TW202102636A - 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 by the adhesive composition, and an optical film in which the adhesive layer is laminated.

In display devices (FPD: Flat Panel Displays) such as organic EL display devices or liquid crystal display devices, various components such as display elements such as organic EL elements and liquid crystal cells, optical films such as polarizers 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, so they are not only ultraviolet (UV), but are caused by short-wavelength visible light below 420nm. Deterioration can easily become a problem. In order to solve this problem, Patent Document 1 describes an adhesive composition and an adhesive layer optical film formed of the composition. The adhesive composition contains: (meth)acrylic resin and A light-selective absorption compound (BONASORB UA-3911 manufactured by Orient Chemical Industries, Inc.) of an indole structure that selectively absorbs a wavelength around 400 nm.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2017-165941 A

In addition, from the viewpoint of thinning, there has been an increase in the number of optical films used in organic EL display devices in display devices that are polymerized with polymerizable liquid crystal compounds in an aligned state. It is known that compared with the conventional optical film formed by the stretched resin film, the optical film formed by the polymer in the aligned state of the polymerizable liquid crystal compound will crack when exposed to an environment where high temperature and low temperature conditions change repeatedly. (Crack) tends to grow easily.

The optical film composed of the adhesive layer formed of the adhesive composition described in Reference 1 can improve the deterioration of visible light at a wavelength of around 420 nm, but the suppression of absorption crack growth is insufficient.

The present invention includes the following inventions.

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

[2] The adhesive composition 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 photoradical 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], which further contains a crosslinking agent (E).

[8] The adhesive composition according to [7], wherein the crosslinking agent (E) is an isocyanate crosslinking 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 having 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 merocyanidin 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 merocyanidin structure at a wavelength of 405 nm. The unit of gram absorbance 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 merocyanidin 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 merocyanidin structure at a wavelength of 405 nm, and ε (440) represents a merocyanine at a wavelength of 440 nm The gram absorption coefficient of the light selective absorption compound (B) of the element structure].

[14] The adhesive composition according to any one of [1] to [13], wherein the light selective absorption compound (B) having a merocyanidin 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 merocyanidin 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 that may have a substituent, and 6 to 15 carbon atoms that may have a substituent _{The -CH 2} -contained in the aforementioned aliphatic hydrocarbon group or aromatic hydrocarbon group may 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, and 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 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].

[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 that may have a substituent, and a carbon number that may have a substituent Aromatic hydrocarbon group or heterocyclic group of 6 to 15, the -CH2- contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group may 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, and 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 of the adhesive composition according to any one of [1] to [16].

[18] The adhesive layer according to [17], which satisfies the following formula (3);

A(405)≧0.5 (3)

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

[19] The adhesive layer according to [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 405nm, and A(440) represents the absorbance at a wavelength of 440nm].

[20] An adhesive layer-attached optical film in which an optical film is laminated on at least one surface of the adhesive layer as described in any one of [17] to [19].

[21] The adhesive layer-attached optical film according to [20], wherein the optical film is a polarizing plate.

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

The optical film containing the adhesive layer formed by the adhesive composition of the present invention has good crack resistance performance under the environment where high temperature conditions and low temperature conditions repeatedly change, cracks (cracks) will not grow.

1: Adhesive layer

1a: Adhesive layer

2: Peel off the film

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

3,6: Protective film

4, 7: Adhesive layer

5: Polarizing film

8: retardation film

30: Light-emitting element

40: Optical film

50, 50a: 1/4 wavelength retardation layer

60: Adhesive layer or adhesive layer

70: 1/2 wavelength retardation layer

80: Positive C layer

100: Polarizing plate

110: retardation 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 optical film of the present invention.

Fig. 3 shows an example of the layer structure of the adhesive layer optical film of the present invention.

Fig. 4 shows an example of the layer structure of the adhesive layer optical film of the present invention.

Fig. 5 shows an example of the layer structure of the adhesive layer optical film of the present invention.

<Adhesive composition>

The adhesive composition of the present invention contains a resin (A), a light selective absorption compound (B) having a partial anthocyanin structure, and a photocurable component (C).

The adhesive composition of the present invention may further contain: a photoinitiator (D), a crosslinking agent (E), a silane compound and the like.

<Resin (A)>

The resin (A) is not particularly limited as long as it is a resin used in the adhesive composition. The resin (A) is preferably a resin having a glass transition temperature of 40°C or less. The glass transition temperature (Tg) of the resin (A) is more preferably 20°C or less, particularly preferably 10°C or less, and more preferably 0°C or less. In addition, the glass transition temperature of the resin (A) is usually -80°C or higher, preferably -60°C or higher, particularly preferably -50°C or higher, more preferably -45°C or higher, and particularly preferably -30°C or higher. When the glass transition temperature of the resin (A) is below 40°C, it is advantageous 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 above -80°C, it is advantageous for the adhesive layer formed by the adhesive composition containing the resin (A) The durability (missing appearance during high temperature test: cohesion failure, etc.) is improved. The glass transition temperature can be measured by a differential scanning calorimetry (DSC: Differential Scanning Calorimetry).

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

The (meth)acrylic resin is preferably a polymer having a constituent unit derived from (meth)acrylate as a main component (preferably containing 50% by mass or more). The structural unit derived from the (meth)acrylate may include more than one structural unit derived from a monomer other than the (meth)acrylate (for example, a structural unit derived from a monomer having a polar functional group). In the present specification, the so-called (meth)acrylic acid means that it can be either acrylic acid or methacrylic acid, and when it is referred to as (meth)acrylate, etc., "(meth)" also has the same meaning.

(Meth)acrylates include (meth)acrylates 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, R _2A represents an alkyl group having 1 to 14 carbons or an aralkyl group having 7 to 20 carbons, and the hydrogen atom of the alkyl group or the aralkyl group may be Substituted by an alkoxy group having 1 to 10 carbons. ]

In the formula (a), R _{2A is} preferably an alkyl group having 1 to 14 carbons, and particularly preferably an alkyl group having 1 to 8 carbons.

The (meth)acrylate represented by formula (I) can be listed as follows:

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) ) 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, isoamyl (meth)acrylate, isohexyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid such as 2-ethylhexyl ester, isooctyl (meth)acrylate, isononyl (meth)acrylate, isostearyl (meth)acrylate, isoamyl (meth)acrylate, etc.的 branched alkyl ester;

Cyclohexyl (meth)acrylate, isobornyl (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, cyclohexyl α-ethoxyacrylate, etc. The alkyl ester containing alicyclic skeleton;

(Meth)acrylic acid esters containing aromatic ring skeletons, such as phenyl (meth)acrylate, etc.

In addition, substituent-containing alkyl (meth)acrylates in which the substituent is introduced into the alkyl (meth)acrylate can also be cited. The substituent of the substituent-containing alkyl (meth)acrylate is a group substituted for 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 alkyl (meth)acrylate include 2-methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, ( 2-(2-phenoxyethoxy) ethyl meth)acrylate, phenoxy diethylene glycol (meth)acrylate, phenoxy poly(ethylene glycol) (meth)acrylate, and the like.

In addition to using these (meth)acrylates individually, they can also be used in a plurality of different types.

The (meth)acrylic resin (A) preferably contains: a structural unit of alkyl acrylate (a1) whose glass transition temperature Tg derived from a homopolymer is less than 0°C, and a Tg derived from a homopolymer of 0°C or higher The constituent unit of alkyl acrylate (a2). Containing the structural unit derived from the alkyl acrylate (a1) and the structural unit derived from the alkyl acrylate (a2) is advantageous for improving the high-temperature durability of the adhesive layer. Alkyl (meth)acrylate For example, the Tg of the homopolymer may adopt literature values such as POLYMER HANDBOOK (Wiley-Interscience).

Specific examples of 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 Octyl ester, 2-ethylhexyl acrylate, n- and isononyl acrylate, n- and isodecyl acrylate, n-dodecyl acrylate and other alkyl acrylates whose alkyl groups have 2 to 12 carbon atoms.

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

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, isobornyl acrylate, stearyl acrylate, tertiary butyl acrylate, and the like.

The alkyl acrylate (a2) may be used alone or in combination of two or more. Among them, from the viewpoint of high-temperature durability, the alkyl acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc., and particularly preferably contains methyl acrylate.

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

The structural unit derived from a monomer other than the (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 heterocyclic groups such as a hydroxyl group, a carboxyl group, a substituted or unsubstituted amine group, and an epoxy group.

Monomers having polar functional groups include: 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, and (meth)acrylate 1 -Hydroxybutyl, 1-hydroxypentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 2-hydroxypentyl (meth)acrylate, 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 Base) 4-hydroxyhexyl acrylate, 4-hydroxyheptyl (meth)acrylate, 4-hydroxyoctyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate, (meth) 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)acrylate 6 -Hydroxyheptyl, 6-hydroxyoctyl (meth)acrylate, 6-hydroxynonyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, ( 7-hydroxyoctyl (meth)acrylate, 7-hydroxynonyl (meth)acrylate, 7-hydroxydecyl (meth)acrylate, 7-hydroxyundecyl (meth)acrylate, 8 (meth)acrylate -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-hydroxyldecyl (meth)acrylate, (meth) ) 9-hydroxytridecyl acrylate, 10-hydroxydecyl (meth)acrylate, 10-hydroxyundecyl (meth)acrylate, 10-hydroxydodecyl (meth)acrylate, 10 (meth)acrylate -Hydroxytridecyl ester, 10-hydroxytetradecyl (meth)acrylate, 11-hydroxyundecyl (meth)acrylate, 11-hydroxydodecyl (meth)acrylate, 11-hydroxyl (meth)acrylate Tridecyl ester, 11-hydroxytetradecyl (meth)acrylate, 11-hydroxypentadecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, 12-hydroxytridecyl (meth)acrylate Ester, 12-hydroxytetradecyl (meth)acrylate, 13-hydroxy (meth)acrylate Pentadecyl ester, 13-hydroxy tetradecyl (meth)acrylate, 13-hydroxy pentadecyl (meth) acrylate, 14-hydroxy tetradecyl (meth) acrylate, 14-hydroxy pentadecyl (meth) acrylate Monomers with hydroxyl groups such as esters, 15-hydroxypentadecyl (meth)acrylate, 15-hydroxyheptadedecyl (meth)acrylate, etc.;

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

Acrylic morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl acrylate modified by caprolactone, Monomers with heterocyclic groups such as 3,4-epoxycyclohexyl methyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran, etc.;

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

Among them, in terms of the reactivity of the (meth)acrylate polymer and the crosslinking agent, the monomers having a hydroxyl group or the monomers having a carboxyl group are preferred, and the monomers having a hydroxyl group and the monomers having a carboxyl group are particularly preferred. Any one of the body.

