JP2019007001A - Adhesive sheet and film with adhesive layer - Google Patents

Abstract

To provide an adhesive sheet having a function for advantageously suppressing deterioration in a retardation film and an organic EL light-emitting element due to UV rays, by exhibiting high absorption selectivity with respect to UV rays and visible light having a short wavelength in the vicinity of 405 nm.SOLUTION: The adhesive sheet is an adhesive layer formed from an adhesive composition containing at least a (meth)acrylic resin and a light selective absorption compound, and satisfies the following expressions (1) and (2). They are: (1) A(350)≥0.5 and (2) A(405)≥0.5, where in expression (1), A(350) represents an absorbance at a wavelength of 350 nm, and in expression (2), A(405) represents an absorbance at a wavelength of 405 nm.SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive sheet and a film with a pressure-sensitive adhesive layer using the pressure-sensitive adhesive sheet.

  Various members such as an organic EL element, a display element such as a liquid crystal cell, and an optical film such as a polarizing plate are used in a display apparatus (FPD: flat panel display) such as an organic EL display apparatus and a liquid crystal display apparatus. Since organic EL compounds and liquid crystal compounds used for these members are organic substances, deterioration due to ultraviolet rays (UV) tends to be a problem. In order to solve such a problem, for example, Patent Document 1 describes a polarizing plate in which an ultraviolet absorber having excellent ultraviolet absorption performance in a wavelength region of 370 nm or less is added to a protective film of the polarizing plate.

JP 2006-308936 A

  In addition, with the progress of thinning of display devices in recent years, development of a liquid crystal retardation film obtained by aligning and photocuring a polymerizable liquid crystal compound has been advanced. It has become clear that these liquid crystal retardation films and organic EL light-emitting elements tend to deteriorate not only with ultraviolet light but also with short wavelength visible light near 400 nm. However, although the polarizing plate described in Patent Document 1 has excellent ultraviolet absorption performance in a wavelength region of 370 nm or less, it has low visible light absorption performance near 400 nm, and deterioration of a liquid crystal retardation film or an organic EL light-emitting element. In some cases, the suppression was not sufficient. Furthermore, in recent display devices, better display characteristics have been demanded.

  The objective of this invention is providing the adhesive sheet which has a favorable inhibitory function about the deterioration by the ultraviolet-ray and short wavelength visible light of a phase difference film or an organic electroluminescent light emitting element.

The present invention includes the following inventions.
[1] A pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A) and a light selective absorption compound, which satisfies the following formulas (1) and (2).
A (350) ≧ 0.5 (1)
A (405) ≧ 0.5 (2)
[In Formula (1), A (350) represents the light absorbency in wavelength 350nm.
In formula (2), A (405) represents the absorbance at a wavelength of 405 nm. ]
[2] The pressure-sensitive adhesive sheet according to [1], further satisfying the following formula (3).
A (440) ≦ 0.1 (3)
[In Formula (3), A (440) represents the light absorbency in wavelength 440nm. ]
[3] The pressure-sensitive adhesive sheet according to [1], further satisfying the following formula (4).
A (405) / A (440)> 5 (4)
[In Formula (4), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]
[4] Any one of [1] to [3], wherein the light selective absorption compound includes a compound that selectively absorbs light having a wavelength of 350 nm and a compound that selectively absorbs light having a wavelength of 405 nm. The pressure-sensitive adhesive sheet described in 1.
[5] The pressure-sensitive adhesive sheet according to [4], wherein the compound that selectively absorbs light having a wavelength of 405 nm is a compound that satisfies formula (5).
ε (405) ≧ 20 (5)
[In Formula (5), (epsilon) (405) represents the gram extinction coefficient of the compound in wavelength 405nm. The unit of the gram extinction coefficient is L / (g · cm). ]
[6] The pressure-sensitive adhesive sheet according to [5], wherein the compound that selectively absorbs light having a wavelength of 405 nm is a compound that satisfies formula (6).
ε (405) / ε (440) ≧ 20 (6)
[In formula (6), ε (405) represents the gram extinction coefficient of the compound at a wavelength of 405 nm, and ε (440) represents the gram extinction coefficient at a wavelength of 440 nm. ]
[7] The pressure-sensitive adhesive sheet according to any one of [4] to [6], wherein the compound that selectively absorbs light having a wavelength of 405 nm is a compound having a merocyanine structure in the molecule.
[8] The pressure-sensitive adhesive sheet according to any one of [1] to [7], wherein the pressure-sensitive adhesive composition further contains a crosslinking agent.
[9] The pressure-sensitive adhesive sheet according to [8], wherein the content of the crosslinking agent (B) is 0.01 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A).
[10] The content of the light selective absorption compound according to any one of [1] to [9], which is 0.01 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A). Adhesive sheet.
[11] The optical film with an adhesive layer according to any one of [1] to [10], wherein the optical film is laminated on at least one surface of the adhesive sheet.
[12] The polarizing plate with the pressure-sensitive adhesive layer according to [11], wherein the optical film is a polarizing plate.
[13] A display device comprising the optical film with an adhesive according to any one of [11] and [12].

  The pressure-sensitive adhesive sheet of the present invention exhibits high absorption selectivity for ultraviolet light and short-wavelength visible light near 405 nm, thereby favorably suppressing deterioration of retardation films and organic EL light-emitting elements due to ultraviolet light and short-wavelength visible light. It has a function. In addition, the pressure-sensitive adhesive sheet of the present invention exhibits high absorption selectivity for visible light with a short wavelength of around 405 nm even after a weather resistance test, and can keep the deterioration of ultraviolet light and visible light with a short wavelength from being suppressed. it can. When the pressure-sensitive adhesive sheet of the present invention is used in a display device, good display characteristics and durability can be imparted.

An example of the layer structure of the adhesive sheet of this invention is shown. An example of the layer structure of the optical laminated body containing the adhesive sheet of this invention is shown. An example of the layer structure of the optical laminated body containing the adhesive sheet of this invention is shown. An example of the layer structure of the optical laminated body containing the adhesive sheet of this invention is shown.

The pressure-sensitive adhesive sheet of the present invention is molded from a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A) and a light selective absorption compound, and satisfies the following formulas (1) and (2).
A (350) ≧ 0.5 (1)
A (405) ≧ 0.5 (2)
[In Formula (1), A (350) represents the light absorbency in wavelength 350nm.
In formula (2), A (405) represents the absorbance at a wavelength of 405 nm. ]

  The larger the value of A (350), the higher the absorption at a wavelength of 350 nm. When the value of A (350) is less than 0.5, the absorption at a wavelength of 350 nm is low, and the effect of suppressing deterioration of a display device such as a retardation film or an organic EL element in ultraviolet rays is small. The value of A (350) is preferably 0.5 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more.

  The larger the value of A (405), the higher the absorption at a wavelength of 405 nm. When the value of A (405) is less than 0.5, absorption at a wavelength of 405 nm is low, and the effect of suppressing deterioration of a display device such as a retardation film or an organic EL element in ultraviolet light or short-wavelength visible light is small. The value of A (405) is preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. The upper limit is not particularly limited, but is usually 10 or less.

The pressure-sensitive adhesive sheet of the present invention preferably further satisfies any of the following formula (3) and formula (4), and more preferably satisfies both the following formula (3) and formula (4).
A (440) ≦ 0.1 (3)
[In Formula (3), A (440) represents the light absorbency in wavelength 440nm. ]
A (405) / A (440) ≧ 5 (4)
[In Formula (4), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]

  The smaller the value of A (440), the lower the absorption at a wavelength of 440 nm. When the value of A (440) exceeds 0.1, there is a tendency that good color expression in the display device is impaired. Moreover, since the light emission of a display apparatus is inhibited, a brightness | luminance will also fall. The value of A (440) is preferably 0.05 or less, more preferably 0.04 or less, and particularly preferably 0.03. Although there is no lower limit in particular, it is usually 0.00001 or more.

  The value of A (405) / A (440) represents the magnitude of absorption at a wavelength of 405 nm with respect to the magnitude of absorption at a wavelength of 440 nm, and the larger this value, the more specific the pressure-sensitive adhesive sheet of the present invention is in the wavelength range near 405 nm. It means that there is a typical absorption. The value of A (405) / A (440) is preferably 10 or more, more preferably 30 or more, and particularly preferably 60 or more.

The pressure-sensitive adhesive layer of the present invention is formed from a pressure-sensitive adhesive composition containing at least a (meth) acrylic resin (A) and a light selective absorption compound.
The pressure-sensitive adhesive composition preferably further contains a cross-linking agent.

  The light selective absorption compound is not particularly limited as long as it is a compound that selectively absorbs light having a wavelength of 350 nm or light having a wavelength of 405 nm. The light selective absorption compound preferably includes a compound that selectively absorbs light having a wavelength of 350 nm and a compound that selectively absorbs light having a wavelength of 405 nm.

  Examples of the compound that selectively absorbs light having a wavelength of 350 nm (hereinafter sometimes referred to as a light selective absorption compound (A)) include an ultraviolet absorber. Although it does not specifically limit as an ultraviolet absorber, For example, an oxybenzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a salicylic acid ester type ultraviolet absorber, a benzophenone type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, a triazine type ultraviolet absorber And organic ultraviolet absorbers such as agents. More specifically, for example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6 -(Linear and side chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone and the like. These organic ultraviolet absorbers may be used alone or in combination of two or more.

  Commercially available UV absorbers may be used. For example, as a triazine UV absorber, “Kemisorb 102” manufactured by Chemipro Kasei Co., Ltd., “Adekastab LA46”, “Adekastab LAF70” manufactured by ADEKA Co., Ltd., BASF Japan "Tinuvin 109", "Tinuvin 171", "Tinubin 234", "Tinuvin 326", "Tinubin 327", "Tinubin 328", "Tinubin 928", "Tinubin 400", "Tinubin 460", "Tinubin" 405 "," Tinubin 477 "and the like. As benzotriazole ultraviolet absorbers, “ADEKA STAB LA31” and “ADEKA STAB LA36” manufactured by ADEKA Corporation, “Sumisorb 200”, “Sumisorb 250”, “Sumisorb 300”, “Sumisorb 340” manufactured by Sumika Chemtex Co., Ltd. And “Sumisorb 350”, “Kemisorb 74”, “Kemisorb 79” and “Kemisorb 279” manufactured by Chemipro Kasei Co., Ltd., “TINUVIN 99-2”, “TINUVIN 900” and “TINUVIN 928” manufactured by BASF, etc. It is done.

  Further, the ultraviolet absorber may be an inorganic ultraviolet absorber. Inorganic UV absorbers 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 zinc oxide doped with silica and alumina. These inorganic ultraviolet absorbers can be used alone or in combination of two or more. Moreover, you may use together an organic type ultraviolet absorber and an inorganic type ultraviolet absorber.

The compound that selectively absorbs light having a wavelength of 405 nm (hereinafter sometimes referred to as a light selective absorption compound (B)) is preferably a compound that satisfies the following formula (5), and further has the following formula (6). It is more preferable that the compound satisfies the above.
ε (405) ≧ 20 (5)
[In Formula (5), (epsilon) (405) represents the gram extinction coefficient of the compound in wavelength 405nm. The unit of the gram extinction coefficient is L / (g · cm). ]
ε (405) / ε (440) ≧ 20 (6)
[In formula (6), ε (405) represents the gram extinction coefficient of the compound at a wavelength of 405 nm, and ε (440) represents the gram extinction coefficient at a wavelength of 440 nm. ]
The gram absorbance coefficient is measured by the method described in the examples.

