TW201815936A - Light absorbing composition - Google Patents

Abstract

An object of the present invention is to provide a light absorbing composition which exhibits light selective absorption for short wavelength visible light around 400 nm and at the same time has high affinity with materials of constituent members of a display device and/ or has high solubility in various solvents. The light absorbing composition comprises at least two kinds of light selective absorptive compounds, wherein at least two kinds of said light selective absorptive compounds have the same conjugated structure.

Description

   Light absorbing composition   

The present invention relates to a light-absorbing composition, a polymer composition containing the light-absorbing composition, an optical film, and a display device.

In flat display devices (FPDs) such as organic EL display devices and liquid crystal display devices, various members such as display elements such as organic EL elements or liquid crystal cells, and optical films such as polarizing plates or retardation plates are used. The materials such as the organic EL compound and the liquid crystal compound used in these members are organic substances, and therefore there is a problem of deterioration due to ultraviolet (UV). In order to solve such a problem, countermeasures such as adding a UV absorber to a protective film of a polarizing plate used in a display device have been made. For example, Patent Document 1 attempts to prevent deterioration of a member by adding a UV absorber to a polarizing plate protective film used in these display devices.

In addition, in recent years, the thickness of display devices is being reduced, and the thickness of optical films is required to be reduced. Optical films without protective films have also been developed. In such an optical film, it is necessary to mix the components added to the conventional protective film to other members, for example, to impart a UV absorption function to an adhesive layer laminated on the optical film. Patent Document 2 discloses a pressure-sensitive adhesive sheet in which one side of a substrate is coated with a UV absorber synthesized from a monomer mixture containing a UV-absorbing monomer.

    [Prior technical literature]         [Patent Literature]    

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

Patent Document 2: Japanese Patent Application Laid-Open No. 2008-56859

The UV absorber must exhibit the function of absorbing light in the ultraviolet region to prevent deterioration of the member. On the other hand, it must have light selective absorptivity that does not show absorption characteristics for blue light (for example, a visible light region exceeding 430 nm).

In addition, in order to combine the UV absorber with a constituent member of a display device such as an adhesive or an optical film, it is necessary to have a high affinity with the constituent member or a high solubility in a solvent. When the UV absorber has insufficient affinity, for example, when a UV absorber is added to the adhesive, the UV absorber may bleed out, hinder the adhesion function, and dissolve the solvent in the adhesive coating solution. When the property is lowered, the UV absorber cannot be uniformly dispersed in the constituent member, and the light absorption function becomes insufficient. Furthermore, when a UV absorber is added to an optical film such as a retardation film, and the film is stretched by heating, the UV absorber oozes out on the surface of the film, and the light absorption function cannot be sufficiently exhibited. Therefore, in order to be used as a UV absorber, it is necessary to have excellent affinity with the material of the constituent members of the display device and excellent solubility in various solvents.

Here, an object of the present invention is to provide a light-absorptive composition which exhibits selective absorptivity for short-wavelength visible light in the vicinity of 400 nm, and has high affinity with a material constituting a display device and / or various solvents. Light-absorbing composition with high solubility.

The present invention provides the following preferred embodiments.

[1] A light-absorbing composition, which is an absorbent composition containing at least two kinds of light-selective absorbing compounds, wherein the at least two kinds of light-selective absorbing compounds have the same conjugated structure.

[2] The light absorbing composition according to the above [1], wherein the difference between the maximum value and the minimum value of the maximum absorption wavelength of the at least two kinds of light selective absorption compounds having the same conjugated structure is 5 nm the following.

[3] The light-absorbing composition according to [1] or [2], wherein the at least two kinds of light-selective absorbing compounds are those represented by the following formula (I) or formula (II): In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. When the alkyl group has at least one methylene group, at least one of the methylene group may be substituted by an oxygen atom or a sulfur atom. R ² and R ³ independently of each other represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a methylene group, a secondary amine group, an oxygen atom, or a sulfur atom, X ¹ and X ² independently represent an electron attracting group, and X ¹ and X ² can be connected to each other to form a ring structure]; In the formula, R ¹ , X ¹ , and X ² have the same definitions as the foregoing, and A ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and the alkyl group has at least one In the case of a methylene group, at least one of the methylene groups may be substituted with a secondary amine group, an oxygen atom, and a sulfur atom, and the aromatic hydrocarbon group and the aromatic heterocyclic group may have a substituent].

[4] The light-absorbing composition according to [3], wherein the light-selective absorbing compound represented by the formula (I) is represented by the following formula (I-2): In the formula, R ¹ has the same definition as the foregoing, and R ⁴ represents a hydrogen atom or an alkyl group having 2 to 50 carbon atoms. When the alkyl group has at least one methylene group, at least one of the methylene groups can be oxygenated. Atomic substitution; the light-selective absorbing compound represented by the aforementioned formula (II) is one represented by the following formula (II-2) In the formula, R ¹ and R ⁴ have the same definitions as the foregoing.

[5] The light-absorbing composition according to any one of the above [1] to [4], wherein at least two kinds of light-selective absorptions having the same conjugated system structure included in the light-absorbing composition The ratio of the content of the light-selective absorbing compound having the largest content in the light-absorbing composition to the content of other light-selective absorbing compounds is 1:10 to 10: 1.

[6] The light-absorbing composition according to any one of the above [1] to [5], which satisfies the following formulae (1), (2), and (3): ε (420) / ε ( 400) ≦ 0.3 (1)

λ max ≦ 420nm (2)

ε (400) ≧ 20 (3) In the formula, ε (420) represents a gram extinction coefficient at a wavelength of 420 nm, and ε (400) represents a gram absorption coefficient λ max at a wavelength of 400 nm, which represents a maximum absorption wavelength.

[7] A polymer composition comprising the light-absorbing composition according to any one of the above [1] to [6], and a polymer.

[8] The polymer composition according to the above [7], wherein the content of the light-absorbing composition is 1 to 15 parts by mass based on 100 parts by mass of the polymer.

[9] An optical film composed of the polymer composition according to [7] or [8].

[10] The optical film according to the aforementioned [9], wherein the thickness is 0.1 to 18 μm.

[11] A laminated polarizing film comprising the optical film according to [9] or [10] and a polarizing film.

[12] The laminated polarizing film according to the above [11], which satisfies the following formulae (4) and (5): Ap (400) ≧ 0.4 (4)

Ap (420) / Ap (400) ≦ 0.3 (5) In the formula, Ap (400) represents the absorbance of the optical film in the direction of the transmission axis of the polarizing film at the wavelength of 400nm, and Ap (420) represents the wavelength at 420nm. Absorbance of optical film in the direction of the polarization axis of the polarizing film].

[13] A laminated retardation film comprising the optical film according to [9] or [10] and a retardation film.

[14] An elliptical polarizing film comprising the optical film, the polarizing film, and the retardation film according to [9] or [10].

[15] A display device comprising the film according to any one of [9] to [14].

According to the present invention, it is possible to provide a light-absorptive composition which has a selective absorptivity for short-wavelength visible light display light near 400 nm, and has high affinity with the material of the constituent members of the display device and / or high solubility in various solvents. .

1‧‧‧ polarizing film

2‧‧‧ surface treatment layer

3‧‧‧Second protective film

4‧‧‧first protective film

6‧‧‧ interlayer adhesive

7‧‧‧ retardation film

10‧‧‧ polarizing plate

15‧‧‧ polarizer with adhesive

20‧‧‧ Adhesive Tablets

30‧‧‧Image display element (glass substrate)

40‧‧‧ Optical Laminate

FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an optical laminate in an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of a layer structure of an optical multilayer body in one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various changes can be made without departing from the scope of the present invention.

The light-absorbing composition of the present invention is a composition containing at least two kinds of light-selective absorbing compounds, and the at least two kinds of light-selective absorbing compounds have the same conjugated structure. In addition, in the present invention, the conjugated structure means a molecular structure in which a π-electron system is along a molecular chain instead of being non-polarized. Examples of the conjugate structure include a structure surrounded by the following quadrangles. In addition, in the following chemical formula, a part bonded to a conjugated structure (a structure surrounded by a square) is a methylene group, but the conjugated structure is not limited to extend, and the relevant part is not limited to the methylene group, for example Examples include methine and the like.

The carbon number of the conjugated structure is preferably 1 to 20, more preferably 2 to 15, and even more preferably 3 to 10. When the carbon number of the conjugated structure is within the above range, the light-absorptive composition of the present invention has difficulty in absorbing blue light, and tends to selectively absorb light for short-wavelength visible light around 400 nm.

In the light-absorbing composition of the present invention, at least two kinds of light-selective absorbing compounds contained in the composition have the same conjugated structure. Therefore, when the light-absorbing composition of the present invention is added to the adhesive sheet, it is possible to suppress the bleeding of the light-selective absorbing compound in the adhesive, and it is difficult to hinder the adhesive function of the adhesive. Furthermore, since the light-selective absorbing compound can be suppressed from oozing out, a high concentration of the light-selective absorbing compound can be blended in the adhesive, and an adhesive sheet having excellent thinness and light absorption can be obtained. With the reduction in thickness of the display device, each member must also be reduced in thickness. However, when the thickness of the member is reduced, the concentration of the light absorber formulated in the member must be increased. According to the light-absorptive composition of the present invention, since it is possible to suppress bleeding, it is possible to cope with a request for a thin member. In addition, when the light-absorbing composition of the present invention is added to the optical film, it is possible to suppress the exudation of the light-selective absorbing compound and to prevent the optical function from being blocked. In addition, in the present invention, in addition to the limitation that at least two kinds of light-selective absorbing compounds contained in the light-absorbing composition have the same conjugated structure, they may contain different conjugates from the conjugated structure. Other light-selective absorbing compounds of the structure.

In a preferred embodiment of the present invention, the conjugated structure of any one light-selective absorbing compound is the same as the conjugated structure of at least one other light-selective absorbing compound. That is, when the light-selective absorbing compound A having the conjugated structure a is contained in the composition, the light-selective absorbing compound B having the same conjugated structure a is also contained in the composition. Furthermore, when the light-selective absorbing compound C having a conjugated structure b is further contained in the composition, it is preferred that the light-selective absorbing compound D having a conjugated structure b is further contained in the composition. That is, in the light-absorbing composition of the present invention, for example, when four kinds of light-selective absorbing compounds A to D are contained, it is preferable that only one kind of light-selective absorbing compound does not have another conjugated structure. . In this case, the selective absorbing compound can be more inhibited from leaking out of the constituent members (optical film, adhesive, etc.) of the display device, and the obstacle of the optical function of the optical film and / or the adhesive function of the adhesive can be further suppressed.

In the light-absorbing composition of the present invention, the maximum and minimum values of the maximum absorption wavelength (hereinafter, also referred to as "λ max") among at least two kinds of light-selective absorbing compounds having the same conjugated structure. The difference is preferably 5 nm or less, more preferably 4 nm or less, still more preferably 3 nm or less, particularly preferably 2 nm or less, such as 1 nm or less. The difference between the maximum value and the minimum value of λ max is 5 nm or less, which means that the structures of various light-selective absorbing compounds having the same conjugated structure are similar (having similar structures). When the difference between the maximum value and the minimum value of λ max of the light-selective absorbing compound is below the above-mentioned upper limit value, it is possible to further suppress the light-selective absorbing compound from leaking out of the constituent members of the display device, and to obtain a more light-selective absorbing property. Excellent light-absorbing composition. The lower limit of the difference between the maximum value and the minimum value of λ max of the light-selective absorbing compound is, for example, 0 nm or more.

In one aspect of the present invention, from the viewpoint of exhibiting high light selective absorption, the light selective absorption compound is preferably represented by the following formula (I) or formula (II): In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. When the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted with an oxygen atom or a sulfur atom. R ² and R ³ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A ¹ represents a methylene group, a secondary amine group, an oxygen atom, or a sulfur atom, and X ¹ and X ² independently represent an electron attraction X ¹ and X ² can be connected to each other to form a ring structure; In the formula, R ¹ , X ¹ , and X ^{2 have the} same definitions as above, and A ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, or an aromatic heterocyclic group, wherein the alkyl group has at least 1 In the case of each methylene group, at least one of the methylene groups may be substituted with a secondary amine group, an oxygen atom, and a sulfur atom, and the aromatic hydrocarbon group and the aromatic heterocyclic group may have a substituent.

When the light-absorbing composition of the present invention contains both the compound represented by the formula (I) and the compound represented by the formula (II), X ¹ , X ^2, and R ¹ in the formula may be different from each other. It can be the same.

In the formulae (I) and (II), R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. From the viewpoint of exhibiting high light selective absorption, it is preferably 1 to 8 carbon atoms, more preferably carbon. Alkyl groups having 1 to 5 carbon atoms are more preferred. When the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted with an oxygen atom or a sulfur atom. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, n-hexyl, n-octyl, n-decyl, methoxy, and ethyl. Oxy, isopropoxy, and polypropylene glycol groups.

In the formulae (I) and (II), X ¹ and X ² are independent of each other and represent an electron attracting group. Examples of the electron-attracting group include -CN (cyano), -NO ₂ (nitro), a halogen atom, an alkyl group substituted with a halogen atom, -Y ¹ -R ⁴ [wherein R ⁴ represents hydrogen Atoms and alkyl groups having 2 to 50 carbon atoms, in which, when the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted by an oxygen atom, and a carbon atom on the alkyl group may also be bonded. Substituents are attached; Y ¹ represents -CO-, -COO-, -OCO-, -NR ⁶ CO-, or -CONR ^7- (R ⁶ and R ⁷ each independently represent a hydrogen atom and an alkane having 1 to 6 carbon atoms Or phenyl)]]. X ¹ and X ² may also be connected to each other to form a ring structure. Examples of the ring structure include: a ring structure of 4 to 8 member rings, preferably a ring structure of 5 member ring or 6 member ring, as this example Examples include a Meldrum's acid structure, a barbituric acid structure, and a dimedone structure.

