KR20220119464A - adhesive composition - Google Patents

Abstract

[Problem] To provide a pressure-sensitive adhesive composition capable of sufficiently absorbing the light of light having a wavelength of around 400 nm without precipitating the compound even after long-term storage (good bleed resistance).
[Solutions] A pressure-sensitive adhesive composition comprising a resin (A), a light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule, and an initiator (C). The pressure-sensitive adhesive composition is composed of a radically curable component (D), a crosslinking agent (E), a silane compound (F), and a light selective absorption compound (G) other than the light selective absorption compound (B) containing an indole structure and a polymerizable group in the molecule It is preferable to further include at least one selected from the group.

Description

adhesive composition

The present invention relates to an optical film in which a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition are laminated.

In display devices (FPD: flat panel display), such as an organic electroluminescent display (organic electroluminescent display device) and a liquid crystal display device, various members, such as an organic electroluminescent element, display elements, such as a liquid crystal cell, optical films, such as a polarizing plate, are used is becoming Among these members, since organic EL elements, liquid crystal compounds, and the like are organic substances, deterioration by ultraviolet (UV) light tends to be a problem. In addition, the liquid crystal retardation film and organic EL light emitting device formed by orientation and photocuring of a polymerizable liquid crystal compound are not only deteriorated by ultraviolet rays, but also are exposed to short wavelength visible light near wavelength 400 nm (eg, wavelength 390 nm to 410 nm). It was found that there is a tendency to deteriorate even in

In order to suppress deterioration due to ultraviolet rays or short-wavelength visible light near 400 nm, Patent Document 1 describes forming a pressure-sensitive adhesive layer containing an ultraviolet absorber, and the pressure-sensitive adhesive layer is an acrylic acid copolymer and a triazine-based ultraviolet absorber. It is described that is formed of a pressure-sensitive adhesive composition comprising a.

Moreover, in patent document 2, the adhesive composition containing the indole-type ultraviolet absorber (BONASORB UA-3901 by Orient Chemical Industries, Ltd.) which does not have a polymeric group is described.

Patent Document 1: Japanese Patent Laid-Open No. 2016-157077 Patent Document 2: Japanese Patent Laid-Open No. 2017-48340

Most of the triazine-based ultraviolet absorbers described in Patent Document 1 are compounds exhibiting a maximum absorption wavelength at a wavelength of less than 360 nm, cannot efficiently absorb light near a wavelength of 400 nm, and sufficiently absorb light near a wavelength of 400 nm In order to do this, it was necessary to mix|blend a triazine type ultraviolet absorber in a large amount with an adhesive composition. However, when a triazine type ultraviolet absorber is mix|blended in large quantity, there existed a problem that a ultraviolet absorber would precipitate during long-term storage or in a high temperature environment.

In addition, although the indole-based ultraviolet absorber described in Patent Document 2 can efficiently absorb light having a wavelength of 380 nm to 400 nm, it is easy to precipitate, and there is a problem in that it is precipitated only by adding a small amount to the pressure-sensitive adhesive composition. there was.

The present invention includes the following inventions.

[1] A pressure-sensitive adhesive composition comprising a resin (A), a light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule, and an initiator (C).

[2] The pressure-sensitive adhesive composition according to [1], wherein the polymerizable group is a radically polymerizable group.

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

[4] The pressure-sensitive adhesive composition according to [1] to [3], wherein the initiator (C) is a radical polymerization initiator.

[5] The pressure-sensitive adhesive composition according to [1] to [4], wherein the initiator (C) is a photo-radical polymerization initiator.

[6] The pressure-sensitive adhesive composition according to [1] to [5], wherein the initiator (C) is an oxime ester compound.

[7] The pressure-sensitive adhesive composition according to any one of [1] to [6], further comprising a radical curable component (D).

[8] The pressure-sensitive adhesive composition according to [7], wherein the radical curable component (D) is a (meth)acrylate compound.

[9] The pressure-sensitive adhesive composition according to [7] or [8], wherein the radical curable component (D) is a polyfunctional (meth)acrylate compound.

[10] The pressure-sensitive adhesive composition according to any one of [1] to [9], further comprising a crosslinking agent (E).

[11] The pressure-sensitive adhesive composition according to [10], wherein the crosslinking agent (E) is an isocyanate crosslinking agent.

[12] The pressure-sensitive adhesive composition according to any one of [10] or [11], wherein the resin (A) has a glass transition temperature of 40°C or less.

[13] The pressure-sensitive adhesive composition according to [12], wherein the resin (A) having a glass transition temperature of 40°C or less is a (meth)acrylic resin.

[14] The pressure-sensitive adhesive according to any one of [1] to [13], wherein the light-selective absorption compound (B) having an indole structure and a polymerizable group in the molecule is a compound exhibiting maximum absorption at a wavelength of 360 nm or more and 420 nm or less. composition.

[15] The pressure-sensitive adhesive composition according to any one of [1] to [14], wherein the light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule satisfies the formula (1).

ε(400)≥0.05 (One)

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

[16] The pressure-sensitive adhesive composition according to [1] to [15], wherein the light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule is a compound represented by formula (I) or (II).

[In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, or a substituent represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR ^1A -, -SO ₂ -, -CO-, -O-, -S-, or -CF ₂ - may be substituted.

R ^1A represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E ¹ represents an electron withdrawing group.

Z represents a linking group.

A represents a polymerizable group.

In formula (II), R ¹² and R ¹⁷ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or a substituent represents an aromatic ^hydrocarbon group having ₆ to ₁₈ carbon atoms which may have - or -CF ₂ - may be substituted.

R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, a group containing a polymerizable group, or a substituent which may have represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR ^12A -, -SO ₂ -, -CO-, -O-, -S-, or -CF ₂ - may be substituted.

However, at least one of R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represents a group containing a polymerizable group.

R ^11A and R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E ¹¹ represents an electron withdrawing group.]

[17] The pressure-sensitive adhesive composition according to [16], wherein R ² and R ¹² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms.

[18] The pressure-sensitive adhesive composition according to [16], wherein the compound represented by the formula (I) is a compound represented by the formula (III), and the compound represented by the formula (II) is a compound represented by the formula (IV).

[R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , E ¹ , R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and E ¹¹ each have the same meaning as above.

R ⁷ represents a hydrogen atom, a cyano group, a methyl group, or a phenyl group.

Z ¹ represents an alkanediyl group having 1 to 12 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, -OR ^2A -*1, -SR ^2B -*1 or -NR ^1D -R ^2C -*1.

Z ² is a single bond, *2-CO-O-, *2-O-CO-, *2-S(=O) ₂ -, *2-O-SO ₂ -, *2-CO-NR ^1B -, *2-NR ^1C -CO-, *2-R ^2D OP(=O)-OR ^2E -, *2-NR ^1E -CO-O-, *2-O-CO-NR ^1F -, *2 -(OR ^2F ) _s1 -, *2-CO-S-, *2-S-CO-, or a C1-C4 perfluoroalkanediyl group.

R ^1B , R ^1C , R ^1D , R ^1E and R ^1F each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ^2A , R ^2B , R ^2C , R ^2D , R ^2E and R ^2F each independently represent a divalent hydrocarbon group having 1 to 18 carbon atoms.

Z ¹ represents a divalent linking group.

A ¹ represents a polymerizable group.

*1 represents a bond with Z ² .

*2 represents a bond with Z ¹ ]

[19] A pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition according to any one of [1] to [18].

[20] The pressure-sensitive adhesive layer according to [19], which satisfies the following formula (2).

A(400)≥0.4 (3)

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

[21] The pressure-sensitive adhesive layer according to [19] or [20], wherein the pressure-sensitive adhesive layer has a thickness of 10 µm or less.

[22] An optical film with an adhesive layer in which an optical film is laminated on at least one surface of the adhesive layer according to any one of [19] to [21].

[23] The optical film with an adhesive layer according to [22], wherein the optical film is a polarizing plate.

[24] An image display device comprising the optical film with an adhesive layer according to [22] or [23].

The pressure-sensitive adhesive composition of the present invention is capable of sufficiently absorbing the light of light having a wavelength of around 400 nm without precipitation of the compound (good bleed resistance) even when stored for a long period of time.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows typically an example of the laminated constitution of the adhesive layer of this invention.
Fig. 2 is a schematic cross-sectional view schematically showing an example of the layer configuration of the optical laminate of the present invention.
Fig. 3 is a schematic cross-sectional view schematically showing an example of the layer configuration of the optical laminate of the present invention.
Fig. 4 is a schematic cross-sectional view schematically showing an example of the layer configuration of the optical laminate of the present invention.
Fig. 5 is a schematic cross-sectional view schematically showing an example of the layer configuration of the optical laminate of the present invention.

The pressure-sensitive adhesive composition of the present invention contains a resin (A), a light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule, and an initiator (C).

<Resin (A)>

Resin (A) of this invention will not be specifically limited if it is resin used for an adhesive composition. It is preferable that resin (A) does not show maximum absorption in the range of wavelength 300 nm - wavelength 780 nm.

It is preferable that resin (A) is resin whose glass transition temperature (Tg) is 40 degrees C or less. As for the glass transition temperature (Tg) of resin (A), it is more preferable that it is 20 degrees C or less, It is still more preferable that it is 10 degrees C or less, It is especially preferable that it is 0 degrees C or less. The glass transition temperature of the resin (A) is usually -80°C or higher, preferably -70°C or higher, more preferably -60°C or higher, still more preferably -55°C or higher, and particularly preferably -50°C or higher. desirable. It is advantageous for the improvement of the adhesiveness to the to-be-adhered body of the adhesive layer formed from the adhesive composition containing resin (A) as the glass transition temperature of resin (A) is 40 degrees C or less. Moreover, it is advantageous for the improvement of durability of the adhesive layer formed from the adhesive composition containing resin (A) as the glass transition temperature of resin (A) is -80 degreeC or more. On the other hand, the glass transition temperature can be measured by differential scanning calorimetry (DSC).

As resin (A), (meth)acrylic-type resin, silicone resin, rubber-type resin, urethane-type resin, etc. are mentioned, It is preferable that it is (meth)acrylic-type resin.

As (meth)acrylic resin, it is preferable that it is a polymer which has the structural unit derived from (meth)acrylic acid ester as a main component (preferably 50 mass % or more is included). The structural unit derived from the (meth)acrylic acid ester may include a structural unit derived from a monomer other than one or more (meth)acrylic acid esters (eg, a structural unit derived from a monomer having a polar functional group). In addition, in this specification, (meth)acrylic acid means any of acrylic acid or methacrylic acid may be sufficient, and "(meth)" at the time of calling (meth)acrylate etc. is the same meaning.

As (meth)acrylic acid ester, the (meth)acrylic acid ester represented by a following formula (a) is mentioned.

[In the formula (a), R _1A is a hydrogen atom or a methyl group, R _2A is an alkyl group having 1 to 14 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atom in the alkyl group or the aromatic hydrocarbon group is a carbon number It may be substituted with an alkoxy group of 1 to 10.]

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

As (meth)acrylic acid ester represented by Formula (I),

(meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)acrylic acid n-butyl, (meth)acrylic acid n-pentyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid n- Heptyl, (meth)acrylic acid n-octyl, (meth)acrylic acid n-nonyl, (meth)acrylic acid n-decyl, (meth)acrylic acid n-dodecyl, (meth)acrylic acid lauryl, (meth)acrylic acid stearyl, etc. straight-chain alkyl esters of (meth)acrylic acid;

(meth)acrylic acid i-propyl, (meth)acrylic acid i-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid i-pentyl, (meth)acrylic acid i-hexyl, (meth)acrylic acid 2-ethylhexyl, ( Branched alkyl esters of (meth)acrylic acid, such as i-octyl meth)acrylic acid, i-nonyl (meth)acrylic acid, i-stearyl (meth)acrylic acid, and i-amyl (meth)acrylic acid;

(meth)acrylic acid cyclohexyl, (meth)acrylic acid isoboronyl, (meth)acrylic acid adamantyl, (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid cyclododecyl, (meth)acrylic acid methylcyclohexyl, (meth) alicyclic skeleton-containing alkyl esters of (meth)acrylic acid such as trimethylcyclohexyl acrylate, (meth)acrylic acid tert-butylcyclohexyl, and α-ethoxyacrylic acid cyclohexyl;

aromatic ring skeleton-containing esters of (meth)acrylic acid such as (meth)acrylic acid phenyl and (meth)acrylic acid benzyl;

and the like.

In addition, as the substituent-containing (meth)acrylic acid ester, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid ethoxymethyl, (meth)acrylic acid phenoxyethyl, (meth)acrylic acid 2-(2-phenoxyethoxy) ) ethyl and the like.

As (meth)acrylic acid ester, (meth)acrylic-acid phenoxydiethylene glycol, (meth)acrylic-acid phenoxypoly(ethylene glycol), etc. are mentioned.

These (meth)acrylic acid esters can be used independently, respectively, and may use a different some plurality.

The resin (A) of the present invention is a structural unit derived from the (meth)acrylic acid alkylester (a1) having a homopolymer glass transition temperature Tg of less than 0°C among (meth)acrylic acid alkylesters, and a homopolymer having a Tg of 0°C or higher. It is preferable to contain the structural unit derived from (meth)acrylic-acid alkylester (a2). This is advantageous in improving the high temperature durability of the pressure-sensitive adhesive layer. For Tg of the homopolymer of the (meth)acrylic acid alkylester, literature values, such as POLYMER HANDBOOK (Wiley-Interscience), can be employ|adopted, for example.

Specific examples of the (meth)acrylic acid alkylester (a1) include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate, and n-heptyl acrylate , n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, n-dodecyl acrylate, etc. having 2 to 12 carbon atoms in the alkyl group (meth) Acrylic acid alkylester is included.

(meth)acrylic acid alkylester (a1) may use only 1 type, and may use 2 or more types together. Among them, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, etc. are preferable, and n-butyl acrylate is particularly preferable from the viewpoint of followability and reworkability when laminated on an optical film.

