TWI820319B - Adhesive composition - Google Patents

Abstract

An objective of the present invention is to provide an optical film with adhesive layer obtained by laminating an adhesive layer and an optical film, which has good bleeding resistance when being stored for a long period of time. Also provided are an adhesive layer having good bleeding resistance and an adhesive composition capable of forming the adhesive layer.

As a solution, the adhesive composition of the present invention comprises a resin (A), a photoselective absorption compound (B) having a merocyanine structure and a polymerizable group in the molecule, and a photoinitiator (D). The adhesive composition may further contain a photcurable component (C).

Description

Adhesive composition

The present invention relates to an adhesive composition, an adhesive layer formed from the adhesive composition, and an optical film laminated with the adhesive layer.

In display devices (FPD: flat panel display) such as organic EL display devices and liquid crystal display devices, various components such as display elements such as organic EL elements and liquid crystal cells, and optical films such as polarizing plates and retardation films are used. Among them, organic EL compounds and liquid crystal compounds that are often used in organic EL display devices are mostly compounds with weak weather resistance among organic compounds. Therefore, not only ultraviolet (UV), but also short-wavelength visible light with a wavelength of 420 nm or less is caused. Deterioration can also easily become a problem. In order to solve this problem, Patent Document 1 describes an adhesive composition containing (meth)acrylic resin, and an adhesive layer optical film formed from the composition. It is a light selective absorption compound (BONASORB UA-3911 manufactured by Orient Chemical Industries) which has an indole structure and selectively absorbs light with a wavelength near 400 nm.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-165941

Furthermore, from the viewpoint of thinning, optical films used in organic EL display devices among display devices have recently been increasingly made of polymers in which polymerizable liquid crystal compounds are in an aligned state. Compared with conventional optical films formed by stretched resin films, it is known that optical films formed of polymers using polymerizable liquid crystal compounds as aligned states tend to crack when placed in an environment where high-temperature conditions and low-temperature conditions repeatedly change. (Broken) Has a tendency to become elongated easily.

Although the optical film laminated with an adhesive layer composed of an adhesive composition described in cited document 1 improves the deterioration of visible light with a wavelength of around 420 nm, it does not sufficiently suppress the growth of absorption cracks.

The present invention includes the following inventions.

[1] An adhesive composition containing: a resin (A), a photocurable component (C), and a light-selective absorption compound (B) having a merocyanine structure.

[2] The adhesive composition as described in [1] further contains a photoinitiator (D).

[3] The adhesive composition according to [2], wherein the photoinitiator (D) is a photoradical generator.

[4] The adhesive composition according to any one of [1] to [3], wherein the photocurable component (C) is a photoradically curable component.

[5] The adhesive composition according to [4], wherein the photocurable component (C) contains a (meth)acrylate compound.

[6] The adhesive composition according to [4] or [5], wherein the photocurable component (C) contains a polyfunctional (meth)acrylate compound.

[7] The adhesive composition according to any one of [1] to [6], further containing a cross-linking agent (E).

[8] The adhesive composition according to [7], wherein the cross-linking agent (E) is an isocyanate cross-linking agent.

[9] The adhesive composition according to any one of [1] to [8], wherein the resin (A) is a resin having a glass transition temperature of 40°C or less.

[10] The adhesive composition according to any one of [1] to [9], wherein the resin (A) is a (meth)acrylic resin.

[11] The adhesive composition according to any one of [1] to [10], wherein the resin (A) is a (meth)acrylic resin with a weight average molecular weight of 500,000 or more.

[12] The adhesive composition according to any one of [1] to [11], wherein the light selective absorption compound (B) having a merocyanin structure satisfies the following formula (1);

ε(405)≧5 (1)

[In formula (1), ε (405) represents the gram absorption coefficient of the light-selective absorption compound (B) having a merocyanin structure at a wavelength of 405 nm. The unit of gram absorption coefficient is L/(g·cm)].

[13] The adhesive composition according to any one of [1] to [12], wherein the light selective absorption compound (B) having a merocyanin structure satisfies the following formula (2);

ε(405)/ε(440)≧20 (2)

[In formula (2), ε (405) represents the gram absorption coefficient of the light-selective absorption compound (B) having a merocyanin structure at a wavelength of 405 nm, and ε (440) represents a merocyanin structure at a wavelength of 440 nm. The gram absorption coefficient of the light-selective absorption compound (B) of the elemental structure].

[14] The adhesive composition according to any one of [1] to [13], wherein the light-selective absorption compound (B) having a merocyanin structure does not have a polymerizable group.

[15] The adhesive composition according to any one of [1] to [14], wherein the light selective absorption compound (B) having a merocyanin structure is a compound represented by formula (I);

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 25 that may have a substituent, and a carbon number of 6 to 15 that may have a substituent. The aromatic hydrocarbon group or heterocyclic group, the -CH ₂ - contained in the aforementioned aliphatic hydrocarbon group or aromatic hydrocarbon group can be substituted by -NR ^1A -, -SO ₂ -, -CO-, -O- or -S-.

R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group.

R ^1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹ and R ² can be bonded to each other to form a ring structure, R ² and R ³ can be bonded to each other to form a ring structure, R ² and R ⁴ can be bonded to each other to form a ring structure, R ³ and R ⁶ can be bonded to each other to form a ring structure, R ⁵ and R ⁷ can be bonded to each other to form a ring structure, R ⁶ and R ⁷ can be bonded to each other to form a ring structure].

[16] The adhesive composition according to [15], wherein the compound represented by formula (I) is a compound represented by formula (II);

[In formula (II), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and a carbon number which may have a substituent. 6 to 15 aromatic hydrocarbon groups or heterocyclic groups, the -CH2- contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group can be substituted by -NR11A-, -SO2-, -CO-, -O- or -S-.

R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group.

R ^11A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹¹ and R ¹² may be bonded to each other to form a ring structure, R ¹² and R ¹³ may be bonded to each other to form a ring structure, and R ¹² and R ¹⁴ may be bonded to each other to form a ring structure].

[17] An adhesive layer formed from the adhesive composition described in any one of [1] to [16].

[18] The adhesive layer as described in [17], which satisfies the following formula (3);

A(405)≧0.5 (3)

[In formula (3), A (405) represents the absorbance at a wavelength of 405 nm].

[19] The adhesive layer as described in [18], which further satisfies the following formula (4);

A(405)/A(440)≧5 (4)

[In formula (4), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm].

[20] An optical film with an adhesive layer, in which an optical film is laminated on at least one side of the adhesive layer according to any one of [17] to [19].

[21] The optical film with an adhesive layer as described in [20], wherein the optical film is a polarizing plate.

[22] An image display device containing the optical film with an adhesive layer as described in [20] or [21].

The optical film containing the adhesive layer formed from the adhesive composition of the present invention will not have cracks (ruptures) elongated in an environment where high temperature conditions and low temperature conditions repeatedly change, and has good crack resistance.

1: Adhesive layer

1a: Adhesive layer

2: Peel off film

10, 10A, 10B, 10C: Optical film with adhesive layer, optical laminate

3,6:Protective film

4,7:Adhesive layer

5:Polarizing film

8: Phase difference film

30:Light-emitting components

40: Optical film

50,50a: 1/4 wavelength phase difference layer

60: Adhesive layer or adhesive layer

70:1/2 wavelength phase difference layer

80: Positive C layer

100:Polarizing plate

110: Phase difference film

FIG. 1 shows an example of the layer structure of the adhesive layer of the present invention.

FIG. 2 shows an example of the layer structure of the adhesive layer-attached optical film of the present invention.

FIG. 3 shows an example of the layer structure of the adhesive layer-attached optical film of the present invention.

FIG. 4 shows an example of the layer structure of the adhesive layer-attached optical film of the present invention.

FIG. 5 shows an example of the layer structure of the adhesive layer-attached optical film of the present invention.

<Adhesive composition>

The adhesive composition of the present invention contains: resin (A), a light-selective absorbing compound having a cyanidin structure (B), and a photocurable component (C).

The adhesive composition of the present invention may further contain: photoinitiator (D), cross-linking agent (E), silane compound, etc.

<Resin(A)>

The resin (A) is not particularly limited as long as it is used in the adhesive composition. The resin (A) is preferably a resin with a glass transition temperature of 40°C or lower. The glass transition temperature (Tg) of the resin (A) is more preferably 20°C or lower, still more preferably 10°C or lower, still more preferably 0°C or lower. In addition, the glass transition temperature of the resin (A) is usually -80°C or higher, preferably -60°C or higher, especially -50°C or higher, more preferably -45°C or higher, particularly preferably -30°C or higher. When the glass transition temperature of the resin (A) is 40°C or lower, it is beneficial to improve the adhesion between the adhesive layer formed of the adhesive composition containing the resin (A) and the optical film. In addition, when the glass transition temperature of the resin (A) is -80°C or above, it is advantageous for the adhesive layer formed from the adhesive composition containing the resin (A). Improvement of durability (appearance loss during high temperature test: cohesion failure, etc.). The glass transition temperature can be measured by Differential Scanning Calorimetry (DSC: Differential Scanning Calorimetry).

Examples of resins having a glass transition temperature of 40° C. or less include (meth)acrylic resins, polysiloxane resins, rubber resins, urethane resins, and the like, and (meth)acrylic resins are preferred.

The (meth)acrylic resin is preferably a polymer containing a structural unit derived from (meth)acrylate as a main component (preferably it contains 50% by mass or more). The structural units derived from (meth)acrylate may include more than one structural unit derived from monomers other than (meth)acrylate (eg, structural units derived from monomers having polar functional groups). In this specification, (meth)acrylic acid means either acrylic acid or methacrylic acid, and when others are called (meth)acrylate, etc., "(meth)" also has the same meaning.

Examples of the (meth)acrylate include (meth)acrylate represented by the following formula (a):

[式(a)中，R_1A表示氫原子或甲基，R_2A表示碳數1至14的烷基或碳數7至20的芳烷基，該烷基或該芳烷基的氫原子可經碳數1至10的烷氧基所取代。]

[In formula (a), R _1A represents a hydrogen atom or a methyl group, and R _2A represents an alkyl group having 1 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. The hydrogen atom of the alkyl group or the aralkyl group may be Substituted with an alkoxy group having 1 to 10 carbon atoms. ]

In formula (a), R _2A is preferably an alkyl group having 1 to 14 carbon atoms, particularly preferably an alkyl group having 1 to 8 carbon atoms.

Examples of (meth)acrylates represented by formula (I) include:

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate , n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, (meth)acrylate ) Linear alkyl esters of (meth)acrylic acid such as lauryl acrylate and stearyl (meth)acrylate;

Isopropyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, isopentyl (meth)acrylate, isohexyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid such as 2-ethylhexyl, isooctyl (meth)acrylate, isononyl (meth)acrylate, isostearyl (meth)acrylate, isopentyl (meth)acrylate, etc. branched alkyl esters;

Cyclohexyl (meth)acrylate, isocamphenyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclododecyl (meth)acrylate, (meth)acrylate (meth)acrylic acid such as methylcyclohexyl acrylate, trimethylcyclohexyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, α-ethoxycyclohexyl acrylate, etc. Alkyl esters containing alicyclic skeleton;

Esters of (meth)acrylic acid containing an aromatic ring skeleton, such as phenyl (meth)acrylate, etc.

In addition, a substituent-containing (meth)acrylic acid alkyl ester in which a substituent is introduced into an alkyl group in (meth)acrylic acid alkyl ester can also be cited. The substituent of the substituent-containing alkyl (meth)acrylate is a group that replaces the hydrogen atom of the alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the substituent-containing (meth)acrylic acid alkyl ester include 2-methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate 2-(2-phenoxyethoxy)ethyl methacrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy poly(ethylene glycol) (meth)acrylate, etc.

These (meth)acrylates may be used individually, or a plurality of different ones may be used.

The (meth)acrylic resin (A) preferably contains a structural unit derived from an alkyl acrylate (a1) in which the glass transition temperature Tg of the homopolymer is less than 0°C, and the Tg derived from the homopolymer is 0°C or more. The structural unit of alkyl acrylate (a2). Those containing a structural unit derived from alkyl acrylate (a1) and a structural unit derived from alkyl acrylate (a2) are beneficial to improving the high-temperature durability of the adhesive layer. Alkyl (meth)acrylates For the Tg of the homopolymer, literature values such as POLYMER HANDBOOK (Wiley-Interscience) can be used.

Specific examples of the alkyl acrylate (a1) include ethyl acrylate, n- and isopropyl acrylate, n- and isobutyl acrylate, n-pentyl acrylate, n- and isohexyl acrylate, n-heptyl acrylate, n- and isopropyl acrylate. Alkyl acrylates in which the carbon number of the alkyl group is about 2 to 12, such as octyl ester, 2-ethylhexyl acrylate, n- and isononyl acrylate, n- and isodecyl acrylate, and n-dodecyl acrylate.

As for alkyl acrylate (a1), only 1 type may be used or 2 or more types may be used in combination. Among them, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, etc. are preferred from the viewpoint of followability or reproducibility when laminating the adhesive sheet of the present invention on an optical film.

The alkyl acrylate (a2) is an alkyl acrylate other than the alkyl acrylate (a1). Specific examples of the alkyl acrylate (a2) include methyl acrylate, cyclohexyl acrylate, isocamphenyl acrylate, stearyl acrylate, tertiary butyl acrylate, and the like.

As for alkyl acrylate (a2), only 1 type may be used or 2 or more types may be used in combination. Among them, from the viewpoint of high-temperature durability, the alkyl acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isocamphenyl acrylate, etc., and particularly preferably contains methyl acrylate.

The structural unit derived from the (meth)acrylate represented by formula (a) is preferably 50 mass % or more, preferably 60 to 95 mass %, among all the structural units contained in the (meth)acrylic resin. , especially preferably 65 to 95% by mass.

The structural unit derived from a monomer other than (meth)acrylate is preferably a structural unit derived from a monomer having a polar functional group, and particularly preferably a structural unit derived from a (meth)acrylate having a polar functional group. Examples of the polar functional group include a hydroxyl group, a carboxyl group, a substituted or unsubstituted amino group, a heterocyclic group such as an epoxy group, and the like.

