Adhesive composition

Abstract

This invention provides an adhesive composition that does not leach even after long-term storage (good resistance to leaching) and is capable of sufficiently absorbing light with wavelengths around 400 nm. An adhesive composition comprises: a resin (A), a light-selective absorbing compound (B) containing an indole structure and polymerizable groups within its molecule, and an initiator (C). Preferably, the adhesive composition further comprises at least one selected from a free radical curing component (D), a crosslinking agent (E), a silane compound (F), and a light-selective absorbing compound (G) other than the light-selective absorbing compound (B) containing an indole structure and polymerizable groups within its molecule.

Description

Technical Field

[0001] The present invention relates to adhesive compositions and optical films having adhesive layers formed from the adhesive compositions laminated thereon. Background Technology

[0002] In display devices such as organic electroluminescent displays (organic EL display devices) and liquid crystal displays (FPDs: flat panel displays), various components such as organic EL elements, liquid crystal cells, and optical films such as polarizers can be used. Among these components, organic EL light-emitting elements and liquid crystal compounds are organic materials, and therefore, degradation caused by ultraviolet (UV) light is prone to become a problem. Furthermore, it has been found that liquid crystal phase retardation films and organic EL light-emitting elements formed by orienting polymeric liquid crystal compounds and photocuring not only tend to degrade under UV light, but also tend to degrade under short-wavelength visible light around 400 nm (e.g., wavelengths of 390 nm to 410 nm).

[0003] In order to suppress degradation caused by ultraviolet light or short-wavelength visible light around 400 nm, Patent Document 1 describes the provision of an adhesive layer containing an ultraviolet absorber, and describes that the adhesive layer is formed by an adhesive composition containing an acrylic copolymer and a triazine-based ultraviolet absorber.

[0004] In addition, Patent Document 2 describes an adhesive composition containing an indole-based ultraviolet absorber (BONASORB UA-3901 manufactured by Orient Chemical Industries) that does not have polymerizable groups.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2016-157077

[0008] Patent Document 2: Japanese Patent Application Publication No. 2017-48340 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] Most of the triazine-based UV absorbers described in Patent Document 1 are compounds that exhibit maximum absorption wavelengths below 360 nm, and cannot efficiently absorb light near 400 nm. To fully absorb light near 400 nm, a large amount of triazine-based UV absorber needs to be incorporated into the adhesive composition. However, if a large amount of triazine-based UV absorber is incorporated, there is a problem of UV absorber precipitation under high temperature conditions during long-term storage.

[0011] In addition, although the indole-based ultraviolet absorber described in Patent Document 2 can efficiently absorb light with wavelengths around 380 nm to 400 nm, it has the problem of easy precipitation, which occurs even when a small amount is added to the adhesive composition.

[0012] Methods for solving problems

[0013] This invention includes the following inventions.

[0014] [1] An adhesive composition comprising a resin (A), a light-selective absorbing compound (B) comprising an indole structure and polymerizable groups within the molecule, and an initiator (C).

[0015] [2] The adhesive composition according to [1], wherein the polymerizable group is a free radical polymerizable group.

[0016] [3] The adhesive composition according to [1] or [2], wherein the polymerizable group is (meth)acryloyl.

[0017] [4] The adhesive composition according to any one of [1] to [3], wherein the initiator (C) is a free radical polymerization initiator.

[0018] [5] The adhesive composition according to any one of [1] to [4], wherein the initiator (C) is a photoradical polymerization initiator.

[0019] [6] The adhesive composition according to any one of [1] to [5], wherein the initiator (C) is an oxime ester compound.

[0020] [7] The adhesive composition according to any one of [1] to [6] further comprises a free radical curing component (D).

[0021] [8] The adhesive composition according to [7], wherein the free radical curing component (D) is a (meth)acrylate compound.

[0022] [9] The adhesive composition according to [7] or [8], wherein the free radical curing component (D) is a polyfunctional (meth)acrylate compound.

[0023]

[10] The adhesive composition according to any one of [1] to [9] further comprises a crosslinking agent (E).

[0024]

[11] The adhesive composition according to

[10] , wherein the crosslinking agent (E) is an isocyanate crosslinking agent.

[0025]

[12] The adhesive composition according to any one of

[10] or

[11] , wherein the glass transition temperature of the resin (A) is below 40°C.

[0026]

[13] According to the adhesive composition of

[12] , wherein the resin (A) with a glass transition temperature of 40°C or less is a (meth)acrylic resin.

[0027]

[14] The adhesive composition according to any one of [1] to

[13] , wherein the light-selective absorbing compound (B) containing an indole structure and a polymerizable group within the molecule is a compound that exhibits maximum absorption at wavelengths above 360 ​​nm and below 420 nm.

[0028]

[15] The adhesive composition according to any one of [1] to

[14] , wherein the light-selective absorbing compound (B) containing an indole structure and a polymerizable group within the molecule satisfies formula (1).

[0029] ε(400)≥0.05 (1)

[0030] [In equation (1), ε(400) represents the gamma absorption coefficient of the light-selective absorbing compound (B) at a wavelength of 400 nm. The unit of gamma absorption coefficient is L / (g·m).]

[0031]

[16] The adhesive composition according to [1] to

[15] , wherein the light-selective absorbing compound (B) containing an indole structure and a polymerizable group within the molecule is a compound represented by formula (I) or (II).

[0032]

[0033] In formula (I), R 1 R 2 R 3 R 4 R 5 and R 6 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms that may have substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group may be replaced with -NR. 1A -, -SO2-, -CO-, -O-, -S- or -CF2-.

[0034] R 1A It represents a hydrogen atom, an alkyl group with 1 to 25 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms.

[0035] E 1 This indicates an electron-withdrawing group.

[0036] Z represents the linking group.

[0037] A represents a polymerizable group.

[0038] In equation (II), R 12 and R 17 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms that may have substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group may be replaced with -NR. 11A -, -SO2-, -CO-, -O-, -S- or -CF2-.

[0039] R 11 R 13 R 14 R 15 and R 16 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a group containing a polymerizable group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms that may have substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group may be replaced with -NR. 12A -, -SO2-, -CO-, -O-, -S- or -CF2-.

[0040] Among them, R 11 R 13 R 14 R 15 and R 16 At least one of them represents a group containing a polymerizable group.

[0041] R 11A and R 12A Each can be independently represented by a hydrogen atom, an alkyl group with 1 to 25 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms.

[0042] E 11 This indicates an electron-withdrawing group.

[0043]

[17] The adhesive composition according to

[16] , wherein R 2 and R 12 Each is an aromatic hydrocarbon group with 6 to 18 carbon atoms.

[0044]

[18] The adhesive composition according to

[16] , wherein the compound represented by formula (I) is the compound represented by formula (III) and the compound represented by formula (II) is the compound represented by formula (IV).

[0045]

[0046] [R 1 R 3 R 4 R 5 R 6 E 1 R 11 R 13 R 14 R 15 R 16 R 17 and E 11 They represent the same meanings as described above.

[0047] R 7 It represents a hydrogen atom, cyano group, methyl group, or phenyl group.

[0048] Z 1 -OR indicates alkyldiyl groups with 1 to 12 carbon atoms, divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, and alkyl diols. 2A -*1、-SR 2B -*1 or -NR 1D -R 2C -*1.

[0049] Z 2 This represents a single bond, *2-CO-O-, *2-O-CO-, *2-S(=O)2-, *2-O-SO2-, and *2-CO-NR. 1B -、*2-NR 1C -CO-、*2-R 2D OP(=O)-OR 2E -、*2-NR 1E -CO-O-、*2-O-CO-NR 1F -、*2-(OR 2F ) s1 -, *2-CO-S-, *2-S-CO-, or perfluoroalkyl dimethyl groups with 1 to 4 carbon atoms.

[0050] R 1B R 1C R 1D R 1E and R 1F Each can be independently represented as an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0051] R 2A R 2B R 2C R 2D R 2E and R 2F Each of these groups independently represents a divalent hydrocarbon group with 1 to 18 carbon atoms.

[0052] Z 1This indicates a divalent linker group.

[0053] A 1 It indicates a polymerizable group.

[0054] *1 indicates that it is related to Z 2 The connection key.

[0055] *2 indicates that it is related to Z 1 The connection key.

[0056]

[19] An adhesive layer formed from any one of the adhesive compositions described in [1] to

[18] .

[0057]

[20] The adhesive layer according to

[19] satisfies the following formula (2).

[0058] A(400)≥0.4 (2)

[0059] [In equation (2), A(400) represents the absorbance at a wavelength of 400 nm.]

[0060]

[21] The adhesive layer according to

[19] or

[20] , wherein the film thickness of the adhesive layer is less than 10 μm.

[0061]

[22] An optical film having an adhesive layer, wherein at least one side of the adhesive layer in any one of

[19] to

[21] is laminated with the optical film.

[0062]

[23] The optical film with an adhesive layer according to

[22] , wherein the optical film is a polarizing plate.

[0063]

[24] An image display device comprising an optical film with an adhesive layer as described in

[22] or

[23] .

[0064] Invention Effects

[0065] The adhesive composition of the present invention does not precipitate compounds even after long-term storage (good resistance to exudation) and can fully absorb light with a wavelength of around 400 nm. Attached Figure Description

[0066] Figure 1 A schematic cross-sectional view illustrating an example of the layer composition of the adhesive layer of the present invention.

[0067] Figure 2 A schematic cross-sectional view illustrating an example of the layer configuration of the optical laminate of the present invention.

[0068] Figure 3 A schematic cross-sectional view illustrating an example of the layer configuration of the optical laminate of the present invention.

[0069] Figure 4 A schematic cross-sectional view illustrating an example of the layer configuration of the optical laminate of the present invention.

[0070] Figure 5 A schematic cross-sectional view illustrating an example of the layer configuration of the optical laminate of the present invention. Detailed Implementation

[0071] The adhesive composition of the present invention comprises a resin (A), a light-selective absorbing compound (B) containing an indole structure and polymerizable groups within the molecule, and an initiator (C).

[0072] <Resin (A)>

[0073] The resin (A) of the present invention is not particularly limited to any resin used in the adhesive composition. Preferably, resin (A) does not exhibit significant absorption in the wavelength range of 300 nm to 780 nm.

[0074] Resin (A) is preferably a resin with a glass transition temperature (Tg) of 40°C or lower. More preferably, the glass transition temperature (Tg) of resin (A) is 20°C or lower, even more preferably 10°C or lower, and particularly preferably 0°C or lower. Furthermore, the glass transition temperature of resin (A) is generally -80°C or higher, preferably -70°C or higher, more preferably -60°C or higher, even more preferably -55°C or higher, and particularly preferably -50°C or higher. If the glass transition temperature of resin (A) is 40°C or lower, it is advantageous to improve the adhesion of the adhesive layer formed from the adhesive composition containing resin (A) to the adhered object. Furthermore, if the glass transition temperature of resin (A) is -80°C or higher, it is advantageous to improve the durability of the adhesive layer formed from the adhesive composition containing resin (A). It should be noted that the glass transition temperature can be measured using a differential scanning calorimeter (DSC).

[0075] Examples of resins (A) include (meth)acrylic resins, silicone resins, rubber resins, and urethane resins, with (meth)acrylic resins being the most preferred.

[0076] As a (meth)acrylic resin, a polymer with structural units derived from (meth)acrylates as the main component (preferably comprising 50% by mass or more) is preferred. The structural units derived from (meth)acrylates may include more than one type of structural unit derived from monomers other than (meth)acrylates (e.g., structural units derived from monomers having polar functional groups). It should be noted that in this specification, (meth)acrylic acid can be either acrylic acid or methacrylic acid; furthermore, "(meth)" when referred to as (meth)acrylate, etc., has the same meaning.

[0077] Examples of (meth)acrylates include those represented by the following formula (a).

[0078]

[0079] In formula (a), R 1A R represents a hydrogen atom or a methyl group. 2A This refers to an alkyl group having 1 to 14 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, wherein the hydrogen atom of the alkyl group or the aromatic hydrocarbon group can be replaced by an alkoxy group having 1 to 10 carbon atoms.

[0080] In equation (a), R 2A Preferably, it is an alkyl group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

[0081] Examples of (meth)acrylates represented by formula (I) include

[0082] (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, (Meth)acrylate, and other linear alkyl esters of (meth)acrylate;

[0083] Isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, isohexyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, isononyl methacrylate, isostearyl methacrylate, isostearyl methacrylate, isoamyl methacrylate, and other branched alkyl esters of (meth)acrylic acid.

[0084] Cyclohexyl methacrylate, isobornyl methacrylate, adamantane methacrylate, dicyclopentyl methacrylate, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, α-ethoxycyclohexyl methacrylate, and other alkyl esters of (meth)acrylic acid containing an alicyclic skeleton;

[0085] Phenyl methacrylate, benzyl methacrylate, and other esters of methacrylic acid containing an aromatic ring skeleton.

[0086] In addition, examples of substituent-containing (meth)acrylates include 2-methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and 2-(2-phenoxyethoxy)ethyl (meth)acrylate.

[0087] Other examples of (meth)acrylates include phenoxy diethylene glycol methacrylate and phenoxy poly(ethylene glycol) methacrylate.

[0088] These (meth)acrylates can be used individually or in combination with different (meth)acrylates.

[0089] The resin (A) of the present invention preferably contains structural units of alkyl methacrylate (a1) homopolymers with a glass transition temperature (Tg) less than 0°C, and structural units of alkyl methacrylate (a2) homopolymers with a Tg greater than 0°C. This is advantageous in improving the high-temperature durability of the adhesive layer. The Tg of the alkyl methacrylate homopolymer can be, for example, a value from literature such as POLYMER HANDBOOK (Wiley-Interscience).

[0090] Specific examples of (meth)acrylate alkyl esters (a1) include ethyl acrylate, n-propyl acrylate and isopropyl acrylate, n-butyl acrylate and isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate and isohexyl acrylate, n-heptyl acrylate, n-octyl acrylate and isooctyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate and isononyl acrylate, n-decyl acrylate and isodecyl acrylate, n-dodecyl acrylate and other (meth)acrylate alkyl esters with approximately 2 to 12 carbon atoms in the alkyl group.

[0091] Alkyl methacrylate (a1) can be used in combination with only one type or in combination with two or more types. From the viewpoint of conformability and reprocessability when laminated onto an optical film, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, etc. are preferred, and n-butyl acrylate is particularly preferred.

[0092] Alkyl methacrylate (a2) is an alkyl methacrylate other than alkyl methacrylate (a1). Specific examples of alkyl methacrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate, tert-butyl acrylate, etc.

[0093] Alkyl methacrylate (a2) can be used in combination with one or more types. From the viewpoint of high-temperature durability, alkyl methacrylate (a2) preferably includes methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc., and more preferably includes methyl acrylate.

[0094] The structural unit derived from the (meth)acrylate shown in formula (a) is preferably 50% or more by mass, more preferably 60 to 95% by mass, and more preferably 65 to 95% by mass, of all structural units contained in the (meth)acrylate resin.

