TW201906966A - Adhesive composition and film with adhesive layer - Google Patents

Abstract

The present invention provides an adhesive composition having a good suppressing function for deterioration of a retardation film and an organic EL light emitting element due to visible light having a short wavelength in the vicinity of 400 nm from ultraviolet rays. The adhesive composition of the present invention comprises the compound represented by the formula (I). [In the formula, R1 and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, a heterocyclic group. R1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group. R6 and R7 each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an electron withdrawing group.].

Description

   Adhesive composition and film with adhesive layer   

The present invention relates to an adhesive composition and a film with an adhesive layer using the adhesive composition.

Display devices such as organic EL display devices and liquid crystal display devices (FPD: flat panel displays) use various components such as organic EL elements, display elements such as liquid crystal cells, and optical films such as polarizing plates. Use adhesive. In addition, the organic EL compounds and liquid crystal compounds used in these members are estimated to be deteriorated by ultraviolet rays (UV). In addition to ultraviolet rays, it has been found that visible light in a short wavelength range also promotes performance degradation. Therefore, in addition to ultraviolet rays, optical films such as polarizing plates are expected to have absorption characteristics for light around 400 nm. On the other hand, in order to impart good absorption characteristics to a display device, it is necessary to not show absorption characteristics in a visible light range (for example, blue light) exceeding 440 nm, and it is extremely important to have high absorption selectivity for short-wavelength visible light near 400 nm.

As a means to solve such a problem, Patent Document 1 describes adding a UV absorber to a protective film of a polarizing plate.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-308936

However, the polarizing plate described in the aforementioned Patent Document 1 has low absorption characteristics for visible light near 400 nm, and is not necessarily satisfactory in light resistance. Furthermore, in recent years, display devices such as liquid crystal displays have problems of fatigue and decreased vision when the display is visually recognized for a long period of time. As a countermeasure, it is necessary to be able to cut off short-wavelength visible light. On the other hand, for good color expression, it is preferable that light is not easily absorbed near a wavelength of 440 nm. Therefore, an optical film capable of selectively absorbing light in the vicinity of a wavelength of 420 nm is desired.

An object of the present invention is to provide a film (optical laminate) with an adhesive layer and an adhesive composition capable of forming the film with the adhesive layer. The film with the adhesive layer, when used in a display device, has Excellent display characteristics, and it is possible to suppress deterioration of the optical film caused by short-wavelength visible light in the vicinity of ultraviolet to 400 nm.

The present invention includes the following inventions.

[1] An adhesive composition containing a compound represented by formula (I).

[Wherein R ¹ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbons which may have a substituent, an aralkyl group having 7 to 15 carbons which may have a substituent, and 6 to 15 carbons the aryl group, a heterocyclic group, or an aralkyl group the alkyl group contained in the --CH ₂ - may be _{^{-NR 1A -, - - SO 2}} -, - O- or substituted -S-, - CO.

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

R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. -CH ₂ -contained in the alkyl group may be substituted by -NR ^1B- , -CO-, -SO _2- , -O-, or -S-.

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.

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

[2] The adhesive composition according to [1], wherein the compound represented by the formula (I) is a compound satisfying the formula (1).

ε (405) ≧ 20 (1) [wherein ε (405) represents the gram absorption coefficient of the compound at a wavelength of 405 nm. The unit of gram absorption coefficient is L / (g‧cm). ]

[3] The adhesive composition according to [1], wherein the compound represented by the formula (I) is a compound satisfying the formula (2).

ε (420) ≧ 5 (2) [where ε (420) represents the gram absorption coefficient of the compound at a wavelength of 420 nm. The unit of gram absorption coefficient is L / (g‧cm). ]

[4] The adhesive composition according to any one of [1] to [3], further comprising a (meth) acrylic resin (A) and a crosslinking agent (B).

[5] The adhesive composition according to [4], wherein the content of the compound represented by the formula (I) is 0.01 to 20 parts by mass based on 100 parts by mass of the (meth) acrylic resin.

[6] The adhesive composition according to [4] or [5], wherein the content of the cross-linking agent (B) is 0.01 to 10 parts by mass based on 100 parts by mass of the (meth) acrylic resin (A). Serving.

[7] An optical multilayer body comprising an adhesive layer formed of the adhesive composition according to any one of [1] to [6], and a resin film.

[8] The optical laminate according to [7], wherein the resin film is at least one film selected from a retardation film and a polarizing film.

[9] An optical multilayer body comprising the adhesive layer formed of the adhesive composition according to any one of [1] to [6], a polarizing film, and a retardation film.

[10] The optical laminate according to any one of [7] to [9], wherein the thickness of the adhesive layer is 0.1 to 30 μm.

[11] The optical laminate according to any one of [7] to [10], wherein the adhesive layer satisfies the following formula (5).

A (405) ≧ 0.5 (5) [where A (405) represents the absorbance of the adhesive layer at a wavelength of 405 nm. ]

[12] The optical laminate according to [11], wherein the adhesive layer system satisfies the following formula (6).

A (420) ≧ 0.1 (6) [wherein A (420) represents the absorbance of the adhesive layer at a wavelength of 420 nm. ]

[13] The optical multilayer body according to [11] or [12], wherein the adhesive layer further satisfies the following formula (7).

A (440) ≦ 0.1 (7) [where A (440) represents the absorbance of the adhesive layer at a wavelength of 440 nm. ]

[14] A display device including the optical multilayer body according to any one of [7] to [13].

The present invention provides a film (optical laminate) with an adhesive layer, which has good display characteristics and can suppress deterioration of an optical film caused by short-wavelength visible light in the range of ultraviolet to 400 nm. In addition, an adhesive that can form the film with the adhesive layer is also provided.

10‧‧‧ Optical Film

10A, 10B, 10C‧‧‧Optical multilayer

1‧‧‧adhesive layer

20‧‧‧ resin film

7, 60‧‧‧ Adhesive layer

7a‧‧‧Adhesive layer

8‧‧‧ protective film

9‧‧‧ polarizing film

40‧‧‧ Optical Film

50, 50a‧‧‧1 / 4 wavelength retardation layer

70‧‧‧1 / 2 wavelength retardation layer

80‧‧‧ positive C floor

30‧‧‧Light-emitting element

FIG. 1 shows an example of the layer structure of the optical multilayer body of the present invention.

Fig. 2 shows an example of the layer structure of the optical multilayer body of the present invention.

FIG. 3 shows an example of the layer configuration of the optical multilayer body of the present invention.

FIG. 4 shows an example of the layer structure of the optical multilayer body of the present invention.

The adhesive composition of the present invention contains at least one compound represented by formula (I) (hereinafter, also referred to as compound (I)).

<Compound (I)>

[Wherein R ¹ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbons which may have a substituent, an aralkyl group having 7 to 15 carbons which may have a substituent, and 6 to 15 carbons the aryl group, a heterocyclic group, or an aralkyl group the alkyl group contained in the --CH ₂ - may be _{^{-NR 1A -, - - SO 2}} -, - O- or substituted -S-, - CO.

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

R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. -CH ₂ -contained in the alkyl group may be substituted by -NR ^1B- , -CO-, -SO _2- , -O-, or -S-.

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.

R ¹ and R ² can be connected to each other to form a ring structure, R ² and R ³ can be connected to each other to form a ring structure, R ² and R ⁴ can be connected to each other to form a ring structure, R ³ and R ⁶ can be connected to each other to form a ring structure, R ⁶ And R ⁷ can be connected 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, secondary butyl, and n-pentyl. Group, n-hexyl, 1-methylbutyl, 3-methylbutyl, n-octyl, n-decyl, 2-hexyl-octyl and the like.

Examples of the substituent which the alkyl group having 1 to 25 carbon atoms represented by R ¹ and R ⁵ may have include the group described in the following group A.

Group A: Examples include nitro, hydroxyl, carboxyl, sulfonate, cyano, amine, halogen atom, alkoxy group having 1 to 6 carbon atoms, alkylsilyl group having 1 to 12 carbon atoms, and carbon number 2 Alkylcarbonyl to 8, * -R ^a1- (OR ^a2 ) _t1 -R ^a3 (R ^a1 and R ^a2 each independently represent an alkanediyl group having 1 to 6 carbon atoms, and R ^a3 represents an alkane group having 1 to 6 carbon atoms Base, t1 represents an integer of 1 to 3), and the like.

Examples of alkyl silyl groups having 1 to 12 carbon atoms include monosilyl silyl groups such as methylsilyl, ethylsilyl, and propylsilyl; dimethylsilyl, diethylsilyl, and methylethyl Dialkylsilyl groups such as trisilyl groups; trialkylsilyl groups such as trimethylsilyl groups, triethylsilyl groups, and tripropylsilyl groups.

Examples of the alkylcarbonyl group having 2 to 8 carbon atoms include methylcarbonyl and ethylcarbonyl.

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 benzyl and phenylethyl. The -CH ₂ -contained in the aralkyl group may be a group substituted with -COO-, for example, 2-phenylethyl acetate.

Examples of the substituent which the aralkyl group having 7 to 15 carbon atoms represented by R ¹ and R ⁵ may have include the group described in the group A described above.

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 anthryl group.

The heterocyclic group having 3 to 5 carbon atoms represented by R ¹ and R ⁵ may be, for example, pyridyl, pyrrolidinyl, quinolinyl, thienyl, imidazolyl, 3 to 15 aliphatic heterocyclic groups such as azolyl, pyrrolyl, thiazolyl, furanyl and aromatic heterocyclic groups having 3 to 15 carbons, preferably 3 to 9 aromatic heterocyclic groups .

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

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ² , R ³ and R ⁴ are the same as the alkyl group having 1 to 6 carbon atoms represented by R ^1B . Examples of the substituent which the alkyl group having 1 to 6 carbon atoms represented by R ² , R ³ and R ⁴ may have include the group described in the above group A.

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, naphthyl, and anthracenyl; and 7 to 15 carbon atoms such as benzyl and phenylethyl. Aralkyl.

Examples of the substituent which the aromatic hydrocarbon group represented by R ² , R ³ and R ⁴ may have include the group described in the group A described above.

Examples of the aromatic heterocyclic group represented by R ² , R ³ and R ⁴ include pyridyl, pyrrolidinyl, quinolinyl, thienyl, imidazolyl, An aromatic heterocyclic group having 3 to 9 carbon atoms such as an azole group, a pyrrolyl group, a thiazolyl group, and a furyl group.

Examples of the aromatic heterocyclic group represented by R ² , R ^3, and R ⁴ include a substituent, and examples thereof include the groups described in the group A described above.

Examples of the alkyl group having 1 to 25 carbon atoms represented by R ⁶ and R ⁷ are the same as 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).

^* -X ¹ -R ¹¹ (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 * ¹ -CO-, * ¹ -COO-, * ¹ -OCO-, * ¹ -NR ¹² CO-, or * ¹ -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.

* ¹ represents a bond with R ¹¹ .

* Indicates a bond with a carbon atom. ]

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

Examples of the alkyl group substituted with a halogen atom include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosecondary butyl, and perfluorotributyl. , Perfluoropentyl and perfluorohexyl. The number of carbon atoms of the alkyl group substituted with a halogen atom is usually 1 to 25.

Examples of the alkyl group having 1 to 25 carbon atoms represented by R ¹¹ are the same as the alkyl groups represented by R ¹ and R ⁵ .

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹² and R ¹³ include the same group as the alkyl group having 1 to 6 carbon atoms represented by R ^1A .

R ⁶ and R ⁷ may be connected to each other to form a ring structure. The ring structure formed by R ⁶ and R ⁷ may be, for example, Mie acid structure, barbituric acid structure, 5,5-dimethyl-1,3- Cyclohexanedione structure and so on. The ring structure formed by R ⁶ and R ⁷ may have a substituent, and examples thereof include an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms.

The ring structure formed by bonding R ² and R ^{3 to} each other is a nitrogen-containing ring structure containing a nitrogen atom bonded to R ² , and examples thereof include a nitrogen-containing heterocyclic ring having 4 to 14 members. The ring structure formed by R ² and R ^{3 being} bonded to each other may be a monocyclic ring, a polycyclic ring, or a heteroatom other than nitrogen as a ring constituting unit. These rings may have a substituent. The ring structure formed by R ² and R ^{3 being} bonded to each other, specifically, for example, a pyrrolidine ring, a dihydropyrrole ring, an imidazolidine ring, an imidazoline ring, Oxazoline ring, thiazoline ring, piperidine ring, morpholin ring, piperidine Ring, indole ring, isoindole ring, pyrrole ring, pyrimidine ring, and rings described below.

The ring structure formed by bonding R ¹ and R ^{2 to} each other is a nitrogen-containing ring structure containing nitrogen atoms bonded to R ¹ and R ² , and examples thereof include a nitrogen-containing heterocyclic ring having 4 to 14 members. The ring structure formed by R ¹ and R ^{2 being} bonded to each other may be a monocyclic ring, a polycyclic ring, or a heteroatom other than nitrogen as a ring constituting unit. These rings may have a substituent. Specifically, for example, the ring structure formed by R ¹ and R ^{2 being} bonded to each other may be the same as the ring structure formed by R ² and R ^{3 being} bonded to each other.

The ring structure formed by bonding R ² and R ^{4 to} each other may be, for example, a nitrogen-containing ring structure of a 4- to 14-membered ring, and preferably a nitrogen-containing ring structure of a 5- to 9-membered ring. The ring structure formed by R ² and R ^{4 being} bonded to each other may be a monocyclic ring, a polycyclic ring, or a heteroatom other than nitrogen as a ring constituting unit. These rings may have a substituent. Specifically, the ring structure formed by R ² and R ^{4 being} bonded to each other may be the same as those exemplified for the ring structure formed by R ² and R ³ .