Examples of monomers having polar functional groups include: (1-hydroxymethylmeth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, and 1 (meth)acrylate. -Hydroxybutyl ester, 1-hydroxypentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 2-hydroxypentyl methacrylate, 2-hydroxyhexyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-(meth)acrylate Hydroxypentyl ester, 3-hydroxyhexyl (meth)acrylate, 3-hydroxyheptyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, (meth)acrylate 4-hydroxyhexyl acrylate, 4-hydroxyheptyl (meth)acrylate, 4-hydroxyoctyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate, (meth)acrylate 3-Chloro-2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 5-hydroxyheptyl (meth)acrylate, 5-hydroxyoctyl (meth)acrylate, 5-hydroxynonyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid 6 -Hydroxyheptyl ester, 6-hydroxyoctyl (meth)acrylate, 6-hydroxynonyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, ( 7-hydroxyoctyl methacrylate, 7-hydroxynonyl (meth)acrylate, 7-hydroxydecyl (meth)acrylate, 7-hydroxyundecyl (meth)acrylate, (meth)acrylic acid 8 -Hydroxyoctyl ester, 8-hydroxynonyl (meth)acrylate, 8-hydroxydecyl (meth)acrylate, 8-hydroxyundecyl (meth)acrylate, 8-hydroxydodecyl (meth)acrylate , 9-hydroxynonyl (meth)acrylate, 9-hydroxydecyl (meth)acrylate, 9-hydroxyundecyl (meth)acrylate, 9-hydroxydodecyl (meth)acrylate, (meth)acrylate ) 9-hydroxytridecyl acrylate, 10-hydroxydecyl (meth)acrylate, 10-hydroxyundecyl (meth)acrylate, 10-hydroxydodecyl (meth)acrylate, 10 (meth)acrylate -Hydroxytridecyl, 10-hydroxytetradecyl (meth)acrylate, 11-hydroxyundecyl (meth)acrylate, 11-hydroxydodecyl (meth)acrylate, 11-hydroxy(meth)acrylate Tridecyl ester, 11-hydroxytetradecanyl (meth)acrylate, 11-hydroxypentadecanate (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, 12-hydroxytridecyl (meth)acrylate Ester, 12-hydroxytetradecane (meth)acrylate, 13-hydroxy(meth)acrylate Pentadecyl, 13-hydroxytetradecanyl (meth)acrylate, 13-hydroxypentadecanate (meth)acrylate, 14-hydroxytetradecanate (meth)acrylate, 14-hydroxypentadecanate (meth)acrylate Monomers with hydroxyl groups such as ester, 15-hydroxypentadecanate (meth)acrylate, 15-hydroxypentadecanate (meth)acrylate, etc.;

(Meth)acrylic acid, carboxyalkyl (meth)acrylate (such as carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate), maleic acid, maleic anhydride, Monomers with carboxyl groups such as fumaric acid and crotonic acid;

Acrylylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidinone, vinylpyridine, (meth)acrylate tetrahydrofurfuryl acrylate, caprolactone modified tetrahydrofurfuryl acrylate, Monomers with heterocyclic groups such as 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran;

Monomers with substituted or unsubstituted amine groups such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate .

Among them, in terms of the reactivity between the (meth)acrylate polymer and the cross-linking agent, a monomer having a hydroxyl group or a monomer having a carboxyl group is preferred, and a monomer having a hydroxyl group and a monomer having a carboxyl group are particularly preferred. Any one in the body.

Preferred monomers having a hydroxyl group are 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 4-carboxybutyl acrylate, 5-carboxypentyl acrylate, and 6-carboxyhexyl acrylate. In particular, good durability can be obtained by using 2-carboxyethyl acrylate, 4-carboxybutyl acrylate, and 5-carboxypentyl acrylate.

As the monomer having a carboxyl group, acrylic acid is preferably used.

From the viewpoint of preventing excessive peeling force of the separation film that can be laminated on the outer surface of the adhesive layer, the (meth)acrylic resin (A) preferably does not substantially contain a structure derived from a monomer having an amine group. unit. The term "substantially not contained" here means that it is 0.1 parts by mass or less in 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).

The content of the structural unit derived from the monomer having a polar functional group is preferably 20 parts by mass or less, particularly preferably 0.5 part by mass or more, relative to 100 parts by mass of all structural units of the (meth)acrylic resin (A). parts by mass or less, more preferably not less than 0.5 parts by mass and not more than 10 parts by mass, particularly preferably not less than 1 part by mass and not more than 7 parts by mass.

The content of the structural unit derived from the monomer having an aromatic group is preferably 20 parts by mass or less, more preferably 4 parts by mass or more, relative to 100 parts by mass of all structural units of the (meth)acrylic resin (A). parts or less, more preferably not less than 4 parts by mass and not more than 16 parts by mass.

Structural units derived from monomers other than (meth)acrylate can also be listed: structural units derived from styrene-based monomers, structural units derived from vinyl-based monomers, and structural units derived from a molecule having multiple (methyl) groups. Structural units of acrylyl monomers, structural units derived from (meth)acrylamide-based monomers, etc.

Examples of styrenic monomers include: styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, and propylstyrene. , alkyl styrenes such as butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, etc.; halogenated benzene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, etc. Ethylene; nitrostyrene; acetyl styrene; methoxystyrene; and divinylbenzene, etc.

Vinyl-based monomers include: fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, 2-ethylhexanoate vinyl ester, vinyl laurate, etc.; halogenated vinyl chloride, vinyl bromide, etc. Ethylene; vinylidene halides such as vinylidene chloride; nitrogen-containing heteroaromatic ethylene such as vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.; butadiene, isoprene, chloroprene, etc. Conjugated dienes; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

Monomers having multiple (meth)acrylyl groups in the 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, tripropylene glycol di(meth)acrylate, etc. have in the molecule Monomers with 2 (meth)acrylyl groups; trimethylolpropane tris(meth)acrylate and other monomers with 3 (meth)acrylyl groups in the molecule.

Examples of (meth)acrylamide-based monomers include: N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxy) Propyl)(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(methyl) Acrylamide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxybutyl)(meth)acrylamide , N-[2-(2-Pendant oxygen-1-imidazolinyl)ethyl](meth)acrylamide, 2-acrylamide-2-methyl-1-propanesulfonic acid, N- (Methoxymethyl)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(propoxymethyl)(meth)acrylamide, N-(1- Methylethoxymethyl)(meth)acrylamide, N-(1-methylpropoxymethyl)(meth)acrylamide, N-(2-methylpropoxymethyl) (Meth)acrylamide, N-(butoxymethyl)(meth)acrylamide, N-(1,1-dimethylethoxymethyl)(meth)acrylamide, N -(2-methoxyethyl)(meth)acrylamide, N-(2-ethoxyethyl)(meth)acrylamide, N-(2-propoxyethyl)(methyl) acrylamide, N-[2-(1-methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl](methane acrylamide, N-[2-(2-methylpropoxy)ethyl](meth)acrylamide, N-(2-butoxyethyl)(meth)acrylamide, N-[2-(1,1-dimethylethoxy)ethyl](meth)acrylamide, etc. Among them, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl)acrylamide methyl)acrylamide and N-(2-methylpropoxymethyl)acrylamide.

The weight average molecular weight (Mw) of the (meth)acrylic resin (A) is preferably 500,000 to 2.5 million. When the weight average molecular weight is more than 500,000, the durability of the adhesive layer in high temperature environments can be improved, and defects such as floating and peeling between the adherend and the adhesive layer and cohesion and damage of the adhesive sheet can be easily suppressed. Heavy When the weight average molecular weight is 2.5 million or less, it is advantageous from the viewpoint of coatability. From the viewpoint of achieving both the durability of the adhesive layer and the coating properties of the adhesive, the weight average molecular weight is preferably 600,000 to 1.8 million, more preferably 700,000 to 1.7 million, and particularly preferably 1,000,000 to 1.6 million. . In addition, the molecular weight distribution (Mw/Mn) expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw/Mn) is usually 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 to standard polystyrene.

When the (meth)acrylic resin (A) is dissolved in ethyl acetate to form a solution with a concentration of 20% by mass, the viscosity at 25°C is preferably 20 Pa. s or less, preferably 0.1 to 15Pa. s. A viscosity within this range is advantageous from the viewpoint of coating properties when applying the adhesive composition to a base material. Viscosity can be measured with a Brookfield viscometer.

The (meth)acrylic resin (A) can be produced by a conventional method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method. The solution polymerization method is particularly preferred. Examples of the solution polymerization method include mixing monomers and organic solvents, adding a thermal polymerization initiator in a nitrogen atmosphere, and stirring at a temperature of 40 to 90°C, preferably about 50 to 80°C for 3 to 15 hours. method. In order to control the reaction, monomers or thermal polymerization initiators may be added continuously or intermittently during polymerization. The monomer or thermal polymerization initiator may be added to an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropyl alcohol; acetone and methyl isobutyl ketone. Ketones and so on. As the thermal polymerization initiator, a conventional thermal polymerization initiator can be used. In addition, a photopolymerization initiator can be used instead of the thermal polymerization initiator, and a polymerization method based on ultraviolet rays or the like can be used.

The content of the resin (A) in 100 mass% of the solid content of the adhesive composition is usually 50 mass% to 99.9 mass%, preferably 60 mass% to 99 mass%, particularly preferably 70 mass% to 95 mass% .

〈Light selective absorption compound (B)〉

The light-selective absorption compound (B) is a compound containing an anthocyanin structure in the molecule.

The so-called partial anthocyanin structure in the present invention refers to the partial structure represented by >N-C=C-C=C<. However, part of the anthocyanin structure of the present invention does not contain an aromatic condensed ring (such as a benzotriazole ring, a benzimidazole (benzotriazole) ring, or a partial structure represented by >N-C=C-C=C< as a ring component). Benzimidazole ring, indole ring, isoindole ring, quinoline ring, etc.).

唑啉(Oxazolino)基、氮丙啶(Aziridino)基、乙烯基、α-甲基乙烯基、丙烯醯基、甲基丙烯醯基、烯丙基、苯乙烯基、(甲基)丙烯醯胺等乙烯性不飽和基等。 Furthermore, the light-selective absorption compound (B) having a merocyanin structure in the present invention preferably does not contain a polymerizable group in the molecule. Here, examples of the polymerizable group include epoxy group, oxetanyl group,

Oxazolino group, Aziridino group, vinyl group, α-methylvinyl group, acrylyl group, methacrylyl group, allyl group, styryl group, (meth)acrylamide Ethylenically unsaturated groups, etc.

The light-selective absorption compound (B) having a partial anthocyanin structure in the molecule preferably satisfies the following formula (1), and more preferably satisfies the following formula (2).

ε(405)≧5 (1)

In formula (1), ε(405) represents the gram absorption coefficient of the light-selective absorption compound (B) having a merocyanin structure at a wavelength of 405 nm. The unit of gram absorption coefficient is L/(g·cm).

ε (405)/ ε (440)≧5 (2)

In the formula (2), ε (405) represents the gram absorption coefficient at a wavelength of 405 nm of the light selective absorption compound (B) having a merocyanin structure and a polymerizable group. ε(440) represents the gram absorption coefficient of the light-selective absorption compound (B) having a merocyanin structure at a wavelength of 440 nm.

The light-selective absorption compound (B) having a merocyanin structure has an ε (405) value of preferably 5L/(g‧cm) or more, more preferably 10L/(g‧cm) or more, and more preferably 20L /(g‧cm) or more, preferably 30L/(g‧cm) or more, usually 500L/(g‧cm) or less. The compound with a larger value of ε (405) is more likely to absorb light with a wavelength of 405nm, and more likely to exhibit the function of inhibiting deterioration caused by ultraviolet rays or short-wavelength visible light.

The light-selective absorption compound (B) having a merocyanin structure has an ε (405)/ ε (440) value of preferably 20 or more, more preferably 40 or more, still more preferably 70 or more, and particularly preferably 80 above. The adhesive layer formed from an adhesive composition containing a compound with a larger value of ε (405)/ ε (440) can absorb light with a wavelength near 405 nm without hindering the color performance of the display device. In addition, optical deterioration of a display device such as a laminated optical film (retardation film) or an organic EL element can be suppressed.

Examples of the light selective absorption compound (B) having a merocyanin structure include compounds represented by formula (I).

[In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 25 that may have a substituent, and a carbon number of 6 to 15 that may have a substituent. The aromatic hydrocarbon group or heterocyclic group, the -CH ₂ - contained in the aforementioned aliphatic hydrocarbon group or aromatic hydrocarbon group can be replaced by -NR ^1A -, -SO ₂ -, -CO-, -O- or -S-;

R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, and an electron-withdrawing group;

R ^1A represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms;

R ¹ and R ² can be bonded to each other to form a ring structure, R ² and R ³ can be bonded to each other to form a ring structure, R ² and R ⁴ can be bonded to each other to form a ring structure, R ³ and R ⁶ They can be bonded to each other to form a ring structure, R ⁵ and R ⁷ can be bonded to each other to form a ring structure, and R ⁶ and R ⁷ can be bonded to each other to form a ring structure. ]

The aliphatic hydrocarbon groups with 1 to 25 carbon atoms represented by R ¹ to R ⁵ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, secondary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecayl, eleven Linear or branched chain alkyl groups with 1 to 25 carbon atoms such as lauryl, myristyl, cetyl, stearyl, etc.; carbon atoms of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Cycloalkyl groups having 3 to 25 carbon atoms; cycloalkylalkyl groups having 4 to 25 carbon atoms such as cyclohexylmethyl and the like, preferably alkyl groups having 4 to 25 carbon atoms.

Examples of substituents that the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R ¹ to R ⁵ may have include a hydroxyl group, a cyano group, a halogen atom, a mercapto group, an amino group, a nitro group, and the like.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of the aromatic hydrocarbon group having 6 to 15 carbon atoms represented by R ¹ to R ⁵ include: aryl groups having 6 to 15 carbon atoms such as phenyl, naphthyl, anthracenyl, biphenyl, etc.; benzyl, phenyl Aralkyl groups having 7 to 15 carbon atoms such as ethyl, naphthylmethyl, phenyl, etc.

