) to the thioxanthone compound (T) is AM(KE1) / AM(T), AM(KE1) / AM(T) is preferably 4 to 0.2. By keeping AM(KE1) / AM(T) in this range, the active energy ray-polymerizable resin composition can have an excellent balance of storage stability, adhesiveness, and moist heat resistance.

[0051] <Sulfide compounds (S)> The sulfide compound (S) is not particularly limited as long as it is an organic compound in which two hydrocarbon groups are bonded to a divalent sulfur atom, except for the thioxanthone compound (T). By including the sulfide compound (S), the resin composition can have excellent storage stability, and even when stored at high temperatures, the moist heat resistance and flexibility are not deteriorated, so that the resin composition containing the sulfide compound (S) can be applied to high-temperature applications. In this specification, even if a sulfide compound has a sulfonium salt structure, it is classified as a sulfonium salt-based acid generator (KE2).

[0052] The sulfide compound (S) is preferably contained in an amount of 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on 100% by mass of the entire resin composition. If it is 0.01% by mass or more, effects such as storage stability can be obtained, and if it is 10% by mass or less, moist heat resistance can be further improved.

[0053] [Sulfide compounds having aromatic rings (S1)] Sulfide compounds (S1) having an aromatic ring are preferred because they are highly effective in improving the storage stability of resin compositions, and can be classified into sulfide compounds (S11) having an aromatic ring but no nitrogen atom, and sulfide compounds (S12) having an aromatic ring and a nitrogen atom. Furthermore, sulfide compounds (S11) having an aromatic ring but no nitrogen atom can be classified into sulfide compounds (S111) having one or less phenol structures in one molecule and sulfide compounds (S112) having two or more phenol structures. Among these, sulfide compounds (S11) having an aromatic ring but no nitrogen atom are preferred, since the sulfide compound (S) having a nitrogen atom may have reduced cationic reactivity. Furthermore, sulfide compound (S111) is preferred because it has the best balance of storage stability, adhesive strength, and moist heat resistance.

[0054] Examples of the sulfide compound (S11) having an aromatic ring but no nitrogen atom include methyl phenyl sulfide, 2-methyl-3-(methylthio)furan, furfuryl methyl sulfide, ethyl phenyl sulfide, benzyl methyl sulfide, 4-(methylthio)toluene, allyl phenyl sulfide, methoxymethyl phenyl sulfide, 4-(methylthio)benzyl alcohol, 3-methoxythioanisole, 2-methoxythioanisole, 4-methoxythioanisole, 2-(phenylthio)ethanol, furfuryl isopropyl sulfide, 2-(benzylthio)ethanol, benzyl sulfide, 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(octylthiomethyl)-6-methylphenol, and 2,4-bis[(dodecylthio)methyl]-6-methylphenol.

[0055] Examples of the sulfide compound (S12) having an aromatic ring and a nitrogen atom include 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane and 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(o-benzoyloxime).

[0056] [Sulfide compounds without aromatic rings (S2)] Examples of the sulfide compound (S2) having no aromatic ring include allyl methyl sulfide, ethyl vinyl sulfide, 2-hydroxyethyl methyl sulfide, 3-hydroxypropyl methyl sulfide, 4-methylthio-2-butanone, methylthiomethyl acetate, (methylthio)methyl acetate, 2-hydroxyethyl sulfide, methyl 3-(methylthio)propionate, ethyl (methylthio)acetate, 2-hydroxyethyl isobutyl sulfide, butyl 2-hydroxyethyl sulfide, (methylthio)acetaldehyde dimethyl acetal, tert-butyl sulfide, sec-butyl sulfide, and se c-butyl sulfide, heptyl methyl sulfide, isobutyl sulfide, 3-(methylthio)propyl acetate, ethyl 3-(methylthio)propionate, 3-(methylthio)-1-hexanol, ethyl 2-hydroxyethyl sulfide, 4-hydroxythiane, 2-hydroxyethyl isopropyl sulfide, 2-(propylthio)ethanol, 2-hydroxyethyl sulfide, 2,2-bis[[3-(dodecylthio)propionic acid]methyl]-1,3-propanediyl bis[3-(dodecylthio)propionic acid], and ditridecyl 3,3'-thiobispropionate.

[0057] The active energy ray-polymerizable resin composition of the present invention contains a sulfide compound (S), which improves the storage stability of an active energy ray-polymerizable resin composition using an acid generator (KE). Although the mechanism is not clear, it is thought that the sulfide compound may stabilize the acid generator (KE), such as an iodonium salt-based acid generator or a sulfonium salt-based acid generator, or that when an iodonium salt-based acid generator or a sulfonium salt-based acid generator is cleaved by heat, the coexistence of the sulfide compound (S) may make it more likely to be deactivated before acid is generated.

[0058] <Compound (M)> The compound (M) is a compound having an α,β-ethylenically unsaturated double bond group. The active energy ray-polymerizable resin composition of the present invention preferably contains a compound (M). A larger content of the compound (M) is preferable because the content of the compound (K) in the resin composition decreases, thereby improving the storage stability of the resin composition of the present invention. The compound (M) is contained in an amount of preferably 1 to 99 mass %, more preferably 50 to 95 mass %, based on 100 mass % of the active energy ray-polymerizable resin composition. Furthermore, the compound (M) is preferably a compound having two or more α,β-ethylenically unsaturated double bond groups, since this can further improve the resistance to moist heat.

[0059] Compound (M) can be classified according to its mass average molecular weight (hereinafter referred to as Mw) into compounds (Ma) having an α,β-ethylenically unsaturated double bond group with a mass average molecular weight of less than 1,000, compounds (Mb) having an α,β-ethylenically unsaturated double bond group with a mass average molecular weight of 1,000 to 60,000, and compounds (Mc) having an α,β-ethylenically unsaturated double bond group with a mass average molecular weight of more than 60,000. Among these, it is preferable from the viewpoint of storage stability to include at least one of compounds (Mb) having an α,β-ethylenically unsaturated double bond group with a mass average molecular weight of 1,000 to 60,000 and compounds (Ma) having an α,β-ethylenically unsaturated double bond group with a mass average molecular weight of less than 1,000. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement, and can be measured by the method described in the Examples section.

[0060] [Compound (Ma)] The compounds (Ma) are compounds having an α,β-ethylenically unsaturated double bond group with a mass average molecular weight of less than 1,000, and are classified into compounds (Ma1) having a hydroxyl group and an α,β-ethylenically unsaturated double bond group, compounds (Ma2) having two or more cycloalkane skeletons and / or cycloalkene skeletons and an α,β-ethylenically unsaturated double bond group, and compounds (Ma3) having other α,β-ethylenically unsaturated double bond groups. Among these, at least one of the compound (Ma1) and the compound (Ma2) is preferred. The compound (Ma1) is preferred from the viewpoint of excellent adhesion to the substrate, and the compound (Ma2) is preferred from the viewpoint of excellent resistance to moist heat.

[0061] As the compound (Ma), it is preferable to use at least one of the compound (Ma1) and the compound (Ma2) as the main component. The content of compound (Ma1) and compound (Ma2) in 100% by mass of compound (Ma) is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, from the viewpoints of adhesion and moist heat resistance. When both the compound (Ma1) and the compound (Ma2) are contained, the total content thereof is preferably within the above range.

[0062] (Compound (Ma1)) The compound (Ma1) has a mass-average molecular weight of less than 1,000 and contains a hydroxyl group and an α,β-ethylenically unsaturated double bond group. By including the compound (Ma1) in the resin composition, hydrogen bonds are formed with the hydroxyl groups of the substrate, improving adhesive strength.