[0095] As structural units derived from monomers other than (meth)acrylates, structural units derived from monomers having polar functional groups are preferred, and structural units derived from (meth)acrylates having polar functional groups are more preferred. Examples of polar functional groups include hydroxyl, carboxyl, substituted or unsubstituted amino groups, epoxy groups, and other heterocyclic groups.

[0096] As monomers with polar functional groups, examples include

[0097] 1-Hydroxymethyl methacrylate, 1-Hydroxyethyl methacrylate, 1-Hydroxyheptyl methacrylate, 1-Hydroxybutyl methacrylate, 1-Hydroxypentyl methacrylate, 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl methacrylate, 2-Hydroxybutyl methacrylate, 2-Hydroxypentyl methacrylate, 2-Hydroxyhexyl methacrylate, 3-Hydroxypropyl methacrylate, 3-Hydroxybutyl methacrylate, 3-Hydroxypentyl methacrylate, 3-Hydroxyhexyl methacrylate, 4-Hydroxybutyl methacrylate, 4-Hydroxypentyl methacrylate, 4-Hydroxyethyl methacrylate 4-Hydroxyhexyl methacrylate, 4-Hydroxyheptaacrylate, 4-Hydroxyoctyl methacrylate, 2-Chloro-2-Hydroxypropyl methacrylate, 3-Chloro-2-Hydroxypropyl methacrylate, 2-Hydroxy-3-phenoxypropyl methacrylate, 5-Hydroxypentyl methacrylate, 5-Hydroxyhexyl methacrylate, 5-Hydroxyheptaacrylate, 5-Hydroxyoctyl methacrylate, 5-Hydroxynonyl methacrylate, 6-Hydroxyhexyl methacrylate, 6-Hydroxyheptaacrylate, 6-Hydroxyoctyl methacrylate, 6-Hydroxynonyl methacrylate, 6-Hydroxydecyl methacrylate, 7-Hydroxyheptaacrylate, (methyl... 7-Hydroxyoctyl acrylate, 7-Hydroxynonyl acrylate, 7-Hydroxydecyl acrylate, 7-Hydroxyundecyl acrylate, 8-Hydroxyoctyl acrylate, 8-Hydroxynonyl acrylate, 8-Hydroxydecyl acrylate, 8-Hydroxyundecyl acrylate, 8-Hydroxydodecyl acrylate, 9-Hydroxynonyl acrylate, 9-Hydroxydecyl acrylate, 9-Hydroxyundecyl acrylate, 9-Hydroxydodecyl acrylate, 9-Hydroxytridecyl acrylate, 10-Hydroxydecyl acrylate, 10-Hydroxyundecyl acrylate, 10-Hydroxydodecyl methacrylate, 10-Hydroxytridecyl methacrylate, 10-Hydroxytetradecyl methacrylate, 11-Hydroxyundecyl methacrylate, 11-Hydroxydodecyl methacrylate, 11-Hydroxytridecyl methacrylate, 11-Hydroxytetradecyl methacrylate, 11-Hydroxypentadecanyl methacrylate, 12-Hydroxydodecyl methacrylate, 12-Hydroxytridecyl methacrylate, 12-Hydroxytetradecyl methacrylate, 13-Hydroxypentadecanyl methacrylate, 13-Hydroxytetradecyl methacrylate, 13-Hydroxypentadecanyl methacrylateMonomers containing hydroxyl groups, such as 14-hydroxytetradecyl (meth)acrylate, 14-hydroxypentadecanyl (meth)acrylate, 15-hydroxypentadecanyl (meth)acrylate, and 15-hydroxyheptadecyl (meth)acrylate;

[0098] Monomers containing carboxyl groups, such as (meth)acrylic acid, (meth)acrylic acid carboxylalkyl esters (e.g., (meth)acrylic acid carboxyl ethyl ester, (meth)acrylic acid carboxyl pentyl ester), maleic acid, maleic anhydride, fumaric acid, crotonic acid, etc.

[0099] Monomers containing heterocyclic groups, such as acrylomorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl acrylate (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexyl methyl methacrylate (meth)acrylate, glycidyl methacrylate (meth)acrylate, and 2,5-dihydrofuran.

[0100] Monomers such as aminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, and dimethylaminopropyl methacrylate, which have substituted or unsubstituted amino groups.

[0101] From the perspective of the reactivity of (meth)acrylate polymers with crosslinking agents, monomers having hydroxyl groups and / or monomers having carboxyl groups are preferred, and monomers having both hydroxyl and carboxyl groups are more preferred.

[0102] As monomers containing hydroxyl groups, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate are preferred. In particular, good durability can be obtained by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 5-hydroxypentyl acrylate.

[0103] Acrylic acid is preferred as a monomer containing a carboxyl group.

[0104] From the viewpoint of preventing excessive peel force of the release film that can be laminated onto the outer surface of the adhesive layer, the resin (A) (preferably a (meth)acrylic resin) preferably contains substantially no structural units derived from monomers having amino groups. Here, "substantially no" means 0.1 parts by mass or less out of 100 parts by mass of all structural units constituting the (meth)acrylic resin.

[0105] The content of structural units from monomers having polar functional groups is preferably 20 parts by mass or less relative to 100 parts by mass of all structural units of the (meth)acrylic resin, more preferably 0.5 parts by mass or more and 15 parts by mass or less, even more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less.

[0106] The content of structural units from monomers having aromatic groups is preferably 20 parts by mass or less, more preferably 4 parts by mass or more and 20 parts by mass or less, and even more preferably 4 parts by mass or more and 16 parts by mass or less, relative to 100 parts by mass of all structural units of the (meth)acrylic resin.

[0107] Structural units derived from monomers other than (meth)acrylates can also include structural units derived from styrene monomers, structural units derived from vinyl monomers, structural units derived from monomers having multiple (meth)acryloyl groups within the molecule, and structural units derived from (meth)acrylamide monomers.

[0108] Examples of styrene monomers include styrene; alkyl styrene such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.

[0109] Examples of vinyl monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; vinyl chloride, vinyl bromide, and other halogenated vinylides; vinylidene chloride, and other unsymmetrical dihalogenated vinylides; vinylpyridine, vinylpyrrolidone, vinyl carbazole, and other nitrogen-containing heteroaromatic vinyl compounds; butadiene, isoprene, chloroprene, and other conjugated dienes; and acrylonitrile, methacrylonitrile, and other unsaturated nitriles.

[0110] Examples of monomers having multiple (meth)acryloyl groups within a molecule include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate, which have two (meth)acryloyl groups within a molecule; and trimethylolpropane tri(meth)acrylate, which has three (meth)acryloyl groups within a molecule.

[0111] Examples of (meth)acrylamide monomers include N-hydroxymethyl (meth)acrylamide, N-(2-hydroxyethyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(4-hydroxybutyl) (meth)acrylamide, N-(5-hydroxypentyl) (meth)acrylamide, N-(6-hydroxyhexyl) (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-(3-dimethylaminopropyl) (meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl) (meth)acrylamide, N-[2-(2-oxo-1-imidazolyl)ethyl] (meth)acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl)acrylamide, N-(ethoxymethyl) (meth)acrylamide, and N-(propoxy)acrylamide. Methyl (methyl)acrylamide, N-(1-methylethoxymethyl)acrylamide, N-(1-methylpropoxymethyl)acrylamide, N-(2-methylpropoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, N-(1,1-dimethylethoxymethyl)acrylamide, N-(2-methoxyethyl)acrylamide, N-(2-ethoxyethyl)acrylamide, N-(2-propoxyethyl)acrylamide, N-[2-(1-methylethoxy)ethyl](methyl)acrylamide, N-[2-(1-methylpropoxy)ethyl](methyl)acrylamide, N-[2-(2-methylpropoxy)ethyl](methyl)acrylamide, N-(2-butoxyethyl)(methyl)acrylamide, N-[2-(1,1-dimethylethoxy)ethyl](methyl)acrylamide, etc. From a durability point of view, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, and N-(2-methylpropoxymethyl)acrylamide are preferred. (Methacrylamide)acrylamide monomers can sometimes cause a decrease in the peel strength of the release film that can be laminated onto the outer surface of the adhesive layer. Therefore, in 100 parts by weight of all structural units of resin (A), the content of (meth)acrylamide monomers is preferably 1.0 parts by weight or less, more preferably 0.5 parts by weight or less, further preferably 0.3 parts by weight or less, and particularly preferably 0.1 parts by weight or less.

[0112] The weight-average molecular weight (Mw) of resin (A) (preferably a (meth)acrylic resin) is preferably between 500,000 and 2,500,000. If the weight-average molecular weight is 500,000 or higher, the durability of the adhesive layer at high temperatures is improved, and it is easier to suppress adverse conditions such as peeling and agglomeration of the adhesive sheet between the adhered object and the adhesive sheet. If the weight-average molecular weight is 2,500,000 or lower, it is advantageous from a coating properties perspective. From the viewpoint of balancing the durability of the adhesive sheet and the coating properties of the adhesive composition, the weight-average molecular weight is preferably between 600,000 and 1,800,000, more preferably between 700,000 and 1,700,000, and particularly preferably between 1,000,000 and 1,600,000. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is typically 2 to 10, preferably 3 to 8, and more preferably 3 to 6. The weight-average molecular weight can be analyzed by gel permeation chromatography and is a value converted from standard polystyrene.

[0113] When dissolving resin (A) (preferably a (meth)acrylic) in ethyl acetate to prepare a 20% by mass solution, the viscosity at 25°C is preferably 20 Pa·s or less, more preferably 0.1 to 15 Pa·s. A viscosity within this range is advantageous from the viewpoint of coatability when applying the adhesive composition to a substrate. It should be noted that the viscosity can be measured using a Brookfield viscometer.

[0114] Resin (A) (preferably a (meth)acrylic resin) can be manufactured using known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, with solution polymerization being particularly preferred. As a solution polymerization method, an example is the mixing of a monomer and an organic solvent, the addition of a thermal polymerization initiator under a nitrogen atmosphere, and stirring for approximately 3 to 15 hours at a temperature of 40–90°C, preferably around 50–80°C. To control the reaction, the monomer and thermal polymerization initiator can be added continuously or intermittently during polymerization. The monomer and thermal polymerization initiator can also be added to the organic solvent. Examples of such organic solvents include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Known thermal polymerization initiators can be used. Alternatively, a photopolymerization initiator can be used instead of a thermal polymerization initiator, thereby employing polymerization methods utilizing ultraviolet light, etc.

[0115] The content of resin (A) is typically 50% to 99.9% by mass, preferably 60% to 95% by mass, and more preferably 70% to 90% by mass, in 100% by mass of the solids component of the adhesive composition.

[0116] <Light-selective absorption compounds containing indole structures and polymerizable groups within the molecule (B)>

[0117] The indole structure in this invention refers to the structure formed by the fusion of a benzene ring and a pyrrole ring.

[0118] Examples of polymerizable groups include cationic polymerizable groups such as epoxy, oxacyclobutyl, oxazolinyl, aziridinyl, and vinyl ether groups; free radical polymerizable groups such as olefin unsaturated groups; and alkoxysilyl groups. In the light-selective absorbing compound (B) containing both an indole structure and a polymerizable group within the molecule, the polymerizable group is preferably a free radical polymerizable group such as an olefin unsaturated group. Specific examples of olefin unsaturated groups include vinyl, α-methylvinyl, acryloyl, methacryloyl, allyl, styryl, and (meth)acrylamido.

[0119] The light-selective absorbing compound (B) (hereinafter sometimes referred to as light-selective absorbing compound (B)) preferably contains an indole structure and a polymeric group within the molecule, and also contains an electron-withdrawing group.

[0120] Indole structures can be directly bonded to polymerizable groups or bonded via linking groups. Indole structures can also be directly bonded to electron-withdrawing groups or bonded via linking groups.

[0121] The light-selective absorption compound (B) preferably exhibits maximum absorption at wavelengths above 360 ​​nm and below 420 nm, and more preferably at wavelengths above 370 nm and below 410 nm. By exhibiting maximum absorption at wavelengths above 360 ​​nm, even a small amount can efficiently absorb light near 380 nm.

[0122] The light-selective absorbing compound (B) preferably satisfies the following formula (1), and more preferably satisfies formula (2).

[0123] ε(400)≥0.05 (1)

[0124] [In equation (1), ε(400) represents the gamma at a wavelength of 400 nm for the light-selective absorption compound (B) containing an indole structure and polymerizable groups within the molecule. The unit of gamma is L / (g·m).]

[0125] The value of ε(400) is preferably 0.1 L / (g·m) or more, more preferably 0.15 L / (g·m) or more, even more preferably 0.2 L / (g·m) or more, even more preferably 0.3 L / (g·m) or more, and particularly preferably 0.4 or more. Furthermore, the value of ε(400) is typically 10000 L / (g·m) or less. Compounds with a higher ε(400) value are more likely to absorb light around wavelength 400 nm (wavelength 390–410 nm) and are more likely to exhibit the function of suppressing degradation caused by short-wavelength visible light.

[0126] The light-selective absorption compound (B) is preferably the compound shown in formula (I) or the compound shown in formula (II).

[0127]

[0128] In formula (I), R 1 R 2 R 3 R 4 R 5 and R 6 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms that may have substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group may be replaced with -NR. 1A -, -SO2-, -CO-, -O-, -S- or -CF2-.

[0129] R 1A It represents a hydrogen atom, an alkyl group with 1 to 25 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms.

[0130] E 1 This indicates an electron-withdrawing group.

[0131] Z represents the linking group.

[0132] A represents a polymerizable group.

[0133] In equation (II), R 12 and R 17 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms that may have substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group may be replaced with -NR. 11A -, -SO2-, -CO-, -O-, -S- or -CF2-.

[0134] R 11R 13 R 14 R 15 and R 16 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a group containing a polymerizable group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms that may have substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group may be replaced with -NR. 12A -, -SO2-, -CO-, -O-, -S- or -CF2-.

[0135] Among them, R 11 R 13 R 14 R 15 and R 16 At least one of them represents a group containing a polymerizable group.

[0136] R 11A and R 12A Each can be independently represented by a hydrogen atom, an alkyl group with 1 to 25 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms.

[0137] E 11 This indicates an electron-withdrawing group.

[0138] As E 1 and E 11 Examples of electron-withdrawing groups include cyano, nitro, halogen atom, alkyl group substituted with halogen atom, -SO2F, and groups shown in formula (I-1).

[0139] *-X 1 -R 111 (I-1)

[0140] [In the formula, R] 111 A hydrocarbon group representing 1 to 25 carbon atoms, which may contain hydrogen atoms or halogen atoms, wherein at least one of the methylene groups contained in the hydrocarbon group may be replaced by an oxygen atom.

[0141] X 1 This represents -CO-*3, -COO-*3, -CS-*3, -CSS-*3, and -CSNR. 112 -*3、-CONR 113 -*3、-CNR 114 -*3 or -SO2-*3.

[0142] R 112 R 113 and R 114 Each can independently represent a hydrogen atom or an alkyl or phenyl group having 1 to 6 carbon atoms.

[0143] *3 indicates that R 111 The connection key.

[0144] * indicates a bond with a carbon atom.