Examples of substituents that the aromatic hydrocarbon group having 6 to 15 carbon atoms represented by R ¹ to R ⁵ may have include: hydroxyl group, cyano group, halogen atom, mercapto group, amino group, nitro group, alkoxy group, and alkylthio group , alkoxycarbonyl group, acyl group, acyloxy group, -C(NR ^2A )R ^2B , -CONR ^3A R ^3B , -SO ₂ R ^4A (R ^2A , R ^2B , R ^3A and R ^3B each independently represent hydrogen Atom or alkyl group having 1 to 6 carbon atoms, R ^4A represents an alkyl group having 1 to 6 carbon atoms), etc.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, and decyloxy. Alkoxy groups having 1 to 12 carbon atoms such as undecyloxy group and dodecyloxy group.

Examples of the alkylthio group include alkylthio groups having 1 to 12 carbon atoms such as methylthio group, ethylthio group, propylthio group, and butylthio group.

Examples of the acyl group include acyl groups having 2 to 13 carbon atoms, such as an acetyl group, a propyl group, a butyl group, and the like.

Examples of the acyloxy group include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, secondary butylcarbonyloxy, and tertiary butyloxy. C 2 to 13 carbonyloxy groups such as ylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy and 2-ethylhexylcarbonyloxy.

Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, and 2-ethylhexyloxycarbonyl , nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodeoxycarbonyl and other alkoxycarbonyl groups having 2 to 13 carbon atoms.

-CONR ^3A R ^3B includes aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, ethylaminocarbonyl group, methylmethylaminocarbonyl group and the like.

Examples of -C(NR ^2A )R ^2B include a methylimino group, a dimethylimino group, a methylethylimino group, and the like.

Examples of -SO ₂ R ^4A include methylsulfonyl group, ethylsulfonyl group, and the like.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^2B and R ^3B include methyl, ethyl, n-propyl, isopropyl, n-butyl, Tertiary butyl, secondary butyl, etc.

唑啉(Oxazoline)環基、噻唑啉(Thiazoline)環基、哌啶(Piperidine)環基、嗎啉(Morpholine)環基、哌嗪(Piperazine)環基、吲哚環基、異吲哚環基、喹啉環基、噻吩(Thiophene)環基、吡咯(Pyrrole)環基、噻唑啉環基及呋喃(Furan)環基等之碳數4至20的脂肪族雜環基或碳數3至20的芳香族雜環基等。 Examples of heterocyclic groups represented by R ¹ to R ⁵ include: pyrrolidine (Pyrrolidine) ring group, dihydropyrrole (Pyrroline) ring group, imidazolidine (Imidazolidine) ring group, imidazoline (Imidazoline) ring group,

Oxazoline ring group, Thiazoline ring group, Piperidine ring group, Morpholine ring group, Piperazine ring group, Indole ring group, Isoindole ring group , aliphatic heterocyclic groups with 4 to 20 carbon atoms or 3 to 20 carbon atoms such as quinoline ring group, thiophene ring group, pyrrole ring group, thiazoline ring group and furan ring group. Aromatic heterocyclic groups, etc.

Examples of alkyl groups having 1 to 25 carbon atoms represented by R ⁶ and R ⁷ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, secondary butyl, n- Pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecayl, undecyl , lauryl, myristyl, cetyl, stearyl, etc. linear or branched chain alkyl groups with 1 to 25 carbon atoms, etc.

Examples of the electron-withdrawing group represented by R ⁶ and R ⁷ include a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, and a group represented by the formula (I-1).

*-X ¹ -R ¹¹¹ (I-1)

[In the formula, R ¹¹¹ represents a hydrogen atom or a hydrocarbon group with 1 to 25 carbon atoms that may have a halogen atom, and at least one of the methylene groups contained in the hydrocarbon group may be substituted with an oxygen atom;

X ¹ means -CO-* ¹ , -COO-* ¹ , -CS-* ¹ , -CSS-* ¹ , -CSNR ¹¹² -* ¹ , -CONR ¹¹³ -* ¹ , -CNR ¹¹⁴ -* ¹ or -SO _twenty ^one ;

R ¹¹² , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group;

* ¹ is the bonding part with R ¹¹¹ ;

*Indicates the bonding site with the carbon atom. ]

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of alkyl groups substituted by halogen atoms include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoro-secondary butyl, and perfluoro-tertiary. Perfluoroalkyl groups such as butyl, perfluoropentyl and perfluorohexyl, etc. The carbon number of the alkyl group substituted by a halogen atom is usually 1 to 25, preferably 1 to 12.

Examples of the hydrocarbon group having 1 to 25 carbon atoms that may have a halogen atom represented by R ¹¹¹ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, secondary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecayl, eleven Linear or branched chain alkyl groups with 1 to 25 carbon atoms such as lauryl, myristyl, cetyl, stearyl, etc.; carbon atoms of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Cycloalkyl groups with 3 to 25 carbon atoms; cycloalkylalkyl groups with 4 to 25 carbon atoms in cyclopropylmethyl, cyclohexylmethyl, etc.; 6 carbon atoms in phenyl, naphthyl, anthracenyl, biphenyl, etc. Aryl groups with 25 to 25 carbon atoms; aralkyl groups with 7 to 25 carbon atoms such as benzyl, phenylethyl, naphthylmethyl, phenyl, etc.; monofluoromethyl, difluoromethyl, trifluoromethyl, 2, 2,2-Trifluoroethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl and other fluorinated alkyl groups having 1 to 25 carbon atoms; monochloromethyl, Dichloromethyl, trichloromethyl, 2,2,2-trichloroethyl, perchloroethyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, etc. have carbon numbers from 1 to 25 alkyl chloride; monobromomethyl, dibromomethyl, tribromomethyl, 2,2,2-tribromoethyl, perbromoethyl, perbromopropyl, perbromobutyl, perbromo Brominated alkyl groups with 1 to 25 carbon atoms such as pentyl, perbromohexyl, etc.; monoiodomethyl, diiodomethyl, triiodomethyl, 2,2,2-triiodoethyl, periodoethyl, Periodopropyl, periodobutyl, periodopentyl, periodohexyl, and other iodinated alkyl groups having 1 to 25 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹¹² , R ¹¹³ and R ¹¹⁴ are the same as the alkyl group having 1 to 6 carbon atoms represented by R ^1A .

R ¹¹¹ is preferably a hydrocarbon group having 4 to 25 carbon atoms which may have a halogen atom, and particularly preferably a hydrocarbon group having 4 to 12 carbon atoms which may have a halogen atom.

X ¹ is preferably -CO-* ¹ and -COO-* ¹ .

The electron-withdrawing groups represented by R ⁶ and R ⁷ are preferably each independently a cyano group, a nitro group, a fluoro group, a trifluoromethyl group, or a group represented by formula (I-1).

唑啉環、噻唑啉環、哌啶環、嗎啉環、哌嗪環、吲哚環、異吲哚環等。R¹及R²相互地鍵結所形成之環可具有取代基，該取代基可列舉出甲基、乙基、丙基、丁基、異丁基等之碳數1至12的烷基；甲氧基、乙氧基、丙氧基、丁氧基等之碳數1至12的烷氧基等。 The ring structure formed by R ¹ and R ² being bonded to each other is a nitrogen-containing ring structure including a nitrogen atom to which R ¹ and R ² are bonded. Examples include nitrogen-containing heterocyclic rings with 4 to 10 members. The ring structure formed by R ¹ and R ² being bonded to each other may be a single ring, a polycyclic ring or a condensed ring. Specific examples include: pyrrolidine ring, dihydropyrrole ring, imidazolidine ring, imidazoline ring,

Zozoline ring, thiazoline ring, piperidine ring, morpholine ring, piperazine ring, indole ring, isoindole ring, etc. The ring formed by R ¹ and R ² being bonded to each other may have a substituent, and the substituent may include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, isobutyl, etc.; Alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.

唑啉環、噻唑啉環、哌啶環、嗎啉環、哌嗪環、吲哚環、異吲哚環及以下述式(I-3)所表示之環結構。 The ring structure formed by R ² and R ³ being bonded to each other is a nitrogen-containing ring structure including a nitrogen atom to which R ² is bonded. Examples include nitrogen-containing heterocyclic rings with 4 to 10 members. The ring structure formed by R ² and R ³ being bonded to each other may be a single ring, a polycyclic ring or a condensed ring. Specific examples include: pyrrolidine ring, dihydropyrrole ring, imidazolidine ring, imidazoline ring,

An oxazoline ring, a thiazoline ring, a piperidine ring, a morpholine ring, a piperazine ring, an indole ring, an isoindole ring, and a ring structure represented by the following formula (I-3).

[In formula (I-3), X represents a nitrogen atom, an oxygen atom, and a sulfur atom;

Ring W1 represents a ring having a nitrogen atom and X as constituent elements.

*Indicates the bonding part. ]

Ring W ¹ is preferably a 5-membered ring or a 6-membered ring containing a nitrogen atom and X as constituent elements.

Specific examples of the ring structure represented by formula (I-3) include the following rings.

[In the formula, * represents the bonding part. ]

The ring structure formed by R ² and R ³ being bonded to each other may have a substituent. Examples of the substituent include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl. ; Alkoxy groups with 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.

The ring structure formed by R ² and R ³ being bonded to each other is preferably a ring structure represented by the following formula (I-4).

[In formula (1-4), R ¹ has the same meaning as above. m2 represents an integer from 1 to 7.

R ^11a , R ^11b , R ^11c and R ^11d each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. ]

*Indicates the bonding site with the carbon atom.

m2 is preferably 2 or 3, particularly preferably 2.

The ring structure formed by R ² and R ⁴ being bonded to each other may include a nitrogen-containing heterocyclic structure of a 4- to 10-membered ring, preferably a nitrogen-containing heterocyclic structure of a 5- to 9-membered ring. The ring structure formed by R ² and R ⁴ being bonded to each other may be a single ring or a polycyclic ring. These rings may have substituents. Examples of this ring structure include a pyrrole ring, an indole ring, a pyrimidine (Pyrimidine) ring, and the rings described below.

The ring structure formed by R ² and R ⁴ being bonded to each other may have a substituent. Examples of the substituent include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl. ;Alkoxy groups with 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.; Amino, methylamino, dimethylamino, etc. are represented by -NR ^22A R ^22B The group represented (R ^22A and R ^22B each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms); carbon number 1 of methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, etc. Alkylthio groups with 12 to 12; heterocyclic groups with 4 to 9 carbon atoms such as pyrrolidinyl, piperidinyl, morpholinyl, etc.

The ring structure formed by R ³ and R ⁶ being bonded to each other is a ring structure in which R ³ -C=CC=CR ⁶ forms the skeleton of the ring. Examples include phenyl and the like.

Examples of the ring structure formed by R ⁵ and R ⁷ being bonded to each other include the ring structures described below. The ring structure formed by R ⁵ and R ⁷ being bonded to each other may have a substituent. Examples of the substituent include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl. ; Alkoxy groups with 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.

Examples of the ring structure formed by R ⁶ and R ⁷ being bonded to each other include the ring structures described below. The ring structure formed by R ⁶ and R ⁷ being bonded to each other may have a substituent (R ¹ to R ¹⁶ in the following formula). Examples of the substituent include methyl, ethyl, propyl, butyl, iso Alkyl groups having 1 to 12 carbon atoms such as butyl; alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.; ethylenically unsaturated groups described below, etc.

[In the formula, * represents the bonding site with the carbon atom. ]

It is preferable that at least one of R ⁶ and R ⁷ is an electron-withdrawing group.

The compound represented by formula (I) is preferably a compound represented by formula (II).

[In formula (II), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and a carbon number which may have a substituent. 6 to 15 aromatic hydrocarbon groups or heterocyclic groups, the -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group can be passed through -NR ^11A -, -SO ₂ -, -CO-, -O- or -S- replaced.

R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group.

R ^11A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹¹ and R ¹² may be bonded to each other to form a ring structure, R ¹² and R ¹³ may be bonded to each other to form a ring structure, and R ¹² and R ¹⁴ may be bonded to each other to form a ring structure. ]

The aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R ¹¹ to R ¹⁵ which may have a substituent may be the same as the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R ¹ which may have a substituent. .

Examples of the aromatic hydrocarbon group having 6 to 15 carbon atoms that may have a substituent represented by R ¹¹ to R ¹⁵ are the same as the aromatic hydrocarbon group having 6 to 15 carbon atoms that may have a substituent represented by R ¹ .

Examples of the heterocyclic ring represented by R ¹¹ to R ¹⁵ are the same as the heterocyclic ring represented by R ¹ .

Examples of the alkyl group having 1 to 25 carbon atoms represented by R ¹⁶ and R ¹⁷ are the same as the alkyl group having 1 to 25 carbon atoms represented by R ⁶ .

Examples of the electron-withdrawing group represented by R ¹⁶ and R ¹⁷ are the same as the electron-withdrawing group represented by R ⁶ .

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^11A include the same ones as the alkyl group having 1 to 6 carbon atoms represented by R ^1A .

Examples of the ring structure that R ¹¹ and R ¹² can bond to each other to form are the same as the ring structures that R ¹ and R ² can bond to each other to form.

Examples of the ring structure that R ¹² and R ¹³ can bond to each other to form are the same as the ring structures that R ² and R ³ can bond to each other to form. The ring structure formed by R ¹² and R ¹³ being bonded to each other is preferably a single ring structure.

Examples of the ring structure that R ¹² and R ¹⁴ can bond to each other to form are the same as the ring structures that R ² and R ⁴ can bond to each other to form. The ring structure formed by R ¹² and R ¹⁴ being bonded to each other is preferably a single ring structure. The ring structure formed by R ¹² and R ¹⁴ being bonded to each other is preferably an aromatic ring, more preferably a pyrimidine ring structure.

R ¹¹ , R ¹³ and R ¹⁵ are preferably each independently an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, particularly preferably an alkyl group having 1 to 25 carbon atoms which may have a substituent, and more preferably An alkyl group having 1 to 12 carbon atoms which may have a substituent.

In particular, R ¹¹ is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.

It is preferable that R ¹² and R ¹⁴ are each independently an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or R ¹² and R ¹⁴ are bonded to each other to form a ring structure.