The alkyl group having 2 to 50 carbon atoms in R ⁴ preferably has a carbon number of 3 or more from the standpoint of affinity with the materials constituting the constituent members of the display device and / or solubility in various solvents. 6 or more. In addition, it is preferably 40 or less, more preferably 30 or less, and even more preferably 12 or less. The carbon number is preferably 2 to 40 (for example, 2 to 20), the carbon number is more preferably 3 to 40 (for example, 3 to 18), still more preferably 3 to 30 (for example, 3 to 16), and particularly preferably 6 To 12 (e.g. 6 to 14).

When an alkyl group having 2 to 50 carbon atoms in R ⁴ has at least one methylene group, at least one methylene group may be substituted with an oxygen atom. Examples of the alkyl group include ethoxy group and propoxy group. And 2-methoxyethoxymethyl. In addition, polyglycol groups such as a diethylene glycol group and a triethylene glycol group, and polypropylene glycols such as a dipropylene glycol group and a tripropylene glycol group are also exemplified.

A carbon atom on the alkyl group of R ⁴ may be bonded to a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, and an alkylsulfonyl group having 1 to 6 carbon atoms. , Carboxyl, fluoroalkyl with 1 to 6 carbons, alkoxy with 1 to 6 carbons, alkylthio with 1 to 6 carbons, N-alkylamino with 1 to 6 carbons, 2 with carbons N, N-dialkylamine groups of 12 to 12, N-alkylaminesulfonyl groups of 1 to 6 carbons, N, N-dialkylaminesulfonyl groups of 2 to 12 carbons, and the like.

When R ⁴ is an alkyl group having 2 to 50 carbon atoms, R ^{4 is more} preferably an alkyl group having a branched structure from the viewpoints of affinity with a hydrophobic substance and solubility in a hydrophobic solvent.

Here, an alkyl group having a branched structure means that at least one of the carbon atoms of the alkyl group is a tertiary carbon or a tertiary carbon alkyl group. Specific examples of the alkyl group having a branched structure having 3 to 12 carbon atoms include an alkyl group having the following structure.

From the viewpoint of light-selective absorptivity and affinity with the materials of the constituent members of the display device and / or solubility in various solvents, X ¹ and X ² are each preferably -CN (cyano),- NO ₂ (nitro), a halogen atom, or -Y ¹ -R ⁴ , wherein Y ¹ is -CO-, -COO-, or -OCO-, more preferably -CN (cyano), or -Y ¹ -R ⁴ , wherein Y ¹ is -COO-.

In the formula (I), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. From the viewpoint of exhibiting high light selective absorption, a hydrogen atom or carbon number 1 is preferred. Alkyl to 10, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms Radical, very preferably a hydrogen atom.

In Formula (I), A ¹ represents a methylene group, a secondary amine group, an oxygen atom, or a sulfur atom. The secondary amine group is a substituent represented by the general formula -NR ^5- , and R ⁵ represents, for example, a carbon number of 1 to 15, preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 5 and an aliphatic hydrocarbon group and a lipid. Cyclic hydrocarbon group or aromatic hydrocarbon group. From the viewpoint of exhibiting high light selective absorption, A ^{1 is} preferably a methylene group or an oxygen atom.

In the formula (II), A ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, or an aromatic heterocyclic group. When the alkyl group has at least one methylene group, at least one of the methylene group may be substituted with a secondary amine group, an oxygen atom, or a sulfur atom, and the aromatic hydrocarbon group and the aromatic heterocyclic group may have a substitution. base. Examples of the alkyl group represented by A ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, n-hexyl, methoxy, ethoxy, and isopropyloxy. Wait. Examples of the substituent which the aromatic hydrocarbon group and the aromatic heterocyclic group represented by A ² may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, and a nitro group. Such an aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The aromatic heterocyclic group is preferably an aromatic heterocyclic group having 3 to 9 carbon atoms, and examples thereof include pyridyl, quinolinyl, thienyl, imidazolyl, and the like. Oxazolyl, pyrrolyl, thiazolyl, and furyl. From the viewpoint of ease of production, A ^{2 is} preferably phenyl or naphthyl, and more preferably phenyl.

When the light-absorbing composition of the present invention contains at least two or more compounds represented by the formula (I), R ¹ to R ³ , X ¹ , X ^2, and A ^{1 in} the formula (I) representing each compound are each It may be different or the same, but at least one of R ¹ to R ³ , X ¹ , X ^2, and A ¹ is different. In a preferred embodiment of the present invention, when the light-absorbing composition of the present invention contains at least two kinds of the compound represented by the formula (I), the light-selective absorption of the light-absorbing composition of the present invention is further increased. From the viewpoint of sex, R ¹ to R ³ , X ¹ and A ^{1 in} the formula (I) representing each compound are each the same, and X ² is different. When the light-absorbing composition of the present invention contains at least two or more compounds represented by the formula (II), each of R ¹ , X ¹ , X ² and A ^{2 in} the formula (II) representing each compound may be a phase Differences can also be the same, but at least one is different. In a preferred embodiment of the present invention, when the light-absorbing composition of the present invention contains at least two or more kinds of the compound represented by the formula (II), the selective absorption of light from the light-absorbing composition of the present invention is further improved. From the viewpoint of sex, R ¹ , X ¹ and A ² in the formula (II) representing each compound are each the same, and X ² is different.

Examples of the light-selective absorbing compound represented by the formula (I) include compounds represented by the following formula.

In formula (I-1-2), A ¹ , R ¹ to R ⁴ , X ¹ and Y ¹ each have the same meaning as described above.

The light-selective absorbing compound represented by the formula (I) has the light-selective absorption property, affinity with the material of the constituent members of the display device, and / or excellent solubility in various solvents, and is preferably the following formula (I -2) The light-selective absorbing compound shown.

In formula (I-2), R ¹ and R ^{4 have the} same definitions as described above.

Specific examples of the compound represented by the formula (I-2) include the following compounds.

From the viewpoint of light selective absorption and ease of production, the light selective absorption compound represented by the formula (II) is preferably a light selective absorption compound represented by the following formula (II-2).

In the formula, R ¹ and R ⁴ have the same definitions as above.

Specific examples of the compound represented by the formula (II-2) include the following compounds.

Examples of the light-selective absorbing compound represented by the formula (II) include compounds represented by the following formula.

For the compound represented by the formula (I-2), for example, 2-methylpyrroline is made into a 1,2-dimethylpyrrolium salt by a methylating agent, and then, it is reacted with N, N'-diphenylmethyl脒 reaction. Finally, a compound represented by the formula (I-2) can be produced by reacting an active methylene compound in the presence of acetic anhydride and an amine catalyst. The compounds represented by the formulae (I) and (I-1-2) can be produced by the same method as the compound represented by the formula (I-2). The compounds represented by the formulae (II) and (II-2) can be obtained by reacting 3-methylamidinoindole with an active methylene compound (Knoevenagel reaction), and the reaction may be used in combination with an amine catalyst. When R ¹ in the formulae (II) and (II-2) is an alkyl group having 1 to 10 carbon atoms, the 3-formaminoindole is reacted with a halogenated alkyl in the presence of a base catalyst, and then reacted with an active methylene group. The compound reacts to produce the desired light-selective absorbing compound. Moreover, you may use a commercial item as these compounds.

Among the at least two kinds of light-selective absorbing compounds having the same conjugated structure contained in the light-absorbing composition of the present invention, the light-selective absorbing compound having the largest content in the light-absorbing composition is a compound _{At cmax} , the ratio of the content of the compound _cmax in the light-absorbing composition to the total amount of other light-selective absorbing compounds ([content of compound _cmax ]: [total amount of other light-selective absorbing compounds]) , Preferably 1:10 to 10: 1, more preferably 1: 8 to 8: 1, still more preferably 1: 6 to 6: 1, particularly preferably 1: 5 to 5: 1, particularly preferably 1: 4 to 4: 1, especially 1: 3 to 3: 1, such as 1: 2 to 2: 1. When the ratio is within the above range, it is possible to suppress the bleeding of the light-selective absorbing compound, and it is difficult to hinder the adhesion function as an adhesive or the optical function as an optical film.

The light-absorbing composition is excellent in affinity with a constituent member (for example, an adhesive or an optical film) of a display device and / or has excellent solubility in various solvents. When the solubility of the solvent constituting the adhesive coating liquid is excellent, the light-selective absorbing compound can be uniformly dispersed in the adhesive sheet, so that an adhesive having excellent light absorption can be obtained. Examples of the solvent include methanol, ethanol, ethylene glycol, isopropanol, 1-butanol, 2-butanol, propylene glycol, methylcythrene, butylcythrene, and propylene glycol monomethyl. Alcohol solvents such as ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, ethyl lactate; acetone, 2-butane Ketone solvents such as ketones, cyclopentanone, cyclohexanone, methylpentyl ketone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, heptane; aromatics such as toluene, xylene, and xylene Hydrocarbon solvents; nitrile solvents such as acetonitrile; tetrahydrofuran, dimethoxyethane, 1,4-bis Ether solvents such as alkane; and chlorinated hydrocarbon solvents such as dichloromethane, chloroform, and chlorobenzene.

The solvent includes a hydrophilic solvent and a hydrophobic solvent. For example, although alcohol solvents depend on the number of carbons, they are generally hydrophilic solvents. On the other hand, aliphatic hydrocarbon solvents such as pentane, hexane, and heptane are generally hydrophobic solvents. From the viewpoint of increasing the selectivity of the solvent, the light-absorbing composition is preferably soluble in a hydrophilic solvent or a hydrophobic solvent, and more preferably the light-absorbing composition is soluble in a hydrophilic solvent and hydrophobic. Solvent, that is, amphiphilic.

The light-absorbing composition of the present invention is particularly excellent in affinity with an adhesive, an optical film, and the like. When the polymer (especially an acrylic resin) constituting the adhesive has excellent affinity, it is possible to suppress the light-absorbing selective compound from exuding from the adhesive sheet, and it is difficult to hinder the adhesive function of the adhesive sheet. The light-absorbing composition of the present invention is compatible with polymers (especially, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, Polystyrene, polyfluorene, polyetherfluorene, polyvinylidene fluoride / polymethyl methacrylate, ethyl cellulose, ethylene-vinyl acetate copolymer saponification, and polyvinyl chloride) have excellent affinity and can be suppressed It is difficult to hinder the optical function of the optical film because the selective absorbing compound is exuded from the optical film. In addition, if the polymer (especially, triethyl cellulose and cycloolefin polymer) constituting the protective film has excellent affinity, the selective absorbing compound can be suppressed from exuding light from the protective film.

The light-absorbing composition preferably satisfies the following formula (1).

ε (420) / ε (400) ≦ 0.3 (1)

In the formula (1), ε (420) represents the gram absorption coefficient of the light-absorbing composition at a wavelength of 420 nm, and ε (400) represents the gram absorption coefficient of the light-absorbing composition at a wavelength of 400 nm. The value of ε (420) / ε (400) represents the absorption intensity (gram absorption coefficient) at a wavelength of 420nm relative to the absorption intensity (gram absorption coefficient) at a wavelength of 400nm. The smaller the value, the shorter the wavelength is near 420nm. Compared with the absorption in the region, it has specific absorption in the wavelength region around 400 nm, which indicates that it has light selective absorption. The smaller this value is, the less yellowish becomes a transparent compound.

When the light-absorbing composition satisfies the above formula (1), it can absorb light with a wavelength of 400 nm, but it is difficult to absorb light with a wavelength of 420 nm, and it is difficult to absorb blue visible light. Therefore, the light-absorbing composition of the present invention can provide As a light absorber that is difficult to hinder good color performance. Furthermore, when the optical laminated body contains the light-absorbing composition described above, it is possible to suppress members (for example, optical films such as retardation films, display elements such as organic EL elements and liquid crystal display elements) constituting the optical laminated body. Short-wavelength visible light (that is, light near a wavelength of 400 nm) deteriorates performance. The value of ε (420) / ε (400) in the light-absorbing composition is preferably 0.3 or less, more preferably 0.25 or less, still more preferably 0.2 or less, particularly preferably 0.15 or less, and particularly preferably 0.1. Hereinafter, it is very preferably 0.05 or less, for example, 0.03 or less. The lower limit of this value is not particularly limited, but from the viewpoint of maintaining the absorption energy around 400 nm of the light-absorbing composition, it is usually preferably 0.005 or more. In a preferred embodiment of the present invention, the value of ε (420) / ε (400) is 0.01 to 0.17.

The light-absorbing composition preferably satisfies the following formulae (2) and (3) in addition to the formula (1).

λ max ≦ 420nm (2)

ε (400) ≧ 20 (3)

In the formula (2), λ max represents the maximum absorption wavelength of the light-absorbing composition. In the formula (3), ε (400) represents the gram absorption coefficient of the light-absorbing composition at a wavelength of 400 nm, and the unit of the gram absorption coefficient is defined by L / (g‧cm).

When the above formulae (2) and (3) are satisfied, the maximum absorption of the light-absorptive composition refers to a composition that is present on a wavelength side shorter than 420 nm and exhibits high absorption around a wavelength of 400 nm. By satisfying such a formula, the light-absorbing composition described above can have members having high light resistance, such as an optical film containing the composition, which hardly affect display characteristics. In the present invention, the maximum absorption λ max of the light-absorbing composition is more preferably 410 nm or less, and still more preferably 400 nm or less. The maximum absorption λ max of the light-absorbing composition is, for example, 370 nm or more.