[0145] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0146] Examples of alkyl groups substituted with halogen atoms include monofluoromethyl, monofluoroethyl, monochloromethyl, monochloroethyl, monobromomethyl, monobromoethyl, monoiodomethyl, monoiodoethyl, difluoromethyl, difluoroethyl, dichloromethyl, dichloroethyl, dibromomethyl, dibromoethyl, diiodomethyl, diiodoethyl, trifluoromethyl, trichloromethyl, tribromomethyl, and triiodomethyl alkyl halogenates. The number of carbon atoms in the alkyl group substituted with halogen atoms is typically 1 to 25.

[0147] As R 111 Examples of hydrocarbon groups with 1 to 25 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, myristyl, cetyl, stearyl, 2-ethylhexyl, 4-butyloctyl, etc., which are straight-chain or branched alkyl groups with 1 to 25 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., which are cycloalkyl groups with 3 to 25 carbon atoms; cyclopropylmethyl, cyclohexylmethyl, etc., which are cycloalkylalkyl groups with 4 to 25 carbon atoms; phenyl, naphthyl, anthracene, biphenyl, etc., which are aryl groups with 6 to 25 carbon atoms; and benzyl, phenylethyl, naphthylmethyl, phenyl, etc., which are aralkyl groups with 7 to 25 carbon atoms.

[0148] R 111 Preferably, it is an alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms, or a fluorinated alkyl group having 1 to 25 carbon atoms.

[0149] As R 112 R 113 and R 114 Examples of alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and sec-butyl.

[0150] X 1 Preferred types are -CO-*3, -COO-*3, and -CONR. 113 -*3, or -SO2-*3.

[0151] E 1 and E 11The electron-withdrawing groups shown are preferably cyano, nitro, or the group shown in formula (I-1), and more preferably cyano, nitro, or *-COR. 111 The indicated groups, *-COOR 111 The indicated groups, *-CONR 113 R 111 The indicated group, *-SO2R 111 The indicated groups, -CF3, -C2F5, are further preferably cyano, nitro, and *-COOR. 111 The indicated group, *-SO2R 111 The indicated group is particularly preferred to be cyano.

[0152] The linking group shown in Z is not particularly limited as long as it is a divalent linking group.

[0153] The polymerizable group shown in A can be exemplified by the aforementioned polymerizable groups, preferably free radical polymerizable groups, and more preferably (meth)acryloyl groups.

[0154] As R 1 ~R 6 R 11 ~R 17 The halogen atoms shown can be fluorine, chlorine, bromine, and iodine.

[0155] As R 1 ~R 6 R 11 ~R 17 The heterocyclic groups shown can be categorized as those obtained by removing one hydrogen atom from a heterocycle. Specifically, examples include pyrrolidine cyclic groups, pyrrololin cyclic groups, imidazoline cyclic groups, imidazoline cyclic groups, oxazoline cyclic groups, thiazoline cyclic groups, piperidine cyclic groups, morpholine cyclic groups, piperazine cyclic groups, indole cyclic groups, isoindole cyclic groups, quinoline cyclic groups, thiophene cyclic groups, pyrrole cyclic groups, thiazoline cyclic groups, furan cyclic groups, pyridine cyclic groups, dioxane cyclic groups, morpholine cyclic groups, thiazoline cyclic groups, triazole cyclic groups, tetraazole cyclic groups, dioxofuran cyclic groups, pyrazine cyclic groups, purine cyclic groups, and other aliphatic heterocyclic groups with 4 to 30 carbon atoms or aromatic heterocyclic groups with 3 to 20 carbon atoms. These heterocyclic groups can be structures formed by hydrogenation of unsaturated bonds, or they can be structures formed by further fusion of cyclic skeletons (such as benzimidazole rings), or structures formed by further substitution of hydrogen atoms on heterocycles with heterocyclic groups, halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, etc.

[0156] As R 1 ~R 6 R 11 ~R 17Examples of aliphatic hydrocarbon groups with 1 to 25 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isodecyl, n-dodecyl, undecyl, myristyl, cetyl, stearyl, etc., which are straight-chain or branched alkyl groups with 1 to 25 carbon atoms; cycloalkyl groups with 3 to 25 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; and cycloalkylalkyl groups with 4 to 25 carbon atoms, such as cyclopropylmethyl, cyclohexylmethyl, etc. From the viewpoint of solubility, branched alkyl groups with 3 to 25 carbon atoms, such as 2-ethylhexyl, 2-butyloctyl, etc., are preferred.

[0157] As R 1 ~R 6 R 11 ~R 17 Examples of substituents that aliphatic hydrocarbon groups with 1 to 25 carbon atoms can have include heterocyclic groups, halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, acetamido groups, amino groups, and alkylamino groups with 1 to 12 carbon atoms. Examples of heterocyclic groups include those with R... 1 The heterocyclic group shown is the same as the group shown.

[0158] As R 1 ~R 6 R 11 ~R 17 Examples of aromatic hydrocarbon groups with 6 to 18 carbon atoms include aryl groups with 6 to 18 carbon atoms such as phenyl, naphthyl, anthraceneyl, biphenyl, and methylphenyl; and aralkyl groups with 7 to 18 carbon atoms such as benzyl, phenylethyl, naphthylmethyl, and phenoxy. As R 1 ~R 6 R 11 ~R 17 The aromatic hydrocarbon groups with 6 to 18 carbon atoms shown are formed by replacing -CH2- with -SO2-, -CO-, -O-, -S- or -CF2-, such as phenoxy, naphthoxy and other aryloxy groups.

[0159] As R 1 ~R 6 R 11 ~R 17 Examples of substituents that can exist in aromatic hydrocarbon groups with 6 to 18 carbon atoms include heterocyclic groups, halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, acetamido groups, amino groups, and alkylamino groups with 1 to 12 carbon atoms. Examples of heterocyclic groups include those with R... 1 The heterocyclic group shown is the same as the group shown.

[0160] From the perspective of absorption wavelength control and solubility, R 1 and R11 Each of the following is preferably an aliphatic hydrocarbon group having 1 to 25 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, 2-ethylhexyl, 4-butoxy, and particularly preferably methyl, ethyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, 4-butyloctyl.

[0161] From a durability point of view, R 2 Preferably, it is an aromatic hydrocarbon group with 6 to 18 carbon atoms, more preferably an aryl group with 6 to 18 carbon atoms, and even more preferably a phenyl group.

[0162] As R 11 R 13 R 14 R 15 and R 16 The groups shown that contain polymeric groups are not particularly limited as long as they have polymeric groups at the ends. Specifically, the groups shown in formula (I-2) can be cited.

[0163] *-R 115 -X 2 (I-2)

[0164] In formula (I-2), X 2 It indicates a polymerizable group.

[0165] R 115 This refers to an alkyldiyl group with 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms, wherein the -CH2- group in the alkyldiyl or divalent aromatic hydrocarbon group can be substituted with -O-, -CO-, -CS-, or -NR. 116 -

[0166] R 116 It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0167] * indicates a bond with a carbon or nitrogen atom.

[0168] As X 2 The polymerizable group shown can be any polymerizable group that is the same as the polymerizable group shown in A, preferably a free radical polymerizable group, more preferably (meth)acryloyl group.

[0169] As R 115Examples of alkyldiyl groups with 1 to 12 carbon atoms include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl.

[0170] As R 115 Examples of divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms include phenylene, naphthylene, and phenylenemethylene.

[0171] As R 116 Alkyl groups with 1 to 6 carbon atoms shown can be exemplified by those related to R. 112 The alkyl groups with 1 to 6 carbon atoms shown are the same as the alkyl groups.

[0172] R 11 R 13 R 14 R 15 and R 16 In this context, at least one group represents a group containing a polymerizable group.

[0173] Preferred R 11 It is a group that contains a polymerizable group.

[0174] Preferred R 12 It is an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, and even more preferably a phenyl group.

[0175] Preferred R 17 Cyano, nitro, *-COR 111A (R 111A The group indicated by *-COOR (representing an aliphatic hydrocarbon group with 1 to 24 carbon atoms that can have substituents) 111B (R 111B The group indicated by *-CONR (representing an aliphatic hydrocarbon group with 1 to 23 carbon atoms that may have substituents) is a group that can have substituents. 11A R 111C (R 111C The group indicated by *-SO2R represents an aliphatic hydrocarbon group with 1 to 23 carbon atoms that can have substituents. 111D (R 111D The group indicated by the aliphatic hydrocarbon group having 1 to 24 carbon atoms (which may have substituents), or the aliphatic hydrocarbon group having 1 to 25 carbon atoms substituted with fluorine atoms, is more preferably cyano, nitro, or *-COR. 111A The indicated groups, *-COOR 111B The indicated groups, *-CONR 11AR 111C The indicated group, *-SO2R 111D The indicated groups, -CF3, -C2F5, are further preferably cyano, nitro, and *-COOR. 111A The indicated group, *-SO2R 111D The indicated group is particularly preferred to be cyano.

[0176] The compound represented by formula (I) is preferably the compound represented by formula (III).

[0177]

[0178] [R 1 R 3 R 4 R 5 R 6 and E 1 It means the same as above.

[0179] R 7 It represents a hydrogen atom, cyano group, methyl group, or phenyl group.

[0180] Z 1 -OR indicates alkyldiyl groups with 1 to 12 carbon atoms, divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, and alkyl diols. 2A -*1、-SR 2B -*1 or -NR 1D -R 2C -*1.

[0181] Z 2 This represents a single bond, *2-CO-O-, *2-O-CO-, *2-S(=O)2-, *2-O-SO2-, and *2-CO-NR. 1B -、*2-NR 1C -CO-、*2-R 2D OP(=O)-OR 2E -、*2-NR 1E -CO-O-、*2-O-CO-NR 1F -、*2-(OR 2F ) s1 -, *2-CO-S-, *2-S-CO-, or perfluoroalkyl dimethyl groups with 1 to 4 carbon atoms.

[0182] R 1B R 1C R 1D R 1E and R 1F Each can be independently represented as an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0183] R 2AR 2B R 2C R 2D R 2E and R 2F Each of these groups independently represents a divalent hydrocarbon group with 1 to 18 carbon atoms.

[0184] *1 indicates that it is related to Z 2 The connection key.

[0185] *2 indicates that it is related to Z 1 The connection key.

[0186] As Z 1 Examples of alkyldiyl groups with 1 to 12 carbon atoms shown can be related to R. 115 The groups shown are the same as the alkyldiyl groups with 1 to 12 carbon atoms.

[0187] As Z 1 Examples of divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms include phenylene and naphthylene.

[0188] As R 1B R 1C R 1D R 1E and R 1F Alkyl groups with 1 to 6 carbon atoms shown can be exemplified by those related to R. 112 The groups shown are alkyl groups with 1 to 6 carbon atoms.

[0189] As R 2A R 2B R 2C R 2D R 2E and R 2F Examples of divalent hydrocarbon groups with 1 to 18 carbon atoms include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl, which are alkyldiyl groups with 1 to 18 carbon atoms; and phenylene, naphthylene, and other divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms.

[0190] Z 1 Preferred option: -OR 2A -*1(More preferably R) 2A It is an alkyldiyl group having 1 to 8 carbon atoms, more preferably an alkyldiyl group having 4 to 8 carbon atoms.

[0191] Z 2Preferably, *2-O-CO-, *2-O-SO2-, or *2-NR 1C -CO-(more preferably R) 1C (For hydrogen atoms).

[0192] The compound shown in formula (II) is more preferably the compound shown in formula (JV).

[0193]

[0194] In equation (IV), R 11 R 13 R 14 R 15 R 16 R 17 and E 11 They represent the same meanings as described above.

[0195] Z 1 This indicates a divalent linker group.

[0196] A 1 Indicates a polymerizable group.

[0197] As Z 1 The divalent linking group shown is not particularly limited, and examples include alkyldiyl groups with 1 to 12 carbon atoms. Examples of alkyldiyl groups with 1 to 12 carbon atoms include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl, with alkyldiyl groups with 1 to 8 carbon atoms being preferred. Furthermore, the -CH2- group contained in the alkyldiyl group with 1 to 12 carbon atoms can be replaced by -O-, -NR... 111 (R 111 (Indicates alkyl groups with 1 to 6 hydrogen atoms) - substitution.

[0198] As A 1 The polymerizable group shown can be any group that is the same as the polymerizable group shown in A, preferably a free radical polymerizable group, more preferably (meth)acryloyl group.

[0199] -Z 1 -A 1 The indicated group is preferably -Z. 1A -O-CO-CH=CH2、-Z 1A -O-CO-CH=C(CH3)H、-Z 1A -NR 111A -CO-CH=CH2、-Z1A -NR 111A The group represented by -CO-CH=C(CH3)H. Z 1A R represents an alkyldiyl group with 1 to 12 carbon atoms. 111A It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0200] Examples of light-selective absorption compounds (B) include the compounds described below.

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213] The compound represented by formula (I), where A is an olefinic unsaturated group, can be obtained, for example, by reacting the compound represented by formula (Ia) with the compound represented by formula (c1).

[0214]

[0215] R in equation (Ia) 1 R 2 R 3 R 4 R 3 R 6 and E 1 This indicates the same meaning as above. Z in equation (c) 3 A represents a divalent linker group. 1 This indicates a polymerizable group belonging to the olefin family.

[0216] The amount of the compound shown in formula (c1) used is preferably 0.5 to 5 moles relative to 1 mole of the compound shown in formula (Ia).

[0217] The reaction between the compound shown in formula (Ia) and the compound shown in formula (c1) can be carried out using a known esterification reaction, preferably in the presence of a base and a carbodiimide condensing agent. Examples of bases include triethylamine, diisopropylethylamine, pyridine, piperidine, pyrrolidine, proline, and N,N-dimethylaminopyridine. Examples of carbodiimide condensing agents include N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. The amount of base used is preferably 0.001 to 0.5 moles per mole of the compound shown in formula (Ia). The amount of carbodiimide condensing agent used is preferably 0.5 to 5 moles per mole of the compound shown in formula (Ia).

[0218] The reaction between the compound shown in formula (Ia) and the compound shown in formula (c1) is preferably carried out in an organic solvent. Examples of organic solvents include toluene, acetonitrile, dichloromethane, and trichloromethane.

[0219] To prevent the reaction between the olefinic unsaturated groups contained in the compound shown in formula (c1), a polymerization inhibitor can be added. Examples of polymerization inhibitors include 2,6-di-tert-butyl-4-methylphenol (BHT) and 4-methoxyphenol.

[0220] The reaction of the compound shown in formula (Ia) with the compound shown in formula (c1) is carried out by mixing the compound shown in formula (Ia) with the compound shown in formula (c1).

[0221] The reaction temperature of the compound shown in formula (Ia) with the compound shown in formula (c1) is preferably -20 to 120°C, and the reaction time is usually preferably 1 to 50 hours.

[0222] Examples of compounds represented by formula (Ia) include the following compounds.

[0223]

[0224] Examples of compounds represented by formula (c1) include 4-hydroxybutyl acrylate and 2-hydroxyethyl acrylate.

[0225] The compound shown in formula (Ia) can be obtained by reacting the compound shown in formula (Ib) with the compound shown in formula (c2).