The monomer having a hydroxyl group is preferably 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 4-carboxybutyl acrylate, 5-carboxypentyl acrylate, and 6-carboxyhexyl acrylate. In particular, 2-carboxyethyl acrylate, 4-carboxybutyl acrylate, and 5-carboxypentyl acrylate can be used to obtain good durability.

The monomer having a carboxyl group is preferably acrylic acid.

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 the structural units constituting the (meth)acrylic resin (A).

With respect to 100 parts by mass of all the structural units of 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, and more preferably 0.5 parts by mass or more and 15 parts by mass Parts or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, particularly preferably 1 parts by mass or more and 7 parts by mass or less.

With respect to 100 parts by mass of all structural units of the (meth)acrylic resin (A), the content of the structural unit derived from the monomer having an aromatic group is preferably 20 parts by mass or less, particularly preferably 4 parts by mass or more and 20 parts by mass Parts or less, more preferably 4 parts by mass or more and 16 parts by mass or less.

The structural units derived from monomers other than (meth)acrylates can also include: structural units derived from styrene-based monomers, structural units derived from vinyl-based monomers, derived from multiple (methyl) groups in the molecule The structural unit of acryl-based monomers, the structural unit derived from (meth)acrylamide-based monomers, etc.

Styrenic monomers include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene , Butyl styrene, hexyl styrene, heptyl styrene, octyl styrene and other alkyl styrene; fluorostyrene, chlorostyrene, bromostyrene, dibromo styrene, iodostyrene and other halogenated benzene Ethylene; Nitrostyrene; Acetylstyrene; Methoxystyrene; Divinylbenzene, etc.

Vinyl monomers include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and other fatty acid vinyl esters; halogenation of vinyl chloride, vinyl bromide, etc. Ethylene; vinylidene dihalide such as vinylidene chloride; nitrogen-containing heteroaromatic ethylene such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, etc.; butadiene, isoprene, chloroprene, etc. The conjugated dienes; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

Monomers having plural (meth)acrylic acid 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)acrylic groups; monomers with 3 (meth)acrylic groups in the molecule, such as trimethylolpropane tri(meth)acrylate.

The (meth)acrylamide-based monomers include: N-methylol (meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxyl 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-oxobutyl)(meth)acrylamide , N-[2-(2-Oxy-1-imidazolinyl)ethyl](meth)propenamide, 2-propenylamino-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)(formaldehyde Base) acrylamide, N-[2-(1-methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl](formula Yl)acrylamide, N-[2-(2-methylpropoxy)ethyl](meth)acrylamide, N-(2-butoxyethyl)(meth)acrylamide, N-[2-(1,1-dimethylethoxy)ethyl](meth)acrylamide and the like. Among them, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl) Yl)acrylamide and N-(2-methylpropoxymeth)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 under high temperature environment can be improved, and the floating and peeling between the adherend and the adhesive layer and the aggregation failure of the adhesive sheet can be easily suppressed. weight When the weight average molecular weight is 2.5 million or less, it is advantageous from the viewpoint of coatability. From the viewpoint of having both the durability of the adhesive layer and the coatability of the adhesive, the weight average molecular weight is preferably 600,000 to 1.8 million, particularly preferably 700,000 to 1.7 million, and particularly preferably 1 million to 1.6 million. . In addition, the molecular weight distribution (Mw/Mn) represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2 to 10, preferably 3 to 8, more preferably 3 To 6. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value converted from standard polystyrene.

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 20Pa. s or less, particularly preferably 0.1 to 15Pa. s. When the viscosity is in this range, it is advantageous from the viewpoint of coating properties when the adhesive composition is applied to the substrate. Viscosity can be measured by 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, and an emulsion polymerization method, and the solution polymerization method is particularly preferred. The solution polymerization method includes, for example, 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, the monomer or thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer or thermal polymerization initiator may be added to the organic solvent. The aforementioned organic solvents include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone and methyl isobutyl ketone Ketones and so on. The thermal polymerization initiator can be a conventional thermal polymerization initiator. In addition, a photopolymerization initiator may be used instead of the thermal polymerization initiator, and a polymerization method based on ultraviolet rays or the like may be used.

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

〈Light selective absorption compound (B)〉

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

The so-called merocyanidin structure in the present invention means a partial structure represented by >N-C=C-C=C<. However, the merocyanidin structure of the present invention does not contain aromatic condensed rings (such as benzotriazole ring, benzimidazole ( 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。 In addition, the light selective absorption compound (B) having a merocyanidin structure in the present invention preferably contains no polymerizable group in the molecule. Here, the polymerizable group may include epoxy group, oxetanyl group,

Oxazolino group, aziridino group, vinyl group, α-methyl vinyl group, acryloyl group, methacryloyl group, allyl group, styryl group, (meth)acrylamide group And other ethylenic unsaturated groups.

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

ε(405)≧5 (1)

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

ε (405)/ ε (440)≧5 (2)

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

For the light selective absorption compound (B) with a merocyanidin structure, the value of ε (405) is preferably 5L/(g‧cm) or more, particularly preferably 10L/(g‧cm) or more, and more preferably 20L /(g‧cm) or more, particularly preferably 30L/(g‧cm) or more, usually 500L/(g‧cm) or less. The greater the value of ε (405), the easier it is to absorb light with a wavelength of 405nm, and the easier it is to exhibit the function of inhibiting the deterioration caused by ultraviolet light or short-wavelength visible light.

For the light selective absorption compound (B) having a merocyanidin structure, the value of ε (405)/ ε (440) is preferably 20 or more, more preferably 40 or more, still more preferably 70 or more, particularly preferably 80 the above. The adhesive layer formed by the adhesive composition containing the compound with a larger value of ε (405)/ ε (440) can absorb light near 405 nm wavelength without hindering the color performance of the display device. In addition, it is possible to suppress light degradation of display devices such as laminated optical films (retardation films) or organic EL elements.

Examples of the light selective absorption compound (B) having a merocyanidin 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 1 to 25 carbon atoms that may have a substituent, and 6 to 15 carbon atoms that may have a substituent The aromatic hydrocarbon group or heterocyclic group of the aforementioned aliphatic hydrocarbon group or aromatic hydrocarbon group -CH ₂ -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, and 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 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 having 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, isododecyl, undecyl Straight-chain or branched chain alkyl groups with carbon numbers of 1 to 25, such as cyclopropyl, lauryl, myristyl, cetyl, stearyl, etc.; the carbons of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Cycloalkyl having 3 to 25; cycloalkylalkyl having 4 to 25 carbons such as cyclohexylmethyl, etc., preferably alkyl having 4 to 25 carbons.

Examples of the substituent that the aliphatic hydrocarbon group having 1 to 25 carbons 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, and a nitro group.

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

The aromatic hydrocarbon groups having 6 to 15 carbons represented by R ¹ to R ⁵ include aryl groups having 6 to 15 carbons such as phenyl, naphthyl, anthryl, and biphenyl; benzyl, phenyl C7-15 aralkyl groups such as ethyl, naphthylmethyl, phenyl, etc.

Examples of the substituents that the aromatic hydrocarbon group having 6 to 15 carbons represented by R ¹ to R ⁵ may have include hydroxyl, cyano, halogen, mercapto, amino, nitro, alkoxy, and alkylthio. , Alkoxycarbonyl, acyl, acyloxy, -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 an alkyl group having 1 to 6 carbon atoms, R ^4A represents an alkyl group having 1 to 6 carbon atoms) and the like.

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

Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, An alkoxy group having 1 to 12 carbons such as undecyloxy and dodecyloxy.

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

Examples of the acyl group include an acyl group, a propyl group, and a butanyl group having 2 to 13 carbon atoms.

The acyloxy group includes methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, secondary butylcarbonyloxy, tertiary butyl Carbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy, 2-ethylhexylcarbonyloxy and other acyloxy groups having 2 to 13 carbon atoms.

Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, and 2-ethylhexyloxycarbonyl. , Nonoxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl and other alkoxycarbonyl groups having 2 to 13 carbons.

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

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

Examples of -SO ₂ R ^4A include methylsulfonyl and ethylsulfonyl.

The alkyl groups 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。 The heterocyclic groups represented by R ¹ to R ⁵ include: Pyrrolidine ring group, Pyrroline ring group, Imidazolidine ring group, Imidazoline ring group,

Oxazoline ring group, Thiazoline ring group, Piperidine ring group, Morpholine ring group, Piperazine ring group, Indole ring group, Isoindole ring group , Quinoline ring group, thiophene (Thiophene) ring group, pyrrole (Pyrrole) ring group, thiazoline ring group and furan (Furan) ring group and other aliphatic heterocyclic groups with 4 to 20 carbons or 3 to 20 carbon The aromatic heterocyclic group and so on.

The 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, and n-butyl. Pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl , Lauryl, myristyl, cetyl, stearyl and other linear or branched chain alkyl groups with 1 to 25 carbon atoms.