When the light-absorbing composition satisfies the above formula (3), the light-absorbing composition contains high light-absorbing properties. Therefore, even if the light-absorbing composition is contained in a small amount, it is contained in the adhesive. In the case of the light-absorbing composition, it is difficult to hinder the adhesion function of the adhesive, and when the light-absorbing composition is contained in the protective film, it is difficult to hinder the optical function as a protective film. The value of ε (400) is preferably 20 [L / (g‧cm)] or more, more preferably 30 [L / (g‧cm)] or more, and even more preferably 40 [L / (g‧cm) ], More preferably 50 [L / (g‧cm)] or more, particularly preferably 80 [L / (g‧cm)] or more, and very preferably 90 [L / (g‧cm)] or more. The value of ε (400) is usually 300 [L / (g‧cm)] or less.

In another aspect of the present invention, a polymer composition (hereinafter, also referred to as "the polymer composition of the present invention") containing the light-absorbing composition and the polymer is provided. By using this polymer composition, various members (for example, an adhesive sheet, a protective film, a polarizing film, a retardation film, a front panel, etc.) which comprise an optical laminated body can be obtained. Since the optical laminated body contains the light-absorbing composition having excellent light selective absorption, and it is difficult to absorb blue visible light, it is difficult to hinder good color performance. In addition, the performance of display elements and optical films that are components of display devices is not only ultraviolet, but even visible light in a short wavelength region, that is, light near a wavelength of 400 nm, will deteriorate its performance. The components constituting the optical laminate can suppress deterioration caused by visible light passing through a short wavelength.

The thickness of the optical film of the present invention is not particularly limited, but it is usually preferably 18 μm or less, more preferably 13 μm or less, and still more preferably 8 μm or less. When the thickness of the optical film is equal to or less than the above-mentioned upper limit value, even if the concentration of the light-absorptive composition contained in the optical film is high, bleeding does not occur. Therefore, it is easy to obtain a thin optical laminated body, and it can also play a role Stable light absorption and functions of the optical film (for example, retardation function of the retardation film and adhesion function of the adhesive sheet). The lower limit value of the thickness of the optical film of the present invention is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 2 μm or more. When the thickness of the optical film is equal to or less than the above upper limit, it is preferable from the viewpoint of thinning. The thickness of the optical film can be measured by, for example, a laser microscope, an ellipsometer, or the like.

In another embodiment of the present invention, an adhesive and an optical film (also referred to as "the optical film of the present invention") composed of the polymer composition are also provided. In the present invention, examples of the optical film include a polarizing film, a retardation film, a protective film, an adhesive sheet, and a front panel. Examples of such optical films and adhesives are members constituting the optical laminate. In addition, in the present invention, the optical laminated body means a laminated body containing the optical film of the present invention, and includes a laminated polarizing film, a laminated retardation film, and an elliptical polarizing film described later.

Here, regarding the optical laminated body, the schematic sectional drawing which shows an example of several preferable layer structures in FIG.1 and FIG.2. The example shown in FIG. 1 is a case where the first protective film 4 which can have the surface treatment layer 2 is attached to one surface of the polarizing film 1 with the surface opposite to the surface treatment layer 2, and the other On the surface, a second protective film 3 is attached to form a polarizing plate 10. An adhesive sheet 20 is provided on the outside of the second protective film 3 constituting the polarizing plate 10, and a polarizing plate 15 with an adhesive is formed. Next, the surface of the adhesive sheet 20 on the side opposite to the polarizing plate 10 is adhered to the image display element 30 to further constitute an optical laminated body 40. The optical laminated body is applicable to an image display device. In addition, a member containing the light-absorbing composition of the present invention is more suitable to be arranged on the viewing side than an image display element such as an optical film or an organic EL element which is liable to deteriorate. With this arrangement, it is possible to suppress a reduction in the function of a component that is easily deteriorated.

In the example shown in FIG. 2, the first protective film 4 that can have the surface treatment layer 2 is attached to one surface of the polarizing film 1 with a surface opposite to the surface treatment layer 2, and the polarizing film 1 On the other surface, a second protective film 3 is attached, and on the outside of the second protective film 3, a retardation film 7 is attached through an interlayer adhesive 6 to form a polarizing plate 10. An adhesive sheet 20 is provided on the outside of the retardation film 7 constituting the polarizing plate 10, and a polarizing plate 15 with an adhesive is formed. Next, the surface of the adhesive sheet 20 on the side opposite to the retardation film 7 is bonded to the image display element 30 to form an optical laminated body 40.

In these examples, the first protective film 4 and the second protective film 3 are generally composed of a triethylammonium cellulose film or a polycycloolefin, but they may also be composed of a transparent resin film as described below. The surface treatment layer that can be formed on the surface of the first protective film 4 may be a hard coat layer, an anti-glare layer, an anti-reflection layer, an antistatic layer, or the like. A plurality of these layers may be provided.

As shown in the example of FIG. 2, when the retardation film 7 is laminated on the polarizing plate 10, if the liquid crystal display device is a small-to-medium-sized liquid crystal display device, a quarter wave plate may be used as a preferred example of the retardation film 7. At this time, it is generally arranged that the absorption axis of the polarizing film 1 and the slow axis of the retardation film 7 belonging to the 1/4 wavelength plate cross at almost 45 degrees. However, depending on the characteristics of the image display element 30, this angle is also 45 degree shift. On the other hand, in the case of a large liquid crystal display device such as a television, a phase difference film having various phase difference values is used in accordance with the characteristics of the image display element 30 for the purpose of phase difference compensation or viewing angle compensation of the image display element 30. At this time, it is generally arranged such that the absorption axis of the polarizing film 1 and the slow axis of the retardation film 7 have a nearly vertical or almost parallel relationship. When the retardation film 7 is constituted by a quarter-wave plate, a uniaxially or biaxially stretched film is suitably used. In addition, when the retardation film 7 is provided for the purpose of phase difference compensation or viewing angle compensation of the image display element 30, as a user of the retardation film 7, in addition to a uniaxial or biaxially stretched film, it may be: Films that are aligned in the thickness direction in addition to the axial or biaxial extension, films that are coated with a phase difference expressing substance such as liquid crystal on a support film, and are fixed by alignment are called optical compensation films.

As in the example shown in FIG. 2, when the retardation film 7 is bonded through the interlayer adhesive 6 in the configuration of the polarizing plate 10, a common example of this interlayer adhesive 6 is the use of a general acrylic adhesive. It is also possible to use an adhesive or an adhesive sheet composed of the polymer composition of the present invention. When the large-scale liquid crystal display device described above is arranged such that the absorption axis of the polarizing film 1 and the slow axis of the retardation film 7 are almost perpendicular or nearly parallel, when the polarizing plate 10 is manufactured, the polarizing film 1 and the phase When the differential film 7 is bonded by the interlayer adhesive 6, roll-to-roll bonding can be performed.

A retardation film with an adhesive sheet and an adhesive is formed on the retardation film. In addition to adhering the adhesive sheet to the image display element to become an optical laminate, it can also be pasted on the retardation film side. Polarizer.

Here, a polarizing film (also referred to as a “polarizing element”) refers to an optical film having a function of emitting polarized light to incident light such as natural light. A polarizing plate has a linear polarizing plate that absorbs linearly polarized light having a vibrating surface that is incident on the polarizing plate surface and penetrates the linearly polarized light having a vibrating surface perpendicular to the polarizing plate; The linearly polarized light of the directional vibration plane is a polarized light separation film having the property of penetrating the linearly polarized light of the perpendicular vibration plane; the elliptical polarizer is laminated with a polarizer and a retardation film described later. As a specific example of a polarizing plate, particularly a linear polarizing plate (also referred to as a polarizing element or a polarizing element film), a uniaxially stretched polyvinyl alcohol-based resin film can be adsorbed and aligned with iodine or a dichroic dye. Those with dichroic pigments. Alternatively, a coating-type thin film polarizing film may be used. As the coating-type thin film polarizing film, for example, exemplified in Japanese Patent Application Laid-Open No. 2012-58381, Japanese Patent Application Laid-Open No. 2013-37115, International Publication No. 2012/147633, and International Publication No. 2014/091921 can be used. The thickness of the polarizer is not particularly limited, and a thickness of 0.5 to 35 μm is usually used.

The retardation film refers to an optical film exhibiting optical anisotropy, and examples thereof include polyvinyl alcohol, polycarbonate, polyester, polyarylate, polymethacrylate, polyimide, and polyolefin. , Polycycloolefins (polymers of norbornene or tetracyclododecene or derivatives thereof), polystyrene, polyfluorene, polyetherfluorene, polyvinylidene fluoride / polymethyl methacrylate, liquid crystal polymer Polymer films made from polymers such as esters, acetocellulose, saponified ethylene-vinyl acetate copolymers, and polyvinyl chloride, are stretched films obtained by stretching about 1.01 to 6 times. Among these, a polymer film in which a polycarbonate film or a polycycloolefin film is uniaxially stretched or biaxially stretched is preferred. In one aspect of the present invention, a phase is obtained by forming a composition containing the polymer and the light-absorbing composition of the present invention into a film, and uniaxially or biaxially extending the obtained film. Poor film. Moreover, a film which exhibits optical anisotropy by coating / alignment of a polymerizable liquid crystal compound can also be used as a retardation film.

Furthermore, a protective film is attached to these optical films, and it can also be used as an optical film. As the protective film, a transparent resin film is used. Examples of the transparent resin include ethyl acetate cellulose resins represented by triethyl cellulose and diethyl cellulose, and polymethyl methacrylate as examples. Typical methacrylic resins, polyester resins, polyolefin resins, polycarbonate resins, polyetheretherketone resins, polyfluorene resins, and the like. In the resin constituting the protective film, ultraviolet rays such as a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a triazine-based compound, a cyanoacrylate-based compound, and a nickel salt-based compound may be blended. The absorbent at this time can appropriately suppress deterioration of the display device by an effect multiplied by the effect of the light-absorbing composition of the present invention. As the protective film, an ethyl acetate cellulose-based resin film such as a triethyl acetate cellulose film can be suitably used.

Among the optical films described above, a linear polarizing plate is often used in a state where a protective film is attached to one or both sides of a polarizing film constituting the polarizing film, for example, a polarizing plate containing a polyvinyl alcohol resin. In addition, the aforementioned elliptical polarizing plate is composed of a linear polarizing plate and a retardation film. However, most of the polarizing plates are in a state where a protective film is attached to one or both sides of the polarizing plate.

A protective film is a film used for the purpose of protecting the surface of an optical film or the like belonging to a protected body from being damaged or soiled. Examples of the base material of the protective film include polyolefins such as polyethylene, polypropylene, and polymethylpentene; fluorinated polyolefins such as polyvinyl fluoride, polyvinylidene fluoride, and polyvinyl fluoride; and polyethylene naphthalate Polyesters such as polyesters, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymers; nylon 6, nylon 6,6, etc. Polyamines; polyvinyl polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polyvinyl alcohol, and vinylon; triethylamidine Cellulose polymers such as cellulose, diacetyl cellulose, cellophane, and triethyl cellulose; polymethylmethacrylate, polyethylmethacrylate, polyethylacrylate, polybutylacrylate, etc. Acrylic polymer; others such as polystyrene, polycarbonate, polyarylate, polyimide, polyurethane, etc.

An adhesive sheet refers to a sheet containing an adhesive. The adhesive is an agent for bonding a member such as the optical film to another member. The polymer constituting the adhesive is not particularly limited, and examples thereof include poly (meth) acrylate (acrylic resin), silicone polymer, polyurethane, and rubber. The above polymers can be used alone or in combination. Among them, an acrylic resin is preferably used as the polymer from the viewpoint that the functionality of the adhesive can be easily imparted by selecting the type of the monomer introduced into the polymer. In addition, (meth) acrylate means an acrylate and / or a methacrylate.

By using the polymer composition of this invention, each member which comprises an optical laminated body can be obtained. For example, in one embodiment of the present invention, it is composed of a polymer composition containing the light-absorbing composition and polymer of the present invention, and an adhesive sheet, a protective film, a retardation film, a polarizing film, and a front film can be provided. Panel, etc.

The polymer contained in the polymer composition is preferably selected from the above-mentioned acrylic resin [poly (meth) acrylate], polyurethane, polyester, At least one of the group consisting of polycarbonate, polycycloolefin, and triethyl cellulose.

When a UV absorber is prepared in the adhesive sheet (especially when a high concentration is prepared), the adhesive function of the adhesive sheet may be hindered. However, the adhesive sheet composed of the polymer composition of the present invention can maintain adhesion. Function, and excellent light selective absorption. Furthermore, it can suppress the bleeding of the adhesive sheet, so it exhibits stable light absorption over a long period of time. In a display device using this adhesive sheet, it is not necessary to dispose another member having a light absorbing function, so that the thickness and weight of the display device can be reduced.

In one aspect of the present invention, the polymer composition may contain a cross-linking agent in addition to the polymer and the light-absorbing composition as required. The crosslinking agent is, for example, a compound that reacts with a constituent unit derived from a poly (meth) acrylate, particularly a monomer containing a hydroxyl group or a polar functional group, to crosslink the poly (meth) acrylate. Specific examples include isocyanate-based compounds, epoxy-based compounds, aziridine-based compounds, metal chelate compounds, and the like. Among these, isocyanate-based compounds, epoxy-based compounds, and aziridine-based compounds have at least two hydroxyl groups in the molecule that can interact with the poly (meth) acrylate (A) and polar functional groups depending on the occasion. Reactive functional group.