[0226]

[0227] R in the formula 1 R 2R 3 R 4 R 5 R 6 and E 1 This indicates the same meaning as above.

[0228] The amount of the compound shown in formula (c2) used is preferably 0.5 to 5 moles relative to 1 mole of the compound shown in formula (Ib).

[0229] The reaction between the compound shown in formula (Ib) and the compound shown in formula (c2) is preferably carried out in the presence of a base. Examples of bases include pyridine, pyrrolidine, piperidine, triethylamine, and diisopropylethylamine. The amount of base used is preferably 0.5 to 5 moles relative to 1 mole of the compound shown in formula (Ib).

[0230] The reaction between the compound shown in formula (Ib) and the compound shown in formula (c2) is preferably carried out in an organic solvent. Examples of organic solvents include acetonitrile, isopropanol, toluene, chloroform, and dichloromethane.

[0231] The reaction of the compound shown in formula (Ib) with the compound shown in formula (c2) is carried out by mixing the compound shown in formula (Ia) with the compound shown in formula (c1).

[0232] The reaction temperature of the compound shown in formula (Ia) with the compound shown in formula (c1) is preferably 0 to 120°C, and the reaction time is usually preferably 1 to 50 hours.

[0233] The content of the light-selective absorbing compound (B) relative to 100 parts by weight of resin (A) is typically 0.1 to 50 parts by weight, preferably 1 to 25 parts by weight, more preferably 2 to 15 parts by weight, further preferably 3 to 12 parts by weight, and particularly preferably 4 to 10 parts by weight.

[0234] <Initiator (C)>

[0235] The adhesive composition of the present invention comprises an initiator (C). The initiator (C) can be any of a compound that initiates a polymerization reaction by absorbing thermal energy (thermal polymerization initiator) or a compound that initiates a polymerization reaction by absorbing light energy (photopolymerization initiator). It should be noted that, here, the light is preferably visible light, ultraviolet light, X-rays, or active energy rays such as electron beams.

[0236] Examples of thermal polymerization initiators include compounds that generate free radicals through heating (thermal free radical generators), compounds that generate acids through heating (thermal acid generators), and compounds that generate bases through heating (thermal base generators).

[0237] Examples of photopolymerization initiators include compounds that generate free radicals by absorbing light energy (photoradical generators), compounds that generate acids by absorbing light energy (photoacid generators), and compounds that generate bases by absorbing light energy (photoalkali generators).

[0238] The initiator (C) is preferably selected from those suitable for the polymerization reaction of the free radical curable component (D) described later, preferably a free radical polymerization initiator, and more preferably a photoradical polymerization initiator.

[0239] Examples of free radical polymerization initiators include alkyl benzophenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds. The preferred free radical polymerization initiator is a photoradiopolymerization initiator, and from the viewpoint of the reactivity of the polymerization reaction, an oxime ester-based photoradiopolymerization initiator is more preferred. By using an oxime ester-based photoradiopolymerization initiator, the reactivity rate of the free radical curing component (D) can be improved even under curing conditions with low illuminance or light intensity.

[0240] Examples of alkylphenyl ketone compounds include α-aminoalkylphenyl ketone compounds, α-hydroxyalkylphenyl ketone compounds, and α-alkoxyalkylphenyl ketone compounds.

[0241] Examples of α-aminoalkylphenyl ketone compounds include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butane-1-one, with 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one being preferred. α-Aminoalkylphenyl ketone compounds can be commercially available, such as Irgacure (registered trademark) 127, 184, 369, 369E, 379EG, 651, 907, 1173, 2959 (all manufactured by BASF Japan Co., Ltd.) and SEIKUOL (registered trademark) BEE (manufactured by Seiko Chemical Co., Ltd.).

[0242] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0243] Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone. Commercially available benzophenone compounds are also available.

[0244] Examples of oxime ester compounds include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxanepentylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine. Oxime compounds can be commercially available products such as Irgacure OXE-01, OXE-02, OXE-03 (manufactured by BASF Japan), N-1919, NCI-730, NCI-831, NCI-930 (manufactured by ADEKA), and PBG3057 (manufactured by TRONLY).

[0245] Examples of phosphine compounds include phenyl(2,4,6-trimethylbenzoyl)phosphine oxide and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, among other acylphosphine oxides. Examples of phosphine compounds include Irgacure (registered trademark) TPO and Irgacure 819 (manufactured by BASF Japan Co., Ltd.).

[0246] Photoacid-generating agents include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, and iron-aromatic complexes.

[0247] Aromatic iodonium salts are compounds containing a diaryliodonium cation; typical examples of this cation include diphenyliodonium. Aromatic sulfonium salts are compounds containing a triarylsulfonium cation; typical examples of this cation include triphenylsulfonium and 4,4'-bis(diphenylsulfonyl)diphenyl sulfide. Aromatic diazonium salts are compounds containing a diazonium cation; typical examples of this cation include benzenediazonium. Additionally, iron-aromatic complexes are typically cyclopentadienyl iron(II)aromatic cation complexes.

[0248] The cations and anions given above pair to form photocation generators. If we consider examples of anions that constitute photocation generators, we can look to specific phosphorus-based anions [(Rf]]. n PF 6-n ] - hexafluorophosphate anion PF6 - SbF6, anion of hexafluoroantimonate - The pentafluorohydroxyantimonate anion SbF5(OH) - AsF6 hexafluoroarsenate anion - Tetrafluoroborate anion BF4- Tetra(pentafluorophenyl)borate anion B(C6F5)4 - Etc. Among these, from the viewpoint of the curability of the cationic polymerizable compound and the safety of the resulting light-selective absorption layer, a special phosphorus-based anionic [(Rf]] is preferred. n PF 6-n ] - hexafluorophosphate anion PF6 - Tetra(pentafluorophenyl)borate anion B(C6F5)4 - SbF6, anion of hexafluoroantimonate - .

[0249] Examples of photoalkali-producing agents include carbamate compounds, α-amino ketone compounds, quaternary ammonium compounds, O-acyl oxime compounds, and aminocyclopropenone compounds.

[0250] Examples of carbamate compounds include 1-(2-anthraquinone)ethyl 1-piperidinecarboxylic acid, 1H-2-ethylimidazol-1-carboxylic acid 1-(2-anthraquinone)ethyl 1-piperidinecarboxylic acid 9-anthraquinone methyl 1-piperidinecarboxylic acid, N,N-diethylcarboxylic acid 9-anthraquinone methyl 1-, N-propylcarboxylic acid 9-anthraquinone methyl 1-, N-cyclohexylcarboxylic acid 9-anthraquinone methyl 1-, 1H-imidazol-1-carboxylic acid 9-anthraquinone methyl 1-, N,N-dioctylcarboxylic acid 9-anthraquinone methyl 1-(4-hydroxypiperidine)carboxylic acid 9-anthraquinone methyl 1-piperidinecarboxylic acid 1-pyrene methyl 1-piperidinecarboxylic acid, 1,6-hexamethylenedicarboxylic acid bis[1-(2-anthraquinone)ethyl 1-], 1,6-hexamethylenedicarboxylic acid bis(9-anthraquinone methyl 1-], etc.

[0251] As α-aminoketone compounds, examples include the following compounds. Examples include 1-phenyl-2-(4-morpholinylbenzoyl)-2-dimethylaminobutane and 2-(4-methylthiobenzoyl)-2-morpholinylpropane.

[0252] Examples of quaternary ammonium compounds that can be used as photoalkali-producing agents include 1-(4-phenylthiobenzoylmethyl)-1-aza-cation-4-azabicyclo[2,2,2]octanetetraphenylborate, 5-(4-phenylthiobenzoylmethyl)-1-aza-5-aza-cation-bicyclo[4,3,0]-5-nonenetetraphenylborate, and 8-(4-phenylthiobenzoylmethyl)-1-aza-8-aza-cation-bicyclo[5,4,0]-7-undecenetetraphenylborate.

[0253] Examples of aminocyclopropene ketone compounds that can be used as photoalkali-generating agents include 2-diethylamino-3-phenylcyclopropene ketone, 2-diethylamino-3-(1-naphthyl)cyclopropene ketone, 2-pyrrolidinyl-3-phenylcyclopropene ketone, 2-imidazolyl-3-phenylcyclopropene ketone, and 2-isopropylamino-3-phenylcyclopropene ketone.

[0254] Examples of heat-generating alkali agents include 2-(4-biphenyl)-2-propyl carbamate and carbamate derivatives such as 1,1-dimethyl-2-cyanoethyl carbamate, urea derivatives such as N,N,N'-trimethylurea, dihydropyridine derivatives such as 1,4-dihydronicotinamide, dicyandiamide, organic salts, inorganic salts, and salts formed by acids and bases.

[0255] The content of initiator (C) relative to 100 parts by weight of resin (A) is generally 0.01 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, further preferably 0.75 to 4 parts by weight, and particularly preferably 1 to 3 parts by weight.

[0256] The adhesive composition of the present invention may further comprise a free radical curing component (D), a crosslinking agent (E), a silane compound (F), a light selective absorbing compound (G) other than the light selective absorbing compound (B) (hereinafter, sometimes referred to as the light selective absorbing compound (G)), an antistatic agent, etc., and preferably comprises at least one selected from the free radical curing component (D), the crosslinking agent (E), the silane compound (F), and the light selective absorbing compound (G).

[0257] <Free radical curing component (D)>

[0258] Examples of free radical curable components (D) include compounds or oligomers that are cured by free radical polymerization reactions.

[0259] Examples of free radical polymerizable components (D) include (meth)acrylate compounds, styrene compounds, and vinyl compounds.

[0260] The adhesive composition of the present invention may contain two or more free radical curing components (D).

[0261] Examples of (meth)acrylic acid compounds include (meth)acrylate monomers having at least one (meth)acryloyloxy group within the molecule, (meth)acrylamide monomers, and (meth)acrylic acid oligomers having at least two (meth)acryloyl groups within the molecule. (Meth)acrylic acid oligomers are preferably (meth)acrylate oligomers having at least two (meth)acryloyloxy groups within the molecule. A single (meth)acrylic acid compound may be used alone, or two or more may be used in combination.

[0262] Examples of (meth)acrylate monomers include monofunctional (meth)acrylate monomers having one (meth)acryloyloxy group in the molecule, difunctional (meth)acrylate monomers having two (meth)acryloyloxy groups in the molecule, and polyfunctional (meth)acrylate monomers having three or more (meth)acryloyloxy groups in the molecule.

[0263] Examples of monofunctional (meth)acrylate monomers include alkyl (meth)acrylates. In alkyl (meth)acrylates, when the alkyl group has 3 or more carbon atoms, it can be linear, branched, or cyclic. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0264] In addition, examples of monofunctional (meth)acrylate monomers include aralkyl (meth)acrylates such as benzyl (meth)acrylate; (meth)acrylates of terpene alcohols such as isobornyl (meth)acrylate; (meth)acrylates with a tetrahydrofurfuryl (meth)acrylate structure such as tetrahydrofurfuryl (meth)acrylate; (meth)acrylates with a cycloalkyl group at the alkyl group such as cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and 1,4-cyclohexanediethanol monoacrylate; (meth)acrylates with an aminoalkyl group at the alkyl group such as N,N-dimethylaminoethyl (meth)acrylate; and (meth)acrylates with an ether bond at the alkyl group such as 2-phenoxyethyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, and phenoxy polyethylene glycol (meth)acrylate.

[0265] Furthermore, examples of monofunctional (meth)acrylate monomers include monofunctional (meth)acrylates having a hydroxyl group at the alkyl site and monofunctional (meth)acrylates having a carboxyl group at the alkyl site. Examples of monofunctional (meth)acrylates having a hydroxyl group at the alkyl site include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, and pentaerythritol mono(meth)acrylate. Examples of monofunctional (meth)acrylates having a carboxyl group at the alkyl site include 2-carboxyethyl (meth)acrylate, ω-carboxy-polycaprolactone (n=2) mono(meth)acrylate, 1-[2-(meth)acryloyloxyethyl]phthalic acid, 1-[2-(meth)acryloyloxyethyl]hexahydrophthalic acid, 1-[2-(meth)acryloyloxyethyl]succinic acid, 4-[2-(meth)acryloyloxyethyl]trimethic acid, and N-(meth)acryloyloxy-N',N'-dicarboxymethyl-p-phenylenediamine.

[0266] The preferred monomer for (meth)acrylamide is (meth)acrylamide having a substituent at the N-position. A typical example of this N-position substituent is an alkyl group, but it can also form a ring with the nitrogen atom of (meth)acrylamide. This ring may have an oxygen atom as a cyclizing atom in addition to a carbon atom and the nitrogen atom of (meth)acrylamide. Furthermore, substituents such as alkyl groups or oxo groups (=O) can be bonded to the carbon atom constituting the ring.

[0267] Examples of N-substituted (meth)acrylamides include N-methyl (meth)acrylamides, N-ethyl (meth)acrylamides, N-isopropyl (meth)acrylamides, N-n-butyl (meth)acrylamides, N-tert-butyl (meth)acrylamides, N-hexyl (meth)acrylamides, and other N-alkyl (meth)acrylamides; and N,N-dimethyl (meth)acrylamides, N,N-diethyl (meth)acrylamides, and other N,N-dialkyl (meth)acrylamides. Furthermore, the N-substituent can also be an alkyl group having a hydroxyl group; examples include N-hydroxymethyl (meth)acrylamides, N-(2-hydroxyethyl)(meth)acrylamides, and N-(2-hydroxypropyl)(meth)acrylamides. In addition, specific examples of N-substituted (meth)acrylamides that form the aforementioned 5-membered or 6-membered rings include N-acryloylpyrrolidine, 3-acryloyl-2-oxazolidinone, 4-acryloylmorpholine, N-acryloylpiperidine, and N-methacryloylpiperidine.

[0268] Examples of difunctional (meth)acrylate monomers include

[0269] Ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate and other alkylene glycol di(meth)acrylates;

[0270] Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate and poly1,4-butanediol di(meth)acrylate and other polyoxyalkylene glycol di(meth)acrylates;

[0271] Di(meth)acrylates of halogen-substituted alkylene glycols, such as tetrafluoroethylene glycol di(meth)acrylate;

[0272] Di(meth)acrylates of aliphatic polyols such as trimethylolpropane di(meth)acrylate, bis(trimethylolpropane di(meth)acrylate, and pentaerythritol di(meth)acrylate;

[0273] Hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, and other di(meth)acrylates of hydrogenated dicyclopentadiene or tricyclodecanediol;

[0274] 1,3-Dioxane-2,5-diyldi(meth)acrylate [also known as: dioxanediol di(meth)acrylate] and other dioxanediols or dioxanediols di(meth)acrylates;

[0275] Di(meth)acrylates of ethylene oxide adducts of bisphenol A and ethylene oxide adducts of bisphenol F, etc.

[0276] Acrylic adducts of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether, etc., epoxy di(meth)acrylates of bisphenol A or bisphenol F; organosilicon di(meth)acrylates;

[0277] Di(meth)acrylate of neopentyl hydroxypentanoate;

[0278] 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane; 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane;

[0279] 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane] di(meth)acrylate;

[0280] Tris(hydroxyethyl) isocyanurate di(meth)acrylate, etc.