[0063] The compound (Ma1) is not particularly limited as long as it has a hydroxyl group in its structure, and examples thereof include 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, (meth) hydroxyl group-containing aliphatic (meth)acrylic esters such as fatty acid ester-based (meth)acrylic esters such as 12-hydroxylauryl acrylate, ethyl-α-(hydroxymethyl) (meth)acrylate, and monofunctional (meth)acrylic acid; or (meth)acrylic esters having a terminal hydroxyl group obtained by ring-opening addition of ε-caprolactone lactone to a compound having a hydroxyl group-containing α,β-ethylenically unsaturated double bond group, or alkylene oxide-added (meth)acrylic esters obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to a compound having a hydroxyl group-containing α,β-ethylenically unsaturated double bond group;

[0064] For example, hydroxyl group-containing aliphatic vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, or alkylene oxide adduct vinyl ethers having hydroxyl groups at the terminals of repeated additions of alkylene oxides such as ethylene oxide or propylene oxide;

[0065] For example, hydroxyl group-containing aliphatic (meth)allyl alcohols or (meth)allyl ethers such as (meth)allyl alcohol, isopropenyl alcohol, dimethyl (meth)allyl alcohol, hydroxyethyl (meth)allyl ether, hydroxypropyl (meth)allyl ether, hydroxybutyl (meth)allyl ether, hydroxyhexyl (meth)allyl ether, hydroxyoctyl (meth)allyl ether, hydroxydecyl (meth)allyl ether, hydroxydodecyl (meth)allyl ether, hydroxyoctadecyl (meth)allyl ether, glyceryl (meth)allyl ether, or alkylene oxide adduct (meth)allyl ethers having hydroxyl groups at the terminals of repeated additions of alkylene oxides such as ethylene oxide or propylene oxide;

[0066] For example, compounds having an α,β-ethylenically unsaturated double bond group having multiple hydroxyl groups, such as propenediol, butenediol, heptenediol, octenediol, and glycerol di(meth)acrylate; For example, hydroxyl group-containing (meth)acrylamides such as N-hydroxyethyl(meth)acrylamide (N-hydroxyethylacrylamide and N-hydroxyethylmethacrylamide are collectively referred to as "N-hydroxyethyl(meth)acrylamide", the same applies below), N-hydroxypropyl(meth)acrylamide, N-hydroxybutyl(meth)acrylamide, N-hydroxyhexyl(meth)acrylamide, and N-hydroxyoctyl(meth)acrylamide;

[0067] Examples of the monomers include, but are not limited to, monomers having a hydroxyl group and an ethenyl group, such as vinyl alcohol, etc. These may be used alone or in combination of two or more. As the compound (Ma1), from the viewpoint of adhesion to the substrate, compounds having an α,β-ethylenically unsaturated double bond group having 2 to 18 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and 2-hydroxyethyl (meth)acrylate adducted with 1 to 2 mol of ε-caprolactone, are particularly preferred.

[0068] (Compound (Ma2)) The compound (Ma2) is a compound having a mass average molecular weight of less than 1,000 and having two or more cycloalkane skeletons and / or cycloalkene skeletons and α,β-ethylenically unsaturated double bond groups.

[0069] The compound (Ma2) may be a single cycloalkene skeleton or a cycloalkene skeleton, or may have a bridged cyclo ring structure, as long as it has at least two cycloalkene skeletons in total. Examples include compounds (Ma21) in which the ring structures are separated by an alkyl group, an ether group, an ester group, or the like, and compounds having a bridged cyclo ring structure, such as compounds (Ma22) having a norbornane or norbornene skeleton, and compounds (Ma23) having an adamantane structure. However, due to their excellent resistance to moist heat, compounds (Ma22) having a norbornane or norbornene skeleton and compounds (Ma23) having an adamantane structure are preferred.

[0070] Examples of the compound (Ma21) having two or more cycloalkane skeletons and / or cycloalkene skeletons and having an α,β-ethylenically unsaturated double bond group with the ring structures separated from each other include hydrogenated biphenol A diacrylate and 3,3-dicyclopropyl acrylate. The α,β-ethylenically unsaturated double bond group-containing compound (Ma22) having a norbornene and / or norbornane skeleton may be any compound having a norbornene and / or norbornane skeleton and one or more ethylenically unsaturated double bonds, and examples thereof include dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, and isobornyl (meth)acrylate.

[0071] Among the compounds (Ma22) having a norbornane or norbornene skeleton, compounds having three or more cyclic skeletons are particularly preferred because they increase bulkiness, thereby suppressing cure shrinkage and improving adhesive strength, and specific examples of such compounds include dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dimethyloldicyclopentanedi(meth)acrylate.

[0072] The α,β-ethylenically unsaturated double bond group-containing compound (Ma23) having an adamantane skeleton is a radical polymerizable compound having three or more cyclic skeletons, and is preferable from the viewpoint of excellent heat resistance and adhesiveness. Specific examples of compound (Ma23) include 3-hydroxy-1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl(meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate, 2-propyl-2-adamantyl(meth)acrylate, 3,5-dihydroxy-1-adamantyl(meth)acrylate, 1,3-adamantyldiol di(meth)acrylate, 1,3,5-adamantyltri(meth)acrylate, 3-hydroxy-1,5-adamantyldi(meth)acrylate, and 3,5-dihydroxy-1-adamantyl(meth)acrylate. In view of excellent adhesiveness, 3-hydroxy-1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, and 2-ethyl-2-adamantyl acrylate are preferred.

[0073] [Compound (Mb)] Compound (Mb) is a compound having an α,β-ethylenically unsaturated double bond group and a mass average molecular weight of 1000 to 60000, and is a compound generally referred to as an oligomer. Compound (Mb) is further classified into compounds (Mb1) which are polyurethane oligomers, compounds (Mb2) which are polyester oligomers, compounds (Mb3) which are polyepoxy oligomers, and compounds (Mb4) which have an α,β-ethylenically unsaturated double bond group and a mass average molecular weight of 1000 to 60000. At least one oligomer selected from the group consisting of compounds (Mb1), (Mb2), and (Mb3) is preferred, and can be used without any particular limitation. Compound (Mb) is preferred because it has excellent flex resistance. Of these, compound (Mb1) is preferred because it has a urethane bond with high polarity, resulting in a good balance between the toughness of the coating film and the adhesion to the substrate, and it has particularly excellent flex resistance.

[0074] The mass-average molecular weight of the compound (Mb) is 1000 to 60,000, and from the viewpoint of compatibility of the polymerized coating film and good flex resistance, it is preferably in the range of 5000 to 50,000. When the mass-average molecular weight of the compound (Mb) is in this range, the flowability of the active energy ray-polymerizable resin composition and compatibility with other compounds (M) other than the compound (Mb) are improved, thereby improving the coatability of the active energy ray-polymerizable resin composition. Furthermore, when used as an adhesive, this is preferable because the polymerized coating film has excellent flex resistance and whitening of the coating film can be suppressed.

[0075] The content of compound (Mb) is preferably 1 to 40% by mass, and more preferably 2 to 20% by mass, relative to 100% by mass of the active energy ray-polymerizable resin composition. If it is 1% by mass or more, the flex resistance is further improved, and if it is 40% by mass or less, the viscosity does not become too high, making it easy to control the film thickness during coating.

[0076] (Compound (Mb1)) Compound (Mb1) is a polyurethane oligomer, and is a compound obtained by reacting a compound having at least one isocyanate group with compound (Ma1), or a compound obtained by reacting a urethane prepolymer having terminal isocyanate groups obtained by reacting a compound having at least one isocyanate group with a polyhydric alcohol with compound (Ma1), or a compound obtained by reacting a urethane prepolymer having terminal isocyanate groups obtained by reacting a compound having at least one isocyanate group with a polyhydric alcohol with a compound having at least one amino group with compound (Ma1). Polyurethane oligomer (Mb1) also includes those containing urea-linked groups obtained by reacting an isocyanate group with an amino group.

[0077] The compound (Mb1) is preferably a compound (Mb1) consisting of a diol compound, a compound having two isocyanate groups, and the compound (Ma1). This is because, theoretically, a structure having acrylate groups at both ends of one molecule results in a good balance between flexibility and crosslinking density, and excellent substrate adhesion and toughness, resulting in good flex resistance.

[0078] Examples of compounds having at least one isocyanate group include monofunctional polyisocyanates and polyfunctional isocyanates, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, etc. More specific examples of monofunctional polyisocyanates include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl ... Examples of the isocyanate include phenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methylbenzyl isocyanate, (S)-(-)-α-methylbenzyl isocyanate, (R)-(-)-1-(1-naphthyl)ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, and p-toluenesulfonyl isocyanate.

[0079] Of the polyfunctional isocyanates, more specific examples of aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 4,4',4"-triphenylmethane triisocyanate.