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

The compound represented by formula (I) in which R ² and R ^{3 are} bonded to each other to form a ring structure may be, for example, a compound represented by formula (IA), and R ² and R ^{4 are} bonded to each other to form a ring structure in formula (I). Examples of the compound include compounds represented by 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.

The rings W ¹ and W ² each independently represent a nitrogen-containing ring. ]

The rings W ¹ and W ² each independently represent a nitrogen-containing ring containing a nitrogen atom as a constituent unit of the ring. The rings W ¹ and W ² may be monocyclic, polycyclic, or may contain heteroatoms other than nitrogen as a constituent unit of the ring. The rings W ¹ and W ² may be an aliphatic ring or an aromatic ring.

The rings W ¹ and W ² are each preferably a ring of 5 members to 9 members.

The compound represented by formula (I-A) is preferably a compound represented by formula (I-A-1).

[In the formula (IA), R ¹ , R ⁴ , R ⁵ , R ^6, and R ⁷ each have 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. ]

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹⁴ and R ¹⁵ include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, secondary butyl, and n-pentyl. Group, n-hexyl, 1-methylbutyl and the like.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^1D are the same as the alkyl group having 1 to 6 carbon atoms represented by R ^1A .

The compound represented by the formula (I-B) is preferably a compound represented by the formula (I-B-1) and a compound represented by the formula (I-B-2).

[In formula (IB-1), R ¹ , R ^6, and R ⁷ each have the same meaning as described above.

R ¹⁶ each independently represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms. ]

[In formula (IB-2), R ³ , R ⁵ , R ^6, and R ⁷ each have the same meaning as described above.

R ³⁰ represents a hydrogen atom, a cyano group, a nitro group, a halogen atom, a mercapto group, an amine group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, carbon Amidino having 2 to 13 carbon atoms, fluorenyl group having 2 to 13 carbon atoms, or alkoxycarbonyl group having 2 to 13 carbon atoms.

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 which may have a substituent, or a heterocyclic group. ]

Examples of the halogen atom represented by R ³⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the fluorenyl group having a carbon number of 2 to 13 represented by R ³⁰ include ethenyl, propionyl and butylamyl.

Examples of the fluorenyloxy group having 2 to 13 carbon atoms represented by R ³⁰ include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, and butylcarbonyloxy.

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.

The aromatic hydrocarbon group having 6 to 18 carbons represented by R ³⁰ may be, for example, an aryl group having 6 to 18 carbons such as phenyl, naphthyl, and biphenyl; the carbon number is 7 to 18 such as benzyl, phenylethyl, etc. Aralkyl of 18.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ³⁰ are the same as the alkyl group having 1 to 12 carbon atoms represented by R ¹⁴ .

Examples of the alkoxy 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 carbons, an alkoxy group having 1 to 12 carbons, an amine group, or a mercapto group.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ³¹ are the same as the alkyl group having 1 to 12 carbon atoms represented by R ¹⁴ .

Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ³¹ are the same as 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 methylthio, ethylthio, propylthio, butylthio, pentylthio, and hexylthio.

The amine group which may have a substituent represented by R ³¹ may be, for example, an amine group; an amine group substituted with an alkyl group having 1 to 8 carbon atoms such as N-methylamino group, N-ethylamino group; N, N-dimethylamino, N, N-diethylamino, N, N-methylethylamino and the like are substituted with two alkyl groups having 1 to 8 carbons and the like.

Examples of the heterocyclic ring represented by R ³¹ include a nitrogen-containing heterocyclic group having 4 to 9 carbon atoms such as pyrrolidinyl, pyridinyl, and morpholinyl.

Examples of the compound represented by formula (I) in which R ³ and R ^{6 are} bonded to each other to form a ring structure, and R ² and R ^{4 are} bonded to each other to form a ring structure include compounds represented by formula (IC).

[In Formula (IC), R ¹ , R ⁶ and R ^{7 have} the same meanings 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 hydroxyl 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, and an aromatic hydrocarbon group which may have a substituent. ]

Represented by the R ²⁵ alkyl having 1 to 25 carbon atoms, the alkyl group can be exemplified as represented by R ¹ and the carbon number of 1 to 25 of the same person.

Examples of the aromatic hydrocarbon group represented by R ²⁵ include aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenylethyl; biphenyl groups and the like, preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms . The substituent which the aromatic hydrocarbon group represented by R ²⁵ may have, for example, a hydroxyl group.

Examples of the compound represented by formula (I) in which R ¹ and R ^{2 are} bonded to each other to form a ring structure, and R ³ and R ^{6 are} bonded to each other to form a ring structure include compounds represented by formula (ID).

[In the formula (ID), R ⁴ , R ⁵ , and R ^{7 have} the same meanings as described above.

R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a hydroxyl group, and an aralkyl group. ]

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are the same as the alkyl group having 1 to 12 carbon atoms represented by R ^1A and R ^1B . Examples of the substituent which the alkyl group having 1 to 12 carbons represented by R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ may have include a hydroxyl 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 and phenylethyl.

Examples of the compound (I) in which R ⁶ and R ^{7 are} bonded to each other to form a ring structure include a compound represented by the formula (IE).

[In the formula (IC), R ¹ , R ² , R ^3, and R ⁵ each have the same meaning as described above. The ring W ³ represents a ring structure. ]

The ring W ³ may be a single ring or a polycyclic ring. The ring W ³ may be aliphatic or aromatic. The ring W ³ may be, for example, a 5-membered ring to a 9-membered ring, or may be a heterocyclic ring containing heteroatoms such as a nitrogen atom, an oxygen atom, and a sulfur atom as constituent units of the ring.

The compound represented by the formula (I-E) is preferably a compound represented by the formula (IE-1).

[In formula (IE-1), R ¹ , R ³ , R ^4, and R ⁵ each have the same meaning as described above.

R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^q each independently represent a hydrogen atom or an alkyl group, aralkyl group, or aryl group having 1 to 12 carbon atoms which may have a substituent, and the alkyl group or the aralkyl group contains − CH ₂ -group can be substituted with -NR ^2D- , -C (= O)-, -C (= S)-, -O-, -S-, R ¹⁷ and R ¹⁸ can be bonded to each other to form a ring structure, R ¹⁸ and R ¹⁹ may be bonded to each other to form a ring structure, and R ¹⁹ and R ^q may be bonded to each other to form a ring structure.

R ^2D represents a hydrogen atom or an alkyl group, aralkyl group, or aryl group having 1 to 12 carbon atoms which may have a substituent. The -CH ₂ -group contained in the alkyl group or the aralkyl group may be substituted with -C ( = O)-, -C (= S)-, -O-, -S-. m, p, and q each independently represent an integer of 1 to 3. ]

The compound (I) preferably satisfies at least one of the following formula (1) and formula (2).

ε (405) ≧ 20 (1)

ε (420) ≧ 5 (2) [where ε (405) represents the gram absorption coefficient of the compound at a wavelength of 405nm, ε (420) represents the gram absorption coefficient of the compound at a wavelength of 420nm, and the unit of the gram absorption coefficient is defined as L / (g‧cm). ]

The larger the value of ε (405) of the compound (I), the easier it is to absorb light having a wavelength of 405 nm, and it is possible to suppress deterioration of the retardation film under ultraviolet rays or short-wavelength visible light. If the value of ε (405) is less than 20 L / (g · cm), if the content of the compound (I) in the adhesive layer is not increased, it is difficult to exhibit a short-wavelength visible light of a retardation film or an organic EL device. This results in a tendency to deteriorate the suppression function. If the content of the compound (I) is increased, the compound (I) may ooze out or be unevenly dispersed, and the light absorption function may be insufficient. The value of ε (405) is preferably 20L / (g‧cm) or more, more preferably 30L / (g‧cm) or more, and still more preferably 40L / (g‧cm) or more, usually 500L / (g‧ cm) or less.

The larger the value of ε (420) of the compound (I), the easier it is to absorb light having a wavelength of 420 nm. If the value of ε (420) is less than 5, the content of the compound (I) in the adhesive composition is increased in order to exert the function of suppressing deterioration due to short-wavelength visible light of the retardation film or the organic EL light-emitting element. If the content of the compound (I) in the adhesive composition is increased, the compound (I) may ooze out or be unevenly dispersed, and the light absorption function may be insufficient. The value of ε (420) is preferably 5L / (g‧cm) or more, more preferably 10L / (g‧cm) or more, and still more preferably 20L / (g‧cm) or more, usually 500L / (g‧ cm) or less.

The compound (I) preferably satisfies at least one of the following formulas (3) and (4).

ε (405) / ε (440) ≧ 20 (3)

ε (420) / ε (440) ≧ 4 (4) [where ε (405) and ε (420) have the same meanings as described above. Represents the molar absorption coefficient of a compound at a wavelength of 440 nm, and ε (440) represents the molar absorption coefficient of a compound at a wavelength of 440 nm. ]

The larger the value of ε (405) / ε (440) of the compound (I), the less it will hinder the color performance of the display device. It can absorb light near 405nm and can suppress the light of display devices such as retardation films or organic EL elements. Degradation. 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.

The larger the value of ε (420) / ε (440) of the compound (I), the less it will hinder the color performance of the display device. It can absorb light near 420nm and can suppress the light of display devices such as retardation films or organic EL elements. Degradation. Therefore, the value of ε (420) / ε (440) is preferably 4 or more, more preferably 6 or more, still more preferably 10 or more, and particularly preferably 20 or more.

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

The content of the compound represented by the formula (I) in the solid content of the adhesive composition is 100% by mass, usually 0.01 to 20% by mass, preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, Still more preferably, it is 0.1 to 5 mass%.

In the present invention, as the adhesive constituting the adhesive layer, for example, an adhesive having a matrix polymer such as acrylic, rubber, urethane, polysiloxane, or polyvinyl ether can be used. Among these, from the viewpoint of high heat resistance and light resistance, the adhesive layer constituting the optical film of the present invention is preferably formed from an adhesive composition containing a (meth) acrylic resin as a matrix polymer. By.

The adhesive composition of the present invention preferably further contains a resin, a cross-linking agent, and a silane compound, and more preferably an antistatic agent.

The (meth) acrylic resin (A) is preferably a polymer containing a constituent unit derived from a (meth) acrylate as a main component (preferably containing 50% by mass or more). The (meth) acrylate-derived constitutional unit may contain one or more types of constitutional units derived from a monomer other than (meth) acrylates (for example, a constitutional unit derived from a monomer having a polar functional group). In addition, in the present specification, the term "(meth) acrylic acid" means that either acrylic acid or methacrylic acid may be used. In addition, the term "(meth)" in the case of (meth) acrylic acid ester or the like means the same. Meaning.

The (meth) acrylate is, for example, a (meth) acrylate represented by the following formula (I).

[In the formula (I), R ¹ is represented by 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, the alkyl group or the hydrogen of the aralkyl group The atom may be substituted 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.

Examples of the (meth) acrylate represented by the formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate. , N-amyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic acid Linear alkyl esters of (meth) acrylic acid such as n-decyl ester, n-dodecyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; (meth) acrylic acid; Isopropyl ester, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, isohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Branched alkyl groups of (meth) acrylic acid such as esters, isooctyl (meth) acrylate, isononyl (meth) acrylate, isostearyl (meth) acrylate, isoamyl (meth) acrylate, etc. Esters; cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, adamantane (meth) acrylate, dicyclopentyl (meth) acrylate, cyclododecyl (meth) acrylate, (Meth) acrylic acid methyl ring Hexyl ester, trimethylcyclohexyl (meth) acrylate, tert-butyl cyclohexyl (meth) acrylate, cyclohexyl α-ethoxyacrylate, and alicyclic skeleton-containing alkane Esters; (meth) acrylic acid-containing aromatic ring skeleton-containing esters such as phenyl (meth) acrylate and the like.

Further, for example, a substituent-containing alkyl (meth) acrylate having a substituent introduced into an alkyl group in the alkyl (meth) acrylate can be mentioned. The substituent of the (meth) acrylic acid alkyl ester containing a substituent is a group which replaces a hydrogen atom of an alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the (meth) acrylic acid-containing alkyl esters include 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and benzene (meth) acrylate. Ethoxyethyl ester, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy poly (ethyl) methacrylate Glycol) esters and the like.

These (meth) acrylic acid esters may be used individually or in plurality.

The (meth) acrylic resin (A) preferably contains a structural unit derived from a (meth) acrylic acid alkyl ester (a1) having a glass transition temperature Tg of less than 0 ° C derived from a homopolymer and a homopolymer-derived resin. Tg is a structural unit of an alkyl (meth) acrylate (a2) at 0 ° C or higher. It is beneficial to improve the high temperature durability of the adhesive layer. The Tg of the homopolymer of the (meth) acrylic acid alkyl ester can be, for example, a literature value such as POLYMER HANDBOOK (Wiley-Interscience).

Specific examples of the alkyl (meth) acrylate (a1) include ethyl acrylate, n- and iso-propyl acrylate, n- and iso-butyl acrylate, n-amyl acrylate, n- and isohexyl acrylate, n-heptyl acrylate, N- and isooctyl acrylate, 2-ethylhexyl acrylate, n- and isononyl acrylate, n- and isodecyl acrylate, and n-dodecyl acrylate and other alkyl groups having a carbon number of about 2 to 12 (methyl ) Alkyl acrylate.