R ¹² and R ¹³ are preferably bonded to each other to form a ring structure, more preferably a ring structure represented by the above formula (I-4). Among the ring structures represented by formula (I-4), the ring structure represented by formula (I-4-1) or the ring structure represented by formula (I-4-2) is particularly preferred. It is a ring structure represented by formula (I-4-1). The ring structure represented by formula (I-4), formula (I-4-1) or formula (I-4-2) may further have a substituent.

Preferably, either one of R ¹⁶ and R ¹⁷ is an ethylenically unsaturated group, and the other is an electron-withdrawing group.

The electron-withdrawing groups represented by R ¹⁶ and R ¹⁷ are preferably each independently a cyano group, a nitro group, a fluoro group, a trifluoromethyl group, or a group represented by formula (I-1). Particularly preferred is cyano.

The ethylenically unsaturated groups represented by R ¹⁶ and R ¹⁷ are preferably each independently a vinyl group, an acryl group, a methacryl group, or a group represented by formula (I-2). More preferably ^, *-CO-O-(CH ₂ ⁾ n integer)].

The compound represented by formula (II) in which R ¹² and R ¹³ are bonded to each other to form a ring structure is preferably a compound represented by formula (II-A-1) or a compound represented by formula (II-A-2). represents the compound. The compound represented by formula (II) in which R ¹² and R ¹⁴ are bonded to each other to form a ring structure is preferably a compound represented by formula (II-B-1).

[In formula (II-A-1), formula (II-A-2) and formula (II-B-1), R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each have the same meaning as above.

R ^11e , R ^11f , R ^11g , R ^11h , R ^11k , R ^11m and R ¹¹ⁿ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

R ^11q and R ^11p each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a group represented by -NR ^22A R ^22B (R ^22A and R ^22B each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). alkyl) or heterocycle. ]

Examples of the light-selective absorption compound (B) having a merocyanin structure include the following compounds.

The light-selective absorption compound having an anthocyanin structure in the molecule can be produced by the method described in Japanese Patent Application Laid-Open No. 2017-142412 or International Publication No. 2019/004046.

The content of the light-selective absorption compound (B) having a merocyanin structure is usually 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass relative to 100 parts by mass of the resin (A). parts, preferably 2 to 7 parts by mass.

Two or more types of light-selective absorption compounds (B) having a merocyanin structure may be included.

〈Photocurable component (C)〉

The adhesive composition of the present invention may contain a photocurable component (C).

The photocurable component (C) may be a photoradically curable component such as a compound or oligomer that is cured by a radical polymerization reaction by irradiation with light. In addition, it may also be a photocationically curable component such as a compound or an oligomer that is cured by a cationic polymerization reaction by irradiation with light. Furthermore, the light here is preferably active energy rays of visible light, ultraviolet rays, X-rays or electron beams.

From the viewpoint of the reactivity of the light-selective absorption compound (B) having a partial anthocyanin structure in the molecule, the photocurable component (C) is preferably a photoradically curable component.

〈Photoradically polymerizable component〉

Examples of the photoradically polymerizable component include radically polymerizable (meth)acrylic compounds.

Examples of the (meth)acrylic compound include (meth)acrylate monomers having at least one (meth)acryloxy group in the molecule, (meth)acrylamide monomers, and (meth)acrylamide monomers having at least one (meth)acryloxy group in the molecule. (Meth)acrylyl group-containing compounds such as (meth)acrylic acid oligomers having at least 2 (meth)acrylyl groups. The (meth)acrylic oligomer is preferably a (meth)acrylate oligomer having at least two (meth)acryloxy groups in the molecule. Only one type of (meth)acrylic compound may be used alone or two or more types may be used in combination.

Examples of the (meth)acrylate monomer include monofunctional (meth)acrylate monomers having one (meth)acryloxy group in the molecule and two (meth)acryloxy groups in the molecule. Bifunctional (meth)acrylate monomers with an oxygen group, and polyfunctional (meth)acrylate monomers with three or more (meth)acryloxy groups in the molecule.

Examples of the monofunctional (meth)acrylate monomer include alkyl (meth)acrylate. In the (meth)acrylic acid alkyl ester, when the carbon number of the alkyl group is 3 or more, it may be linear, branched, or cyclic. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)propyl acrylate. Isopropyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.

In addition, monofunctional (meth)acrylate monomers may also include (meth)aryl acrylic acid esters such as benzyl methacrylate; and (meth)terpene alcohols such as isocamphenyl (meth)acrylate. (meth)acrylate; tetrahydrofurfuryl (meth)acrylate and other (meth)acrylates with tetrahydrofurfuryl structure; (meth)acrylate, cyclohexylmethyl methacrylate, dicyclopentyl acrylate Ester, dicyclopentenyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate and other (meth)acrylates having a cycloalkyl group in the alkyl position; (meth)acrylic acid N, Aminoalkyl acrylate such as N-dimethylaminoethyl ester; 2-phenoxyethyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, (meth)acrylate Ethyl carbitol acrylate, phenoxypolyethylene glycol (meth)acrylate, etc. are (meth)acrylates with ether bonds in the alkyl position.

Furthermore, examples of the monofunctional (meth)acrylate monomer include: monofunctional (meth)acrylate having a hydroxyl group at the alkyl group site; monofunctional (meth)acrylate having a carboxyl group at the alkyl group site. Examples of monofunctional (meth)acrylates having a hydroxyl group at the alkyl group include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2- or 3-hydroxypropyl ester, (meth)acrylic acid 4 -Hydroxybutyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, neopentylerythritol mono(meth)acrylate. Examples of monofunctional (meth)acrylates having a carboxyl group at the alkyl site include: (2-carboxyethylmeth)acrylate, mono(meth)acrylic acid ω-carboxy-polycaprolactone (n=2), 1-[2-(Meth)acryloxyethyl]phthalic acid, 1-[2-(meth)acryloxyethyl]hexahydrophthalic acid, 1-[2-( Meth)acryloxyethyl]succinic acid, 4-[2-(meth)acryloxyethyl]trimellitic acid, N-(meth)acryloxy-N',N' -Dicarboxymethyl p-phenylenediamine, etc.

The (meth)acrylamide monomer is preferably (meth)acrylamide having a substituent at the N-position. A typical example of the substituent at the N-position is an alkyl group, but it can also be used together with the nitrogen atom of (meth)acrylamide. A ring is formed. In addition to carbon atoms and nitrogen atoms of (meth)acrylamide, this ring may also have oxygen atoms as ring constituent members. Furthermore, a substituent such as an alkyl group or a pendant oxygen (=O) may be bonded to the carbon atoms constituting the ring.

唑啉酮、4-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶等。 Examples of N-substituted (meth)acrylamide include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-isopropyl(meth)acrylamide. , N-n-butyl(meth)acrylamide, N-tertiary butyl(meth)acrylamide, N-hexyl(meth)acrylamide-like N-alkyl(meth)acrylamide Amine; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, etc. In addition, the N-substituent may be an alkyl group having a hydroxyl group. Examples thereof include N-hydroxymethyl (meth) acrylamide, N-(2-hydroxyethyl) (meth) acrylamide, N -(2-Hydroxypropyl)(meth)acrylamide, etc. Furthermore, specific examples of the N-substituted (meth)acrylamide forming a 5-membered ring or a 6-membered ring include N-acrylylpyrrolidine and 3-acrylyl-2-

Zozolinone, 4-acrylyl morpholine, N-acrylyl piperidine, N-methacrylyl piperidine, etc.

Examples of 2-functional (meth)acrylate monomers include:

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

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 Polyoxyalkylene glycol di(meth)acrylate such as meth)acrylate, polypropylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate;

Tetrafluoroethylene glycol di(meth)acrylate and other halogen-substituted alkylene glycol di(meth)acrylates;

Di(methyl)propane di(meth)acrylate, di(trimethylol)propane di(meth)acrylate, neopenterythritol di(meth)acrylate and other aliphatic polyols base) acrylate;

Hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc. Hydrogenated dicyclopentadiene or di(meth)acrylic acid of tricyclodecane dialkyl alcohol ester;

烷-2,5-二基酯[別名：二(甲基)丙烯酸二

烷甘醇酯]等之二

烷甘醇或二

烷二烷醇的二(甲基)丙烯酸酯； 1,3-Di(meth)acrylic acid

Alk-2,5-diyl ester [alias: di(meth)acrylic acid di

Alkane glycol ester] etc. 2

Alkane glycol or di

Di(meth)acrylates of alkanediols;

The diacrylate of bisphenol A's ethylene oxide adduct, the diacrylate of bisphenol F's ethylene oxide adduct, etc. Bis(methyl) of the alkylene oxide adduct of bisphenol A or bisphenol F )Acrylate;

The acrylic acid adduct of bisphenol A diglycidyl ether, the acrylic acid adduct of bisphenol F diglycidyl ether, etc. Bisphenol A or bisphenol F bis(meth)acrylic epoxy ester; bis(methyl) Acrylic polysiloxane;

Di(meth)acrylate of neopentyl glycol hydroxytrimethylacetate;

2,2-bis[4-(meth)acryloxyethoxyethoxyphenyl]propane;

2,2-bis[4-(meth)acryloxyethoxyethoxycyclohexyl]propane;

烷]的二(甲基)丙烯酸酯； 2-(2-Hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-di

alkane] di(meth)acrylate;

Tris(hydroxyethyl)isocyanuric acid di(meth)acrylate, etc.

Examples of trifunctional or higher polyfunctional (meth)acrylate monomers include: glyceryl tri(meth)acrylate, alkoxylated glyceryl tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate. , di(trimethylol)propane tris(meth)acrylate, di(trimethylol)propane tetra(meth)acrylate, neopentylerythritol tris(meth)acrylate, tetrakis(meth)acrylate Neopenterythritol acrylate, dipenterythritol tetra(meth)acrylate, dipenterythritol penta(meth)acrylate, dipenterythritol hexa(meth)acrylate, etc. have three or more functions Poly(meth)acrylate of aliphatic polyol; poly(meth)propylene of trifunctional or higher halogen-substituted polyol Acid ester; tri(meth)acrylate of alkylene oxide adduct of glycerol; tri(meth)acrylate of alkylene oxide adduct of trimethylolpropane; 1,1,1-tris[( Methyl acryloyloxyethoxyethoxy]propane; tris(hydroxyethyl)isocyanuric acid tri(meth)acrylate, etc.

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

Examples of (meth)acrylic oligomers include (meth)acrylic urethane oligomers, polyester (meth)acrylic oligomers, and (meth)acrylic epoxy ester oligomers.

(Meth)acrylic urethane oligomer is a compound having a urethane bond (-NHCOO-) and at least two (meth)acrylyl groups in the molecule. Specifically, it can be: the urethanation reaction product of a hydroxyl-containing (meth)acrylic acid monomer having at least one (meth)acrylyl group and at least one hydroxyl group in the molecule, and a polyisocyanate; Or a urethane compound containing an isocyanate group at the terminal obtained by reacting a polyol and a polyisocyanate, and a (methyl) compound each having at least 1 (meth)acrylyl group and at least 1 hydroxyl group in the molecule Products of the urethane esterification reaction of acrylic monomers, etc.

The hydroxyl-containing (meth)acrylic acid monomer used in the above-mentioned urethane esterification reaction can be, for example, a hydroxyl-containing (meth)acrylate monomer. Specific examples include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl methacrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glyceryl di(meth)acrylate, di(meth)acrylate Trimethylolpropane acrylate, pentaerythritol tris(meth)acrylate, and dipenterythritol penta(meth)acrylate. Specific examples other than hydroxyl-containing (meth)acrylate monomers include N-hydroxyalkyl (meth)acrylamide such as N-hydroxyethyl (meth)acrylamide and N-hydroxymethyl (meth)acrylamide. base) acrylamide monomer.

Examples of polyisocyanates used in the urethane reaction with hydroxyl-containing (meth)acrylic monomers include: hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, Dicyclohexylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (such as hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, etc.), tris Di- or tri-isocyanates such as phenylmethane triisocyanate and dibenzylbenzene triisocyanate, and polyisocyanates obtained by polymerizing the above diisocyanates.

In addition, in addition to aromatic, aliphatic or alicyclic polyols, polyols that are used to form urethane compounds containing isocyanate groups at the terminals through reaction with polyisocyanates can also be used. Ester polyols, polyether polyols, etc. Aliphatic and alicyclic polyols include: 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, Trimethylolethane, trimethylolpropane, di(trimethylol)propane, neopentylerythritol, dineopenterythritol, dimethylolheptane, dimethylolpropionic acid, dimethylol Butyric acid, glycerin, hydrogenated bisphenol A, etc.

Polyester polyol is obtained by dehydration condensation reaction of the above-mentioned polyol and polybasic carboxylic acid or the anhydride. When "(anhydride)" is added to those that can become anhydrides to indicate polybasic carboxylic acids or examples of the anhydride, there are succinic acid (anhydride), adipic acid (anhydride), maleic acid (anhydride), and Conic acid (anhydride), trimellitic acid (anhydride), pyromelic acid (dianhydride), phthalic acid (anhydride), isophthalic acid, terephthalic acid, hexahydrophthalic acid (anhydride) wait.

In addition to polyalkylene glycol, polyether polyols may be polyoxyalkylene-modified polyols obtained by the reaction of the above-mentioned polyols or dihydroxybenzenes and alkylene oxides.

The so-called polyester (meth)acrylate oligomer refers to an oligomer having an ester bond and at least two (meth)acryloxy groups in the molecule.

The polyester (meth)acrylate oligomer can be obtained by dehydration condensation reaction using (meth)acrylic acid, polybasic carboxylic acid or the anhydride, and polyol, for example.

Examples of polybasic carboxylic acids or anhydrides include: succinic anhydride, adipic acid, maleic anhydride, itaconic anhydride, trimellitic anhydride, pyromelite dianhydride, hexahydrophthalic anhydride, and phthalic acid. , succinic acid, maleic acid, itaconic acid, trimellitic acid, pyromelite acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.

Examples of polyhydric alcohols include: 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylol ethane, Trimethylolpropane, di(trimethylol)propane, neopentylerythritol, dineopenterythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerol, hydrogenated Bisphenol A, etc.