(meth)acrylic acid alkylester (a2) is (meth)acrylic acid alkylester other than (meth)acrylic acid alkylester (a1). Specific examples of the (meth)acrylic acid alkyl ester (a2) include methyl acrylate, cyclohexyl acrylate, isoboronyl acrylate, stearyl acrylate, t-butyl acrylate, and the like.

(meth)acrylic acid alkylester (a2) may use only 1 type, and may use 2 or more types together. Especially, from a viewpoint of high temperature durability, it is preferable that (meth)acrylic acid alkylester (a2) contains methyl acrylate, cyclohexyl acrylate, isoboronyl acrylate, etc., and it is more preferable that methyl acrylate is included.

The structural unit derived from the (meth)acrylic acid ester represented by the formula (a) is preferably 50% by mass or more, preferably 60 to 95% by mass, among all the structural units contained in the (meth)acrylic resin, It is more preferable that it is 65-95 mass % or more.

As the structural unit derived from a monomer other than (meth)acrylic acid ester, a structural unit derived from a monomer having a polar functional group is preferable, and a structural unit derived from a (meth)acrylic acid ester having a polar functional group is more preferable. Examples of the polar functional group include a hydroxy group, a carboxyl group, a substituted or unsubstituted amino group, and a heterocyclic group such as an epoxy group.

As a monomer having a polar functional group,

(meth)acrylic acid 1-hydroxymethyl, (meth)acrylic acid 1-hydroxyethyl, (meth)acrylic acid 1-hydroxyheptyl, (meth)acrylic acid 1-hydroxybutyl, (meth)acrylic acid 1-hydroxypentyl; (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 2-hydroxypentyl, (meth)acrylic acid 2-hydroxyhexyl; (meth)acrylic acid 3-hydroxypropyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 3-hydroxypentyl, (meth)acrylic acid 3-hydroxyhexyl, (meth)acrylic acid 3-hydroxyheptyl; (meth)acrylic acid 4-hydroxybutyl, (meth)acrylic acid 4-hydroxypentyl, (meth)acrylic acid 4-hydroxyhexyl, (meth)acrylic acid 4-hydroxyheptyl, (meth)acrylic acid 4-hydroxyoctyl; (meth)acrylic acid 2-chloro-2-hydroxypropyl, (meth)acrylic acid 3-chloro-2-hydroxypropyl, (meth)acrylic acid 2-hydroxy-3-phenoxypropyl, (meth)acrylic acid 5-hydroxy Roxypentyl, (meth)acrylic acid 5-hydroxyhexyl, (meth)acrylic acid 5-hydroxyheptyl, (meth)acrylic acid 5-hydroxyoctyl, (meth)acrylic acid 5-hydroxynonyl, (meth)acrylic acid 6-hydroxy Hydroxyhexyl, (meth)acrylic acid 6-hydroxyheptyl, (meth)acrylic acid 6-hydroxyoctyl, (meth)acrylic acid 6-hydroxynonyl, (meth)acrylic acid 6-hydroxydecyl, (meth)acrylic acid 7-hydroxy Hydroxyheptyl, (meth)acrylic acid 7-hydroxyoctyl, (meth)acrylic acid 7-hydroxynonyl, (meth)acrylic acid 7-hydroxydecyl, (meth)acrylic acid 7-hydroxyundecyl, (meth)acrylic acid 8- Hydroxyoctyl, (meth)acrylic acid 8-hydroxynonyl, (meth)acrylic acid 8-hydroxydecyl, (meth)acrylic acid 8-hydroxyundecyl, (meth)acrylic acid 8-hydroxydodecyl, (meth)acrylic acid 9-hydroxynonyl, (meth)acrylic acid 9-hydroxydecyl, (meth)acrylic acid 9-hydroxyundecyl, (meth)acrylic acid 9-hydroxydodecyl, (meth)acrylic acid 9-hydroxytridecyl, ( meth)acrylic acid 10-hydroxydecyl, (meth)acrylic acid 10-hydroxyundecyl, (meth)acrylic acid 10-hydroxydo Decyl, acrylic acid 10-hydroxytridecyl, (meth)acrylic acid 10-hydroxytetradecyl, (meth)acrylic acid 11-hydroxyundecyl, (meth)acrylic acid 11-hydroxydodecyl, (meth)acrylic acid 11-hydroxy hydroxytridecyl, (meth)acrylic acid 11-hydroxytetradecyl, (meth)acrylic acid 11-hydroxypentadecyl, (meth)acrylic acid 12-hydroxydodecyl, (meth)acrylic acid 12-hydroxytridecyl, (meth)acrylic acid ) Acrylic acid 12-hydroxytetradecyl, (meth)acrylic acid 13-hydroxypentadecyl, (meth)acrylic acid 13-hydroxytetradecyl, (meth)acrylic acid 13-hydroxypentadecyl, (meth)acrylic acid 14-hydroxy Monomers having a hydroxyl group, such as tetradecyl, (meth)acrylic acid 14-hydroxypentadecyl, (meth)acrylic acid 15-hydroxypentadecyl, and (meth)acrylic acid 15-hydroxyheptadecyl;

Monomers having a carboxyl group such as (meth)acrylic acid, carboxyalkyl (meth)acrylate (eg, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate), maleic acid, maleic anhydride, fumaric acid, crotonic acid;

Acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexyl monomers having a heterocyclic group such as methyl (meth)acrylate, glycidyl (meth)acrylate, and 2,5-dihydrofuran;

and monomers having a substituted or unsubstituted amino group, such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate.

Among them, from the viewpoint of reactivity between the (meth)acrylic acid ester polymer and the crosslinking agent, a monomer having a hydroxyl group or a monomer having a carboxyl group is preferable, and it is more preferable to include both a monomer having a hydroxyl group and a monomer having a carboxyl group.

As a monomer which has a hydroxyl group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate are preferable. In particular, good durability can be obtained by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and 5-hydroxypentyl acrylate.

It is preferable to use acrylic acid as a monomer which has a carboxyl group.

From the viewpoint of preventing the enhancement of the peeling force of the separate film that can be laminated on the outer surface of the pressure-sensitive adhesive layer, the resin (A) (preferably (meth)acrylic resin) contains a structural unit derived from a monomer having an amino group substantially It is preferable not to Here, "not included" means that it is 0.1 mass part or less in 100 mass parts of all structural units which comprise (meth)acrylic-type resin.

The content of the structural unit derived from the monomer having a polar functional group is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, with respect to 100 parts by mass of all structural units of the (meth)acrylic resin, More preferably, they are 0.5 mass part or more and 10 mass parts or less, Especially preferably, they are 1 mass part or more and 7 mass parts or less.

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

As a structural unit derived from monomers other than (meth)acrylic acid ester, a structural unit derived from a styrene-type monomer, a structural unit derived from a vinyl-type monomer, and a structure derived from the monomer which has several (meth)acryloyl group in a molecule|numerator. A unit, a structural unit derived from a (meth)acrylamide type monomer, etc. are mentioned.

Examples of the styrene-based monomer include styrene; alkyl styrenes such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodine styrene; nitrostyrene; acetyl styrene; methoxystyrene; and divinylbenzene.

Examples of the vinyl-based monomer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing heteroaromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated dienes such as butadiene, isoprene and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

Examples of the monomer having a plurality of (meth)acryloyl groups in the molecule include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedioldi(meth) Two (meth) in molecules such as acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate a monomer having an acryloyl group; The monomer which has three (meth)acryloyl groups in molecules, such as trimethylol propane tri(meth)acrylate, is mentioned.

As a (meth)acrylamide type monomer, N-methylol (meth)acrylamide, N-(2-hydroxyethyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N -(4-hydroxybutyl)(meth)acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(6-hydroxyhexyl)(meth)acrylamide, N,N-dimethyl ( Meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl -3-oxobutyl)(meth)acrylamide, N-[2-(2-oxo-1-imidazolidinyl)ethyl](meth)acrylamide, 2-acryloylamino-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)(meth)acrylamide, N-[2-(1-methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl](meth) acrylamide, N-[2-(2-methylpropoxy)ethyl](meth)acrylamide, N-(2-butoxyethyl)(meth)acrylamide, N-[2-(1,1-dimethyl toxy)ethyl] (meth)acrylamide, etc. are mentioned. Among them, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, and N-( 2-methylpropoxymethyl)acrylamide is preferred. Since the (meth)acrylamide type monomer may cause a fall in the peeling force of the separate film which can be laminated|stacked on the outer surface of an adhesive layer, in 100 mass parts of total structural units of resin (A), (meth)acryl It is preferable that content of an amide-type monomer is 1.0 mass part or less, It is more preferable that it is 0.5 mass part or less, It is still more preferable that it is 0.3 mass part or less, It is especially preferable that it is 0.1 mass part or less.

The weight average molecular weight (Mw) of resin (A) (preferably (meth)acrylic-type resin) becomes like this. Preferably it is 500,000-2.5 million. When the weight average molecular weight is 500,000 or more, the durability of the pressure-sensitive adhesive layer in a high-temperature environment is improved, and problems such as floating peeling between the adherend and the pressure-sensitive adhesive sheet and cohesive failure of the pressure-sensitive adhesive sheet are easily suppressed. It is advantageous from a viewpoint of coatability that a weight average molecular weight is 2.5 million or less. From a viewpoint of coexistence of the durability of an adhesive sheet, and the coatability of an adhesive composition, a weight average molecular weight becomes like this. Preferably it is 600,000-1.8 million, More preferably, it is 700,000-1.7 million, Especially preferably, it is 1 million-1.6 million. . Moreover, the molecular weight distribution (Mw/Mn) represented by ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is 2-10 normally, Preferably it is 3-8, More preferably, it is 3-6. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value in terms of standard polystyrene.

When the resin (A) (preferably (meth)acrylic resin) is dissolved in ethyl acetate to obtain a solution having a concentration of 20% by mass, the viscosity at 25°C is preferably 20 Pa·s or less, and 0.1 to 15 It is more preferable that it is Pa.s. It is advantageous from a viewpoint of the coatability at the time of coating an adhesive composition to a base material as it is a viscosity of the said range. In addition, a viscosity can be measured with a Brookfield viscometer.

The resin (A) (preferably (meth)acrylic resin) can be produced by known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, particularly solution polymerization. desirable. As the solution polymerization method, for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added under a nitrogen atmosphere, and the mixture is stirred for about 3 to 15 hours under a temperature condition of 40 to 90°C, preferably 50 to 80°C. method can be found. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during polymerization. The said monomer and thermal-polymerization initiator may be in the state added to the organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. are mentioned. As the thermal polymerization initiator, a known thermal polymerization initiator can be used. Moreover, you may use the polymerization method by an ultraviolet-ray etc. using a photoinitiator instead of a thermal-polymerization initiator.

Content of resin (A) is 50 mass % - 99.9 mass % normally in 100 mass % of solid content of an adhesive composition, Preferably they are 60 mass % - 95 mass %, More preferably, they are 70 mass % - 90 mass % .

<Light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule>>

The indole structure in the present invention means a structure in which a benzene ring and a pyrrole ring are condensed.

Examples of the polymerizable group include cationically polymerizable groups such as an epoxy group, an oxetanyl group, an oxazolino group, an aziridino group, and a vinyl ether group; radically polymerizable groups such as ethylenically unsaturated groups; and an alkoxysilyl group. The polymerizable group in the photoselective absorption compound (B) containing an indole structure and a polymerizable group in the molecule is preferably a radically polymerizable group such as an ethylenically unsaturated group. Specific examples of the ethylenically unsaturated group include a vinyl group, α-methylvinyl group, acryloyl group, methacryloyl group, allyl group, styryl group, (meth)acrylamide group, and the like.

The light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule (hereinafter sometimes referred to as a light-selective absorption compound (B)) contains an indole structure and a polymerizable group and an electron withdrawing group in the molecule It is preferable to do

The indole structure and the polymerizable group may be directly bonded, or may be bonded via a linking group. The indole structure and the electron withdrawing group may be directly couple|bonded, and may be couple|bonded through the coupling group.

The light-selective absorption compound (B) preferably exhibits maximum absorption at a wavelength of 360 nm or more and 420 nm or less, and more preferably exhibits maximum absorption at a wavelength of 370 nm or more and 410 nm or less. By exhibiting maximum absorption at a wavelength of 360 nm or more, it is possible to efficiently absorb light in the vicinity of 380 nm even with a small amount of addition.

The light selective absorption compound (B) preferably satisfies the following formula (1), and more preferably satisfies the formula (2).

ε(400)≥0.05 (One)

[In formula (1), ε(400) represents the gram extinction coefficient at a wavelength of 400 nm of the photoselective absorption compound (B) containing an indole structure and a polymerizable group in the molecule. The unit of gram extinction coefficient is L/(g·m)]

The value of ε (400) is preferably 0.1 L/(g·m) or more, more preferably 0.15 L/(g·m) or more, still more preferably 0.2 L/(g·m) or more, and 0.3 L It is still more preferably /(g·m) or more, and particularly preferably 0.4 or more. In addition, the value of (epsilon) (400) is 10000 L/(g*m) or less normally. A compound with a larger value of ε(400) is more likely to absorb light having a wavelength of around 400 nm (wavelength 390 to 410 nm), and is more likely to exhibit a function of suppressing deterioration due to short wavelength visible light.

The light selective absorption compound (B) is preferably a compound represented by formula (I) or a compound represented by formula (II).

[In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, or a substituent represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR ^1A -, -SO ₂ -, -CO-, -O-, -S-, or -CF ₂ - may be substituted.

R ^1A represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E ¹ represents an electron withdrawing group.

Z represents a linking group.

A represents a polymerizable group.

In formula (II), R ¹² and R ¹⁷ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or a substituent represents an aromatic ^hydrocarbon group having ₆ to ₁₈ carbon atoms which may have - or -CF ₂ - may be substituted.

R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, a group containing a polymerizable group, or a substituent which may have represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR ^12A -, -SO ₂ -, -CO-, -O-, -S-, or -CF ₂ - may be substituted.

However, at least one of R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represents a group containing a polymerizable group.

R ^11A and R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

E ¹¹ represents an electron withdrawing group.]