The alkyl (meth) acrylate (a1) may be used alone or in combination of two or more. Among these, from the viewpoints of followability and reworkability when laminated on an optical film, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and the like are preferred.

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

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

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

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

Examples of the monomer having a polar functional group include 1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxyheptyl (meth) acrylate, and 1 (meth) acrylic acid. -Hydroxybutyl ester, 1-hydroxypentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( 2-hydroxypentyl methacrylate, 2-hydroxyhexyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3- Hydroxypentyl ester, 3-hydroxyhexyl (meth) acrylate, 3-hydroxyheptyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, (formyl) Base) 4-hydroxyhexyl acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate, 2-chloro-2-hydroxypropyl (meth) acrylate, (meth) 3-chloro-2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 5-hydroxyheptyl (meth) acrylate, 5-hydroxyoctyl (meth) acrylate, (meth) propyl 5-hydroxynonyl acid, 6-hydroxyhexyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate, 6-hydroxyoctyl (meth) acrylate, 6-hydroxynonyl (meth) acrylate , 6-hydroxydecyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 7-hydroxyoctyl (meth) acrylate, 7-hydroxynonyl (meth) acrylate, (meth) acrylic acid 7-hydroxydecyl ester, 7-hydroxyundecyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 8-hydroxynonyl (meth) acrylate, 8-hydroxydecyl (meth) acrylate Ester, 8-hydroxyundecyl (meth) acrylate, 8-hydroxydodecyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 9-hydroxydecyl (meth) acrylate, 9-hydroxyundecyl (meth) acrylate, 9-hydroxydodecyl (meth) acrylate, 9-hydroxytridecyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 10-hydroxyundecyl (meth) acrylate, 10-hydroxydodecyl (meth) acrylate, 10-hydroxytridecyl (meth) acrylate, 10-hydroxytetradecane (meth) acrylate Ester, 11-hydroxyundecane (meth) acrylate, 11- (meth) acrylate Dodecyl ester, 11-hydroxytridecyl (meth) acrylate, 11-hydroxytetradecanyl (meth) acrylate, 11-hydroxypentadecanyl (meth) acrylate, (meth) acrylic acid 12-hydroxydodecyl, 12-hydroxytridecyl (meth) acrylate, 12-hydroxytetradecanyl (meth) acrylate, 13-hydroxytridecyl (meth) acrylate, (methyl ) 13-hydroxytetradecanyl acrylate, 13-hydroxypentadecanyl (meth) acrylate, 14-hydroxytetradecanyl (meth) acrylate, 14-hydroxypentadecanyl (meth) acrylate, ( Monomers having a hydroxyl group, such as 15-hydroxypentadecyl methacrylate and 15-hydroxy 17-octadecyl (meth) acrylate; (meth) acrylic acid, carboxyalkyl (meth) acrylate (for example, carboxy Ethyl (meth) acrylate, carboxypentyl (meth) acrylate), maleic acid, maleic anhydride, fumaric acid, butenoic acid, and other monomers having a carboxyl group; allyl methacrylate, ethylene Caprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofuran methyl (meth) acrylate, caprolactone denatured tetrahydrofuran methacrylate, 3,4-epoxycyclohexyl methyl( (Meth) acrylate, epoxypropyl (meth) acrylate, 2,5-dihydrofuran and other monomers having heterocyclic groups; amino ethyl (meth) acrylate, N, N-dimethyl Monomers having a substituted or unsubstituted amine group, such as aminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like.

Among these, from the viewpoint of the reactivity of the (meth) acrylate polymer and the cross-linking agent, a monomer having a hydroxyl group and / or a carboxyl group is preferable, and any one of a monomer including a hydroxyl group and a carboxyl group is more preferable.

The monomer having a hydroxyl group is preferably 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, or 6-hydroxyhexyl acrylate. 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, acrylic acid is preferably used.

From the viewpoint of preventing the peeling force of the release film laminated on the outer surface of the adhesive layer from increasing, it is preferable that the monomer having an amine group is substantially not contained. The term "substantially free" means that the content of 100 parts by weight of the total constituent units constituting the (meth) acrylate resin (A) is 0.1 part by weight or less.

The content of the structural unit derived from the monomer having a polar functional group in the (meth) acrylate polymer is preferably 20 parts by mass or less with respect to 100 parts by mass of the total structural unit of the (meth) acrylate polymer. It is more preferably 0.5 parts by mass or more and 15 parts by mass or less, still 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 in the (meth) acrylate polymer is preferably 20 parts by mass or less with respect to 100 parts by mass of the total structural unit of the (meth) acrylate polymer. It is more preferably 4 parts by mass or more and 20 parts by mass or less, and still more preferably 4 parts by mass or more and 16 parts by mass or less.

Examples of the structural unit derived from a monomer other than (meth) acrylate include a structural unit derived from a styrene-based monomer, a structural unit derived from a vinyl-based monomer, and a structural unit derived from a plurality of (meth) acrylfluorenyl groups in the molecule. The structural unit of the monomer, the structural unit derived from a (meth) acrylamide-based monomer, and the like.

Examples of the styrene-based monomer include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, and propylstyrene Alkyl styrenes such as butylstyrene, hexylstyrene, heptylstyrene, octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; Nitrostyrene; ethylfluorenylstyrene; methoxystyrene; and divinylbenzene.

Examples of the vinyl-based monomer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and bromoethylene; and Dihaloethylene such as vinylene; vinyl aromatic pyrene, vinylpyrrolidone, and ethylene carbazole; nitrogen-containing aromatic ethylene; butadiene, isoprene, and chloroprene; conjugated diene; and acrylonitrile, Unsaturated nitriles such as methacrylonitrile.

Monomers having a plurality of (meth) acrylfluorene groups in the molecule include, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, three Monomers having 2 (meth) acrylfluorene groups in the molecule such as propylene glycol di (meth) acrylate; Trimethylolpropane tri (meth) acrylates having 3 (meth) acrylfluorene groups in the molecule Monomer.

Examples of the (meth) acrylamide-based monomer include N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, and N- (3-hydroxyl) (Propyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6- Hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (methyl) Acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamine Amine, N- [2- (2-sideoxy-1-imidazolidinyl) ethyl] (meth) acrylamide, 2-propenylamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- ( 1-methylethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2-methylpropoxymethyl) (Meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, N- (1,1-dimethylethoxymethyl) (meth) acrylamide , N- (2-methoxyethyl) (methyl ) Acrylamide, N- (2-ethoxyethyl) (meth) acrylamide, N- (2-propoxyethyl) (meth) acrylamide, N- [2- (1 -Methylethoxy) ethyl] (meth) acrylamide, N- [2- (1-methylpropoxy) ethyl] (meth) acrylamide, N- [2- (2 -Methylpropoxy) ethyl] (meth) acrylamide, N- (2-butoxyethyl) (meth) acrylamide, N- [2- (1,1-dimethyl Ethoxy) ethyl] (meth) acrylamide and the like. Among these, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxy Methacrylamide and N- (2-methylpropoxymethyl) acrylamide and the like.

The weight average molecular weight (Mw) of the (meth) acrylic resin (A) is preferably from 500,000 to 2.5 million. If the weight average molecular weight is 500,000 or more, the durability of the adhesive layer in a high-temperature environment will be improved, and problems such as floating peeling between the adherend and the adhesive layer, or aggregation failure of the adhesive layer can be easily suppressed. When the weight average molecular weight is 2.5 million or less, it is advantageous from the viewpoint of the applicability when the adhesive composition is processed into a sheet shape (applied to a substrate), for example. From the viewpoint of considering both the durability of the adhesive layer and the coatability of the adhesive composition, the weight average molecular weight is preferably 600,000 to 1.8 million, more preferably 700,000 to 1.7 million, and particularly preferably 1 million 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 converted into standard styrene.

When the (meth) acrylic resin (A) is dissolved in ethyl acetate to make a solution with a concentration of 20% by mass, the viscosity at 25 ° C. is preferably 20 Pa · s or less, more preferably 0.1 to 15 Pa · s . If the viscosity is within this range, it is advantageous from the viewpoint of the applicability when the adhesive composition is applied to the 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, and particularly preferably -40 to 0 ° C. If Tg is below the upper limit value, it is beneficial to improve the wettability of the adhesive layer to the substrate of the adherend, and if it is above the lower limit value, it is beneficial to improve the durability of the adhesive layer. The glass transition temperature can be measured by a differential scanning thermal analyzer (DSC).

The (meth) acrylic resin (A) can be produced, for example, by a known method such as a solution polymerization method, a block polymerization method, a suspension polymerization method, and an emulsion polymerization method, and is particularly preferably a solution polymerization method. For the solution polymerization method, for example, the following method may be used. A monomer and an organic solvent are mixed, and a thermal polymerization initiator is added under a nitrogen atmosphere, and the mixture is stirred at a temperature of about 40 to 90 ° C, preferably about 50 to 80 ° C. About 3 to 15 hours. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer and the thermal polymerization initiator may be added to an organic solvent.

As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. Examples of the thermal polymerization initiator include 2,2'-azobisisobutylonitrile, 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). -1-nitrile), 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; Laurel peroxide Fluorenyl, tertiary butyl peroxide, benzoylperoxide, tertiary butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, Organic peroxides such as tert-butyl peroxyneodecanoate, tert-butyl pervalerate, and (3,5,5-trimethylhexyl) peroxide; potassium persulfate, ammonium persulfate , Inorganic peroxides, etc. Further, a redox-based initiator such as a peroxide and a reducing agent may be used in combination.

The proportion of the polymerization initiator is about 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of the monomers constituting the (meth) acrylic resin. For the polymerization of the (meth) acrylic resin, a polymerization method using active energy rays (for example, ultraviolet rays) can also 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 propanol and isopropanol; acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. Ketones and so on.

The content of the resin (A) in the solid content of 100% by mass of the adhesive composition is usually 60% to 99.9% by mass, preferably 70% to 99.5% by mass, and more preferably 80% to 99% by mass. %.

The adhesive composition may contain a crosslinking agent (b). This crosslinking agent (b) reacts with a polar functional group (for example, a hydroxyl group, an amino group, a carboxyl group, a heterocyclic group, etc.) in the (meth) acrylic resin (A). The cross-linking agent (B) forms a cross-linked structure with a (meth) acrylic resin or the like, and forms a cross-linked structure that is advantageous for durability and reworkability.

Examples of the cross-linking agent (b) include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-based cross-linking agents, etc., particularly the pot life of the adhesive composition From the viewpoints of durability and cross-linking speed of the adhesive layer, an isocyanate-based cross-linking agent is preferred.

The isocyanate-based compound is preferably a compound having at least two isocyanate groups (-NCO) in the molecule, and examples thereof include aliphatic isocyanate-based compounds (for example, hexamethylene diisocyanate, etc.), and alicyclic isocyanate-based compounds ( For example isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate), aromatic isocyanate compounds (such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate , Triphenylmethane triisocyanate, etc.). The cross-linking agent (B) may also be an adduct of the polyol compound of the isocyanate compound [for example, an adduct of glycerol, trimethylolpropane, etc.], a trimeric isocyanate compound, Biuret type compounds, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and other urethane prepolymer type isocyanates in addition reactions Derivatives of compounds and the like. The crosslinking agent (B) can be used alone or in combination of two or more kinds. Among these, representative examples include aromatic isocyanate compounds (for example, toluene diisocyanate, xylene diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate), or a plurality thereof. An adduct of an alcohol compound (for example, glycerol, trimethylolpropane), or a trimeric isocyanate. If the cross-linking agent (B) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound or a trimeric isocyanate, is it because it is advantageous to form an optimal cross-linking density (or cross-linking structure)? ), So the durability of the adhesive layer can be improved. In particular, if it is an adduct of a toluene diisocyanate-based compound and / or a polyol compound thereof, the durability can be improved even when the adhesive layer is used for a polarizing plate, for example.

The content of the crosslinking agent (b) is usually 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic resin (A). .

The resin composition may further contain a silane compound (D).

Examples of the silane compound (D) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3 , 4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

The silane compound (D) may be a polysiloxane oligomer. Specific examples of the polysiloxane oligomer are shown below in the form of a combination of monomers.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer Compounds, 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomers and other oligomers containing mercaptopropyl groups; mercaptomethyltrimethoxysilane-tetramethoxysilane oligomers, mercaptomethyltrimethoxysilane -Tetraethoxysilane oligomers, mercaptomethyltriethoxysilane-tetramethoxysilane oligomers, mercaptomethyltriethoxysilane-tetraethoxysilane oligomers and other oligomers containing mercaptomethyl; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropyl Triethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropyl triethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropyl methyldimethoxy Silane-tetramethoxysilane oligomer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropylmethyldiethoxysilane- Tetramethoxysilane oligomer, 3-ring 3-glycidoxypropyl-containing oligomers such as oxypropyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers; 3-methacryloxypropyltrimethoxysilane- Tetramethoxysilane oligomer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane Polymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer , 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer , 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers, and other oligomers containing methacryloxypropylpropyl; 3-propenyloxypropyltrimethoxy Silane-tetramethoxysilane oligomer, 3-propenyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane oligomer , 3-propenyloxypropyltriethoxysilane-tetra Oxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer Compounds, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. contain propylene Oligopropyl oligomers; vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetraethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer Polymer, vinyl triethoxysilane-tetraethoxysilane oligomer, vinyl methyldimethoxysilane-tetramethoxysilane oligomer, vinyl methyldimethoxysilane-tetraethoxysilane oligomer Compounds, vinyl methyldiethoxysilane-tetramethoxysilane oligomers, vinyl methyldiethoxysilane-tetraethoxysilane oligomers, and other oligomers containing vinyl groups; 3-aminopropyl Trimethoxysilane-tetramethoxysilane oligomer, 3-aminopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetramethoxysilane oligomer, 3 -amine Propyltriethoxysilane-tetraethoxysilane oligomer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-aminopropylmethyldimethoxysilane- Tetraethoxysilane oligomer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. Amine-containing oligomers and the like.