[0281] Examples of polyfunctional (meth)acrylate monomers with three or more functions include glycerol tri(meth)acrylate, alkoxylated glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; poly(meth)acrylates of halogenated polyols with three or more functions; tri(meth)acrylates of glycerol epoxy alkane adducts; tri(meth)acrylates of trimethylolpropane epoxy alkane adducts; 1,1,1-tris[(meth)acryloyloxyethoxyethoxy]propane; tri(hydroxyethyl)isocyanurate tri(meth)acrylate, etc.

[0282] Alternatively, commercially available products can be used. Examples of commercially available products include A-DPH-12E, A-TMPT, and A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0283] Examples of (meth)acrylic acid oligomers include urethane (meth)acrylic acid oligomers, polyester (meth)acrylic acid oligomers, and epoxy (meth)acrylic acid oligomers.

[0284] So-called urethane (meth)acrylic acid oligomers are compounds having an urethane bond (-NHCOO-) and at least two (meth)acryloyl groups within the molecule. Specifically, they can be urethane esterification products of hydroxyl-containing (meth)acrylic acid monomers having at least one (meth)acryloyl group and at least one hydroxyl group within the molecule, respectively, and polyisocyanates; urethane compounds containing terminal isocyanate groups obtained by reacting polyols with polyisocyanates; and urethane esterification products of hydroxyl-containing (meth)acrylic acid monomers having at least one (meth)acryloyl group and at least one hydroxyl group within the molecule, respectively.

[0285] The hydroxyl-containing (meth)acrylate monomers used in the above-mentioned carbamate esterification reaction can be, for example, hydroxyl-containing (meth)acrylate monomers, including 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Specific examples other than hydroxyl-containing (meth)acrylate monomers include N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, and other N-hydroxyalkyl (meth)acrylamide monomers.

[0286] Examples of polyisocyanates that can be provided for carbamate reactions with hydroxyl-containing (meth)acrylic acid monomers include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, phenyldimethyl diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates of these diisocyanates (e.g., hydrogenated toluene diisocyanate, hydrogenated phenyldimethyl diisocyanate, etc.), triphenylmethane triisocyanate, dibenzylbenzene triisocyanate, and other di- or tri-isocyanates, as well as polyisocyanates obtained by polymerizing the above-mentioned diisocyanates.

[0287] In addition, polyols used to prepare urethane compounds containing terminal isocyanate groups through reaction with polyisocyanates can be aromatic, aliphatic, or alicyclic polyols, as well as polyester polyols, polyether polyols, etc. Examples of aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, and hydrogenated bisphenol A.

[0288] Polyester polyols are substances obtained through the dehydration condensation reaction of the aforementioned polyols with polycarboxylic acids or their anhydrides. Examples of polycarboxylic acids or their anhydrides, when labeled with "(anhydride)", include succinic acid (anhydride), adipic acid, maleic acid (anhydride), itaconic acid (anhydride), trimellitic acid (anhydride), pyromellitic acid (anhydride), phthalic acid (anhydride), isophthalic acid, terephthalic acid, and hexahydrophthalic acid (anhydride), etc.

[0289] In addition to polyalkylene glycols, polyether polyols can also be polyoxyalkylene modified polyols obtained by reacting the aforementioned polyols or dihydroxybenzenes with epoxides.

[0290] Polyester (meth)acrylate oligomers are oligomers that have ester bonds and at least two (meth)acryloyloxy groups in their molecules.

[0291] Polyester (meth)acrylate oligomers can be obtained, for example, by dehydration condensation reaction of (meth)acrylic acid, polycarboxylic acid or its anhydride, and polyol.

[0292] Examples of polycarboxylic acids or their anhydrides include succinic anhydride, adipic acid, maleic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, phthalic acid, succinic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid.

[0293] Examples of polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, and hydrogenated bisphenol A.

[0294] Epoxy (meth)acrylic acid oligomers can be obtained by the addition reaction of polyglycidyl ethers with (meth)acrylic acid. Epoxy (meth)acrylic acid oligomers have at least two (meth)acryloyloxy groups within the molecule.

[0295] Examples of polyglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

[0296] Examples of styrene compounds include styrene; alkyl styrene such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.

[0297] Examples of vinyl monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; vinyl chloride, vinyl bromide, and other halogenated vinyl monomers; vinylidene chloride and other unsymmetrical dihaloethylene; vinylpyridine, vinylpyrrolidone, vinyl carbazole, and other nitrogen-containing heteroaromatic vinyl monomers; butadiene, isoprene, chloroprene, and other conjugated dienes; and acrylonitrile, methacrylonitrile, and other unsaturated nitriles.

[0298] The free radical curing component (D) is preferably a (meth)acrylate compound, more preferably a polyfunctional (meth)acrylate compound. The polyfunctional (meth)acrylate compound is preferably trifunctional or more.

[0299] The content of the free radical curing component (D) relative to 100 parts by weight of resin (A) is generally 0.5 to 100 parts by weight, preferably 1 to 70 parts by weight, more preferably 3 to 50 parts by weight, even more preferably 5 to 30 parts by weight, and particularly preferably 7.5 to 25 parts by weight.

[0300] <Crosslinking agent (E)>

[0301] Examples of crosslinking agents (E) include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and metal chelate-based crosslinking agents. In particular, from the viewpoints of the usability of the adhesive composition, the durability of the adhesive layer, and the crosslinking speed, isocyanate-based crosslinking agents are preferred.

[0302] As an isocyanate-based crosslinking agent, compounds having at least two isocyanate groups (-NCO) within the molecule are preferred. Examples include aliphatic isocyanate compounds (such as hexamethylene diisocyanate), alicyclic isocyanate compounds (such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated phenylmethylene diisocyanate), and aromatic isocyanate compounds (such as toluene diisocyanate, phenylmethylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). Alternatively, the crosslinking agent (E) may also be an adduct (addition compound) of the isocyanate compound using a polyol compound [e.g., an adduct using glycerol, trimethylolpropane, etc.], an isocyanurate ester, a biuret-type compound, or a derivative of an isocyanate compound of the urethane prepolymer type obtained by an addition reaction with polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. Two or more crosslinking agents (E) may be used alone or in combination. Among these, representative examples include aromatic isocyanate compounds (e.g., toluene diisocyanate, phthalimide diisocyanate), aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate) or their adducts using polyol compounds (e.g., glycerol, trimethylolpropane), or isocyanurate bodies. If the crosslinking agent (F) is an aromatic isocyanate compound and / or an adduct of it using a polyol compound, or an isocyanurate ester, the durability of the adhesive layer may be improved, perhaps due to the advantage of forming an optimal crosslinking density (or crosslinking structure). In particular, if it is a toluene diisocyanate compound and / or an adduct of it using a polyol compound, durability may be improved, for example, even when the adhesive layer is applied to the polarizing plate, etc.

[0303] The content of crosslinking agent (E) relative to 100 parts by weight of resin (A) is generally 0.01 to 25 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.15 to 7 parts by weight, further preferably 0.2 to 5 parts by weight, and particularly preferably 0.25 to 2 parts by weight.

[0304] <Silane Compounds (F)>

[0305] Examples of silane compounds (F) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropylethoxydimethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

[0306] Silane compounds (F) can be organosilicon oligomers. Specific examples of organosilicon oligomers are described below in the form of combinations of monomers.

[0307] Oligomers containing mercaptopropyl groups, such as 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomers, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomers, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomers, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomers; oligomers containing mercaptomethyl groups, such as mercaptomethyltrimethoxysilane-tetramethoxysilane oligomers, mercaptomethyltrimethoxysilane-tetramethoxysilane oligomers, mercaptomethyltriethoxysilane-tetramethoxysilane oligomers, and mercaptomethyltriethoxysilane-tetraethoxysilane oligomers; 3-epoxypropoxypropyltrimethoxysilane-tetramethoxysilane copolymers, 3-epoxypropoxypropyltrimethoxysilane-tetramethoxysilane copolymers, and 3-epoxypropoxypropyltrimethoxysilane-tetramethoxysilane copolymers. 3-Glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc., containing 3-glycidoxypropyl group; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane Oligomers, including 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane oligomers, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomers, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomers, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomers, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomers, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers, and other oligomers containing methacryloxypropyl groups; 3-propane... Oligomers containing acryloyloxypropyltrimethoxysilane-tetramethoxysilane, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane, etc.Vinyltrimethoxysilane-tetramethoxysilane oligomers, vinyltrimethoxysilane-tetraethoxysilane oligomers, vinyltriethoxysilane-tetramethoxysilane oligomers, vinyltriethoxysilane-tetraethoxysilane oligomers, vinylmethyldimethoxysilane-tetramethoxysilane oligomers, vinylmethyldimethoxysilane-tetraethoxysilane oligomers, vinylmethyldiethoxysilane-tetramethoxysilane oligomers, vinylmethyldiethoxysilane-tetraethoxysilane oligomers, etc., containing vinyl groups; 3-aminopropyltrimethoxysilane -Tetramethoxysilane copolymers, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymers, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymers, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymers, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymers, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymers, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymers, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymers, and other copolymers containing amino groups, etc.

[0308] The silane compound (F) can be a silane compound represented by the following formula (f1).

[0309]

[0310] In formula (f1), A represents an alkyldiyl group with 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group with 3 to 20 carbon atoms. The -CH2- group constituting the alkyldiyl group and the alicyclic hydrocarbon group can be replaced with -O- or -CO-. 41 R represents an alkyl group having 1 to 5 carbon atoms. 42 R 43 R 44 R 45 and R 46 Each can independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

[0311] Examples of alkyldiyl groups with 1 to 20 carbon atoms, represented by A in formula (f1), include methylene, 1,2-ethylenediyl, 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,12-dodecanediyl, 1,14-tetradecanediyl, 1,16-hexadecanediyl, 1,18-octadecanediyl, and 1,20-eicosenediyl. Examples of divalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms include 1,3-cyclopentanediyl and 1,4-cyclohexanediyl. Examples of groups obtained by substituting -CH2- for the alkyl diene and the alicyclic hydrocarbon group with -O- or -CO- include -CH2CH2-O-CH2CH2-, -CH2CH2-O-CH2CH2-O-CH2CH2-, -CH2CH2-O-CH2CH2-O-CH2CH2-, -CH2CH2-CO-O-CH2CH2-, -CH2CH2-O-CH2CH2-CO-O-CH2CH2-, -CH2CH2CH2CH2-O-CH2CH2-, and -CH2CH2CH2CH2-O-CH2CH2CH2CH2-.

[0312] As R 41 ~R 45 Examples of alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and pentyl, are shown as R. 42 ~R 45 Examples of alkoxy groups with 1 to 5 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, and pentoxy.

[0313] Examples of silane compounds represented by formula (f1) include (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,4-bis(triethoxysilyl)butane, 1,5- bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(tripropoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(tripropoxysilyl)octane, etc. (tri-C1-5) Alkoxymethylsilyl)C1-10 alkanes; bis(dimethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(dimethoxyethylsilyl)ethane, 1,4-bis(dimethoxymethylsilyl)butane, 1,4-bis(dimethoxyethylsilyl)butane, 1,6-bis(dimethoxymethylsilyl)hexane, 1,6-bis(dimethoxyethylsilyl) Alkyl hexane, 1,8-bis(dimethoxymethylsilyl)octane, 1,8-bis(dimethoxyethylsilyl)octane, etc. (bis(diC1-5alkoxy-C1-5alkylsilyl)C1-10 alkanes); 1,6-bis(methoxydimethylsilyl)hexane, 1,8-bis(methoxydimethylsilyl)octane, etc. (bis(mono-C1-5alkoxy-diC1-5alkylsilyl)C1-10 alkanes, etc. Among them, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, and 1,8-bis(trimethoxysilyl)octane are preferred, as are bis(triC1-3alkoxysilyl)C1-10 alkanes, with 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane being particularly preferred.

[0314] The content of silane compound (F) relative to 100 parts by weight of resin (A) is generally 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.15 to 7 parts by weight, further preferably 0.2 to 5 parts by weight, and particularly preferably 0.25 to 2 parts by weight.

[0315] <Light-selective absorption compound (G)>

[0316] The light-selective absorption compound (G) is a light-selective absorption compound other than the light-selective absorption compound (B), such as a compound (ultraviolet absorber) that absorbs light with wavelengths from 250 nm to 380 nm (preferably with wavelengths above 250 nm and below 360 nm).

[0317] The light-selective absorption compound (G) is any compound that absorbs light with a wavelength of 250 nm to 380 nm. Its structure is not particularly limited. Preferred compounds include benzotriazole compounds, benzophenone compounds, triazine compounds, salicylic acid compounds, cyanoacrylate compounds, benzoxazine compounds, etc.

[0318] Light-selective absorbing compounds (G) can be commercially available, such as "Kemisorb 102" manufactured by CHEMIPRO KASEI Co., Ltd., "ADKSTAB LA46" and "ADKSTAB LAF70" manufactured by ADEKA Co., Ltd., and triazine-based ultraviolet absorbers such as Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 928, Tinuvin 400, Tinuvin 460, Tinuvin 405, and Tinuvin 477 manufactured by BASF Japan; "ADKSTAB LA31" and "ADKSTAB LA36" manufactured by ADEKA Co., Ltd., and "Sumisorb 200", "Sumisorb 250", "Sumisorb 300", and "Sumisorb" manufactured by Sumika Chemtex Co., Ltd. Benzotriazole-based ultraviolet absorbers include “340” and “Sumisorb 350”, “Kemisorb 74”, “Kemisorb 79” and “Kemisorb 279” manufactured by CHEMIPRO KASEI Co., Ltd., and “TINUVIN 99-2”, “TINUVIN 900” and “TINUVIN 928” manufactured by BASF.

[0319] In addition, the light-selective absorbing compound (G) can be an inorganic ultraviolet absorber. Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, indium oxide, tin oxide, talc, kaolin, calcium carbonate, titanium oxide-based composite oxides, zinc oxide-based composite oxides, ITO (tin-doped indium oxide), and ATO (antimony-doped tin oxide). Examples of titanium oxide-based composite oxides include titanium oxide doped with silicon dioxide and aluminum oxide.

[0320] The content of the light-selective absorbing compound (G) relative to 100 parts by weight of resin (A) is typically 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, even more preferably 0.5 to 7.5 parts by weight, and particularly preferably 1 to 5 parts by weight.

[0321] The adhesive composition may further contain one or more solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, pigments, rust inhibitors, inorganic fillers, light-scattering particles, and other additives.

[0322] The adhesive layer of the present invention can be formed, for example, by dissolving or dispersing the adhesive composition of the present invention in a solvent to prepare a solvent-containing adhesive composition, then applying it to the surface of a substrate, allowing it to dry, and then subjecting it to irradiation with active energy rays. The adhesive layer of the present invention can also be referred to as a photocured product of the adhesive composition.

[0323] As a substrate, a plastic film is suitable; specifically, a release film that has undergone a release treatment can be cited as an example. Examples of release films include films in which one side of a film containing resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate has undergone a release treatment such as silicone treatment.