  A compound having a larger ε (405) value absorbs light having a wavelength of 405 nm and suppresses deterioration of the retardation film in ultraviolet light or visible light having a short wavelength. When the value of ε (405) is less than 20 L / (g · cm), unless the content of the light selective absorption compound (B) in the pressure-sensitive adhesive composition is increased, the ultraviolet rays of the retardation film and the organic EL light emitting device In addition, the deterioration suppressing function due to visible light having a short wavelength tends to be hardly exhibited. When the content of the light selective absorption compound (B) increases, the light selective absorption compound (B) may bleed out or disperse unevenly, and the light absorption function may be insufficient. The value of ε (405) is preferably 20 L / (g · cm) or more, more preferably 30 L / (g · cm) or more, and even more preferably 40 L / (g · cm) or more. Preferably, it is usually 500 L / (g · cm) or less.

  A compound with a larger ε (405) / ε (440) value absorbs light near 405 nm without inhibiting the color expression of the display device, and suppresses light deterioration of the display device such as a retardation film or an organic EL element. can do. The value of ε (405) / ε (440) is preferably 20 or more, more preferably 40 or more, still more preferably 70 or more, and particularly preferably 80 or more.

［式中、Ｒ^１及びＲ^５は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜２５のアルキル基、置換基を有していてもよい炭素数７〜１５のアラルキル基、炭素数６〜１５のアリール基、複素環基を表し、該アルキル基又はアラルキル基に含まれる−ＣＨ_２−は−ＮＲ^１Ａ−、−ＣＯ−、−ＳＯ_２−、−Ｏ−又は−Ｓ−に置換されていてもよい。
Ｒ^１Ａは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜６のアルキル基、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、該アルキル基に含まれる−ＣＨ_２−は−ＮＲ^１Ｂ−、−ＣＯ−、−ＳＯ_２−、−Ｏ−又は−Ｓ−で置換されていてもよい。
Ｒ^１Ｂは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｒ^６及びＲ^７は、それぞれ独立して、水素原子、炭素数１〜２５のアルキル基又は電子吸引性基を表すか、Ｒ^６及びＲ^７が互いに連結して環構造を形成してもよい。
Ｒ^１及びＲ^２は互いに連結して環構造を形成してもよく、Ｒ^２及びＲ^３は互いに連結して環構造を形成してもよく、Ｒ^２及びＲ^４は互いに連結して環構造を形成してもよく、Ｒ^３及びＲ^６は、互いに連結して環構造を形成してもよい。］ The compound that selectively absorbs light having a wavelength of 405 nm is preferably a compound having a merocyanine structure in the molecule. The compound containing a merocyanine structure in the molecule is a compound containing a partial structure represented by-(NC = C-C = C)-in the molecule, for example, a merocyanine compound, a cyanine compound Examples thereof include compounds, indole compounds, and benzotriazole compounds. Preferred are merocyanine compounds, cyanine compounds and benzotriazole compounds, and more preferred are compounds represented by formula (I).

[Wherein, R ¹ and R ⁵ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 25 carbon atoms, or an optionally substituted carbon group having 7 to 7 carbon atoms. 15 represents an aralkyl group, an aryl group having 6 to 15 carbon atoms, or a heterocyclic group, and —CH ₂ — contained in the alkyl group or aralkyl group represents —NR ^1A —, —CO—, —SO ₂ —, —O. -Or -S- may be substituted.
R ^1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ² , R ³ and R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted aromatic hydrocarbon group. Or an aromatic heterocyclic group which may have a substituent, and —CH ₂ — contained in the alkyl group is —NR ^1B —, —CO—, —SO ₂ —, —O— or —S—. May be substituted.
R ^1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an electron-withdrawing group, or R ⁶ and R ⁷ may be linked to each other to form a ring structure. .
R ¹ and R ² may be connected to each other to form a ring structure, R ² and R ³ may be connected to each other to form a ring structure, and R ² and R ⁴ are connected to each other to form a ring structure. R ³ and R ⁶ may be linked to each other to form a ring structure. ]

Examples of the alkyl group having 1 to 25 carbon atoms represented by R ¹ and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-cyanopropyl group, an n-butyl group, a tert-butyl group, Examples include sec-butyl group, n-pentyl group, n-hexyl group, 1-methylbutyl group, 3-methylbutyl group, n-octyl group, n-decyl, 2-hexyl-octyl group and the like.
Examples of the substituent that the alkyl group having 1 to 25 carbon atoms represented by R ¹ and R ⁵ may have include the groups described in the following group A.
Group A: nitro group, hydroxy group, carboxy group, sulfo group, cyano group, amino group, halogen atom, alkoxy group having 1 to 6 carbon atoms, alkylsilyl group having 1 to 12 carbon atoms, alkyl having 2 to 8 carbon atoms Carbonyl group, * —R ^a1 — (O—R ^a2 ) _t1 —R ^a3 (R ^a1 and R ^a2 each independently represents an alkanediyl group having 1 to 6 carbon atoms, and R ^a3 represents 1 to C 1 carbon atoms, 6 represents an alkyl group, and s1 represents an integer of 1 to 3).
Examples of the alkylsilyl group having 1 to 12 carbon atoms include monoalkylsilyl groups such as methylsilyl group, ethylsilyl, and propylsilyl group; dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group, and methylethylsilyl group; trimethylsilyl, triethylsilyl, And trialkylsilyl groups such as tripropylsilyl group.
Examples of the alkylcarbonyl group having 2 to 8 carbon atoms include a methylcarbonyl group and an ethylcarbonyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the aralkyl group having 7 to 15 carbon atoms represented by R ¹ and R ⁵ include a benzyl group and a phenylethyl group. Examples of the group in which —CH ₂ — contained in the aralkyl group is replaced with —SO ₂ — or —COO— include a 2-phenylethyl acetate group.
Examples of the substituent that the aralkyl group having 7 to 15 carbon atoms represented by R ¹ and R ⁵ may have include the groups described in the above group A.
Examples of the aryl group having 6 to 15 carbon atoms represented by R ¹ and R ⁵ include a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of the substituent that the aryl group having 6 to 15 carbon atoms represented by R ¹ and R ⁵ may have include those described in Group A above.
Examples of the heterocyclic group having 6 to 15 carbon atoms represented by R ¹ and R ⁵ include carbons such as pyridyl group, pyrrolidyl group, quinolyl group, thiophene group, imidazolyl group, oxazolyl group, pyrrole group, thiazolyl group, and furanyl group. The aromatic heterocyclic group of number 3-9 is mentioned.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^1A and R ^1B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n -A pentyl group, n-hexyl group, etc. are mentioned.

The R ^{2, R 3} and an alkyl group having 1 to 6 carbon atoms represented by ^{R 4,} include those similar to the alkyl group having 1 to 6 carbon atoms represented by ^{R 1B.}
Examples of the substituent that the alkyl group having 1 to 6 carbon atoms represented by R ² , R ^3, and R ⁴ may have include those described in Group A above.
Examples of the aromatic hydrocarbon group represented by R ² , R ³ and R ⁴ include aryl groups having 6 to 15 carbon atoms such as phenyl group, naphthyl group and anthracenyl group; 7 to 7 carbon atoms such as benzyl group and phenylethyl group. There are 15 aralkyl groups.
Examples of the substituent that the aromatic hydrocarbon group represented by R ² , R ^3, and R ⁴ may have include those described in Group A above.
Examples of the aromatic heterocycle represented by R ² , R ³ and R ⁴ include 3 carbon atoms such as pyridyl group, pyrrolidyl group, quinolyl group, thiophene group, imidazolyl group, oxazolyl group, pyrrole group, thiazolyl group and furanyl group. -9 aromatic heterocyclic groups.
Examples of the substituent that the aromatic heterocyclic ring represented by R ² , R ^3, and R ⁴ may have include the groups described in Group A above.

The alkyl group having 1 to 25 carbon atoms represented by R ⁶ and ^{R 7,} include those similar to the alkyl group having 1 to 25 carbon atoms represented by ^{R 1} and ^{R 5.}
Examples of the substituent that the alkyl group having 1 to 25 carbon atoms represented by R ⁶ and R ⁷ may have include those described in Group A above.

［式中、Ｒ^１１は、水素原子又は炭素数１〜２５のアルキル基を表し、該アルキル基に含まれるメチレン基の少なくとも１つは酸素原子に置換されていてもよい。
Ｘ^１は、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＳ−、−ＣＳＯ−、−ＣＳＳ−、−ＮＲ^１２ＣＯ−又はＣＯＮＲ^１３−を表す。
Ｒ^１２及びＲ^１３は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基又はフェニル基を表す。］ The alkyl group having 1 to 25 carbon atoms represented by R ⁶ and ^{R 7,} include those similar to the alkyl group having 1 to 25 carbon atoms represented by ^{R 1} and ^{R 5.}
Examples of the electron-withdrawing group represented by R ⁶ and R ⁷ include a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, and a group represented by the formula (I-1). .

[Wherein, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 25 carbon atoms, and at least one of the methylene groups contained in the alkyl group may be substituted with an oxygen atom.
X ¹ represents —CO—, —COO—, —OCO—, —CS—, —CSO—, —CSS—, —NR ¹² CO— or CONR ¹³ —.
R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. ]

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 trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and Examples include perfluoroalkyl groups such as perfluorohexyl groups. As carbon number of the alkyl group substituted by the halogen atom, it is 1-25 normally.

R ⁶ and R ⁷ may be linked to each other to form a ring structure. Examples of the ring structure formed from R ⁶ and R ⁷ include a Meldrum's acid structure, a barbituric acid structure, and a dimedone structure. It is done.
Examples of the alkyl group having 1 to 25 carbon atoms represented by R ¹¹ include the same alkyl groups represented by R ¹ and R ⁵ .

The ring structure formed by combining R ² and R ³ with each other is a nitrogen-containing ring structure containing a nitrogen atom bonded to R ² , for example, a 4- to 14-membered nitrogen-containing heterocyclic ring. Can be mentioned. The ring structure formed by connecting R ² and R ³ to each other may be monocyclic or polycyclic. Specific examples include a pyrrolidine ring, a pyrroline ring, an imidazolidine ring, an imidazoline ring, an oxazoline ring, a thiazoline ring, a piperidine ring, a morpholine ring, a piperazine ring, an indole ring, and an isoindole ring.

The ring structure formed by bonding R ¹ and R ² to each other is a nitrogen-containing ring structure containing a nitrogen atom to which R ¹ and R ² are bonded, for example, a 4- to 14-membered ring (preferably 4- to 8-membered) nitrogen-containing heterocycles. The ring structure formed by connecting R ¹ and R ² to each other may be monocyclic or polycyclic. Specific examples include the same ring structure formed by connecting R ² and R ³ to each other.

Examples of the ring structure formed by combining R ² and R ⁴ with each other include a 4- to 14-membered nitrogen-containing ring structure, and a 5- to 9-membered nitrogen-containing ring structure is preferable. The ring structure formed by combining R ² and R ⁴ with each other may be monocyclic or polycyclic. These rings may have a substituent, and examples of such a ring structure include those exemplified as the ring structure formed by R ² and R ³ .

The ring structure formed by connecting R ³ and R ⁶ to each other is a ring structure in which R ³ —C═C—C═C—R ⁶ forms a ring skeleton. For example, a phenyl group etc. are mentioned.

［式（Ｉ−Ａ）、式（Ｉ−Ｂ）中、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ上記と同じ意味を表す。
環Ｗ^１及び環Ｗ^２は、それぞれ独立して、含窒素環を表す。］ Examples of the compound represented by the formula (I) in which R ² and R ³ are linked to each other to form a ring structure include the compound represented by the formula (IA), and R ² and R ⁴ are Examples of the compound represented by the formula (I) which is linked to form a ring structure include a compound represented by the formula (IB).