The silane compound (D) may be a silane compound represented by the following formula (d1). When the adhesive composition contains a silane compound represented by the following formula (d1), adhesion (or adhesion) can be further improved, and thus an adhesive layer having good peel resistance can be formed. In particular, even when an adhesive layer is used (or laminated) on a transparent electrode or glass in a high-temperature environment, adhesion (or adhesion) can be maintained and high durability can be exhibited.

(In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and -CH ₂ -constituting the alkanediyl group and the alicyclic hydrocarbon group may be substituted with -O- or -CO-, R ⁷ represents an alkyl group having 1 to 5 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms or carbon number 1 Alkoxy to 5.)

In the formula (d1), B represents an alkyldiyl group having 1 to 20 carbon atoms such as methylene, ethylene, propyl, butyl, hexyl, heptyl, and octyl; and cyclobutyl ( (Such as 1,2-cyclobutyl), cyclopentyl (such as 1,2-cyclopentyl), cyclohexyl (such as 1,2-cyclohexyl), cyclooctyl (such as 1,2 -Cyclocyclooctyl) and other bivalent alicyclic hydrocarbon groups having 3 to 20 carbons; or -CH ₂ -constituting the alkanediyl groups and the aforementioned alicyclic hydrocarbon groups, substituted by -O- or -CO- base. Preferred B is an alkanediyl group having 1 to 10 carbon atoms. R ⁷ represents an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, and pentyl; R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms, or a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a secondary butoxy group, as exemplified in the aforementioned R ⁷ Alkoxy groups having 1 to 5 carbon atoms such as a radical, tertiary butoxy. Preferably, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkoxy group having 1 to 5 carbon atoms. These silane compounds (D) can be used individually or in combination of 2 or more types.

Specific examples of the silane compound represented by (d1) include (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, and 1,2-bis (triethoxysilyl). ) Ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1 , 4-bis (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 (trimethyl Oxysilyl) octane, 1,8-bis (triethoxysilyl) octane, 1,8-bis (tripropoxysilyl) octane, and other bis (triC1-5 alkoxysilyl) ) C1-10 alkane; bis (dimethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (dimethoxyethyl) Silyl) ethane, 1,4-bis (dimethoxymethylsilyl) butane, 1,4-bis (dimethoxyethylsilyl) butane, 1,6-bis (dimethyl) Oxymethylsilyl) hexane, 1,6-bis (dimethoxyethylsilyl) hexane, 1,8-bis (dimethoxymethylsilyl) octane, 1,8- Bis (dimethoxyethylsilyl) ) Octane and other bis (diC1-5alkoxyC1-5alkylsilyl) C1-10 alkane; 1,6-bis (methoxydimethylsilyl) hexane, 1,8-bis ( Bis (mono-C1-5 alkoxy-di-C1-5 alkylsilyl) C1-10 alkane and the like. Among these, 1,2-bis (trimethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, and 1,4-bis (trimethoxysilyl) butyl are preferred. Bis (trimethylsilyl), 1,5-bis (trimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane, etc. C1-3 alkoxysilyl) C1-10 alkane, particularly preferably 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane.

The content of the silane compound (A) is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the (meth) acrylic resin (A). Still more preferably, it is 0.1 to 1 part by weight. If it is below the above upper limit value, it is advantageous to suppress the oozing of the silane compound (D) from the adhesive layer. If it is above the above lower limit value, it is easy to improve the adhesion of the adhesive layer and the metal layer or glass substrate (Or adhesiveness), which is conducive to the improvement of peel resistance and the like.

The adhesive composition may further contain an antistatic agent.

Examples of the antistatic agent include a surfactant, a siloxane compound, a conductive polymer, and an ionic compound. An ionic compound is preferred. Examples of the ionic compound include a user. Examples of the cationic component constituting the ionic compound include organic cations and inorganic cations. Examples of the organic cation include a pyridine cation, a pyrrolidine cation, a piperidine cation, an imidazole cation, an ammonium cation, a sulfonium cation, and a sulfonium 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, from the viewpoint of compatibility with (meth) acrylic resins, pyridine cation, imidazole cation, pyrrolidine cation, lithium cation, and potassium cation are preferred. The anionic component constituting the ionic compound may be either an inorganic anion or an organic anion, and from the viewpoint of antistatic performance, an anionic component containing a fluorine atom is preferred. An anionic component containing a fluorine atom includes, for example hexafluorophosphate anion (PF ₆ ^-), bis (trifluoromethane sulfonic acyl) imide anion _{[(CF 3 SO 2) 2} N -], bis (fluoromethyl sulfonylurea yl) imide anion ^{_{[(FSO 2) 2 N -}} ], tetrakis (pentafluorophenyl) borate _{[(C 6 F 5) 4} B -] and the like. These ionic compounds can be used individually or in combination of 2 or more types. In particular, bis (trifluoromethane sulfonic acyl) imide anion _{[(CF 3 SO 2) 2} N -], bis (sulfo-fluoro-acyl) imide anion ^{_{[(FSO 2) 2 N -}} ], tetrakis (pentafluoro phenyl) borate anion _{[(C 6 F 5) 4} B -] is preferred.

From the viewpoint that the antistatic property of the adhesive layer formed of the adhesive composition is excellent in stability over time, an ionic compound that is solid at room temperature is preferred.

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

The adhesive composition may contain one or two or more solvents, cross-linking catalysts, tackifiers, plasticizers, softeners, pigments, rust inhibitors, inorganic fillers, light-scattering fine particles and other additives.

<Composition and Manufacturing Method of Adhesive Layer and Optical Film with Adhesive Layer>

The present invention includes an adhesive layer composed of the aforementioned adhesive composition. This adhesive layer can be formed, for example, by dissolving or dispersing the aforementioned adhesive composition in a solvent to form a solvent-containing adhesive composition, and then applying the adhesive composition to the surface of an optical film or a release film to perform Formed on drying.

The present invention also includes an optical laminate, which includes a resin film and the aforementioned adhesive layer laminated on at least one side of the resin film.

1 to 4 are schematic cross-sectional views showing an example of an optical laminate including an adhesive layer formed by the adhesive composition of the present invention.

The optical laminate 10 shown in FIG. 1 is a laminate of a resin film 2 and an adhesive layer 1 laminated on one side of the resin film 2. The resin film 2 may be laminated on both sides of the adhesive layer 1.

The optical laminated body 10A shown in FIG. 2 is a laminated body including a protective film 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 8, an adhesive layer 1, and a resin film 2.

The optical laminated body 10B shown in FIG. 3 and the optical laminated body 10C shown in FIG. 3 include a protective film 8, an adhesive layer 7, a polarizing film 9, an adhesive layer 7, a protective film 8, and an adhesive layer. 1. A laminated body of an optical film 40, an adhesive layer 7a, and a light emitting element 30 (a liquid crystal cell, an organic EL unit). The optical film 40 is an optical laminated body having a multilayer structure. The optical film 40 may have a multilayer structure as shown in the drawing, or may have a single-layer structure. The adhesive layer 7 may be an adhesive layer formed of a known adhesive, and the adhesive layer 7 may be an adhesive layer formed of a known adhesive, or may be an adhesive formed by the adhesive composition of the present invention.剂 层。 The agent layer.

When the adhesive layer 1 is laminated on the surface of the resin film 2, a primer layer may be formed on the bonding surface of the resin film 2 and / or the adhesive layer 1, and surface activation treatments such as plasma treatment and corona treatment may also be performed.

The optical laminated body 10 may include a release film (release film) laminated on the outer surface of the adhesive layer 1. The isolation film is usually peeled off when the adhesive layer 1 is used (for example, when laminated on a transparent conductive electrode or a glass substrate). The separator may be, for example, a polyimide terephthalate, a polybutylene terephthalate, a polycarbonate, a polyarylate, or the like on a film forming the adhesive layer 1 on the surface of the film. Removal of silicon and oxygen.

The optical laminated body 10 can dissolve or disperse the components constituting the above-mentioned adhesive composition into a solvent-containing adhesive composition, and then apply and dry the surface of the resin film 2 to form an adhesive. Layer 1 was thus prepared. The optical laminate 10 can also be produced by forming the adhesive layer 1 on the release-treated surface of the release film in the same manner as described above, and laminating (transferring) the adhesive layer 1 on the surface of the resin film 2.

The thickness of the adhesive layer is usually 0.1 to 30 μm. From the viewpoint of the durability of the optical film with the adhesive layer or the reworkability of the optical film with the adhesive layer, it is preferably 3 to 30 μm, more preferably 5 Up to 25 μm. When the thickness of the adhesive layer is equal to or less than the above-mentioned upper limit value, reworkability is good, and when it is equal to or more than the above-mentioned lower limit value, durability is good.

The storage elastic modulus of the adhesive layer at 23 ° C is usually 100 MPa or more, preferably 300 MPa or more, more preferably 500 MPa or more, and preferably 10,000 MPa or less. The storage elastic modulus of the adhesive layer can be measured using a commercially available viscoelasticity measuring device, such as a viscoelasticity measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETRIC.

The pressure-sensitive adhesive layer preferably satisfies the following formula (5).

A (405) ≧ 0.5 (5) [where A (405) represents the absorbance of the adhesive layer at a wavelength of 405 nm. ] The larger the value of A (405), the higher the absorption at the wavelength of 405nm. If the value of A (405) is less than 0.5, the absorption at the wavelength of 405nm is low, and it is easy to cause display devices such as organic EL elements and retardation under ultraviolet Deterioration of the film. 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 adhesive layer preferably satisfies the following formula (6).

A (420) ≧ 0.1 (6) [wherein A (420) represents the absorbance of the adhesive layer at a wavelength of 420 nm].

A larger value of A (420) indicates a higher absorption at a wavelength of 420nm. If the value of A (420) is less than 0.1, the absorption at a wavelength of 420nm is low, which may easily cause display devices such as organic EL elements and retardation films under ultraviolet rays. Degradation. The value of A (420) is preferably 0.1 or more, more preferably 0.15 or more, and particularly preferably 0.2 or more.

The adhesive layer preferably satisfies the following formula (7).

A (440) ≦ 0.1 (7) [In formula (7), A (440) represents the absorbance of the adhesive layer at a wavelength of 440 nm].

A smaller value of A (440) indicates a lower absorption at a wavelength of 440nm. If the value of A (440) exceeds 0.1, it tends to impair the good color performance of the display device. In addition, since the light emission of the display device is hindered, the brightness is also reduced. The value of A (440) is preferably 0.05 or less, more preferably 0.04 or less, and particularly preferably 0.03.

The adhesive layer preferably satisfies at least one of the following formulae (8) and (9).

A (405) / A (440) ≧ 5 (8)

A (420) / A (440) ≧ 1.5 (9) [where A (405) represents the absorbance of the adhesive layer at a wavelength of 405nm, A (440) represents the absorbance of the adhesive layer at a wavelength of 440nm, and A ( 420) represents the absorbance of the adhesive layer at a wavelength of 420 nm. ]

The value of A (405) / A (440) indicates the magnitude of the absorbance at a wavelength of 405nm relative to the magnitude of the absorbance at a wavelength of 440nm. A larger value indicates a specific absorption in a wavelength range around 405nm. The value of A (405) / A (440) is preferably 10 or more, more preferably 30 or more, and particularly preferably 60 or more.

The value of A (420) / A (440) indicates the magnitude of the absorbance at a wavelength of 420nm relative to the magnitude of the absorbance at a wavelength of 440nm. A larger value indicates a specific absorption in a wavelength range around 420nm. The value of A (420) / A (440) is preferably 1.5 or more, more preferably 3 or more, and particularly preferably 5 or more.

<Resin film>

The resin film 2 constituting the optical laminate 10 of the present invention is preferably an optical film. The optical film refers to a film having optical functions such as light transmission, reflection, and absorption.

The resin film 2 may have a single-layer structure or a multilayer structure. Optical films with a single layer structure include, for example, polarizers, retardation films, brightness enhancement films, anti-glare films, anti-reflection films, diffusion films, and light-condensing films. Examples of the optical film having a multilayer structure include a polarizing plate, a retardation plate, and a laminated body of the optical film having a single-layer structure described above. When a single-layer optical film is laminated, it can pass through an adhesive layer or an adhesive layer.

The resin film 2 is preferably a retardation film or a polarizing plate.

<Phase retardation film>

The retardation film refers to an optical film exhibiting optical anisotropy, and examples thereof include a polyvinyl alcohol resin, a polycarbonate resin, a polyester resin, a polyarylate resin, a polyimide resin, and an olefin. Resins, cycloolefin resins, styrene resins, polyfluorene and polyetherfluorene resins, polyvinylidene fluoride / polymethyl methacrylate, liquid crystal polyester resins, A stretched film obtained by stretching a resin film composed of a cellulose-based resin, an ethylene-vinyl acetate copolymer saponified product, a polyvinyl chloride-based resin, an acrylic resin, or the like, by about 1.01 to 6 times. Among them, a resin film obtained by uniaxially or biaxially stretching a cycloolefin resin film, a cellulose resin film, a polyester resin film, and a polycarbonate film is preferred. The retardation film may be a retardation film in which a liquid crystal compound is applied to a substrate and optical anisotropy is exhibited through alignment. In this specification, the retardation film includes a zero retardation film, and also includes a film called a uniaxial retardation film, a low photoelastic modulus retardation film, a wide viewing angle retardation film, and the like.