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 a carbon number of 1 to 25 that may have a halogen atom, and at least one methylene group contained in the hydrocarbon group may be substituted by 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 ₂ -* ¹ ;

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 position with R ^111;

* Indicates the bonding site with carbon atom. ]

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

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

The hydrocarbon groups with 1 to 25 carbon atoms and which may have halogen atoms 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, isododecyl, eleven Straight-chain or branched chain alkyl groups with carbon numbers of 1 to 25, such as cyclopropyl, lauryl, myristyl, cetyl, stearyl, etc.; the carbons of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Cycloalkyl with 3 to 25; Cycloalkylalkyl with 4 to 25 carbons such as cyclopropylmethyl, cyclohexylmethyl, etc.; and 6 carbons such as phenyl, naphthyl, anthryl, biphenyl, etc. Aryl groups of 7 to 25 carbons such as benzyl, phenylethyl, naphthylmethyl, phenyl, etc.; monofluoromethyl, difluoromethyl, trifluoromethyl, 2, 2,2-Trifluoroethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl and other fluorinated alkyl groups with 1 to 25 carbon atoms; monochloromethyl, Dichloromethyl, trichloromethyl, 2,2,2-trichloroethyl, perchloroethyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, etc. carbon number 1 to Chlorinated alkyl group of 25; monobromomethyl, dibromomethyl, tribromomethyl, 2,2,2-tribromoethyl, perbromoethyl, perbromopropyl, perbromobutyl, perbromo Brominated alkyl groups of 1 to 25 carbons such as pentyl and perbromohexyl; monoiodomethyl, diiodomethyl, triiodomethyl, 2,2,2-triiodoethyl, periodoethyl, Periodopropyl, periodobutyl, periodopentyl, periodohexyl and other iodinated alkyl groups with 1 to 25 carbon atoms.

The alkyl group having 1 to 6 carbon atoms represented by R ¹¹² , R ¹¹³ and R ¹¹⁴ may be the same as the alkyl group having 1 to 6 carbon atoms represented ^{by R 1A.}

R ^{111 is} preferably a hydrocarbon group with 4 to 25 carbons which may have a halogen atom, and particularly preferably a hydrocarbon group with 4 to 12 carbons which may have a halogen atom.

X ^{1 is} preferably -CO-* ¹ and -COO-* ¹ .

Preferably, the electron withdrawing groups represented by R ⁶ and R ⁷ are each independently a cyano group, a nitro group, a fluoro group, a trifluoromethyl group, and a group represented by the 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 mutually bonding is a nitrogen-containing ring structure including a nitrogen atom to which R 1} and R ^{2 are} bonded, and examples thereof include a 4-membered ring to a 10-membered ring nitrogen-containing heterocyclic ring. The ring structure formed by the mutual bonding of R ¹ and R ² may be a monocyclic ring, a polycyclic ring, or a condensed ring. Specific examples include: pyrrolidine ring, dihydropyrrole ring, imidazoline ring, imidazoline ring,

Oxazoline ring, thiazoline ring, piperidine ring, morpholine ring, piperazine ring, indole ring, isoindole ring, etc. The ring formed by R ¹ and R ² bonded to each other may have a substituent. Examples of the substituent include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl; Alkoxy groups with 1 to 12 carbons 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 bonded to each other is a ^{nitrogen-containing ring structure including a nitrogen atom to which R 2} is bonded, and examples thereof include a 4-membered to 10-membered nitrogen-containing heterocyclic ring. The ring structure formed by R ² and R ³ bonding to each other may be a monocyclic ring, a polycyclic ring, or a condensed ring. Specific examples include: pyrrolidine ring, dihydropyrrole ring, imidazoline ring, imidazoline ring,

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

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

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

* Indicates the bonding position. ]

The ring W ^{1 is} preferably a 5-membered ring or a 6-membered ring having a nitrogen atom and X as constituent elements.

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

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

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

The ring structure formed by R ² and R ³ mutually bonding is preferably a ring structure represented by the following formula (I-4).

[In formula (1-4), R ¹ represents 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 carbon atom.

m2 is preferably 2 or 3, more preferably 2.

The ring structure formed by bonding R ² and R ^{4 to} each other includes a nitrogen-containing heterocyclic structure of a 4-membered ring to a 10-membered ring, and a nitrogen-containing heterocyclic structure of a 5-membered ring to a 9-membered ring is preferable. The ring structure formed by R ² and R ⁴ bonding to each other may be a monocyclic ring or a polycyclic ring. These rings may have substituents. Examples of this ring structure include a pyrrole ring, an indole ring, a pyrimidine ring, and the rings described below.

The ring structure formed by R ² and R ⁴ bonded to each other may have a substituent. Examples of the substituent include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl. ;Methoxy, ethoxy, propoxy, butoxy and other alkoxy groups with carbon numbers 1 to 12; amino groups, methylamino groups, dimethylamino groups, etc. are defined by -NR ^22A R ^22B The group represented (R ^22A and R ^22B each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms); methylthio, ethylthio, propylthio, butylthio, pentylthio, etc. have 1 carbon atoms Alkylthio to 12; C4-9 heterocyclic groups such as pyrrolidinyl, piperidinyl, morpholinyl, etc.

The ring structure formed by R ³ and R ⁶ being mutually bonded is a ring structure in which R ³ -C=CC=CR ⁶ forms a skeleton of the ring. For example, phenyl group etc. can be mentioned.

The ring structure formed by the mutual bonding of R ⁵ and R ^{7 includes the ring structures described below.} The ring structure formed by R ⁵ and R ⁷ 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 with 1 to 12 carbons 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 structure described below. The ring structure formed by R ⁶ and R ⁷ 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, and butoxy groups; ethylenically unsaturated groups described later, etc.

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

It is preferable that at least any 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 that may have a substituent, and a carbon number that may have a substituent 6 to 15 aromatic hydrocarbon groups or heterocyclic groups, the aliphatic hydrocarbon group or aromatic hydrocarbon group contains -CH ₂ -can be -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, and 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 with 1 to 25 carbons and which may have substituents represented by R ¹¹ to R ¹⁵ can be the same as the aliphatic hydrocarbon group with 1 to 25 carbons and which may have substituents represented ^{by R 1} .

The aromatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent represented by R ¹¹ to R ¹⁵ may be the same as the aromatic hydrocarbon group having 6 to 15 carbon atoms which 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.}

The alkyl group having 1 to 25 carbon atoms represented by R ¹⁶ and R ¹⁷ may be the same as the alkyl group having 1 to 25 carbon atoms represented ^{by R 6.}

The electron withdrawing group represented by R ¹⁶ and R ¹⁷ may be the same as the electron withdrawing group represented ^{by R 6.}

The alkyl group having 1 to 6 carbon atoms represented by R ^11A may be the same as the alkyl group having 1 to 6 carbon atoms represented ^{by R 1A.}

Examples of the ring structure formed by R ¹¹ and R ^{12 that} can be bonded to each other are the same as the ring structure formed by R ¹ and R ^{2 that} can be bonded to each other.

Examples of the ring structure formed by R ¹² and R ^{13 that} can be bonded to each other are the same as the ring structure formed by R ² and R ^{3 that} can be bonded to each other. The ring structure formed by R ¹² and R ^{13 that} can be bonded to each other is preferably a single ring structure.

Examples of the ring structure formed by R ¹² and R ^{14 that} can be bonded to each other are the same as the ring structure formed by R ² and R ^{4 that} can be bonded to each other. The ring structure formed by R ¹² and R ^{14 that} can be bonded to each other is preferably a single ring structure. The ring structure formed by R ¹² and R ¹⁴ may be bonded to each other is preferably an aromatic ring, and more preferably a pyrimidine ring structure.

Preferably, R ¹¹ , R ¹³ and R ¹⁵ are each independently an aliphatic hydrocarbon group having a carbon number of 1 to 25 which may have a substituent, particularly preferably an alkyl group having a carbon number of 1 to 25 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, particularly preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.

Preferably, R ¹² and R ¹⁴ are each independently an aliphatic hydrocarbon group having a carbon number of 1 to 25, 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 the formula (I-4), the ring structure represented by the formula (I-4-1) or the ring structure represented by the formula (I-4-2) are preferred, and particularly preferred It is a ring structure represented by formula (I-4-1). The ring structure represented by the formula (I-4), the formula (I-4-1) or the formula (I-4-2) may further have a substituent.

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

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

Preferably, the ethylenically unsaturated group represented by R ¹⁶ and R ¹⁷ are each independently a vinyl group, an acrylic group, a methacryl group, and a group represented by the formula (I-2). More preferably *-CO-O-(CH ₂ )nX ² [X ² represents a vinyl group, an acrylic group or a methacrylic group, and represents an integer of n=1 to 10 (preferably n=2 to 6 Integer)].

The compound represented by formula (II) in which R ¹² and R ¹³ are mutually bonded 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 carbons.

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

The light selective absorption compound (B) having a merocyanidin structure includes the following compounds.

The light selective absorption compound having a partial 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.

Relative to 100 parts by mass of the resin (A), the content of the light selective absorption compound (B) having a merocyanidin 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 Parts, more preferably 2 to 7 parts by mass.

It may contain two or more light selective absorption compounds (B) having a merocyanidin structure.

〈Light-curable component (C)〉

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

The photocurable component (C) may be a photoradical curable component such as a compound or an oligomer that is cured by a radical polymerization reaction by light irradiation. In addition, it may also be a photocationic curable component such as a compound or an oligomer that is cured by cationic polymerization through light irradiation. In addition, the light referred to herein is preferably an active energy ray such as visible light, ultraviolet light, X-ray, or electron beam.

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

<Optical radical polymerizable ingredients>

Examples of the optical radical polymerizable component include radical polymerizable (meth)acrylic compounds.

Examples of (meth)acrylic compounds include: (meth)acrylate monomers having at least one (meth)acryloyloxy group in the molecule, (meth)acrylamide monomers, and (Meth)acrylic acid group-containing compounds such as (meth)acrylic acid oligomers having at least two (meth)acrylic acid groups. The (meth)acrylic oligomer is preferably a (meth)acrylate oligomer having at least two (meth)acryloyloxy groups in the molecule. (Meth)acrylic compound can be used individually by 1 type or in combination of 2 or more types.

Examples of (meth)acrylate monomers include monofunctional (meth)acrylate monomers having one (meth)acryloxy group in the molecule, and two (meth)acrylic acid ester monomers in the molecule. A bifunctional (meth)acrylate monomer of an oxy group, and a multifunctional (meth)acrylate monomer having 3 or more (meth)acryloxy groups in the molecule.