[0080] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0081] Examples of the aromatic aliphatic polyisocyanate include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

[0082] Examples of alicyclic polyisocyanates include 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,4-bis(isocyanatemethyl)cyclohexane.

[0083] In addition, 2-methylpentane-2,4-diol adducts of some of the above polyisocyanates, trimers having an isocyanurate ring, etc. can also be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, and modified polyisocyanates thereof can also be used. Modified polyisocyanates that can be used include those having a carbodiimide group, a uretdione group, a uretoimine group, a biuret group reacted with water, or an isocyanurate group, or two or more of these groups. Reaction products of polyols and diisocyanates can also be used as compounds having at least two isocyanate groups.

[0084] The compound having an isocyanate group is preferably an aliphatic diisocyanate or alicyclic diisocyanate compound from the viewpoint of flex resistance.

[0085] Furthermore, examples of polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500, and relatively high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000, and each can be used without any particular restrictions. The number average molecular weight is a polystyrene-equivalent number average molecular weight determined by gel permeation chromatography (GPC) measurement.

[0086] More specifically, examples of relatively low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (addition mole number of 10 or less), ... aliphatic or alicyclic diols such as propylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, and dimer diol;

[0087] Examples include 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-norbornylidene)diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, and addition type bisphenols in which alkylene oxides are added to bisphenols.

[0088] Examples of the raw material bisphenol for the addition type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide. More specifically, the relatively high molecular weight polyols include high molecular weight polyether polyols, high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. High molecular weight polycarbonate polyols can be obtained by reacting the above-mentioned relatively low molecular weight diols with carbonate esters or phosgene.

[0089] Examples of commercially available high molecular weight polyester polyols include the Vylon series manufactured by Toyobo Co., Ltd., the Kuraray Polyol P series manufactured by Kuraray Co., Ltd., and the Kyowapol series manufactured by Kyowa Hakko Chemical Co., Ltd. As a commercially available product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Chemical Industry Co., Ltd. can be used. Commercially available high molecular weight polycarbonate polyols include, for example, Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals Corporation, Kuraray Polyol PMHC series and Kuraray Polyol C series manufactured by Kuraray Co., Ltd.

[0090] Commercially available high molecular weight polyurethane polyols include, for example, the Vylon UR series manufactured by Toyobo Co., Ltd., and Takelac E158 (hydroxyl value = 20, acid value < 3), Takelac E551T (hydroxyl value = 30, acid value < 3), and Takelac Y2789 (hydroxyl value = 10, acid value < 2), all manufactured by Mitsui Chemicals Polyurethanes, Inc. Other examples of high molecular weight polyols that can be used include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly(β-methyl-γ-valerolactone) diol, and polyvalerolactone diol.

[0091] The polyhydric alcohol is preferably a high molecular weight polyether diol or a high molecular weight polyester diol from the viewpoint of adhesion.

[0092] Specific examples of amines having an amino group include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-2-hydroxyethylethylene)diamine, (di-2-hydroxyethylpropylene)diamine, (2-hydroxypropylethylene)diamine, (di-2-hydroxypropylethylene)diamine, and piperazine; alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; Aromatic diamines such as phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, and 4,4'-bis-(sec-butyl)diphenylmethane can be used.

[0093] (Compound (Mb2)) Compound (Mb2) is a polyester oligomer, such as a compound obtained by esterifying a hydroxyl group at the end of a polyester obtained by polycondensing a polybasic acid and a polyhydric alcohol in the main chain skeleton with a compound having an α,β-ethylenically unsaturated double bond group having one or more carboxyl groups in the molecule, such as (meth)acrylic acid or maleic acid, or a compound obtained by esterifying a carboxyl group at the end of a polyester or in the polyester chain with the aforementioned compound (Ma1), such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. Other examples of polyester oligomers that can be used as polyester oligomer (Mb2) include polyester oligomers obtained from acid anhydrides, glycidyl (meth)acrylate, and compounds having at least one hydroxyl group.

[0094] As the polyhydric alcohol, the same polyhydric alcohols as those explained in the synthesis of compound (Mb1) can be used.

[0095] The polybasic acid may be aliphatic, alicyclic, or aromatic, and may be used without any particular limitation. Specific examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, and maleic anhydride. These aliphatic dicarboxylic acids and their anhydrides may be used. Also usable are anhydride derivatives such as succinic anhydride derivatives (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl succinic anhydride, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc.), and maleic anhydride derivatives (2-methyl maleic anhydride, 2,3-dimethyl maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride, 2,3-diphenyl maleic anhydride, etc.).

[0096] More specifically, examples of alicyclic polybasic acids include alicyclic dicarboxylic acids such as dimer acid, cyclopropane-1α,2α-dicarboxylic acid, cyclopropane-1α,2β-dicarboxylic acid, cyclopropane-1β,2α-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α,2β-dicarboxylic acid, cyclobutane-1α,3β-dicarboxylic acid, cyclobutane-1α,3α-dicarboxylic acid, (1R)-cyclopentane-1β,2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β,2β)-cyclopentane-1,3-dicarboxylic acid, (1β,3β)-cyclopentane-1,3-dicarboxylic acid, (1S,2S)-1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the dicarboxylic acid include saturated alicyclic dicarboxylic acids such as carboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, and tetrahydrophthalic acid, and unsaturated alicyclic dicarboxylic acids having one or two unsaturated double bonds in the ring such as 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,3-dicarboxylic acid, and 2,5-hexadiene-1α,4α-dicarboxylic acid. These alicyclic dicarboxylic acids and anhydrides thereof can be used.

[0097] In addition, hydrogenated phthalic anhydride derivatives such as derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride) and derivatives of tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) can also be used as alicyclic dicarboxylic acid anhydrides.

[0098] More specifically, examples of aromatic polybasic acids include aromatic dicarboxylic acids such as o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2,2'-biphenyl dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid, 1,2-azuledicarboxylic acid, and 1,3-azuledicarboxylic acid. , 4,5-azulenedicarboxylic acid, (−)-1,3-acenaphthenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,5-anthracenedicarboxylic acid, 1,8-anthracenedicarboxylic acid, 2,3-anthracenedicarboxylic acid, 1,2-phenanthrenedicarboxylic acid, 4,5-phenanthrenedicarboxylic acid, 3,9-perylenedicarboxylic acid, and other aromatic dicarboxylic acid anhydrides; and phthalic anhydride, 4-methylphthalic anhydride, and these aromatic dicarboxylic acids and their anhydrides can be used.

[0099] Furthermore, acid anhydrides such as chlorendic anhydride, HET acid anhydride, biphenyldicarboxylic anhydride, himic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, and octahydro-1,3-dioxo-4,5-isobenzofurandicarboxylic anhydride can also be used as polybasic acids.

[0100] (Compound (Mb3)) Compound (Mb3) is a polyepoxy oligomer obtained by reacting a compound having a glycidyl group with a compound having an α,β-unsaturated double bond group having one or more carboxyl groups in the molecule, such as (meth)acrylic acid or maleic acid, and representative examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. Bisphenol type polyepoxy oligomers are obtained by reacting bisphenol type diglycidyl ether, obtained by reacting bisphenols with epichlorohydrin, with a compound having an α,β-unsaturated double bond group having one or more carboxyl groups in the molecule, such as (meth)acrylic acid.

[0101] The epoxidized oil polyepoxy oligomer can be one obtained by reacting an oil such as epoxidized soybean oil with a compound having an α,β-unsaturated double bond group with one or more carboxyl groups in the molecule, such as (meth)acrylic acid or maleic acid. The novolac polyepoxy oligomer can be one obtained by reacting a novolac epoxy resin with a compound having an α,β-unsaturated double bond group with one or more carboxyl groups in the molecule, such as (meth)acrylic acid. The alicyclic polyepoxy oligomer can be one synthesized by reacting an alicyclic epoxy resin with a compound having an α,β-unsaturated double bond group with one or more carboxyl groups in the molecule, such as (meth)acrylic acid.

[0102] <Radical polymerization initiator (E)> The active energy ray-polymerizable resin composition of the present invention may further contain a radical polymerization initiator (E). By using the radical polymerization initiator (E), the radical polymerization reaction can be promoted. In this specification, even if a compound falls under the category of the radical polymerization initiator (E), it is classified as a sulfide compound (S) if it has a sulfide structure.