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

The so-called zero retardation film refers to an in-plane retardation value R _e and a thickness direction retardation value R _{th of} -15 to 15 nm, which are optically isotropic films. Examples of the zero retardation film include cellulose resins, polyolefin resins (linear polyolefin resins, polycyclic olefin resins, etc.) or polyethylene terephthalate resin resin films. From the viewpoint of easy control of the retardation value and easy acquisition, a cellulose-based resin or a polyolefin-based resin is preferred. The zero retardation film can also be used as a protective film. Examples of the zero retardation film include "Z-TAC" (trade name) sold by Fujifilm, "ZeroTAC (registered trademark)" sold by Konica Minolta, and ZEON from Japan. (Shares) sold "ZF-14" (trade name), etc.

A film exhibiting optical anisotropy by coating and alignment of a liquid crystal compound, or a film exhibiting optical anisotropy by coating of an inorganic layered compound, for example, called a temperature-compensated retardation film, JX-day "NH Film" (trade name; rod-shaped liquid crystal tilt-aligned film) sold by Min Nisshin Energy Co., Ltd., and "WV Film" (trade name; disc-shaped liquid crystal tilt) sold by Fuji Film (stock) Aligned film), "VAC Film" (trade name; fully biaxially oriented film) sold by Sumitomo Chemical Co., Ltd., "new VAC Film" (trade name; double marketed) sold by Sumitomo Chemical Co., Ltd. Shaft-aligned film).

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

Films exhibiting optical anisotropy by applying and aligning liquid crystal compounds include the following first to fifth forms.

First form: a retardation film in which a rod-like liquid crystal compound is aligned in a horizontal direction on a supporting substrate

Second aspect: a phase difference film in which the rod-like liquid crystal compound is aligned in a vertical direction on a supporting substrate

Third aspect: a phase difference film in which the alignment direction of the rod-like liquid crystal compound changes in a spiral shape in a plane

Fourth form: retardation film of disc-shaped liquid crystal compound obliquely aligned

Fifth aspect: a retardation film in which the discotic liquid crystal compound is aligned in a vertical direction on a supporting substrate

For example, as the optical film used in the organic electroluminescence display (organic EL display device), the first form, the second form, and the fifth form are preferably used. Moreover, the retardation film laminated | stacked of these forms can also be used.

When the retardation film is a layer made of a polymer in an aligned state of a polymerizable liquid crystal compound (hereinafter, also referred to as "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersibility. The so-called inverse wavelength dispersion refers to an optical characteristic in which the phase difference value of the liquid crystal alignment plane at a short wavelength is small and the phase difference value of the liquid crystal alignment plane at a long wavelength is small. Preferably, the retardation film satisfies the following formula (10 ) And formula (11). In addition, Re (λ) represents an in-plane phase difference value for light having a wavelength of λnm.

Re (450) / Re (550) ≦ 1 (10)

1 ≦ Re (630) / Re (550) (11)

In the optical film of the present invention, when the retardation film is in the first form and has inverse wavelength dispersibility, it is preferable to reduce the coloration during black display of the display device. If 0.82 ≦ Re (450) in the above formula (10), /Re(550)≦0.93 is more preferable. More preferably, it is 120 ≦ Re (550) ≦ 150.

When the retardation film is a film having an optically anisotropic layer, the polymerizable liquid crystal compound may be, for example, "3.8." In the LCD Handbook (edited by the LCD Handbook Editorial Board, published by Maruzen Co., Ltd. on October 30, 2012). 6-cell (fully crosslinked) ", compounds having polymerizable groups among the compounds described in" 6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material ", and Japanese Patent Application Laid-Open No. 2010-31223, Japanese Patent Japanese Patent Application Publication No. 2010-270108, Japanese Patent Application Publication No. 2011-6360, Japanese Patent Application Publication No. 2011-207765, Japanese Patent Application Publication No. 2011-162678, Japanese Patent Application Publication No. 2016-81035, International Publication No. 2017/043438, and The polymerizable liquid crystal compound and the like described in Japanese Patent Application Publication No. 2011-207765.

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

In the second aspect, the front retardation value Re (550) need only be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the retardation value R _{th in the} thickness direction need only be adjusted to -10 to- A range of 300 nm, preferably a range of -20 to -200 nm, is sufficient. The phase difference value R _th in the thickness direction, which indicates the anisotropy of the refractive index in the thickness direction, can be calculated from the phase difference value R ₅₀ measured in the plane with the fast axis as the tilt axis at an angle of 50 degrees and the phase difference value R _{0 in the} plane. Out. That is, the thickness direction retardation value R _th, the retardation value R ₀ may be within the plane, as in a fast axis _50, the thickness of the retardation film is d, and the phase difference of the tilt axis 50 degrees measured retardation value R The average refractive index of the film, n ₀ , can be calculated by calculating n _x , n _y, and n _z from the following equations (12) to (14), and substituting these into equation (15).

R _th = [(n _x + n _y ) / 2-n _z ] × d (15)

R ₀ = (n _x -n _y ) × d (12)

((n _x + n _y + n _z ) / 3 = n ₀ (14)

Here,

The retardation film may be a multilayer film having two or more layers. For example, a single-sided or double-area layer protective film of a retardation film, or a laminate of two or more retardation films through an adhesive or an adhesive.

When the optical film is a multilayer film laminated with two or more retardation films, the constitution of the optical laminated body including the optical film of the present invention may be, for example, the constitution including the following optical film 40 shown in FIG. The optical film 40 is a 1 / 4-wavelength retardation layer 50 that provides a 1 / 4-wavelength phase difference to the transmitted light, and a 1 / 2-wavelength retardation layer 70 that provides a 1 / 2-wavelength phase difference to the transmitted light. , Laminate through adhesive or adhesive 60. In addition, for example, a structure including an optical film 40 shown in FIG. 4 may be used. The optical film 40 is formed by laminating the 1/4 wavelength retardation layer 50a and the positive C layer 80 through an adhesive or an adhesive.

The 1 / 4-wavelength retardation layer 50 that gives a 1 / 4-wavelength phase difference and the 1 / 2-wavelength retardation layer 70 that gives a 1 / 2-wavelength phase difference to the transmitted light in FIG. 3 may be the first described above. The optical film of the aspect may be an optical film of the fifth aspect. When it is the structure of FIG. 3, it is preferable that at least one is a 5th form.

In the structure shown in FIG. 4, the quarter-wave retardation layer 50 a is preferably the optical film of the first embodiment described above, and more preferably satisfies the expressions (8) and (9).

<Polarizer>

A polarizing plate is usually used in a state where a protective film is laminated on one or both sides of a polarizer. An adhesive layer is usually formed on one side. In addition, the elliptically polarizing plate of the laminated polarizing plate and the retardation film is mostly in a state where a protective film is bonded to one side or both sides of the polarizer. When forming an adhesive layer on such an elliptical polarizing plate, an adhesive layer is usually formed on the retardation film side.

A polarizer is a film having the following properties: absorption of linearly polarized light having a vibration plane parallel to its absorption axis, and transmission of linearly polarized light having a vibration plane perpendicular to the absorption axis (parallel to the transmission axis). A vinyl alcohol-based resin film is a film in which a dichroic dye is adsorbed and aligned. Examples of the dichroic pigment include iodine or a dichroic organic dye.

A polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. Polyvinyl acetate resins include, for example, polyvinyl acetate homopolymers of vinyl acetate, and monomers copolymerizable with vinyl acetate (e.g., unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids) (A copolymer of (meth) acrylamide having an ammonium group) and vinyl acetate.

The saponification degree of the polyvinyl alcohol-based resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may also be denatured. For example, it may be polyvinylaldehyde or polyvinylacetal denatured with aldehydes. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, and preferably 1500 to 5000. The average degree of polymerization of the polyvinyl alcohol-based resin can be obtained in accordance with JIS K 6726.

Generally, a film made of a polyvinyl alcohol-based resin is used as a raw material film of a polarizer. The polyvinyl alcohol resin can be formed into a film by a known method. The thickness of the raw material film is usually 1 to 150 μm , and in consideration of ease of extension, etc., it is preferably 10 μm or more.

The polarizer can be produced, for example, by a step of uniaxially stretching the raw material film, a step of dyeing the film with a dichroic dye to adsorb the dichroic dye, a step of treating the film with an aqueous boric acid solution, and The film is washed with water and finally dried to produce the film. The thickness of the polarizer is usually 1 to 30 μm , and from the viewpoint of thinning the resin film 1 with an adhesive layer, it is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm. m or less.

The protective film is preferably a transparent thermoplastic resin. Examples of the thermoplastic resin include films made of resins such as cellulose acetate resin, polyolefin resin, (meth) acrylate resin, polyimide resin, polycarbonate resin, and polyester resin.

For bonding the polarizer and the protective film, a well-known adhesive can be used. The adhesive may be an aqueous adhesive or an active energy hardening adhesive.

The light-concentrating film is used for users who control the optical path, etc., so it can be a 稜鏡 array sheet or a lens array sheet, a sheet provided with dots, and the like.

The brightness enhancement film is intended to improve the brightness of a liquid crystal display device using a polarizing plate. Specifically, for example, a multilayer polarizing film having a refractive index anisotropy that is mutually different, and a reflective polarizing spacer designed to make the reflectivity anisotropic; a cholesteric liquid crystal polymer alignment A circularly polarizing spacer such as a film or an alignment liquid crystal layer supported on a substrate film.

The optical laminated body of the present invention is preferably a laminated film containing a polarizing plate, an adhesive layer and a retardation film in this order.

The optical laminate including the adhesive layer formed by the adhesive composition of the present invention can be laminated on display elements such as organic EL elements and liquid crystal cells, and used in display devices such as organic EL display devices or liquid crystal display devices (FPD: Flat panel display).

    [Example]    

Hereinafter, the present invention will be described in more detail through examples and comparative examples. In the examples and comparative examples, "%" and "part" are "mass%" and "mass part" unless otherwise specified.

In addition, in the following examples, the measurement of weight average molecular weight and number average molecular weight was performed in the following manner in a gel permeation chromatography (hereinafter referred to as GPC) apparatus (GPC-8120, manufactured by Tosoh Corporation) As a column, four "TSKgel XL (manufactured by Tosoh Corporation)" and one "Shodex GPC KF-802 (manufactured by Showa Denko Corporation)" are arranged in series, and tetrahydrofuran is used as the extraction The solution was prepared under the conditions of a sample concentration of 5 mg / mL, a sample introduction amount of 100 μL, a temperature of 40 ° C., and a flow rate of 1 mL / min, and was calculated by standard polystyrene conversion.

<Preparation of acrylic resin>

Based on the composition shown in Table 1, the acrylic resin (A) and acrylic resin (B) were prepared by the following method.

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

A reaction vessel including a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer was charged with 81.8 parts of ethyl acetate as a solvent, 70.4 parts of butyl acrylate as a monomer (A-1), 20.0 parts of methyl acrylate, and acrylic acid 2 -A mixed solution of 8.0 parts of phenoxyethyl ester, 1.0 part of 2-hydroxyethyl acrylate as monomer (A-2), and 0.6 part of acrylic acid as monomer (A-3), replacing the air in the device with nitrogen Made without oxygen, the internal temperature was raised to 55 ° C. Thereafter, a total amount of a solution in which 0.14 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of ethyl acetate was added. The temperature was maintained for 1 hour after the starter was added, and then, the internal temperature was maintained at 54 to 56 ° C, and the ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / Hr. At the time when the concentration became 35%, the addition of ethyl acetate was stopped, and the temperature was maintained at this temperature from the start of the addition of ethyl acetate until 12 hours had passed. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20% to prepare an ethyl acetate solution of the acrylic resin. The obtained acrylic resin had a weight average molecular weight Mw of 1.42 million and a Mw / Mn of 5.2 in terms of polystyrene in terms of GPC. Let this be an acrylic resin (A).

[Polymerization Example 2]: Preparation of acrylic resin (B)

A reaction vessel including a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer was charged with 81.8 parts of ethyl acetate as a solvent, 96.0 parts of butyl acrylate as a monomer (A-1), and as a monomer (A-3). In the mixed solution of 4.0 parts of acrylic acid, nitrogen was used to replace the air in the device to make it oxygen-free, and the internal temperature was raised to 55 ° C. Thereafter, a total amount of a solution in which 0.14 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of ethyl acetate was added. The temperature was maintained for 1 hour after the starter was added, and then, the internal temperature was maintained at 54 to 56 ° C, and the ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / Hr. At the time when the concentration became 35%, the addition of ethyl acetate was stopped, and the temperature was maintained at this temperature from the start of the addition of ethyl acetate until 12 hours had passed. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20% to prepare an ethyl acetate solution of the acrylic resin. The weight average molecular weight Mw of the obtained acrylic resin in terms of polystyrene obtained by GPC was 76,000 and Mw / Mn was 4.1. Let this be an acrylic resin (B).

In Table 1, the symbols in the monomer composition column indicate the following monomers, respectively.