(Meth)acrylic epoxy ester oligomer can be obtained by the addition reaction of polyglycidyl ether and (meth)acrylic acid. The (meth)acrylic acid epoxy ester oligomer has at least 2 (meth)acryloxy groups in the molecule.

Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

The photoradically curable component preferably contains a (meth)acrylate compound, and particularly preferably contains a polyfunctional (meth)acrylate compound.

〈Photocationic hardening component〉

Examples of the photocationically curable component include epoxy compounds, oxyethylene compounds, vinyl compounds, and the like.

Examples of the epoxy compound include alicyclic epoxy compounds, aromatic epoxy compounds, hydrogenated epoxy compounds, aliphatic epoxy compounds, and the like.

An alicyclic epoxy compound is a compound having one or more epoxy groups bonded to an alicyclic ring in the molecule. Examples of the epoxy group bonded to the alicyclic ring include oxabicyclohexyl and oxabicycloheptyl. wait. The alicyclic epoxy compound may be a compound containing one alicyclic epoxy group, or a compound containing two or more alicyclic epoxy groups.

Examples of alicyclic epoxy compounds include: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3 ,4-epoxy-6-methylcyclohexanecarboxylate, ethylene bis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl)hexanedi acid ester, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, diethylene glycol bis(3,4-epoxycyclohexylmethyl ether), ethylene glycol bis(3,4-epoxycyclohexylmethyl ether) (3,4-epoxycyclohexyl methyl ether), 2,3,14,15-diepoxy-7,11,18,21-tetraoxatrihelix[5.2.2.5.2.2]heconocane , 3-(3,4-epoxycyclohexyl)-8,9-epoxy-1,5-dioxaspiral[5.5]undecane, 4-vinylcyclohexene dioxide, lemon dioxide Olein, bis(2,3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, etc.

Aromatic epoxy compounds are compounds having an aromatic ring and an epoxy group in the molecule. Examples of aromatic epoxy compounds include bisphenol-type epoxy compounds such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S, or their oligomers; phenols Phenolic epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenolic phenolic epoxy resin, etc.; glycidyl ether of 2,2',4,4'-tetrahydroxydiphenylmethane, Polyfunctional epoxy compounds such as glycidyl ether of 2,2',4,4'-tetrahydroxydiphenylketone; multifunctional epoxy resins such as epoxidized polyvinylphenol.

Hydrogenated epoxy compounds are glycidyl ethers of polyols with alicyclic rings. In the presence of a catalyst and under pressure, aromatic polyols can be selectively hydrogenated with aromatic rings to obtain nuclear hydrogenated polyhydroxy compounds. , and then the core hydrogenated polyhydroxy compound is prepared by glycidyl etherification. Specific examples of aromatic polyols include bisphenol-type compounds such as bisphenol A, bisphenol F, and bisphenol S; phenolic-type resins such as phenol-type phenolic resins and cresol-type phenolic resins, hydroxybenzaldehyde-type phenolic resins, etc. ; Polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxydiphenylketone, polyvinyl alcohol, etc. By reacting epichlorohydrin Glycidyl ether can be formed from an alicyclic polyol obtained by hydrogenating the aromatic ring of an aromatic polyol. Among the hydrogenated epoxy compounds, preferred examples include hydrogenated glycidyl ether of bisphenol A.

Aliphatic epoxy compounds are compounds having at least one oxirane ring (3-membered cyclic ether) bonded to an aliphatic carbon atom in the molecule. For example, there are monofunctional epoxy compounds such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, new Bifunctional epoxy compounds such as pentanediol diglycidyl ether; trifunctional or higher epoxy compounds such as trimethylolpropane triglycidyl ether and neopentylerythritol tetraglycidyl ether; 4-vinyl dioxide Epoxy compounds such as cyclohexene and limonene dioxide have an epoxy group directly bonded to an alicyclic ring and an ethylene oxide ring bonded to an aliphatic carbon atom.

Oxygen compounds are compounds containing one or more oxygen rings (oxygen groups) in the molecule. Examples of oxyethyl compounds include: 3-ethyl-3-hydroxymethyl oxyethyl, 2-ethylhexyl oxyethyl , 1,4-bis[(3-ethyloxy-3-yl)methoxymethyl]benzene, 3-ethyl-3[{(3-ethyloxy-3-yl)methoxy }Methyl]oxyoxane, 3-ethyl-3-(phenoxymethyl)oxyoxane, 3-(cyclohexyloxyoxy)methyl-3-ethyloxyoxane, etc.

Examples of the vinyl compound include aliphatic or alicyclic vinyl ether compounds. Examples of vinyl compounds include n-pentyl vinyl ether, isopentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, and n-dodecyl vinyl ether. Vinyl ethers of alkyl or alkenyl alcohols having 5 to 20 carbon atoms, such as ethers, stearyl vinyl ether, octadecyl vinyl ether, etc.; 2-hydroxyethyl vinyl ether, 3-hydroxypropylethylene Hydroxyl-containing vinyl ethers such as hydroxyl ether, 4-hydroxybutyl vinyl ether, etc.; cyclohexyl vinyl ether, 2-methylcyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, benzyl vinyl ether, etc. Vinyl ethers of monoalcohols with aliphatic or aromatic rings; glycerol monovinyl ether, 1,4-butanediol monovinyl ether, 1,4-butanediol divinyl ether, 1,6- Hexanediol divinyl ether, neopentyl glycol divinyl ether, neopentyl erythritol divinyl ether, neopentyl tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane Alkane trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane monovinyl ether, Mono- to multi-vinyl ethers of polyhydric alcohols such as 1,4-dihydroxymethylcyclohexane divinyl ether; diethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol monobutyl ether Polyalkylene glycol mono- to divinyl ethers based on monovinyl ethers, etc.; glycidyl vinyl ether, ethylene glycol vinyl ether ester of methacrylate, etc.

The content of the photocurable component (C) is usually 0.1 to 300 parts by mass, preferably 0.5 to 100 parts by mass, particularly preferably 1 to 50 parts by mass, and more preferably 5 to 50 parts by mass relative to 100 parts by mass of the resin (A). 30 parts by mass.

<Photoinitiator (D)>

The adhesive composition of the present invention preferably further contains a photoinitiator (D).

The photoinitiator (D) is a compound (polymerization initiator) that causes a polymerization reaction by absorbing the energy of light. Moreover, the light here is preferably visible light, ultraviolet rays, X-rays or active energy rays such as electron beams.

Specific examples of the photoinitiator (D) include: a compound that generates radicals by absorbing light energy (photo radical generator), and a compound that generates cations (acid) by absorbing light energy (photocation generator). agent), a compound that generates anions (base) by absorbing light energy (photobase generator).

The photoinitiator (D) may contain two or more types, and may be used in combination with a photoradical generator and a photocation generator.

From the viewpoint of the reactivity of the polymerization reaction, the photoinitiator (D) is preferably a photoradical generator.

Examples of the photoradical generator include alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds.

Examples of alkylphenone compounds include α -aminoalkylphenone compounds, α -hydroxyalkylphenone compounds, and α -alkoxyalkylphenone compounds.

Examples of α -aminoalkylphenone compounds include: 2-methyl-2-morpholin-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1 -(4-morpholinophenyl)-2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl methyl)butan-1-one, etc., preferably 2-methyl-2-morpholin-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1 -(4-morpholinophenyl)-2-benzylbutan-1-one, etc. As α -aminoalkylphenone compounds, Irgacure (registered trademark) 127, 184, 369, 369E, 379EG, 651, 907, 1173, 2959 (the above products are manufactured by BASF Japan Co., Ltd.) and Seikuol (registered trademark) can also be used. BEE (manufactured by Seiko Chemical Co., Ltd.) and other commercial products.

Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of the diphenyl ketone compound include diphenyl ketone, methyl o-phenyl benzoate, 4-phenyl diphenyl ketone, and 4-phenyl diphenyl sulfide. substance, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)diphenylketone, 2,4,6-trimethyldiphenylketone, etc. Commercially available benzophenone compounds can be used.

Examples of oxime ester compounds include: N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy-1-( 4-Phenylthiophenyl)octane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H -Carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl- 2,4-dioxolemethyloxy)benzylyl}-9H-carbazol-3-yl]ethane-1-imine, etc. As the oxime ester compound, Irgacure OXE-01, OXE-02, OXE-03 (the above manufactured by BASF Japan Co., Ltd.), N-1919, NCI-730, NCI-831, NCI-930 (manufactured by ADEKA Corporation), Commercially available products such as PBG3057 (manufactured by TRONLY Co., Ltd.).

Examples of the phosphine compound include phenyl (2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide, and the like. Phosphine oxide. Examples of the phosphine compound include Irgacure (registered trademark) TPO, Irgacure 819 (manufactured by BASF Japan Co., Ltd.), and the like.

The photoradical generator is preferably an oxime ester compound.

Examples of the photocation generator include onium salts such as aromatic iodonium salts and aromatic sulfonium salts; aromatic diazonium salts; iron-aromatic hydrocarbon complexes, and the like.

The aromatic ionium salt is a compound having a diaryl ionium salt cation. Typical examples of the cation include diphenyl ionium salt cation. The aromatic sulfonium salt is a compound having a triarylsulfonium salt cation. Typical examples of the cation include triphenylsulfonium salt cation, 4,4′-bis(diphenylsulfonium)diphenylsulfide cation, and the like. The aromatic diazonium salt is a compound having a diazonium salt cation, and a typical example of the cation is a benzene diazonium salt cation. In addition, the iron-propadiene complex is typically a cyclopentadienyl iron (II) allene cation complex salt.

The cations shown above are paired with anions (anions) to form a photocation generating agent. Examples of anions constituting the photocation generator include special phosphorus anions [(Rf) _n PF _6-n ]-, hexafluorophosphate anions PF ₆ -, hexafluorantimonate anions SbF ₆ -, Pentafluorohydroxyantimonate anion SbF ₅ (OH)-, hexafluoroarsenate anion AsF ₆ -, tetrafluoroborate anion BF ₄ -, tetrafluoroborate anion B (C ₆ F ₅ ) ₄ -etc. Among them, the special phosphorus-based anion [(Rf) _n PF _6-n ]- and the hexafluorophosphate anion PF are preferred from the viewpoint of the hardening properties of the cationic polymerizable compound and the safety of the obtained light selective absorption layer. ₆ -, four (pentafluorophenyl) borate anion B (C ₆ F ₅ ) ₄ -.

The content of the photoinitiator (D) is usually 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 5 parts by mass relative to 100 parts by mass of the resin (A). 3 parts by mass.

〈Crosslinking agent (E)〉

The adhesive composition of the present invention may contain a cross-linking agent (E).

Examples of the cross-linking agent (E) include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-based cross-linking agents, etc., especially from adhesive compositions. From the viewpoints of pot life, durability of the adhesive layer, and cross-linking speed, isocyanate-based cross-linking agents are preferred.

The isocyanate cross-linking agent is preferably a compound having at least two isocyanate groups (-NCO) in the molecule. Examples thereof include aliphatic isocyanate compounds (such as hexamethylene diisocyanate, etc.), alicyclic isocyanate compounds, etc. Compounds (such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate), aromatic isocyanate compounds (such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate) Isocyanate, triphenylmethane triisocyanate, etc.). In addition, the cross-linking agent (E) may be an adduct formed from a polyol compound of the aforementioned isocyanate compound [for example, an adduct formed from glycerol, trimethylolpropane, etc.], isocyanuride Acid ester compounds, biuret-type compounds, and urethane for addition reaction with polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. Prepolymer-type isocyanate compounds and other derivatives. The cross-linking agent (E) can be used alone or in combination of two or more types. Among these, representative examples include aromatic isocyanate compounds (such as toluene diisocyanate, xylene diisocyanate), aliphatic isocyanate compounds (such as hexamethylene diisocyanate), or polyol compounds (such as hexamethylene diisocyanate). For example, adducts formed from glycerin, trimethylolpropane), or isocyanurates. When the cross-linking agent (E) is an aromatic isocyanate compound and/or an adduct formed of a polyol compound or an isocyanate compound, it may be beneficial to optimize the cross-linking density (or cross-linking The formation of structure) can improve the durability of the adhesive layer. In particular, toluene diisocyanate-based compounds and/or adducts of these polyol compounds can improve durability even when, for example, applying an adhesive layer to a polarizing plate.

The content of the cross-linking agent (E) is usually 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the resin (A).

The adhesive composition of the present invention may further contain a silane compound (F).

Examples of the silane compound (F) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, etc.

The silane compound (F) may be a polysiloxane oligomer. Specific examples of the polysiloxane oligomer in the form of a combination of monomers are as follows.

3-Mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-Mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-Mercaptopropyltriethoxysilane-tetramethoxysilane oligomer mercaptopropyl-containing oligomers, 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomer, etc.; mercaptomethyltrimethoxysilane-tetramethoxysilane oligomer, mercaptomethyltrimethoxysilane - Thiol methyl-containing oligomers such as tetraethoxysilane oligomer, mercaptomethyltriethoxysilane-tetramethoxysilane oligomer, mercaptomethyltriethoxysilane-tetraethoxysilane oligomer; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane Ethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane Oxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer , 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer and other copolymers containing 3-glycidoxypropyl; 3-methacrylyloxypropyltrimethoxy Silane-tetramethoxysilane oligomer, 3-methacryloxypropyltrimethoxysilane Alkyl-tetraethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetraethyl Oxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethyl Oxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetraethyl Oxysilane oligomers and other methacryloxypropyl oligomers; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropyltrimethoxy Silane-tetraethoxysilane oligomer, 3-acryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane oligomer substance, 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3- Acryloxypropylmethyl diethoxysilane-tetramethoxysilane oligomer, 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. containing acrylic acid group Propyl oligomer; vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, ethylene Triethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxysilane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinyl Vinyl-containing oligomers such as methyldiethoxysilane-tetramethoxysilane oligomer, vinylmethyldiethoxysilane-tetraethoxysilane oligomer, etc.; 3-aminopropyltrimethoxysilane- Tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethyl Oxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc.

The silane compound (F) may be a silane compound represented by the following formula (f1).