[0103] The radical polymerization initiator (E) can be arbitrarily selected from known initiators and used. Specific examples thereof include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzil dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like. Examples of commercially available products include Irgacure 184, 907, 651, 1700, 1800, 819, 369, 261, DAROCUR-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF), Omnirad819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by IGM Resins B.V.), DAROCUR-1173 (manufactured by Merck), Ezacure KIP150, TZT (manufactured by Nippon SiberHegner), Kayacure BMS, and Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.). 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred because of its photobleaching properties.

[0104] The blending ratio of the radical initiator (E) is preferably 0.01 to 20 mass % relative to 100 mass % of the active energy ray-polymerizable resin composition.

[0105] Examples of active energy rays include ultraviolet rays and electron beams. When the radical polymerization reaction is carried out by electron beam irradiation, it is not necessary to include a polymerization initiator.

[0106] In order to improve the performance of the radical initiator (E), an active energy ray sensitizer may be used in combination. Typical examples of the active energy ray sensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds, and anthracenes, benzophenones, perylene, phenothiazine, rose bengal, and the like are preferably used.

[0107] <Other ingredients> In addition to the components described above, additives can be appropriately blended into the active energy ray-polymerizable resin composition of the present invention, as long as the effects of the present invention are not impaired. For example, organic or inorganic fillers can be blended to reduce polymerization cure shrinkage, reduce thermal expansion coefficient, improve dimensional stability, improve elastic modulus, adjust viscosity, improve thermal conductivity, improve strength, improve toughness, and improve coloring. Examples of such fillers include polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like, and the shape thereof is not particularly limited, such as particulate or fibrous. When blending the above polymers, softeners, plasticizers, flame retardants, storage stabilizers, antioxidants, UV absorbers, thixotropy-imparting agents, dispersion stabilizers, fluidity-imparting agents, antifoaming agents, etc., can also be dissolved, semi-dissolved, or micro-dispersed in the active energy ray-polymerizable resin composition as polymer blends or polymer alloys rather than as fillers.

[0108] The active energy ray-polymerizable resin composition of the present invention is preferably substantially free of water or organic solvents in terms of drying equipment and drying energy. However, if the acid generator (KE) or radical initiator (E) is poorly soluble in the cationically polymerizable compound (K) or the compound (M) having an α,β-ethylenically unsaturated double bond group or if the composition has high viscosity, a small amount of water or organic solvent may be added to dissolve the acid generator (KE) or radical initiator (E). The content of water or organic solvent in the active energy ray-polymerizable resin composition is 5% by mass or less. Usable organic solvents are not particularly limited. Specifically, the viscosity of the active energy ray-polymerizable resin composition can be adjusted by adding water or organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents. Alternatively, the viscosity of the active energy ray-polymerizable resin composition can be reduced by heating.

[0109] The thickness of the resin composition layer formed from the active energy ray-polymerizable resin composition of the present invention is not particularly limited and can be appropriately adjusted depending on the intended use. The adjustment of the viscosity and the coating of the resin composition according to these embodiments can be easily carried out by adding a solvent to the active energy ray-polymerizable resin composition as needed.

[0110] When the resin composition layer has a thickness of 0.1 to 6 μm, the viscosity is preferably 1 to 1500 mPa·s, more preferably 10 to 1300 mPa·s, and even more preferably 20 to 1000 mPa·s. If the viscosity is 1500 mPa·s or less, when the resin composition is applied to a substrate (F), a thin film of 0.1 to 6 μm can be formed, and optical properties such as transmittance are also excellent. On the other hand, a viscosity of 1 mPa·s or less is preferred because it makes it easier to control the thickness of the resin composition layer.

[0111] Furthermore, when the resin composition layer has a thickness of 6 to 300 μm, the viscosity is preferably 1500 to 100,000 mPa·s, and more preferably 3,000 to 50,000 mPa·s. The viscosity of the resin composition is significantly affected by the viscosity of the compound (Mb) having an α,β-ethylenically unsaturated double bond group and a mass-average molecular weight of 1,000 to 60,000. Therefore, in order to control the viscosity of the resin composition, it is preferable to use a compound (Mb) having a viscosity of 1 to 100,000 mPa·s.

[0112] Next, the coating process of the active energy ray-polymerizable resin composition will be described. A laminate can be formed by coating one or both sides of a substrate (F) described below with an active energy ray-polymerizable resin composition by a suitable method according to a conventional method, and then laminating another substrate on the surface of the active energy ray-polymerizable resin composition as needed. The required film thickness of the resin composition layer varies depending on the intended use.

[0113] When the resin composition is used in applications such as a laminate for optical elements, such as a hard coat film or polarizing film, as described below, the resin composition is applied as a thin film. The thickness of the resin composition layer formed by application is preferably 0.1 to 6 μm, and more preferably 0.1 to 3 μm. By making the thickness 0.1 μm or more, sufficient adhesion or adhesive strength can be easily obtained when the resin composition is used as a coating agent or adhesive. On the other hand, when the thickness of the resin composition layer exceeds 6 μm, no change in properties such as adhesion or adhesive strength is often observed.

[0114] Furthermore, when the resin composition is used in applications such as a laminate for optical elements, such as a decorative film (meaning a filler sheet for touch panels) described below, the resin composition is applied as a thick film. The thickness of the resin composition layer formed by application is preferably 6 to 300 μm, and more preferably 20 to 250 μm. If the thickness is 6 μm or more, sufficient stress relaxation properties can be obtained, and if it is 300 μm or less, deterioration of coating properties such as streaking can be suppressed.

[0115] The method for applying the active energy ray-polymerizable resin composition of the present invention to a substrate or the like is not particularly limited, and examples thereof include various coating methods such as those using a Mayer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a microgravure coater, a lip coater, a comma coater, a curtain coater, a knife coater, a reverse coater, and a spin coater. Thin film coating, thick film coating, and the like can be used depending on the application, and there are no particular limitations.

[0116] The active energy ray-polymerizable resin composition of the present invention is applied to a substrate by a known, conventional method, and the resulting coating layer is irradiated with active energy rays to polymerize the compound (K) having a cationically polymerizable group such as an oxirane group, thereby polymerizing and curing the composition. Suitable light sources for the active energy ray irradiation are those that primarily emit light in the 150 to 550 nm wavelength range, such as low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, LED lamps, xenon lamps, and metal halide lamps. Laser beams, electron beams, and the like can also be used as active energy rays for exposure.

[0117] When an ultraviolet-absorbing substrate is used as the substrate (F), it is preferable to use a lamp in the ultraviolet irradiation device that irradiates a large amount of light at wavelengths longer than the absorption wavelength of the ultraviolet absorber contained in the protective film. Examples of such lamps include the "D bulb," which has a high irradiation output in the 380 to 400 nm wavelength range, and the "V bulb," which has a high irradiation output in the 405 to 425 nm wavelength range, centered around the 420 nm wavelength range (both of these bulbs are UV lamps manufactured by Heraeus).

[0118] The amount of ultraviolet light irradiation is not particularly limited, but is preferably 320 to 390 nm (UV-A region) or 395 to 445 nm (UV-V region), with an illuminance of 1 to 3000 mW / cm. 2 The light is irradiated at a dose of 10 to 5000 mJ / cm 2 It is preferable to irradiate and expose the film so that the irradiation dose is 10 mJ / cm2 If the irradiation dose is 10,000 mJ / cm or more, the curing of the active energy ray polymerizable resin composition is accelerated and the desired performance can be exhibited. 2 If the irradiation time is less than this, the irradiation time will not be too long and productivity will be excellent.

[0119] <<Laminate>> Next, a laminate obtained by laminating the active energy ray-polymerizable resin composition of the present invention on one or both sides of a substrate (F) will be described. The laminate of the present invention can also be suitably used as a laminate for an optical element. Furthermore, by using the active energy ray-polymerizable resin composition of the present invention, a laminate having a first substrate (F), a resin composition layer, and a second substrate (F) in this order can be made to have excellent adhesion, moist heat resistance, and flex resistance, even when an ultraviolet-absorbing substrate is used as at least one of the substrates (F), or even when both the first substrate (F) and the second substrate (F) are ultraviolet-absorbing substrates.