Monofunctional (meth)acrylate monomers include alkyl (meth)acrylates. In the alkyl (meth)acrylate, when the carbon number of the alkyl group is 3 or more, it may be any of linear, branched and cyclic. The alkyl (meth)acrylate can include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Isopropyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.

In addition, monofunctional (meth)acrylate monomers can also include: (meth)acrylic acid benzyl esters such as aralkyl (meth)acrylate; (meth)acrylic acid isobornyl esters and other terpene alcohol (meth) (Meth)acrylate; tetrahydrofurfuryl (meth)acrylate and other (meth)acrylates with tetrahydrofurfuryl structure; cyclohexyl (meth)acrylate, cyclohexyl methyl methacrylate, dicyclopentan acrylate (Meth)acrylates having a cycloalkyl group at the alkyl position, such as esters, dicyclopentenyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, etc.; (meth)acrylic acid N, N-dimethylaminoethyl (meth)acrylic acid aminoalkyl esters; (meth)acrylic acid 2-phenoxyethyl, (meth)acrylic acid dicyclopentenoxyethyl, (meth) (Meth)acrylic acid esters having ether bonds in the alkyl group, such as ethyl carbitol acrylate, phenoxy polyethylene glycol (meth)acrylate, and the like.

Furthermore, monofunctional (meth)acrylate monomers include: monofunctional (meth)acrylate having a hydroxyl group at the alkyl part; monofunctional (meth)acrylate having a carboxyl group at the alkyl part. Examples of monofunctional (meth)acrylates having a hydroxyl group at the alkyl group include: 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, and 4 (meth)acrylate -Hydroxybutyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, neopentaerythritol mono(meth)acrylate. Examples of monofunctional (meth)acrylates having a carboxyl group at the alkyl group include: 2-carboxyethyl (meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate (n=2), 1-[2-(Meth)acryloyloxyethyl]phthalic acid, 1-[2-(meth)acryloyloxyethyl]hexahydrophthalic acid, 1-[2-( (Meth)acryloyloxyethyl]succinic acid, 4-[2-(meth)acryloyloxyethyl]trimellitic acid, N-(meth)acryloyloxy-N',N' -Dicarboxymethyl p-phenylenediamine and so on.

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 combined with the nitrogen atom of (meth)acrylamide A ring is formed, and this ring may have an oxygen atom as a member of the ring in addition to the carbon atom and the nitrogen atom of (meth)acrylamide. Furthermore, a substituent such as an alkyl group or pendant oxygen (=O) may be bonded to the carbon atom 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-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 like N,N-dialkyl(meth)acrylamide, etc. In addition, the N-substituent may be an alkyl group having a hydroxyl group. Examples include N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N -(2-Hydroxypropyl)(meth)acrylamide and the like. Furthermore, specific examples of the N-substituted (meth)acrylamide forming a 5-membered ring or a 6-membered ring include N-propenylpyrrolidine, 3-propenyl-2-

Oxazolinone, 4-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, and the like.

Examples of bifunctional (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( Alkyl glycol di(meth)acrylates such as meth)acrylate, 1,9-nonanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate;

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;

Halogen-substituted di(meth)acrylate such as tetrafluoroethylene glycol di(meth)acrylate;

Di(meth)acrylic acid trimethylolpropane ester, di(meth)acrylate di(trimethylol)propane ester, neopentylerythritol di(meth)acrylate and other aliphatic polyols基)acrylate;

Hydrogenated dicyclopentadiene di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, etc. hydrogenated dicyclopentadiene or tricyclodecanediol di(meth)acrylic acid 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-bis(meth)acrylic acid

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

Alkyl Glycol Ester] etc.

Alkyl Glycol or Di

Di(meth)acrylate of alkanediol;

Diacrylic acid of bisphenol A ethylene oxide adduct, diacrylic acid of bisphenol F ethylene oxide adduct, bisphenol A or bis(methyl) of bisphenol F ethylene oxide adduct, etc. )Acrylate;

Acrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of bisphenol F diglycidyl ether, bisphenol A or bisphenol F di(meth)acrylate epoxy ester; bis(methyl) Polysiloxane acrylate;

The di(meth)acrylate of neopentyl glycol hydroxytrimethylacetate;

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

2,2-bis[4-(meth)propenyloxyethoxyethoxycyclohexyl]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 and the like.

Examples of polyfunctional (meth)acrylate monomers having three or more functions include: glycerol tri(meth)acrylate, alkoxyglyceryl tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate , Di(trimethylol)propane tri(meth)acrylate, di(trimethylol)propane tetra(meth)acrylate, neopentylerythritol tri(meth)acrylate, tetra(methyl) Tripentaerythritol acrylate, dineopentaerythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, etc. Poly(meth)acrylate of the aliphatic polyol; poly(meth)propylene of the halogen-substituted polyol with more than 3 functions Acid ester; tri(meth)acrylate of alkylene oxide adduct of glycerol; tri(meth)acrylate of alkylene oxide adduct of trimethylolpropane; 1,1,1-tri[( Meth) propylene oxy ethoxy ethoxy] propane; tris (hydroxyethyl) isocyanuric acid tris (meth) acrylate and the like.

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 Shinnakamura Chemical Co., Ltd.).

(Meth)acrylic oligomers include (meth)acrylate urethane oligomers, polyester (meth)acrylate oligomers, (meth)acrylate epoxy ester oligomers, and the like.

The (meth)acrylate urethane oligomer is a compound having a urethane bond (-NHCOO-) and at least two (meth)acrylic groups in the molecule. Specifically, it may be: a hydroxyl-containing (meth)acrylic monomer each having at least one (meth)acrylic acid group and at least one hydroxyl group in the molecule, and a urethane reaction product of polyisocyanate; Or a urethane compound containing an isocyanate group at the end obtained by reacting a polyol with a polyisocyanate, and a (methyl) group each having at least one (meth)acrylic acid group and at least one hydroxyl group in the molecule The urethane reaction product of acrylic monomer, etc.

The hydroxyl-containing (meth)acrylic monomer used in the urethane reaction may be, for example, a hydroxyl-containing (meth)acrylate monomer. Specific examples include: 2-hydroxyethyl (meth)acrylate, ( 2-hydroxypropyl meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glyceryl di(meth)acrylate, di(meth)acrylate Base) trimethylolpropane acrylate, neopentylerythritol tri(meth)acrylate, dineopentylerythritol penta(meth)acrylate. Specific examples other than the hydroxyl-containing (meth)acrylate monomer include: N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, etc. Base) acrylamide monomer.

The polyisocyanates provided for 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 (for example, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, etc.), three Di- or tri-isocyanates such as phenylmethane triisocyanate and dibenzylbenzene triisocyanate, and polyisocyanates obtained by polymerizing the above-mentioned diisocyanates.

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

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

In addition to polyalkylene glycol, the polyether polyol may be a polyoxyalkylene-denatured polyol obtained by the reaction of the above-mentioned polyol or dihydroxybenzenes and alkylene oxide.

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

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

Polybasic carboxylic acids or the anhydrides include: succinic anhydride, adipic acid, maleic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, phthalic acid , Succinic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.

Polyols include: 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, Trimethylolpropane, bis(trimethylol)propane, neopentylerythritol, dineopentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerin, hydrogenated Bisphenol A and so on.

The epoxy ester oligomer of (meth)acrylate can be obtained by the addition reaction of polyglycidyl ether and (meth)acrylic acid. The epoxy (meth)acrylate oligomer has at least 2 (meth)acryloyloxy 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 photo radical curable component preferably contains a (meth)acrylate compound, and more preferably contains a polyfunctional (meth)acrylate compound.

〈Photocationic curable ingredients〉

Examples of the photocationic curable component include epoxy compounds, oxygen compounds, and vinyl compounds.

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

The alicyclic epoxy compound is a compound having one or more epoxy groups bonded to an alicyclic ring in the molecule. The epoxy group bonded to the alicyclic ring includes, for example, oxabicyclohexyl and oxabicycloheptyl Wait. The alicyclic epoxy compound may be a compound containing one alicyclic epoxy group, or two or more alicyclic epoxy groups.

Examples of the alicyclic epoxy compound include: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3 ,4-Epoxy-6-methylcyclohexane carboxylate, ethylene bis(3,4-epoxycyclohexane carboxylate), bis(3,4-epoxycyclohexylmethyl)hexanedi Ester, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, diethylene glycol bis(3,4-epoxycyclohexyl methyl ether), ethylene glycol bis (3,4-epoxycyclohexyl methyl ether), 2,3,14,15-diepoxy-7,11,18,21-tetraoxatrispir [5.2.2.5.2.2] icosane , 3-(3,4-epoxycyclohexyl)-8,9-epoxy-1,5-dioxaspir[5.5]undecane, 4-vinylcyclohexene dioxide, lemon dioxide Oil essence, bis(2,3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, etc.

The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule. 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 the oligomers thereof; phenols Novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin, etc.; 2,2',4,4'-tetrahydroxydiphenylmethane glycidyl ether, Multifunctional epoxy compounds such as glycidyl ether of 2,2',4,4'-tetrahydroxydiphenyl ketone; multifunctional epoxy resins such as epoxidized polyvinyl phenol.

Hydrogenated epoxy compounds are glycidyl ethers of polyhydric alcohols with alicyclic rings, which can selectively hydrogenate aromatic polyhydric alcohols with aromatic rings in the presence of a catalyst and under pressure to obtain nuclear hydrogenated polyhydroxy compounds , And then make this nuclear hydrogenated polyhydroxy compound glycidyl etherification to obtain. Specific examples of aromatic polyols include, for example, bisphenol-type compounds such as bisphenol A, bisphenol F, and bisphenol S; phenolic phenol resins, cresol phenolic resins, hydroxybenzaldehyde phenolic phenolic resins, and other phenolic resins ; Multifunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxydiphenylketone, polyvinyl alcohol. By reacting epichlorohydrin In response to the alicyclic polyol obtained by hydrogenating the aromatic ring of the aromatic polyol, glycidyl ether can be formed. Among the hydrogenated epoxy compounds, preferred ones include hydrogenated glycidyl ether of bisphenol A.