Examples of the electron withdrawing group represented by E ¹ and E ¹¹ include a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, —SO ₂ F, and a group represented by the formula (I-1). have.

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

X ¹ is -CO-*3, -COO-*3, -CS-*3, -CSS-*3, -CSNR ¹¹² -*3, -CONR ¹¹³ -*3, -CNR ¹¹⁴ -*3 or - SO ₂ -*3.

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.

*3 represents a bond with R ¹¹¹ .

* indicates a bond with a carbon atom.]

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

Examples of the alkyl group substituted with a halogen atom include a monofluoromethyl group, a monofluoroethyl group, a monochloromethyl group, a monochloroethyl group, a monobromomethyl group, a monobromoethyl group, a monoiodomethyl group, a monoiodoethyl group, a difluoromethyl group, A halogenated alkyl group of difluoroethyl group, dichloromethyl group, dichloroethyl group, dibromomethyl group, dibromoethyl group, diiodomethyl group, diiodoethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, etc. can be heard The number of carbon atoms in the alkyl group substituted with a halogen atom is usually 1 to 25.

Examples of the hydrocarbon group having 1 to 25 carbon atoms represented by R ¹¹¹ include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, and isopentyl group. , n-hexyl group, isohexyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl group, undecyl group, myristyl group A linear or branched alkyl group having 1 to 25 carbon atoms, such as group, cetyl group, stearyl group, 2-ethylhexyl group, and 4-butyloctyl group: cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. a cycloalkyl group having 3 to 25 carbon atoms; C4-C25 cycloalkylalkyl groups, such as a cyclopropylmethyl group and a cyclohexylmethyl group; C6-C25 aryl groups, such as a phenyl group, a naphthyl group, anthracenyl group, and a biphenyl group; and an aralkyl group having 7 to 25 carbon atoms, such as a benzyl group, a phenylethyl group, a naphthylmethyl group, and a phenyl group.

R ¹¹¹ is preferably an alkyl group having 1 to 25 carbon atoms which may have a halogen atom, an aryl group having 6 to 25 carbon atoms which may have a halogen atom, or a fluorine-substituted alkyl group having 1 to 25 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹¹² , R ¹¹³ and R ¹¹⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a sec-butyl group. have.

X ¹ is preferably -CO-*3, -COO-*3, -CONR ¹¹³ -*3, or -SO ₂ -*3.

The electron withdrawing groups represented by E ¹ and E ¹¹ are each independently preferably a cyano group, a nitro group, or a group represented by the formula (I-1), and a cyano group, a nitro group, or a group represented by *-COR ¹¹¹ , a group represented by *-COOR ¹¹¹ , a group represented by *-CONR ¹¹³ R ¹¹¹ , a group represented by *-SO ₂ R ¹¹¹ , -CF ₃ , more preferably -C ₂ F ₅ , a cyano group; A nitro group, a group represented by *-COOR ¹¹¹ , and a group represented by *-SO ₂ R ¹¹¹ are more preferable, and a cyano group is particularly preferable.

The coupling group represented by Z will not be specifically limited if it is a bivalent coupling group.

The polymerizable group mentioned above is mentioned, as for the polymeric group represented by A, it is preferable that it is a radically polymerizable group, and it is more preferable that it is a (meth)acryloyl group.

Examples of the halogen atom represented by R ¹ to R ⁶ and R ¹¹ to R ¹⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the heterocyclic group represented by R ¹ to R ⁶ and R ¹¹ to R ¹⁷ include a group in which one hydrogen atom has been removed from the heterocyclic ring. Specifically, a pyrrolidine ring group, a pyrroline ring group, an imidazolidine ring group, an imidazoline ring group, an oxazoline ring group, a thiazoline ring group, a piperidine ring group, a morpholine ring group, a piperazine ring group, an indole ring group, isoindole Ventilation, quinoline ring, thiophene ring, pyrrole ring, thiazoline ring and furan ring, pyridine ring, dioxane ring, morpholine ring, thiazine ring, triazole ring, tetrazole ring, dioxofuran ring, pyrazine ring, A C4-C30 aliphatic heterocyclic group, such as a purine ring group, or a C3-C20 aromatic heterocyclic group, etc. are mentioned. These heterocyclic groups may have a structure in which an unsaturated bond is hydrogenated, and a structure in which the cyclic skeleton is further condensed (for example, a benzimidal ring or a benzimidazole ring), a hydrogen atom on the heterocyclic ring is a heterocyclic group, a halogen atom, a nitro group, or a cyano group , a hydroxyl group, a carboxy group, or the like may be further substituted.

Examples of the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R ¹ to R ⁶ and R ¹¹ to R ¹⁷ include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, and sec-butyl group. group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group , isododecyl group, undecyl group, myristyl group, cetyl group, stearyl group, etc. linear or branched alkyl group having 1 to 25 carbon atoms: cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. 3-25 cycloalkyl groups; and cycloalkylalkyl groups having 4 to 25 carbon atoms such as cyclopropylmethyl group and cyclohexylmethyl group, and from the viewpoint of solubility, branched alkyl groups having 3 to 25 carbon atoms such as 2-ethylhexyl group and 2-butyloctyl group It is preferable to be

Examples of the substituent which the aliphatic hydrocarbon group having 1 to 25 carbon atoms represented by R ¹ to R ⁶ and R ¹¹ to R ¹⁷ may have include a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an acetamide group, an amino group, A C1-C12 alkylamino group etc. are mentioned. Examples of the heterocyclic group include the same as the heterocyclic group represented by R ¹ .

Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ¹ to R ⁶ and R ¹¹ to R ¹⁷ include aryl groups having 6 to 18 carbon atoms, such as a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group and a methylphenyl group; and an aralkyl group having 7 to 18 carbon atoms, such as a benzyl group, a phenylethyl group, a naphthylmethyl group, and a phenoxy group. -CH ₂ - contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ¹ to R ⁶ , R ¹¹ to R ¹⁷ is -SO ₂ -, -CO-, -O-, -S- or -CF ₂ - As a group substituted with , aryloxy groups, such as a phenoxy group and a naphthyloxy group, etc. are mentioned.

Examples of the substituent which the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ¹ to R ⁶ and R ¹¹ to R ¹⁷ may have include a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an acetamide group, an amino group, A C1-C12 alkylamino group etc. are mentioned. Examples of the heterocyclic group include the same as the heterocyclic group represented by R ¹ .

From the viewpoint of absorption wavelength control and solubility, R ¹ and R ¹¹ are each independently preferably an aliphatic hydrocarbon group having 1 to 25 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 16 carbon atoms, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group It is more preferable that they are an actual group and 4-butyloxyl group, and it is especially preferable that they are a methyl group, an ethyl group, n-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, and 4-butyloctyl group.

It is preferable that it is a C6 ^- C18 aromatic hydrocarbon group from a durable viewpoint, It is more preferable that it is a C6-C18 aryl group, It is still more preferable that it is a phenyl group.

The group containing the polymerizable group represented by R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is not particularly limited as long as it has a polymerizable group at the terminal, and specifically, it is represented by the formula (I-2) can be heard.

[In formula (I-2), X ² represents a polymerizable group.

R ¹¹⁵ represents an alkanediyl group having 1 to 12 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, -CH ₂ - contained in the alkanediyl group or divalent aromatic hydrocarbon group is -O-, -CO- , -CS- or -NR ¹¹⁶ - may be substituted.

R ¹¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

Examples of the polymerizable group represented by X ² include the same ones as the polymerizable group represented by A, preferably a radical polymerizable group, and more preferably a (meth)acryloyl group.

Examples of the alkanediyl group having 1 to 12 carbon atoms represented by R ¹¹⁵ include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group and a hexane- 1,6-diyl group, ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane -1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ¹¹⁵ include a phenylene group, a naphthylene group, and a phenylenemethylene group.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹¹⁶ include the same groups as the alkyl group having 1 to 6 carbon atoms represented by R ¹¹² .

At least one of R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represents a group comprising a polymerizable group.

It is preferable that R ¹¹ is a group comprising a polymerizable group.

It is preferable that R< ¹² > is a C6-C18 aromatic hydrocarbon group, It is more preferable that it is a C6-C18 aryl group, It is more preferable that it is a phenyl group.

R ¹⁷ is a cyano group, a nitro group, *-COR ^111A (R ^111A represents an aliphatic hydrocarbon group having 1 to 24 carbon atoms which may have a substituent), *-COOR ^111B (Even if R ^111B has a substituent) A ^group represented by an ^{aliphatic hydrocarbon} group having ₁ to 23 carbon atoms which may be optionally It is preferably a group represented by R ^111D (R ^111D represents an aliphatic hydrocarbon group having 1 to 24 carbon atoms which may have a substituent) or an aliphatic hydrocarbon group having 1 to 25 carbon atoms substituted with a fluorine atom, cyano group, nitro group, *- The group represented by COR ^111A , the group represented by *-COOR ^111B , the group represented by *-CONR ^11A R ^111C , the group represented by *-SO ₂ R ^111D , -CF ₃ , -C ₂ F ₅ is more Preferably, it is a cyano group, a nitro group, the group represented by *-COOR ^111A , and the group represented by *-SO ₂ R ^111D are more preferable, It is especially preferable that it is a cyano group.

It is preferable that the compound represented by Formula (I) is a compound represented by Formula (III).

[R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and E ¹ have the same meanings as above.

R ⁷ represents a hydrogen atom, a cyano group, a methyl group, or a phenyl group.

Z ¹ represents an alkanediyl group having 1 to 12 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, -OR ^2A -*1, -SR ^2B -*1 or -NR ^1D -R ^2C -*1.

Z ² is a single bond, *2-CO-O-, *2-O-CO-, *2-S(=O) ₂ -, *2-O-SO ₂ -, *2-CO-NR ^1B -, *2-NR ^1C -CO-, *2-R ^2D OP(=O)-OR ^2E -, *2-NR ^1E -CO-O-, *2-O-CO-NR ^1F -, *2 -(OR ^2F ) _s1 -, *2-CO-S-, *2-S-CO-, or a C1-C4 perfluoroalkanediyl group.

R ^1B , R ^1C , R ^1D , R ^1E and R ^1F each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ^2A , R ^2B , R ^2C , R ^2D , R ^2E and R ^2F each independently represent a divalent hydrocarbon group having 1 to 18 carbon atoms.

*1 represents a bond with Z ² .

*2 represents a bond with Z ¹ ]

Examples of the alkanediyl group having 1 to 12 carbon atoms represented by Z ¹ include the same groups as the alkanediyl group having 1 to 12 carbon atoms represented by R ¹¹⁵ .

A phenylene group, a naphthylene group, etc. are mentioned as a C6-C18 divalent aromatic hydrocarbon group represented by Z< ¹ >.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^1B , R ^1C , R ^1D , R ^1E and R ^1F include the same ones as the alkyl group having 1 to 6 carbon atoms represented by R ¹¹² .

Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by R ^2A , R ^2B , R ^2C , R ^2D , R ^2E and R ^2F include methylene group, ethylene group, propane-1,3-diyl group, butane-1, 4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group having 1 to 18 carbon atoms of an alkanediyl group; and divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as a phenylene group and a naphthylene group.

Z ¹ is preferably -OR ^2A -*1 (more preferably R ^2A is an alkanediyl group having 1 to 8 carbon atoms, still more preferably an alkanediyl group having 4 to 8 carbon atoms).

Z ² is preferably *2-O-CO-, *2-O-SO ₂ -, *2-NR ^1C -CO- (more preferably R ^1C is a hydrogen atom).

As for the compound represented by Formula (II), it is more preferable that it is a compound represented by Formula (IV).

[In formula (IV), R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and E ¹¹ each have the same meaning as above.

Z ¹ represents a divalent linking group.

A ¹ represents a polymerizable group.]

Although it does not specifically limit as a divalent coupling group represented by Z< ¹ >, For example, a C1-C12 alkanediyl group etc. are mentioned. Examples of the alkanediyl group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. Diyl, ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2- diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned, It is preferable that it is a C1-C8 alkanediyl group. In addition, -CH ₂ - contained in the alkanediyl group having 1 to 12 carbon atoms may be substituted with -O- or -NR ¹¹¹ (R ¹¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)-.

Examples of the polymerizable group represented by A ¹ include the same ones as the polymerizable group represented by A, preferably a radically polymerizable group, and more preferably a (meth)acryloyl group.

The group represented by -Z ¹ -A ¹ is -Z ^1A -O-CO-CH=CH ₂ , -Z ^1A -O-CO-CH=C(CH ₃ )H, -Z ^1A -NR ^111A -CO- It is preferably a group represented by CH=CH ₂ , -Z ^1A -NR ^111A -CO-CH=C(CH ₃ )H. Z ^1A represents an alkanediyl group having 1 to 12 carbon atoms, and R ^111A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the light-selective absorption compound (B) include compounds described below.

The compound represented by the formula (I) in which A is an ethylenically unsaturated group can be obtained, for example, by reacting the compound represented by the formula (Ia) with the compound represented by the formula (c1).

[R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and E ¹ in formula (Ia) have the same meanings as above. Z ³ in the formula (c) represents a divalent linking group, and A ¹ represents an ethylenically polymerizable group.]

It is preferable that the usage-amount of the compound represented by Formula (c1) is 0.5-5 mol with respect to 1 mol of compound represented by Formula (Ia).

The reaction of the compound represented by the formula (Ia) with the compound represented by the formula (c1) can be performed using a known esterification reaction, but is preferably carried out in the presence of a base and a carbodiimide condensing agent. Examples of the base include triethylamine, diisopropylethylamine, pyridine, piperidine, pyrrolidine, proline, and N,N-dimethylaminopyridine. Examples of the carbodiimide condensing agent include N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. have. It is preferable that the usage-amount of a base is 0.001-0.5 mol with respect to 1 mol of the compound represented by Formula (Ia). It is preferable that the usage-amount of a carbodiimide condensing agent is 0.5-5 mol with respect to 1 mol of the compound represented by Formula (Ia).

The reaction of the compound represented by the formula (Ia) with the compound represented by the formula (c1) is preferably performed in an organic solvent. Examples of the organic solvent include toluene, acetonitrile, dichloromethane, and trichloromethane.