[0120] When the active energy ray-polymerizable resin composition of the present invention is used in a polymerization reaction by active energy rays, it is preferable that the substrate (F) be used to form a laminate comprising a transparent film-like substrate (transparent film) and a resin composition layer located on at least one side of the transparent film.

[0121] The transparent film laminate can be obtained as follows. A laminate can be obtained by coating one side of a transparent film with the active energy ray-polymerizable resin composition of the present invention and laminating another transparent film on the surface of the resin composition layer, or by further coating one or both sides of this laminate with the active energy ray-polymerizable resin composition and further laminating it on another transparent film, glass, or a transparent molded body.

[0122] The active energy ray polymerization reaction of the active energy ray-polymerizable resin composition proceeds by irradiating with active energy rays when the active energy ray-polymerizable resin composition is applied or laminated, or even after lamination, and it is preferable to irradiate with active energy rays after lamination to proceed with the polymerization reaction.

[0123] <Base material (F)> The substrate (F) can be a film substrate, a glass plate, a paper product, or the like, and can be used without any particular limitation. On the other hand, when used as an adhesive for bonding two or more substrates (F), it is necessary to use a substrate that is easily permeable to active energy rays in order to polymerize by irradiating with active energy rays, and it is particularly preferable to use a transparent film or a transparent glass plate. Even if one of the substrates is one that is difficult for active energy rays to transmit, such as wood, a metal plate, a plastic plate, or a paper product, it can still be used by using a transparent film or a transparent glass plate for the other, irradiating from the transparent film or transparent glass plate side, and polymerizing and curing.

[0124] As the substrate (F), a film substrate is preferably used, and examples thereof include transparent film substrates (transparent films) such as cellophane and various plastic films, with various plastic films being preferred. The film substrate may be a single layer, or a multilayer substrate formed by laminating multiple substrates may also be used.

[0125] When transparent films are used in a multilayer structure, they may be of the same or different compositions. For example, a polycycloolefin film may be used on one side and a polyacrylic film on the other side. The thickness of the transparent film can be determined as appropriate, but is generally about 1 to 500 μm from the viewpoints of strength, workability such as handleability, thinness, etc. In particular, a thickness of 1 to 300 μm is preferred, and 5 to 200 μm is more preferred. A transparent film thickness of 5 to 150 μm is particularly suitable.

[0126] The transparent film can also be used as an optical film for information and communication devices such as displays and touch panels.

[0127] Among various transparent films, the optical film is preferably a transparent film mainly used for optical purposes. Here, the optical film is a transparent film that has been specially treated and has optical functions (functions such as light transmission, light diffusion, light collection, refraction, scattering, and haze). These optical films can be used alone or in combination.

[0128] The various transparent films used as optical films are made of thermoplastic resins that are excellent in, for example, transparency, mechanical strength, thermal stability, moisture blocking properties, isotropy, etc. Examples of the various transparent films are also called various plastic films or plastic sheets, and include polyvinyl alcohol films, polytriacetylcellulose films, polypropylene, polyethylene, polycycloolefins, ethylene-vinyl acetate copolymer and other polyolefin films, polyethylene terephthalate, polybutylene terephthalate and other polyester films, polycarbonate films, polynorbornene films, polyarylate films, polyacrylic films, polyphenylene sulfide films, polystyrene films, polyvinyl films, polyamide films, polyimide films, polyoxirane films, etc.

[0129] <Laminate for optical elements> In one embodiment of the present invention, a laminate for optical elements can be constructed by forming a resin composition layer made of the active energy ray-polymerizable resin composition of the present invention on at least one main surface of an optical film as the substrate (F).

[0130] The laminate for optical elements is used by being attached to a glass plate of a liquid crystal display device, a PDP module, a touch panel module, an organic EL module, or the like, or to a transparent film such as the above-mentioned various plastic films.

[0131] The basic layer structure of the laminate for optical elements is a sheet-like double-sided active energy ray-polymerizable resin composition laminate such as transparent film / resin layer / transparent film or transparent film / resin layer / transparent film / resin layer / transparent film.Furthermore, the laminate is used as a laminate for optical elements in which a multilayer optical film such as transparent film / resin layer / transparent film / resin layer / transparent film / resin layer / transparent film, glass, or an optical molded product is fixed to an optical member. Any of these transparent films is at least an optical film.

[0132] Specific examples of the laminate for optical elements include hard coat films, antistatic coat films, antiglare coat films, polarizing films, retardation films, elliptically polarizing films, antireflection films, light diffusion films, brightness enhancement films, prism films (also referred to as prism sheets), decorative films (meaning filling sheets for touch panels), and light guide films (also referred to as light guide plates). The resin composition of the present invention may be used as an adhesive to further attach the laminate for optical elements to glass plates of liquid crystal displays, PDP modules, touch panel modules, organic EL modules, and the like. In another embodiment, the resin composition of the present invention may be used as an adhesive to attach the laminate for optical elements to the various optical films.

[0133] Hereinafter, a polarizing film will be taken as an example of the laminate for optical elements, and the embodiment of the laminate will be described more specifically.The polarizing film is also called a polarizing plate, and is a sheet-like laminate for optical elements having a multilayer structure, in which two polyacetyl cellulose-based protective films (hereinafter referred to as "TAC films"), which are polytriacetyl cellulose-based films, are laminated on both sides of a polyvinyl alcohol-based polarizer, or one or both sides of a polyvinyl alcohol-based polarizer is laminated with a polycycloolefin-based film, a polyacrylic film, a polycarbonate film, a polyester film, etc., which are polynorbornene-based films, via an adhesive, and the active energy ray polymerizable resin composition of the present invention can be suitably used as the adhesive for polarizing films.

[0134] When transparent protective films are provided on both sides of the polarizer, the transparent protective films on the front and back may be made of the same polymer material, or may be made of different polymer materials.

[0135] As the protective film used in the polarizing plate (polarizing film), a TAC film, a polycycloolefin film, a polyacrylic film, a polycarbonate film, a polyester film, etc. are preferably used. An ultraviolet absorbing substrate containing an ultraviolet absorber can also be used for the protective film. As the ultraviolet absorbing substrate, a substrate that absorbs most of the ultraviolet light of 400 nm or less is used. When the laminate of the present invention is a polarizing plate, at least one of the two protective films may be an ultraviolet absorbing substrate.

[0136] More specifically, a polarizing plate (polarizing film) using the active energy ray-polymerizable resin composition of the present invention can be obtained as follows.

[0137] (I) An active energy ray-polymerizable resin composition is applied to one surface of a transparent protective film as a first substrate (F) to form a first resin composition layer; an active energy ray-polymerizable resin composition is applied to one surface of a second transparent protective film as a second substrate (F) to form a second resin composition layer; Next, a first resin composition layer and a second resin composition layer are superimposed simultaneously or sequentially on each surface of the polyvinyl alcohol-based polarizer, and then the layers are irradiated with active energy rays to polymerize and cure the first resin composition layer and the second resin composition layer.

[0138] (II) A production method including applying an active energy ray-polymerizable resin composition to one surface of a polyvinyl alcohol-based polarizer to form a first resin composition layer, covering the surface of the formed first resin composition layer with a first transparent protective film as a first substrate (F), applying an active energy ray-polymerizable resin composition to the other surface of the polyvinyl alcohol-based polarizer to form a second resin composition layer, covering the surface of the formed second resin composition layer with a second transparent protective film as a second substrate (F), and irradiating with active energy rays to polymerize and cure the first polymerizable resin composition layer and the second resin composition layer.

[0139] (III) A method of producing a film by dripping an active energy ray-polymerizable resin composition onto an edge of a first substrate (F) where a first transparent protective film and a polyvinyl alcohol-based polarizer are superimposed, and onto an edge of a second transparent protective film (F) superimposed on the side of the polyvinyl alcohol-based polarizer where the first transparent protective film is not present, and then passing the film between rolls to spread the resin composition between the layers. Next, the film is irradiated with active energy rays to polymerize and cure the active energy ray-polymerizable resin composition. There are, but are not particularly limited to, [Example]

[0140] Specific examples of the present invention will be described below in conjunction with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, and "RH" represents relative humidity. The blend amounts in the table are in parts by mass, and values ​​other than the solvent are calculated as non-volatile content. Note that blank spaces in the table indicate that no blend was made.