The aliphatic epoxy compound is a compound 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; trimethylolpropane triglycidyl ether, neopentyl erythritol tetraglycidyl ether and other trifunctional epoxy compounds; 4-vinyl dioxide Cyclohexene, limonene dioxide, etc. have epoxy compounds with an epoxy group directly bonded to an alicyclic ring and an oxirane ring bonded to aliphatic carbon atoms.

Oxygen compounds are compounds containing more than one oxygen ring (oxygen group) in the molecule. Oxygen compounds include 3-ethyl-3-hydroxymethyloxygen and 2-ethylhexyloxygen. , 1,4-bis[(3-ethyloxy-3-yl)methoxymethyl]benzene, 3-ethyl-3[{(3-ethyloxy-3-yl)methoxy }Methyl]oxo, 3-ethyl-3-(phenoxymethyl)oxo, 3-(cyclohexyloxyoxy)methyl-3-ethyloxo, and the like.

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 such as ether, stearyl vinyl ether, octadecenyl vinyl ether, etc., with carbon numbers of 5 to 20; 2-hydroxyethyl vinyl ether, 3-hydroxypropyl ethylene Vinyl ether, 4-hydroxybutyl vinyl ether and other hydroxyl-containing vinyl ethers; 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 erythritol tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane Alkyl trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane monovinyl ether, 1,4-Dihydroxymethyl cyclohexane divinyl ether and other polyhydric alcohols mono-to-polyvinyl ether; diethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol monobutyl Polyalkylene glycol mono to divinyl ether such as monovinyl ether; glycidyl vinyl ether, ethylene glycol vinyl ether methacrylate, etc.

Relative to 100 parts by mass of the resin (A), 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 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. In addition, the light referred to herein is preferably an active energy ray such as visible light, ultraviolet light, X-ray, or electron beam.

Specific examples of the photoinitiator (D) include compounds that generate free radicals by absorbing the energy of light (photo-radical generators), and compounds that generate cations (acids) by absorbing the energy of light (photocations). Agent), a compound that generates anion (base) by absorbing the energy of light (photobase generator).

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

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

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

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

The α -amino alkyl phenone compound can be exemplified by: 2-methyl-2-morpholine-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1 -(4-morpholinephenyl)-2-benzylbutane-1-one, 2-dimethylamino-1-(4-morpholinephenyl)-2-(4-methylphenylmethyl) Yl)butane-1-one, etc., preferably 2-methyl-2-morpholine-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1 -(4-morpholinephenyl)-2-benzylbutan-1-one and the like. α -Aminoalkylphenone compounds can also be used Irgacure (registered trademark) 127, 184, 369, 369E, 379EG, 651, 907, 1173, 2959 (the above are made by BASF Japan Co., Ltd.), Seikuol (registered trademark) Commercial products such as BEE (manufactured by Seiko Chemical Co., Ltd.).

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

The benzophenone compound includes, for example, benzophenone, methyl phthalate, 4-phenylbenzophenone, and 4-benzophenone-4'-methyldiphenyl sulfide. , 3,3',4,4'-tetra(tertiary butylperoxycarbonyl) diphenyl ketone, 2,4,6-trimethyl diphenyl ketone, etc. Commercial products can be used for the benzophenone compound.

Examples of oxime ester compounds include: N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy-1-( 4-Phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H -Carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl- 2,4-Dioxolenemethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine and the like. The oxime ester compound can also use Irgacure OXE-01, OXE-02, OXE-03 (the above are made by BASF Japan Co., Ltd.), N-1919, NCI-730, NCI-831, NCI-930 (made by ADEKA), Commercial products such as PBG3057 (manufactured by TRONLY).

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

The light radical 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-arene complexes.

The aromatic iodonium salt is a compound having a diaryl iodonium salt cation, and the cation typically includes a diphenyl iodonium salt cation. The aromatic sulfonate is a compound having a triarylsulfonate cation, and the cation typically includes a triphenylsulfonate cation or 4,4'-bis(diphenylsulfonyl)diphenylsulfide cation. The aromatic diazonium salt is a compound having a diazonium salt cation, and the cation typically includes a benzene diazonium salt cation. In addition, the iron-allene complex is typically a cyclopentadienyl iron(II) allene cation complex salt.

The cation system shown above and an anion (anion) are paired to constitute a photocation generator. When citing examples of the anions constituting the photocation generator, there are special phosphorus anions [(Rf) _n PF _6-n ]-, hexafluorophosphate anion PF ₆ -, hexafluoroantimonate anion SbF ₆ -, Pentafluorohydroxyantimonate anion SbF ₅ (OH)-, hexafluoroarsenate anion AsF ₆ -, tetrafluoroborate anion BF ₄ -, four (pentafluorophenyl) borate anion B(C ₆ F ₅ ) ₄ -etc. Among them, from the viewpoints of the curability of the cationic polymerizable compound and the safety of the resulting light selective absorption layer, the special phosphorus anion [(Rf) _n PF _6-n ]-, the hexafluorophosphate anion PF are preferred ₆ -, Si (pentafluorophenyl) borate anion B(C ₆ F ₅ ) ₄ -.

Relative to 100 parts by mass of the resin (A), 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 0.2 parts by mass. 3 parts by mass.

〈Crosslinking agent (E)〉

The adhesive composition of the present invention may contain a crosslinking agent (E).

The cross-linking agent (E) includes isocyanate-based cross-linking agents, epoxy-based cross-linking agents, Aziridine-based cross-linking agents, metal chelate-based cross-linking agents, etc., especially from the adhesive composition From the viewpoints of pot life, durability of the adhesive layer, and crosslinking speed, an isocyanate-based crosslinking agent is preferred.

The isocyanate-based crosslinking agent is preferably a compound having at least two isocyanate groups (-NCO) in the molecule, for example, aliphatic isocyanate-based compounds (for example, hexamethylene diisocyanate, etc.), alicyclic isocyanate-based Compounds (e.g. isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate), aromatic isocyanate compounds (e.g. toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate) Isocyanate, triphenylmethane triisocyanate, etc.). In addition, the crosslinking agent (E) may be an adduct formed from a polyol compound of the aforementioned isocyanate compound (adduct) [for example, an adduct formed from glycerin, trimethylolpropane, etc.], isocyanurate Acid ester compounds, biuret compounds, and urethanes that undergo addition reaction with polyether polyols or polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. Derivatives such as prepolymer type isocyanate compounds. The crosslinking agent (E) can be used alone or in combination of two or more kinds. Among these, representative ones include aromatic isocyanate compounds (e.g., toluene diisocyanate, xylene diisocyanate), aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate), or these polyol compounds ( For example, adducts formed by glycerol, trimethylolpropane), or isocyanurates. When the crosslinking agent (E) is an aromatic isocyanate compound and/or these adducts formed by a polyol compound or an isocyanurate compound, it may be beneficial to the optimum crosslinking density (or crosslinking The formation of the structure) can improve the durability of the adhesive layer. Especially in the case of toluene diisocyanate-based compounds and/or these adducts formed of polyol compounds, durability can be improved even when, for example, an adhesive layer is applied to a polarizing plate.

Relative to 100 parts by mass of the resin (A), the content of the crosslinking 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.

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

Examples of the silane compound (F) include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxy) silane, and 3-glycidoxypropyl trimethoxysilane. , 3-glycidoxy propyl triethoxysilane, 3-glycidoxy propyl methyl dimethyl dimethyl siloxane, 3-glycidoxy propyl ethoxy dimethyl siloxane, 2-( 3,4-Epoxycyclohexyl) ethyl trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-Mercaptopropyl trimethoxysilane, etc.

The silane compound (F) may be a polysiloxane oligomer. When a specific example of the polysiloxane oligomer is expressed in the form of a combination of monomers, it is as follows.

3-Mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer Mercapto-containing propyl oligomers such as 3-mercaptopropyl triethoxysilane-tetraethoxysilane oligomers; mercaptomethyltrimethoxysilane-tetramethoxysilane oligomers, mercaptomethyltrimethoxysilane oligomers -Tetraethoxysilane oligomer, mercaptomethyltriethoxysilane-tetramethoxysilane oligomer, mercaptomethyltriethoxysilane-tetraethoxysilane oligomer and other mercapto-containing methyl oligomers; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltri Ethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethyl Oxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer , 3-glycidoxy propyl methyl diethoxysilane-tetraethoxy silane copolymer, etc. containing 3-glycidoxy propyl copolymer; 3-methacryloxy propyl trimethoxy Silane-tetramethoxysilane oligomer, 3-methacryloxypropyltrimethoxysilane Alkyl-tetraethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetraethyl Oxysiloxane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethyl Oxysiloxane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetraethyl Methacryloxypropyl oligomers such as oxysilane oligomers; 3-propyleneoxypropyltrimethoxysilane-tetramethoxysilane oligomers, 3-propyleneoxypropyltrimethoxy Silane-tetraethoxysilane oligomer, 3-propenoxypropyl triethoxysilane-tetramethoxysilane oligomer, 3-propenoxypropyl triethoxysilane-tetraethoxysilane oligomer Compounds, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3- Propyleneoxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propyleneoxypropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. containing propyleneoxy group Propyl oligomer; vinyl trimethoxysilane-tetramethoxysilane oligomer, vinyl trimethoxysilane-tetraethoxysilane oligomer, vinyl triethoxysilane-tetramethoxysilane oligomer, ethylene Triethoxysilane-tetraethoxysilane oligomer, vinyl methyl dimethoxysilane-tetramethoxysilane oligomer, vinyl methyl dimethoxysilane-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 Oxysiloxane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, Amine 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 carbons or a divalent alicyclic hydrocarbon group with 3 to 20 carbons. The -CH ₂ -constituting the alkanediyl group and the alicyclic hydrocarbon group can be controlled by -O -Or -CO- substituted; R ⁴¹ represents an alkyl group having 1 to 5 carbons, and R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent an alkyl group having 1 to 5 carbons or a carbon number of 1 To 5 alkoxy. ]

The alkanediyl groups having 1 to 20 carbon atoms represented by A 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. The divalent alicyclic hydrocarbon group having a carbon number of 3 to 20 includes 1,3-cyclopentanediyl and 1,4-cyclohexanediyl. _{The -CH 2} -substituted by -O- or -CO- constituting the alkanediyl group and the alicyclic hydrocarbon _{group may include: -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 -.