The content of the light-absorbing composition (preferably the total amount of light-selective absorbing compounds contained in the light-absorbing composition) with respect to 100 parts by mass of the polymer (solid content) in the polymer composition, It is preferably 1 to 15 parts by mass, more preferably 1.5 to 12 parts by mass, still more preferably 2 to 10 parts by mass, and particularly preferably 2.2 to 8 parts by mass. When the content of the light-absorbing composition is greater than or equal to the above-mentioned lower limit, the amount of absorbed light increases, and it is possible to suppress components (for example, optical films such as retardation films, image display devices such as organic EL elements) constituting the optical laminate. Deterioration caused by short-wavelength visible light. When the content of the light-absorbing composition is equal to or less than the above-mentioned upper limit value, the adhesive function can be sufficiently exhibited when the polymer composition is used as the adhesive, and it is more difficult to hinder the optical function of the optical film obtained by using the polymer composition. . In addition, since the light-absorbing composition has excellent solubility in various solvents, even if the content is high (for example, the light-absorbing composition (preferably, with respect to 100 parts by mass of the polymer (solid content)) The content of the total amount of light-selective absorbing compounds contained in the light-absorbing composition is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, still more preferably 2 parts by mass or more, and particularly preferably 2.2 parts by mass Or more), it is still possible to suppress bleeding, and it is difficult to hinder the adhesion function as an adhesive or the optical function as an optical film.

When the polymer composition of the present invention is an adhesive composition constituting an adhesive sheet, in a preferred embodiment of the present invention, the polymer composition of the present invention contains: (A) an acrylic resin The total solid content of the resin (polymer) is based on 50 to 99.9% by mass of the (meth) acrylate monomer represented by the following formula (A-1), and (A-2) has a polar functional group. A copolymer of 0.1 to 50% by mass of an unsaturated monomer as a constituent component, an acrylic resin having a weight-average molecular weight of 500,000 to 2 million; and (B) a crosslinking agent, based on 100 parts by mass of the aforementioned acrylic resin, containing 0.01 To 10 parts by mass.

In the aforementioned formula (A-1), R ^p is a hydrogen atom or a methyl group. R ^q represents an alkyl or aralkyl group having 1 to 20 carbon atoms, preferably an alkyl or aralkyl group having 1 to 10 carbon atoms. The hydrogen atom constituting the alkyl group or the aralkyl group may be -O- (C ₂ H ₄ O) _n -R ^r substitution. Here, n is preferably 0 to 4, more preferably an integer of 0 to 3. R ^{r is} preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and more preferably carbon. The aryl group having 1 to 12 is more preferably an aryl group having 1 to 10 carbon atoms.

As a (meth) acrylic acid ester monomer (A-1) represented by the said Formula (A-1) (henceforth, it may be called "monomer (A-1)"). Specifically, the acrylic acid methyl ester is illustrated. Linear alkyl acrylates such as esters, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, and lauryl acrylate; isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, etc. Branched alkyl acrylates; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate, etc. Alkyl methacrylate; branched methacrylates such as isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, etc .; phenyl acrylate, benzyl acrylate And other acrylates with aromatic groups; 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, phenoxy acrylate, phenyl methacrylate, benzyl methacrylate, etc. Aromatic methacrylate and the like. These can be used alone or in combination. Among them, n-butyl acrylate is preferred from the standpoint of adhesiveness.

In the unsaturated monomer (A-2) having a polar functional group (hereinafter referred to as "monomer (A-2)"), examples of the polar functional group include a free carboxyl group, a hydroxyl group, and an amine group. , A heterocyclic group containing an epoxy ring, and the like. The monomer (A-2) is preferably a (meth) acrylic compound having a polar functional group. Examples of this include unsaturated monomers having free carboxyl groups such as acrylic acid, methacrylic acid, and β-carboxyethyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Hydroxy unsaturated monomers such as propyl ester, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, and diethylene glycol mono (meth) acrylate; acrylic fluorenyl morpholine, vinyl hexamethylene Lactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl (meth) acrylate, caprolactam modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (methyl Group) acrylate, epoxypropyl (meth) acrylate, and 2,5-dihydrofuran and other unsaturated monomers having a heterocyclic group; N, N-dimethylaminoethyl (meth) acrylic acid An unsaturated monomer having an amine group, such as an ester, is different from a heterocyclic ring. These monomers (A-2) may be used individually, or a plurality of different kinds may be used.

Among these, from the viewpoint of improving the adhesion of the adhesive composition and further improving the durability, it is preferable to contain an unsaturated monomer having a hydroxyl group as one monomer (A) constituting the acrylic resin (A). -2).

The acrylic resin using the monomer (A-1) and the monomer (A-2) as constituent units (hereinafter referred to as the "acrylic resin (A)") is based on the total amount of the solid components. The constituent unit derived from the monomer (A-1) is contained in a ratio of preferably 50 to 99.9% by mass, and more preferably 70 to 99.9% by mass. The constituent unit derived from the monomer (A-2) is contained in a ratio of preferably 0.1 to 50% by mass, and more preferably 0.1 to 30% by mass. When the ratio of the monomer (A-1) to the monomer (A-2) is within the aforementioned range, an adhesive composition having excellent processability can be provided.

In addition, the acrylic resin (A) may contain other monomers (hereinafter referred to as "monomers (A- 3) "). Examples of other monomers include (meth) acrylates having an alicyclic structure in the molecule, styrene-based monomers, vinyl-based monomers, and a plurality of (meth) acrylfluorenyl groups in the molecule. Monomers, (meth) acrylamide derivatives, and the like.

The alicyclic structure refers to a cycloalkane structure having a carbon number of usually 5 or more, preferably about 5 to 7. Specific examples of the acrylate having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentyl acrylate, cyclododecyl acrylate, methyl cyclohexyl acrylate, and trimethyl acrylate. Cyclohexyl ester, tertiary butyl cyclohexyl acrylate, α-ethoxy cyclohexyl acrylate, cyclohexyl phenyl acrylate, and the like; specific examples of methacrylic acid esters having an alicyclic structure include: Isobornyl acrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecyl methacrylate, methyl cyclohexyl methacrylate, trimethylcyclohexyl methacrylate, formazan Tert-butyl cyclohexyl acrylate, cyclohexyl phenyl methacrylate, and the like.

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

Examples of the vinyl-based monomer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl caseinate, vinyl 2-ethylhexanoate, and vinyl laurate; and ethylene such as vinyl chloride and ethylene bromide. Vinyl halide; vinylidene chloride, vinylidene chloride; vinyl pyridine, vinyl pyrrolidone, vinyl carbazole and other nitrogen-containing aromatic ethylene; butadiene, isoprene, chloroprene, etc. Olefin monomers; furthermore, acrylonitrile, methacrylonitrile, and the like.

Examples of the monomer having a plurality of (meth) acrylfluorene groups in the molecule include 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate , 1,9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate and other monomers having two (meth) acrylfluorene groups in the molecule; trimethylolpropane tri (meth) acrylate and other monomers having 3 (methyl) in the molecule ) Acrylic fluorenyl monomers and the like.

Examples of the (meth) acrylamide derivative include N-hydroxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, and 3-hydroxypropyl (meth) acryl Ammonium amine, 4-hydroxybutyl (meth) acrylamide, 5-hydroxypentyl (meth) acrylamide, 6-hydroxyhexyl (meth) acrylamide, N-methoxymethyl (methyl Acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide , N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-dimethylamine Propyl (meth) acrylamide, N- (1,1-dimethyl-3-ketobutyl) (meth) acrylamide, N- [2- (2-oxo-1- Imidazolidinyl) ethyl] (meth) acrylamide, 2-propenylamino-2-methyl-1-propanesulfonic acid, and the like.

The monomer (A-1), the monomer (A-2), and the monomer (A-3) may be used alone or in combination. In the present invention, the acrylic resin (A) usable in the adhesive composition is derived from the constituent units of the monomer (A-3) based on the total amount of the solid content of the acrylic resin (A). It is contained in a ratio of 0 to 20 parts by mass, preferably 0 to 10 parts by mass.

In one embodiment of the present invention, the adhesive composition may contain one type or two or more types of the acrylic resin (A).

The weight average molecular weight (Mw) of the aforementioned acrylic resin (A) by standard polystyrene conversion by gel permeation chromatography (GPC) is preferably 500,000 to 2 million, and more preferably 600,000 to 1.8 million. Even more preferred is 700,000 to 1.7 million. When the weight average molecular weight in terms of this standard polystyrene is 500,000 or more, the adhesion under high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate (image display device) and the adhesive sheet is reduced. It is preferred because the reworkability tends to be improved. When the weight average molecular weight is 2 million or less, when the adhesive sheet is bonded to an optical film or the like, even if the size of the optical film changes, the adhesive sheet changes in accordance with the size change. There is no difference between the brightness of the surrounding portion of the image display element and the brightness of the central portion, and it is preferable to suppress white spots and color unevenness. The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually in the range of about 2 to 10.

The acrylic resin (A) can be produced separately, for example, by various known methods such as a solution polymerization method, an emulsion polymerization method, a block polymerization method, and a suspension polymerization method. In the production of this acrylic resin, a polymerization initiator is usually used. The polymerization initiator is used in an amount of about 0.001 to 5 parts by mass based on 100 parts by mass of the total of all the monomers used in the production of the acrylic resin.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like can be used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like. Examples of the thermal polymerization initiator include: 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclo Hexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxy) Azovaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-hydroxymethylpropionitrile) and other azo compounds; Lauryl peroxide, tert-butyl hydroperoxide, benzoamidine peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxide dicarboxylic acid, dicarboxylic peroxide Organic peroxides such as dipropyl acid, tert-butyl peroxyneodecanate, tert-butyl peroxypivalate, (3,5,5-trimethylhexyl) peroxide; persulfuric acid Inorganic peroxides such as potassium, ammonium persulfate, and hydrogen peroxide. In addition, a redox-based initiator in which a peroxide and a reducing agent are used in combination can also be used as a polymerization initiator.

As a method for producing the acrylic resin (A), among the methods described above, a solution polymerization method is preferred. When a specific example of the solution polymerization method is given for explanation, it may be mentioned that a desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added under a nitrogen environment, and the temperature is about 40 to 90 ° C, preferably 50 to 80. Method of stirring for about 3 to 15 hours at about ℃. In addition, in order to control the reaction, the monomer and the thermal polymerization initiator are added to the polymerization continuously or intermittently, and may be added in a state of being dissolved in an organic solvent. Here, as the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone and 2-butanone Ketones such as methyl isobutyl ketone and the like.

The adhesive composition may contain an acrylic resin different from the acrylic resin (A) in addition to the acrylic resin (A). As such an acrylic resin, for example, a (meth) acrylate-based structural unit (for example, poly (meth) acrylate) is used as a main component, and the weight average molecular weight is, for example, 50,000 to 300,000. The range is lower.

When the adhesive composition contains an acrylic resin different from the acrylic resin (A), the content of the acrylic resin different from the acrylic resin (A) is usually 50 parts by mass or less with respect to 100 parts by mass of the acrylic resin (A). It is more preferably 30 parts by mass or less.

The acrylic resin contained in the adhesive composition (a mixture of two or more types) is dissolved in ethyl acetate, and the solid content concentration is adjusted to a solution of 20% by mass, preferably at 25 ° C. The display concentration is 20 Pa · s or less, and more preferably a viscosity of 0.1 to 7 Pa · s. When the viscosity at this time is 20 Pa · s or less, the adhesion under high temperature and high humidity is improved, the possibility of floating or peeling between the display element and the adhesive sheet tends to be low, and the reworkability is improved. Therefore, it is better. Viscosity can be measured by a Brookfield viscometer.

In the adhesive composition, as the cross-linking agent, for example, an acrylic resin (A) may be reacted with a constituent unit derived from an unsaturated monomer having a polar functional group, and the acrylic resin (A) may be used. Crosslinked compounds. Specific examples include isocyanate-based compounds, epoxy-based compounds, Aziridine-based compounds, metal chelate compounds, and the like. Among these, the isocyanate-based compound, epoxy-based compound, and aziridine-based compound have at least two functional groups in the molecule that can react with the polar functional group in the acrylic resin (A).

The isocyanate-based compound is a compound having at least two isocyanate groups (-NCO) in the molecule, and examples thereof include toluene diisocyanate, hexamethylene diisocyanate, isoflurone diisocyanate, and xylene diisocyanate. Esters, hydrogenated diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. In addition, adducts obtained by reacting these isocyanate-based compounds with polyols such as glycerin or trimethylolpropane, or dimers, trimers, etc. of isocyanate-based compounds can also be used as adhesives.联 剂。 Union agent. You may mix and use 2 or more types of isocyanate-type compounds.

The epoxy-based compound is a compound having at least two epoxy groups in the molecule, and examples thereof include bisphenol A epoxy resin, ethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl. Ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N-bicyclo Oxypropylaniline, N, N, N ', N'-tetraepoxypropyl-m-xylylenediamine, 1,3-bis (N, N'-diepoxypropylaminomethyl) cyclohexyl Alkanes, etc. Two or more types of epoxy compounds may be used in combination.

The aziridine-based compound is a compound that is also called ethyleneimine and has at least two three-membered rings containing one nitrogen atom and two carbon atoms in the molecule. Examples include diphenylmethane- 4,4'-bis (1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylene ethylmelamine, m-xylylenediamine bis-1 -(2-methylaziridine), ginsane-1-aziridinylphosphine oxide, hexamethylene-1,6-bis (1-aziridinylformamide), trimethylolpropane- Tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and the like.