[Monomer (A-1)]

BA: Butyl acrylate

MA: methyl acrylate

PEA: 2-phenoxyethyl acrylate

[Monomer (A-2)]

HEA: 2-hydroxyethyl acrylate

[Monomer (A-3)]

AA: Acrylic

<Synthesis of Light Selective Absorptive Compound>

[Synthesis example 1]

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 2.0 g of 2-phenyl-1-methylindole-3-carboxaldehyde and piperidine (Wako Pure Chemical Industries, Ltd.) were charged. 0.72 g, butyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.3 g, 1-butanol (manufactured by Wako Pure Chemical Industries, Ltd.), 8 g, and stirred with a magnetic stirrer. Warm in an oil bath and keep at an internal temperature of 80 ° C for 18 hours. After that, it was cooled to room temperature, and the precipitated crystals were collected by filtration, and the crystals were dried under reduced pressure at 60 ° C to obtain 2.7 g of a compound represented by UVA-01 as a powder. The yield was 87%.

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was possible to confirm the formation of the compound represented by UVA-01.

¹ H-NMR (CDCl3) δ: 0.94 (t, 3H), 1.42 (sext, 2H), 1.69 (quin, 2H), 3.71 (s, 3H), 4.23 (t, 2H), 7.40-7.43 (m, 5H), 7.56-7.58 (m, 3H), 8.14 (s, 1H), 8.45-8.47 (m, 1H)

<Measurement of gram absorption coefficient ε>

In order to measure the gram absorption coefficient of the obtained light-selective absorbing compound (1), the light-selective absorbing compound (1) was dissolved in 2-butanone. The obtained solution was put into a 1 cm quartz cell, and the quartz cell was set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the absorbance was measured by a two-beam method in a wavelength range of 1 nm step 300 to 800 nm. From the value of the obtained absorbance, the concentration of the light-absorbing compound in the solution, and the optical path length of the quartz cell, the gram absorption coefficient ε of each wavelength was calculated from the following formula.

ε (λ) = A (λ) / CL

[Where ε (λ) represents the gram absorption 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 represents the optical path of the quartz cell Cm. ]

As a result of measuring the absorption maximum wavelength (λmax) of the compound represented by UVA-01, λmax = 389nm (in 2-butanone), the value of ε (405) is 43L / (g‧cm), and the value of ε (420) It is 8.8L / (g‧cm).

[Synthesis example 2]

A 200 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 10 g of a compound represented by UVA-M-02 synthesized with reference to Japanese Patent Application Laid-Open No. 2014-194508, and acetic anhydride (and 3.7 g by Kwang Pure Pharmaceutical Co., Ltd., 5.8 g by 2-ethoxyethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 60 g by acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer . At an internal temperature of 25 ° C, 4.7 g of N, N-diisopropylethylamine (hereinafter, abbreviated as DIPEA. Made by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, and the temperature was maintained at 25 ° C after the dropwise addition was completed. 2 hours. The resulting mixture was subjected to a reduced pressure evaporator to remove acetonitrile. Insoluble matter produced by adding toluene to the obtained oily substance was removed by filtration. The filtrate was concentrated again using a reduced-pressure evaporator, and the concentrated solution was subjected to column chromatography (silica dioxide) for purification, and the target substance was obtained by recrystallization from toluene. This crystal was dried under reduced pressure at 60 ° C to obtain 5.2 g of a compound represented by UVA-02 as a yellow powder. The yield was 65%.

The gram absorption coefficient was obtained by the same method as above. The value of ε (405) of the compound represented by UVA-02 was 58L / (g‧cm), and the value of ε (420) was 1.9L / (g‧cm). .

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, the production of the compound represented by UVA-02 was confirmed.

¹ H-NMR (CDCl3) δ: 1.21 (t, 3H), 2.10 (quin, 2H), 2.98-3.04 (m, 5H), 3.54-3.72 (m, 6H), 4.31 (t, 2H), 5.53 ( d, 2H), 7.93 (d, 2H)

[Synthesis example 3]

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 3.0 g of 2-phenyl-1-methylindole-3-carboxaldehyde and piperidine (Wako Pure Chemical Industries, Ltd.) were charged. 1.2 g, 2-ethoxyethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.2 g, 12 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer. Warm in an oil bath and keep at an internal temperature of 80 ° C for 18 hours. After that, it was cooled to room temperature, and acetonitrile was removed by a reduced-pressure evaporator. The obtained crude crystals were dissolved in toluene, and the toluene solution was separated and washed with 1% hydrochloric acid for a total of 2 times in a separating funnel, and then the pure water was used to separate the aqueous layer to a pH of 6 or higher. Wash the liquid. After the washed toluene solution was dried with thenardite, toluene was removed using a reduced-pressure evaporator, and the obtained crystals were dried under reduced pressure at 60 ° C to obtain 4.0 g of a compound represented by UVA-03 as a yellow powder. The yield was 84%.

The gram absorption coefficient was obtained by the same method as above. The value of ε (405) of the compound represented by UVA-03 was 38L / (g · cm), and the value of ε (420) was 8.4L / (g‧cm). .

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was confirmed that the compound represented by UVA-03 was produced.

¹ H-NMR (CDCl3) δ: 1.21 (t, 3H), 3.56 (q, 2H), 3.69-3.73 (m, 5H), 4.37 (m, 2H), 7.36-7.44 (m, 5H), 7.56- 7.58 (m, 3H), 8.42-8.46 (m, 1H)

[Synthesis example 4]

A 200 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 10 g of a compound represented by UVA-M-02 synthesized with reference to Japanese Patent Application Laid-Open No. 2014-194508, and acetic anhydride (and 3.6 g by Kog Pure Chemical Industries Co., Ltd., 6.9 g with 2-ethylhexyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g with acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and stir with a magnetic stirrer . At an internal temperature of 25 ° C, 4.5 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 1 hour, and after the dropwise addition was completed, the temperature was maintained at 25 ° C for another 2 hours. After the reaction was completed, acetonitrile was removed using a reduced-pressure evaporator, and the residue was purified by column chromatography (silica dioxide). The solvent was removed from the extract containing UVA-04 using a reduced-pressure evaporator to obtain yellow crystals. . The crystals were dried under reduced pressure at 60 ° C to obtain 4.6 g of a compound represented by UVA-04 as a yellow powder. The yield is 50%.

When the gram absorption coefficient was obtained in the same manner as described above, the value of ε (405) was 47 L / (g · cm), and the value of ε (420) was 1.5 L / (g · cm).

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, the production of the compound represented by UVA-04 was confirmed.

¹ H-NMR (CDCl3) δ: 0.87-0.94 (m, 6H), 1.32-1.67 (m, 8H), 1.59-1.66 (m, 2H), 2.09 (quin, 2H), 3.00 (m, 5H), 3.64 (t, 2H), 4.10 (dd, 2H), 5.52 (d, 2H), 7.87 (d, 2H)

[Synthesis example 5]

A 200 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 10.0 g of 2-phenyl-1-methylindole-3-carboxaldehyde and piperidine (Wako Pure Chemical Industries, Ltd.) were charged. Manufactured) 3.6 g, cyanoacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.0 g, ethanol (made by Wako Pure Chemical Industries, Ltd.) 40 g, and stirred with a magnetic stirrer. Warm in an oil bath and keep at an internal temperature of 80 ° C for 24 hours. Thereafter, it was cooled to room temperature, and the precipitated crystals were collected by filtration, and the obtained crystals were dried under reduced pressure at 60 ° C., thereby obtaining 10 g of a compound represented by UVA-M-03 as a yellow powder. The yield was 78%.

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was confirmed that the compound represented by UVA-M-03 was produced.

¹ H-NMR (DMSO-d6) δ: 3.71 (s, 3H), 7.34-7.42 (m, 2H), 7.51-7.95 (m, 6H), 8.26-8.29 (m, 1H)

[Synthesis example 6]

1.4 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 2.0 g of chloroform to obtain a solution (1 ).

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 2.0 g of the compound represented by UVA-M-03 obtained in Synthesis Example 5 and triethylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) were charged. Co., Ltd.) 1.2 g, 20 mg of N, N-dimethyl-4-aminopyridine (DMAP, manufactured by Tokyo Chemical Industry Co., Ltd.), 8 g of chloroform, stirred with a magnetic stirrer, and cooled the internal temperature with an ice bath To 0 ° C. The dissolving solution (1) was dropped into the flask whose internal temperature was maintained at 0 ° C. over 2 hours, and the temperature was maintained at 0 ° C. for 6 hours after the completion of the dropwise addition. After that, chloroform was removed using a reduced-pressure evaporator. The obtained oil was dissolved in ethyl acetate, and the solution was separated and washed with 10% dilute sulfuric acid in a separating funnel, and then the ethyl acetate solution was separated with pure water so that the pH of the aqueous layer was 6 or more Wash the liquid. The washed organic layer was dried with thenardite. After the thenardite was removed, ethyl acetate was removed with a reduced pressure evaporator to obtain 2.5 g of a compound represented by UVA-05 as a yellow oil. The yield was 83%.

The gram absorption coefficient was obtained by the same method as above. The value of ε (405) of the compound represented by UVA-05 was 38L / (g‧cm), and the value of ε (420) was 8.3L / (g‧cm). .

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was confirmed that the compound represented by UVA-05 was produced.

¹ H-NMR (CDCl3) δ: 1.26 (t, 1H), 2.04 (s, 1H), 3.37 (s, 3H), 3.64-3.71 (m, 12H), 4.37 (dd, 2H), 7.35-7.46 ( m, 5H), 7.54-7.59 (m, 3H), 8.42-8.46 (m, 1H)

[Synthesis example 7]

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 3.0 g of 2-phenyl-1-methylindole-3-carboxaldehyde and piperidine (Wako Pure Chemical Industries, Ltd.) were charged. Manufactured) 1.2 g, 2-ethylhexyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.8 g, acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 12 g, and stirred with a magnetic stirrer. Warm in an oil bath and keep at an internal temperature of 80 ° C for 18 hours. After that, it was cooled to room temperature, and acetonitrile was removed by a reduced-pressure evaporator. The obtained oil was dissolved in ethyl acetate, and the ethyl acetate solution was separated and washed twice with 1% hydrochloric acid in a separatory funnel. Then, pure water was used so that the pH of the aqueous layer was 6 or more. Separate and wash. The washed ethyl acetate solution was dried with thenardite, and the ethyl acetate was removed by a vacuum evaporator to obtain 5.5 g of a compound represented by UVA-06 as an orange oil. The yield was 104%.

The gram absorption coefficient was obtained by the same method as above, and the value of ε (405) of the compound represented by UVA-06 was 31L / (g‧cm), and the value of ε (420) was 6.2L / (g‧cm ).

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, the production of the compound represented by UVA-06 was confirmed.

¹ H-NMR (CDCl3) δ: 0.90 (t, 6H), 1.03-1.62 (m, 10H), 2.35 (s, 1H), 3.72 (s, 3H), 4.13 (q, 2H), 7.16-7.26 ( m, 1H), 7.36-7.44 (m, 4H), 7.56-7.58 (m, 2H), 8.44-8.49 (m, 1H)

[Synthesis example 8]

A 200 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 10 g of a compound represented by UVA-M-02 synthesized with reference to Japanese Patent Application Laid-Open No. 2014-194508, and acetic anhydride (and (Guangguang Pure Chemical Industry Co., Ltd.) 6.3g, Mie acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.4g, triethylamine (Wako Pure Chemical Industries, Ltd.) 6.3g, acetonitrile (Wako Pure Chemical Industries, Ltd.) 130 g), stirred with a magnetic stirrer. Use an oil bath to warm the internal temperature to 78 ° C and maintain the temperature for 30 minutes. After that, the internal temperature was cooled to room temperature, and acetonitrile was removed by a reduced-pressure evaporator. The obtained oil was purified by column chromatography (silica dioxide). The column liquid containing the target compound was extracted, and the solvent was removed using a reduced pressure evaporator to obtain yellow crystals. The crystals were dried under reduced pressure at 60 ° C to obtain 1.5 g of a compound represented by UVA-07 as a yellow powder. The yield is 20%.

The gram absorption coefficient was obtained by the same method as above, then the value of ε (405) of the compound represented by UVA-07 was 72L / (g‧cm), and the value of ε (420) was 5.0L / (g‧cm ).

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was possible to confirm the formation of the compound represented by UVA-07.

¹ H-NMR (CDCl3) δ: 1.70 (s, 6H), 2.16 (quin, 2H), 3.15-3.22 (m, 5H), 3.77 (t, 2H), 6.95 (d, 2H), 8.10 (d, 2H)

[Synthesis example 9]

According to the method described in the patent document (DE101 09 243 A1), a compound represented by UVA-08 was synthesized. The purification is performed by column chromatography (silica dioxide).

The gram absorption coefficient was calculated in the same manner as described above. The value of ε (405) was 55L / (g‧cm) and the value of ε (420) was 17L / (g‧cm).

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, the production of the compound represented by UVA-08 was confirmed.

¹ H-NMR (CDCl3) δ: 1.31 (t, 3H), 2.09 (quin, 2H), 3.01 (m, 5H), 3.64 (t, 2H), 4.23 (q, 2H), 5.52 (d, 1H) , 7.92 (d, 1H)

[Synthesis example 10]

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 5.0 g of 2-phenyl-1-methylindole-3-carboxaldehyde and piperidine (Wako Pure Chemical Industries, Ltd.) were charged. Manufactured) 1.8 g, malononitrile (made by Tokyo Chemical Industry Co., Ltd.) 1.5 g, ethanol (made by Wako Pure Chemical Industries, Ltd.) 20 g, and stirred with a magnetic stirrer. Warm in an oil bath and keep at an internal temperature of 80 ° C for 18 hours. Thereafter, it was cooled to room temperature, and the precipitated crystals were collected by filtration, and the crystals were dried under reduced pressure at 60 ° C., thereby obtaining 4.9 g of a compound represented by UVA-09 as a yellow powder. The yield was 82%.