[In formula (IA) and formula (IB), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the same meaning as described above.
Ring W ¹ and ring W ² each independently represent a nitrogen-containing ring. ]

Ring W ¹ and ring W ² represent a nitrogen-containing ring containing a nitrogen atom as a ring structural unit. Ring W ¹ and ring W ² may each independently be monocyclic or polycyclic, and may contain a hetero atom other than nitrogen as a structural unit of the ring. Ring W ¹ and ring W ² are preferably each independently a 5-membered to 9-membered ring.

［式（Ｉ−Ａ）中、Ｒ^１、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ上記と同じ意味を表す。
Ａ^１は、−ＣＨ_２−、−Ｏ−、−Ｓ−又は−ＮＲ^１Ｄ−を表す。
Ｒ^１４及びＲ^１５は、それぞれ独立して、水素原子又は炭素数１〜１２のアルキル基を表す。
Ｒ^１Ｄは、水素原子又は炭素数１〜６のアルキル基を表す。］ The compound represented by the formula (IA) is preferably a compound represented by the formula (IA-1).

[In formula (IA), R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent the same meaning as described above.
A ¹ represents —CH ₂ —, —O—, —S—, or —NR ^1D —.
R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
R ^1D represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

［式（Ｉ−Ｂ−１）中、Ｒ^１、Ｒ^６及びＲ^７は、それぞれ上記と同じ意味を表す。
Ｒ^１６は、それぞれ独立して、水素原子又は炭素数１〜１２のアルキル基、アリール基を表す。］ The compound represented by the formula (IB) is preferably a compound represented by the formula (IB-1) and a compound represented by the formula (IB-2).

[In formula (IB-1), R ¹ , R ⁶ and R ⁷ each represent the same meaning as described above.
R ¹⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group. ]

［式（Ｉ−Ｂ−２）中、Ｒ^３、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ上記と同じ意味を表す。
Ｒ^３０は、水素原子、シアノ基、ニトロ基、ハロゲン原子、メルカプト基、アミノ基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数６〜１８の芳香族炭化水素基、炭素数２〜１３のアシル基、炭素数２〜１３のアシルオキシ基又は炭素数２〜１３のアルコキシカルボニル基を表す。
Ｒ^３１は、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、メルカプト基、炭素数１〜１２のアルキルチオ基、置換基を有していてもよいアミノ基又は複素環基を表す。］

[In formula (IB-2), R ³ , R ⁵ , R ⁶ and R ⁷ each represent the same meaning as described above.
R ³⁰ is a hydrogen atom, a cyano group, a nitro group, a halogen atom, a mercapto group, an amino group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aromatic hydrocarbon having 6 to 18 carbon atoms. Group, a C2-C13 acyl group, a C2-C13 acyloxy group, or a C2-C13 alkoxycarbonyl group.
R ³¹ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a mercapto group, an alkylthio group having 1 to 12 carbon atoms, an amino group or a heterocyclic group which may have a substituent. Represent. ]

Examples of the halogen atom represented by R ³⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The acyl group having a carbon number of 2 to 13 represented by R ³⁰ represented by R ^30, an acetyl group, and the like propionyl group and butyryl group.
Examples of the acyloxy group having 2 to 13 carbon atoms represented by R ³⁰ include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.
Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms represented by R ³⁰ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group.
Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ³⁰ include aryl groups having 6 to 18 carbon atoms such as phenyl group, naphthyl group, and biphenyl group; and 7 carbon atoms such as benzyl group and phenylethyl group. -18 aralkyl groups.
Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^30, include those similar to the alkyl group having 1 to 12 carbon atoms represented by ^{R 14.}
Examples of the alkyl group having 1 to 12 carbon atoms represented by R ³⁰ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
R ³⁰ is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, or a mercapto group.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^31, include those similar to the alkyl group having 1 to 12 carbon atoms represented by ^{R 14.}
The alkoxy group having 1 to 12 carbon atoms represented by R ^31, include those similar to the alkoxy group having 1 to 12 carbon atoms represented by ^{R 30.}
Examples of the alkylthio group having 1 to 12 carbon atoms represented by R ³¹ include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, and a hexylthio group.
The amino group optionally having a substituent represented by R ³¹ is an amino group; substituted with one alkyl group having 1 to 8 carbon atoms such as an N-methylamino group or an N-ethylamino group. An amino group; an amino group substituted with two alkyl groups having 1 to 8 carbon atoms such as an N, N-dimethylamino group, an N, N-diethylamino group, and an N, N-methylethylamino group;
Examples of the heterocyclic ring represented by R ³¹ include nitrogen-containing heterocyclic groups having 4 to 9 carbon atoms such as a pyrrolidinyl group, piperidinyl group, and morpholinyl group.

［式（Ｉ−Ｃ）中、Ｒ^１、Ｒ^６及びＲ^７は上記と同じ意味を表す。
Ｒ^２１、Ｒ^２２は、それぞれ独立して、水素原子、炭素数１〜１２のアルキル基又はヒドロキシ基を表す。
Ｘ^２及びＸ^３は、それぞれ独立して、−ＣＨ_２−又は−Ｎ（Ｒ^２５）＝を表す。
Ｒ^２５は、水素原子、炭素数１〜２５のアルキル基、置換基を有していてもよい芳香族炭化水素基を表す。］ The compound represented by the formula (I) in which R ³ and R ⁶ are connected to each other to form a ring structure, and R ² and R ⁴ are bonded to each other to form a ring structure includes the compound represented by the formula (IC) The compound etc. which are represented by these are mentioned.

[In formula (IC), R ^1, R ⁶ and R ⁷ represent the same meaning as described above.
R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxy group.
X ² and X ³ each independently represent —CH ₂ — or —N (R ²⁵ ) ═.
R ²⁵ represents a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an aromatic hydrocarbon group which may have a substituent. ]

The alkyl group having 1 to 25 carbon atoms represented by R ^25, include those similar to the alkyl group having 1 to 25 carbon atoms represented by ^{R 1.}
Examples of the aromatic hydrocarbon group represented by R ²⁵ include aryl groups such as phenyl group and naphthyl group: aralkyl groups such as benzyl group and phenylethyl group: biphenyl group and the like, and aromatics having 6 to 20 carbon atoms. It is preferably a hydrocarbon group. Examples of the substituent that the aromatic hydrocarbon group represented by R ²⁵ may have include a hydroxy group.

R ³ and R ⁶ are preferably each independently an electron-withdrawing group.

［式（Ｉ−D）中、Ｒ^４、Ｒ⁵、Ｒ⁷は上記と同じ意味を表す。
Ｒ^２5、Ｒ^２6、Ｒ^２7及びＲ^２8は、それぞれ独立して、水素原子、置換基を有してもよい炭素数１〜１２のアルキル基、ヒドロキシ基、アラルキル基を表す。］ The compound represented by the formula (I) in which R ¹ and R ² are linked to each other to form a ring structure, and R ³ and R ⁶ are bonded to each other to form a ring structure includes the compound represented by the formula (ID) The compound etc. which are represented by these are mentioned.

[In the formula (ID), R ⁴ , R ⁵ and R ⁷ represent the same meaning as described above.
R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydroxy group or an aralkyl group. ]

As a C1-C12 alkyl group represented by R <^25> , R < ²⁶ >, R < ²⁷ > and R < ²⁸ >, the same thing as the C1-C12 alkyl group represented by R ^{< 1A>} and R ^<1B > is mentioned. Examples of the substituent that the alkyl group having 1 to 12 carbon atoms represented by R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ may have a hydroxy group.
Examples of the aralkyl group represented by R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ include aralkyl groups having 7 to 15 carbon atoms such as benzyl group and phenylethyl group.

［式（Ｉ−Ｅ）中、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ上記と同じ意味を表す。
環Ｗ^３は、環状化合物を表す]
環Ｗ^３は、５員環〜９員環の環であり、窒素原子、酸素原子、硫黄原子等のヘテロ原子を環の構成単位として含んでいてもよい。 Examples of compound (I) in which R ⁶ and R ⁷ are linked to each other to form a ring structure include compounds represented by formula (IE).

[In formula (IE), R ¹ , R ³ , R ⁴ and R ⁵ each represent the same meaning as described above.
Ring W ³ represents a cyclic compound]
Ring W ³ is a 5-membered to 9-membered ring, and may contain a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom as a structural unit of the ring.

［式（Ｉ−Ｃ−１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^５は、それぞれ上記と同じ意味を表す。
Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^ｑは、それぞれ独立して、水素原子又は置換基を有してもよい炭素数１〜１２のアルキル基、アラルキル基、アリール基を表し、該アルキル基又はアラルキル基に含まれる−ＣＨ_２−基は−ＮＲ^１Ｄ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｓ）−、−Ｏ−、−Ｓ−に置換されていてもよく、Ｒ^１７及びＲ^１８は互いに連結して環構造を形成してもよく、Ｒ^１８及びＲ^１９は互いに連結して環構造を形成してもよく、Ｒ^１９及びＲ^ｑは、互いに連結して環構造を形成してもよい。ｍ、ｐ、ｑはそれぞれ独立して０〜３の整数を表す。］ The compound represented by the formula (IE) is preferably a compound represented by the formula (IE-1).

[In formula (I-C-1), R ¹ , R ² , R ³ and R ⁵ each have the same meaning as described above.
R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^q each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an aralkyl group or an aryl group which may have a substituent, The —CH ₂ — group contained in the aralkyl group may be substituted with —NR ^1D —, —C (═O) —, —C (═S) —, —O—, —S—, R ¹⁷ and R ¹⁸ may be connected to each other to form a ring structure, R ¹⁸ and R ¹⁹ may be connected to each other to form a ring structure, and R ¹⁹ and R ^q are connected to each other to form a ring structure. May be. m, p, q each independently represents an integer of 0-3. ]

Examples of the compound represented by the formula (I) include the following compounds.

The total content of the light selective absorption compound is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A). More preferably, it is 0.1-10 mass parts, More preferably, it is 0.1-5 mass parts.
The mass ratio of the light selective absorption compound (A) to the light selective absorption compound (B) (light selective absorption compound (A) / light selective absorption compound (B)) is usually 0.05 to 20, preferably 0. .1-10.

<(Meth) acrylic resin (A)>
The (meth) acrylic resin (A) is preferably a polymer containing a structural unit derived from a (meth) acrylic acid ester as a main component (preferably containing 50% by mass or more). A structural unit derived from a (meth) acrylate ester is a structural unit derived from a monomer other than one or more (meth) acrylate esters (for example, a structural unit derived from a monomer having a polar functional group). May be included. In the present specification, (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used, and “(meth)” in the case of (meth) acrylate or the like has the same meaning. .

［式（Ｉ）中、Ｒ₁ は水素原子又はメチル基で表し、Ｒ₂ は炭素数１〜１４のアルキル基または炭素数７〜２０のアラルキル基を表し、該アルキル基または該アラルキル基の水素原子は、炭素数１〜１０のアルコキシ基で置き換わっていてもよい。］ Examples of (meth) acrylic acid esters include (meth) acrylic acid esters represented by the following formula (I).