Examples of the metal chelate compound include, for example, aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, and other polyvalent metals coordinated with acetamidine or ethyl Compounds of ethyl acetoacetate and the like.

Among these cross-linking agents, isocyanate-based compounds, in particular, ditolyl diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate, or these isocyanate-based compounds and glycerol can be preferably used. Or an adduct obtained by reacting a polyhydric alcohol such as trimethylolpropane, or a mixture of an isocyanate-based compound as a dimer, a trimer, or the like, and mixing these isocyanate-based compounds. Preferred isocyanate-based compounds include toluene diisocyanate, an adduct obtained by reacting toluene diisocyanate with a polyol, a dimer of toluene diisocyanate, and a terpolymer of toluene diisocyanate, and diisocyanate. Hexamethylene, an adduct obtained by reacting hexamethylene diisocyanate with a polyol, a dimer of hexamethylene diisocyanate, and a tris of hexamethylene diisocyanate Polymer. These can be used alone or in combination of two or more.

In the present invention, the adhesive composition preferably contains 0.01 to 10 parts by mass relative to 100 parts by mass of the solid content of the aforementioned acrylic resin (a total of 100 parts by mass when it contains two or more acrylic resins). The crosslinking agent is 0.01 to 0.08 parts by mass, and more preferably 0.01 to 0.06 parts by mass. When the amount of the cross-linking agent is 0.01 parts by mass or more, the durability of the adhesive sheet tends to be improved, so it is preferable. When it is 10 parts by mass or less, the adhesive obtained from the adhesive composition is applied to a liquid crystal display. The white point on the device becomes inconspicuous.

In the present invention, the adhesive composition preferably contains a silane-based compound, and particularly preferably, the acrylic resin before the crosslinking agent is contained contains a silane-based compound. Since the silane-based compound improves the adhesion to the glass, by including the silane-based compound, the adhesion between the display element and the adhesive sheet sandwiched in the glass substrate can be improved.

Examples of the silane-based compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, and N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidylpropyltrimethoxysilane, 3-glycidylpropyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloro Propylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylmethyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-epoxy Propylpropyltrimethoxysilane, 3-glycidylpropyltriethoxysilane, 3-glycidylpropyldimethoxymethylsilane, 3-glycidylpropylethoxy Dimethylsilane and so on. These can be used alone or in combination of two or more.

The silane-based compound may be a siloxane oligomer type. When a siloxy oligomer is represented as a (monomer) oligomer, the following is mentioned, for example.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxyoxide Mercaptopropyl-containing copolymers such as 3-mercaptosilane and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercapto Methyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer, etc. Copolymers containing mercaptomethyl; 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxy Silane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer Compound, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyl Methoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-methacryloxypropyl Copolymers containing methacryloxypropyl, such as methyldiethoxysilane-tetraethoxysilane copolymer; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropane Triethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyldi Methoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-propenyloxypropylmethyldiethyl Copolymers containing acryloxypropyl, such as ethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane- Ethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane Methoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, and vinylmethyldiethylene Copolymers containing vinyl groups such as oxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethylene Ethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-amine Propylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldi Copolymers containing amine groups, such as ethoxysilane-tetramethoxysilane copolymers and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymers.

The blending amount of the silane-based compound in the adhesive composition is usually about 0.01 to 10 parts by mass, based on 100 parts by mass of the solid content of the acrylic resin (the total amount is 100 parts by mass when two or more kinds are used). A ratio of 0.01 to 5 parts by mass is used. When the amount of the silane-based compound is 0.01 parts by mass or more with respect to 100 parts by mass of the solid content of the acrylic resin, it is preferable to improve the adhesion between the adhesive sheet and the display element. In addition, when the amount is 10 parts by mass or less, it is preferable because the silane-based compound tends to be inhibited from exuding from the adhesive sheet.

In addition, the adhesive composition may contain a crosslinking catalyst, an antistatic agent, an antioxidant, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and a resin other than an acrylic resin. . Examples of the antioxidant include hydroquinone, dibutylhydroxytoluene, 2,2'-methylenebis (6-thirdbutyl-4-cresol), 3,9-bis [2- [3- (3-Third-butyl-4-hydroxy-5-methylphenyl) propanyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [ 5,5] undecane, 1,3,5-ginseng (3,5-di-third-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione, 6,6'-di-third-butyl-4,4'-butenyl di-m-cresol and other phenolic antioxidants; triisodecyl phosphite, phosphite (4-nonylphenyl) ester, 2,2'-methylenebis (4,6-di-third-butylphenyl) 2-ethylhexyl phosphite, and (2,4- Phosphorus-based antioxidants such as di-third butylphenyl) ester; 3,3'-thiodipropionate di (tridecyl) ester, bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxapropoxy] methyl] -1,3-propanediyl, bis [3- (dodecylthio) Propionic acid] 2,2-bis [[3- (dodecylthio) -1-sideoxypropoxy] methyl] -1,3-propanediyl and other sulfur-based antioxidants; methacrylic acid 2,2,6,6-tetramethyl-4-piperidine, methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidine, bis (2,2,6,6- Tetramethyl-1-undecyloxypiperidin-4-yl) ester, butane-1,2,3,4-tetracarboxylic acid (1,2,2,6,6-pentamethyl- 4-piperidinyl) esters and other amine-based inhibitors.

In addition, it is also useful to mix an ultraviolet curable compound in the adhesive composition and irradiate ultraviolet rays after the formation of the adhesive sheet to cure the adhesive sheet to make it a harder adhesive sheet. Among them, if the cross-linking agent and the cross-linking catalyst are mixed together in the adhesive composition, the adhesive sheet can be prepared by short-term ripening. In the obtained optical laminated body, there is a polarizing plate or a protection that can be suppressed. The occurrence of floating or peeling between the film and the adhesive sheet, the occurrence of foaming in the adhesive sheet is suppressed, and the reworkability also becomes good. Examples of the crosslinking catalyst include hexamethylenediamine, ethylenediamine, polyethylenimine, hexamethylenetetramine, diethylenetriamine, and triethylenetetramine. Amine compounds such as isoflurone diamine, trimethylene diamine, polyamine resin, and melamine resin. When an amine-based compound is formulated as a crosslinking catalyst in the adhesive composition, an isocyanate-based compound is preferably used as the crosslinking agent.

Each of the components constituting the adhesive may be dissolved in a solvent to form the adhesive composition. Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cyperidine, butyl cyperidine, and propylene glycol monomethyl ether; ethyl acetate and acetic acid Ester solvents such as butyl ester, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, ethyl lactate; acetone, 2-butanone, methyl isobutyl ketone, cyclic Ketone solvents such as pentanone, cyclohexanone, methylpentyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitriles such as acetonitrile Solvents; ether solvents such as tetrahydrofuran and dimethoxyethane; and chlorinated hydrocarbon solvents such as chloroform and chlorobenzene. Among these, 2-butyl ketone, methyl isobutyl ketone, and the like are preferred from the viewpoint of the solubility of each component and the reduction in environmental load.

For the adhesive sheet, for example, the above-mentioned adhesive composition can be used as an organic solvent solution, and the solution can be laminated on a film or layer (such as a polarizing plate or a protective film) by a die coater or a gravure coater. Film, etc.). In addition, the sheet-shaped adhesive formed on the plastic film (also referred to as a separation film) subjected to a release treatment may be laminated and transferred to the film or layer.

According to another aspect of the present invention, there is provided a laminated polarizing film including the optical film of the present invention and a polarizing film (also referred to as a "laminated polarizing film of the present invention"). Here, the polarizing film refers to an optical film having a function of emitting polarized light to incident light such as natural light. The polarizing film is a linear polarizing film that absorbs linearly polarized light having a vibrating surface that is incident on the film surface and penetrates the linearly polarized light having a vibrating surface perpendicular to the polarizing film. The linearly polarized light of a vibrating surface in a certain direction allows a polarized light separation film having the property of penetrating the linearly polarized light perpendicular to its vibrating surface; an elliptical polarizing plate having a polarizing film and a retardation film described later is laminated. As a specific example of the polarizing film, particularly a linear polarizing film (also referred to as a polarizing element), a uniaxially stretched polyvinyl alcohol-based resin film or a polymer of a polymerizable liquid crystal compound is adsorbed and aligned with iodine or Those with dichroic dyes such as dichroic dyes. The laminated polarizing film is a laminated optical film containing a polarizing film and the optical film of the present invention, such as an adhesive sheet, a protective film, and a retardation film. A laminated optical film containing a polarizing film and an adhesive sheet, particularly a laminated optical film in which an adhesive sheet is laminated on a polarizing film, also referred to as a polarizing plate with an adhesive.

The laminated polarizing film of the present invention preferably satisfies the following formula (4).

Ap (400) ≧ 0.4 (4)

In the formula (4), Ap (400) represents the absorbance in the direction of the transmission axis of the polarizing film at a wavelength of 400 nm. The larger the value of Ap (400), the higher the absorption at the wavelength of 400nm. When this value is less than 0.4, the absorption at the wavelength of 400nm is weak, and it is difficult to ensure sufficient high light resistance to short-wavelength visible light near 400nm. Therefore, the value of Ap (400) in the laminated polarizing film of the present invention is preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.8 or more, still more preferably 1 or more, and particularly preferably 1.2 or more. It is particularly preferably 1.5 or more, and very preferably 1.8 or more, such as 2 or more. The upper limit of the value of Ap (400) is not particularly limited, but it is usually preferably 5 or less from the viewpoint of suppressing the bleeding of the light-absorbing composition in the laminated polarizing film.

The laminated polarizing film of the present invention preferably satisfies the following formula (5).

Ap (420) / Ap (400) ≦ 0.3 (5)

In the formula (5), Ap (400) represents the absorbance in the transmission axis direction of the polarizing film at a wavelength of 400 nm, and Ap (420) represents the absorbance in the transmission axis direction of the polarizing film at a wavelength of 420 nm. The value of Ap (420) / Ap (400) indicates that the absorption intensity at a wavelength of 420nm is relative to the absorption intensity at a wavelength of 400nm. The smaller this value is, the smaller the value is, compared with the absorption in the wavelength region near 420nm. Specific absorption in the wavelength region. The smaller this value is, the less yellowish it is, and there is a tendency to obtain a transparent laminated polarizing film.

When the laminated polarizing film satisfies the above formula (5), it can absorb light with a wavelength of 400 nm, but it is difficult to absorb light with a wavelength of 420 nm, and it is difficult to absorb blue visible light. Therefore, it is difficult to hinder good color performance, and it can further reduce blue light. Features. When the above-mentioned laminated polarizing film is combined in the optical laminated body, it is possible to suppress members (for example, optical films such as retardation films, display elements such as organic EL elements or liquid crystal display elements) constituting the optical laminated body from having short wavelengths. Visible light (that is, light near a wavelength of 400 nm) can cause degradation in performance. The value of Ap (420) / Ap (400) in the laminated polarizing film is preferably 0.25 or less, more preferably 0.2 or less, and still more preferably 0.15 or less, such as 0.1 or less. The lower limit of this value is not particularly limited, but from the viewpoint of maintaining the absorption energy around 400 nm of the multilayer polarizing film, it is usually preferably 0.01 or more. In a preferred embodiment of the present invention, the value of Ap (420) / Ap (400) is 0.05 to 0.15.

According to another aspect of the present invention, there is provided a laminated retardation film (also referred to as a "laminated retardation film of the present invention") including the optical film of the present invention and a laminated retardation film. Here, the retardation film is an optical film showing optical anisotropy, and examples thereof include polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, and polycycloolefin. Polymer films such as polystyrene, polyfluorene, polyetherfluorene, polyvinylidene fluoride / polymethyl methacrylate, ethyl cellulose, vinyl-vinyl acetate copolymer saponification, polyvinyl chloride, etc. A stretched film or the like obtained by stretching to about 1.01 to 6 times. Among these, a polymer film in which a polycarbonate film and a cycloolefin-based resin film are uniaxially stretched or biaxially stretched is preferred. When the optical laminate in the present invention contains a retardation film, it is preferable to include a retardation film exhibiting optical anisotropy by coating / aligning a polymerizable liquid crystal compound from the viewpoint of thinning.

The laminated retardation film is a laminated optical film containing a retardation film and the optical film of the present invention, such as an adhesive sheet, a protective film, and a polarizing film. Furthermore, the present invention also provides an elliptical polarizing film (also referred to as "elliptical polarizing film of the present invention") including the optical film, polarizing film, and retardation film of the present invention. The elliptical polarizing film is a laminated optical film including a retardation film, a polarizing film, and the optical film of the present invention. In addition, a laminated optical film containing a retardation film and an adhesive sheet, especially a laminated optical film in which an adhesive sheet is laminated on the retardation film, is also called a retardation film with an adhesive.

The laminated retardation film of the present invention preferably satisfies the following formula (6).

100nm ≦ Re (550) ≦ 170nm (6)

By having the optical characteristics represented by the above formula (6), the multilayer retardation film system of the present invention can function as a 1/4 wavelength plate. In addition, in the multilayer retardation film of the present invention, theoretically, Re (550) = 137.5 nm is preferred, but as a range for obtaining good display characteristics, it is preferable to satisfy the following formula (6-1).