The gram absorption coefficient was obtained by the same method as above. The value of ε (405) of the compound represented by UVA-09 was 93L / (g‧cm), and the value of ε (420) was 24L / (g‧cm).

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was confirmed that the compound represented by UVA-09 was produced.

¹ H-NMR (CDCl3) δ: 3.71 (s, 3H), 7.34-7.38 (m, 2H), 7.44-7.47 (m, 4H), 7.60-7.63 (m, 3H), 8.37-8.40 (m, 1H )

[Synthesis Example 11]

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 3.0 g of 2-phenyl-1-methylindole-3-carboxaldehyde and piperidine (Wako Pure Chemical Industries, Ltd.) were charged. 1.1 g), 1.6 g of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 12 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer. Warm in an oil bath and keep at an internal temperature of 80 ° C for 18 hours. Thereafter, it was cooled to room temperature, and the precipitated crystals were collected by filtration, and the obtained crystals were dried under reduced pressure at 60 ° C., thereby obtaining 3.6 g of a compound represented by UVA-10 as a yellow powder.

The gram absorption coefficient was obtained by the same method as above. The value of ε (405) of the compound represented by UVA-10 was 49L / (g‧cm), and the value of ε (420) was 9.6L / (g‧cm). .

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was confirmed that the compound represented by UVA-10 was produced.

¹ H-NMR (CDCl3) δ: 1.34 (t, 3H), 3.72 (s, 3H), 4.29 (q, 2H), 7.38-7.43 (m, 5H), 7.56-7.58 (m, 3H), 8.15 ( s, 1H), 8.41-8.47 (m, 1H)

[Synthesis example 12]

A 200 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 10 g of a compound represented by UVA-M-02 synthesized with reference to Japanese Patent Application Laid-Open No. 2014-194508, and acetic anhydride (and 3.6 g by Kwang Pure Pharmaceutical Co., Ltd., 6.6 g by 2-ethylbutyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g by acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer . At an internal temperature of 25 ° C, 4.5 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 1 hour, and after the dropwise addition was completed, the temperature was maintained at 25 ° C for another 2 hours. After that, the acetonitrile was removed using a reduced pressure evaporator, and the residue was purified by column chromatography (silica dioxide), and the solvent containing the compound represented by UVA-11 was removed using a reduced pressure evaporator. To obtain yellow crystals. This crystal was dried under reduced pressure at 60 ° C to obtain 3.0 g of a compound represented by UVA-11 as a yellow powder.

The gram absorption coefficient was obtained by the same method as above, and the value of ε (405) of the compound represented by UVA-11 was 48L / (g‧cm), and the value of ε (420) was 1.1L / (g‧cm ).

[Synthesis example 13]

A 200 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 10 g of a compound represented by UVA-M-02 synthesized with reference to Japanese Patent Application Laid-Open No. 2014-194508, and acetic anhydride (and 3.6 g, manufactured by Kwang Pure Pharmaceutical Co., Ltd., 10 g of 2-octylhexyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred with a magnetic stirrer. At an internal temperature of 25 ° C., 4.5 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture for one hour. After the dropwise addition was completed, the temperature was maintained at an internal temperature of 25 ° C. for 2 hours. Thereafter, acetonitrile was removed using a reduced pressure evaporator, and the residue was subjected to column chromatography (silica dioxide) for purification. The solvent containing UVA-12 was removed using a reduced pressure evaporator to obtain yellow crystals. The crystals were dried under reduced pressure at 60 ° C to obtain 4.6 g of a compound represented by UVA-12 as a yellow powder. The yield was 56%.

The gram absorption coefficient was obtained by the same method as above. The value of ε (405) of the compound represented by UVA-12 was 45L / (g‧cm), and the value of ε (420) was 2.1L / (g‧cm). .

[Synthesis Example 14]

A 300 mL four-neck flask equipped with a Dessert condenser, a thermometer, and a stirrer was placed in a nitrogen atmosphere, and 20 g of malonaldehyde diphenylamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged with 1,3-dimethylbar 13.8 g of bitumic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 46 g of methanol were stirred at room temperature. 8.6 g of triethylamine (made by Wako Pure Chemical Industries, Ltd.) was added dropwise from a dropping funnel over 30 minutes, and stirring was continued at room temperature for 1 hour. Then, the internal temperature was raised to 65 ° C using an oil bath, and the mixture was refluxed for 1 hour. After the reaction was completed, the internal temperature was cooled to room temperature, and the precipitated crystals were collected by filtration, and the wet crystals were washed with methanol. The washed wet crystals were dried under reduced pressure at 40 ° C to obtain 18.5 g of a compound represented by UVA-M-04 as an orange powder. The yield was 84%.

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, the production of the compound represented by UVA-M-04 was confirmed.

¹ H-NMR (DMSO- d ₆ ) δ (ppm): 3.07 (s, 6H), 7.04-7.07 (m, 1H), 7.26-7.32 (m, 4H), 7.43 (dd, 1H), 8.07 (d , 1H), 8.55 (d, 1H), 11.4 (s, 1H)

[Synthesis Example 15]

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 2.0 g of the compound represented by UVA-M-04 and 1.6 g of morpholin (made by Wako Pure Chemical Industries, Ltd.) 2 -10 g of propanol (manufactured by Nacalai Tesque), stirred with a magnetic stirrer. The oil was heated to an internal temperature of 83 ° C, and the mixture was boiled under reflux for 3 hours. After the reaction was completed, the mixture was cooled to room temperature. The precipitated crystals were obtained by filtration, and the wet crystals were washed four times with 2-propanol, and then dried under reduced pressure at 40 ° C to obtain 1.6 g of a compound represented by UVA-13 as an orange powder. The yield was 82%.

The gram absorption coefficient was obtained by the same method as above, and the value of ε (405) of the compound represented by UVA-13 was 314L / (g‧cm), and the value of ε (420) was 85L / (g‧cm).

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was confirmed that the compound represented by UVA-13 was produced.

¹ H-NMR (CDCl3) δ (ppm): 3.27 (s, 3H), 3.29 (s, 3H), 3.50-3.59 (m, 4H), 3.72-3.78 (m, 4H), 7.19-7.32 (m, 2H), 7.95-8.06 (m, 1H)

[Synthesis Example 16]

A 100 mL-four-neck flask equipped with a Dessert condenser and a thermometer was placed in a nitrogen atmosphere, and 2.0 g of the compound represented by UVA-M-04, 10 g of diethylamine (made by Wako Pure Chemical Industries, Ltd.), 2- 10 g of propanol (manufactured by Nacalai Tesque) was stirred with a magnetic stirrer. The oil was heated to an internal temperature of 52 ° C, and the temperature was maintained for 5 hours. After the reaction was completed, the temperature was cooled to room temperature. 2-propanol was removed using a reduced-pressure evaporator, and the obtained oil was purified by column chromatography (silica dioxide) to obtain 1.1 g of a compound represented by UVA-14 as an orange powder. The yield was 58%.

The gram absorption coefficient was calculated in the same manner as above. The value of ε (405) of the compound represented by UVA-14 was 303 L / (g · cm), and the value of ε (420) was 81 L / (g · cm).

As a result of ¹ H-NMR analysis, the following peaks were observed. Therefore, it was confirmed that the compound represented by UVA-14 was produced.

¹ H-NMR (CDCl3) δ (ppm): 1.26-1.37 (m, 6H), 3.34 (s, 3H), 3.35 (s, 3H), 3.43-3.56 (m, 4H), 7.27-7.39 (m, 2H), 8.04 (d, 1H)

[Synthesis Example 17]

With reference to Anal. Chem. 2017, 89, 9432-9437, a compound represented by UVA-15 was synthesized from a compound represented by formula (M-1).

Table 2 shows the results of measuring the absorption coefficients of the obtained light-absorbing compounds.

<Preparation of adhesive composition and adhesive sheet>

(a-1) Preparation of Adhesive Compositions of Examples 1 to 21 and Comparative Example 1

For 100 parts by mass of the solid content of the acrylic resin (A), a cross-linking agent, a silane compound, and a light-selective absorbing compound were blended in the amounts shown in Table 3, respectively. 2-butanone was further added so that the solid content concentration was 14%, and agitator (Three-one motor manufactured by Yamato Scientific Co., Ltd.) was used to stir at 300 rpm for 30 minutes to prepare each adhesive composition. In addition, a cross-linking agent and a light-selective absorbing compound are prepared as 2-butanone solutions and added to the acrylic resin.

(a-2) Preparation of adhesive compositions of Examples 22 to 34 and Comparative Example 2

Except that the acrylic resin (A) was changed to the acrylic resin (B), each adhesive composition was prepared according to the formulation shown in Table 3 by the same method as in the foregoing Examples 1 to 21 and Comparative Example 2.

(a-3) Examples 35 to 36

Substitute the light-selective absorbing compound with a compound represented by UVA-15, and add the amount shown in Table 3 to 100 parts by mass of the solid content of the acrylic resin (A). The adhesive composition was prepared in the same manner as in Examples 1 to 21.

The cross-linking agents, silane compounds, and light-selective absorbing compounds shown in Table 3 are each shown below.

[Crosslinking agent (B)]

Coronate-L: Ethyl acetate solution of adducts such as toluene diisocyanate and trimethylolpropane (solid content concentration 75%), made by Japan Polyurethane Co., Ltd.

[Silane compound]

KBM-403: 3-glycidoxypropyltrimethoxysilane, liquid, manufactured by Shin-Etsu Chemical Industry Co., Ltd. (hereinafter, abbreviated as "KBM-403").

[Light-selective absorbing compound (ultraviolet absorber)]

KEMISORB 73 [λmax = 353nm, ε (405) = 1.4L / (g‧cm), ε (420) without absorption]: 2- (3,5-di-tertiary pentyl-2-hydroxyphenyl) benzene Benzotriazole, solid, manufactured by CHEMIPRO Chemical Co., Ltd. (hereinafter, abbreviated as "KEMISORB 73").

SUMISORB 300 [λmax = 354nm, ε (405) = 1.9L / (g‧cm), ε (420) without absorption]: 2- (3-tertiarybutyl-2-hydroxy-5-methylphenyl) -5-Chlorobenzotriazole, solid, manufactured by Sumika Chemtex Co., Ltd. (hereinafter, abbreviated as "SUMISORB 300").

The gram absorbance coefficients of KEMISORB 73 and SUMISORB 300 can be obtained by the same method as described above.

(b) Production of adhesive sheet

Each adhesive composition prepared in the above (a) was applied to a polyethylene terephthalate film (SP-PLR382050 manufactured by LINTEC Corporation) with a release treatment so that the dry film thickness was 20 μm. , Hereinafter, abbreviated as "separation film"), the release-treated surface was dried at 100 ° C for 1 minute to prepare an adhesive sheet.

<Measurement of Absorbance of Adhesive Layer>

In order to measure the absorbance of the obtained adhesive layer, the adhesive layer was bonded to glass, the release film was peeled off, and then a cycloolefin polymer (COP) film was bonded to the adhesive layer (ZF-14, manufactured by Japan Zeon Corporation). A laminated body for evaluating an adhesive layer was produced. The produced laminated body for evaluation of the adhesive layer was set on a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the absorbance was measured by a two-beam method in a wavelength range of 1 nm step 300 to 800 nm. The absorbance of the produced adhesive layer is shown in Table 4.

<Production of Optical Laminate (Examples 37 to 71, Comparative Examples 3 and 4)>

For the production of optically anisotropic layers or laminates, the "photo-alignment film-forming composition", "friction alignment polymer composition", "polymerizable liquid crystal compound-containing composition" shown below, and "Polarizer".

<Modulation of Composition for Forming Photo-Alignment Film>

5 parts of a photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the obtained mixture was stirred at 80 ° C. for 1 hour, thereby obtaining a composition for forming a photo-alignment film. The following photo-alignment materials were synthesized by the method described in Japanese Patent Application Laid-Open No. 2013-33248.

<Preparation of polymerizable liquid crystal compound-containing composition A>

A polymerizable liquid crystal compound A, a polyacrylate compound (leveling agent) (BYK-361N; manufactured by BYK-Chemie), and a polymerization initiator and a solvent described below are mixed as components to obtain a polymerizable composition Composition of liquid crystal compound.

Polymerizable liquid crystal compound A (12.0 parts):

The polymerizable liquid crystal compound A is synthesized by a method described in Japanese Patent Application Laid-Open No. 2010-31223. The maximum absorption wavelength λmax (LC) of the polymerizable liquid crystal compound A was 350 nm.

Polymerization initiator (0.72 parts): 2-dimethylamino-2-benzyl-1- (4-morpholinylphenyl) butane-1-one (IRGACURE369; manufactured by Ciba Chemical Co., Ltd.)