[0324] The conditions (drying temperature, drying time) for drying the coating film formed by the solvent-containing adhesive composition can be appropriately set according to its composition and concentration, preferably 60-150°C and 1-60 minutes.

[0325] The irradiation of the coated film after drying with active energy rays is preferably ultraviolet irradiation. The preferred ultraviolet irradiation intensity is 10 mW / cm². 2 ~3000mW / cm 2 In addition, the cumulative ultraviolet light intensity is preferably 10 mJ / cm². 2 ~5000mJ / cm 2 .

[0326] Ultraviolet lamps used for ultraviolet irradiation can be mercury lamps, metal halide lamps, or LED lamps.

[0327] The adhesive layer of the present invention is preferably an adhesive layer that satisfies the following formula (2).

[0328] A(400)≥0.4 (2)

[0329] [In equation (2), A(400) represents the absorbance at a wavelength of 400 nm.]

[0330] A higher value for A(400) indicates higher absorption at a wavelength of 400 nm. If the value of A(400) is less than 0.4, the absorption at 400 nm is low, which can easily lead to the degradation of components that are easily degraded by light near ultraviolet light (such as display devices like organic EL elements and liquid crystal phase retardation films). The value of A(400) is preferably 0.5 or higher, more preferably 0.75 or higher, even more preferably 1.0 or higher, and particularly preferably 1.5 or higher. There is no particular upper limit, and it is usually 10 or lower.

[0331] The thickness of the adhesive layer of the present invention is generally less than 200 μm, preferably less than 100 μm, more preferably less than 20 μm, further preferably less than 12 μm, and particularly preferably less than 7 μm. Additionally, it is generally 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 2 μm or more.

[0332] According to the present invention, ultraviolet light can be sufficiently absorbed even in the adhesive layer of a thin film less than 12 μm, which is advantageous from the viewpoint of thin-film display devices.

[0333] The gel fraction of the adhesive layer of the present invention is typically 50-99.9% by mass, preferably 60-99% by mass, more preferably 70-95% by mass, and even more preferably 75-90% by mass.

[0334] <Optical film with adhesive layer>

[0335] The adhesive composition of the present invention and the adhesive layer formed therefrom can be used, for example, for bonding optical films.

[0336] An optical film with an adhesive layer, wherein an optical film is laminated on at least one side of the adhesive layer of the present invention, is also included in the present invention.

[0337] The optical film with an adhesive layer of the present invention can be formed by dissolving or dispersing the adhesive composition in a solvent to prepare an adhesive composition containing a solvent, then coating it onto the surface of the optical film, drying it, and then irradiating it with active energy rays. Alternatively, it can also be obtained by similarly forming an adhesive layer on a release film and then laminating (transferring) the adhesive layer onto the surface of the optical film.

[0338] Optical films are films that possess optical functions such as transmission, reflection, and absorption of light. Optical films can be single-layer or multi-layered. Examples of optical films include polarizing films, phase retardation films, brightness enhancement films, anti-glare films, anti-reflection films, diffusion films, and light-concentrating films, with polarizing films, phase retardation films, or laminates thereof being preferred.

[0339] Concentrating films are films used for purposes such as controlling the light path. They can be prism array sheets, lens array sheets, sheets with dots attached, etc.

[0340] Brightness enhancement films are used to improve the brightness of liquid crystal display devices that employ polarizers. Specifically, examples include reflective polarizers designed by stacking multiple thin films with different refractive indices to create anisotropy in reflectivity, and circularly polarized polarizers that are alignment films or alignment liquid crystal layers of cholesteric liquid crystal polymers supported on a substrate film.

[0341] A polarizing film is a film that absorbs linearly polarized light with a vibration plane parallel to its absorption axis and transmits linearly polarized light with a vibration plane orthogonal to the absorption axis (parallel to the transmission axis). For example, a film that adsorbs dichroic pigments onto a polyvinyl alcohol-based resin film and orients the dichroic pigments can be used.

[0342] Examples of dichroic pigments include iodine and dichroic organic dyes.

[0343] The degree of saponification of polyvinyl alcohol (PVA) resins is typically 85 mol% to 100 mol%, preferably 98 mol% or higher. PVA resins can be modified, for example, by producing aldehyde-modified PVA formal or PVA acetal. The degree of polymerization of PVA resins is typically 1000 to 10000, preferably 1500 to 5000.

[0344] Typically, films obtained by forming polyvinyl alcohol (PVA) based resins are used as the base film for polarizing films. PVA based resins can be formed using known methods. The thickness of the base film is typically 1–150 μm, but is preferably 10 μm or more, taking into account ease of stretching, etc.

[0345] The polarizing film is manufactured, for example, by performing a uniaxial stretching process on the raw film, a dyeing process on the film with a dichroic dye to adsorb the dichroic dye, a treatment process on the film with a boric acid aqueous solution, and a washing process on the film, followed by drying. The thickness of the polarizing film is typically 1 to 30 μm, and from the viewpoint of thin-film optical laminates with an adhesive layer, it is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less.

[0346] At least one side of the polarizing film is preferably a polarizing plate with a protective film provided by an adhesive.

[0347] As an adhesive, a known adhesive can be used, such as a water-based adhesive or an active energy ray curing adhesive.

[0348] Examples of commonly used water-based adhesives include (e.g., adhesives formed from aqueous solutions of polyvinyl alcohol resins, water-based two-component urethane emulsion adhesives, aldehyde compounds, epoxy compounds, melamine compounds, hydroxymethyl compounds, isocyanate compounds, amine compounds, and crosslinking agents such as polyvalent metal salts). Among these, water-based adhesives formed from aqueous solutions of polyvinyl alcohol resins are suitable. It should be noted that when using water-based adhesives, it is preferable to perform a drying process after laminating the polarizing film and the protective film to remove water contained in the water-based adhesive. After the drying process, a curing process can be performed, for example, at a temperature of approximately 20–45°C. The adhesive layer formed from the water-based adhesive is typically 0.001–5 μm thick.

[0349] The term "active energy ray curable adhesive" refers to an adhesive that cures upon exposure to active energy rays such as ultraviolet rays or electron beams. Examples include curable compositions containing polymerizable compounds and photopolymerization initiators, curable compositions containing photoreactive resins, and curable compositions containing adhesive resins and photoreactive crosslinking agents. Ultraviolet curable adhesives are preferred.

[0350] Methods for bonding polarizing films and protective films include surface activation treatments such as saponification, corona treatment, and plasma treatment on at least one of the bonding surfaces. When bonding protective films to both sides of the polarizing film, the adhesive used to bond these resin films can be the same type of adhesive or different types of adhesive.

[0351] As a protective film, a film formed of a light-transmitting thermoplastic resin is preferred. Specifically, films comprising polyolefin resins; cellulose resins; polyester resins; (meth)acrylic resins; or mixtures or copolymers thereof can be cited. When protective films are provided on both sides of the polarizing film, the protective films used can be films comprising different thermoplastic resins or films comprising the same thermoplastic resin.

[0352] When a protective film is laminated on at least one side of a polarizing film, the protective film is preferably a protective film containing a polyolefin resin or a cellulose resin. By using these films, the shrinkage of the polarizing film in high-temperature environments can be effectively suppressed without impairing its optical properties. It should be noted that the protective film can also be an oxygen barrier layer.

[0353] A preferred configuration for a polarizing plate is a polarizing plate in which a protective film is laminated on at least one side of the polarizing film via an adhesive layer. When the protective film is laminated only on one side of the polarizing film, it is more preferable to laminate it on the viewing side. The protective film laminated on the viewing side is preferably a protective film containing a triacetyl cellulose-based resin or a cyclic olefin-based resin. The protective film can be an unstretched film or can be stretched in an optional direction to have a phase difference. Surface treatment layers such as a hard coating or an anti-glare layer can be provided on the surface of the protective film laminated on the viewing side.

[0354] When a protective film is laminated on both sides of the polarizing film, the protective film on the panel side (the side opposite to the viewing side) is preferably a protective film or a phase retardation film containing a triacetyl cellulose resin, a cyclic olefin resin, or an acrylic resin. The phase retardation film may be a zero-delay film, as described later.

[0355] A phase retardation film is an optical film that exhibits optical anisotropy. Examples include stretched films obtained by stretching a polymer film containing polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycyclic olefin, polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride / polymethyl methacrylate, acetyl cellulose, ethylene-vinyl acetate copolymer saponification, and polyvinyl chloride to approximately 1.01 to 6 times its original size. Among stretched films, polymer films obtained by uniaxially or biaxially stretching acetyl cellulose, polyester, polycarbonate films, and cyclic olefin resin films are preferred. Alternatively, a phase retardation film can also exhibit optical anisotropy by coating a liquid crystal compound onto a substrate and aligning it.

[0356] It should be noted that in this specification, the phase retardation film includes zero-delay films, as well as films referred to as uniaxial phase retardation films, low photoelastic modulus phase retardation films, and large viewing angle phase retardation films.

[0357] The so-called zero-delay film refers to a film with a frontal delay R e Delay R in the thickness direction th All are optically isotropic films with a retardation value of -15 to 15 nm. Examples of zero-retardation films include resin films containing cellulose-based resins, polyolefin-based resins (chain-like polyolefins, polycyclic olefins, etc.), or polyethylene terephthalate-based resins. Cellulose-based resins or polyolefin-based resins are preferred for ease of control and availability. Zero-retardation films can also be used as protective films. Examples of zero-retardation films include "Z-TAC" (trade name) sold by Fujifilm Inc., "Zerotac" (registered trademark) sold by Konica Minolta Opto Co., Ltd., and "ZF-14" (trade name) sold by ZEON Co., Ltd.

[0358] In the optical film of the present invention, the phase retardation film is preferably a phase retardation film that exhibits optical anisotropy by coating a liquid crystal compound and aligning it.

[0359] Examples of films that exhibit optical anisotropy through the coating and orientation of liquid crystal compounds include the first to fifth methods.

[0360] Method 1: A phase retardation film in which rod-shaped liquid crystal compounds are oriented horizontally relative to the supporting substrate.

[0361] The second method: a phase retardation film in which rod-shaped liquid crystal compounds are oriented vertically relative to the supporting substrate.

[0362] The third method: a phase reversal film in which rod-shaped liquid crystal compounds change their orientation in a spiral shape within the plane.

[0363] Fourth method: A tilted retardation film is formed in the disk-shaped liquid crystal compound.

[0364] Fifth method: Biaxial retardation film in which a disk-shaped liquid crystal compound is oriented perpendicularly to the supporting substrate.

[0365] For example, as an optical film used in organic electroluminescent displays, the first, second, and fifth methods can be appropriately used. Alternatively, phase retardation films of these methods can be stacked and used.

[0366] When the retardation film is a layer containing a polymer in an oriented state of a polymeric liquid crystal compound (hereinafter, sometimes referred to as an "optical anisotropy layer"), the retardation film preferably has inverse wavelength dispersibility. Inverse wavelength dispersibility is an optical characteristic that the in-plane phase difference at short wavelengths is smaller than the in-plane phase difference at long wavelengths. Preferably, the retardation film satisfies the following equations (7) and (8). It should be noted that Re(λ) represents the in-plane phase difference value for light with wavelength λnm.

[0367] Re(450) / Re(550)≤1 (7)

[0368] 1≤Re(630) / Re(550) (8)

[0369] In the optical film of the present invention, when the phase retardation film is of the first type and has inverse wavelength dispersion, since the coloring during black display in the display device is reduced, it is preferable that 0.82≤Re(450) / Re(550)≤0.93 in the above formula (7). Furthermore, it is preferable that 120≤Re(550)≤150.

[0370] Examples of polymeric liquid crystal compounds that are polymeric liquid crystal compounds in which the phase retardation film is a film having an optical anisotropic layer include compounds having polymeric groups described in "3.8.6 Network (fully cross-linked type)" and "6.5.1 Liquid Crystal Materials b. Polymerizable Nematic Liquid Crystal Materials" of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2012), as well as polymeric liquid crystal compounds described in Japanese Patent Application Publication Nos. 2010-31223, 2010-270108, 2011-6360, 2011-207765, 2011-162678, 2016-81035, International Publication No. 2017 / 043438, and Japanese Patent Application Publication No. 2011-207765.

[0371] For example, the method described in Japanese Patent Application Publication No. 2010-31223 can be cited as a method for manufacturing a phase retardation film from a polymer in an oriented state of a polymeric liquid crystal compound.

[0372] In the second approach, the frontal phase difference value Re(550) only needs to be adjusted to the range of 0–10 nm, preferably to the range of 0–5 nm, while the phase difference value R in the thickness direction... th Simply adjust it to a range of -10 to -300 nm, preferably -20 to -200 nm. The phase difference value R in the thickness direction, representing the refractive index anisotropy in the thickness direction, is... th The phase difference value R can be measured by tilting the plane by 50 degrees using the fast axis in the plane as the tilt axis. 50 The phase difference R0 within the plane is calculated. That is, the phase difference R0 in the thickness direction is... th The phase difference R can be determined by tilting the plane by 50 degrees using the fast axis as the tilt axis, based on the in-plane phase difference value R0. 50 The thickness d of the retardation film and the average refractive index n0 of the retardation film are obtained by the following equations (10) to (12). x n y and n z Substitute them into equation (9) to calculate.

[0373] R th =[(n x +n y ) / 2-n z ]×d (9)

[0374] R0=(n x -n y )×d (10)

[0375] R50 =(n x -n y ′)×d / cos(φ) (11)

[0376] (n x +n y +n z ) / 3=n0 (12)

[0377] Here,

[0378] φ=sin -1 [sin(40°) / n0]

[0379] n y ′=n y ×n z / 〔n y 2 ×sin 2 (φ)+n z 2 ×cos 2 (φ)〕 1 / 2

[0380] Examples of films exhibiting optical anisotropy through the coating and orientation of liquid crystal compounds, and films exhibiting optical anisotropy through the coating of inorganic layered compounds, include films called temperature-compensated phase retardation films, "NH FILM" (trade name: film with tilted orientation of rod-shaped liquid crystals) sold by JX Nippon Minerals & Energy Co., Ltd., "WV FILM" (trade name: film with tilted orientation of disc-shaped liquid crystals) sold by Fujifilm Co., Ltd., "VAC FILM" (trade name: film with fully biaxial orientation) sold by Sumitomo Chemical Co., Ltd., and "new VAC FILM" (trade name: film with biaxial orientation) sold by Sumitomo Chemical Co., Ltd., etc.

[0381] Phase retardation films can also be multilayer films with two or more layers. For example, a phase retardation film in which a protective film is laminated on one or both sides of the phase retardation film, or a phase retardation film obtained by laminating two or more phase retardation films with an adhesive or bonding agent.

[0382] An example of the adhesive layer and the optical laminate of the present invention is shown below. Figures 1-5 .

[0383] Figure 1 The optical film 10 with an adhesive layer described herein is in a state in which a release film (isolation film) 2 is attached to the adhesive layer 1 in order to temporarily protect the adhesive layer 1 formed by the adhesive composition of the present invention.

[0384] Figure 2The optical film 10A described herein with an adhesive layer comprises a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 1 formed from the adhesive composition of the present invention, and a release film 2. The protective film 3 may have a phase difference. In addition, a hard coating or the like may be further laminated on the protective film 3.