130nm ≦ Re (550) ≦ 150nm (6-1)

In the laminated retardation film of the present invention, the retardation film preferably has reverse wavelength dispersibility. The reverse wavelength dispersibility means an optical characteristic in which the in-plane retardation value at a short wavelength is greater than the in-plane retardation value at a long wavelength, and it is preferable that the retardation film satisfy the following formulae (7) and (8). In addition, Re (λ) represents an in-plane phase difference value for light having a wavelength of λ nm.

Re (450) / Re (550) ≦ 1 (7)

1 ≦ Re (630) / Re (550) (8)

In the multilayer retardation film of the present invention, when the retardation film has inverse wavelength dispersibility, it is preferable to reduce the coloration of the display device when the display is black. If 0.82 ≦ Re (450) / Re (550) in the aforementioned formula (7), ) ≦ 0.93 is more preferable.

In the laminated retardation film of the present invention, the retardation film is preferably a layer made of an oriented polymer of a polymerizable liquid crystal compound (hereinafter, referred to as a “optical anisotropic layer”). The polymerizable liquid crystal compound refers to a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group refers to a group capable of performing a related polymerization reaction by living radicals or oxygen generated from a photopolymerization initiator. Examples of the photopolymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, a propenyloxy group, a methacrylic acid group, and an oxy group. And oxetanyl. Among these, acryloxy, methacryloxy, vinyloxy, oxy radical, and oxetanyl are preferred, and acryloxy is more preferred. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal, but from the viewpoint of controlling the thickness of a dense film, a thermotropic liquid crystal is preferred. In the thermotropic liquid crystal, a phase order structure may be a nematic liquid crystal or a smectic liquid crystal.

In the present invention, as the polymerizable liquid crystal compound, a structure of the following formula (III) is particularly preferred from the viewpoint of exhibiting the aforementioned reverse wavelength dispersibility.

In formula (III), Ar represents a divalent aromatic group, and the divalent aromatic group contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a carbon number. The carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group substituted by 1 to 4 alkoxy group, cyano group or nitro group may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom.

L ¹ , L ² , B ^1, and B ² are each independently a single bond or a divalent linking group.

k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ≦ k + l. Here, when 2 ≦ k + 1, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.

E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms. Here, a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom. -CH ₂ -may be substituted by -O- or -Si-.

P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.

G ¹ and G ² are each independently, preferably 1,4-phenyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, and may be substituted by 1,4-cyclohexyl substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenyl substituted with methyl, unsubstituted 1,4-phenyl, or unsubstituted 1,4-trans-cyclohexyl, particularly preferably unsubstituted 1,4-phenyl, or unsubstituted 1,4-trans-cyclohexyl.

Furthermore, it is preferable that at least one of G ¹ and G ² is present, at least one of which is a divalent alicyclic hydrocarbon group, and more preferably, it is bonded to G ¹ and G ² of L ¹ or L ² , At least one is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are independent of each other, preferably, a single bond, -O-, -CH ₂ CH _2- , -CH ₂ O-, -COO-, -OCO-, -N = N-, -CR ^a = CR ^b- , or -C≡C-. Here, R ^a and R ^b represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L ¹ and L ² are each independently, more preferably a single bond, -O-, -CH ₂ CH _2- , -COO-, or -OCO-.

B ¹ and B ² are independent of each other, preferably, a single bond, -O-, -S-, -CH ₂ O-, -COO-, or -OCO-, more preferably, a single bond, -O-, -COO-, or -OCO-.

From the viewpoint of exhibiting inverse wavelength dispersion, k and l are preferably in a range of 2 ≦ k + l ≦ 6, k + l = 4 is preferable, k = 2 and l = 2 are more preferable. When k = 2 and l = 2, a symmetrical structure is preferred.

E ¹ and E ² are each independently an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by P ¹ or P ² include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, and an allyloxy group. , Methacryloxy, oxy radical, and oxetanyl. Among them, acryloxy, methacryloxy, vinyloxy, oxy radical, and oxetanyl are preferred, and acryloxy is more preferred.

Ar preferably has an aromatic heterocyclic ring. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, Azole ring, benzo Azole ring, and phenanthroline ring and the like. Among these, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazolyl group is more preferable. When Ar contains a nitrogen atom, the nitrogen atom preferably has a π electron.

In formula (III), the total number N _π of π electrons contained in the divalent aromatic group represented by Ar is preferably 10 or more, more preferably 14 or more, and still more preferably 18 or more. Moreover, it is preferably 30 or less, more preferably 26 or less, and still more preferably 24 or less.

Examples of the aromatic group represented by Ar include the following groups.

In the formulae (Ar-1) to (Ar-20), the * symbol indicates a connection point, and Z ⁰ , Z ^1, and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group. , Nitro, alkylsulfinyl having 1 to 12 carbons, alkylsulfinyl having 1 to 12 carbons, carboxyl, fluoroalkyl having 1 to 12 carbons, alkoxy having 1 to 6 carbons , Alkylthio groups having 1 to 12 carbon atoms, N-alkylamino groups having 1 to 12 carbon atoms, N, N-dialkylamino groups having 2 to 12 carbon atoms, and N-alkanes having 1 to 12 carbon atoms Aminosulfonyl or N, N-dialkylaminesulfonyl having 2 to 12 carbons.

Q ^1, Q ² and Q ³ each independently represents ^{-CR 2 'R 3' -,} - S -, - NH -, - NR 2 '-, - CO- or -O, wherein, R ^2' and R ^{3 '} Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group, or a halogen atom, and m represents an integer of 0 to 6.

Examples of the aromatic hydrocarbon group among Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthryl, and biphenyl, and phenyl and naphthalene are preferred. And more preferably phenyl. Examples of the aromatic heterocyclic group include furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl, and the like, which contain at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom. The aromatic heterocyclic group of 20 is preferably a furyl group, a thienyl group, a pyridyl group, a thiazolyl group, or a benzothiazolyl group.

Y ¹ , Y ² and Y ³ are each independently and may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. A polycyclic aromatic hydrocarbon group refers to a polycyclic aromatic hydrocarbon group or a group derived from a condensed aromatic ring group. A polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from a collection of aromatic rings.

Z ⁰ , Z ¹ and Z ² are each independently, preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, and Z ^{0 is more} preferable A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group. Z ¹ and Z ^{2 are more} preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group.

Q ¹ , Q ² and Q ^{3 are} preferably -NH-, -S-, -NR ^{2 '} -, -O-, and R ^{2' is} preferably a hydrogen atom. Among these, -S-, -O-, and -NH- are particularly preferred.

Among the formulae (Ar-1) to (Ar-20), from the viewpoint of molecular stability, the formulae (Ar-6) and (Ar-7) are preferred.

In the formulae (Ar-14) to (Ar-20), Y ¹ may be an aromatic heterocyclic group together with the nitrogen atom and Z ⁰ bonded thereto. Examples thereof include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. This aromatic heterocyclic group may have a substituent. Moreover, Y ¹ may be the aforementioned substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom and Z ⁰ to which it is bonded.

The optical anisotropic layer is formed by hardening a composition containing the polymerizable liquid crystal compound (also referred to as a "composition for forming an optical anisotropic layer") by, for example, light irradiation. The composition for forming an optical anisotropic layer may contain various additives, and examples of the additives include the above-mentioned polymerization initiator, polymerization inhibitor, photosensitizer, and coating agent. The total content of the polymerizable liquid crystal compound in 100 parts by mass of the solid content of the composition for forming an optically anisotropic layer is usually 70 to 99.5 parts by mass, and preferably 80 to 99 parts by mass. It is more preferably 80 parts by mass to 94 parts by mass, and still more preferably 80 parts by mass to 90 parts by mass. If the total content is within the above range, the orientation of the obtained optical anisotropic layer tends to be high. Here, the solid content means the total amount of the components after the solvent is removed from the composition.

In another embodiment of the present invention, a display device including any one of the above-mentioned optical film, laminated polarizing film, laminated retardation film, or elliptical polarizing film may be provided. Since the display device described above contains a member of the light-absorbing composition, it is possible to suppress deterioration of optical films such as retardation films and display elements, and to exhibit a function of reducing blue light. In addition, since the light-absorbing composition is excellent in light selective absorption of light in the vicinity of a wavelength of 400 nm, it is difficult to absorb light in the vicinity of 430 nm of a blue light wavelength, so that the image display device can exhibit good colors.

    [Example]    

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In the examples and comparative examples, "%" and "part" refer to "mass%" and "mass part" unless otherwise specified.

<Determination of gel permeation chromatography>

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

<Preparation of acrylic resin>

According to 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)

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 81.8 parts of ethyl acetate as a solvent, 70.4 parts of butyl acrylate, 20.0 parts of methyl acrylate as monomers (A-1), And a mixed solution of 8.0 parts of 2-phenoxyethyl acrylate, 1.0 parts of 2-hydroxyethyl acrylate and 0.6 parts of acrylic acid as the monomer (A-2), while replacing the air in the apparatus with nitrogen so as not to contain the apparatus The internal temperature was raised to 55 ° C while oxygen. Then, the solution in which 0.14 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of ethyl acetate was added in the entire amount. One hour after the addition of the polymerization initiator, the temperature was maintained, and then, while the internal temperature was maintained at 54 to 56 ° C, 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 terminated, and further maintained at this temperature for 12 hours from the start of the addition of ethyl acetate. Finally, ethyl acetate was added so that the concentration of the acrylic resin was adjusted 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 GPC of polystyrene was 1.42 million, and Mw / Mn was 5.2. Let this be an acrylic resin (a).

[Polymerization Example 2] Preparation of acrylic resin (b)

In a reaction vessel provided with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 81.8 parts of ethyl acetate as a solvent, 96.0 parts of butyl acrylate as a monomer (A-1), and monomer (A- 2) A mixed solution of 4.0 parts of acrylic acid, the internal temperature of the device was raised to 55 ° C. while replacing the air in the device with nitrogen to make the device free of oxygen. Then, the solution in which 0.14 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of ethyl acetate was added in the entire amount. The polymerization initiator was maintained at this temperature for one hour after the addition, while the internal temperature was maintained at 54 to 56 ° C while ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / hr. The addition of ethyl acetate was terminated at a time point of 35%, and the temperature was maintained at this temperature until 12 hours had passed since the addition of ethyl acetate. Finally, ethyl acetate was added so that the concentration of the acrylic resin became 20%, and an ethyl acetate solution of the acrylic resin was prepared. The weight average molecular weight Mw of the obtained acrylic resin in terms of polystyrene equivalent of GPC was 750,000, and Mw / Mn was 4.1. Let this be an acrylic resin (b).

<Preparation of adhesive composition and adhesive sheet>

(a) Preparation of adhesive composition

As described below, an acrylic resin (a), a light-selective absorbing compound (ultraviolet absorber), a cross-linking agent, and a silane-based compound were mixed to prepare each adhesive composition.

The crosslinking agent and the silane-based compound are as follows. The structures and physical properties of the light-selective absorbing compounds (compounds (1) to (9)) are shown in Table 2. The addition amounts of the light-selective absorbing compounds (compounds (1) to (9)) are shown in Tables 3 and 5, but the addition amounts are parts by mass relative to 100 parts by mass of the solid content in the acrylic resin. The crosslinking agent and the light-selective absorbing compound are each mixed with 2-butanone and added to the acrylic resin.

[Crosslinking agent]

˙CORONATEL: ethyl acetate solution of trimethylolpropane adduct of toluene diisocyanate (solid content concentration 75%), made by Japan Polyurethane Co., Ltd.

˙TAKENATE D-110N: Ethyl acetate solution of trimethylolpropane adduct of xylene diisocyanate (solid content concentration 75%), manufactured by Mitsui Chemicals Co., Ltd. (hereinafter referred to as "D110N")

[Silane-based compound]

˙KBM-403: 3-Glycidylpropyltrimethoxysilane, liquid, manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[Light-selective absorbing compound]

<Synthesis of Light Selective Absorptive Compound>

(Synthesis example 1)

In a 200 mL-four-neck flask equipped with a Dimroth condenser and a thermometer, in a nitrogen environment, feed 10 g of intermediate 1 powder synthesized by referring to a patent document (Japanese Patent Application Laid-Open No. 2011-184414), and acetic anhydride. (3.7 g of Wako Pure Chemical Industries, Ltd.), 2.5 g of morpholine (manufactured by Wako Pure Chemical Industries, Ltd.), and 15 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) were stirred with a magnetic stirrer. The internal temperature was raised to 72 ° C and stirred for 3 hours. After the reaction was completed, it was cooled to room temperature, and the solvent was distilled off using an evaporator. A mixed solution of 17 g of methanol and 3 g of water was added to the obtained concentrated liquid to obtain crystals. This crystal was dried under reduced pressure at 40 ° C to obtain 2.0 g of compound (1) as a yellow powder. The yield is 70%.

In addition, using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation) to measure the absorption maximum wavelength (λ max), λ max = 389 nm (in 2-butanone), and ε (400) was 171 L / (g‧ cm), ε (420) / ε (400) is 0.0251.

The ¹ H-NMR measurement of the compound (1) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) δ: 1.55 (s, 6H), 3.55-3.73 (m, 8H), 6.83 (q, 1H), 7.87 (d, 1H), 8.00 (d, 1H)

(Synthesis example 2)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, 3 g of intermediate 2 powder (made by Wako Pure Chemical Industries, Ltd.) and 2-ethoxyethyl cyanoacetate ( 2.2 g of Tokyo Chemical Industry Co., Ltd. and 12 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were stirred with a magnetic stirrer. After the internal temperature was raised to 75 ° C, 1.1 g of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred for 6 hours. After the reaction was completed, it was cooled to room temperature, and the solvent was distilled off using an evaporator. To the obtained concentrated liquid, 20 g of toluene and 30 g of a 4.1% by mass aqueous hydrochloric acid solution were added, and the toluene solution was separated and washed. Furthermore, 40 g of water was added to the toluene solution, and liquid separation and washing were performed. The toluene was distilled off using an evaporator to obtain crystals. This crystal was dried under reduced pressure at 40 ° C to obtain 3.5 g of compound (2) as a yellow powder. The yield was 73%.