[0141] <Method for measuring mass average molecular weight> The "mass average molecular weight" is a value measured using a gel permeation chromatograph "HLC-8220GPC" manufactured by Tosoh Corporation. The polystyrene-equivalent mass average molecular weight was measured using four separation columns connected in series: "TSK-GEL SUPER H5000," "TSK-GEL SUPER H4000," "TSK-GEL SUPER H3000," and "TSK-GEL SUPER H2000" manufactured by Tosoh Corporation, using tetrahydrofuran at a temperature of 40°C as the mobile phase at a flow rate of 0.6 ml / min.

[0142] <Method for measuring hydroxyl value> The hydroxyl value was measured as follows. Approximately 1 g of sample was precisely weighed and placed in a stoppered Erlenmeyer flask. 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1) mixture was added and dissolved. Then, exactly 5 ml of an acetylating agent (a solution prepared by dissolving 25 g of acetic anhydride in pyridine to a volume of 100 ml) was added and stirred for approximately 1 hour. Phenolphthalein test solution was added as an indicator and the mixture was stirred for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color, and the hydroxyl value was calculated using the following formula. The hydroxyl value was the value for the resin in its dry state (unit: mgKOH / g). Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (non-volatile content / 100) + D Where S: sample amount (g) a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml) b: Amount of 0.1N alcoholic potassium hydroxide solution consumed in the blank experiment (ml) F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

[0143] The materials used in the examples and comparative examples are as follows. <Cationic polymerizable compound (K)> [Oxirane compound (K1)] ((K11) Oxirane Compounds Having No Alkoxysilyl Groups) "(K111) Oxirane compounds with aromatic rings and no alkoxysilyl groups" JER828: Bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation) "(K112) Oxirane compounds without aromatic rings or alkoxysilyl groups" 16HDDGE: 1,6-Hexanediol diglycidyl ether CEL2021P: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celloxide 2021P, manufactured by Daicel Corporation) ((K12) Oxirane Compound Having an Alkoxysilyl Group) KBE-402: 3-glycidoxypropylmethyldiethoxysilane (Shin-Etsu Chemical Co., Ltd.) [Cyclic hetero compounds other than oxirane compounds (K2)] OXT-101: 3-ethyl-3-hydroxymethyloxetane (Aronoxetane OXT-101, manufactured by Toagosei Co., Ltd.)

[0144] <Sulfide compounds (S)> [Sulfide compounds having aromatic rings (S1)] ((S11) Sulfide compounds having an aromatic ring and no nitrogen atom) Irganox 1035: 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF) Irganox 1520: 2,4-bis(octylthiomethyl)-6-methylphenol (BASF) Irganox 1726: 2,4-bis[(dodecylthio)methyl]-6-methylphenol (BASF) ((S12) Sulfide compounds having an aromatic ring and a nitrogen atom) Omnirad907: 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (IGM resins BV) OXE01: 1-[4-(phenylthio)phenyl]octane-1,2-dione 2-(O-benzoyloxime) (BASF, Irgacure OXE01) [Sulfide compounds without aromatic rings (S2)] AO-412S: 2,2-bis[[3-(dodecylthio)-1-oxopropyloxy]methyl]-1,3-propanediyl bis[3-(dodecylthio)propionic acid] (ADEKA Corporation, ADK STAB AO-412S) AO-503: Ditridecyl 3,3'-thiobispropionate (ADEKA Corporation, Adeka Stab AO-503)

[0145] <Acid Generator (KE)> [Iodonium salt-based acid generator (KE1)] Omnicat 250: 4-Isobutylphenyl (4-methylphenyl) Hexafluorophosphate (IGM resins BV) WPI-124: Bis[4-n-alkyl(C10-13)phenyl]iodonium tetrakispentafluorophenylborate (Fujifilm Wako Pure Chemical Industries, Ltd.) [Sulfonium salt acid generator (KE2)] CPI-110P: San-Apro triarylsulfonium PF6 salt type photoacid generator CPI-101A: San-Apro triarylsulfonium SbF6 salt type photoacid generator

[0146] <Thioxanthone compounds (T)> DETX-S: 2,4-diethylthioxanthone 2-ITX: 2-isopropylthioxanthone <Radical polymerization initiator (E)> TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO manufactured by IGM resins BV)

[0147] <Compound (M) Having an α,β-Ethylenically Unsaturated Double Bond Group> [Compound (Ma)] (Compound (Ma1)) 4HBA: 4-hydroxybutyl acrylate CHDMMA: Cyclohexanedimethanol monomethacrylate (Compound (Ma2)) IBXA: Isobornyl acrylate TCDDA: Tricyclodecane dimethanol diacrylate (Compound (Ma3)) EOEOEA: Ethoxyethoxyethyl acrylate DPGDA: Dipropylene glycol diacrylate TMPTA: Trimethylolpropane triacrylate

[0148] [Compound (Mb)] (Compound (Mb1)) Oligomer 1: Purple UV3000B: Polyurethane acrylate, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Mw=18,000 Oligomer 2: An oligomer produced by the following method was used. (Compound (Mb3)) Oligomer 3: An oligomer produced by the following method was used.

[0149] <Production of Oligomer 2> A five-neck separable flask equipped with a stirrer, reflux condenser, gas inlet, thermometer, and dropping funnel was charged with 81.6 parts of polytetramethylene glycol (PTG850, manufactured by Hodogaya Chemical Co., Ltd., hydroxyl value 127.1 mgKOH / g) and 41.4 parts of isophorone diisocyanate, and the temperature was raised to 60°C while introducing dry air. 0.05 parts of dibutyltin dilaurate was added and the mixture was allowed to react for 1 hour. Separately, 27.0 parts of 4-hydroxybutyl acrylate and 0.15 parts of hydroquinone monomethyl ether were charged to a dropping funnel and added dropwise to the separable flask over 1 hour. After the dropwise addition, stirring was continued for 3 hours at 80°C. The absence of an isocyanato group absorption peak was confirmed by infrared absorption spectroscopy, and the reaction was terminated to obtain Oligomer 2. The mass-average molecular weight of the product was 4,000.

[0150] <Production of Oligomer 3> A five-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer was charged with 96.9 parts of bisphenol F epoxy resin (Mitsubishi Chemical Corporation: JER1007P, epoxy equivalent 2250), 3.2 parts of acrylic acid, 0.1 parts of hydroquinone monomethyl ether, and 20 parts of MEK. The mixture was heated to 60°C while introducing dry air and dissolved. 0.5 parts of tetrabutylammonium borate was added, and the mixture was heated to 100°C and reacted for 8 hours to obtain Oligomer 3. The mass-average molecular weight of Oligomer 3 was 5100.

[0151] [Example 1] 50 parts of JER828 as a cationically polymerizable compound (K), 45.5 parts of 16HDDGE, 0.5 parts of Irganox1035 as a sulfide compound (S), 3 parts of Omnicat250 as an acid generator (KE), and 1 part of DETX as a thioxanthone compound (T) were charged into a light-shielded 300 ml glass bottle, thoroughly stirred with a disperser, and then thoroughly degassed to obtain an active energy ray-polymerizable resin composition.

[0152] [Examples 2 to 30, Comparative Examples 1 to 5] As shown in Tables 1 to 3, active energy ray-polymerizable resin compositions were obtained in the same manner as in Example 1, except that the compositions and blending amounts (parts by mass) were changed.

[0153] Evaluation of active energy ray-polymerizable resin composition The storage stability of the active energy ray-polymerizable resin composition of the present invention at high temperature (70° C.) was evaluated by the following method. The results are shown in Tables 1 to 3.