The alkyl groups having 1 to 5 carbon atoms represented by R ⁴¹ to R ⁴⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, and pentyl. ^{The alkoxy groups with carbon numbers from 1 to 5 represented by 42} to R ⁴⁵ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tertiary butoxy. And pentoxy.

The silane compound represented by the formula (f1) includes, for example, (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl) Yl)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) 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 10alkanes; bis(dimethoxymethylsilyl)methane, 1,2 -Bis(dimethoxymethylsilyl)ethane, 1,2-bis(dimethoxyethylsilyl)ethane, 1,4-bis(dimethoxymethylsilyl)butane , 1,4-bis(dimethoxyethylsilyl)butane, 1,6-bis(dimethoxymethylsilyl)hexane, 1,6-bis(dimethoxyethylsilyl) Yl)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. The bis (mono C1 to 5 alkoxy two C1 to 5 alkyl silyl) C1 to 10 alkane and so on. Among them, preferred are 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, and 1,4-bis(trimethoxysilyl)butane , 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.

Relative to 100 parts by mass of the resin (A), 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, more preferably 0.1 to 1 parts by mass Copies.

The adhesive composition may further contain an antistatic agent.

Examples of the antistatic agent include surfactants, silicone compounds, conductive polymers, ionic compounds, and the like, and ionic compounds are preferred. The ionic compound can be exemplified by conventional ones. Examples of the cationic component constituting the ionic compound include organic cations and inorganic cations. Examples of organic cations include pyridinium salt cations, pyrrolidine salt cations, piperidine salt cations, imidazole salt cations, ammonium salt cations, sulfonium salt cations, and phosphonium salt cations. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation, and cesium cation; alkaline earth metal cations such as magnesium cation and calcium cation. In particular, from the viewpoint of compatibility with (meth)acrylic resins, pyridinium cations, imidazolium cations, pyrrolidine cations, lithium cations, and potassium cations are preferred. The anion component constituting the ionic compound may be either inorganic anion or organic anion, and in terms of antistatic performance, it is preferably an anion component containing a fluorine atom. Examples of the anion component containing fluorine atom include hexafluorophosphate anion [(PF ₆ -)], bis(trifluoromethanesulfonyl) imine anion [(CF ₃ SO ₂ ) ₂ N-], bis( Fluorosulfonyl) imine anion [(FSO ₂ ) ₂ N-], tetrakis(pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B-] and the like. This ionic compound can be used alone or in combination of two or more kinds. Particularly preferred are bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N-], bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N-], four (Pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B-].

In terms of the stability of the antistatic performance of the adhesive layer formed from the adhesive composition over time, it is preferably an ionic compound that is solid at room temperature.

The content of the antistatic agent relative to 100 parts by mass of the resin (A) 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.

The adhesive composition may further contain one or more solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, pigments, rust inhibitors, inorganic fillers, light scattering particles, etc. The additives.

<Adhesive layer>

The adhesive layer of the present invention can be formed, for example, by dissolving or dispersing the adhesive composition of the present invention in a solvent to form a solvent-containing adhesive composition, and then coating this 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 referred to as a photocured material of the adhesive composition.

The base material is preferably a plastic film, specifically, a release film after a mold release treatment is applied. Examples of peeling films include: applying polysiloxane treatment to one side of a film made of resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, etc. Mold release handler.

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

The active energy ray irradiation after drying of the coating film is preferably ultraviolet irradiation. The illuminance of the irradiated ultraviolet rays is preferably 10 mW/cm ² to 3000 mW/cm ² . In addition, the cumulative light quantity of ultraviolet rays is preferably 10 mJ/cm ² to 5000 mJ/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 satisfying the following formula (3), and more preferably an adhesive layer satisfying the following formula (4).

A(405)≧0.5 (3)

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

A(405)/A(440)≧5 (4)

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

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, which makes it easy to deteriorate components (such as display devices such as organic EL elements or liquid crystal retardation films, etc.) due to light near the wavelength of 400nm Cause degradation. The value of A(405) is preferably 0.6 or more, more 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 405nm relative to the absorption at a wavelength of 440nm. The larger the value, the specific absorption in the wavelength region near the wavelength of 405nm. The value of A(405)/A(440) is preferably 10 or more, more 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% by mass, preferably 60 to 99% by mass, particularly preferably 70 to 95% by mass, and more preferably 75 to 90% by mass.

<Optical film with adhesive layer>

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

An adhesive layer optical film in which an optical film is laminated on at least one surface of the adhesive layer of the present invention is also included in 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 this on the surface of the optical film and irradiating active energy rays after drying And formed. In addition, an adhesive layer may be formed on the release film in the same manner, and the adhesive layer may be laminated (transferred) on the surface of the optical film.

The optical film is a film with optical functions such as light penetration, reflection, and absorption. The optical film may be a single-layer film or a multilayer film. The optical film includes, for example, a polarizing film, a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, a condensing film, etc., and a polarizing film, a retardation film, or these laminated films are preferred.

The light-concentrating film is used for the purpose of light path control, etc. It can be a scalloped array sheet, a lens array sheet, a sheet with dots, etc.

The brightness enhancement film is used for the purpose of enhancing the brightness in a liquid crystal display device to which a polarizing plate is applied. Specific examples include: a reflective polarizing separator designed by laminating a plurality of films with different refractive index anisotropy to produce anisotropy in reflectance, an alignment film of cholesteric liquid crystal polymer or its alignment liquid crystal The layer is supported on the circularly polarized separator on the base film, etc.

Polarizing film is a film with the following properties, that is, it absorbs linearly polarized light with a vibration plane parallel to its absorption axis, and transmits linearly polarized light with a vibration plane orthogonal to the absorption axis (parallel to the penetration axis) For the film, for example, a film in which a dichroic dye is adsorbed and aligned on 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 generally 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formaldehyde and polyvinyl acetal modified by aldehydes may also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.

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

For example, the polarizing film is a step of uniaxially stretching the blank material film, a step of dyeing the film with a dichroic pigment to adsorb the dichroic pigment, a step of treating the film with an aqueous solution of boric acid, and a step of washing the film, and finally drying And made. The thickness of the polarizing film is usually 1 to 30 μm, and 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, it is a polarizing plate in which a protective film is provided on at least one surface of the polarizing film via an adhesive.

The adhesive system uses a conventional adhesive, and may be a water-based adhesive or an active energy ray-curable adhesive.

The water-based adhesives include commonly used water-based adhesives (for example, adhesives composed of polyvinyl alcohol-based resin aqueous solutions, water-based two-component urethane-based emulsified adhesives, aldehyde compounds, epoxy compounds, melamine-based compounds, Crosslinking agents such as methylol compounds, isocyanate compounds, amine compounds, polyvalent metal salts, etc.). Among these, an aqueous adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be preferably used. Moreover, in the case of using a water-based adhesive, after bonding 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, a aging step for aging, for example, at a temperature of about 20 to 45° C. can be set. The adhesive layer formed by the water-based adhesive is usually 0.001 to 5 μm.

The active energy ray-curable adhesive means an adhesive that is cured by irradiating active energy rays such as ultraviolet rays or electron beams. Examples include: curable compositions containing polymerizable compounds and photopolymerization initiators, The curable composition containing a photoreactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, etc., are preferably an ultraviolet curable adhesive.

The method of bonding the polarizing film and the protective film may include a method of applying surface activation treatment such as saponification treatment, corona treatment, plasma treatment, etc., to at least any one of these bonding surfaces. When a protective film is attached to both sides of the polarizing film, the adhesive used for attaching these resin films may be the same type of adhesive or different types of adhesives.

The protective film is preferably a film formed of a thermoplastic resin having translucency. Specific examples include films composed of polyolefin-based resins; cellulose-based resins; polyester-based resins; (meth)acrylic resins or mixtures or copolymers thereof. When a protective film is provided on both sides of the polarizing film, The protective film used may be a film composed of different thermoplastic resins or a film 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 resin or cellulose resin. By using these films, the shrinkage of the polarizing film in a high temperature environment can be effectively suppressed without compromising the optical properties of the polarizing film. The protective film may also be an oxygen shielding layer.

The preferred configuration of the polarizing plate is a polarizing plate in which a protective film is laminated on at least one surface of the polarizing film via an adhesive layer. In the case where the protective film is laminated on only one side of the polarizing film, it is particularly preferable to laminate on the viewing side. The protective film laminated on the viewing side is preferably a protective film composed 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. On the surface of the protective film laminated on the viewing side, a surface treatment layer such as a hard coat layer or an anti-glare layer can be provided.

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 later.

The retardation film is an optical film that exhibits optical anisotropy. Examples include: polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, Polymer film composed of polyether, polyether, polyvinylidene fluoride/polymethyl methacrylate, cellulose acetate, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc., extending from about 1.01 to Stretched film obtained by 6 times. Among the stretched films, a polymer film obtained by uniaxially stretching 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, retardation films also include zero retardation films, and also include films called uniaxial retardation films, low photoelasticity retardation films, wide viewing angle retardation films, and the like.

Called zero retardation film, a front retardation value R _e is meant the thickness direction retardation R _th are both -15 to 15nm, and the optical properties of the film were the like. Examples of zero retardation films include resin films composed of cellulose resins, polyolefin resins (chain polyolefin resins, polycyclic olefin resins, etc.) or polyethylene terephthalate resins. In terms of easy control of the retardation value and easy acquisition, a cellulose-based resin or a polyolefin-based resin is preferred. The zero retardation film can also be used as a protective film. Examples of zero-blocking 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. "ZF-14" (trade name) sold by a limited company.

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.