[In formula (I), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group having 1 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and hydrogen of the alkyl group or the aralkyl group. The atom may be replaced by an alkoxy group having 1 to 10 carbon atoms. ]

In the formula (I), R ² is preferably an alkyl group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

As the (meth) acrylic acid ester represented by the formula (I),
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, N-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, (meth) acrylic acid Linear alkyl esters of (meth) acrylic acid such as lauryl, stearyl (meth) acrylate;
I-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, i-pentyl (meth) acrylate, i-hexyl (meth) acrylate, (meth) acrylic acid Branches of (meth) acrylic acid such as 2-ethylhexyl, i-octyl (meth) acrylate, i-nonyl (meth) acrylate, i-stearyl (meth) acrylate, i-amyl (meth) acrylate, etc. Alkyl ester;
(Meth) acrylic acid cyclohexyl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid cyclododecyl, (meth) acrylic acid methylcyclohexyl, ( An alicyclic skeleton-containing alkyl ester of (meth) acrylic acid, such as trimethylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclohexyl α-ethoxyacrylate;
(Meth) acrylic acid aromatic ring skeleton-containing ester such as (meth) acrylic acid phenyl;
Etc.
Moreover, the substituent containing (meth) acrylic-acid alkylester by which the substituent was introduce | transduced into the alkyl group in (meth) acrylic-acid alkylester can also be mentioned. The substituent of the substituent-containing (meth) acrylic acid alkyl ester is a group that replaces the hydrogen atom of the alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the substituent-containing (meth) acrylic acid alkyl ester include 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and (meth) acrylic acid 2- (2-phenoxyethoxy) ethyl, (meth) acrylic acid phenoxydiethylene glycol, (meth) acrylic acid phenoxypoly (ethylene glycol), and the like.

  These (meth) acrylic acid esters can be used alone or in combination.

  The (meth) acrylic resin (A) is a structural unit derived from an alkyl acrylate ester (a1) whose homopolymer has a glass transition temperature Tg of less than 0 ° C., and an alkyl acrylate whose homopolymer has a Tg of 0 ° C. or higher. It is preferable to contain the structural unit derived from ester (a2). The inclusion of the structural unit derived from the acrylic acid alkyl ester (a1) and the structural unit derived from the acrylic acid alkyl ester (a2) is advantageous in increasing the high temperature durability of the pressure-sensitive adhesive layer. Literature values such as POLYMER HANDBOOK (Wiley-Interscience) can be adopted as the Tg of the (meth) acrylic acid alkyl ester homopolymer.

  Specific examples of the alkyl acrylate ester (a1) include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate. Alkyl such as n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, and n-dodecyl acrylate Examples thereof include alkyl acrylates having about 2 to 12 carbon atoms.

  Acrylic acid alkyl ester (a1) may be used alone or in combination of two or more. Of these, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of followability and reworkability when the pressure-sensitive adhesive sheet of the present invention is laminated on an optical film.

  Acrylic acid alkyl ester (a2) is an acrylic acid alkyl ester other than acrylic acid alkyl ester (a1). Specific examples of acrylic acid alkyl ester (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, Includes stearyl acrylate, t-butyl acrylate, and the like.

  Acrylic acid alkyl ester (a2) may be used alone or in combination of two or more. Among these, from the viewpoint of high-temperature durability, the alkyl acrylate ester (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and the like, and more preferably contains methyl acrylate.

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

As a 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 structure derived from (meth) acrylic acid ester having a polar functional group Units are more preferred. 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,
1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxyheptyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 1-hydroxypentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 3-hydroxyhexyl (meth) acrylate, 3-hydroxyheptyl (meth) acrylate, (Meth) acrylic acid 4-hydroxybutyl, (meth) 4-hydroxypentyl crylate, 4-hydroxyhexyl (meth) acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate, 2-chloro-2-hydroxypropyl (meth) acrylate (Meth) acrylate 3-chloro-2-hydroxypropyl, (meth) acrylate 2-hydroxy-3-phenoxypropyl, (meth) acrylate 5-hydroxypentyl, (meth) acrylate 5-hydroxyhexyl, (meth) ) 5-hydroxyheptyl acrylate, 5-hydroxyoctyl (meth) acrylate, 5-hydroxynonyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, (meta ) 6-hydroxyoctyl acrylate, (meta 6-hydroxynonyl acrylate, 6-hydroxydecyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 7-hydroxyoctyl (meth) acrylate, 7-hydroxynonyl (meth) acrylate, (meth) 7-hydroxydecyl acrylate, 7-hydroxyundecyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 8-hydroxynonyl (meth) acrylate, 8-hydroxydecyl (meth) acrylate, (meta ) 8-hydroxyundecyl acrylate, 8-hydroxydodecyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 9-hydroxydecyl (meth) acrylate, 9-hydroxyundecyl (meth) acrylate, 9-hydroxydodecyl (meth) acrylate, (meth) acrylic 9-hydroxytridecyl silylate, 10-hydroxydecyl (meth) acrylate, 10-hydroxyundecyl (meth) acrylate, 10-hydroxydodecyl (meth) acrylate, 10-hydroxytridecyl acrylate, (meth) 10-hydroxytetradecyl acrylate, 11-hydroxyundecyl (meth) acrylate, 11-hydroxydodecyl (meth) acrylate, 11-hydroxytridecyl (meth) acrylate, 11-hydroxytetradecyl (meth) acrylate , (Meth) acrylic acid 11-hydroxypentadecyl, (meth) acrylic acid 12-hydroxydodecyl, (meth) acrylic acid 12-hydroxytridecyl, (meth) acrylic acid 12-hydroxytetradecyl, (meth) acrylic acid 13 -Hydroxypentadecyl (Meth) acrylic acid 13-hydroxytetradecyl, (meth) acrylic acid 13-hydroxypentadecyl, (meth) acrylic acid 14-hydroxytetradecyl, (meth) acrylic acid 14-hydroxypentadecyl, (meth) acrylic acid 15 A monomer having a hydroxy group such as hydroxypentadecyl, 15-hydroxyheptadecyl (meth) acrylate;
Monomers having a carboxyl group such as (meth) acrylic acid, carboxyalkyl (meth) acrylate (for example, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate), maleic acid, maleic anhydride, fumaric acid, crotonic acid, etc. body;
Acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, A monomer having a heterocyclic group such as 2,5-dihydrofuran;
Examples thereof include monomers having a substituted or unsubstituted amino group such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate.
Of these, from the viewpoint of the reactivity between the (meth) acrylic acid ester polymer and the crosslinking agent, a monomer having a hydroxy group or a monomer having a carboxyl group is preferred, and a monomer having a hydroxy group and a carboxyl group are preferred. More preferably, any of the monomers having a group is included.

As the monomer having a hydroxy 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.
As the monomer having a carboxyl group, it is preferable to use acrylic acid.

  From the viewpoint of preventing an increase in peelability of a separate film that can be laminated on the outer surface of the pressure-sensitive adhesive sheet, the (meth) acrylic resin (A) substantially includes a structural unit derived from a monomer having an amino group. Preferably not. Here, “substantially free” means that it is 0.1 part by mass or less in 100 parts by mass of all the structural units constituting the (meth) acrylic resin (a).

  The content of the structural unit derived from the monomer having a polar functional group is preferably 20 parts by mass or less, more preferably 0 with respect to 100 parts by mass of all structural units of the (meth) acrylic resin (A). 0.5 parts by mass or more and 15 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less.

  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 with respect to 100 parts by mass of all structural units of the (meth) acrylic resin (A). Part to 20 parts by mass, more preferably 4 parts to 16 parts by mass.

  As structural units derived from monomers other than (meth) acrylic acid esters, structural units derived from styrene monomers, structural units derived from vinyl monomers, and a plurality of (meth) acryloyl groups in the molecule Examples thereof include a structural unit derived from a monomer having a group and a structural unit derived from a (meth) acrylamide monomer.

  Examples of styrenic monomers include styrene; alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; fluorostyrene, Halogenated styrene such as chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.

  Examples of vinyl monomers include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, etc .; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride, etc. Examples thereof include vinylidene halides; 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.

  As monomers having a plurality of (meth) acryloyl groups in the molecule, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( Two (meth) acryloyl groups in the molecule such as (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate A monomer having three (meth) acryloyl groups in the molecule such as trimethylolpropane tri (meth) acrylate.

  (Meth) acrylamide monomers include 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, -Acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1-methyl) Ethoxymethyl) (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] ( T) acrylamide, N- [2- (1-methylpropoxy) ethyl] (meth) acrylamide, N- [2- (2-methylpropoxy) ethyl] (meth) acrylamide, N- (2-butoxyethyl) (meth) ) Acrylamide, N- [2- (1,1-dimethylethoxy) ethyl] (meth) acrylamide, and the like. Of these, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide and N- (2-methylpropoxymethyl) acrylamide are preferable.

  The weight average molecular weight (Mw) of the (meth) acrylic resin (A) is preferably 500,000 to 2.5 million. When the weight average molecular weight is 500,000 or more, the durability of the pressure-sensitive adhesive sheet in a high-temperature environment is improved, and there are problems such as lifting and peeling between the adherend and the pressure-sensitive adhesive sheet and cohesive failure of the pressure-sensitive adhesive sheet. Easy to suppress. A weight average molecular weight of 2.5 million or less is advantageous from the viewpoint of coatability. From the viewpoint of achieving both durability of the pressure-sensitive adhesive sheet and coating properties of the pressure-sensitive adhesive composition, the weight average molecular weight is preferably 600,000 to 1,800,000, more preferably 700,000 to 1,700,000, and particularly preferably 100. 10 to 1.6 million. The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2 to 10, preferably 3 to 8, and more preferably 3 to 6. . The weight average molecular weight can be analyzed by gel permeation chromatography and is a value in terms of standard polystyrene.

  When the (meth) acrylic acid resin (A) 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, preferably 0.1 to 15 Pa · s. It is more preferable that When the viscosity is within this range, it is advantageous from the viewpoint of coatability when the pressure-sensitive adhesive composition is applied to a substrate. The viscosity can be measured with a Brookfield viscometer.

  The glass transition temperature (Tg) of the (meth) acrylic resin (A) is, for example, −60 to 20 ° C., preferably −50 to 15 ° C., more preferably −45 to 10 ° C., particularly −40 to 0 ° C. May be. When Tg is less than or equal to the upper limit, it is advantageous for improving the wettability of the pressure-sensitive adhesive sheet to the adherend substrate, and when Tg is more than the lower limit, it is advantageous for improving the durability of the pressure-sensitive adhesive sheet. The glass transition temperature can be measured with a differential scanning calorimeter (DSC).

  The (meth) acrylic resin (A) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method, and the solution polymerization method is particularly preferable. As the solution polymerization method, for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added in a nitrogen atmosphere, and the temperature is 40 to 90 ° C., preferably about 50 to 80 ° C. A method of stirring for about an hour can be mentioned. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer or thermal initiator may be added to an organic solvent.

  As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. As thermal polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate) ), 2,2′-azobis (2-hydroxymethylpropionitrile) and other azo compounds; lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, Diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxyneode Organic peroxides such as noate, t-butyl peroxypivalate and (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate and hydrogen peroxide . Moreover, the redox initiator etc. which used the peroxide and the reducing agent together can also be used.

  The ratio of a polymerization initiator is about 0.001-5 mass parts with respect to 100 mass parts of total amounts of the monomer which comprises (meth) acrylic-type resin (A). For the polymerization of the (meth) acrylic resin, a polymerization method using active energy rays (for example, ultraviolet rays) may be used.

  Examples of organic solvents 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. Is mentioned.

  Content of (meth) acrylic-type resin (A) is 60 mass%-99.9 mass% normally in 100 mass% of adhesive compositions, Preferably it is 70 mass%-99.5 mass%, More preferably, it is 80 mass%-99 mass%.