[0154] <High temperature storage stability> The active energy ray-polymerizable resin composition was stored in a thermostatic bath at 70°C for 24 hours, and 1.1 ml of the resin composition before and after storage was used as a measurement sample. Measurement was performed using an E-type viscometer (TVE-33LT, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 5 rpm and 25°C, and the viscosity was evaluated based on the rate of change in viscosity. Viscosity change rate = viscosity after storage / viscosity before storage [Evaluation criteria] ◎: 0.95 or more and less than 1.05, very good 〇: 1.05 or more and less than 1.1, or 0.9 or more and less than 0.95, excellent △: 1.1 or more and less than 1.15, or 0.85 or more and less than 0.9, usable ×: 1.15 or more or less than 0.85, not practical

[0155] Evaluation of laminates The obtained active energy ray-polymerizable resin composition was used to prepare the following laminates X1 and X2, which were then evaluated by the following methods. The results are shown in Tables 1 to 3.

[0156] <Production of Laminate X1 (Polarizing Plate)> As transparent films (1) and (2), a UV-absorbing substrate, a polytriacetyl cellulose (hereinafter abbreviated as TAC) film containing a UV absorber manufactured by Fujifilm Corporation (trade name "Fujitac: 80 μm", transmittance at wavelengths of 300 to 380 nm is 20% T or less), was used. 2 Within one hour after the surface treatment, the obtained active energy ray-polymerizable resin composition was applied to a film thickness of 4 μm using a wire bar coater to form a resin composition layer. The polyvinyl alcohol-based polarizer was sandwiched between the resin composition layer and the polyvinyl alcohol-based polarizer to obtain a laminate consisting of "transparent film (1) (ultraviolet absorbing TAC film) / resin composition layer / PVA-based polarizer / resin composition layer / transparent film (2) ultraviolet absorbing TAC film." The four sides of this laminate were fixed with cellophane tape so that the transparent film (2) was in contact with the tin plate, and it was fixed to the tin plate. The maximum illuminance was 500 mW / cm using an ultraviolet irradiation device (Heraeus V-bulb). 2 , cumulative light intensity 1000mJ / cm 2 The transparent film (1) was irradiated with ultraviolet light (UV-V region) from the transparent film (1) side to prepare a laminate X1 (polarizing plate).

[0157] <Production of laminate X2> The obtained active energy ray polymerizable resin composition was heated to 100°C and then coated to a thickness of 8 μm using a bar coater on a 50 μm thick polyethylene terephthalate (hereinafter abbreviated as PET) film having a transmittance of 20%T or less at wavelengths of 300 to 380 nm. A 50 μm thick PET film was then bonded to this using a nip roll to obtain a laminate consisting of "transparent film (1) (PET film) / resin composition layer / transparent film (2) (PET film)". After that, the laminate was irradiated with an ultraviolet ray irradiation device (Heraeus V-bulb) at a maximum irradiance of 500 mW / cm. 2 , cumulative light intensity 1000mJ / cm 2 The laminate was irradiated from one side with ultraviolet light of 1000 kJ / cm2 to obtain a laminate X2.

[0158] For each, the laminate X1 and laminate X2 produced using the active energy ray-polymerizable resin composition immediately after production were used for evaluation as "initial." Furthermore, the laminate X1 and laminate X2 produced using the active energy ray-polymerizable resin composition after storage at 70°C for 24 hours were used for evaluation as "after storage (70°C for 24 hours)."

[0159] <Adhesive strength> The adhesive strength was measured in accordance with JIS K6 854-4 Adhesives - Peel Adhesion Strength Test Method - Part 4: Floating Roller Method. Specifically, the obtained laminate X1 was cut into a size of 25 mm × 150 mm using a cutter to prepare a measurement sample. The sample was attached to a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) and a laminator to obtain a measurement laminate of a polarizing plate and a metal plate. A peeling trigger was provided in advance between the transparent film and the polarizer in the measurement laminate. This measurement laminate was peeled at a 90° angle at a speed of 300 mm / min under conditions of 23°C and 50% relative humidity, and the peel strength was measured. The peel strength between the polyvinyl alcohol-based polarizer and the transparent film (2) was measured. This peel strength was evaluated as adhesion strength using a four-point scale. [Evaluation criteria] ◎: Unable to peel or polarizing plate is broken, very good ○: Peeling force is 2.0 (N / 25mm) or more, excellent △: Peeling force is 1.0 (N / 25mm) or more and less than 2.0 (N / 25mm), practical use possible ×: Peeling force is less than 1.0 (N / 25 mm), not practical

[0160] <Moisture and heat resistance> The laminate X2 bonded with each adhesive was cut into a size of 50 mm x 40 mm and exposed for 1000 hours under conditions of 60°C-90% RH and 85°C-85% RH. After exposure, the presence or absence of peeling at the edge of the laminate A was visually evaluated using the following four-point scale. If peeling occurred under the conditions of 85°C and 85% RH, it was marked with an X, △, or ◯. [Evaluation criteria] ◎: No peeling even under conditions of 85℃-85%RH, excellent ○: Excellent, no peeling at all under conditions of 60℃-90%RH △: Peeling of less than 1 mm occurs under conditions of 60°C-90%RH, and it is usable. ×: Peeling of 1mm or more occurs under conditions of 60℃-90%RH, and it is not suitable for practical use.

[0161] <Bending resistance> The laminate X2 was cut into a size of 120 mm wide x 200 mm long, and the bending tester (manufactured by Yuasa System Co., Ltd.) was set so that the inner diameter (diameter) when bent was 2 mm, and the bending test was repeated 300,000 times, with one cycle consisting of bending and releasing 180°. The bending property was evaluated by the appearance after the test from the following perspectives. Appearance: The test laminate was visually inspected for the presence of bubbles and the presence of lifting or peeling of the resin composition layer under the following conditions. [Evaluation criteria] ◎: No bubbles, lifting or peeling are observed, and it is extremely excellent. ○: Some bubbles, lifting, and peeling are observed, but excellent △: Air bubbles, lifting and peeling are observed, but practically usable ×: Air bubbles, lifting and peeling are evident, and the product is not suitable for practical use.

[0162] [Table 1]

[0163] [Table 2]

[0164] [Table 3]

[0165] [Example 41] 50 parts of JER828 as a cationically polymerizable compound (K), 46 parts of 16HDDGE, 0.5 parts of Irganox1035 as a sulfide compound (S), and 4 parts of CPI-110P as an acid generator (KE) were charged into a light-shielded 300 ml glass bottle, thoroughly stirred with a disperser, and then thoroughly degassed to obtain an active energy ray-polymerizable resin composition.

[0166] [Examples 42 to 54, Comparative Examples 6 to 10] As shown in Tables 4 and 5, active energy ray-polymerizable resin compositions were obtained in the same manner as in Example 41, except that the compositions and blending amounts (parts by mass) were changed.

[0167] Evaluation of active energy ray-polymerizable resin composition The storage stability of the active energy ray-polymerizable resin composition of the present invention at high temperatures (70° C. or 100° C.) was evaluated by the following method. The results are shown in Tables 4 and 5.

[0168] <High temperature storage stability> The active energy ray-polymerizable resin composition was stored in a thermostatic chamber at 70°C or 100°C for 24 hours, and 1.1 ml of the resin composition before and after storage was used as a measurement sample. Measurement was performed using an E-type viscometer (TVE-33LT, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 5 rpm and 25°C, and the viscosity was evaluated based on the rate of change in viscosity. Viscosity change rate = viscosity after storage / viscosity before storage [Evaluation criteria] ◎: 0.95 or more and less than 1.05, very good 〇: 1.05 or more and less than 1.1, or 0.9 or more and less than 0.95, excellent △: 1.1 or more and less than 1.15, or 0.85 or more and less than 0.9, usable ×: 1.15 or more or less than 0.85, not practical

[0169] Evaluation of laminates The obtained active energy ray-polymerizable resin composition was used to prepare the following laminate Y1, which was then evaluated by the following methods. The results are shown in Tables 4 and 5.