The film that exhibits optical anisotropy by coating and alignment of liquid crystal compounds can be exemplified by the following first to fifth forms.

The first form: a phase difference film in which the rod-shaped liquid crystal compound is aligned in the horizontal direction relative to the supporting substrate

The second form: the phase difference film in which the rod-shaped liquid crystal compound is aligned in the vertical direction relative to the supporting substrate

The third type: phase difference film that makes the alignment direction of the rod-shaped liquid crystal compound spirally changed in the plane

Fourth type: retardation film that makes the disc-shaped liquid crystal compound obliquely aligned

Fifth form: biaxial retardation film in which the disc-shaped liquid crystal compound is aligned in the vertical direction with respect to the supporting substrate

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

In the case where the retardation film is a layer composed of a polymer in which the polymerizable liquid crystal compound is in an aligned state (hereinafter sometimes referred to as "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersion . The so-called inverse wavelength dispersion is an optical characteristic that the retardation value in the liquid crystal alignment plane at short wavelengths is small. 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 value of the in-plane phase difference with respect to the light of the wavelength λ.

Re(450)/Re(550)≦1 (7)

1≦Re(630)/Re(550) (8)

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

When the retardation film is a film with an optically anisotropic layer, the polymerizable liquid crystal compound can be listed in the "Liquid Crystal Handbook" (Edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2012) 3.8.6 Network (completely cross-linked type)" and "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material" among the compounds having a polymerizable group, as well as those described in Japanese Patent Application Laid-Open No. 2010-31223, JP 2010-270108, JP 2011-6360, JP 2011-207765, JP 2011-162678, JP 2016-81035, JP 2017 /043438 and Japanese Special Publication No. 2011-207765, the polymerizable liquid crystal compound, etc.

As a method of manufacturing a retardation film from a polymer in which a polymerizable liquid crystal compound is in an aligned state, for example, the method described in JP 2010-31223 A, etc. can be cited.

In the case of the second type, the frontal retardation 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 thickness direction retardation value R _th can be adjusted to -10 It can be adjusted to the range of -300nm, preferably -20 to -200nm. _{The thickness direction retardation value R th} means the refractive index anisotropy in the thickness direction _{, which can be measured from the retardation value R 50} measured with the in-plane fast axis as the tilt axis and the in-plane retardation value R 50 and the in-plane retardation value. R ₀ to calculate. That is, the retardation value R _{th in the} thickness direction can be determined from the in-plane retardation value R ₀ and the retardation value R measured at 50 degrees with the fast axis as the tilt axis by the following equations (10) to (12) _50. The thickness d of the retardation film and the average refractive index n _{0 of the} retardation film are calculated by calculating n _x , n _y and n _z , and substituting these into formula (9).

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 express optical anisotropy by coating and alignment of liquid crystal compounds, or films that express optical anisotropy by coating inorganic layered compounds include: what are called temperature-compensated retardation films The film is sold by JX Nippon Oil & Energy Co., Ltd. "NH Film" (product name; rod-shaped liquid crystal obliquely aligned film), sold by Fuji Film Co., Ltd. "WV Film" (product Name; a film with disc-shaped liquid crystal in an oblique orientation), "VAC Film" (trade name; fully biaxially oriented film) sold by Sumitomo Chemical Co., Ltd., and sold by Sumitomo Chemical Co., Ltd. "New VAC Film" (product name: biaxially oriented film) and so on.

The retardation film may be a multilayer film having two or more layers. For example, a retardation film having a protective film laminated on one side or both sides, or a retardation film of two or more layers laminated with an adhesive or adhesive interposed therebetween may be mentioned.

An example of the layer structure 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 by the adhesive composition of the present invention, the adhesive layer optical film 10 described in FIG. 1 is formed by attaching a release film (separation film) 2 to the adhesive layer 1 surface. The state.

The adhesive layer optical film 10A described in FIG. 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 peeling film 2 Agent layer optical film. The protective film 3 may have a phase difference. In addition, a hard coat layer or the like may be further laminated on the protective film 3.

The adhesive layer optical film 10B described in FIG. 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 adhesive layer optical film of the retardation film 8.

The optical laminate 10C described in FIG. 4 and the optical laminate 10D described in FIG. 5 include: a protective film 3, an adhesive layer 4, a polarizing film 5, an adhesive layer 1 formed from the adhesive composition of the present invention The adhesive layer 7, the retardation film 110, the adhesive layer 1a, and the optical laminate of the 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.

As shown in Figs. 4 and 5, when the retardation film is a multilayer film, as shown in Fig. 4, it can be enumerated that a layer including an intermediary adhesive layer or an adhesive layer 60 is laminated to impart 1/ to the transmitted light. The phase difference between the 1/4 wavelength retardation layer 50 with a retardation of 4 wavelengths and the 1/2 wavelength retardation layer 70 with a retardation of 1/2 wavelength to the transmitted light The structure of the level difference film 110. In addition, as shown in FIG. 5, a configuration including an optical film 40 in which a quarter-wave retardation layer 50a and a positive C layer 80 are laminated via an adhesive layer or an adhesive layer 60 can be cited.

The 1/4 wavelength retardation layer 50 that imparts a retardation of 1/4 wavelength and the 1/2 wavelength retardation layer 70 that imparts a retardation of 1/2 wavelength of FIG. 4 can be the above-mentioned first type of optical Film or fifth type optical film. In the case of the configuration of FIG. 4, it is particularly preferable that at least one side is in the fifth form.

In the case of the configuration of FIG. 5, the 1/4 wavelength retardation layer 50a is preferably the above-mentioned first type of optical film, and more preferably satisfies formulas (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 by the aforementioned adhesive composition can be laminated on display elements such as organic EL elements and liquid crystal cells and used in organic EL Display devices such as display devices or liquid crystal display devices.

[Example 1

The following examples and comparative examples illustrate the present invention in more detail. The "%" and "parts" in the examples and comparative examples are "% by mass" and "parts by mass" unless otherwise specified.

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

In a nitrogen environment, a 200mL four-necked flask equipped with a Dimroth condenser and a thermometer was added with the compound represented by the formula (aa) synthesized with reference to Japanese Patent Application Publication No. 2014-194508 10g, acetic anhydride (manufactured by Wako Pure Chemical Industries Co., Ltd.) 3.6g, cyanoacetic acid 2-butyloctyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) 10g, and acetonitrile (manufactured by Wako Pure Chemical Industries Co., Ltd.) 60g, And use a magnetic stirrer (magnetic stirrer) for stirring. After dropping 4.5 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) at an internal temperature of 25°C into the obtained mixture within 1 hour, the mixture was further kept at an internal temperature of 25°C for 2 hours. After that, acetonitrile was removed using a vacuum evaporator, and it was supplied to column chromatography (gel) for purification. The effluent containing the compound represented by the formula (UVA-1) was used to remove the solvent using a vacuum evaporator to obtain a yellow color crystallization. The crystal was dried under reduced pressure at 60°C to obtain 4.6 g of a compound represented by the formula (UVA-1) as a yellow powder. The yield was 56%.

<Measurement of gram absorbance coefficient ε>

The obtained 2-butanone solution (concentration: 0.006 g/L) of the compound represented by the formula (UVA-1) was placed in a 1 cm quartz cell, and the quartz cell was installed in a spectrophotometer UV-2450 (Shimadzu (Manufactured by Mfg. Co., Ltd.), and the absorbance in the wavelength range of 300 to 800 nm is measured by the dual 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 absorbance coefficient per wavelength is calculated.

ε(λ)=A(λ)/CL

[In the formula, ε(λ) represents the gram absorbance 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 optical path length of the quartz cell (cm). ]

The ε(405) of the compound represented by the formula (UVA-1) is 45L/(g‧cm), and the value of ε(440) is 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 were put into the opposite side equipped with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirrer. In the container, the internal temperature was increased to 60°C while replacing the air in the device with nitrogen so as to contain no oxygen. 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 the internal temperature was maintained at 50 to 70°C, ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hr, and the concentration of the acrylic resin became 35 The addition of ethyl acetate was stopped at the time of %, and the temperature was kept at this temperature until 12 hours had passed since the start of the addition of ethyl acetate. 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 weight average molecular weight Mw of the obtained acrylic resin measured by GPC in terms of polystyrene was 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. In addition, the monomer composition in the obtained acrylic resin was 96% by mass of butyl acrylate, 3% by mass of 2-hydroxyethyl acrylate, and 1% by mass of acrylic acid.

<Preparation of adhesive composition>

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

In the ethyl acetate solution (resin concentration: 20%) of the resin (A-1) obtained above, 2.5 parts of the compound represented by the formula (UVA-1) was mixed with 100 parts relative to the solid content of the solution, 1 part of photoinitiator (manufactured by ADEKA; brand name "NCI-730", photo-radical generator), 10 parts of photocurable ingredient (manufactured by Shinnakamura Chemical Co., Ltd.; brand name "A-DPH-12E"), Crosslinking agent (manufactured by Tosoh; brand name "Coronate L", isocyanate compound, 75% solid content) 0.3 parts and silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.; brand name "KBM-3066") 0.28 parts, and then used The adhesive composition (1) was obtained by adding 2-butanone so that the solid content concentration became 14%. The blending amount of the above-mentioned crosslinking agent (Coronate L) is the number of parts by mass based on the active ingredient.

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

In the ethyl acetate solution (resin concentration: 20%) of the resin (A-1), 2.5 parts of the compound represented by the formula (UVA-1) and the crosslinking agent ( Tosoh Corporation; product name "Coronate L", isocyanate compound, solid content 75%) 0.3 parts and silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.; product name "KBM-3066") 0.28 parts, and then the solid content concentration becomes 2-butanone was added at 14% to obtain the adhesive composition (2). In addition, the blending amount of the above-mentioned crosslinking agent (Coronate L) is the number of parts by mass based on the active ingredient.