  The crosslinking agent (B) reacts with a polar functional group (for example, a hydroxy group, an amino group, a carboxyl group, a heterocyclic group, etc.) in the (meth) acrylic resin (A). The crosslinking agent (B) forms a crosslinked structure with (meth) acrylic resin and the like, and forms a crosslinked structure advantageous for durability and reworkability.

  Examples of the crosslinking agent (B) include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, metal chelate-based crosslinking agents, and the like. In particular, pot life of the pressure-sensitive adhesive composition and durability of the pressure-sensitive adhesive layer, cross-linking From the viewpoint of speed and the like, an isocyanate-based crosslinking agent is preferable.

  As the isocyanate compound, a compound having at least two isocyanato groups (—NCO) in the molecule is preferable. For example, an aliphatic isocyanate compound (for example, hexamethylene diisocyanate), an alicyclic isocyanate compound (for example, isophorone diisocyanate). , Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), aromatic isocyanate compounds (for example, tolylene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). The crosslinking agent (B) is an adduct (adduct) of the isocyanate compound with a polyhydric alcohol compound [for example, an adduct with glycerol, trimethylolpropane or the like], an isocyanurate, a burette type compound, a polyether polyol, or a polyester. It may be a derivative such as a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like. A crosslinking agent (B) can be used individually or in combination of 2 or more types. Of these, typically, aromatic isocyanate compounds (for example, tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate) or their polyhydric alcohol compounds (for example, glycerol, trimethylolpropane). ) Or isocyanurate. If the crosslinking agent (B) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound thereof, or an isocyanurate, it is advantageous for forming an optimal crosslinking density (or crosslinked structure). The durability of the pressure-sensitive adhesive layer can be improved. In particular, when it is an adduct of a tolylene diisocyanate compound and / or these polyhydric alcohol compounds, durability can be improved even when, for example, an adhesive layer is applied to a polarizing plate.

  Content of a crosslinking agent (b) is 0.01-15 mass parts normally with respect to 100 mass parts of (meth) acrylic-type resin (a), Preferably it is 0.05-10 mass parts, and more. Preferably it is 0.1-5 mass parts.

The pressure-sensitive adhesive composition of the present invention may further contain a silane compound (d).
Examples of the silane compound (d) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, Examples include 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
The silane compound (D) may be a silicone oligomer. A specific example of the silicone oligomer is expressed in the form of a combination of monomers as follows.

  3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetraethoxysilane Mercaptopropyl group-containing oligomers such as oligomers; mercaptomethyltrimethoxysilane-tetramethoxysilane oligomers, mercaptomethyltrimethoxysilane-tetraethoxysilane oligomers, mercaptomethyltriethoxysilane-tetramethoxysilane oligomers, mercaptomethyltriethoxysilane-tetraethoxy Mercaptomethyl group-containing oligomers such as silane oligomers; 3-glycidoxypropyl Limethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetra Ethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyl group-containing copolymers such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; Cypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxy Silane oligomer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-methacryloyloxy Propylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. Methacryloyloxypropyl group-containing oligomers of: 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldiethoxy Silane-tetramethoxysilane oligomer, 3-acryloyloxypropylme Acrylyloxypropyl group-containing oligomer such as rudiethoxysilane-tetraethoxysilane oligomer; vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxy Silane-tetraethoxysilane oligomer, vinylmethyldimethoxysilane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, vinylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. Vinyl group-containing oligomer; 3-aminopropyltrimethoxysilane-tetramethoxysilane Limer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetra Amino group-containing compounds such as methoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc. Copolymer etc.

  The silane compound (d) may be a silane compound represented by the following formula (d1). When the pressure-sensitive adhesive composition contains a silane compound represented by the following formula (d1), it is possible to further improve the adhesion to a substrate, glass, transparent electrode, etc., so that it is difficult for floating and foaming to occur in a high temperature environment. An adhesive layer having good durability can be formed.

（式中、Ｂは、炭素数１〜２０のアルカンジイル基又は炭素数３〜２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置換されてもよく、Ｒ^ｄ７は炭素数１〜５のアルキル基を示し、Ｒ^ｄ８、Ｒ^ｄ９、Ｒ^ｄ１０、Ｒ^ｄ１１及びＲ^ｄ１２はそれぞれ独立して、炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基を示す）

(In formula, B shows a C1-C20 alkanediyl group or a C3-C20 bivalent alicyclic hydrocarbon group, and comprises the said alkanediyl group and the said alicyclic hydrocarbon group. —CH ₂ — may be substituted with —O— or —CO—, R ^d7 represents an alkyl group having 1 to 5 carbon atoms, and R ^d8 , R ^d9 , R ^d10 , R ^d11 and R ^d12 are each Independently, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is shown)

In the formula (d1), B represents an alkanediyl group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group; a cyclobutylene group (for example, 1,2-cyclobutylene group), cyclopentylene group (for example, 1,2-cyclopentylene group), cyclohexylene group (for example, 1,2-cyclohexylene group), cyclooctylene group (for example, 1,2- A divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, such as a cyclooctylene group), or —CH ₂ — constituting the alkanediyl group and the alicyclic hydrocarbon group is —O— or The group substituted by -CO- is shown. Preferred B is an alkanediyl group having 1 to 10 carbon atoms. R ^d7 represents an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group, or a pentyl group, and R ^d8 , R ^d9 , R ^{d10, R d11} and ^{R d12} are each independently said ^{R 21} exemplary of alkyl groups of 1 to 5 carbon atoms, or a methoxy group, an ethoxy group, a propoxy group, i- propoxy, butoxy, s- butoxy group And an alkoxy group having 1 to 5 carbon atoms such as a t-butoxy group. Desirable R ^d8 , R ^d9 , R ^d10 , R ^d11 and R ^d12 are each independently an alkoxy group having 1 to 5 carbon atoms. These silane compounds (d) can be used alone or in combination of two or more.

  Specific examples of the silane compound represented by the formula (d1) 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 (triC1-5alkoxysilyl) C1-10alkanes such as su (tripropoxysilyl) octane; bis (dimethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (dimethoxy) Ethylsilyl) ethane, 1,4-bis (dimethoxymethylsilyl) butane, 1,4-bis (dimethoxyethylsilyl) butane, 1,6-bis (dimethoxymethylsilyl) hexane, 1,6-bis (dimethoxyethylsilyl) ) Bis (diC1-5alkoxyC1-5alkylsilyl) C1-10alkanes such as hexane, 1,8-bis (dimethoxymethylsilyl) octane, 1,8-bis (dimethoxyethylsilyl) octane; Bis (methoxydimethylsilyl) hexane, 1,8-bis (methoxydimethylsilane) Le) bis octane (mono C1-5 alkoxy - di C1-5 alkylsilyl) such as C1-10 alkanes. Of these, 1,2-bis (trimethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) Bis (triC1-3alkoxysilyl) C1-10alkanes such as pentane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane are preferred, and in particular, 1,6-bis (Trimethoxysilyl) hexane and 1,8-bis (trimethoxysilyl) octane are preferred.

  Content of a silane compound (d) is 0.01-10 mass parts normally with respect to 100 mass parts of (meth) acrylic-type resin (a), Preferably it is 0.03-5 mass parts, More Preferably it is 0.05-2 mass parts, More preferably, it is 0.1-1 mass part. It is advantageous for suppression of bleeding out of the silane compound (d) from the pressure-sensitive adhesive layer if it is not more than the above upper limit value, and adhesion between the pressure-sensitive adhesive layer and a metal layer, a glass substrate or the like if it is not less than the above lower limit value. It is easy to improve the property (or adhesiveness), which is advantageous for improving the peel resistance.

The pressure-sensitive adhesive composition may further contain an antistatic agent.
Examples of the antistatic agent include surfactants, siloxane compounds, conductive polymers, ionic compounds, and the like, and ionic compounds are preferable. Examples of the ionic compound include conventional ones. Examples of the cation component constituting the ionic compound include organic cations and inorganic cations. Examples of the organic cation include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation. In particular, a pyridinium cation, an imidazolium cation, a pyrrolidinium cation, a lithium cation, and a potassium cation are preferable from the viewpoint of compatibility with a (meth) acrylic resin. The anionic component constituting the ionic compound may be either an inorganic anion or an organic anion, but an anionic component containing a fluorine atom is preferred in terms of antistatic performance. Examples of the anion component containing a fluorine atom include hexafluorophosphate anion (PF _6- ), bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N-], bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N-], tetra (pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B-] and the like. These ionic compounds can be used alone or in combination of two or more. In particular, bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N—], bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N—], tetra (pentafluorophenyl) borate anion [(C ₆ F _{5) 4} B-] is preferred.
From the viewpoint of the temporal stability of the antistatic performance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, an ionic compound that is solid at room temperature is preferable.

  Content of an antistatic agent is 0.01-20 mass parts with respect to 100 mass parts of (meth) acrylic-type resin (a), Preferably it is 0.1-10 mass parts, More preferably, it is 1-7. Mass.

  The pressure-sensitive adhesive composition may 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.

<Configuration and production method of pressure-sensitive adhesive layer and optical film with pressure-sensitive adhesive layer>
The pressure-sensitive adhesive sheet of the present invention is formed, for example, by dissolving or dispersing the pressure-sensitive adhesive composition in a solvent to form a solvent-containing pressure-sensitive adhesive composition, and then applying this to the surface of the substrate and drying it. Is done. The optical film with the pressure-sensitive adhesive layer is a method of peeling the base material after laminating the optical film on the pressure-sensitive adhesive sheet surface of the formed base material with the pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive composition on a resin film such as an optical film. The method of apply | coating an object and drying is mentioned.
As the substrate, a plastic film is suitable, and specifically, a release film that has been subjected to a mold release treatment can be mentioned. Examples of the release film include those obtained by performing release treatment such as silicone treatment on one surface of a film made of a resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate and the like. For temporary protection of the pressure-sensitive adhesive sheet, a release film may be attached to the pressure-sensitive adhesive layer sheet.

FIG. 1 shows an example of the layer structure of the pressure-sensitive adhesive sheet of the present invention. The pressure-sensitive adhesive sheet 1 shown in FIG. 1 is in a state where a release film 2 is stuck for temporary protection. The release film may be laminated on one side of the pressure-sensitive adhesive sheet or may be laminated on both sides.
An optical laminate in which an optical film is laminated on at least one surface of the pressure-sensitive adhesive layer of the present invention is also included in the present invention. The optical laminated body containing the adhesive sheet of this invention is shown in FIGS. 2A is an optical laminate including a protective form 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 3, a pressure sensitive adhesive sheet 1, and a release film 2. The protective film 3 may have a phase difference. The layer configuration of the protective form 8, the adhesive layer 7, the polarizing film 9, the adhesive layer 7, and the protective film 3 corresponds to a polarizing plate indicated by the optical film 40. The optical laminate 10B shown in FIG. 3 and the optical laminate 10C shown in FIG. 4 are a protective form 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 3, an adhesive sheet 1, and an optical film. 40, an optical laminate including the pressure-sensitive adhesive layer 7a and the light emitting element 30 (liquid crystal cell, OLED cell).

  The optical film 40 is a film having optical functions such as transmission, reflection, and absorption of light, and may be a single layer film or a multilayer film. Examples of the optical film 40 include a polarizing film (polarizing plate), a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a condensing film, a window film, and the like. A polarizing film, a retardation film A window film or a laminated film thereof is preferable.

  A retardation film is an optical film exhibiting optical anisotropy, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride. Examples thereof include a stretched film obtained by stretching a polymer film composed of ride / polymethyl methacrylate, acetylcellulose, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc. by about 1.01 to 6 times. Among these, a polymer film obtained by uniaxially stretching or biaxially stretching a polycarbonate film or a cycloolefin-based resin film is preferable. In the present specification, the retardation film includes a zero retardation film, and also includes a film called a uniaxial retardation film, a low photoelasticity retardation film, a wide viewing angle retardation film, or the like.