[In the formula, A represents an alkanediyl group with 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group with 3 to 20 carbon atoms. The -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group can be passed through -O - or -CO- substituted; R ⁴¹ represents an alkyl group with 1 to 5 carbon atoms, R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represents an alkyl group with 1 to 5 carbon atoms or a carbon number of 1 to 5 alkoxy groups. ]

Examples of the alkanediyl group represented by A having 1 to 20 carbon atoms include: methylene, 1,2-ethanediyl, 1,3-propanediyl, 1,4-butanediyl, 1, 5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl base, 1,12-dodecanediyl, 1,14-tetradecanediyl, 1,16-hexadecanediyl, 1,18-octadecanediyl and 1,20-eicosanediyl base. Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include 1,3-cyclopentanediyl and 1,4-cyclohexanediyl. The -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group substituted by -O- or -CO- can be listed as follows: -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH 2 -O-CH _{2 CH 2} -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -CO-O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -CO-O-CH 2 CH ₂ -, -CH _{2 CH 2 CH 2} CH ₂ -O-CH ₂ CH ₂ -and-CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ CH ₂ -.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ⁴¹ to R ⁴⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl and pentyl. Examples of the alkoxy group having 1 to 5 carbon atoms represented by ⁴² to R ⁴⁵ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tertiary butoxy. and pentyloxy.

Examples of the silane compound represented by formula (f1) include: (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, and 1,2-bis(triethoxysilyl) ethane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1 ,4-bis(triethoxy Silyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)pentane Hexane, 1,6-bis(triethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,8-Bis(tripropoxysilyl)octane and other bis(triC1 to 5 alkoxysilyl)C1 to 10 alkane; 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(dimethoxyethylsilica) Bis(di-C1 to 5 alkoxy) hexane, 1,8-bis(dimethoxymethylsilyl)octane, 1,8-bis(dimethoxyethylsilyl)octane, etc. C1 to 5 alkylsilyl) C1 to 10 alkane; 1,6-bis(methoxydimethylsilyl)hexane, 1,8-bis(methoxydimethylsilyl)octane, etc. Bis (mono C1 to 5 alkoxy di-C1 to 5 alkylsilyl) C1 to 10 alkane, etc. Among these, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, and 1,4-bis(trimethoxysilyl)butane are preferred , 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, etc. C1 to 3 alkoxysilyl) C1 to 10 alkane, particularly preferably 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane.

The content of the silane compound (F) is usually 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, particularly preferably 0.05 to 2 parts by mass, and more preferably 0.1 to 1 part by mass relative to 100 parts by mass of the resin (A). share.

The adhesive composition may further contain an antistatic agent.

Examples of antistatic agents include surfactants, siloxane compounds, conductive polymers, ionic compounds, and the like, and ionic compounds are preferred. Examples of ionic compounds include commonly used ones. Examples of cationic components constituting the ionic compound include organic cations, inorganic cations, and the like. Examples of organic cations include pyridinium salt cations, pyrrolidinium salt cations, piperidinium salt cations, imidazolium salt cations, ammonium salt cations, sulfonium salt cations, and phosphonium salt cations. Examples of inorganic cations include alkali metal cations such as lithium cations, potassium cations, sodium cations, and cesium cations; and alkaline earth metal cations such as magnesium cations and calcium cations. Especially from the viewpoint of compatibility with (meth)acrylic resins, pyridinium salt cations, imidazolium salt cations, pyrrolidinium salt cations, lithium cations, and potassium cations are preferred. The anion component constituting the ionic compound may be either an inorganic anion or an organic anion. In terms of antistatic properties, an anion component containing a fluorine atom is preferred. Examples of the anion component containing a fluorine atom include hexafluorophosphate anion [(PF ₆ -)], bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N-], bis( Fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N-], tetrakis (pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B-], etc. This plasma compound can be used alone or in combination of two or more types. Particularly preferred ones are bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N-], bis(fluorosulfonyl)imide anion [(FSO ₂ ) 2 N-], tetrafluoromethane acyl imide anion [(CF 3 SO 2 ) ₂ N-], (Pentafluorophenyl)borate anion [(C ₆ F ₅ ) ₄ B-].

In terms of the stability of the antistatic properties of the adhesive layer formed of the adhesive composition over time, an ionic compound that is solid at room temperature is preferred.

The content of the antistatic agent is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 parts by mass relative to 100 parts by mass of the resin (A).

The adhesive composition may further contain one or more solvents, cross-linking catalysts, tackifiers, plasticizers, softeners, pigments, anti-rust agents, inorganic fillers, light-scattering particles, etc. of additives.

〈Adhesive layer〉

The adhesive layer of the present invention can be formed by, for example, dissolving or dispersing the adhesive composition of the present invention in a solvent to form a solvent-containing adhesive composition, and then coating the adhesive composition on the surface of the substrate and irradiating active energy rays after drying. And formed. The adhesive layer of the present invention can also be called a photohardened product of the adhesive composition.

The base material is preferably a plastic film, and specific examples thereof include a release film subjected to a release treatment. Examples of the release film include a film made of resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, etc., which is subjected to polysiloxane treatment on one side. Mold release handler.

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

The active energy ray irradiation after drying the coating film is preferably ultraviolet irradiation. The illumination intensity of the irradiated ultraviolet rays is preferably 10mW/cm ² to 3000mW/cm ² . In addition, the integrated light amount of ultraviolet rays is preferably 10mJ/cm ² to 5000mJ/cm ² .

The ultraviolet lamp for ultraviolet irradiation can be a mercury lamp, a metal halide lamp, or an LED lamp.

The adhesive layer of the present invention is preferably an adhesive layer that satisfies the following formula (3), and is particularly preferably an adhesive layer that further satisfies the following formula (4).

A(405)≧0.5 (3)

[In formula (3), A (405) represents the absorbance at a wavelength of 405 nm. ]

A(405)/A(440)≧5 (4)

[In formula (4), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]

The larger the value of A(405), the higher the absorption at the wavelength of 405nm. When the value of A(405) is less than 0.5, the absorption at the wavelength of 405nm is low, making components that are easily degraded by light with a wavelength near 400nm (such as display devices such as organic EL elements or liquid crystal retardation films) susceptible to cause deterioration. The value of A(405) is preferably 0.6 or more, particularly preferably 0.8 or more, and particularly preferably 1.0 or more. The upper limit is not particularly limited, but is usually 10 or less.

The value of A(405)/A(440) represents the magnitude of the absorption at a wavelength of 405 nm relative to the absorption at a wavelength of 440 nm. The larger the value, the greater the value, indicating specific absorption in the wavelength region near the wavelength of 405 nm. The value of A(405)/A(440) is preferably 10 or more, particularly preferably 30 or more, more preferably 75 or more, and particularly preferably 100 or more.

The thickness of the adhesive layer of the present invention is usually 0.1 to 30 μm, preferably 0.5 to 25 μm, more preferably 1 to 15 μm, particularly preferably 2.5 to 10 μm.

The gel fraction of the adhesive layer of the present invention is usually 50 to 99.9 mass%, preferably 60 to 99 mass%, especially 70 to 95 mass%, and more preferably 75 to 90 mass%.

〈Optical film with adhesive layer〉

The adhesive composition of the present invention and the adhesive layer formed from the adhesive composition can be used, for example, in laminating optical films.

The present invention also includes an adhesive layer optical film in which an optical film is laminated on at least one side of the adhesive layer of the present invention.

The adhesive layer optical film of the present invention can be formed by dissolving or dispersing the aforementioned adhesive composition in a solvent to form a solvent-containing adhesive composition, and then coating the adhesive composition on the surface of the optical film and irradiating active energy rays after drying. And formed. In addition, an adhesive layer can be formed on a release film in the same manner and can be obtained by laminating (transferring) the adhesive layer on the surface of the optical film.

Optical film is a film that has optical functions such as transmitting, reflecting, and absorbing light. Optical films can be single-layer films or multi-layer films. Examples of optical films include polarizing films, retardation films, brightness improvement films, anti-glare films, anti-reflection films, diffusion films, light-condensing films, and the like. Preferably, they are polarizing films, retardation films, or laminated films thereof.

The condensing film is used for the purpose of controlling the light path, etc., and can be a lens array sheet, a lens array sheet, a sheet with dots, etc.

Brightness improving films are used for the purpose of improving the brightness of liquid crystal display devices using polarizing plates. Specific examples include: a reflective polarizing separator designed by laminating a plurality of films with different refractive index anisotropies to produce anisotropy in reflectivity, an alignment film made of cholesterol liquid crystal polymer, or an alignment liquid crystal thereof. A circularly polarizing separator layer supported on a base film, etc.

A polarizing film is a film that has the following properties, that is, it has the property of absorbing linearly polarized light with a vibration plane parallel to its absorption axis, and transmitting linearly polarized light with a vibration plane that is orthogonal to the absorption axis (parallel to the transmission axis). As the film, for example, a film in which a dichroic dye is adsorbed and oriented to a polyvinyl alcohol-based resin film can be used.

Examples of dichroic dyes include iodine and dichroic organic dyes.

The degree of saponification of the polyvinyl alcohol-based resin is usually 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin can be modified, for example, it can also be polyvinyl formaldehyde and polyvinyl acetal modified by aldehydes. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.

Usually, a film formed of a polyvinyl alcohol-based resin is used as a base film of a polarizing film. The polyvinyl alcohol-based resin can be formed into a film by conventional methods. The thickness of the blank film is usually 1 to 150 μm, taking into consideration the ease of stretching, etc., preferably 10 μm or more.

The polarizing film includes, for example, the steps of uniaxially stretching the base film, dyeing the film with a dichroic pigment to adsorb the dichroic pigment, treating the film with a boric acid aqueous solution, washing the film with water, and finally drying. And made. The thickness of the polarizing film is usually 1 to 30 μm. From the viewpoint of thinning the adhesive layer optical laminate, it is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less.

Preferably, a polarizing plate is provided with a protective film on at least one side of the polarizing film via an adhesive.

The adhesive is a conventional adhesive, which may be a water-based adhesive or an active energy ray-hardening adhesive.

Examples of the water-based adhesive include commonly used water-based adhesives (for example, adhesives composed of polyvinyl alcohol-based resin aqueous solutions, water-based two-liquid urethane-based emulsion adhesives, aldehyde compounds, epoxy compounds, melamine-based compounds, Cross-linking agents such as methylol compounds, isocyanate compounds, amine compounds, multi-metal salts, etc.). Among these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be preferably used. Moreover, when a water-based adhesive is used, after laminating the polarizing film and the protective film, it is preferable to perform a drying step for removing water contained in the water-based adhesive. After the drying step, an aging step such as aging at a temperature of about 20 to 45° C. may be provided. The adhesive layer formed by the water-based adhesive is usually 0.001 to 5 μm.

Active energy ray-curable adhesive means an adhesive that is cured by irradiation with active energy rays such as ultraviolet rays or electron beams. Examples thereof include: a curable composition containing a polymerizable compound and a photopolymerization initiator; Curable compositions containing photoreactive resins, curable compositions containing binder resins and photoreactive cross-linking agents, etc. are preferably ultraviolet curable adhesives.

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

The protective film is preferably a film formed of a translucent thermoplastic resin. Specific examples include films composed of polyolefin resins, cellulose resins, polyester resins, (meth)acrylic resins, mixtures and copolymers thereof, and the like. When protective films are provided on both sides of the polarizing film, The protective films used may be films composed of different thermoplastic resins or films composed of the same thermoplastic resin.

When the protective film is laminated on at least one side of the polarizing film, the protective film is preferably a protective film composed of polyolefin-based resin or cellulose-based resin. By using these films, the shrinkage of the polarizing film in a high-temperature environment can be effectively suppressed without damaging the optical properties of the polarizing film. The protective film may also be an oxygen shielding layer.

A preferred configuration of the 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 on only one side of the polarizing film, it is particularly preferred that the protective film be laminated on the viewing side. The protective film laminated on the viewing side is preferably a protective film made of cellulose triacetate resin or cycloolefin resin. The protective film may be an unstretched film, or may be stretched in any direction to have a phase difference. A surface treatment layer such as a hard coat layer or an anti-glare layer may be provided on the surface of the protective film laminated on the viewing side.

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 made of cellulose triacetate resin, cycloolefin resin or acrylic resin. Protective film or retardation film. The retardation film may be a zero retardation film described below.

The retardation film is an optical film showing optical anisotropy. Examples thereof include: polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, Polymer membranes composed of polystyrene, polyether styrene, polyvinylidene fluoride/polymethyl methacrylate, cellulose acetate, ethylene-vinyl acetate copolymer saponified product, polyvinyl chloride, etc., extending from about 1.01 to 6 times the stretch film obtained. Among the stretched films, a polymer film obtained by uniaxially or biaxially stretching cellulose acetate, polyester, polycarbonate film or cycloolefin resin film is preferred. In addition, the retardation film may also be a retardation film that exhibits optical anisotropy by coating and aligning a liquid crystal compound on a substrate.

In addition, in this specification, the retardation film also includes a zero retardation film, and also includes films called uniaxial retardation films, low photoelasticity retardation films, wide viewing angle retardation films, and the like.

The so-called zero retardation film means that the front retardation value R _e and the thickness direction retardation R _th are both -15 to 15 nm, and the optical properties are isotropic. Examples of zero-retardation films include: resin films composed of cellulose-based resins, polyolefin-based resins (chain polyolefin-based resins, polycycloolefin-based resins, etc.) or polyethylene terephthalate-based resins. In terms of easy control of the retardation value and easy acquisition, cellulose-based resins or polyolefin-based resins are preferred. Zero retardation film can also be used as a protective film. Examples of zero-retardation films include: "Z-TAC" (trade name) sold by Fujifilm Co., Ltd., "Zerotac" (trade name) sold by Konica Minolta Opto Co., Ltd., and Nippon Zeon Co., Ltd. Co., Ltd. sells "ZF-14" (trade name), etc.

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

Films that exhibit optical anisotropy through coating and alignment of liquid crystal compounds include the following first to fifth types.

The first type: a retardation film in which a rod-shaped liquid crystal compound is aligned in a horizontal direction relative to a supporting substrate

Second type: a retardation film in which a rod-shaped liquid crystal compound is aligned in a vertical direction relative to a supporting substrate

The third type: a retardation film that causes the alignment direction of rod-shaped liquid crystal compounds to spirally change within the plane.