In order to inhibit reaction of the ethylenically unsaturated groups contained in the compound represented by Formula (c1), you may add a polymerization inhibitor. Examples of the polymerization inhibitor include 2,6-di-t-butyl-4-methylphenol (BHT) and 4-methoxyphenol.

The reaction of the compound represented by the formula (Ia) and the compound represented by (c1) is carried out by mixing the compound represented by the formula (Ia) and the compound represented by (c1).

It is preferable that the reaction temperature of the compound represented by formula (Ia) and the compound represented by (c1) is -20 to 120 degreeC, and it is preferable that the reaction time is normally 1 to 50 hours.

Examples of the compound represented by the formula (Ia) include the compounds described below.

Examples of the compound represented by the formula (c1) include 4-hydroxybutyl acrylate and 2-hydroxyethyl acrylate.

The compound represented by the formula (Ia) can be obtained by reacting the compound represented by the formula (Ib) with the compound represented by the formula (c2).

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and E ¹ have the same meanings as above.]

It is preferable that the usage-amount of the compound represented by Formula (c2) is 0.5-5 mol with respect to 1 mol of compound represented by Formula (Ib).

The reaction between the compound represented by the formula (Ib) and the compound represented by the formula (c2) is preferably performed in the presence of a base. Examples of the base include pyridine, pyrrolidine, piperidine, triethylamine, and diisopropylethylamine. It is preferable that the usage-amount of a base is 0.5-5 mol with respect to 1 mol of the compound represented by Formula (Ib).

The reaction of the compound represented by the formula (Ib) with the compound represented by the formula (c2) is preferably performed in an organic solvent. Examples of the organic solvent include acetonitrile, isopropanol, toluene, trichloromethane, and dichloromethane.

The reaction of the compound represented by the formula (Ib) and the compound represented by (c2) is carried out by mixing the compound represented by the formula (Ia) and the compound represented by (c1).

It is preferable that the reaction temperature of the compound represented by formula (Ia) and the compound represented by (c1) is 0-120 degreeC, and it is preferable that the reaction time is normally 1-50 hours.

Content of the light selective absorption compound (B) is 0.1-50 mass parts normally with respect to 100 mass parts of resin (A), Preferably it is 1-25 mass parts, More preferably, it is 2-15 mass parts, further Preferably it is 3-12 mass parts, Especially preferably, it is 4-10 mass parts.

<Initiator (C)>

The pressure-sensitive adhesive composition of the present invention contains an initiator (C). The initiator (C) may be either a compound causing a polymerization reaction by absorbing heat energy (thermal polymerization initiator) or a compound causing a polymerization reaction by absorbing light energy (photo polymerization initiator). On the other hand, it is preferable that light here is an active energy ray like visible light, an ultraviolet-ray, an X-ray, or an electron beam.

As the thermal polymerization initiator, a compound that generates radicals by heating or the like (thermal radical generator), a compound that generates an acid by heating or the like (thermal acid generator), a compound that generates a base by heating or the like (thermal base generator), etc. can be heard

As a photoinitiator, a compound which generates a radical by absorbing the energy of light (photoradical generator), a compound which generates an acid by absorbing the energy of light (photoacid generator), a base by absorbing the energy of light The compound (photobase generator) etc. which generate|occur|produce are mentioned.

It is preferable to select the thing suitable for the polymerization reaction of the radically curable component (D) mentioned later, and, as for an initiator (C), it is preferable that it is a radical polymerization initiator, and it is more preferable that it is a radical photopolymerization initiator.

As a radical polymerization initiator, an alkylphenone compound, a benzoin compound, a benzophenone compound, an oxime ester compound, a phosphine compound, etc. are mentioned, for example. It is preferable that it is a radical photopolymerization initiator, and, as for a radical polymerization initiator, it is more preferable that it is an oxime ester system photoradical polymerization initiator from a reactive viewpoint of a polymerization reaction. By using an oxime ester-based photo-radical polymerization initiator, the reaction rate of the radical curing component (D) can be increased even under curing conditions with low illuminance or light quantity.

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

Examples of the α-aminoalkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)- 2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, etc. are mentioned, Preferably 2-methyl -2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, etc. can The α-aminoalkylphenone compound is Igacure (registered trademark) 127, 184, 369, 369E, 379EG, 651, 907, 1173, 2959 (above, manufactured by BASF Japan Co., Ltd.), Seikuol (registered trademark) BEE ( You may use commercial items, such as the Seiko Chemical company make).

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As the benzophenone compound, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butyl Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. A commercial item may be used for a benzophenone compound.

As the oxime ester compound, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one -2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9 -ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine can The oxime compound is Igacure OXE-01, OXE-02, OXE-03 (above, manufactured by BASF Japan), N-1919, NCI-730, NCI-831E, NCI-930 (made by ADEKA), PBG3057 (TRONLY) You may use commercial items, such as a company make).

Examples of the phosphine compound include acylphosphine oxides such as phenyl (2,4,6-trimethylbenzoyl)phosphine oxide and diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide. Examples of the phosphine compound include Igacure (registered product) TPO and Igacure 819 (manufactured by BASF Japan Co., Ltd.).

The photo-acid generator may be an onium salt such as an aromatic iodonium salt or an aromatic sulfonium salt; aromatic diazonium salts; An iron-arene complex etc. are mentioned.

The aromatic iodonium salt is a compound having a diaryliodonium cation, and examples of the cation include typically a diphenyliodonium cation. The aromatic sulfonium salt is a compound having a triarylsulfonium cation, and examples of the cation include a triphenylsulfonium cation and a 4,4'-bis(diphenylsulfonio)diphenylsulfide cation. have. An aromatic diazonium salt is a compound which has a diazonium cation, and a benzenediazonium cation is mentioned typically as said cation. In addition, the iron-arene complex is typically a cyclopentadienyl iron(II) arene cation complex salt.

Said cation is paired with an anion (anion) and comprises a photocation generating agent. Examples of anions constituting the photocation generator include a special phosphorus anion [(Rf) _n PF _6-n ] ^- , hexafluorophosphate anion PF ₆ ^- , hexafluoroantimonate anion SbF ₆ ^- , pentafluoro rhohydroxyantimonate anion SbF ₅ (OH) ^- , hexafluoroacetate anion AsF ₆ ^- , tetrafluoroborate anion BF ₄ ^- , tetrakis(pentafluorophenyl)borate anion B(C ₆ F ₅ ) ₄ ^- and so on. Among them, from the viewpoint of the curability of the cationically polymerizable compound and the safety of the resulting light selective absorption layer, a special phosphorus anion [(Rf) _n PF _6-n ] ^- , hexafluorophosphate anion PF ₆ ^- , tetrakis (pentafluoro Phenyl) borate anion B(C ₆ F ₅ ) ₄ ^- , hexafluoroantimonate anion SbF ₆ ^- is preferred.

Examples of the photobase generator include carbamate compounds, α-aminoketone compounds, quaternary ammonium compounds, O-acyloxime compounds, aminocyclopropenone compounds, and the like.

As the carbamate compound, for example, 1-(2-anthraquinonyl)ethyl 1-piperidinecarboxylate, 1-(2-anthraquinonyl)ethyl 1H-2-ethylimidazole-1-carboxylate , 9-anthrylmethyl 1-piperidinecarboxylate, 9-anthrylmethyl N,N-diethyl carbamate, 9-anthrylmethyl N-propyl carbamate, 9-anthrylmethyl N-cyclohexylcarbamate Mate, 9-anthrylmethyl 1H-imidazole-1-carboxylate, 9-anthrylmethyl N,N-dioctylcarbamate, 9-anthrylmethyl 1-(4-hydroxypiperidine)carboxyl rate, 1-pyrenylmethyl-1-piperidinecarboxylate, bis[1-(2-anthraquinonyl)ethyl]1,6-hexanediylbiscarbamate, bis(9-anthrylmethyl)1; 6-hexanediylbiscarbamate is mentioned.

As the α-aminoketone compound, for example, the following are known. 1-phenyl-2-(4-morpholinobenzoyl)-2-dimethylaminobutane, 2-(4-methylthiobenzoyl)-2-morpholinopropane, etc. are mentioned.

Examples of the quaternary ammonium compound used as the photobase generator include 1-(4-phenylthiophenacyl)-1-azonia-4-azabicyclo[2,2,2]octanetetraphenylborate, 5-(4- Phenylthiophenacyl)-1-aza-5-azoniabicyclo[4,3,0]-5-nonene tetraphenylborate, 8-(4-phenylthiophenacyl)-1-aza-8-azoni Abicyclo[5,4,0]-7-undecenetetraphenylborate etc. are mentioned.

Examples of the aminocyclopropenone compound serving as the photobase generator include 2-diethylamino-3-phenylcyclopropenone, 2-diethylamino-3-(1-naphthyl)cyclopropenone, and 2-pyrrolidinyl. -3-phenylcyclopropenone, 2-imidazolyl-3-phenylcyclopropenone, 2-isopropylamino-3-phenylcyclopropenone, and the like.

Examples of the thermal base generator include carbamate derivatives such as 2-(4-biphenyl)-2-propyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate, urea and N,N,N'- urea derivatives such as trimethylurea; dihydropyridine derivatives such as 1,4-dihydronicotinamide; dicyandiamide; and salts composed of acids and bases such as organic salts and inorganic salts.

Content of initiator (C) is 0.01-20 mass parts normally with respect to 100 mass parts of resin (A), It is preferable that it is 0.3-10 mass parts, It is more preferable that it is 0.5-5 mass parts, It is 0.75-4 mass parts It is more preferable, Especially preferably, it is 1-3 mass parts.

The pressure-sensitive adhesive composition of the present invention comprises a radically curable component (D), a crosslinking agent (E), a silane compound (F), a light selective absorption compound (G) other than the light selective absorption compound (B) (hereinafter, a light selective absorption compound (G) ), may further contain an antistatic agent, etc., at least selected from the group consisting of a radical curable component (D), a crosslinking agent (E), a silane compound (F), and a light selective absorption compound (G) It is preferable to include one.

<Radically curable component (D)>

As a radical-curable component (D), radical-curable components, such as a compound or oligomer which harden|cure by a radical polymerization reaction, are mentioned.

As a radically polymerizable component (D), a (meth)acrylate-type compound, a styrene-type compound, a vinyl-type compound, etc. are mentioned.

The adhesive composition of this invention may contain 2 or more types of radical curable component (D).

As the (meth)acrylic compound, a (meth)acrylate monomer having at least one (meth)acryloyloxy group in the molecule, a (meth)acrylamide monomer, and at least two (meth)acryloyl groups in the molecule (meth)acryloyl group containing compounds, such as a (meth)acryl oligomer, are mentioned. The (meth)acryl oligomer is preferably a (meth)acrylate oligomer having at least two (meth)acryloyloxy groups in the molecule. A (meth)acrylic-type compound may be used individually by 1 type, and may use 2 or more types together.

As a (meth)acrylate monomer, the monofunctional (meth)acrylate monomer which has one (meth)acryloyloxy group in a molecule|numerator, and bifunctional (meth)acrylate which has two (meth)acryloyloxy groups in a molecule|numerator Monomers and polyfunctional (meth)acrylate monomers having three or more (meth)acryloyloxy groups in the molecule are exemplified.

Alkyl (meth)acrylate is mentioned as a monofunctional (meth)acrylate monomer. Alkyl (meth)acrylate WHEREIN: When the carbon number of the alkyl group is 3 or more, any of linear, branched, and cyclic|annular form may be sufficient. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate ) acrylate and 2-ethylhexyl (meth)acrylate.

Moreover, as a monofunctional (meth)acrylate monomer, Aralkyl (meth)acrylates, such as benzyl (meth)acrylate; (meth)acrylates of terpene alcohols such as isobornyl (meth)acrylate; (meth)acrylates having a tetrahydrofurfuryl structure such as tetrahydrofurfuryl (meth)acrylate; A cycloalkyl group at the alkyl group moiety, such as cyclohexyl (meth) acrylate, cyclohexylmethyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl (meth) acrylate, and 1,4-cyclohexanedimethanol monoacrylate (meth)acrylate having; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; 2-phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate having an ether bond in the alkyl moiety (meth)acrylate, etc. are also mentioned.

Moreover, as a monofunctional (meth)acrylate monomer, the monofunctional (meth)acrylate which has a hydroxyl group in an alkyl part; and monofunctional (meth)acrylates having a carboxyl group in the alkyl moiety. Examples of the monofunctional (meth)acrylate having a hydroxyl group in the alkyl moiety include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. and 2-hydroxy-3-phenoxypropyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, and pentaerythritol mono(meth)acrylate. Examples of the monofunctional (meth)acrylate having a carboxyl group in the alkyl moiety include 2-carboxyethyl (meth)acrylate, ω-carboxypolycaprolactone (n=2) mono(meth)acrylate, and 1-[2-(meth)acrylate. ) 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, etc. are mentioned.

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 may form a ring together with the nitrogen atom of (meth)acrylamide, and this ring is an oxygen atom in addition to a carbon atom and the nitrogen atom of (meth)acrylamide. may have as ring members. Further, a substituent such as alkyl or oxo (=O) may be bonded to the carbon atom constituting the ring.

As N-substituted (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-t-butyl N-alkyl(meth)acrylamide such as (meth)acrylamide and N-hexyl(meth)acrylamide; N,N-dialkyl (meth)acrylamide, such as N,N- dimethyl (meth)acrylamide and N,N- diethyl (meth)acrylamide, etc. are mentioned. In addition, the N-substituent group may be an alkyl group having a hydroxyl group, and examples thereof include N-hydroxymethyl (meth)acrylamide, N-(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxyl). propyl) (meth)acrylamide etc. are mentioned. In addition, specific examples of the N-substituted (meth)acrylamide forming the 5-membered ring or 6-membered ring include N-acryloylpyrrolidine, 3-acryloyl-2-oxazolidinone, and 4-acryloylmorpholine. , N-acryloylpiperidine, N-methacryloylpiperidine, and the like.