  As a film that exhibits optical anisotropy by coating and orientation of a liquid crystalline compound and a film that exhibits optical anisotropy by coating an inorganic layered compound, a film called a temperature-compensated retardation film, JX “NH film” (trade name; film with rod-like liquid crystal tilted) sold by liquid crystal film, “WV film” (trade name; film with disc-like liquid crystal tilt-aligned) sold by FUJIFILM Corporation And “VAC film” (trade name: fully biaxially oriented film) and “new VAC film” (trade name: biaxially oriented film) sold by Sumitomo Chemical Co., Ltd.

The zero Letters retardation film, and the retardation R _th for the front retardation R _e and the thickness direction, both a -15～15Nm, refers to isotropic film optically. Examples of the zero retardation film include a resin film made of a cellulose resin, a polyolefin resin (a chain polyolefin resin, a polycycloolefin resin, etc.) or a polyethylene terephthalate resin, and the retardation value can be easily controlled and obtained. Cellulose resin or polyolefin resin is preferable because it is easy. The zero retardation film can also be used as a protective film. Zero retardation films include “Z-TAC (trade name)” sold by FUJIFILM Corporation, “Zero Tac (registered trademark)” sold by Konica Minolta Co., Ltd., and ZEON Corporation (sold by ZEON Corporation). “ZF-14 (trade name)”.

  In the optical film of the present invention, the retardation film is preferably a retardation film obtained by curing a polymerizable liquid crystal compound.

  As a film in which optical anisotropy is expressed by coating and orientation of a liquid crystalline compound, the first form: a retardation film in which a rod-like liquid crystal compound is oriented in a horizontal direction with respect to a supporting substrate, the second form: a rod-like form Retardation film in which the liquid crystal compound is oriented in the direction perpendicular to the supporting substrate, third form: Retardation film in which the orientation direction of the rod-like liquid crystal compound is spirally changed in the plane, Fourth form: Examples include a retardation film in which a discotic liquid crystal compound is tilted and oriented, and a fifth embodiment: a biaxial retardation film in which a discotic liquid crystal compound is oriented in a direction perpendicular to a supporting substrate.

  For example, as an optical film used for an organic electroluminescence display, the first form, the second form, and the fifth form are suitably used. Alternatively, these may be stacked and used.

When the retardation film is a layer made of a polymer in the alignment state of the polymerizable liquid crystal compound (hereinafter sometimes referred to as “optically anisotropic layer”), the retardation film may have reverse wavelength dispersion. preferable. Reverse wavelength dispersion is an optical characteristic in which the in-plane retardation value of a liquid crystal alignment at a short wavelength is smaller than the in-plane retardation value of a liquid crystal alignment at a long wavelength. (7) and Formula (8) are satisfied. 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 in the first form and has reverse wavelength dispersion, it is preferable because coloring at the time of black display on the display device is reduced. It is more preferable that Re (450) / Re (550) ≦ 0.93. Further, 120 ≦ Re (550) ≦ 150 is preferable.

  As the polymerizable liquid crystal compound in the case where the retardation film is a film having an optically anisotropic layer, “3” of Liquid Crystal Manual (Edited by Liquid Crystal Handbook Editorial Committee, Maruzen Co., Ltd. issued on October 30, 2000). .8.6 Network (fully crosslinked type) ”,“ 6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material ”, compounds having a polymerizable group, and JP2010-31223A JP, JP 2010-270108, JP 2011-6360, JP 2011-207765, JP 2011-162678, JP 2011-81035, WO 2017/043438. And polymerizable liquid crystal compounds described in JP-A-2011-207765.

  Examples of the method for producing the retardation film from the polymer in the alignment state of the polymerizable liquid crystal compound include a method described in JP 2010-31223 A.

In the case of the second embodiment, the front phase difference 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 thickness direction retardation value R _th is −10 to −. What is necessary is just to adjust to the range of 300 nm, Preferably it is -20--200 nm. Retardation value in the thickness direction R _th, which means the refractive index anisotropy in the thickness direction, the retardation of the retardation values R ₅₀ and the surface to be measured is tilted 50 degrees fast axis in plane as a tilt axis It can be calculated from the value R ₀ . 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, the thickness d of the retardation film, and the level the average refractive index n ₀ of the retardation film, obtains the n _x, n _y and n _z by the following equation (10) to (12), these are substituted into equation (9) can be calculated.

R _th = [(n _x + _ny ) / 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 ′ = _ny × _nz / [ _ny ² × sin ² (φ) + _nz ² × cos ² (φ)] ^1/2

  The retardation film may be a multilayer film having two or more layers. For example, what laminated | stacked the protective film on the single side | surface or both surfaces of retardation film, and the thing on which two or more retardation films were laminated | stacked through the adhesive or the adhesive agent are mentioned.

The thickness of the retardation film is usually 0.1 to 100 μm.
When the retardation film is a multilayer, the total thickness may be 0.5 to 200 μm.

  When the optical film 40 is a multilayer film in which two or more retardation films are laminated, the configuration of the optical laminate including the optical film of the present invention is as follows. A quarter-wave retardation layer 50 that imparts a phase difference of ½ wavelength and a ½ wavelength retardation layer 70 that imparts a phase difference of ½ wavelength to transmitted light via an adhesive or a pressure-sensitive adhesive 60. The structure containing the laminated | stacked optical film 40 is mentioned. Moreover, as shown in FIG. 4, the structure containing the scholarly film 40 which laminated | stacked the quarter wavelength phase difference layer 50a and the positive C layer 80 through the adhesive bond layer or the adhesive layer is also mentioned.

  The ¼ wavelength phase difference layer 50 for imparting a phase difference for ¼ wavelength in FIG. 3 and the ½ wavelength phase difference layer 70 for imparting a phase difference for ½ wavelength to the transmitted light are the above first. The optical film of the fifth form or the optical film of the fifth form may be used. In the case of the configuration of FIG. 3, it is more preferable that at least one of the configurations is the fifth form.

  In the configuration of FIG. 4, the quarter-wave retardation layer 50 a is preferably the optical film of the first form, and more preferably satisfies the expressions (7) and (8).

  The polarizing film is a film having a property of absorbing linearly polarized light having a vibration surface parallel to the absorption axis and transmitting linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the transmission axis). A film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin film can be used. Examples of the dichroic dye include iodine and dichroic organic dyes.

  Usually, what formed the polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. A polyvinyl alcohol-type resin can be formed into a film by a well-known method. The thickness of the raw film is usually 1 to 150 μm, and preferably 10 μm or more in consideration of easiness of stretching.

  The polarizing film is, for example, a step of uniaxially stretching the original film, a step of dyeing the film with a dichroic dye and adsorbing the dichroic dye, a step of treating the film with an aqueous boric acid solution, and A step of washing the film with water is performed, and finally the film is dried to be manufactured. The thickness of the polarizer 2 is usually 1 to 30 μm, and is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less from the viewpoint of thinning the optical film 1 with an adhesive layer.

  A polarizing film formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol resin film uses a single film of a polyvinyl alcohol resin film as a raw film, and this film is uniaxially stretched and dyed with a dichroic dye. In addition to the method of processing (referred to as method (1)), a base film having a polyvinyl alcohol resin layer by applying a coating liquid (such as an aqueous solution) containing a polyvinyl alcohol resin to the base film and drying it. After uniaxial stretching for each base film, the polyvinyl alcohol resin layer after stretching is dyed with a dichroic dye, and then the base film is peeled and removed (method (2) ) And)). As the base film, a film made of the same thermoplastic resin as the thermoplastic resin can be used. Preferably, a polyester resin such as polyethylene terephthalate, a polycarbonate resin, a cellulose resin such as triacetyl cellulose, and a norbornene-based film. It is a film made of a cyclic polyolefin resin such as a resin, a polystyrene resin, or the like. When the above method (2) is used, it is easy to produce a thin polarizing film. For example, it is possible to easily produce a polarizer 2 having a thickness of 7 μm or less.

It is preferable that a protective film is provided on at least one surface of the polarizing film via an adhesive.
As the adhesive, a known adhesive is used, which may be an aqueous adhesive or an active energy ray-curable adhesive.

  As the water-based adhesive, a conventional water-based adhesive (for example, an adhesive comprising a polyvinyl alcohol resin aqueous solution, an aqueous two-component urethane emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, And crosslinking agents such as amine compounds and polyvalent metal salts). Among these, a water-based adhesive made of a polyvinyl alcohol-based resin aqueous solution can be suitably used. In addition, when using a water-system adhesive agent, after bonding a polarizing film and a protective film, it is preferable to implement the process dried to remove the water contained in a water-system adhesive agent. After the drying process, for example, a curing process for curing at a temperature of about 20 to 45 ° C. may be provided. The adhesive layer formed from a water-based adhesive is usually 0.001 to 5 μm.

  The active energy ray-curable adhesive refers to an adhesive that cures when irradiated with active energy rays such as ultraviolet rays and electron beams. For example, a curable composition containing a polymerizable compound and a photopolymerization initiator, light Examples thereof include a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and preferably an ultraviolet curable adhesive.

  When using an active energy ray-curable adhesive, after bonding the polarizing film and the protective film, if necessary, a drying step is performed, and then the active energy ray-curable adhesive is irradiated by irradiating the active energy ray. A curing step for curing is performed. The light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable. The adhesive layer formed from the active energy ray-curable adhesive is usually 0.1 to 20 μm.

  Examples of the method for laminating the polarizing film and the protective film include a method for subjecting at least one of these laminating surfaces to surface activation treatment such as saponification treatment, corona treatment, plasma treatment, and the like. When resin films are bonded to both surfaces of the polarizing film, the adhesive for bonding these resin films may be the same type of adhesive or different types of adhesives.

A preferable configuration of the polarizing plate is a polarizing plate in which a protective film is laminated on at least one surface of the polarizing film via an adhesive layer. 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. The protective film laminated on the viewing side is preferably a protective film made of a triacetyl cellulose resin or a cycloolefin resin. The protective film may be an unstretched film, or may be stretched in any direction and have a phase difference. A surface treatment layer such as a hard coat layer or an antiglare layer may be provided on the surface of the protective film laminated on the viewing side.
When the protective film is laminated on both sides of the polarizing film, the protective film on the panel side (opposite to the viewing side) is a protective film or retardation film made of a triacetyl cellulose resin, cycloolefin resin or acrylic resin. Preferably there is. The retardation film may be a zero retardation film described later.
Another layer or film may be further laminated between the polarizing plate and the panel. When used as a circularly polarizing plate for an organic EL display, a retardation layer having a quarter-wave retardation layer and a half-wave retardation layer, and the above-described quarter-wave layer with reverse wavelength dispersion are stacked. It is preferable. The retardation layer is preferably a liquid crystal retardation film from the viewpoint of thinning.

  The condensing film is used for the purpose of optical path control, and can be a prism array sheet, a lens array sheet, a dot-attached sheet, or the like.

  The brightness enhancement film is used for the purpose of improving the brightness in a liquid crystal display device to which a polarizing plate is applied. Specifically, a reflective polarized light separation sheet, an alignment film of a cholesteric liquid crystal polymer, and an alignment film that are designed so that anisotropy occurs in the reflectance by laminating a plurality of thin film films having different refractive index anisotropies Examples include a circularly polarized light separating sheet that supports a liquid crystal layer on a base film.