The fourth type: a retardation film that makes disc-shaped liquid crystal compounds tilt into alignment

Fifth type: a biaxial retardation film that orients a disc-shaped liquid crystal compound in a vertical direction relative to a supporting substrate

For example, the first type, the second type, and the fifth type can be preferably used as optical films used in organic electroluminescent displays. In addition, these types of retardation films can also be laminated and used.

When the retardation film is a layer composed of a polymer in which a polymerizable liquid crystal compound is in an aligned state (hereinafter sometimes referred to as an "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersion. . The so-called reverse wavelength dispersion is an optical property in which the retardation value in the liquid crystal alignment plane at short wavelengths is small and the retardation value in the liquid crystal alignment plane at longer wavelengths is small. Preferably, the retardation film satisfies the following formula (7) and Formula (8). Re(λ) represents the in-plane phase difference value of light with respect to wavelength λ.

Re(450)/Re(550)≦1 (7)

1≦Re(630)/Re(550) (8)

Among the optical films of the present invention, it is preferable that the retardation film is of the first type and has reverse wavelength dispersion because it can reduce coloration during black display in the display device. In the aforementioned formula (7), 0.82≦Re(450)/Re(550)≦0.93. Furthermore, 120≦Re(550)≦150 is preferred.

Examples of polymerizable liquid crystal compounds when the retardation film is a film having an optically anisotropic layer include: "Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2012)" Among the compounds described in 3.8.6 Network (completely cross-linked type)" and "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material", as well as compounds having a polymerizable group in Japanese Patent Application Laid-Open No. 2010-31223, Japanese Patent Application Publication No. 2010-270108, Japanese Patent Application Publication No. 2011-6360, Japanese Patent Application Publication No. 2011-207765, Japanese Patent Application Publication No. 2011-162678, Japanese Patent Application Publication No. 2016-81035, Japanese International Publication No. 2017 Polymerizable liquid crystal compounds described in /043438 and Japanese Patent Publication No. 2011-207765, etc.

Examples of a method for producing a retardation film from a polymer in which a polymerizable liquid crystal compound is in an aligned state include the method described in Japanese Patent Application Laid-Open No. 2010-31223.

In the case of the second type, the front phase difference value Re (550) can be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the phase difference value R _th in the thickness direction can be adjusted in the range of -10 to the range of -300nm, and preferably can be adjusted in the range of -20 to -200nm. The retardation value R _th in the thickness direction, which means the refractive index anisotropy in the thickness direction, can be measured from the retardation value R ₅₀ measured by tilting the in-plane fast axis as the tilt axis by 50 degrees and the in-plane retardation value. R ₀ to calculate. That is, the phase difference value R _th in the thickness direction can be calculated from the in-plane phase difference value R ₀ and the phase difference value R measured by tilting the fast axis as the tilt axis by 50 degrees according to the following formulas (10) to (12). _50. Use the thickness d of the retardation film and the average refractive index n ₀ of the retardation film to obtain n _x , _ny and n _z , and substitute these into equation (9) to calculate.

R _th =[(n _x +n _y )/2-n _z ]×d (9)

R ₀ =(n _x -n _y )×d (10)

(n _x , n _y and n _z )/3=n ₀ (12)

here,

Films that exhibit optical anisotropy by coating and aligning liquid crystal compounds, or films that exhibit optical anisotropy by coating with inorganic layered compounds, are called temperature compensation retardation films. Films include "NH Film" (trade name; film with tilted alignment of rod-shaped liquid crystals) sold by JX Nippon Oil & Energy Co., Ltd., and "WV Film" (trade name) sold by Fuji Film Co., Ltd. Name; film with tilted alignment of disk-shaped liquid crystals), "VAC Film" sold by Sumitomo Chemical Co., Ltd. (trade name; film with complete biaxial alignment type), and "VAC Film" sold by Sumitomo Chemical Co., Ltd. "new VAC Film" (trade name: biaxially aligned film), etc.

The retardation film may be a multilayer film having two or more layers. For example, a protective film is laminated on one or both sides of a retardation film, or two or more retardation films are laminated via an adhesive or an adhesive agent.

An example of the layer composition of the adhesive layer of the present invention and the optical laminate of the present invention is shown in FIGS. 1 to 5 .

In order to temporarily protect the adhesive layer 1 formed of the adhesive composition of the present invention, the adhesive layer-attached optical film 10 shown in Figure 1 is in a state where a peeling film (separation film) 2 is attached to the adhesive layer 1 state.

The adhesive layer optical film 10A shown in Figure 2 includes: a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 1 formed of the adhesive composition of the present invention, and a release film 2. Agent layer optical film. The protective film 3 may have a phase difference. In addition, a hard coating layer or the like may be laminated on the protective film 3 .

The optical film 10B with an adhesive layer shown in Figure 3 includes: a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 7, a protective film 6, and an adhesive layer formed of the adhesive composition of the present invention. 1. And the optical film of the adhesive layer of the retardation film 8.

The optical laminated body 10C shown in FIG. 4 and the optical laminated body 10D shown in FIG. 5 include a protective film 3, an adhesive layer 4, a polarizing film 5, and an adhesive layer 1 formed of the adhesive composition of the present invention. An optical laminate of adhesive layer 7, retardation film 110, adhesive layer 1a, and light emitting element 30 (liquid crystal cell, organic EL cell). The adhesive layer 1a may be an adhesive layer formed of a conventional adhesive composition, or an adhesive layer formed of the adhesive composition of the present invention.

In the case where the retardation film is a multilayer film as shown in FIGS. 4 and 5 , as shown in FIG. 4 , a laminate including an interposed adhesive layer or an adhesive layer 60 can provide 1/ The phase difference between the 1/4-wavelength retardation layer 50 that provides a phase difference of 4 wavelengths and the 1/2-wavelength retardation layer 70 that provides a phase difference of 1/2 wavelength to the transmitted light. The structure of the differential film 110. In addition, as shown in FIG. 5 , a structure including an optical film 40 in which a quarter-wavelength retardation layer 50 a and a positive C layer 80 are laminated via an adhesive layer or adhesive layer 60 can be exemplified.

The 1/4-wavelength retardation layer 50 that imparts a phase difference of 1/4 wavelength and the 1/2-wavelength phase difference layer 70 that imparts a phase difference of 1/2 wavelength in Figure 4 can be the first type of optics described above. film or fifth type optical film. In the case of the configuration of Figure 4, it is particularly preferred that at least one of the parties is in the fifth type.

In the case of the structure of FIG. 5 , the quarter-wavelength retardation layer 50 a is preferably the optical film of the above-mentioned first type, and more preferably satisfies equations (7) and (8).

〈Liquid crystal display device〉

The resin of the present invention, the adhesive composition containing the resin, and the optical laminate containing the adhesive layer formed from the adhesive composition can be laminated on organic EL elements, liquid crystal cells and other display elements and used in organic EL Display devices such as display devices or liquid crystal display devices.

[Example 1

The present invention will be described in more detail below through examples and comparative examples. "%" and "parts" in the examples and comparative examples are "mass %" and "mass parts" unless otherwise stated.

Synthesis Example 1: Synthesis of a light-selective absorption compound (1) having an anthocyanin structure in the molecule

In a nitrogen environment, a compound represented by formula (aa) synthesized with reference to Japanese Patent Application Laid-Open No. 2014-194508 was added to a 200 mL four-neck flask equipped with a Dimroth condenser and a thermometer. 10g, 3.6g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), 10g of 2-butyloctyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), And stir with a magnetic stirrer. After 4.5 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the obtained mixture at an internal temperature of 25°C within 1 hour, the mixture was further kept at an internal temperature of 25°C for 2 hours. Thereafter, acetonitrile was removed using a reduced pressure evaporator, and the solvent was removed from the effluent containing the compound represented by the formula (UVA-1) by column chromatography (gel) to obtain a yellow color. crystallize. The crystal was dried under reduced pressure at 60° C. to obtain 4.6 g of a compound represented by formula (UVA-1) as a yellow powder. The yield is 56%.

<Measurement of Gram Absorption Coefficient ε>

The obtained 2-butanone solution (concentration: 0.006g/L) of the compound represented by formula (UVA-1) was placed in a 1 cm quartz cell, and the quartz cell was mounted on a spectrophotometer UV-2450 (Shimadzu Seisakusho Co., Ltd.), and measured the absorbance in the wavelength range of 300 to 800 nm by the double-beam method in steps of 1 nm. From the obtained absorbance value, the concentration of the compound represented by the formula (UVA-1) in the solution, and the optical path length of the quartz cell, the gram absorption coefficient per wavelength was calculated.

ε(λ)=A(λ)/CL

[In the formula, ε(λ) represents the gram absorption coefficient (L/(g·cm)) of the resin (A) at the wavelength λnm, A(λ) represents the absorbance at the wavelength λnm, and C represents the concentration (g/L ), L represents the light path length of the quartz groove (cm). ]

The ε(405) of the obtained compound represented by formula (UVA-1) was 45L/(g·cm), and the value of ε(440) was 0.1L/(g·cm).

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

A mixed solution of 150 parts of ethyl acetate as a solvent, 96 parts of butyl acrylate, 3 parts of 2-hydroxyethyl acrylate, and 1 part of acrylic acid was put into a reaction tank equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer. According to the container, while replacing the air in the device with nitrogen to make it oxygen-free, the internal temperature is raised to 60°C. Then, a solution in which 0.4 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of ethyl acetate was added in full. The obtained mixture was maintained at 60°C for 1 hour, and then, while maintaining the internal temperature at 50 to 70°C, ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hr, so that the concentration of the acrylic resin became 35 The addition of ethyl acetate was stopped at %, and the temperature was maintained at this temperature until 12 hours had elapsed since the addition of ethyl acetate was started. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%, and an ethyl acetate solution of the acrylic resin was prepared. The obtained acrylic resin had a polystyrene-converted weight average molecular weight Mw measured by GPC of 1.48 million, and Mw/Mn was 3.45. Let this be resin (A-1). The glass transition temperature measured by DSC is -45°C. Moreover, the monomer composition in the obtained acrylic resin was 96 mass% of butyl acrylate, 3 mass% of 2-hydroxyethyl acrylate, and 1 mass% of acrylic acid.

〈Preparation of adhesive composition〉

[Example 1]: Preparation of adhesive composition (1)

In the ethyl acetate solution of the resin (A-1) obtained above (resin concentration: 20%), 2.5 parts of the compound represented by the formula (UVA-1) was mixed with 100 parts of the solid content of the solution. 1 part of photoinitiator (manufactured by ADEKA Co., Ltd.; trade name "NCI-730", photo radical generator), 10 parts of photocurable component (manufactured by Shin-Nakamura Chemical Co., Ltd.; trade name "A-DPH-12E"), 0.3 parts of a cross-linking agent (manufactured by Tosoh Co., Ltd.; trade name "Coronate L", isocyanate compound, solid content 75%) and 0.28 parts of a silane compound (manufactured by Shin-Etsu Chemical Industry Co., Ltd.; trade name "KBM-3066"), and then use 2-Butanone was added so that the solid content concentration became 14%, and the adhesive composition (1) was obtained. The preparation amount of the above-mentioned cross-linking agent (Coronate L) is the mass part based on the active ingredient.

[Comparative Example 1]: Preparation of adhesive composition (2)

To an ethyl acetate solution of resin (A-1) (resin concentration: 20%), 2.5 parts of a compound represented by formula (UVA-1) and a cross-linking agent (100 parts) relative to the solid content of the solution were mixed. Tosoh Co., Ltd.; trade name "Coronate L", 0.3 parts of an isocyanate compound, solid content 75%) and 0.28 parts of a silane compound (manufactured by Shin-Etsu Chemical Industry Co., Ltd.; trade name "KBM-3066"), so that the solid content concentration becomes 2-Butanone is added at 14% to obtain adhesive composition (2). In addition, the compounding amount of the above-mentioned cross-linking agent (Coronate L) is the mass part based on the active ingredient.

[Comparative Example 2]: Preparation of adhesive composition (3)

To an ethyl acetate solution of resin (A-1) (resin concentration: 20%), an indole-based light selective absorption compound (BONASORB UA-3911 manufactured by Orient Chemical Industries) was mixed with respect to 100 parts of the solid content of the solution. 1 part, cross-linking agent (manufactured by Tosoh Co., Ltd.; trade name "Coronate L", isocyanate compound, solid content 75%) 0.3 part and 0.28 part silane compound (manufactured by Shin-Etsu Chemical Industry Co., Ltd.; trade name "KBM-3066"), Then, 2-butanone was added so that the solid content concentration became 14%, and the adhesive composition (3) was obtained. In addition, the compounding amount of the above-mentioned cross-linking agent (Coronate L) is the mass part based on the active ingredient.

[Preparation Example 1]: Preparation of adhesive composition (4)

To an ethyl acetate solution of resin (A-1) (resin concentration: 20%), a cross-linking agent (manufactured by Tosoh Co., Ltd.; trade name "Coronate L", an isocyanate compound) was mixed with 100 parts of the solid content of the solution. , 75% solid content) 0.3 parts and 0.28 parts of a silane compound (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-3066"), and then 2-butanone was added so that the solid content concentration became 14% to obtain an adhesive composition. Object (4). In addition, the compounding amount of the above-mentioned cross-linking agent (Coronate L) is the mass part based on the active ingredient.

<Preparation of adhesive layer-1>

Using a coater, the adhesive composition of Example 1 was applied to a release-treated release film composed of a polyethylene terephthalate film so that the thickness after drying became 5 μm [from Lintec shares Co., Ltd. with the trade name "PLR-382190"] and dry the mold release surface at 100°C for 1 minute. Then, an ultraviolet irradiation device ("Electrodeless UV Lamp System H Bulb" manufactured by Fusion UV Systems, Inc.) was used to adjust UV-A (wavelength 320 to 390 nm) so that the illumination intensity became 500 mW and the accumulated light amount became 500 mJ, and the The adhesive layer (1) (adhesive sheet) with a release film is produced by irradiating ultraviolet rays.