As a bifunctional (meth)acrylate monomer,

Ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9- alkylene glycol di(meth)acrylates such as 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, poly polyoxyalkylene glycol di(meth)acrylates such as propylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate;

di(meth)acrylates of halogen-substituted alkylene glycols such as tetrafluoroethylene glycol di(meth)acrylate;

di(meth)acrylates of aliphatic polyols such as trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, and pentaerythritol di(meth)acrylate;

di(meth)acrylates of hydrogenated dicyclopentadiene or tricyclodecanedialkanol such as hydrogenated dicyclopentadienyldi(meth)acrylate and tricyclodecanedimethanoldi(meth)acrylate;

di(meth)acrylates of dioxane glycol or dioxane dialkanol such as 1,3-dioxane-2,5-diyldi(meth)acrylate [alias: dioxane glycol di(meth)acrylate];

di(meth)acrylates of alkylene oxide adducts of bisphenol A or bisphenol F such as bisphenol A ethylene oxide adduct diacrylate and bisphenol F ethylene oxide adduct diacrylate;

Epoxydi(meth)acrylates of bisphenol A or bisphenol F, such as an acrylic acid adduct of bisphenol A diglycidyl ether and an acrylic acid adduct of bisphenol F diglycidyl ether; silicone di(meth)acrylate;

di(meth)acrylate of hydroxypivalic acid neopentyl glycol ester;

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

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

Tris (hydroxyethyl) isocyanurate di (meth) acrylate etc. are mentioned.

Examples of the trifunctional or higher polyfunctional (meth)acrylate monomer include glycerin tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tri(meth)acryl. rate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( poly(meth)acrylates of trifunctional or higher aliphatic polyols such as meth)acrylate and dipentaerythritol hexa(meth)acrylate; poly(meth)acrylates of trifunctional or more halogen-substituted polyols; tri(meth)acrylate of an alkylene oxide adduct of glycerin; tri(meth)acrylate of an alkylene oxide adduct of trimethylolpropane; 1,1,1-tris[(meth)acryloyloxyethoxyethoxy]propane; Tris (hydroxyethyl) isocyanurate tri (meth) acrylate etc. are mentioned.

Moreover, you may use a commercial item. As a commercial item, A-DPH-12E, A-TMPT, A-9300 (made by Shin-Nakamura Chemical Co., Ltd.) etc. are mentioned, for example.

As a (meth)acryl oligomer, a urethane (meth)acryl oligomer, a polyester (meth)acryl oligomer, an epoxy (meth)acryl oligomer, etc. are mentioned.

A urethane (meth)acryl oligomer is a compound which has a urethane bond (-NHCOO-) and at least two (meth)acryloyl groups in a molecule|numerator. Specifically, a urethanation reaction product of a hydroxyl group-containing (meth)acrylic monomer and polyisocyanate each having at least one (meth)acryloyl group and at least one hydroxyl group in the molecule, or a terminal isoform obtained by reacting a polyol with a polyisocyanate. It may be a urethanation reaction product of a cyanato group-containing urethane compound and a (meth)acrylic monomer each having at least one (meth)acryloyl group and at least one hydroxyl group in the molecule.

The hydroxyl group-containing (meth)acrylic monomer used in the urethanization reaction may be, for example, a hydroxyl group-containing (meth)acrylate monomer, and specific examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate , pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Specific examples other than the hydroxyl group-containing (meth)acrylate monomer include N-hydroxyalkyl (meth)acrylamide monomers such as N-hydroxyethyl (meth)acrylamide and N-methylol (meth)acrylamide. .

Examples of the polyisocyanate used for the urethanation reaction with the hydroxyl group-containing (meth)acrylic monomer include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and these Diisocyanates obtained by hydrogenating aromatic isocyanates among diisocyanates (eg, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.), triphenylmethane triisocyanate, di- or tri- such as dibenzylbenzene triisocyanate Polyisocyanate and polyisocyanate obtained by multiplying the said diisocyanate, etc. are mentioned.

Moreover, as a polyol used in order to set it as a terminal isocyanato group containing urethane compound by reaction with polyisocyanate, polyester polyol, polyether polyol, etc. other than an aromatic, aliphatic or alicyclic polyol can be used. Examples of the aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylol. propane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerin, hydrogenated bisphenol A, and the like.

A polyester polyol is obtained by the dehydration-condensation reaction of the said polyol and polybasic carboxylic acid or its anhydride. Examples of polybasic carboxylic acids or their anhydrides are expressed by adding "(anhydride)" to what may be anhydride, (anhydride) succinic acid, adipic acid, (anhydride) maleic acid, (anhydride) itaconic acid, (anhydride) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, hexahydro (anhydrous) phthalic acid, and the like.

The polyether polyol may be a polyoxyalkylene-modified polyol obtained by reaction of the polyol or dihydroxybenzenes with an alkylene oxide other than polyalkylene glycol.

A polyester (meth)acrylate oligomer means the oligomer which has an ester bond and at least two (meth)acryloyloxy groups in a molecule|numerator.

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

Examples of the polybasic carboxylic acid or anhydride thereof include succinic anhydride, adipic acid, maleic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, phthalic acid, succinic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like.

Examples of the polyol include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol. , dipentaerythritol, dimethylol heptane, dimethylol propionic acid, dimethylol butanoic acid, glycerin, and hydrogenated bisphenol A.

The epoxy (meth)acryl oligomer can be obtained by addition reaction of polyglycidyl ether and (meth)acrylic acid. The epoxy (meth)acryl oligomer has at least two (meth)acryloyloxy groups in the molecule.

As polyglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl Ether etc. are mentioned.

Examples of the styrene-based compound include styrene; alkyl styrenes such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodine styrene; nitrostyrene; acetyl styrene; methoxystyrene; and divinylbenzene.

Examples of the vinyl-based monomer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing heteroaromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated dienes such as butadiene, isoprene and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

It is preferable that it is a (meth)acrylate compound, and, as for a radically curable component (D), it is more preferable that it is a polyfunctional (meth)acrylate compound. The polyfunctional (meth)acrylate compound is preferably trifunctional or more.

Content of a radically curable component (D) is 0.5-100 mass parts normally with respect to 100 mass parts of resin (A), It is preferable that it is 1-70 mass parts, It is more preferable that it is 3-50 mass parts, 5-30 mass parts It is more preferable that it is a mass part, and it is especially preferable that it is 7.5-25 mass parts.

<Crosslinking agent (E)>

Examples of the crosslinking agent (E) include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, and a metal chelate-based crosslinking agent. It is preferable to be

As the isocyanate-based crosslinking agent, a compound having at least two isocyanato groups (-NCO) in the molecule is preferable, for example, an aliphatic isocyanate-based compound (such as hexamethylene diisocyanate), an alicyclic isocyanate-based compound (such as isophoronedi) isocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), aromatic isocyanate compounds (such as tolylene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.) can In addition, the crosslinking agent (E) is an adduct (adduct) of the polyhydric alcohol compound of the isocyanate compound [eg, an adduct using glycerol, trimethylolpropane, etc.], isocyanurate, biuret-type compound, polyether polyol , polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol and the like may be a derivative such as a urethane prepolymer type isocyanate compound. A crosslinking agent (E) can be used individually or in combination of 2 or more types. Among these, representatively, aromatic isocyanate compounds (eg tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (eg hexamethylene diisocyanate) or polyhydric alcohol compounds thereof (eg glycerol, trimethylolpropane) are used. an adduct or an isocyanurate body. If the crosslinking agent (F) is an aromatic isocyanate-based compound and/or an adduct of a polyhydric alcohol compound thereof, or an isocyanurate compound, it may be because it is advantageous for formation of an optimal crosslinking density (or crosslinked structure), the pressure-sensitive adhesive layer can improve the durability of In particular, if it is a tolylene diisocyanate-based compound and/or an adduct of these polyhydric alcohol compounds, durability can be improved even when, for example, a pressure-sensitive adhesive layer is applied to a polarizing plate.

Content of a crosslinking agent (E) is 0.01-25 mass parts normally with respect to 100 mass parts of resin (A), Preferably it is 0.1-15 mass parts, More preferably, it is 0.15-7 mass parts, More preferably is 0.2 to 5 parts by mass, particularly preferably 0.25 to 2 parts by mass.

<Silane compound (F)>

As the silane compound (F), for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldime oxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

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

3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxylan-tetramethoxysilane oligomer, 3- mercaptopropyl group-containing oligomers such as mercaptopropyltriethoxylan-tetraethoxysilane oligomers; Mercaptomethyltrimethoxysilane-tetramethoxysilane oligomer, mercaptomethyltrimethoxysilane-tetraethoxysilane oligomer, mercaptomethyltriethoxysilane-tetramethoxysilane oligomer, mercaptomethyltriethoxysilane- mercaptomethyl group-containing oligomers such as tetraethoxysilane oligomers; 3-Glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxy Silane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane - 3-glycidoxy such as tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer propyl group-containing copolymer; 3-Methacryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloyloxypropyltriethoxysilane -Tetramethoxysilane oligomer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacrylo Iloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane methacryloyloxypropyl group-containing oligomers such as oligomers; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropyltriethoxysilane-tetrameth Toxysilane oligomer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxy Acryloyloxypropyl such as silane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer group-containing oligomers; Vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinylmethyl Contains vinyl groups such as dimethoxysilane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, and vinylmethyldiethoxysilane-tetraethoxysilane oligomer oligomers; 3-Aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3- Aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyl amino group-containing copolymers such as methyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer;

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

(In formula (f1), A represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group is, It may be substituted with -O- or -CO-, R ⁴¹ represents an alkyl group having 1 to 5 carbon atoms, and R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent 1 to 5 carbon atoms. represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms.)

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by A in the formula (f1) include a methylene group, a 1,2-ethanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, and 1,5 -Pentanediyl group, 1,6-hexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1,10-decanediyl group, 1,12-dode and a candiyl group, a 1,14-tetradecanediyl group, a 1,16-hexadecanediyl group, a 1,18-octadecanediyl group, and a 1,20-icosandiyl group. Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a 1,3-cyclopentanediyl group and a 1,4-cyclohexanediyl group. As a group in which -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group is substituted with -O- or -CO-, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ - O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -CO -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -CO-O-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ - and -CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ CH ₂ -.

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

Examples of the silane compound represented by the formula (f1) include (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3 -bis(trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,4-bis(triethoxysilyl)butane, 1 ,5-bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane , 1,6-bis(tripropoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(tripropoxysilyl) ) bis(tri C1-5 alkoxysilyl) C1-10 alkanes such as octane; 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)hexane, 1,8-bis(dimethoxymethylsilyl)octane, bis(di C1-5 alkoxy C1-5 alkylsilyl) C1-10 alkanes such as 1,8-bis(dimethoxyethylsilyl)octane; Bis(mono C1-5 alkoxydi C1-5 alkylsilyl) C1-10 alkanes such as 1,6-bis(methoxydimethylsilyl)hexane and 1,8-bis(methoxydimethylsilyl)octane; and the like. . Among these, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethane) Bis(tri C1-3 alkoxysilyl) C1-10 alkanes such as oxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, and 1,8-bis(trimethoxysilyl)octane are preferable, and particularly , 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane are preferred.

Content of a silane compound (F) is 0.01-20 mass parts normally with respect to 100 mass parts of resin (A), Preferably it is 0.1-10 mass parts, More preferably, it is 0.15-7 mass parts, More preferably Preferably it is 0.2-5 mass parts, Especially preferably, it is 0.25-2 mass parts.

<Light Selective Absorption Compound (G)>

The light-selective absorption compound (G) is a light-selective absorption compound other than the light-selective absorption compound (B), for example, that absorbs light having a wavelength of 250 nm to 380 nm (preferably a wavelength of 250 nm or more and less than 360 nm). It is a compound (ultraviolet absorber).

Although the structure of the light selective absorption compound (G) is not particularly limited as long as it is a compound that absorbs light having a wavelength of 250 nm to 380 nm, a benzotriazole compound, a benzophenone compound, a triazine compound, a salicylic acid compound, Compounds, such as a cyanoacrylate type compound and a benzoxazine type compound, etc. are preferable.

The light selective absorption compound (G) may be a commercial item, "Kemisorb 102" by Kemipro Chemical Co., Ltd., "ADEKASTAB LA46", "ADEKASTAB LAF70" by ADEKA Co., Ltd., Tinuvin 109 by BASF Japan , Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 928, Tinuvin 400, Tinuvin 460, Tinuvin 405, Tinuvin 477 Triazine-based ultraviolet absorbers; "ADEKA STAB LA31" and "ADEKA STAB LA36" manufactured by ADEKA Co., Ltd., "SmiSorb 200", "SmiSorb 250", "SmiSorb 300", "SmiSorb 340" manufactured by Sumika Chemtex Co., Ltd. ' and "Smisorb 350", "Kemisorb 74", "Kemisorb 79" and "Kemisorb 279" manufactured by Kemipro Chemical Co., Ltd., "TINUVIN 99-2", "TINUVIN 900" and "TINUVIN 928" manufactured by BASF Benzotriazole type ultraviolet absorbers, such as these are mentioned.

In addition, the light selective absorption compound (G) may be an inorganic type ultraviolet absorber. Examples of the inorganic ultraviolet absorber include titanium oxide, zinc oxide, indium oxide, tin oxide, talc, kaolin, calcium carbonate, titanium oxide-based composite oxide, zinc oxide-based composite oxide, ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide). ) and the like. Examples of the titanium oxide-based composite oxide include silica and titanium oxide doped with alumina.

Content of the light selective absorption compound (G) is 0.1-20 mass parts normally with respect to 100 mass parts of resin (A), Preferably it is 0.2-15 mass parts, More preferably, it is 0.3-10 mass parts, More preferably, it is 0.5-7.5 mass parts, Especially preferably, it is 1-5 mass parts.

The pressure-sensitive adhesive composition may further contain one or more additives such as a solvent, a crosslinking catalyst, a tackifier, a plasticizer, a softener, a pigment, a rust inhibitor, an inorganic filler, and light scattering fine particles.