When the absorption maximum wavelength (λ max) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation), λ max = 386 nm (in 2-butanone), and ε (400) was 51 L / (g‧ cm), ε (420) / ε (400) is 0.165.

¹ H-NMR measurement of the compound (2) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) 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 3)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, 10 g of intermediate 3 powder, acetic anhydride (Wako Pure Chemical Industries, Ltd.) synthesized by referring to a patent document (Japanese Patent Application Laid-Open No. 2014-194508) were fed in a nitrogen atmosphere. 3.7 g (manufactured by KK), 5.8 g of 2-ethoxyethyl 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, 4.7 g of N, N-diisopropylethylamine (hereinafter referred to as DIPEA. Manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped from the dropping funnel for 1 hour. After the completion of the dropping, the internal temperature was 25 ° C. Incubate for another 2 hours. After the reaction was completed, acetonitrile was removed using a reduced-pressure evaporator, toluene was added to the obtained oil, and the resulting insoluble component was removed by filtration. The filtrate was concentrated again using a reduced-pressure evaporator, and the concentrated solution was supplied to a column chromatography analyzer (silica gel) for purification, thereby obtaining a target substance for recrystallization from toluene. This crystal was dried under reduced pressure at 60 ° C to obtain 5.2 g of compound (3) as a yellow powder. The yield is 65%.

When the absorption maximum wavelength (λ max) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation), λ max = 389 nm (in 2-butanone), and ε (400) was 125 L / (g‧ cm), ε (420) / ε (400) is 0.0153.

¹ H-NMR measurement of the compound (3) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) 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 4)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, in an atmosphere of nitrogen, 10 g of intermediate 3 powder synthesized by referring to a patent document (Japanese Patent Application Laid-Open No. 2014-194508), acetic anhydride (Wako Pure Chemical Industries, Ltd.) 3.6 g, 2-ethylhexyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.9 g, 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 dropped from the dropping funnel for one hour, and after completion of the dropping, the temperature was maintained at 25 ° C for another two hours. After the reaction was completed, acetonitrile was removed using a reduced-pressure evaporator, and it was supplied to a column chromatography analyzer (silica gel) for purification. The effluent containing compound (4) was removed from the solvent using a reduced-pressure evaporator to obtain yellow crystals. This crystal was dried under reduced pressure at 60 ° C to obtain 4.6 g of a compound (4) as a yellow powder. The yield is 50%.

When the absorption maximum wavelength (λ max) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation), λ max = 389 nm (in 2-butanone), and the value of ε (400) was 108 L / (g‧ cm), and the value of ε (420) / ε (400) is 0.013.

¹ H-NMR measurement of the compound (4) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) 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)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, 2.0 g of cyanoacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and triethylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) were fed in a nitrogen atmosphere. 4.3 g of p-toluenesulfonic acid, 0.2 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 20 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer. The internal temperature was raised to 110 ° C and stirred for 3 hours. After the reaction was completed, 40 g of water was added to the toluene solution, and the solution was separated and washed. The obtained toluene solution was distilled to remove toluene using an evaporator to obtain 4 4.7 g of an intermediate as an oily liquid. The yield is 86%.

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, in a nitrogen environment, feed 2.0 g of intermediate 2 powder (made by Wako Pure Chemical Industries, Ltd.), 4 2.6 g of intermediate, and acetonitrile (and 8.0 g of Guangjun Pharmaceutical Industry Co., Ltd. was stirred with a magnetic stirrer. The internal temperature was raised to 75 ° C, and 0.7 g of piperidine (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped from the dropping funnel for 1 hour. After the dropping was completed, the temperature was maintained at 75 ° C for another 6 hours.

After the reaction was completed, it was cooled to room temperature, and the solvent was distilled off using an evaporator. To the obtained concentrated solution, 10 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 g of water were added, and the ethyl acetate solution was separated and washed. The obtained ethyl acetate solution was distilled to remove ethyl acetate using an evaporator to obtain 3.6 g of a compound (5) as an oily liquid. The yield was 93%.

¹ H-NMR measurement of the compound (5) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) 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 6)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, in a nitrogen atmosphere, 3.0 g of intermediate 2 powder (made by Wako Pure Chemical Industries, Ltd.) and 2-ethylhexyl cyanoacetate ( 2.7 g of Tokyo Chemical Industry Co., Ltd., 1.0 g of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) and 12.0 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer. The internal temperature was raised to 75 ° C, and the temperature was maintained for 6 hours. After completion of the reaction, it was cooled to room temperature, and the precipitated crystals were filtered. This crystal was washed with 10 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and the crystal was further dried under reduced pressure at 40 ° C to obtain 4.3 g of compound (6) as a yellow powder. The yield was 81%.

¹ H-NMR measurement of the compound (6) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) 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 7)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, in a nitrogen environment, 10 g of intermediate powder 3, acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 2.9 g, and isobutyl cyanoacetate were fed. 4.4 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 g acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were stirred with a magnetic stirrer. At an internal temperature of 25 ° C, 3.7 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped from the dropping funnel for 1 hour, and after completion of the dropping, the temperature was maintained at 25 ° C for another 2 hours. After the reaction was completed, an acetonitrile solution was dropped into 150 g of cold water, and the precipitated crystals were filtered. The crystal was washed with a mixed solution of 2 g of water and 10 g of acetonitrile, and the crystal was further washed with 10 g of heptane. The washed crystals were dried under reduced pressure at 70 ° C to obtain 5.2 g of the compound (7) as a yellow powder. The yield is 84%.

When the absorption maximum wavelength (λ max) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation), λ max = 389 nm (in 2-butanone), and ε (400) was 130 L / (g‧ cm), ε (420) / ε (400) is 0.0092.

¹ H-NMR measurement of the compound (7) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) δ: 0.97 (d, 6H), 1.95-2.15 (m, 3H), 3.00 (t, 5H), 3.64 (t, 2H), 3.95 (d, 2H), 5.53 (d , 1H), 7.92 (d, 1H)

(Synthesis example 8)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, in a nitrogen atmosphere, 6.3 g of cyanoacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-n-octyl-1-dodecanol were fed. (Tokyo Chemical Industry Co., Ltd.) 20.0g, p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.6g, toluene (100% by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer . The internal temperature was raised to 110 ° C and stirred for 3 hours. After the reaction was completed, 100 g of water was added to the toluene solution, and the solution was separated and washed. The obtained toluene solution was distilled to remove toluene using an evaporator to obtain 5 22 g of a liquid intermediate. The yield is 90%.

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, in a nitrogen environment, 6 g of intermediate 3 powder, 1.8 g of acetic anhydride (made by Wako Pure Chemical Industries, Ltd.), 5 6.3 g of intermediate, And 18 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) and stirred with a magnetic stirrer. 3.7 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was dripped from the dropping funnel at an internal temperature of 25 ° C for 1 hour. After the dropping was completed, the temperature was maintained at 25 ° C for an additional 2 hours. After the reaction was completed, the acetonitrile solution was dropped into 90 g of cold water, and the precipitated crystals were filtered. The crystal was washed with a mixed solution of 2 g of water and 10 g of acetonitrile, and the crystal was further washed with 10 g of heptane. The washed crystals were dried under reduced pressure at 70 ° C to obtain 6.5 g of compound (8) as a yellow powder. The yield was 92%.

When the absorption maximum wavelength (λ max) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation), λ max = 389 nm (in 2-butanone), and ε (400) was 52 L / (g‧cm ), Ε (420) / ε (400) is 0.0121.

The ¹ H-NMR measurement of the compound (8) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) δ: 0.88 (t, 6H), 1.68 (s, 1H), 2.09 (q, 2H), 2.97-3.03 (t, 5H), 3.64 (t, 2H), 4.07 (d , 2H), 5.52 (d, 1H), 7.90 (d, 1H)

(Synthesis example 9)

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, 14 g of cyanoacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-ethyl-1-butanol (Tokyo Chemical Industry ( 15 g of p-toluenesulfonic acid, 1.4 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 75 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred with a magnetic stirrer. The internal temperature was raised to 110 ° C and stirred for 3 hours. After the reaction was completed, 100 g of water was added to the toluene solution, and the solution was separated and washed. The obtained toluene solution was distilled to remove toluene using an evaporator to obtain 22 g of intermediate 6 as a liquid. The yield is 90%.

In a 200 mL four-necked flask equipped with a Dessert cooling tube and a thermometer, in a nitrogen environment, feed 10 g of intermediate 3 powder, 2.9 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), 6 4.8 g of intermediate, And 30 g of acetonitrile (made by Wako Pure Chemical Industries, Ltd.) and stirred with a magnetic stirrer. At an internal temperature of 25 ° C, 3.7 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped from the dropping funnel for 1 hour. After the dropping was completed, the temperature was maintained at 25 ° C for another 2 hours. After the reaction was completed, an acetonitrile solution was dropped into 150 g of cold water, and the precipitated crystals were filtered. The crystal was washed with a mixed solution of 2 g of water and 10 g of acetonitrile, and the crystal was further washed with 10 g of heptane. The washed crystals were dried under reduced pressure at 70 ° C to obtain 5.7 g of the compound (9) as a yellow powder. The yield is 84%.

When the absorption maximum wavelength (λ max) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation), λ max = 389 nm (in 2-butanone), and ε (400) was 118 L / (g‧ cm), ε (420) / ε (400) is 0.0090.

¹ H-NMR measurement of the compound (9) was performed. The results are as follows.

¹ H-NMR (CDCl ₃ ) δ: 0.91 (t, 6H), 1.41 (q, 4H), 1.58 (q, 2H), 2.98-3.04 (m, 5H), 3.64 (t, 2H), 4.10 (d , 2H), 5.52 (d, 1H), 7.92 (d, 1H)

(a-1) Production Example 1: Preparation of Adhesive Composition (1)

0.50 parts by mass of a cross-linking agent (CORONATE L.) and 0.50 parts by mass of a silane-based compound (KBM-403) were prepared with respect to 100 parts by mass of the solid content of the acrylic resin (a). Furthermore, 2-butanone was added so that solid content concentration might become 14%, and it stirred and mixed at 300 rpm for 30 minutes using the mixer (Three-One Motor made by Yamato Science Co., Ltd.), and prepared the adhesive composition (1).

(a-2) Production Examples 2 to 27: Preparation of Adhesive Compositions (2) to (27)

0.50 parts by mass of a cross-linking agent (CORONATE L) and 0.50 parts by mass of a silane compound (KBM-403) with respect to 100 parts by mass of the solid content of the acrylic resin (a), and a light-selective absorbing compound shown in Table 3 ( Compounds (1) to (9)) were prepared in the amounts shown in Table 3. Further, 2-butanone was added so that the solid content concentration became 14% by mass, and the mixture was stirred and mixed at 300 rpm for 30 minutes using a stirrer (Three-One Motor manufactured by Yamato Scientific Co., Ltd.) to prepare an adhesive composition (2 ) To (27).

For the adhesive compositions (2) to (27) obtained in Production Examples 2 to 27, the maximum absorption wavelength λ max was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). Also, ε (400) and ε (420) were measured, and ε (420) / ε (400) was calculated. The results are shown in Table 4.

(a-3) Production Example 28: Preparation of Adhesive Composition (28)

0.50 parts by mass of a cross-linking agent (CORONATE L) and 0.50 parts by mass of a silane-based compound (KBM-403) were prepared with respect to 100 parts by mass of the solid content of the acrylic resin (b). Further, 2-butanone was added so that the solid content concentration became 14%, and the mixture was stirred and mixed at 300 rpm for 30 minutes using a blender (Yamato Scientific Co., Ltd. Three-One Motor) to prepare an adhesive composition (28).

(a-4) Production Examples 29 to 52: Preparation of Adhesive Compositions (29) to (52)

With respect to 100 parts by mass of the solid content of the acrylic resin (b), 0.50 parts by mass of a cross-linking agent (CORONATE L) and 0.50 parts by mass of a silane-based compound (KBM-403), and a light-selective absorbing compound shown in Table 5, Formulation was performed in the amount shown in Table 5. Further, 2-butanone was added so that the solid content concentration became 14%, and the mixture was stirred and mixed at 300 rpm for 30 minutes using a stirrer (Three-One Motor manufactured by Yamato Scientific Co., Ltd.) to prepare an adhesive composition (29). To (52).

For the adhesive compositions (29) to (52) obtained in Production Examples 29 to 52, the maximum absorption wavelength λ max was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). Also, ε (400) and ε (420) were measured, and ε (420) / ε (400) was calculated. The results are shown in Table 6.

(b-1) Reference example 1

On the release-treated surface of the polyethylene terephthalate film (SP-PLR 382050, manufactured by Lintec, hereinafter referred to as "separator") subjected to release treatment, the adhesive prepared in Production Example 1 was composed. The object (1) was coated with an applicator so that the thickness of the dried adhesive layer was 10 μ, and dried at 100 ° C. for 1 minute to prepare an adhesive sheet (R1).

The optical properties of the obtained adhesive sheet (R1) were measured with a spectrophotometer (UV-3150; manufactured by Shimadzu Corporation). The results are shown in Table 7. T (400) in the table indicates the transmittance (%) at a wavelength of 400 nm, and T (420) indicates the transmittance (%) at a wavelength of 420 nm.