<Preparation of adhesive layer-2>

Using a coater, the adhesive compositions of Comparative Examples 1 and 2 were applied to the release-processed polyethylene terephthalate film so that the thickness after drying became 5 μm. The release-treated surface of the film [trade name "PLR-382190" obtained from Lintec Co., Ltd.] was dried at 100°C for 1 minute to obtain an adhesive layer with a release film. Furthermore, the adhesive layer formed of the adhesive composition of Comparative Example 1 was used as the adhesive layer (2), and the adhesive layer formed of the adhesive composition of Comparative Example 2 was used as the adhesive layer (3).

<Preparation of adhesive layer-3>

Using a coater, the adhesive composition of Preparation Example 1 was applied to a release-treated release film composed of a polyethylene terephthalate film so that the thickness after drying became 25 μm [from The release-treated surface (trade name "PLR-382190" obtained by Lintec Co., Ltd.] was dried at 100°C for 1 minute to obtain an adhesive layer with a release film (4).

<Measurement of gel fraction of adhesive layer>

The gel fraction in the adhesive layer of the present invention is the value measured according to the following (a) to (d). In addition, the larger the gel fraction, the more cross-linking reactions occur in the adhesive, so it can be used as a criterion for judging the cross-link density. The gel fraction of the adhesive layer (1) to (3) is measured according to the following (a) to (d). The results are shown in Table 1.

(a) An adhesive sheet with an area of about 8cm×about 8cm is bonded to a metal mesh made of SUS304 of about 10cm×about 10cm (let its weight be Wm).

(b) Weigh the bonded product obtained in the above (a) and set its mass to Ws, then fold it 4 times by wrapping it with an adhesive sheet, fix it with a stapler (stapler), and then weigh it. Set its quality to Wb.

(c) Place the metal mesh fixed with staples in the above (b) into a glass container, add 60 mL of ethyl acetate and immerse it, and store the glass container at room temperature for 3 days.

(d) Take out the metal mesh from the glass container, dry it at 120° C. for 24 hours, and then weigh it. Let its mass be Wa, and calculate the gel fraction according to the following formula.

Gel fraction (mass %)=[{Wa-(Wb-Ws)-Wm}/(Ws-Wm)]×100

<Absorbance measurement of adhesive layer>

The obtained adhesive layers (1) to (3) were each bonded to the glass, and after peeling off the separation membrane, a cycloolefin polymer (COP: Cycloolefin Polymer) film (Nippon Zeon Co., Ltd.) was bonded on the adhesive layer. The company manufactures ZF-14) and produces a laminate composed of COP film/adhesive layer/glass. The produced laminated body was mounted on a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the absorbance in the wavelength range of 300 to 800 nm was measured in steps of 1 nm by the double-beam method. The absorbance of the produced adhesive layer is shown in Table 1. At wavelength 405nm and wavelength 440nm, the absorbance of glass and the absorbance of COP film are both 0. The results are shown in Table 1.

[Table 1]

<Production of optical film>

[Example 2]: Production of optical film (1)

(i) Production of polarizing film (polarizing element)

A polyvinyl alcohol film ("Kuraray Poval Film VF-PE#3000", manufactured by Kuraray Co., Ltd.) with an average degree of polymerization of about 2400, a saponification degree of 99.9 mol% and a thickness of 30 μm was immersed in pure water at 37°C, and then dried at 30 Immerse in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) at ℃. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid (potassium iodide/boric acid/water (weight ratio) = 12/3.6/100) at 56.5°C. Then, the film was washed with pure water at 10° C. and dried at 85° C. to obtain a polarizing film A with a thickness of about 12 μm in which iodine is adsorbed and aligned with polyvinyl alcohol. Extension is mainly performed in the steps of iodine staining and boric acid treatment, with a total extension ratio of 5.3 times.

(ii) Production of polarizing plates

A transparent protective film ("25KCHCN-TC", Toppan Printing Co., Ltd. obtained by applying a 7 μm hard coat layer to a 25 μm thick cellulose triacetate film via an adhesive composed of an aqueous solution of polyvinyl alcohol resin). (made) and bonded to one side of the polarizing film obtained in (i). A 23 μm thick cycloolefin resin film ("ZF14-023", Nippon Zeon Co., Ltd.) was bonded to the surface opposite to the transparent protective film to produce a polarizing plate (thickness: 67 μm).

(iii) Preparation of the first phase difference layer

The first retardation layer (first liquid crystal cured film layer) is a layer that imparts a λ/4 retardation composed of a layer hardened using a nematic liquid crystal compound, an alignment film, and a transparent base material. In addition, the total thickness of the layer formed by hardening the nematic liquid crystal compound and the alignment layer was 2 μm.

(iv) Preparation of the second phase difference layer

As a composition for forming the alignment layer, 10 parts by mass of polyethylene glycol di(meth)acrylate (A-600 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and trimethylolpropane triacrylate (Shin-Nakamura Chemical Industry Co., Ltd. Co., Ltd. A-TMPT) 10 parts by mass, 1,6-hexanediol di(meth)acrylate (A-HD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and photopolymerization 1.5 parts by mass of Irgacure907 (Irg-907 manufactured by BASF Corporation) as a starting agent was dissolved in 70 parts by mass of methyl ethyl ketone as a solvent to prepare a coating liquid for alignment layer formation.

The base film system prepared a long cyclic olefin-based resin film (manufactured by Nippon Zeon Co., Ltd.) with a thickness of 20 μm, and applied the obtained coating liquid for alignment layer formation to the base film using a bar coater. Single sided.

The coated coating layer is heat treated at 80°C for 60 seconds, and then irradiated with ultraviolet light (UVB) of 220 mJ/cm ² to polymerize and harden the composition for forming the alignment layer, forming a 2.3 μm thick layer on the base film. Alignment layer 1.

20 parts by mass of a photopolymerizable nematic liquid crystal compound (RMM28B manufactured by Merck Corporation) as a composition for forming the retardation layer, and Irgacure 907 (BASF Corporation) as a photopolymerization initiator were mixed 1 mass part of Irg-907) prepared by our company was dissolved in 80 mass parts of propylene glycol monomethyl ether acetate as a solvent to prepare a coating liquid for retardation layer formation.

The coating liquid for forming the retardation layer is applied on the previously obtained alignment layer 1, and the coating layer is heat-treated at a temperature of 80° C. for 60 seconds. Then, ultraviolet (UVB) 220 mJ/cm ² was irradiated to polymerize and harden the composition for forming the retardation layer, thereby forming a retardation layer with a thickness of 0.7 μm on the alignment layer. In this way, the second retardation layer (second liquid crystal cured film layer; thickness 3 μm) composed of the alignment layer 1 and the retardation layer 1 on the base film was obtained. The second phase difference layer is the positive C layer.

(v) Lamination of the first phase difference layer and the second phase difference layer

The first retardation layer and the second retardation layer are bonded together with an ultraviolet curable adhesive (thickness 1 μm) so that the respective liquid crystal layers (the surface opposite to the transparent base material) become the bonding surfaces. . Then, ultraviolet rays are irradiated to harden the ultraviolet curable adhesive. In this way, a retardation layer including two retardation layers, the first liquid crystal layer and the second liquid crystal layer, is produced. The transparent base material is peeled off from both sides of this retardation layer, and the retardation film is obtained. In addition, the thickness of the liquid crystal layer including the first liquid crystal layer, the ultraviolet curable adhesive layer, and the second liquid crystal layer was 6 μm.

(vi) Lamination of polarizing plate and retardation film

The release film-attached adhesive layer (1) is laminated on the cycloolefin-based resin film of the polarizing plate obtained in (ii). The separation film is peeled off from the adhesive layer (1), and the adhesive layer (1) is laminated so as to be joined to the first retardation layer side of the retardation film obtained by the formula (v), thereby obtaining an optical film ( 1).

<Evaluation of crack resistance>

The second retardation layer of the optical film (1) and the adhesive layer (4) with a separation film are laminated. The separation film was peeled off, and the adhesive layer (4) and alkali-free glass [trade name "EAGLE XG" manufactured by Corning Corporation] were laminated to obtain an optical film (1A). The obtained optical film (1A) had the following composition: cellulose triacetate film/polarizing film/ Cyclic olefin film/adhesive layer (1)/1st retardation layer/UV curable adhesive layer/2nd retardation layer/adhesive layer (4)/alkali-free glass.

The cellulose triacetate film side of the optical film (1A) is pressed against the tip of the Erichsen pen (manufactured by Erichsen Co., Ltd.; model 318) as the starting point of the crack. The load of this Erichsen pen is set to 10N. Then, a hot and cold shock test of 150 cycles was performed, with one cycle of -40°C for 30 minutes and 85°C for 30 minutes. After the hot and cold impact test, use a microscope to confirm how many mm the crack has grown from the starting point, and use this as the crack resistance. The results are shown in Table 2.

[Comparative Example 3]: Production of optical films (2) and (2A)

Except that the adhesive layer (1) is changed to the adhesive layer (2), the same procedure is performed to obtain the optical film (2) and the optical film (2A). Crack resistance was evaluated in the same manner as above. The results are shown in Table 2.

[Comparative Example 4]: Production of optical films (3) and (3A)

The optical film (3) and the optical film (3A) were obtained in the same manner except that the adhesive layer (1) was changed to the adhesive layer (3). Crack resistance was evaluated in the same manner as above. The results are shown in Table 2.

[Table 2]

In the optical film with an adhesive layer formed of the adhesive composition of the present invention, the crack lengthened by 4 mm. On the other hand, the adhesion formed by the adhesive composition of the comparative example For agent-coated optical films, the crack length becomes more than 80mm. The adhesive layer optical film containing the adhesive layer formed by the adhesive composition of the present invention has good crack resistance.

[Industrial availability]

The resin of the present invention, the adhesive composition containing the resin, and the optical laminate containing the adhesive layer formed from the adhesive composition can be preferably used in liquid crystal panels and liquid crystal display devices.

Claims (22)

An adhesive composition, which contains: resin (A), a photohardening component (C) and a light-selective absorption compound (B) having a merocyanine structure, wherein, relative to 100 mass of the resin (A) parts, and the content of the photocurable component (C) is 0.1 to 300 parts by mass. The adhesive composition as described in claim 1 further contains a photoinitiator (D). The adhesive composition according to claim 2, wherein the photoinitiator (D) is a photoradical generator. The adhesive composition according to any one of claims 1 to 3, wherein the photocurable component (C) is a photoradically curable component. The adhesive composition according to claim 4, wherein the photocurable component (C) contains a (meth)acrylate compound. The adhesive composition according to claim 4, wherein the photocurable component (C) contains a multifunctional (meth)acrylate compound. The adhesive composition according to any one of claims 1 to 3, further containing a cross-linking agent (E). The adhesive composition according to claim 7, wherein the cross-linking agent (E) is an isocyanate cross-linking agent. The adhesive composition according to any one of claims 1 to 3, wherein the resin (A) is a resin with a glass transition temperature of 40°C or less. The adhesive composition according to any one of claims 1 to 3, wherein the resin (A) is a (meth)acrylic resin. The adhesive composition according to any one of claims 1 to 3, wherein the resin (A) is a (meth)acrylic resin with a weight average molecular weight of 500,000 or more. The adhesive composition according to any one of claims 1 to 3, wherein the light selective absorption compound (B) having a merocyanin structure satisfies the following formula (1), ε(405)≧5 ( 1) In formula (1), ε (405) represents the gram absorption coefficient of the light-selective absorption compound (B) with a merocyanin structure at a wavelength of 405 nm; the unit of the gram absorption coefficient is L/(g·cm) . The adhesive composition according to any one of claims 1 to 3, wherein the light selective absorption compound (B) having a merocyanin structure satisfies the following formula (2), ε(405)/ε( 440)≧20 (2) In formula (2), ε(405) represents the gram absorption coefficient of the light-selective absorption compound (B) having a merocyanin structure at a wavelength of 405 nm; ε(440) represents the wavelength The gram absorption coefficient of the light-selective absorption compound (B) having a merocyanin structure at 440 nm. The adhesive composition according to any one of claims 1 to 3, wherein the light selective absorption compound (B) having a merocyanin structure does not have a polymerizable group. The adhesive composition according to any one of claims 1 to 3, wherein the light selective absorption compound (B) having a merocyanin structure is a compound represented by formula (I),

In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or an aliphatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent. Aromatic hydrocarbon group or heterocyclic group, the -CH ₂ - contained in the aforementioned aliphatic hydrocarbon group or aromatic hydrocarbon group can be replaced by -NR ^1A -, -SO ₂ -, -CO-, -O- or -S-; R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an electron-withdrawing group; R ^1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ¹ and R ² may be bonded to each other R ² and R ³ can bond to each other to form a ring structure, R ² and R ⁴ can bond to each other to form a ring structure, R ³ and R ⁶ can bond to each other to form a ring structure , R ⁵ and R ⁷ may be bonded to each other to form a ring structure, and R ⁶ and R ⁷ may be bonded to each other to form a ring structure. The adhesive composition according to claim 15, wherein the compound represented by formula (I) is a compound represented by formula (II),

In formula (II), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or having 6 carbon atoms which may have a substituent. to 15 aromatic hydrocarbon groups or heterocyclic groups, the -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group can be replaced by -NR ^11A -, -SO ₂ -, -CO-, -O- or -S- Substitution; R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group with 1 to 25 carbon atoms, and an electron-withdrawing group; R ^11A represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms; R ¹¹ and R ¹² may R ¹² and R ¹³ may be bonded to each other to form a ring structure, and R ¹² and R ¹⁴ may be bonded to each other to form a ring structure. An adhesive layer formed from the adhesive composition described in any one of claims 1 to 16. The adhesive layer according to claim 17 satisfies the following formula (3), A(405)≧0.5 (3) In formula (3), A(405) represents the absorbance at a wavelength of 405 nm. The adhesive layer as described in claim 18 further satisfies the following formula (4), A(405)/A(440)≧5 (4) In formula (4), A(405) is expressed at a wavelength of 405 nm The absorbance at the time, A(440) represents the absorbance at the wavelength of 440nm. An optical film with an adhesive layer, in which an optical film is laminated on at least one side of the adhesive layer according to any one of claims 17 to 19. The optical film with an adhesive layer as claimed in claim 20, wherein the optical film is a polarizing plate. An image display device including the optical film with an adhesive layer described in claim 20 or 21.

Images