The pressure-sensitive adhesive layer of the present invention is, for example, by dissolving or dispersing the pressure-sensitive adhesive composition of the present invention in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying it to the surface of a substrate and drying it, followed by irradiation with active energy rays can be formed The adhesive layer of this invention can also be called the photocured material of an adhesive composition.

A plastic film is suitable as a base material, and the release film by which the release process was carried out specifically, is mentioned. Examples of the release film include those in which one side of a film made of a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate or polyarylate has been subjected to a release treatment such as silicone treatment.

Although the conditions (drying temperature, drying time) for drying the coating film formed from the adhesive composition containing a solvent can be set suitably with the composition and density|concentration, Preferably they are 60-150 degreeC and 1 to 60 minutes.

It is preferable that active energy ray irradiation after drying of a coating film is ultraviolet irradiation. It is preferable that the illuminance of the ultraviolet-ray to irradiate is 10 mW/cm<2> - 3000 mW/cm<2>. Moreover, it is preferable that the accumulated light quantity of an ultraviolet-ray is 10 mJ/cm<2> - 5000 mJ/cm<2>.

The ultraviolet lamp which irradiates an ultraviolet-ray may be a mercury lamp, a metal halide lamp, and an LED lamp.

It is preferable that the adhesive layer of this invention is an adhesive layer which satisfy|fills following formula (2).

A(400)≥0.4 (2)

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

The larger the value of A(400), the higher the absorption at a wavelength of 400 nm. When the value of A (400) is less than 0.4, absorption at a wavelength of 400 nm is low, and deterioration of members (such as display devices such as organic EL elements and liquid crystal retardation films, etc.) that are likely to be deteriorated by light in the vicinity of ultraviolet rays occurs. easy. The value of A(400) becomes like this. Preferably it is 0.5 or more, More preferably, it is 0.75 or more, More preferably, it is 1.0 or more, Especially preferably, it is 1.5 or more. Although there is no upper limit in particular, it is usually 10 or less.

The thickness of the adhesive layer of this invention is less than 200 micrometers normally, Preferably it is 100 micrometers or less, More preferably, it is 20 micrometers or less, More preferably, it is 12 micrometers or less, Especially preferably, it is 7 micrometers or less. Moreover, it is 0.1 micrometer or more normally, Preferably it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more, More preferably, it is 2 micrometers or more.

According to the present invention, since ultraviolet rays can be sufficiently absorbed even in the adhesive layer of a thin film having a thickness of, for example, less than 12 µm, it is advantageous from the viewpoint of thinning the display device.

The gel fraction of the adhesive layer of this invention is 50-99.9 mass % normally, It is preferable that it is 60-99 mass %, More preferably, it is 70-95 mass %, More preferably, it is 75-90 mass %.

<Optical film with adhesive layer>

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

The optical film with an adhesive layer in which the optical film was laminated|stacked on at least one surface of the adhesive layer of this invention is also contained in this invention.

The optical film with a pressure-sensitive adhesive layer of the present invention is formed by dissolving or dispersing the pressure-sensitive adhesive composition in a solvent to obtain a pressure-sensitive adhesive composition containing a solvent, then applying it to the surface of the optical film, drying it, and then irradiating with active energy rays. can Moreover, it can obtain also by carrying out similarly to a peeling film, forming an adhesive layer, and laminating|stacking (transferring) this adhesive layer on the surface of an optical film.

An optical film is a film which has optical functions, such as permeation|transmission, reflection, and absorbing light. The optical film may be a single-layered film or a multilayered film. The optical film includes, for example, a polarizing film, a retardation film, a brightness improving film, an anti-glare film, an antireflection film, a diffusion film, a light collecting film, and the like, and is preferably a polarizing film, retardation film, or laminated film thereof.

The condensing film is used for the purpose of controlling an optical path or the like, and may be a prism array sheet, a lens array sheet, a dot laying sheet, or the like.

A brightness improving film is used for the purpose of improving the brightness|luminance in the liquid crystal display to which the polarizing plate is applied. Specifically, a reflective polarization separation sheet designed to produce anisotropy in reflectance by laminating a plurality of thin films with different anisotropy of refractive index, an alignment film of cholesteric liquid crystal polymer, or a liquid crystal layer thereof supported on a base film A circularly polarized light separation sheet etc. are mentioned.

A polarizing film is a film having a property of absorbing linearly polarized light having an oscillation plane parallel to the absorption axis and transmitting linearly polarized light having an oscillation plane perpendicular to the absorption axis (parallel to the transmission axis), for example, polyvinyl alcohol A film in which a dichroic dye is adsorbed and orientated to the system resin film can be used.

As a dichroic dye, an iodine, a dichroic organic dye, etc. are mentioned, for example.

The saponification degree of polyvinyl alcohol-type resin is 85 mol% - 100 mol% normally, Preferably it is 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehyde may be used. The polymerization degree of polyvinyl alcohol-type resin is 1,000-10,000 normally, Preferably it is 1,500-5,000.

Usually, what formed the polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. Polyvinyl alcohol-type resin can be formed into a film by a well-known method. The thickness of a raw film is 1-150 micrometers normally, and when the easiness of extending|stretching etc. are considered, Preferably it is 10 micrometers or more.

Polarizing film, for example, with respect to the raw film, a step of uniaxial stretching, a step of dyeing the film with a dichroic dye to adsorb the dichroic dye, a step of treating the film with an aqueous boric acid solution, and a step of washing the film with water and finally dried. The thickness of a polarizing film is 1-30 micrometers normally, From a viewpoint of thinning of the optical laminated body with an adhesive layer, Preferably it is 20 micrometers or less, More preferably, it is 15 micrometers or less, Especially preferably, it is 10 micrometers or less.

It is preferable that at least one surface of a polarizing film is a polarizing plate in which the protective film is formed through the adhesive agent.

As an adhesive agent, a well-known adhesive agent is used, a water-based adhesive agent may be sufficient and an active energy ray hardening-type adhesive agent may be sufficient.

As the water-based adhesive, a common water-based adhesive (eg, an adhesive made of an aqueous polyvinyl alcohol-based resin solution, a water-based two-part urethane-based emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine-based compound, a methylol compound, an isocyanate compound, an amine compound, a polyvalent metal salt crosslinking agents, such as these) are mentioned. Among these, the water-based adhesive agent which consists of polyvinyl alcohol-type resin aqueous solution can be used suitably. Moreover, when using a water-system adhesive agent, after bonding a polarizing film and a protective film, in order to remove the water contained in a water-system adhesive agent, it is preferable to perform the process of drying. After the drying step, for example, a curing step of curing at a temperature of about 20 to 45°C may be provided. The adhesive layer formed with a water-based adhesive agent is 0.001-5 micrometers normally.

Active energy ray-curable adhesive refers to an adhesive that is cured by irradiating active energy rays such as ultraviolet rays or electron beams, for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photoreactive resin, a binder resin and A curable composition containing a photoreactive crosslinking agent, etc. are mentioned, Preferably it is an ultraviolet curable adhesive.

As a method of bonding a polarizing film and a protective film, the method of performing surface activation processing, such as a saponification process, a corona treatment, and a plasma process, to these at least any one bonding surface, etc. are mentioned. When a protective film is bonded on both surfaces of a polarizing film, the adhesive agent of the same type may be sufficient as the adhesive agent for bonding these resin films, and a different type of adhesive agent may be sufficient as it.

As a protective film, it is preferable that it is a film formed from the thermoplastic resin which has translucency. Specifically, polyolefin resin; Cellulose-based resin; polyester-based resin; (meth)acrylic resin; or a film made of a mixture or copolymer thereof. When a protective film is formed in both surfaces of a polarizing film, the film which consists of a different thermoplastic resin may be sufficient as the protective film used, and the film which consists of the same thermoplastic resin may be sufficient as it.

When the protective film is laminated on at least one side of the polarizing film, the protective film is preferably a protective film made of a polyolefin-based resin or a cellulose-based resin. By using these films, the shrinkage|contraction of the polarizing film in a high-temperature environment can be suppressed effectively, without impairing the optical characteristic of a polarizing film. Moreover, an oxygen shielding layer may be sufficient as a protective film.

As a preferable structure of a polarizing plate, it is a polarizing plate by which the protective film was laminated|stacked on at least one surface of a polarizing film via an adhesive bond layer. When a protective film is laminated|stacked only on one side of a polarizing film, it is more preferable to laminate|stack on the visual recognition side. It is preferable that the protective film laminated|stacked on the visual recognition side is a protective film which consists of a triacetyl cellulose-type resin or a cycloolefin-type resin. An unstretched film may be sufficient as a protective film, and it may extend|stretch in arbitrary directions, and may have retardation. Surface treatment layers, such as a hard-coat layer and an anti-glare layer, may be formed in the surface of the protective film laminated|stacked on the visual recognition side.

When the protective film is laminated on both sides of the polarizing film, the protective film on the panel side (the side opposite to the viewing side) is preferably a protective film or retardation film made of a triacetyl cellulose-based resin, a cycloolefin-based resin, or an acrylic resin. The retardation film may be a zero-retardation film mentioned later.

The retardation film is an optical film exhibiting optical anisotropy, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride. / A stretched film obtained by stretching a polymer film made of polymethyl methacrylate, acetyl cellulose, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc. to about 1.01 to 6 times, etc. are mentioned. It is preferable that it is the polymer film which uniaxially or biaxially stretched the acetyl cellulose, polyester, a polycarbonate film, or a cycloolefin resin film among a stretched film. Moreover, the retardation film in which optical anisotropy was expressed by application|coating and orientation of a liquid crystalline compound to a base material may be sufficient as retardation film.

Meanwhile, in the present specification, the retardation film includes a zero retardation film, and also includes a film called a uniaxial retardation film, a low photoelastic modulus retardation film, a wide viewing angle retardation film, and the like.

The zero retardation film refers to an optically isotropic film having both the front retardation _{Re and the retardation R th in} the thickness direction of -15 to 15 nm. Examples of the zero retardation film include a resin film made of a cellulose-based resin, a polyolefin-based resin (chain polyolefin-based resin, polycycloolefin-based resin, etc.) or a polyethylene terephthalate-based resin, and the retardation value can be easily controlled and obtained. From the viewpoint of being easy to use, a cellulosic resin or a polyolefin-based resin is preferable. The zero retardation film can be used also as a protective film. As a zero retardation film, "Z-TAC" (trade name) sold by Fujifilm Co., Ltd., "Zerotac (registered trademark)" sold by Konica Minolta Opto Co., Ltd., sold by Nippon Zeon Co., Ltd. "ZF-14" (brand name), etc. are mentioned.

The optical film of this invention WHEREIN: As for retardation film, the retardation film which expressed optical anisotropy by application|coating and orientation of a liquid crystalline compound is preferable.

As a film in which optical anisotropy was expressed by application|coating and orientation of a liquid crystalline compound, the following 1st - 5th aspects are mentioned.

First form: retardation film in which the rod-shaped liquid crystal compound is oriented in the horizontal direction with respect to the supporting substrate

Second form: retardation film in which the rod-shaped liquid crystal compound is oriented in a vertical direction with respect to the supporting substrate

Third form: retardation film in which the direction of orientation of the rod-shaped liquid crystal compound is changed in a spiral in the plane

4th form: retardation film in which disc-shaped liquid crystal compound is oriented obliquely

Fifth form: a biaxial retardation film in which a disk-shaped liquid crystal compound is oriented in a vertical direction with respect to a supporting substrate

For example, as an optical film used for an organic electroluminescent display, a 1st form, a 2nd form, and a 5th form are used suitably. Alternatively, a retardation film of this type may be laminated and used.

When the retardation film is a layer made of a polymer in an orientation state of the polymerizable liquid crystal compound (hereinafter, sometimes referred to as an "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersion. Reverse wavelength dispersion is an optical characteristic in which the liquid crystal alignment in-plane retardation value at a short wavelength becomes smaller than the liquid crystal alignment in-plane retardation value at a long wavelength, and preferably, the retardation film satisfies the following formulas (7) and (8) . In addition, Re(λ) represents an in-plane retardation value with respect to light having a wavelength of λ nm.

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 the first aspect and has reverse wavelength dispersion, it is preferable because coloration at the time of black display in a display device is reduced, and 0.82≤Re(450) in the above formula (7) )/Re(550) ? 0.93 is more preferable. 120≤Re(550)≤150 is more preferable.

As a polymerizable liquid crystal compound in the case where the retardation film is a film having an optically anisotropic layer, "3.8.6 network (complete crosslinking)" type)”, “6.5.1 liquid crystal material b. A compound having a polymerizable group among the compounds described in "polymerizable nematic liquid crystal material", and Japanese Patent Laid-Open Nos. 2010-31223, 2010-270108, and 2011-6360, Japanese Patent Application Laid-Open Nos. Polymerizability described in Japanese Patent Application Laid-Open No. 2011-207765, Japanese Patent Application Laid-Open No. 2011-162678, Japanese Patent Application Laid-Open No. 2016-81035, International Publication No. 2017/043438, and Japanese Patent Publication No. 2011-207765 A liquid crystal compound etc. are mentioned.

As for the method of manufacturing retardation film with the polymer in the orientation state of a polymeric liquid crystal compound, the method etc. which were described in Unexamined-Japanese-Patent No. 2010-31223 are mentioned, for example.

In the case of the second aspect, the front retardation value Re (550) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the retardation value R _th in the thickness direction is -10 to -300 In the range of nm, what is necessary is just to adjust preferably in the range of -20 to -200 nm. The retardation value R _th in the thickness direction, which means refractive index anisotropy in the thickness direction, can be calculated from the retardation value R ₅₀ and the in-plane retardation value R ₀ measured by tilting the in-plane fast axis by 50 degrees with the inclination axis. That is, the retardation value R _th in the thickness direction is the in-plane retardation value R ₀ , the retardation value R ₅₀ measured by tilting the fast axis by 50 degrees using the inclination axis, the thickness d of the retardation film, and the average refractive index n ₀ of the retardation film. , n _x , n _y and n _z are obtained by the following equations (10) to (12), and can be calculated by substituting them into equation (9).