[0385] Figure 3 The optical film 10B with adhesive layer described herein is an optical film with adhesive layer comprising a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 7, a protective film 6, an adhesive layer 1 formed by the adhesive composition of the present invention, and a phase difference film 8.

[0386] Figure 4 The optical laminate 10C described in the document and Figure 5 The optical laminate 10D described herein is an optical laminate comprising a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 1 formed from the adhesive composition of the present invention, an adhesive layer 7, a retardation film 110, an adhesive layer 1a, and a light-emitting element 30 (liquid crystal unit, organic EL unit). The adhesive layer 1a may be an adhesive layer formed from a known adhesive composition or an adhesive layer formed from the adhesive composition of the present invention.

[0387] exist Figure 4 and Figure 5 In the case where the phase retardation film is a multilayer film as shown, examples include... Figure 4 The structure shown includes a phase retardation film 110, which is obtained by laminating a quarter-wavelength phase retardation layer 70 that imparts a 1 / 4 wavelength phase difference to the transmitted light and a half-wavelength phase retardation layer 50 that imparts a 1 / 2 wavelength phase difference to the transmitted light via an adhesive layer or bonding agent layer 60. Additionally, examples such as... Figure 5 As shown, it includes an optical film 40, which is obtained by laminating a 1 / 4 wavelength phase retardation layer 50a and a positive C layer 80 via an adhesive layer or bonding agent layer 60.

[0388] Figure 4 The 1 / 4 wavelength phase difference layer 70, which imparts a 1 / 4 wavelength phase difference, and the 1 / 2 wavelength phase difference layer 50, which imparts a 1 / 2 wavelength phase difference to the transmitted light, can be the optical film of the first type described above, or they can be the optical film of the fifth type. Figure 4 In the case of the configuration, at least one of them is more preferably the fifth method.

[0389] exist Figure 5 In the case of the configuration, the 1 / 4 wavelength phase difference layer 50a is preferably the optical film of the first type described above, and more preferably satisfies formulas (7) and (8).

[0390] Liquid crystal display device

[0391] An optical laminate comprising the resin of the present invention, an adhesive composition containing the resin, and an adhesive layer formed from the adhesive composition can be laminated onto display elements such as organic EL elements and liquid crystal cells, thereby being used in display devices such as organic EL display devices and liquid crystal display devices.

[0392] Example

[0393] The present invention will now be described in further detail through examples and comparative examples. Unless otherwise specified, “%” and “parts” in the examples and comparative examples refer to “mass %” and “parts by mass”.

[0394] (Synthetic Example 1) Synthesis of a light-selective absorption compound (1) having polymerizable groups and an indole structure

[0395]

[0396] A 1000 mL four-necked flask equipped with a serpentine condenser and a thermometer was purged with nitrogen. Then, 100 parts of the compound shown in formula (a) (1-methyl-2-phenyl-1H-indole-3-carboxaldehyde), 40 parts of cyanoacetic acid, 76 parts of piperidine, and 300 parts of acetonitrile were added, and the mixture was stirred and kept at 80°C for 4 hours. The precipitated crystals were filtered from the resulting mixture and collected. The obtained crystals were mixed with 500 parts of 5% sulfuric acid and stirred and kept at 80°C for 1 hour. The resulting mixture was purified to obtain 116 parts of the compound shown in formula (b) (2-cyano-3-(1-methyl-2-phenyl-1H-indole-3-yl)-2-acrylic acid).

[0397]

[0398] After purging the 100 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, 5 parts of the compound shown in formula (b), 2.3 parts of 4-hydroxybutyl acrylate, 0.4 parts of N,N-dimethyl-4-aminopyridine, 0.2 parts of 2,6-di-tert-butyl-4-methylphenol, and 50 parts of chloroform were added, and the mixture was cooled to 0°C. While maintaining the temperature at 0–5°C, 2.2 parts of N,N'-diisopropylcarbodiimide were added dropwise to the resulting mixture. After the addition, the resulting mixture was kept at 10°C for 4 hours. The resulting mixture was purified to obtain 4.9 parts of the compound shown in formula (1) (2-cyano-3-(1-methyl-2-phenyl-1H-indol-3-yl)-2-acrylate-4-acryloyloxybutyl ester). The maximum absorption wavelength of the compound shown in formula (1) is 386 nm.

[0399] Identification of the compound represented by formula (1)

[0400] 1H-NMR (CDCl3) δ: 1.75-1.80 (m, 4H), 3.70 (s, 3H), 4.15-4.20 (t, 2H), 4.23-4.27 (t, 2H), 5.78-5.82 (dd, 1H), 6 .06-6.14(dd, 1H), 6.36-6.41(dd, 1H), 7.35-7.43(m, 5H), 7.54-7.57(m, 3H), 8.12(s, 1H), 8.42-8.45(m, 1H)

[0401] <Determination of Absorption Coefficient ε>

[0402] A 0.006 g / L solution of the 2-butanone compound represented by formula (1) was placed in a 1 cm quartz cuvette. The quartz cuvette was set in a UV-2450 spectrophotometer (manufactured by Shimadzu Corporation), and the absorbance in the wavelength range of 300–800 nm was measured in 1 nm increments using the double-beam method. Based on the absorbance values, the concentration of the compound represented by formula (1) in the solution, and the optical path length of the quartz cuvette, the gamma absorptivity for each wavelength was calculated.

[0403] ε(λ)=A(λ) / CL

[0404] [In the formula, ε(λ) represents the gamma-ray absorptivity of the compound represented by formula (1) at wavelength λnm (L / (g·m)), A(λ) represents the absorbance at wavelength λnm, C represents the concentration (g / L), and L represents the optical path length of the quartz cuvette (m).]

[0405] The compound represented by formula (1) has a maximum absorption wavelength of 386 nm and an ε of 0.628 at the maximum absorption wavelength. In addition, the ε (400) of the compound represented by formula (1) is 0.470 L / (g·m).

[0406] (Synthetic Example 2) Synthesis of a light-selective absorption compound (2) having polymerizable groups and an indole structure

[0407]

[0408] Except that 2 parts of 2-hydroxyethyl acrylate were used instead of 2.3 parts of 4-hydroxybutyl acrylate, the same procedure as in Example 1 was followed to obtain 4.3 parts of the compound (2-cyano-3-(1-methyl-2-phenyl-1H-indol-3-yl)-2-acryloyloxyethyl acrylate) of Formula (4). The maximum absorption wavelength of the compound of Formula (2) was 390 nm. The gamma absorptivity was determined in the same manner as in Synthesis Example 1, and the results were ε(λmax) = 0.676 and ε(400) = 0.567 L / (g·m).

[0409] (Synthetic Example 3) Synthesis of a light-selective absorption compound (3) having polymerizable groups and an indole structure

[0410]

[0411] A 200 mL four-necked flask equipped with a thermometer was purged with nitrogen. Then, 10 parts of compound (2-phenyl-1H-indole-3-carboxaldehyde) as shown in formula (c), 9 parts of 6-bromohexane, 7.5 parts of potassium carbonate, and 100 parts of N,N-dimethylacetamide were added. The mixture was stirred at 100°C for 5 hours. The resulting mixture was purified to obtain 9 parts of compound (1-hexyl-2-phenyl-1H-indole-3-carboxaldehyde) as shown in formula (d).

[0412] After purging the 200 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, the entire compound shown in formula (d), 4.2 parts of cyanoacetic acid, 8.1 parts of piperidine, and 72 parts of acetonitrile were added, and the mixture was stirred at 80 °C for 10 hours. The resulting mixture was purified to obtain 12 parts of the compound shown in formula (e) ((2-cyano-3-(1-hexyl-2-phenyl-1H-indol-3-yl)-2-acrylic acid).

[0413]

[0414] After purging the 100 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, 10 parts of the compound shown in formula (e), 3.1 parts of 2-hydroxyethyl acrylate, 0.3 parts of N,N-dimethyl-4-aminopyridine, 0.3 parts of 2,6-di-tert-butyl-4-methylphenol, and 100 parts of chloroform were added, and the mixture was cooled to 0°C. While maintaining the temperature at 0–5°C, 3.6 parts of N,N'-diisopropylcarbodiimide were added dropwise to the resulting mixture. After the addition, the resulting mixture was kept at 10°C for 4 hours. The resulting mixture was purified to obtain 3.5 parts of the compound shown in formula (3) (2-cyano-3-(1-hexyl-2-phenyl-1H-indol-3-yl)-2-acrylic acid-2-acryloyloxyethyl ester). The maximum absorption wavelength of the compound shown in formula (3) is 388 nm.

[0415] Identification of the compound represented by formula (3)

[0416] 1H-NMR(CDCl3)δ: 0.75-0.87(t, 3H), 1.08-1.23(m, 6H), 1.65-1.78(m, 6H), 4.04-4.13(t, 2H), 4.15-4.20(t, 2H), 4.23-4.27(t, 2H) , 5.78-5.82(dd, 1H), 6.06-6.14(dd, 1H), 6.36-6.41(dd, 1H), 7.35-7.43(m, 5H), 7.54-7.57(m, 3H), 8.12(s, 1H), 8.42-8.45(m, 1H)

[0417] The compound shown in equation (3) has a maximum absorption wavelength of 388 nm. The gamma absorption coefficient was calculated in the same manner as in synthesis example 1, and the results were ε(λmax) = 0.617 and ε(400) = 0.485 L / (g·m).

[0418] (Synthetic Example 4) Synthesis of a light-selective absorption compound (4) having polymerizable groups and an indole structure

[0419]

[0420] After purging the 100 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, 5 parts of the compound shown in formula (c) (2-phenyl-1H-indole-3-carboxaldehyde), 5 parts of 6-bromo-1-hexanol, 3.7 parts of potassium carbonate, and 40 parts of N,N-dimethylacetamide were added, and the mixture was stirred at 100 °C for 5 hours. The resulting mixture was purified to obtain 4 parts of the compound shown in formula (f) (1-(6-hydroxyhexyl)-2-phenyl-1H-indole-3-carboxaldehyde).

[0421] After purging the 200 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, the entire compound of formula (f), 1.7 parts malononitrile, and 50 parts acetonitrile were added, followed by dropwise addition of 3.2 parts diisopropylethylamine. The mixture was stirred at room temperature for 3 hours. The resulting mixture was purified to obtain 4.2 parts of 1-(6-hydroxyhexyl)-2-phenyl-3-(2,2-dicyanovinyl)indole, the compound of formula (g).

[0422]

[0423] After purging the 100 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, 3.4 parts of the compound shown in formula (g), 1.7 parts of N,N-dimethylaniline, 0.1 parts of 2,6-di-tert-butyl-4-methylphenol, and 34 parts of N,N-dimethylacetamide were added, and the mixture was cooled to 0°C. While maintaining the temperature at 0–5°C, 1 part of acryloyl chloride was added dropwise to the resulting mixture. After the addition, the resulting mixture was kept at 10°C for 4 hours. The resulting mixture was purified to obtain 1.6 parts of the compound shown in formula (4) (1-(6-acryloyloxyhexyl)-2-phenyl-3-(2,2-dicyanovinyl)indole). The maximum absorption wavelength of the compound shown in formula (4) is 392 nm.

[0424] Identification of the compound represented by formula (4)

[0425] 1 H-NMR (CDCl3) δ: 1.13-1.25 (m, 4H), 1.51-1.59 (m, 2H), 1.68-1.77 (m, 2H), 4.02-4.10 (m, 4H), 5.78-5.82 (dd, 1H ), 6.06-6.14(dd, 1H), 6.36-6.41(dd, 1H), 7.35-7.43(m, 5H), 7.54-7.57(m, 3H), 8.12(s, 1H), 8.42-8.45(m, 1H)

[0426] The compound shown in equation (4) has a maximum absorption wavelength of 392 nm. The gamma absorption coefficient was calculated in the same manner as in synthesis example 1, and the results were ε(λmax) = 0.753 and ε(400) = 0.665 L / (g·m).

[0427] (Synthetic Example 5) Synthesis of a light-selective absorption compound (5) having polymerizable groups and an indole structure

[0428]

[0429] A 200 mL four-necked flask equipped with a thermometer was purged with nitrogen. Ten parts of compound (2-phenyl-1H-indole-3-carboxaldehyde) of formula (c), 8.7 parts of 1-iodobutane, 7.5 parts of potassium carbonate, and 80 parts of N,N-dimethylacetamide were added, and the mixture was stirred at room temperature for 5 hours. The resulting mixture was purified to obtain nine parts of compound (1-butyl-2-phenyl-1H-indole-3-carboxaldehyde) of formula (h).

[0430] After purging the 200 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, the entire compound of formula (h), 6.2 parts of cyanoacetic acid, 12.5 parts of piperidine, and 50 parts of acetonitrile were added, and the mixture was stirred at 80 °C for 15 hours. The resulting mixture was purified to obtain 9.8 parts of the compound of formula (i) ((2-cyano-3-(1-butyl-2-phenyl-1H-indol-3-yl)-2-acrylic acid).

[0431]

[0432] After purging the 100 mL four-necked flask equipped with a thermometer into a nitrogen atmosphere, 7.7 parts of the compound shown in formula (i), 3.3 parts of 4-hydroxybutyl acrylate, 0.3 parts of N,N-dimethyl-4-aminopyridine, 0.3 parts of 2,6-di-tert-butyl-4-methylphenol, and 77 parts of chloroform were added, and the mixture was cooled to 0°C. While maintaining the temperature at 0–5°C, 3.0 parts of N,N'-diisopropylcarbodiimide were added dropwise to the resulting mixture. After the addition, the resulting mixture was kept at 10°C for 4 hours. The resulting mixture was purified to obtain 5.7 parts of the compound shown in formula (5) (2-cyano-3-(1-butyl-2-phenyl-1H-indol-3-yl)-2-acrylic acid-4-acryloyloxybutyl ester). The maximum absorption wavelength of the compound shown in formula (5) is 386 nm.

[0433] Identification of the compound represented by formula (5)

[0434] 1 H-NMR(CDCl3)δ: 0.74-0.81(t, 3H), 1.12-1.21(m, 2H), 1.63-1.70(m, 2H), 1.72-1.83(m, 4H), 4.06-4.11(t, 2H), 4.15-4.20(t, 2H), 4.23-4. 27(t, 2H), 5.78-5.82(dd, 1H), 6.06-6.14(dd, 1H), 6.36-6.41(dd, 1H), 7.35-7.43(m, 5H), 7.54-7.57(m, 3H), 8.12(s, 1H), 8.42-8.45(m, 1H)

[0435] The compound shown in equation (5) has a maximum absorption wavelength of 386 nm. The gamma absorption coefficient was calculated in the same manner as in synthesis example 1, and the results were ε(λmax) = 0.60 and ε(400) = 0.44 L / (g·m).