[0170] <Production Example of Laminate Y1 (Polarizing Plate)> As the transparent film (1), a polytriacetyl cellulose film (trade name "Fujitack: 80 μm") containing no ultraviolet absorber manufactured by Fujifilm Corporation was used, and as the transparent film (2), a polytriacetyl cellulose film (trade name "Fujitack: 80 μm", with a transmittance of 20% T or less at wavelengths of 300 to 380 nm) manufactured by Fujifilm Corporation was used. 2 Within 1 hour after the surface treatment, the obtained active energy ray-polymerizable resin composition was applied to a film thickness of 4 μm using a wire bar coater to form a resin composition layer. The polyvinyl alcohol-based polarizer was sandwiched between the TAC film and the resin composition layer to obtain a laminate consisting of "transparent film (1) (TAC film) / resin composition layer / PVA-based polarizer / resin composition layer / transparent film (2) (ultraviolet-absorbing TAC film)". The four sides of this laminate were fixed with cellophane tape so that the transparent film (2) was in contact with the tin plate, and it was fixed to the tin plate. An ultraviolet irradiation device (D-bulb manufactured by Heraeus) was used to apply a maximum illuminance of 400 mW / cm. 2 , cumulative light intensity 600mJ / cm 2 The transparent film (1) was irradiated with ultraviolet light (UV-A region) from the transparent film (1) side to prepare a laminate Y1 (polarizing plate).

[0171] <Production of laminate Y2> The obtained active energy ray polymerizable resin composition was heated to 100°C and then coated to a thickness of 8 μm using a bar coater on a 50 μm thick PET film having a transmittance of 20%T or less at wavelengths of 300 to 380 nm. A 50 μm thick PET film was then bonded to this using a nip roll to obtain a laminate consisting of "transparent film (1) (PET film) / resin composition layer / transparent film (2) (PET film)". After that, the laminate was irradiated with an ultraviolet ray irradiation device (Heraeus V-bulb) at a maximum illuminance of 500 mW / cm. 2 , cumulative light intensity 1000mJ / cm 2 The laminate was irradiated from one side with ultraviolet light of 1000 kJ / cm2 to obtain a laminate Y2.

[0172] For each, laminate Y1 and laminate Y2 produced using the active energy ray-polymerizable resin composition immediately after production were used for evaluation as "initial". Furthermore, laminate Y1 and laminate Y2 produced using the active energy ray-polymerizable resin composition after storage at 100°C for 24 hours were used for evaluation as "after storage (100°C for 24 hours)".

[0173] <Adhesive strength> The adhesive strength was measured in accordance with JIS K6 854-4 Adhesives - Peel Adhesion Strength Test Method - Part 4: Floating Roller Method. That is, the obtained laminate Y1 was cut into a size of 25 mm × 150 mm using a cutter to prepare a measurement sample. The sample was attached to a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) and a laminator to obtain a measurement laminate of a polarizing plate and a metal plate. A peeling trigger was provided in advance between the transparent film and the polarizer in the measurement laminate. This measurement laminate was peeled at a 90° angle at a speed of 300 mm / min under conditions of 23°C and 50% relative humidity, and the peel strength was measured. At this time, the peel strength between the polyvinyl alcohol-based polarizer and the transparent film (2) was measured. This peel strength was evaluated as adhesive strength using a four-point scale. [Evaluation criteria] ◎: Unable to peel or polarizing plate is broken, very good ○: Peeling force is 2.0 (N / 25mm) or more, excellent △: Peeling force is 1.0 (N / 25mm) or more and less than 2.0 (N / 25mm), practical use possible ×: Peeling force is less than 1.0 (N / 25 mm), not practical

[0174] <Moisture and heat resistance> The laminate A bonded with each adhesive was cut into a size of 50 mm x 40 mm and exposed for 1000 hours under conditions of 60°C-90% RH and 85°C-85% RH. After exposure, the presence or absence of peeling at the edge of the laminate Y1 was visually evaluated using the following four-point scale. If peeling occurred under the conditions of 85°C and 85% RH, it was marked with an X, △, or ◯. [Evaluation criteria] ◎: No peeling even under conditions of 85℃-85%RH, excellent ○: Excellent, no peeling at all under conditions of 60℃-90%RH △: Peeling of less than 1 mm occurs under conditions of 60°C-90%RH, and it is usable. ×: Peeling of 1mm or more occurs under conditions of 60℃-90%RH, and it is not suitable for practical use.

[0175] <Bending resistance> The laminate Y2 was cut into a size of 120 mm wide x 200 mm long, and the bending tester (manufactured by Yuasa System Co., Ltd.) was set so that the inner diameter (diameter) when bent was 2 mm, and the bending test was repeated 300,000 times, with one cycle consisting of bending and releasing 180°. The flexibility was evaluated by observing the appearance after the test from the following perspectives. Appearance: The test laminate was visually inspected for the presence of bubbles and the presence of lifting or peeling of the resin composition layer under the following conditions. [Evaluation criteria] ◎: No bubbles, lifting or peeling are observed, and it is extremely excellent. ○: Some bubbles, lifting, and peeling are observed, but excellent △: Air bubbles, lifting and peeling are observed, but practically usable ×: Air bubbles, lifting and peeling are evident, and the product is not suitable for practical use.

[0176] [Table 4]

[0177] [Table 5]

[0178] As shown in Tables 1 to 5, it was confirmed that the active energy ray-polymerizable resin composition of the present invention has excellent storage stability, high heat resistance, and excellent curability. Furthermore, it was confirmed that the active energy ray-polymerizable resin composition has high heat resistance, and therefore has good adhesiveness, moist heat resistance, and bending resistance even when stored at high temperatures.

Claims

1. An active energy ray-polymerizable resin composition comprising 1 to 99 mass% of a cationically polymerizable compound (K), 0.01 to 10 mass% of a sulfide compound (S) (excluding a thioxanthone compound (T) and a sulfonium salt-based acid generator (KE2)), an acid generator (KE), a compound (M) having an α,β-ethylenically unsaturated double bond group, and a radical polymerization initiator (E), wherein the sulfide compound (S) is a sulfide compound (S111) having one phenol structure in one molecule, and the cationically polymerizable compound (K) is a cationically polymerizable compound (K1) that is an oxirane compound that is a three-membered cyclic ether compound.

2. 2. The active energy ray-polymerizable resin composition according to claim 1, wherein the acid generator (KE) is an iodonium salt-based acid generator (KE1).

3. 2. The active energy ray-polymerizable resin composition according to claim 1, wherein the acid generator (KE) is a sulfonium salt-based acid generator (KE2).

4. The active energy ray-polymerizable resin composition according to any one of claims 1 to 3, further comprising a thioxanthone compound (T).

5. The active-energy ray-polymerizable resin composition according to any one of claims 1 to 4, wherein the compound (M) having an α,β-ethylenically unsaturated double bond group has a mass-average molecular weight of less than 1000 and includes a compound (Ma1) having a hydroxyl group and an α,β-ethylenically unsaturated double bond group.

6. The active-energy ray-polymerizable resin composition according to any one of claims 1 to 5, wherein the compound (M) having an α,β-ethylenically unsaturated double bond group includes a compound (Mb) having an α,β-ethylenically unsaturated double bond group having a mass average molecular weight of 1,000 or more and 60,000 or less.

7. The active-energy ray-polymerizable resin composition according to any one of claims 1 to 6, wherein the compound (M) having an α,β-ethylenically unsaturated double bond group has a mass-average molecular weight of less than 1000 and includes a compound (Ma2) having two or more α,β-ethylenically unsaturated double bond groups and at least one of a cycloalkane skeleton and a cycloalkene skeleton.

8. The active energy ray-polymerizable resin composition according to any one of claims 1 to 7, which is an adhesive.

9. A laminate obtained by laminating a resin composition layer made of the active energy ray-polymerizable resin composition according to any one of claims 1 to 8 on one or both sides of a substrate (F).

10. 10. The laminate according to claim 9, wherein the substrate (F) is a polyacetyl cellulose film, a polynorbornene film, a polypropylene film, a polyacrylic film, a polycarbonate film, a polyester film, a polyvinyl alcohol film, or a polyimide film.

11. A laminate comprising, in this order, a first substrate (F), a resin composition layer made of the active-energy ray-polymerizable resin composition according to any one of claims 1 to 8, and a second substrate (F), wherein at least one of the substrates (F) is an ultraviolet-absorbing substrate, and the ultraviolet-absorbing substrate is a substrate having a transmittance of 20% or less at a wavelength of 300 to 380 nm.

12. The laminate according to claim 11, wherein both the first substrate (F) and the second substrate (F) are the ultraviolet absorbing substrate.

13. The laminate according to any one of claims 9 to 12, which is used for an optical element.

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