R _th =[(n _x +n _y )/2-n _z ]×d (9)

R ₀ =(n _x -n _y )×d (10)

R ₅₀ =(n _x -n _y ')×d/cos(φ) (11)

(n _x +n _y +n _z )/3=n ₀ (12)

here,

φ=sin ^-1 [sin(40°)/n ₀ ]

n _y '=n _y ×n _z /[n _y ² ×sin ² (φ)+n _z ² ×cos ² (φ)] ^1/2

As a film in which optical anisotropy was expressed by application and orientation of a liquid crystalline compound, and a film in which optical anisotropy was expressed by application of an inorganic layer compound, a film called a temperature compensation retardation film, JX Nikko Niseki Energy Co., Ltd. “NH Film” sold by FUJIFILM (trade name; film with oblique orientation of rod-shaped liquid crystal), “WV Film” sold by Fujifilm (brand name; film with disc-shaped liquid crystal oriented obliquely), Sumitomo Chemical Co., Ltd. ) sold by “VAC Film” (trade name; fully biaxially oriented film), and “new VAC film” sold by Sumitomo Chemical Co., Ltd. (brand name; biaxially oriented film).

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

An example of the laminated constitution of the adhesive layer of this invention and the optical laminated body of this invention is shown in FIGS.

The optical film 10 with a pressure-sensitive adhesive layer described in FIG. 1 is a release film (separate film) 2 to the pressure-sensitive adhesive layer surface 1 for temporary protection of the pressure-sensitive adhesive layer 1 surface formed from the pressure-sensitive adhesive composition of the present invention. is in one state

The optical film 10A with an adhesive layer of FIG. 2 is the protective film 3, the adhesive bond layer 4, the polarizing film 5, the adhesive layer 1 formed from the adhesive composition of this invention, and the peeling film 2 It is an optical film with an adhesive layer containing. The protective film 3 may have a phase difference. Moreover, on the protective film 3, the hard-coat layer etc. may be further laminated|stacked.

The optical film 10B with an adhesive layer described in FIG. 3 is the protective film 3, the adhesive bond layer 4, the polarizing film 5, the adhesive bond layer 7, the protective film 6, The adhesive composition of this invention It is an optical film with an adhesive layer containing the formed adhesive layer (1) and retardation film (8).

The optical laminated body 10C of FIG. 4 and the optical laminated body 10D of FIG. 5 are the adhesive layer formed from the protective film 3, the adhesive bond layer 4, the polarizing film 5, and the adhesive composition of this invention. It is an optical laminated body containing (1), the adhesive bond layer 7, the retardation film 110, the adhesive layer 1a, and the light emitting element 30 (liquid crystal cell, organic electroluminescent cell). The adhesive layer formed from a well-known adhesive composition may be sufficient as the adhesive layer 1a, and the adhesive layer formed from the adhesive composition of this invention may be sufficient as it.

As shown in FIGS. 4 and 5, when the retardation film is a multilayer film, as shown in FIG. 4, a quarter-wave retardation layer 70 that imparts a retardation of 1/4 wavelength to the transmitted light and the transmitted light A configuration including a retardation film 110 in which a half-wave retardation layer 50 that imparts a retardation corresponding to a half wavelength is laminated through an adhesive layer or an adhesive layer 60 is exemplified. In addition, as shown in FIG. 5, a configuration diagram including an optical film 40 in which a quarter-wave retardation layer 50a and a positive C layer 80 are laminated through an adhesive layer or an adhesive layer 60 can be heard

4, the quarter-wave retardation layer 70 imparting a phase difference of 1/4 wavelength and the 1/2-wave retardation layer 50 imparting a phase difference of 1/2 wavelength to transmitted light are in the first embodiment. may be an optical film of or may be an optical film of the fifth aspect. In the case of the structure of FIG. 4, it is more preferable that at least one is a 5th aspect.

In the case of the structure of FIG. 5, it is preferable that it is an optical film of the said 1st form, and, as for the quarter-wave retardation layer 50a, it is more preferable that Formula (7) and Formula (8) are satisfy|filled.

<Liquid crystal display device>

The resin of the present invention, the pressure-sensitive adhesive composition containing the resin, and the optical laminate including the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is laminated on a display element such as an organic EL element, a liquid crystal cell, an organic EL display device or liquid crystal It can be used for display apparatuses, such as a display apparatus.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. "%" and "part" in an Example and a comparative example are "mass %" and "part by mass" unless otherwise indicated.

(Synthesis Example 1) Synthesis of light-selective absorptive compound (1) having a polymerizable group and an indole structure

After replacing the inside of a 1000 mL four-neck flask equipped with a dimrod cooling tube and a thermometer with nitrogen atmosphere, the compound represented by formula (a) (1-methyl-2-phenyl-1H-indole-3-carboxyaldehyde) 100 parts, 40 parts of cyanoacetic acid, 76 parts of piperidine, and 300 parts of acetonitrile were put, and it heat-retained at 80 degreeC for 4 hours, stirring. From the obtained mixture, the precipitated crystals were separated by filtration and extracted. The obtained crystal|crystallization and 500 parts of 5% sulfuric acid were mixed, and it heat-retained at 80 degreeC for 1 hour, stirring. The resulting mixture was purified to obtain 116 parts of the compound represented by the formula (b) (2-cyano-3-(1-methyl-2-phenyl-1H-indol-3-yl)-2-propenoic acid).

After replacing the inside of a 100 mL four-neck flask equipped with a thermometer with a nitrogen atmosphere, 5 parts of the compound represented by formula (b), 2.3 parts of 4-hydroxybutyl acrylate, 0.4 of N,N-dimethyl-4-aminopyridine parts, 0.2 parts of 2,6-di-t-butyl-4-methylphenol and 50 parts of trichloromethane were added, and the mixture was cooled to 0°C. 2.2 parts of N,N'- diisopropylcarbodiimide was dripped at the obtained mixture, maintaining 0-5 degreeC. After dripping, the obtained mixture was heat-retained at 10 degreeC for 4 hours. The obtained mixture was purified, and the compound represented by formula (1) (2-cyano-3-(1-methyl-2-phenyl-1H-indol-3-yl)-2-propenoic acid-4-acryloyl oxybutyl) 4.9 parts. The maximum absorption wavelength of the compound represented by Formula (1) was 386 nm.

Identification of the compound represented by formula (1)

¹ H-NMR (CDCl ₃ )δ: 1.75-1.80 (m, 4H), 3.70 (s, 3H), 4.15-4.20 (t, 2H), 4.23-4.27 (t, 2H), 5.78-5.82 (dd, 1H), 6.06-6.14 (dd, 1H), 6.36-6.41 (dd, 1H) 7.35-7.43 (m, 5H), 7.54-7.57 (m, 3H), 8.12 (s, 1H), 8.42-8.45 (m) , 1H)

<Measurement of gram extinction coefficient ε>

The obtained 2-butanone solution (0.006 g/L) of the compound represented by the formula (1) was put into a 1 cm quartz cell, the quartz cell was set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the double beam method The absorbance in the wavelength range of 300 to 800 nm was measured for every 1 nm step. The gram extinction coefficient for each wavelength was computed from the obtained value of the absorbance, the density|concentration of the compound represented by Formula (1) in a solution, and the optical path length of a quartz cell.

ε(λ)=A(λ)/CL

[wherein ε(λ) represents the gram extinction coefficient (L/(g·m)) of the compound represented by formula (1) at a wavelength of λ nm, and A(λ) represents the absorbance at a wavelength of λ nm , C represents the concentration (g/L), and L represents the optical path length (m) of the quartz cell.]

The maximum absorption wavelength of the compound represented by the obtained formula (1) was 386 nm, and ε at the maximum absorption wavelength was 0.628. In addition, epsilon (400) of the obtained compound represented by Formula (1) was 0.470 L/(g*m).

(Synthesis Example 2) Synthesis of light-selective absorptive compound (2) having a polymerizable group and an indole structure

The compound represented by the formula (4) (2-cyano-3-(1) 4.3 parts of -methyl-2-phenyl-1H-indol-3-yl)-2-propenoic acid-2-acryloyloxyethyl) were obtained. The maximum absorption wavelength of the compound represented by Formula (2) was 390 nm. When the gram extinction coefficient was calculated|required in the same manner as in Synthesis Example 1, ε(λmax)=0.676 and ε(400)=0.567 L/(g·m).

(Synthesis Example 3) Synthesis of light-selective absorptive compound (3) having a polymerizable group and an indole structure

After replacing the inside of a 200 mL four-neck flask equipped with a thermometer with nitrogen atmosphere, 10 parts of the compound represented by formula (c) (2-phenyl-1H-indole-3-carboxyaldehyde), 9 parts of 6-bromohexane , 7.5 parts of potassium carbonate and 100 parts of N,N-dimethylacetamide were put, and the mixture was stirred for 5 hours while maintaining at 100°C. The resulting mixture was purified to obtain 9 parts of a compound represented by the formula (d) (1-hexyl-2-phenyl-1H-indole-3-carboxyaldehyde).

After replacing the inside of a 200 mL four-neck flask equipped with a thermometer with a nitrogen atmosphere, the total amount of the compound represented by the obtained formula (d), 4.2 parts of cyanoacetic acid, 8.1 parts of piperidine, and 72 parts of acetonitrile were added, and 80 ° C. and stirred for 10 hours. The resulting mixture was purified to obtain 12 parts of a compound represented by formula (e) ((2-cyano-3-(1-hexyl-2-phenyl-1H-indol-3-yl)-2-propenoic acid).

After replacing the inside of a 100 mL four-neck flask equipped with a thermometer with nitrogen atmosphere, 10 parts of the compound represented by formula (e), 3.1 parts of acrylic acid-2-hydroxyethyl, 0.3 parts of N,N-dimethyl-4-aminopyridine parts, 0.3 parts of 2,6-di-t-butyl-4-methylphenol and 100 parts of trichloromethane were added, and the mixture was cooled to 0°C. To the obtained mixture, 3.6 parts of N,N'-diisopropylcarbodiimide was dripped, maintaining 0-5 degreeC. The mixture obtained after dripping was heat-retained at 10 degreeC for 4 hours. The obtained mixture was purified, and the compound represented by formula (3) (2-cyano-3-(1-hexyl-2-phenyl-1H-indol-3-yl)-2-propenoic acid-2-acryloyl) oxyethyl) was obtained in 3.5 parts. The maximum absorption wavelength of the compound represented by Formula (3) was 388 nm.

Identification of the compound represented by formula (3)

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

The maximum absorption wavelength of the compound represented by Formula (3) was 388 nm. When the gram extinction coefficient was calculated|required in the same manner as in Synthesis Example 1, ε(λmax)=0.617 and ε(400)=0.485 L/(g·m).

(Synthesis Example 4) Synthesis of light-selective absorptive compound (4) having a polymerizable group and an indole structure

After replacing the inside of a 100 mL four-neck flask equipped with a thermometer with a nitrogen atmosphere, 5 parts of the compound represented by formula (c) (2-phenyl-1H-indole-3-carboxyaldehyde), 6-bromo-1- 5 parts of hexanol, 3.7 parts of potassium carbonate, and 40 parts of N,N- dimethylacetamide were put, and it stirred for 5 hours, maintaining at 100 degreeC. The resulting mixture was purified to obtain 4 parts of a compound (1-(6-hydroxyhexyl)-2-phenyl-1H-indole-3-carboxyaldehyde) represented by the formula (f).

After replacing the inside of a 200 mL four-neck flask equipped with a thermometer with a nitrogen atmosphere, the total amount of the compound represented by the obtained formula (f), 1.7 parts of malononitrile and 50 parts of acetonitrile, and 3.2 parts of diisopropylethylamine are added dropwise and stirred at room temperature for 3 hours. The obtained mixture was purified to obtain 4.2 parts of compound 1-(6-hydroxyhexyl)-2-phenyl-3-(2,2-dicyanoethenyl)indole represented by formula (g).

After replacing the inside of a 100 mL four-neck flask equipped with a thermometer with a nitrogen atmosphere, 3.4 parts of the compound represented by formula (g), 1.7 parts of N,N-dimethylaniline, 2,6-di-t-butyl-4- 0.1 part of methylphenol and 34 parts of N,N-dimethylacetamide were put, and it cooled to 0 degreeC. It was dripped at the obtained mixture, maintaining 1 part of acrylic acid chlorides at 0-5 degreeC. After dripping, the obtained mixture was heat-retained at 10 degreeC for 4 hours. The obtained mixture was purified, and 1.6 parts of the compound (1-(6-acryloyloxyhexyl)-2-phenyl-3-(2,2-dicyanoethenyl) indole) represented by Formula (4) was obtained. The maximum absorption wavelength of the compound represented by Formula (4) was 392 nm.

Identification of the compound represented by formula (4)

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

The maximum absorption wavelength of the compound represented by Formula (4) was 392 nm. When the gram extinction coefficient was calculated|required in the same manner as in Synthesis Example 1, ε(λmax)=0.753 and ε(400)=0.665 L/(g·m).

(Synthesis Example 5) Synthesis of light-selective absorptive compound (5) having a polymerizable group and an indole structure

After replacing the inside of a 200 mL four-neck flask equipped with a thermometer with a nitrogen atmosphere, 10 parts of the compound represented by formula (c) (2-phenyl-1H-indole-3-carboxyaldehyde), 8.7 parts of 1-iodobutane, 7.5 parts of potassium carbonate and 80 parts of N,N- dimethylacetamide were put, and it stirred at room temperature for 5 hours. The resulting mixture was purified to obtain 9 parts of a compound represented by the formula (h) (1-butyl-2-phenyl-1H-indole-3-carboxyaldehyde).

After replacing the inside of a 200 mL four-neck flask equipped with a thermometer with a nitrogen atmosphere, the total amount of the compound represented by the obtained formula (h), 6.2 parts of cyanoacetic acid, 12.5 parts of piperidine and 50 parts of acetonitrile were added, and 80° C. and stirred for 15 hours. The resulting mixture was purified to obtain 9.8 parts of a compound represented by formula (i) ((2-cyano-3-(1-butyl-2-phenyl-1H-indol-3-yl)-2-propenoic acid).