Leveling agent (0.12 parts): polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

Solvent: cyclopentanone (100 parts)

[Example 37]

<Manufacture of Polarizing Plate>

Polyvinyl alcohol film with a thickness of 30 μm (average degree of polymerization is about 2400, degree of saponification is above 99.9 mole%), dry-drawn uniaxially stretched about 4 times, and kept in a tight state, immersed in pure water at 40 ° C After 40 seconds, a dyeing aqueous solution having a weight ratio of 0.044 / 5.7 / 100 of iodine / potassium iodide / water at 28 ° C. was immersed in the dyeing treatment for 30 seconds. Thereafter, it was immersed in a boric acid aqueous solution having a weight ratio of potassium iodide / boric acid / water of 11.0 / 6.2 / 100 at 70 ° C. for 120 seconds. Next, it was washed with pure water at 8 ° C for 15 seconds, and then was dried at 60 ° C for 50 seconds and then at 75 ° C for 20 seconds while maintaining a tension of 300N, to obtain a polyvinyl alcohol film adsorption alignment system. Iodine polarizer with a thickness of 12 μm.

A water-based adhesive was injected between the obtained polarizer and a cycloolefin polymer film (COP, ZF-4 manufactured by Japan Zeon Co., Ltd., without UV absorption characteristics, 30 μm), and bonded by a nip roll. The tension of the obtained paste was maintained at 430 N / m and dried at 60 ° C. for 2 minutes to obtain a 42 μm polarizer having a cycloolefin film with a protective film on one side. The above-mentioned water-based adhesive is based on 100 parts of water, 3 parts of carboxy-modified polyvinyl alcohol (Kuraray Co., Ltd .; KURARAY POVAL KL318), and water-soluble polyamine epoxy resin (manufactured by Sumika Chemtex Co., Ltd.) are added. Sumirez Resin 650; 1.5 parts of aqueous solution with a solid concentration of 30%).

The polarization degree Py and the monomer transmittance Ty of the obtained polarizing plate were measured in the following manner.

Used in a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) equipped with a polarizer lens holder. The dual-beam method was used to measure the single transmission in the transmission axis direction in the wavelength range of 2nm step 380 to 680nm. (T ¹ ) and the monomer transmittance (T ² ) in the absorption axis direction. Using the following formulae (p) and (q), calculate the monomer transmittance and polarization at each wavelength, and then perform visibility correction using the 2-degree field of view (C light source) of JIS Z8701 to calculate the visibility correction monomer transmission. Rate (Ty) and visibility correction polarization (Py). As a result, an absorption-type polarizing plate having a visibility-corrected single-transmittance Ty of 43.0% and a visibility-corrected polarization Py of 99.99% was obtained.

Transmittance of monomer Ty (%) = ((T ¹ + T ² ) / 2) × 100 (p)

Polarization Py (%) = ((T ¹ -T ² ) / (T ¹ + T ² )) × 100 (q)

<Manufacture of Optical Anisotropic Layer>

Using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.), a cycloolefin polymer film (COP, ZF-14, manufactured by Japan Zeon Corporation) was used under conditions of 0.3 kW output and a processing speed of 3 m / min. Perform processing once. On the surface to which the corona treatment was applied, a composition for forming a photo-alignment film was bar-coated, dried at 80 ° C. for 1 minute, and using a polarized UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Electric Co., Ltd.) at 100 mJ / cm The accumulated light quantity of ² is subjected to polarized UV exposure. As a result of measuring the film thickness of the obtained alignment film with an ellipsometer M-200 (manufactured by JASCO Corporation), it was 100 nm.

Next, on the alignment film, a coating liquid composed of the polymerizable liquid crystal compound-containing composition A prepared before was applied using a bar coater, and dried at 120 ° C for 1 minute, and then a high-pressure mercury lamp (Unicure VB-15201BY-A, (Made by USHIO Electric Co., Ltd.), irradiates ultraviolet rays (cumulative light amount at a wavelength of 313 nm in a nitrogen environment: 500 mJ / cm ² ) from a surface side coated with a composition containing a polymerizable liquid crystal compound, thereby forming an optical isotropic Optical film of the anisotropic layer 1. The thickness of the obtained optically anisotropic layer 1 was measured with a laser microscope (manufactured by Lext Olympus Co., Ltd.), and was 2 μm.

A corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) was bonded to the optically anisotropic layer 1 side of the obtained optical film after bonding the adhesive composition prepared in Manufacturing Example 2 to output 0.3. A polarizer processed once under the conditions of kW and a processing speed of 3 m / min. At this time, the circularly polarizing plate was formed so that the relationship between the slow axis of the optically anisotropic layer and the absorption axis of the polarizing plate was 45 °. Thereafter, the COP film of the base material was peeled off, thereby obtaining an optical laminated body 1 (circular polarizing plate 1) having an optically anisotropic layer 1 transferred onto a polarizing plate. The thickness of the obtained optical laminated body 1 was 64 μm.

In order to measure the optical characteristics of the optical laminated body 1, a measurement sample is prepared by transferring to glass. A birefringence measuring device (KOBRA-WR; manufactured by Oji Measurement Co., Ltd.) was used to measure the phase difference values of the sample at a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 630 nm. The transmittance was measured with a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation). In addition, a polarized light beam is arranged on the light source side to make a completely linearly polarized light, and the measurement sample is irradiated with the linearly polarized light for measurement. At this time, the transmittance Tp (405) of the optical laminated body at a wavelength of 405 nm and the transmission direction of the polarized plate were measured by linearly polarized light incident parallel to the transmission axis on the polarizing plate side of the optical laminated body. The transmittance Tp (420) of the optical laminate at a wavelength of 420 nm, and the transmittance Tp (440) of the optical laminate at a wavelength of 440 nm in the transmission direction of the polarizing plate. The results are shown in Table 5.

[Examples 38 to 71, Comparative Examples 3 and 4]

Using the adhesive compositions described in Examples 1 to 35 in Table 4 above, an optical laminate (circular polarizing plate) with an optically anisotropic layer transferred was prepared in the same manner as in Example 37 described above. The optical characteristics of the obtained optical laminated body (circular polarizing plate) were measured in the same manner as in Example 1.

<Evaluation of optical laminated body>

The optical laminated body produced as described above was subjected to an optical durability test, a heat resistance test, a moist heat resistance test, and a thermal shock resistance test for evaluation. In addition, each test was performed according to the following method.

Light endurance test (labeled as "SWOM" in Table 6): The optical laminate was put into a daylight-type weathermeter (manufactured by Suga Testing Machine Co., Ltd .: model: SUNSHINE WEATHER METER S80), and the measurement was performed at a wavelength of 450 nm after 100 hours of irradiation , Phase difference at a wavelength of 550nm and a wavelength of 630nm. The change of the phase difference value before and after the optical durability test was evaluated based on the following criteria. The results are shown in Table 6.

[Evaluation criteria for optical durability test]

A: The change in Re before and after the optical durability test is less than 5.

B: The change in Re before and after the optical durability test is 5 or more and less than 10.

C: The change in Re before and after the optical durability test is 10 or more.

Heat resistance test (labeled "heat resistant" in Table 6): Put the optical laminate into a thermostatic bath (manufactured by ESPEC Corporation: Model PL-3KT), and place them in dry conditions at a temperature of 85 ° C for 250 hours and 500 hours. The appearance state of the optical laminated body was visually observed, and evaluation was performed based on the following evaluation criteria. The results are shown in Table 6.

[Evaluation criteria for heat resistance test]

A: After 500 hours, there were almost no changes in the appearance of the samples, such as lifting, peeling, and foaming.

B: After 250 hours, there were almost no changes in the appearance of the sample, such as lifting, peeling, and foaming.

C: After 250 hours, the appearance change of the sample, such as the floating, peeling, and foaming, was significantly confirmed.

Moisture and heat resistance test (labeled as "Moisture and Heat Resistance" in Table 6): Put the optical laminate into a thermostatic bath (manufactured by ESPEC Corporation: Model PH-4KT), and place them at a temperature of 60 ° C and a relative humidity of 90% for 250 hours, After 500 hours, the appearance state of the optical laminate was visually observed, and evaluation was performed according to the following evaluation criteria. The results are shown in Table 6.

[Evaluation Criteria for Humidity and Heat Resistance Test]

A: After 500 hours, there were almost no changes in the appearance of the samples, such as lifting, peeling, and foaming.

B: After 250 hours, there were almost no changes in the appearance of the sample, such as lifting, peeling, and foaming.

C: After 250 hours, the appearance change of the sample, such as the floating, peeling, and foaming, was significantly confirmed.

In Comparative Examples 3 and 4 in which no light-selective absorbing compound was added, the value of Re (450) after the optical durability test significantly changed to 10 or more. On the other hand, the values of A (405) and A (420) exceeded 0.5 and 0.1, and the values of A (405) / A (440) and A (420) / A (440) exceeded 10 and 1, respectively. The optical laminated body (Examples 36 to 70) according to the present invention improved the value of Re (450) after the optical durability test to less than 5. In particular, optical laminates (Examples 36 to 68 and Example 71) containing a light-selective absorbing compound having a specific structure did not float, peel, foam, etc. after each endurance test, and the appearance did not change. It can be seen that the durability is excellent.

Next, the transmittance of the produced optical laminate was measured with a spectrophotometer, and the light extraction efficiency under the OLED display was estimated. The results are shown in Table 7.

The light extraction efficiency is calculated based on the OLED emission spectrum and the transmission spectrum of the optical laminate.

The blue, green, and red light extraction efficiency is the light extraction efficiency at the wavelengths of 420 to 560 nm, 480 to 655 nm, and 535 to 755 nm, respectively.

OLED light extraction efficiency (%) = OLED emission spectrum × transmittance of optical multilayer

According to the optical laminated body (Examples 37 to 70) of the present invention, Comparative Examples 3 and 4 to which no light-selective absorbing compound was added showed the same light extraction efficiency, and it was found that the display characteristics were not impaired.

    [Industrial availability]    

The film with an adhesive layer using the adhesive composition of the present invention has good display characteristics, and can suppress deterioration of an optical film caused by short-wavelength visible light in the range of ultraviolet to 400 nm.

Claims (14)

An adhesive composition containing a compound represented by formula (I); In the formula, R ¹ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbons which may have a substituent, an aralkyl group having 7 to 15 carbons which may have a substituent, and an alkyl group having 6 to 15 carbons Aryl, heterocyclyl, -CH ₂ -contained in the alkyl group or aralkyl group may be substituted with -NR ^1A- , -CO-, -SO _2- , -O-, or -S-; R ^1A represents hydrogen Atoms or alkyl groups having 1 to 6 carbons; R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or An aromatic heterocyclic group having a substituent, the -CH ₂ -contained in the alkyl group may be substituted with -NR ^1B- , -CO-, -SO _2- , -O-, or -S-; R ^1B represents a hydrogen atom Or an alkyl group having 1 to 6 carbons; R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms or an electron-withdrawing group; R ¹ and R ² may be connected to each other to form a ring structure, and R ² and R ³ can be connected to each other to form a ring structure, R ² and R ⁴ can be connected to each other to form a ring structure, R ³ and R ⁶ can be connected to each other to form a ring structure, and R ⁶ and R ⁷ can be connected to each other to form a ring structure.     The adhesive composition according to item 1 of the scope of patent application, wherein the compound represented by the formula (I) is a compound satisfying the formula (1); ε (405) ≧ 20 (1) In the formula, ε (405 ) Represents the gram absorption coefficient of the compound at a wavelength of 405 nm; the unit of the gram absorption coefficient is L / (g‧cm).         The adhesive composition according to item 1 of the scope of patent application, wherein the compound represented by formula (I) is a compound satisfying formula (2); ε (420) ≧ 5 (2) where ε (420 ) Represents the gram absorption coefficient of the compound at a wavelength of 420 nm; the unit of the gram absorption coefficient is L / (g‧cm).         The adhesive composition according to any one of claims 1 to 3, further comprising a (meth) acrylic resin (A) and a crosslinking agent (B).         The adhesive composition according to item 4 of the scope of the patent application, wherein the content of the compound represented by formula (I) is 0.01 to 20 parts by mass based on 100 parts by mass of the (meth) acrylic resin.         The adhesive composition according to item 4 or 5 of the scope of the patent application, wherein the content of the crosslinking agent (B) is 0.01 to 10 parts by mass relative to 100 parts by mass of the (meth) acrylic resin (A).         An optical multilayer body includes an adhesive layer formed by the adhesive composition described in any one of claims 1 to 6 and a resin film.         The optical laminated body according to item 7 of the scope of the patent application, wherein the resin film is at least one film selected from a retardation film and a polarizing film.         An optical multilayer body includes an adhesive layer, a polarizing film, and a retardation film formed from the adhesive composition described in any one of claims 1 to 6 of the scope of patent application.         The optical multilayer body according to any one of claims 7 to 9 in the scope of the patent application, wherein the thickness of the adhesive layer is 0.1 to 30 μm.         The optical multilayer body according to any one of claims 7 to 10 in the scope of the patent application, wherein the adhesive layer satisfies the following formula (5); A (405) ≧ 0.5 (5) where A (405) It indicates the absorbance of the adhesive layer at a wavelength of 405 nm.         The optical multilayer body according to item 11 of the scope of patent application, wherein the adhesive layer satisfies the following formula (6); A (420) ≧ 0.1 (6) where A (420) represents adhesion at a wavelength of 420nm Absorbance of the agent layer.         The optical multilayer body according to item 11 or 12 of the scope of the patent application, wherein the adhesive layer further satisfies the following formula (7); A (440) ≦ 0.1 (7) where A (440) represents a wavelength of 440nm Absorbance of the adhesive layer.         A display device includes the optical multilayer body according to any one of claims 7 to 13 of the scope of patent application.