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

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

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

In an ethyl acetate solution (resin concentration: 20%) of the resin (A-1), a crosslinking agent (manufactured by Tosoh; brand name "Coronate L", isocyanate compound) is mixed with 100 parts of the solid content of the solution , Solid content 75%) 0.3 parts and silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.; product name "KBM-3066") 0.28 parts, and then 2-butanone is added so that the solid content concentration becomes 14% to obtain an adhesive composition物(4). In addition, the blending amount of the above-mentioned crosslinking agent (Coronate L) is the number of parts by mass based on the active ingredient.

<Making of Adhesive Layer-1>

Using a coater, the adhesive composition of Example 1 was applied to a separation film composed of polyethylene terephthalate film that was subjected to mold release treatment so that the thickness after drying became 5 μm [from Lintec shares The mold-releasing treated surface of the product name "PLR-382190"] obtained by Ping Co., Ltd. was dried at 100°C for 1 minute. Then, use an ultraviolet irradiation device (Fusion UV Systems "Electrodeless UV Lamp System H Bulb", adjust the UV-A (wavelength from 320 to 390nm) to 500mW of illuminance and 500mJ of integrated light), and adjust it from the side of the separation film. The adhesive layer (1) (adhesive sheet) with a separation film is produced by irradiating ultraviolet rays.

<Making of Adhesive Layer-2>

Using a coater, the adhesive compositions of Comparative Examples 1 and 2 were respectively applied to the separated polyethylene terephthalate film that was subjected to mold release treatment 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 separation film. In addition, the adhesive layer formed from the adhesive composition of Comparative Example 1 was used as the adhesive layer (2), and the adhesive layer formed from the adhesive composition of Comparative Example 2 was used as the adhesive layer (3).

<Making of Adhesive Layer-3>

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

<Measurement of Gel Fraction of Adhesive Layer>

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

(a) An adhesive sheet with an area of about 8 cm×about 8 cm and a metal mesh of about 10 cm×about 10 cm made of SUS304 (the weight is set as Wm) are bonded together.

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

(c) Put the metal mesh fixed with staples in (b) above into a glass container, add 60 mL of ethyl acetate and immerse, 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, weigh it, set its mass as Wa, and calculate the gel fraction according to the following formula.

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

<Measurement of absorbance of adhesive layer>

The obtained adhesive layers (1) to (3) are each attached to the glass, and after the separation film is peeled off, a cycloolefin polymer (COP: Cycloolefin Polymer) film (Nippon Zeon Co., Ltd.) is attached to the adhesive layer. ZF-14) manufactured by the company, and produced a laminate with a COP film/adhesive layer/glass composition. The produced laminate 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 by the double beam method in steps of 1 nm. The absorbance of the produced adhesive layer is shown in Table 1. The absorbance of the glass and the absorbance of the COP film at a wavelength of 405 nm and a wavelength of 440 nm are both zero. 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 degree of saponification of 99.9 mol% and a thickness of 30 μm ("Kuraray Poval Film VF-PE#3000", manufactured by Kuraray Co., Ltd.) 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 with iodine adsorption aligned to polyvinyl alcohol. The extension is mainly carried out in the steps of iodine dyeing and boric acid treatment, and the total extension ratio is 5.3 times.

(ii) Production of polarizing plate

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

(iii) Fabrication of the first retardation layer

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

(iv) Fabrication of the second retardation layer

10 parts by mass of polyethylene glycol di(meth)acrylate (A-600 manufactured by Shinnakamura Chemical Industry Co., Ltd.) as a composition for forming the alignment layer and trimethylolpropane triacrylate (Shinnakamura Chemical Industry Co., Ltd.) Co., Ltd. A-TMPT) 10 parts by mass, 1,6-hexanediol di(meth)acrylate (Shin Nakamura Chemical Industry Co., Ltd. A-HD-N) 10 parts by mass, and as 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 solution for forming an alignment layer.

The base film prepares a long cyclic olefin resin film (manufactured by Nippon Zeon Co., Ltd.) with a thickness of 20 μm, and coats the resulting coating solution for alignment layer formation on the base film using a bar coater. Single-sided.

After applying a heat treatment to the coated layer at a temperature of 80°C for 60 seconds, irradiate 220mJ/cm ^{2 of} ultraviolet rays (UVB) to polymerize and harden the composition for the formation of the alignment layer to form a thickness of 2.3μm on the base film的Alignment layer 1.

20 parts by mass of a photopolymerizable nematic liquid crystal compound (RMM28B manufactured by Merck) as a composition for forming the retardation layer, and Irgacure907 (BASF Corporation) as a photopolymerization initiator 1 part by mass of Irg-907) was dissolved in 80 parts by mass of propylene glycol monomethyl ether acetate in a solvent to prepare a coating liquid for forming a retardation layer.

The coating liquid for forming the retardation layer was coated on the alignment layer 1 obtained previously, and the coating layer was subjected to a heat treatment at a temperature of 80° C. for 60 seconds. Then, ultraviolet rays (UVB) of 220 mJ/cm ^{2 were} irradiated to polymerize and harden the composition for forming the retardation layer to form a retardation layer with a thickness of 0.7 μm on the alignment layer. In this way, a 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 retardation layer is a positive C layer.

(v) Bonding of the first retardation layer and the second retardation layer

Using an ultraviolet curable adhesive (thickness 1μm), the first retardation layer and the second retardation layer are bonded so that the respective liquid crystal layer (the surface opposite to the transparent substrate) becomes the bonding surface . Then, ultraviolet rays are irradiated to harden the ultraviolet curable adhesive. In this way, a retardation layer including two retardation layers of the first liquid crystal layer and the second liquid crystal layer was produced. In this way, the transparent substrate was peeled off from both sides of the retardation layer to obtain a retardation film. 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) Bonding of polarizer and retardation film

The adhesive layer with separation film (1) is laminated on the cycloolefin resin film of the polarizing plate obtained in (ii). The separation film is peeled from the adhesive layer (1), and the adhesive layer (1) is laminated with the first retardation layer side of the retardation film obtained by the formula (v) to be laminated to obtain an optical film ( 1).

<Crack resistance evaluation>

The second retardation layer of the optical film (1) and the adhesive layer with a separation film (4) 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) has the following composition: cellulose triacetate film/polarizing film/ Cycloolefin film/adhesive layer (1)/first retardation layer/ultraviolet curing adhesive layer/second retardation layer/adhesive layer (4)/alkali-free glass.

The cellulose triacetate film side of the optical film (1A) was pressed against the tip of the Erichsen pen (manufactured by Erichsen; model 318) as the starting point of the crack, and the load of the Erichsen pen was set to 10N. Then, a 150-cycle hot and cold shock test was carried out. The hot and cold shock test was performed at -40°C for 30 minutes and 85°C for 30 minutes as one cycle. After the hot and cold shock test, use a microscope to confirm the length of the crack in mm 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 for changing the adhesive layer (1) to the adhesive layer (2), it was performed in the same manner to obtain an optical film (2) and an optical film (2A). The 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)

Except for changing the adhesive layer (1) to the adhesive layer (3), the same procedure was performed to obtain an optical film (3) and an optical film (3A). The crack resistance was evaluated in the same manner as above. The results are shown in Table 2.

[Table 2]

In the adhesive layer optical film containing the adhesive layer formed by the adhesive composition of the present invention, the crack length becomes 4 mm. On the other hand, the adhesion formed by the adhesive composition of the comparative example In the optical film of the agent layer, the cracks are longer 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 aforementioned adhesive composition can be preferably used in liquid crystal panels and liquid crystal display devices.

Claims (22)

An adhesive composition comprising: resin (A), light hardening component (C), and light selective absorption compound (B) having a merocyanine structure. The adhesive composition according to claim 1, which 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 photoradical 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 or 5, wherein the photocurable component (C) contains a polyfunctional (meth)acrylate compound. The adhesive composition according to any one of claims 1 to 6, which further contains a crosslinking agent (E). The adhesive composition according to claim 7, wherein the crosslinking agent (E) is an isocyanate crosslinking agent. The adhesive composition according to any one of claims 1 to 8, wherein the resin (A) is a resin having a glass transition temperature of 40°C or less. The adhesive composition according to any one of claims 1 to 9, wherein the resin (A) is a (meth)acrylic resin. The adhesive composition according to any one of claims 1 to 10, wherein the resin (A) is a (meth)acrylic resin having a weight average molecular weight of 500,000 or more. The adhesive composition according to any one of claims 1 to 11, wherein the light selective absorption compound (B) having a merocyanidin structure satisfies the following formula (1), ε(405)≧5 (1) In the formula (1), ε(405) represents the gram absorption coefficient of the light selective absorption compound (B) with a merocyanidin 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 12, wherein the light selective absorption compound (B) having a merocyanidin 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) with a merocyanidin structure at a wavelength of 405nm; ε(440) represents a merocyanidin at a wavelength of 440nm The structural light selects the gram-absorption coefficient of the compound (B). The adhesive composition according to any one of claims 1 to 13, wherein the light selective absorption compound (B) having a merocyanidin structure does not have a polymerizable group. The adhesive composition according to any one of claims 1 to 14, wherein the light selective absorption compound (B) having a merocyanidin 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, and an aliphatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent _{The aromatic hydrocarbon group or heterocyclic group, -CH 2} -contained in the aforementioned aliphatic hydrocarbon group or aromatic hydrocarbon group may 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, and 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 They may be bonded 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 that may have a substituent, and a carbon number 6 that may have substituents The aromatic hydrocarbon group or heterocyclic group from 15 to 15, 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- replace; R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, and 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. An adhesive layer formed by the adhesive composition according to any one of claims 1 to 16. The adhesive layer described in claim 17, which satisfies the following formula (3), A(405)≧0.5 (3) In formula (3), A(405) represents the absorbance at a wavelength of 405nm. The adhesive layer described in claim 18 further satisfies the following formula (4), A(405)/A(440)≧5 (4) In formula (4), A(405) represents the absorbance at a wavelength of 405nm, and A(440) represents the absorbance at a wavelength of 440nm. An adhesive layer optical film, which is laminated with an optical film on at least one surface of the adhesive layer according to any one of claims 17 to 19. The optical film with an adhesive layer according to claim 20, wherein the optical film is a polarizing plate. An image display device containing the adhesive layer optical film according to claim 20 or 21.

Images