  The window film means a front plate in a flexible display device such as a flexible display, and is generally disposed on the outermost surface of the display device. Examples of the window film include a resin film made of a polyimide resin. The window film may be a hybrid film of an organic material and an inorganic material such as a resin film containing polyimide and silica. The window film may be provided with a hard coat layer on the surface for imparting functions of surface hardness, antifouling property, and fingerprint resistance. Examples of the wind film include films described in JP-A-2017-94488.

  The optical laminate including the pressure-sensitive adhesive layer sheet of the present invention is laminated on a display element such as an organic EL element or a liquid crystal cell and used for a display device (FPD: flat panel display) such as an organic EL display device or a liquid crystal display device. I can do things.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Unless otherwise specified, “%” and “part” in Examples and Comparative Examples are “% by mass” and “part by mass”.

  In the following examples, the weight average molecular weight and the number average molecular weight were measured as four columns using a gel permeation chromatography (hereinafter referred to as GPC) apparatus (GPC-8120, manufactured by Tosoh Corporation). "TSK gel XL (manufactured by Tosoh Corp.)" and "Shodex GPC KF-802 (manufactured by Showa Denko KK)" were placed in series, 5 in total, and tetrahydrofuran was used as the eluent. The sample concentration was 5 mg / mL, the sample introduction amount was 100 μL, the temperature was 40 ° C., and the flow rate was 1 mL / min.

ジムロート冷却管、温度計を設置した２００ｍＬ−四ツ口フラスコ内を窒素雰囲気とし、特許文献（特開２０１４−１９４５０８）を参考に合成した式（ａａ）で表される化合物１０部、無水酢酸（和光純薬工業株式会社製）３．６部、シアノ酢酸２−エチルヘキシル（ＤＩＰＥＡと称する場合がある；東京化成工業株式会社製）６．９部、およびアセトニトリル（和光純薬工業株式会社製）６０部を仕込み、マグネチックスターラーで撹拌した。内温２５℃にてＤＩＰＥＡ（東京化成工業株式会社製）４．５部を滴下漏斗から１時間かけて滴下し、滴下終了後に内温２５℃にてさらに２時間保温した。反応終了後、減圧エバポレーターを用いてアセトニトリルを除去し、カラムクロマトグラフィー（シリカゲル）に供して精製し、式（ａａ１）で表される光選択吸収性化合物（１）を含む流出液を、減圧エバポレーターを用いて溶媒を除去し、黄色結晶を得た。該結晶を６０℃減圧乾燥することにより、黄色粉末として光選択吸収性化合物（１）を４．６部得た。収率は５０％であった。 (Synthesis Example 1) Synthesis of photoselective absorbing compound (1)

A 200 mL four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 10 parts of a compound represented by the formula (aa) synthesized with reference to a patent document (Japanese Patent Laid-Open No. 2014-194508), acetic anhydride ( 3.6 parts manufactured by Wako Pure Chemical Industries, Ltd.), 6.9 parts of 2-ethylhexyl cyanoacetate (sometimes referred to as DIPEA; manufactured by Tokyo Chemical Industry Co., Ltd.), and acetonitrile (made by Wako Pure Chemical Industries, Ltd.) 60 The parts were charged and stirred with a magnetic stirrer. 4.5 parts of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped from the dropping funnel over 1 hour at an internal temperature of 25 ° C., and the mixture was further kept at an internal temperature of 25 ° C. for 2 hours. After completion of the reaction, acetonitrile is removed using a vacuum evaporator, and the product is purified by column chromatography (silica gel), and the effluent containing the photoselective absorptive compound (1) represented by the formula (aa1) is removed from the vacuum evaporator. Was used to remove the solvent to obtain yellow crystals. The crystal was dried under reduced pressure at 60 ° C. to obtain 4.6 parts of a photoselective absorptive compound (1) as a yellow powder. The yield was 50%.

^{When 1} H-NMR analysis was performed, the following peaks were observed, confirming that photoselective absorptive compound 1 was produced.
¹ H-NMR (CDCl 3) δ: 0.87-0.94 (m, 6H), 1.32-1.67 (m, 8H), 1.59-1.66 (m, 2H); 09 (quin, 2H), 3.00 (m, 5H), 3.64 (t, 2H), 4.10 (dd, 2H), 5.52 (d, 2H), 7.87 (d, 2H) )

<Measurement of Gram extinction coefficient ε>
In order to measure the Gram extinction coefficient of the obtained light selective absorption compound (1), the light selective absorption compound (1) was dissolved in 2-butanone. The obtained solution (0.006 g / L) was put into a 1 cm quartz cell, the quartz cell was set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and a wavelength of 1 nm step from 300 to 800 nm by a double beam method. Absorbance was measured over a range. From the obtained absorbance value, the concentration of the light absorbing compound in the solution, and the optical path length of the quartz cell, the gram extinction coefficient for each wavelength was calculated using the following formula.
ε (λ) = A (λ) / CL
[Wherein, ε (λ) represents the gram extinction coefficient L / (g · cm) of the compound at the wavelength λnm, A (λ) represents the absorbance at the wavelength λnm, C represents the concentration g / L, and L is It represents the optical path length cm of the quartz cell. ]
When the absorption maximum wavelength (λmax) of the photoselective absorptive compound (1) was measured, λmax = 389 nm (in 2-butanone), the value of ε (405) was 47 L / (g · cm), and ε The value of (440) was 0.1 L / (g · cm) or less, and the value of ε (405) / ε (440) was 80 or more.

ジムロート冷却管、温度計を設置した２００ｍＬ−四ツ口フラスコ内に、窒素雰囲気において、特開２０１４−１９４５０８を参考に合成した式（ａａ）で表される化合物１０ｇ、無水酢酸（和光純薬工業株式会社製）３．６ｇ、シアノ酢酸２−ブチルオクチル（東京化成工業株式会社製）１０ｇ、およびアセトニトリル（和光純薬工業株式会社製）６０ｇを仕込み、マグネチックスターラーで撹拌した。内温２５℃にてＤＩＰＥＡ（東京化成工業株式会社製）４．５ｇを、得られた混合物に１時間かけて滴下した後、内温２５℃にてさらに２時間保温した。その後、減圧エバポレーターを用いてアセトニトリルを除去し、カラムクロマトグラフィー（シリカゲル）に供して精製し、式（ａａ２）で表される化合物を含む流出液を、減圧エバポレーターを用いて溶媒を除去し、黄色結晶を得た。該結晶を６０℃減圧乾燥することにより、黄色粉末として式（ａａ２）で表される化合物（光選択吸収化合物（２））を４．６ｇ得た。収率は５６％であった。
上記と同じ方法でグラム吸光度係数を求めると、式（ａａ２）で表される化合物のε（４０５）の値は４５Ｌ／（ｇ・ｃｍ）であり、ε（４２０）の値は２．１Ｌ／（ｇ・ｃｍ）であった。 (Synthesis Example 2) Synthesis of Photoselective Absorbing Compound (2)

In a 200 mL four-necked flask equipped with a Dimroth condenser and a thermometer, in a nitrogen atmosphere, 10 g of a compound represented by the formula (aa) synthesized with reference to JP-A-2014-194508, acetic anhydride (Wako Pure Chemical Industries, Ltd.) 3.6 g), 2-butyloctyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer. After dropping 4.5 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) at an internal temperature of 25 ° C. over 1 hour, the mixture was kept at an internal temperature of 25 ° C. for 2 hours. Thereafter, acetonitrile is removed using a vacuum evaporator, and the product is subjected to column chromatography (silica gel) for purification, and the effluent containing the compound represented by formula (aa2) is removed using a vacuum evaporator to remove the solvent. Crystals were obtained. The crystal was dried at 60 ° C. under reduced pressure to obtain 4.6 g of a compound represented by the formula (aa2) (photoselective absorption compound (2)) as a yellow powder. The yield was 56%.
When the gram absorbance coefficient is determined by the same method as described above, the value of ε (405) of the compound represented by the formula (aa2) is 45 L / (g · cm), and the value of ε (420) is 2.1 L / (G · cm).

(Synthesis Example 3) Synthesis of (meth) acrylic resin In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 81.8 parts of ethyl acetate as a solvent and 70.4 butyl acrylate as a monomer Part, 20.0 parts of methyl acrylate, 8.0 parts of 2-phenoxyethyl acrylate, 1.0 part of 2-hydroxyethyl acrylate and 0.6 part of acrylic acid were charged. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was set to 60 ° C. Thereafter, a solution in which 0.12 part of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., ethyl acetate was continuously introduced into the reaction vessel at an addition rate of 17.3 parts / hr so that the polymer concentration was approximately 35%. Added. After maintaining the internal temperature at 54 to 56 ° C. until 12 hours have elapsed from the start of the addition of ethyl acetate, ethyl acetate was added to adjust the polymer concentration to 20%, and the (meth) acrylic resin An ethyl acetate solution (1) was obtained. The (meth) acrylic resin had a weight average molecular weight Mw of 1.39 million and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of 5.32.

  In addition, the measurement of a weight average molecular weight and a number average molecular weight is 1 column of "TSK gel XL (made by Tosoh Corporation)" and "Shodex GPC KF-802 (made by Showa Denko Corporation)" as a column in a GPC apparatus. A total of 5 tubes are connected in series, and tetrahydrofuran is used as the eluent, sample concentration is 5 mg / mL, sample introduction amount is 100 μL, temperature is 40 ° C., flow rate is 1 mL / min, and calculated by standard polystyrene conversion. did.

(Synthesis Example 4) Synthesis of Adhesive Composition (1) For 100 parts of the solid content of the ethyl acetate solution (1) (resin concentration: 20%) of the (meth) acrylic resin obtained in Synthesis Example 3, 0.4 parts of a cross-linking agent, 0.4 parts of a silane compound, 2 parts of the light selective absorbing compound (1) synthesized in Synthesis Example 1 and 2.0 parts of Sumisorb 350 (manufactured by Sumika Chemtex Co., Ltd.) are mixed. Ethyl acetate was added so that the solid content concentration was 14% to obtain a pressure-sensitive adhesive composition (1). In addition, the compounding quantity of the said crosslinking agent is the weight part as an active ingredient.

Details of the crosslinking agent and the silane compound used in Synthesis Example 4 are as follows.
Crosslinking agent: Trimethylolpropane adduct of tolylene diisocyanate in ethyl acetate solution (solid content concentration 75%), trade name “Coronate L” obtained from Tosoh Corporation.
Silane compound: 3-glycidoxypropyltrimethoxysilane, trade name “KBM403” obtained from Shin-Etsu Chemical Co., Ltd.

(Synthesis Example 5) Synthesis of Adhesive Composition (2) The photoselective absorptive compound was prepared by using 2.0 parts of the photoselective absorptive compound (2) obtained in Synthesis Example 2 and 2-hydroxy-4-methoxybenzophenone (Tokyo). A pressure-sensitive adhesive composition (2) was obtained in the same manner as in Synthesis Example 4 except that the amount was changed to 1.0 part (made by Kasei Kogyo Co., Ltd.).

(Synthesis Example 6) Synthesis of Adhesive Composition (3) The light selective absorption compound (2) and EST-5 (manufactured by Sumitomo Seika Co., Ltd.) 1.0 obtained in Synthesis Example 2 were used as the light selective absorption compound. A pressure-sensitive adhesive composition (3) was obtained in the same manner as in Synthesis Example 4 except that the composition was changed to the part.

(Synthesis Example 7) Synthesis of pressure-sensitive adhesive composition (4) Synthesis Example 4 except that the light selective absorption compound is only 2 parts of the light selective absorption compound (1) obtained in Synthesis Example 1 and the sumisop 350 is not mixed. In the same manner as described above, a (meth) acrylic resin pressure-sensitive adhesive composition (7) was obtained.