[0436] [Polymerization Example 1]: Preparation of acrylic resin (A)

[0437] A mixed solution of 81.8 parts ethyl acetate, 96 parts butyl acrylate, 3 parts 2-hydroxyethyl methyl acrylate, and 1 part acrylic acid was added to a reaction vessel equipped with a condenser, nitrogen inlet, thermometer, and stirrer. The air inside the apparatus was purged with nitrogen to eliminate oxygen, and the internal temperature was raised to 55°C. Then, the entire amount of a solution obtained by dissolving 0.14 parts azobisisobutyronitrile (polymerization initiator) in 10 parts ethyl acetate was added. After adding the initiator, the mixture was maintained at this temperature for 1 hour. Then, while maintaining the internal temperature at 54–56°C, ethyl acetate was continuously added to the reaction vessel at a rate of 17.3 parts / hr. The addition of ethyl acetate was stopped when the concentration of the acrylic resin reached 35%. The mixture was then maintained at this temperature for another 12 hours from the start of ethyl acetate addition. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%, thus preparing an ethyl acetate solution of the acrylic resin. The obtained acrylic resin had a weight-average molecular weight (Mw) of 1.47 million based on GPC-converted polystyrene, a Mw / Mn ratio of 5.5, and a glass transition temperature (Tg) of -52℃ determined by differential scanning calorimetry (DSC). This resin was designated as acrylic resin (A).

[0438] (Example 1)

[0439] To obtain the adhesive composition (1), ethyl acetate was added to a solid content of 100 parts relative to 14% of the ethyl acetate solution of acrylic resin (A) (resin concentration: 20%), along with 0.3 parts of a mixed crosslinking agent (E) (manufactured by Tosoh Corporation: trade name "Coronate L", isocyanate compound, solid content 75%), 0.28 parts of a silane compound (F) (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name "KBM3066"), 10 parts of a free radical curing agent (D) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: trade name "A-DPH-12E", hexafunctional (meth)acrylate compound), 1.5 parts of an initiator (C) (manufactured by ADEKA Co., Ltd.: trade name "NCI-730", oxime ester compound photoradical generator), and 3 parts of a light selective absorption compound (B) (the compound shown in formula (1)). It should be noted that the amount of the crosslinking agent mentioned above is the mass fraction of the active ingredient.

[0440] Examples 2-15 and Comparative Examples 1-6

[0441] Except for changing the components and their contents as shown in Tables 1 to 3, adhesive compositions (2) to (21) were prepared in the same manner as in Example 1. It should be noted that the amount of crosslinking agent is the mass fraction of the active ingredient, and the amount of resin (A) is the mass fraction of the solid component.

[0442] Table 1

[0443]

[0444] Table 2

[0445]

[0446] Table 3

[0447]

[0448] It should be noted that the abbreviations in Tables 1 to 3 represent the following substances respectively. In addition, ε(400) in SB107, SB707, KB74 and UA3911 was determined by the same method as described above.

[0449] Acrylic resin (A): Acrylic resin (A) prepared in Polymerization Example 1

[0450] Compound (1): The compound of formula (1) synthesized in Example 1

[0451] Compound (2): The compound of formula (2) synthesized in Example 2

[0452] Compound (3): The compound of formula (3) synthesized in Example 3

[0453] Compound (4): The compound of formula (4) synthesized in Example 4

[0454] Compound (5): The compound of formula (5) synthesized in Example 5

[0455] RUVA-93: Manufactured by Otsuka Chemicals Co., Ltd., ultraviolet absorber, trade name: RUVA-93, maximum absorption wavelength λmax=337nm, ε(400)=0

[0456] NCI-730: Manufactured by ADEKA Corporation, trade name: NCI-730, oxime ester-based photoradical generator.

[0457] A-DPH-12E: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: A-DPH-12E, a hexafunctional (meth)acrylate compound.

[0458] Coronate L: Manufactured by Tosoh Corporation, trade name: Coronate L, isocyanate compound.

[0459] KBM3066: Manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM3066, silane coupling agent.

[0460] SB107: Manufactured by SHIPRO KASEI Co., Ltd., a benzophenone-based ultraviolet absorber, trade name: SEESORB107, maximum absorption wavelength λmax = 350nm, ε(400) = 0.245

[0461] SB707: Manufactured by SHIPRO KASEI Co., Ltd., a benzotriazole-based ultraviolet absorber, trade name: SEESORB707, maximum absorption wavelength λmax = 343 nm, ε(400) = 0.001

[0462] KB74: Manufactured by CHEMIPRO KASEI Co., Ltd., a benzotriazole-based ultraviolet absorber, trade name: KEMSORB74, maximum absorption wavelength λmax = 342nm, ε(400) = 0.001

[0463] UA3911: Manufactured by Orient Chemical Industries, an indole-based ultraviolet absorber (without polymerizable groups), trade name: BONASORB UA-3901. Maximum absorption wavelength λmax = 393 nm, ε(400) = 1.007.

[0464] <Preparation of Adhesive Layer>

[0465] Using an applicator, each of the above-prepared adhesive compositions was applied to the release-treated surface of a release film (trade name "PLR-382190" from Lintec Corporation) formed of polyethylene terephthalate film after release treatment, with a dried thickness of 5 μm. The film was then dried at 100°C for 1 minute. Next, from the release film side, ultraviolet irradiation was performed using an electrodeless UV lamp system (FUSION UV SYSTEMS "H Bulb"), adjusted to UV-A (wavelength 320–390 nm) with an illuminance of 500 mW and a cumulative light intensity of 500 mJ, thereby creating an adhesive layer (adhesive sheet).

[0466] <Absorbance Measurement of Adhesive Layer>

[0467] The obtained adhesive layers were bonded to glass. After peeling off the diaphragm, a cyclic olefin polymer (COP) film (ZF-14 manufactured by ZEON Corporation, Japan) was bonded to the adhesive layers to create a laminate consisting of a COP film, an adhesive layer, and glass. The laminate was placed on a UV-2450 spectrophotometer (manufactured by Shimadzu Corporation), and the absorbance was measured using the double-beam method in 1 nm increments within the wavelength range of 300–800 nm. The absorbance of the adhesive layer is shown in Table 4. It should be noted that the absorbance of both the glass and the COP film at wavelengths of 300 nm, 330 nm, 350 nm, 380 nm, and 400 nm was 0.

[0468] <Evaluation of the adhesive layer's resistance to leakage>

[0469] A release liner is further laminated onto the surface of the obtained adhesive layer to obtain an adhesive layer with release liners on both sides. The resulting adhesive layer with release liners on both sides is stored in air at 23–25°C for one month. For the stored adhesive layer with release liners on both sides, microscopy is used to confirm the presence or absence of compound crystal precipitation within the surfaces. No crystal precipitation is marked as ○, and crystal precipitation is marked as ×. The evaluation results are shown in Table 4.

[0470] Table 4

[0471] Permeability A400 A300 A330 A350 A380 Example 1 ○ 1.04 1.05 0.61 0.63 1.13 Example 2 ○ 0.42 0.69 0.45 0.35 0.45 Example 3 ○ 1.01 0.92 0.58 0.59 1.06 Example 4 ○ 1.35 0.93 0.62 0.6 1.23 Example 5 ○ 1.27 1.18 0.79 0.84 1.46 Example 6 ○ 1.42 1.18 0.62 0.75 1.52 Example 7 ○ 1.45 5 5 5 1.82 Example 8 ○ 1.29 0.94 0.55 0.65 1.34 Example 9 ○ 1.24 5 5 5 1.50 Example 10 ○ 1.32 1 0.6 0.75 1.49 Example 11 ○ 1.04 5 4.22 3.97 1.38 Example 12 ○ 1.80 0.98 0.61 0.68 1.64 Example 13 ○ 2.00 1.07 0.67 0.76 1.81 Example 14 ○ 1.72 1.3 0.66 0.79 1.70 Example 15 ○ 1.32 5 5 5 1.57 Comparative Example 1 × 0.02 5. 5 5 0.45 Comparative Example 2 × 0.02 3.52 5 5 0.5 Comparative Example 3 × 0.11 5 5 5 2.34 Comparative Example 4 × 0.31 5 5 5 2.29 Comparative Example 5 × 0.03 1.27 2.25 2.15 0.33 Comparative Example 6 × 1.52 1.04 0.63 0.66 1.41

[0472] The adhesive layer formed from the adhesive composition of the present invention exhibits high absorbance around a wavelength of 400 nm, and also shows good resistance to efflorescence. Furthermore, the adhesive composition of the present invention exhibits good absorbance in the wavelength range of 300 nm to 400 nm.

[0473] Industrial availability

[0474] The adhesive composition of the present invention, and the optical laminate comprising an adhesive layer formed by the above adhesive composition, are suitable for use in liquid crystal panels and liquid crystal display devices.

[0475] Explanation of reference numerals in the attached figures

[0476] 1: An adhesive layer formed from the adhesive composition of the present invention

[0477] 1a: Adhesive layer

[0478] 2: Peel-off membrane

[0479] 10, 10A, 10B, 10C, 10D: Optical films with adhesive layers

[0480] 3, 6: Protective film

[0481] 4, 7: Adhesive layer

[0482] 5: Polarizing film

[0483] 8: Phase retardation film

[0484] 30: Light-emitting element

[0485] 40: Optical film

[0486] 70, 50a: 1 / 4 wavelength phase détente layer

[0487] 60: Adhesive layer or bonding agent layer

[0488] 50:1 / 2 wavelength phase difference layer

[0489] 80: Positive C layer

[0490] 100: Polarizing plate

[0491] 110: Phase difference film.

Claims

1. An adhesive composition comprising a resin (A), a light-selective absorbing compound (B) comprising an indole structure and polymerizable groups within the molecule, and an initiator (C). The resin (A) is a (meth)acrylic resin. The polymerizable group is vinyl ether, vinyl, α-methyl vinyl, acryloyl, methacryloyl, allyl, styryl, or (meth)acrylamido. The light-selective absorption compound (B), which contains an indole structure and a polymerizable group within its molecule, is a compound represented by formula (I) or (II). In equation (I), R 1 R 2 R 3 R 4 R 5 and R 6 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms optionally having substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms optionally having substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is optionally substituted with -NR. 1A -, -SO2-, -CO-, -O-, -S- or -CF2-, R 1A This indicates a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. E 1 Indicates an electron-withdrawing group. Z represents the linking group. A represents a polymerizing group. In equation (II), R 12 and R 17 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms optionally having substituents, or an aromatic hydrocarbon group with 6 to 18 carbon atoms optionally having substituents, wherein the -CH2- group contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is optionally substituted with -NR. 11A -, -SO2-, -CO-, -O-, -S- or -CF2-, R 13 R 14 R 15 and R 16 Each group independently represents a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a group containing a polymerizable group, an aliphatic hydrocarbon group with 1 to 25 carbon atoms optionally having a substituent, or an aromatic hydrocarbon group with 6 to 18 carbon atoms optionally having a substituent, wherein the -CH2- group contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is optionally substituted with -NR. 12A -, -SO2-, -CO-, -O-, -S- or -CF2-, R 11 A group that contains a polymerizable group. R 11A and R 12A Each group independently represents a hydrogen atom, an alkyl group with 1 to 25 carbon atoms, or an aromatic hydrocarbon group with 6 to 18 carbon atoms. E 11 This indicates an electron-withdrawing group.

2. The adhesive composition according to claim 1, wherein, The polymerizable group is a free radical polymerizable group.

3. The adhesive composition according to claim 1, wherein, The polymerizable group is (meth)acryloyl.

4. The adhesive composition according to claim 1, wherein, The initiator (C) is a free radical polymerization initiator.

5. The adhesive composition according to claim 1, wherein, Initiator (C) is a photoradical polymerization initiator.

6. The adhesive composition according to claim 1, wherein, The initiator (C) is an oxime ester compound.

7. The adhesive composition according to claim 1, further comprising a free radical curing component (D).

8. The adhesive composition according to claim 7, wherein, The free radical curing component (D) is a (meth)acrylate compound.

9. The adhesive composition according to claim 7, wherein, The free radical curing component (D) is a polyfunctional (meth)acrylate compound.

10. The adhesive composition according to claim 1, further comprising a crosslinking agent (E).

11. The adhesive composition according to claim 10, wherein, The crosslinking agent (E) is an isocyanate crosslinking agent.

12. The adhesive composition according to claim 10, wherein, The glass transition temperature of resin (A) is below 40°C.

13. The adhesive composition according to any one of claims 1 to 12, wherein, The light-selective absorption compound (B), which contains an indole structure and polymerizable groups within its molecule, is a compound that exhibits maximum absorption at wavelengths above 360 ​​nm and below 420 nm.

14. The adhesive composition according to any one of claims 1 to 12, wherein, The light-selective absorption compound (B), which contains an indole structure and a polymerizable group within its molecule, satisfies formula (1). ε(400)≥0.05 (1) In equation (1), ε (400) represents the gamma absorption coefficient of the light-selective absorption compound (B) at a wavelength of 400 nm, and the unit of gamma absorption coefficient is L / (g·m).

15. The adhesive composition according to claim 1, wherein, R 2 and R 12 Each is an aromatic hydrocarbon group with 6 to 18 carbon atoms.

16. The adhesive composition according to claim 1, wherein, The compound represented by formula (I) is the same as the compound represented by formula (III), and the compound represented by formula (II) is the same as the compound represented by formula (IV). In equation (III), R 1 R 3 R 4 R 5 R 6 and E 1 They respectively represent the same meaning as above. R 7 Represents a hydrogen atom, cyano group, methyl group, or phenyl group. Z 1 -OR indicates alkyldiyl groups with 1 to 12 carbon atoms, divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, and alkyl diols. 2A - 1. -SR 2B - 1 or -NR 1D -R 2C - 1, Z 2 Indicates a single key, 2-CO-O-、 2-O-CO-、 2-S(=O)2-、 2-O-SO2-、 2-CO-NR 1B -、 2-NR 1C -CO-、 2-R 2D OP(=O)-OR 2E -、 2-NR 1E -CO-O-、 2-O-CO-NR 1F -、 2-(OR 2F ) s1 -、 2-CO-S-、 2-S-CO- or perfluoroalkyl dimethyl groups with 1 to 4 carbon atoms, R 1B R 1C R 1D R 1E and R 1F Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. R 2A R 2B R 2C R 2D R 2E and R 2F Each of these groups independently represents a divalent hydrocarbon group with 1 to 18 carbon atoms. 1 indicates the relationship with Z 2 The connection key, 2 indicates the relationship with Z 1 The connection key, In equation (IV), R 12 R 13 R 14 R 15 R 16 R 17 and E 11 They respectively represent the same meaning as above. Z 1 Indicates a divalent linker group. A 1 It indicates a polymerizable group.

17. An adhesive layer formed from the adhesive composition of any one of claims 1 to 16.

18. The adhesive layer according to claim 17, which satisfies the following formula (2). A（400）≥0.4　 （2） In equation (2), A(400) represents the absorbance at a wavelength of 400 nm.

19. The adhesive layer according to claim 17 or 18, wherein, The adhesive layer has a film thickness of less than 10 μm.

20. An optical film having an adhesive layer, wherein the optical film is laminated on at least one side of the adhesive layer according to any one of claims 17 to 19.

21. The optical film with an adhesive layer according to claim 20, wherein, The optical film is a polarizing plate.

22. An image display device comprising an optical film with an adhesive layer as described in claim 20 or 21.

Images