After replacing the inside of a 100 mL four-neck flask equipped with a thermometer with nitrogen atmosphere, 7.7 parts of the compound represented by formula (i), 3.3 parts of 4-hydroxybutyl acrylate, 0.3 parts of N,N-dimethyl-4-aminopyridine parts, 0.3 parts of 2,6-di-t-butyl-4-methylphenol and 77 parts of trichloromethane were added, and the mixture was cooled to 0°C. To the obtained mixture, 3.0 parts of N,N'- diisopropylcarbodiimide was dripped, maintaining 0-5 degreeC. After dripping, the obtained mixture was heat-retained at 10 degreeC for 4 hours. The obtained mixture was purified, and the compound represented by formula (5) (2-cyano-3-(1-butyl-2-phenyl-1H-indol-3-yl)-2-propenoic acid-4-acryloyl oxybutyl) 5.7 parts. The maximum absorption wavelength of the compound represented by Formula (5) was 386 nm.

Identification of the compound represented by formula (5)

¹ H-NMR (CDCl ₃ ) δ: 0.74-0.81 (t, 3H), 1.12-1.21 (m, 2H), 1.63-1.70 (m, 2H), 1.72-1.83 (m, 4H), 4.06-4.11 ( t, 2H), 4.15-4.20 (t, 2H), 4.23-4.27 (t, 2H), 5.78-5.82 (dd, 1H), 6.06-6.14 (dd, 1H), 6.36-6.41 (dd, 1H)7.35 -7.43(m, 5H), 7.54-7.57(m, 3H), 8.12(s, 1H), 8.42-8.45(m, 1H)

The maximum absorption wavelength of the compound represented by Formula (5) was 386 nm. When the gram extinction coefficient was calculated|required in the same manner as in Synthesis Example 1, ε(λmax)=0.60 and ε(400)=0.44 L/(g·m).

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

A mixed solution of 81.8 parts of ethyl acetate, 96 parts of butyl acrylate, 3 parts of 2-hydroxyethylmethyl acrylate, and 1 part of acrylic acid was placed in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer as a solvent, followed by nitrogen gas. The internal temperature was raised to 55°C while displacing the air in the device to make it oxygen-free. Then, the whole quantity of the solution which melt|dissolved 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. This temperature was maintained for 1 hour after the addition of the initiator, and then ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/hr while maintaining the internal temperature at 54 to 56°C, when the concentration of the acrylic resin reached 35% The addition of ethyl acetate was stopped, and the temperature was maintained at this temperature until 12 hours had elapsed from the start of the addition of ethyl acetate. Finally, ethyl acetate was added, it adjusted so that the density|concentration of an acrylic resin might be set to 20%, and the ethyl acetate solution of an acrylic resin was prepared. As for the obtained acrylic resin, the weight average molecular weight Mw of polystyrene conversion by GPC was 1.47 million, Mw/Mn was 5.5, and the glass transition temperature (Tg) by differential scanning calorimetry (DSC) measurement was -52 degreeC. Let this be an acrylic resin (A).

(Example 1)

With respect to 100 parts of solid content of ethyl acetate solution (resin concentration: 20%) of acrylic resin (A), 0.3 part of crosslinking agent (E) (Tosoh Corporation make: trade name "Colonate L", isocyanate type compound, solid content 75%), Silane compound (F) (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name "KBM3066") 0.28 parts, radical curable component (D) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.: trade name "A-DPH-12E", hexafunctional (meth)acrylate 10 parts of compound), 1.5 parts of initiator (C) (manufactured by ADEKA Co., Ltd.: trade name "NCI-730", a photoradical generator that is an oxime ester compound) 1.5 parts of a light-selective absorption compound (B) (compound represented by formula (1) ) 3 parts were mixed, and ethyl acetate was added so that solid content concentration might be set to 14 %, and the adhesive composition (1) was obtained. In addition, the compounding quantity of the said crosslinking agent is a mass part as an active ingredient.

Examples 2 to 15 and Comparative Examples 1 to 6

As shown in Tables 1-3, except having changed each component and content of each component, it carried out similarly to Example 1, and produced the adhesive composition (2) - the adhesive composition (21). In addition, the compounding quantity of a crosslinking agent is mass parts as an active ingredient, and resin (A) is mass parts of solid content.

[Table 1]

[Table 2]

[Table 3]

In addition, the abbreviation in Tables 1-3 shows the following, respectively. In addition, ε(400) in SB107, SB707, KB74 and UA3911 was measured in the same manner as described above.

Acrylic resin (A): Acrylic resin (A) prepared in Polymerization Example 1

Compound (1): a compound represented by Formula (1) synthesized in Example 1

Compound (2): a compound represented by Formula (2) synthesized in Example 2

Compound (3): a compound represented by Formula (3) synthesized in Example 3

Compound (4): a compound represented by formula (4) synthesized in Example 4

Compound (5): a compound represented by formula (5) synthesized in Example 5

RUVA-93: manufactured by Otsuka Chemical Co., Ltd., ultraviolet absorber, trade name: RUVA-93, maximum absorption wavelength λmax=337 nm, ε(400)=0

NCI-730: manufactured by ADEKA Co., Ltd., trade name: NCI-730, oxime ester-based photoradical generator

A-DPH-12E: manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: A-DPH-12E, hexafunctional (meth)acrylate compound

Colonate L: Tosoh Corporation make, brand name: Colonate L, isocyanate-based compound

KBM3066: manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: KBM3066, silane coupling agent

SB107: manufactured by Cipro Chemical Co., Ltd., benzophenone-based ultraviolet absorber, trade name: SEESORB107, maximum absorption wavelength λmax=350 nm, ε(400)=0.245

SB707: manufactured by Cipro Chemical Co., Ltd., benzotriazole-based ultraviolet absorber, trade name: SEESORB707, maximum absorption wavelength λmax=343 nm, ε(400)=0.001

KB74: manufactured by Chemipro Chemical Co., Ltd., benzotriazole-based ultraviolet absorber, trade name: KEMSORB74, maximum absorption wavelength λmax=342 nm, ε(400)=0.001

UA3911: manufactured by Orient Chemical Industry Co., Ltd., indole-based ultraviolet absorber (without polymerizable group), trade name: BONASORB UA-3901 Maximum absorption wavelength λmax=393 nm, ε(400)=1.007

<Preparation of adhesive layer>

Each pressure-sensitive adhesive composition prepared above was applied to the release-treated side of a separate film made of a polyethylene terephthalate film [trade name "PLR-382190" obtained from Lintech Co., Ltd.], which had been subjected to release treatment, using an applicator to have a thickness of 5 after drying. It applied so that it might become micrometer, and it dried at 100 degreeC for 1 minute. After that, from the separate film side, using an ultraviolet irradiation device (“electrodeless UV lamp system H bulb” manufactured by Fusion UV Systems), UV-A (wavelength 320 to 390 nm) was irradiated at 500 mW, and the accumulated light amount was 500 mJ. It adjusted so that it might become possible, and the adhesive layer (adhesive sheet) was produced by irradiating with ultraviolet rays.

<Measurement of absorbance of adhesive layer>

After each of the obtained pressure-sensitive adhesive layers are bonded to glass and the separator is peeled off, a cycloolefin polymer (COP) film (ZF-14 manufactured by Nippon Zeon Co., Ltd.) is bonded to the pressure-sensitive adhesive layer, and has a structure of COP film/adhesive layer/glass A laminate was produced. The produced laminate was set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and absorbance was measured in a wavelength range of 300 to 800 nm in 1 nm steps by a double beam method. Table 4 shows the absorbance of the prepared pressure-sensitive adhesive layer. On the other hand, the absorbance of the glass and the absorbance of the COP film at a wavelength of 300 m, a wavelength of 330 nm, a wavelength of 350 nm, a wavelength of 380 nm, and a wavelength of 400 nm are all zero.

<Evaluation of the bleed resistance of the adhesive layer>

A separate film was further laminated|stacked on the surface of the obtained adhesive layer, and the adhesive layer with a double-sided separate film was obtained. The obtained adhesive layer with a double-sided separate film was stored under 23-25 degreeC air for 1 month. The presence or absence of crystallization of the compound in the surface was confirmed for the adhesive layer with a double-sided separate film after storage using the microscope. When there was no crystallization, it was set as 0, and when there was crystallization, it was set as x. Table 4 shows the evaluation results.

[Table 4]

The adhesive layer formed from the adhesive composition of this invention shows high absorbance with respect to wavelength 400nm vicinity, and also has favorable bleed resistance. Moreover, the adhesive composition of this invention shows favorable absorbance over a wavelength of 300 nm - a wavelength of 400 nm.

The adhesive composition of this invention and the optical laminated body containing the adhesive layer formed from the said adhesive composition are used suitably for a liquid crystal panel and a liquid crystal display device.

1: A pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of the present invention
1a: adhesive layer
2: release film
10, 10A, 10B, 10C, 10D: Optical film with adhesive layer
3, 6: protective film
4, 7: adhesive layer
5: Polarizing film
8: retardation film
30: light emitting element
40: optical film
70, 50a: 1/4 wavelength retardation layer
60: adhesive layer or adhesive layer
50: 1/2 wavelength retardation layer
80: positive C layer
100: polarizer
110: retardation film

Claims (24)

A pressure-sensitive adhesive composition comprising a resin (A), a light-selective absorption compound having an indole structure and a polymerizable group in a molecule (B), and an initiator (C). The pressure-sensitive adhesive composition according to claim 1, wherein the polymerizable group is a radically polymerizable group. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the polymerizable group is a (meth)acryloyl group. The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the initiator (C) is a radical polymerization initiator. The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the initiator (C) is a photo-radical polymerization initiator. The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the initiator (C) is an oxime ester compound. The pressure-sensitive adhesive composition according to any one of claims 1 to 6, further comprising a radical curable component (D). The pressure-sensitive adhesive composition according to claim 7, wherein the radical curable component (D) is a (meth)acrylate compound. The pressure-sensitive adhesive composition according to claim 7 or 8, wherein the radical curable component (D) is a polyfunctional (meth)acrylate compound. The pressure-sensitive adhesive composition according to any one of claims 1 to 9, further comprising a crosslinking agent (E). The pressure-sensitive adhesive composition according to claim 10, wherein the crosslinking agent (E) is an isocyanate crosslinking agent. The adhesive composition of Claim 10 or 11 whose glass transition temperature of resin (A) is 40 degrees C or less. The pressure-sensitive adhesive composition according to claim 12, wherein the resin (A) having a glass transition temperature of 40°C or less is a (meth)acrylic resin. The pressure-sensitive adhesive composition according to any one of claims 1 to 13, wherein the light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule is a compound exhibiting maximum absorption at a wavelength of 360 nm or more and 420 nm or less. . The pressure-sensitive adhesive composition according to any one of claims 1 to 14, wherein the light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule satisfies Formula (1).
ε(400)≥0.05 (1)
[In Formula (1), ε(400) represents the gram extinction coefficient at a wavelength of 400 nm of the light-selective absorption compound (B). The unit of gram extinction coefficient is L/(g·m)] The pressure-sensitive adhesive composition according to any one of claims 1 to 15, wherein the light-selective absorption compound (B) containing an indole structure and a polymerizable group in a molecule is a compound represented by formula (I) or (II).

[In formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, or a substituent represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR ^1A -, -SO ₂ -, -CO-, -O-, -S-, or -CF ₂ - may be substituted.
R ^1A represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
E ¹ represents an electron withdrawing group.
Z represents a linking group.
A represents a polymerizable group.
In formula (II), R ¹² and R ¹⁷ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, or a substituent represents an aromatic ^hydrocarbon group having ₆ to ₁₈ carbon atoms which may have - or -CF ₂ - may be substituted.
R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxy group, a group containing a polymerizable group, or a substituent which may have represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is -NR ^12A -, -SO ₂ -, -CO-, -O-, -S-, or -CF ₂ - may be substituted.
However, at least one of R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represents a group containing a polymerizable group.
R ^11A and R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
E ¹¹ represents an electron withdrawing group.] The pressure-sensitive adhesive composition according to claim 16, wherein R ² and R ¹² are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms. The pressure-sensitive adhesive composition according to claim 16, wherein the compound represented by formula (I) is a compound represented by formula (III), and the compound represented by formula (II) is a compound represented by formula (IV).

[R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , E ¹ , R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and E ¹¹ each have the same meaning as above.
R ⁷ represents a hydrogen atom, a cyano group, a methyl group, or a phenyl group.
Z ¹ represents an alkanediyl group having 1 to 12 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, -OR ^2A -*1, -SR ^2B -*1 or -NR ^1D -R ^2C -*1.
Z ² is a single bond, *2-CO-O-, *2-O-CO-, *2-S(=O) ₂ -, *2-O-SO ₂ -, *2-CO-NR ^1B -, *2-NR ^1C -CO-, *2-R ^2D OP(=O)-OR ^2E -, *2-NR ^1E -CO-O-, *2-O-CO-NR ^1F -, *2 -(OR ^2F ) _s1 -, *2-CO-S-, *2-S-CO-, or a C1-C4 perfluoroalkanediyl group.
R ^1B , R ^1C , R ^1D , R ^1E and R ^1F each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^2A , R ^2B , R ^2C , R ^2D , R ^2E and R ^2F each independently represent a divalent hydrocarbon group having 1 to 18 carbon atoms.
Z ¹ represents a divalent linking group.
A ¹ represents a polymerizable group.
*1 represents a bond with Z ² .
*2 represents a bond with Z ¹ ] The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 18. The pressure-sensitive adhesive layer according to claim 19, which satisfies the following formula (2).
A(400)≥0.4 (2)
[In formula (2), A (400) represents the absorbance at a wavelength of 400 nm.] The pressure-sensitive adhesive layer according to claim 19 or 20, wherein the pressure-sensitive adhesive layer has a thickness of 10 µm or less. The optical film with an adhesive layer by which the optical film was laminated|stacked on the at least one surface of the adhesive layer in any one of Claims 19-21. The optical film with a pressure-sensitive adhesive layer according to claim 22, wherein the optical film is a polarizing plate. The image display apparatus containing the optical film with an adhesive layer of Claim 22 or 23.

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