(Synthesis Example 8) Synthesis of pressure-sensitive adhesive composition (5) Synthesis Example 4 except that the light selective absorption compound is only 2 parts of the light selective absorption compound (2) obtained in Synthesis Example 2 and the sumisorp 350 is not overturned. In the same manner as described above, a (meth) acrylic resin pressure-sensitive adhesive composition (5) was obtained.

<Production of pressure-sensitive adhesive sheet>
(Example 1) Preparation of pressure-sensitive adhesive sheet (1) The pressure-sensitive adhesive composition (1) obtained was separated from a polyethylene terephthalate film subjected to a release treatment [trade name “PLR obtained from Lintec Corporation] -382190 "] was applied to the release-treated surface using an applicator so that the thickness after drying was 15 µm, and dried at 100 ° C for 1 minute to prepare an adhesive layer (1).

  The obtained pressure-sensitive adhesive layer (1) was laminated on a 23 μm cycloolefin film with a laminator and then cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a pressure-sensitive adhesive sheet (1).

(Example 2) Preparation of pressure-sensitive adhesive sheet (2) The pressure-sensitive adhesive sheet (2) was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition was replaced with the pressure-sensitive adhesive composition (2) obtained in Synthesis Example 5. )

(Example 3) Preparation of pressure-sensitive adhesive sheet (3) A pressure-sensitive adhesive sheet (3) was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition was replaced with the pressure-sensitive adhesive composition (3) obtained in Synthesis Example 6. )

(Comparative Example 1) Production of pressure-sensitive adhesive sheet (4) A pressure-sensitive adhesive sheet (4) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition was replaced with the pressure-sensitive adhesive composition (4) obtained in Synthesis Example 7. )

(Comparative Example 2) Preparation of pressure-sensitive adhesive sheet (5) A pressure-sensitive adhesive sheet (5) was obtained in the same manner as in Example 1, except that the pressure-sensitive adhesive composition was replaced with the pressure-sensitive adhesive composition (5) obtained in Synthesis Example 8. )

<Preparation of polarizing plate with adhesive>
(Production Example 1) Production of Polarizing Film Polyvinyl alcohol film having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 30 μm [trade name “Kuraray Vinylon VF-PE # 3000” manufactured by Kuraray Co., Ltd.] Was immersed in pure water at 37 ° C. and then immersed in an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (mass ratio) = 0.04 / 1.5 / 100) at 30 ° C. . Then, it was immersed at 56.5 ° C. in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (mass ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C. and then dried at 85 ° C. to obtain a polarizer having a thickness of about 12 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the iodine staining and boric acid treatment steps, and the total stretching ratio was 5.3 times.
A transparent protective film (trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd., hereinafter sometimes referred to as “TAC film”) made of a 25 μm-thick triacetylcellulose film on one side of the obtained polarizer is polyvinyl alcohol. It bonded through the adhesive agent which consists of aqueous solution of a system resin. Next, on the surface opposite to the triacetyl cellulose film in the polarizer, a zero retardation film composed of a cyclic polyolefin resin having a thickness of 23 μm [trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd., hereinafter referred to as “COP film”] In some cases, a polarizing plate was prepared by bonding with an adhesive composed of an aqueous solution of a polyvinyl alcohol resin.

(Example 4) Preparation of polarizing plate with pressure-sensitive adhesive (1) A polarizing plate with pressure-sensitive adhesive (1) except that the 23 μm cycloolefin film was replaced with the polarizing plate obtained in Production Example 1. ) The polarizing plate (1) with an adhesive layer has a configuration of TAC film / adhesive layer / polarizing film / adhesive layer / COP film / adhesive layer.

(Example 5) Production of polarizing plate with adhesive (2) Polarizing plate with adhesive (2) in the same manner as in Example 3 except that the 23 μm cycloolefin film was replaced with the polarizing plate obtained in Production Example 1. ) The polarizing plate with the pressure-sensitive adhesive layer (2) has a configuration of TAC film / adhesive layer / polarizing film / adhesive layer / COP film / pressure-sensitive adhesive layer.

(Comparative Example 3) Preparation of polarizing plate with pressure-sensitive adhesive (3) A polarizing plate with pressure-sensitive adhesive (3) except that the 23 μm cycloolefin film was replaced with the polarizing plate obtained in Production Example 1. ) The polarizing plate with the pressure-sensitive adhesive layer (3) has a configuration of TAC film / adhesive layer / polarizing film / adhesive layer / COP film / pressure-sensitive adhesive layer.

<Measurement of absorbance of adhesive sheet>
The obtained film (1) with a pressure-sensitive adhesive sheet is cut into a size of 30 mm × 30 mm, and the pressure-sensitive adhesive sheet and non-alkali glass (trade name “EAGLE XG” manufactured by Corning) are bonded together to prepare a sample. It was. The absorbance of the prepared sample in the wavelength range of 300 to 800 nm was measured using a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation). The results are shown in Table 1. The higher the absorbance retention, the better the weather resistance without deterioration of the light selective absorption function. In addition, the light absorbency of wavelength 350nm, wavelength 405nm, and wavelength 440nm was 0 for both the COP film alone and the alkali-free glass alone.

The sample after the absorbance measurement was put into a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 24 hours at 63 ° C. and 50% relative humidity, and a 24-hour weather resistance test was performed. The absorbance of the sample taken out was measured by the same method as described above. Based on the measured absorbance, the absorbance retention of the sample at 350 nm and 405 nm was determined based on the following formula. The results are shown in Table 1.
Absorbance retention = (A (405) after endurance test / A (405) before endurance test) × 100
Absorbance retention = (A (350) after endurance test / A (350) before endurance test) × 100

<Measurement of absorbance of polarizing plate with adhesive>
After the obtained polarizing plate with pressure-sensitive adhesive was cut into a size of 30 mm × 30 mm, the pressure-sensitive adhesive layer was bonded to a glass substrate to obtain a measurement sample. The layer configuration of the measurement sample is glass substrate / pressure-sensitive adhesive layer / COP film / adhesive layer / polarizer / adhesive layer / TAC film. As the glass substrate, an alkali-free glass substrate (trade name “Eagle XG” manufactured by Corning) was used.
About the obtained measurement sample, using a spectrophotometer with an integrating sphere (product name “V7100” manufactured by JASCO Corporation), transmission spectra in the transmission axis direction and absorption axis direction of the polarizing plate in the wavelength range of 380 to 780 nm. Was measured, and the absorbance of the polarizing plate with the pressure-sensitive adhesive layer was calculated from the transmission spectrum of the transmission axis aroma of the polarizing plate. In addition, the polarizing plate with an adhesive confirmed the deterioration suppression in visible light with a short wavelength of 405 nm. In addition, the absorbance of each of the TAC film alone, the COP film alone, and the alkali-free glass alone was 0 at a wavelength of 405 nm and a wavelength of 440 nm.

As shown in Table 1, the pressure-sensitive adhesive sheet of the present invention has a good light absorption function near a wavelength of 350 nm and a light absorption function near a wavelength of 405 nm. Therefore, when the pressure-sensitive adhesive sheet of the present invention is laminated on a retardation film or an organic EL element, the pressure-sensitive adhesive sheet of the present invention absorbs ultraviolet rays and visible light having a short wavelength near 405 nm, and the retardation film or organic EL element. UV light and light having a wavelength of around 405 nm can be blocked, and deterioration of the retardation film and the organic EL element can be suppressed from both ultraviolet light and short-wavelength visible light.
Even after the weather resistance test, the pressure-sensitive adhesive sheet of the present invention has a good light absorption function (good absorbance retention) at wavelengths near 350 nm and 405 nm, and has good weather resistance (durability). Therefore, the pressure-sensitive adhesive sheet of the present invention can maintain a function of suppressing deterioration of the retardation film or organic EL element due to ultraviolet rays and short-wavelength visible light. In addition, the pressure-sensitive adhesive sheet of the present invention has a low light absorption performance in the vicinity of a wavelength of 440 nm, and does not inhibit the light emission of the liquid crystal display device, and can express a good color.
In addition, as shown in Table 2, the optical film with the pressure-sensitive adhesive sheet of the present invention also has a good light absorption function near a wavelength of 405 nm. Furthermore, even after the weather resistance test, the light absorption function in the vicinity of a wavelength of 405 nm is good, and the weather resistance (durability) is good.

  The pressure-sensitive adhesive sheet and the optical film with the pressure-sensitive adhesive sheet of the present invention are suitably used for liquid crystal panels and liquid crystal display devices.

DESCRIPTION OF SYMBOLS 1 Adhesive sheet 2 Release film 10A, 10B, 10C Optical laminated body 3 Protective film 4 Optical film 7, 60 Adhesive layer 7a Adhesive layer 8 Protective film 9 Polarizing film 30 Light emitting element 40 Optical film 50, 50a 1/4 wavelength Retardation layer 60 Adhesive layer 70 1/2 wavelength retardation layer 80 Positive C layer 100 Polarizing plate

Claims (13)

A pressure-sensitive adhesive sheet formed from a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A) and a light selective absorption compound, which satisfies the following formulas (1) and (2).
A (350) ≧ 0.5 (1)
A (405) ≧ 0.5 (2)
[In Formula (1), A (350) represents the light absorbency in wavelength 350nm.
In formula (2), A (405) represents the absorbance at a wavelength of 405 nm. ] Furthermore, the adhesive sheet | seat of Claim 1 which satisfy | fills following formula (3).
A (440) ≦ 0.1 (3)
[In Formula (3), A (440) represents the light absorbency in wavelength 440nm. ] Furthermore, the adhesive sheet | seat of Claim 1 which satisfy | fills following formula (4).
A (405) / A (440) ≧ 5 (4)
[In Formula (4), A (405) represents the absorbance at a wavelength of 405 nm, and A (440) represents the absorbance at a wavelength of 440 nm. ]   4. The pressure-sensitive adhesive according to claim 1, wherein the light selective absorption compound comprises a compound that selectively absorbs light having a wavelength of 350 nm and a compound that selectively absorbs light having a wavelength of 405 nm. Sheet. The pressure-sensitive adhesive sheet according to claim 4, wherein the compound that selectively absorbs light having a wavelength of 405 nm is a compound that satisfies formula (5).
ε (405) ≧ 20 (5)
[In Formula (5), (epsilon) (405) represents the gram extinction coefficient of the compound in wavelength 405nm. The unit of the gram extinction coefficient is L / (g · cm). ] The pressure-sensitive adhesive sheet according to claim 5, wherein the compound that selectively absorbs light having a wavelength of 405 nm is a compound that satisfies formula (6).
ε (405) / ε (440) ≧ 20 (6)
[In formula (6), ε (405) represents the gram extinction coefficient of the compound at a wavelength of 405 nm, and ε (440) represents the gram extinction coefficient at a wavelength of 440 nm. ]   The pressure-sensitive adhesive sheet according to any one of claims 4 to 6, wherein the compound that selectively absorbs light having a wavelength of 405 nm is a compound having a merocyanine structure in the molecule.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive composition further contains a crosslinking agent (B).   The pressure-sensitive adhesive sheet according to claim 8, wherein the content of the crosslinking agent (B) is 0.01 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A).   The pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the content of the light selective absorption compound is 0.01 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A).   The optical film with an adhesive layer in any one of Claims 1-10 formed by laminating | stacking an optical film on the at least one surface of an adhesive sheet.   The polarizing plate with an adhesive layer according to claim 11, wherein the optical film is a polarizing plate.   The display apparatus containing the optical film with an adhesive in any one of Claim 11 or 12.

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