(b-2) Reference example 2

On the release-treated surface of the separator, the adhesive composition (1) prepared in Production Example 1 was applied with an applicator so that the thickness of the dried adhesive layer was 5 μm, and dried at 100 ° C. for 1 minute. To produce an adhesive sheet (R2). The optical characteristics of the obtained adhesive sheet (R2) were measured by the same method as in Reference Example 1. The results are shown in Table 7.

(b-3) Comparative Examples 1 to 17

Instead of the adhesive composition (1), the adhesive compositions (2) to (18) prepared in Production Examples 2 to 18 were used, respectively, and Comparative Examples 1 to 17 were produced by the same method as in Reference Example 1. Adhesive sheets (C1) to (C17). The optical characteristics of the obtained adhesive sheets (C1) to (C17) were measured by the same method as in Reference Example 1. The results are shown in Table 7.

(b-4) Examples 1 to 9

Instead of the adhesive composition (1), the adhesive compositions (19) to (27) prepared in Production Examples 19 to 27 were used, respectively, and the compositions of Examples 1 to 9 were prepared by the same method as in Reference Example 1. Adhesive sheets (E1) to (E9). The optical characteristics of the obtained adhesive sheets (E1) to (E9) were measured by the same method as in Reference Example 1. The results are shown in Table 7.

(b-5) Examples 10 to 14

Instead of the adhesive composition (1), the adhesive compositions (19) to (23) prepared in Production Examples 19 to 23 were used, and the adhesives of Examples 10 to 14 were produced by the same method as in Reference Example 2. Tablets (E10) to (E14). The optical properties of the obtained adhesive sheets (E10) to (E14) were measured by the same method as in Reference Example 1. The results are shown in Table 7.

(b-6) Reference example 3

Using the adhesive composition (28) prepared in Production Example 28, an adhesive sheet (R3) of Reference Example 3 was produced in the same manner as in Reference Example 1. The optical characteristics of the obtained adhesive sheet (R3) were measured by the same method as in Reference Example 1. The results are shown in Table 8.

(b-7) Comparative Examples 18 to 34

Using the adhesive composition (29) to (45) prepared in Production Examples 29 to 45, the adhesive sheets (C18) to (C34) of Comparative Examples 18 to 34 were produced in the same manner as in Reference Example 1, respectively. . The optical characteristics of the obtained adhesive sheets (C18) to (C34) were measured by the same method as in Reference Example 1. The results are shown in Table 8.

(b-8) Examples 15 to 21

Using the adhesive composition (46) to (52) prepared in Production Examples 46 to 52, the adhesive sheets (E15) to (E21) of Examples 15 to 21 were produced by the same method as in Reference Example 1. . The optical characteristics of the obtained adhesive sheets (E15) to (E21) were measured by the same method as in Reference Example 1. The results are shown in Table 8.

<Evaluation of Crystal Precipitation of Adhesive Sheet>

[40 ° C heating test (described as "warming" in Tables 7 and 8)]

In a thermostatic bath (manufactured by Espec Co., Ltd .: model PL-3KT), the above-mentioned adhesive sheet was put into each, and left under dry conditions at a temperature of 40 ° C for 7 days and 30 days, respectively, and the adhesive sheet was visually observed. The appearance was evaluated in accordance with the evaluation criteria described below. The results are shown in Tables 7 and 8.

[Evaluation Criteria for 40 ° C Heating Test]

A: In the samples after 30 days, almost no appearance change such as crystal precipitation was observed.

B: In the sample after 7 days, almost no appearance change such as crystal precipitation was observed.

C: In the sample after 7 days, a change in appearance such as crystal precipitation was noticeable.

[-15 ° C cooling test (described as "cooling" in Tables 7 and 8)]

The above-mentioned adhesive sheet was put in a constant temperature bath, and left to stand under dry conditions at a temperature of -15 ° C for 7 days and 30 days, respectively, and the appearance state of the adhesive sheet was visually observed, and evaluated according to the following evaluation criteria. The results are shown in Tables 7 and 8.

[Evaluation Criteria for -15 ° C Cooling Test]

A: In the samples after 30 days, almost no appearance change such as crystal precipitation was observed.

B: In the sample after 7 days, almost no appearance change such as crystal precipitation was observed.

C: In the sample after 7 days, a change in appearance such as crystal precipitation was noticeable.

<Production of laminated optical film>

Next, a laminated optical film was produced as described below. In the production of the laminated optical film, the following polymer film was used. The processing device, measuring device, and measuring method are also described below.

‧Cyclic olefin polymer (COP) film: ZF-14 manufactured by Japan Zeon Corporation

‧Corona treatment device: AGF-B10 made by Kasuga Electric Co., Ltd.

‧Conditions for corona treatment: Use the above-mentioned corona treatment device to perform once with the output of 0.3kW and the processing speed of 3m / min.

‧Polarized UV irradiation device: SPOT CURE SP-7 with polarized unit made by USHIO Electric Co., Ltd.

‧Laser Microscope: LEXT manufactured by Olympus Co., Ltd.

‧High-pressure mercury lamp: UniQure VB-15201 BY-A made by USHIO Electric Co., Ltd.

‧Measurement of in-plane retardation value: measured using a birefringence measuring device (KOBRA-WR manufactured by Oji Measurement Co., Ltd.)

‧Measurement of the film thickness of the alignment film: measured using Ellipsometer M-220 manufactured by JASCO Corporation

In the production of optical anisotropic layers, laminated bodies, etc., the following "composition for forming a photo-alignment film", "friction alignment polymer composition", and "composition containing a polymerizable liquid crystal compound A" are used ", And" Polarizer. "

<Preparation of composition for forming photo-alignment film>

By mixing 5 parts of a photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent), the obtained mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a photo-alignment film.

<Preparation of composition containing polymerizable liquid crystal compound A>

A polymerizable liquid crystal compound A having the following structure and a polymerization initiator, a leveling agent, and a solvent described below are mixed as components to obtain a composition containing the polymerizable liquid crystal compound A. The polymerizable liquid crystal compound A was synthesized by a method described in Japanese Patent Application Laid-Open No. 2010-31223. The maximum absorption wavelength λ max (LC) of the polymerizable liquid crystal compound A is 350 nm.

‧Polymerizable liquid crystal compound A (12.0 parts):

‧Polymerization initiator (0.72 parts): 2-dimethylamino-2-benzyl-1- (4-morpholinylphenyl) butane-1-one (IRGACURE 369; manufactured by Ciba specialty chemicals)

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

‧Solvent (100 parts): cyclopentanone

<Manufacture of Polarizing Plate>

Polyvinyl alcohol film with a thickness of 30 μm (average degree of polymerization is about 2400, saponification degree above 99.9 mol%) is uniaxially stretched to about 4 times by dry stretching, and further maintained in a state of tension, directly in pure water at 40 ° C After immersion for 40 seconds, the dyeing treatment was performed by immersing in a dyeing aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.044 / 5.7 / 100 at 28 ° C 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, then maintained at a tension of 300N, dried at 60 ° C for 50 seconds, and then dried at 75 ° C for 20 seconds, to obtain a thickness of iodine in the polyvinyl alcohol film by absorbing and aligning it. 12 μm polarizer.

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 then bonded with a nip roll. The obtained laminate was dried at 60 ° C. for 2 minutes while maintaining the tension at 430 N / m to obtain a 42 μm polarizing plate having a cycloolefin film on one side as a protective film. In addition, the above-mentioned water-based adhesive was added to 3 parts of carboxy-modified polyvinyl alcohol (manufactured by Toray Co., Ltd .; Kuraray Poval KL 318) in 100 parts of water, and water-soluble polyamine epoxy resin (Sumika Chemical Technology Co., Ltd .; Sumirez Resin 650; 1.5% aqueous solution with a solid concentration of 30%).

The polarization degree Py and the monomer transmittance Ty of the obtained polarizing plate were measured as described below.

The unit transmittance (T1) in the transmission axis direction and the unit transmittance (T2) in the absorption axis direction are used in a spectrophotometer (UV-3150; manufactured by Shimadzu Corporation). The fixture of the polarizer was measured by a two-beam method in a wavelength range of 380 to 680 nm in 2 nm steps. The following formulae (p) and (q) were used to calculate the polarization based on the individual transmittance at each wavelength, and the visual sensitivity was corrected using the 2-degree field of view (C light source) of JIS Z8701 to calculate the visual sensitivity. Correct the monomer transmittance (Ty) and visual sensitivity and correct the polarization (Py). As a result, the obtained absorption-corrected polarizing plate having a transmittance Ty of 43.0% and a polarization Py of 99.99% was obtained.

Monolithic transmittance Ty (%) = ((T1 + T2) / 2) × 100 (p)

Polarization Py (%) = ((T1-T2) / (T1 + T2)) × 100 (q)

<Manufacture of Optical Anisotropic Layer>

A cycloolefin polymer film (COP, ZF-14 manufactured by Japan Zeon Co., Ltd.) was treated with a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) at an output of 0.3 kW and a processing speed of 3 m / min. 1 Times. The corona-treated surface was coated with a composition for forming a photo-alignment film with a bar coater, dried at 80 ° C for 1 minute, and a polarized UV irradiation device (SPOT CURE SP-7; USHIO Electric Co., Ltd. was limited). Co., Ltd.), and a polarized UV exposure was performed with a cumulative light amount of 100 mJ / cm ² . When the film thickness of the obtained alignment film was measured with an Ellipsometer, it was 100 nm.

Next, a coating liquid made of the composition containing the polymerizable liquid crystal compound A previously prepared was applied on the alignment film using a bar coater, and dried at 120 ° C for 1 minute, and then a high-pressure mercury lamp (UniQure VB -15201 BY-A, manufactured by USHIO Electric Co., Ltd.) By irradiating ultraviolet rays from the surface side coated with a coating solution (accumulated light amount at a wavelength of 313 nm in a nitrogen environment: 500 mJ / cm ² ), ultraviolet rays can be obtained. Optical film of a rectangular layer (a retardation film). When the film thickness of the obtained optical anisotropic layer was measured with a laser microscope, it was 2 micrometers.

(c-1) Example 22: Production of laminated optical film (1)

The adhesive sheet (E1) prepared in Example 1 was adhered to the optical anisotropic layer side of the optical film, and the separator of the adhesive sheet (E1) was removed, and the adhesive composition (19) appeared. The surface area layer is the above-mentioned polarizing plate. After that, the corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) was used for processing once under the conditions of an output of 0.3 kW and a processing speed of 3 m / min. The polarizing plate and the optical anisotropic layer were passed through an adhesive The composition (19) was bonded together. At this time, with respect to the absorption axis of the polarizing plate, the relationship of the slow axis of the optical anisotropic layer was laminated to 45 ° to form a circularly polarizing plate. Thereafter, a COP film belonging to the above-mentioned optical film substrate is peeled to obtain a laminated optical film (circular polarizing plate) 1 having an optical anisotropic layer transferred onto a polarizing plate. The thickness of the obtained laminated optical film 1 was 64 μm.

In order to measure the optical characteristics of the laminated optical film 1, a measurement sample was prepared by transferring onto a glass. The retardation values of this sample at a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 630 nm were measured by a birefringence measuring device (KOBRA-WR; manufactured by Oji Measurement Co., Ltd.), and a spectrophotometer (UV-3150; (Manufactured by Shimadzu Corporation) was measured for transmittance at a wavelength of 400 nm and a wavelength of 420 nm. In addition, a polarizing prism is arranged on the light source side to make a completely linearly polarized light, and the linearly polarized light is irradiated to the measurement sample for measurement. At this time, linearly polarized light was incident in parallel with the transmission axis on the polarizer side of the multilayer optical film 1 (circular polarizer 1), and the absorbance Ap (400) of the multilayer optical film with a wavelength of 400 nm in the direction of the transmission axis of the polarizer was measured. And the absorbance Ap (420) of the laminated optical film at a wavelength of 420 nm in the direction of the transmission axis of the polarizing plate. The results are shown in Table 9. The laminated optical film 1 has all the optical characteristics shown by the following formulae (4) to (8).

Ap (400) ≧ 0.4 (4)

Ap (420) / Ap (400) ≦ 0.3 (5)

100nm ≦ Re (550) ≦ 170nm (6)

Re (450) / Re (550) ≦ 1 (7)

1 ≦ Re (630) / Re (550) (8)

(c-2) Reference Examples 4 to 6, Comparative Examples 35 to 39, and Examples 23 to 42

Using the adhesive sheet described in Table 9 below, a laminated optical film (circular polarizing plate) was produced in the same manner as in Example 22. The optical characteristics of the obtained laminated optical film (circular polarizing plate) were measured by the same method as in Example 22.

<Evaluation of laminated optical film>

The laminated optical film produced as described above was subjected to an optical durability test, a heat resistance test, a moist heat resistance test, and a thermal shock test. Each test was performed according to the following method.

[Optical durability test]

The laminated optical film was put into a weathering tester (manufactured by Gas Tester Co., Ltd .: model SUN SHINE WEATHER METER S80), and after irradiating for 100 hours, the retardation values Re (λ) of 450 nm, 550 nm, and 630 nm were measured. The change in the retardation value before and after the optical durability test was evaluated based on the following criteria. The results are shown in Table 10.

[Evaluation Criteria for Optical Durability Test]

A: Change in retardation value before and after optical durability test △ Re (λ) is less than 5

B: Change in retardation value before and after the optical durability test ΔRe (λ) is 5 or more and less than 10

C: Change in retardation value before and after the optical durability test ΔRe (λ) is 10 or more

[Heat resistance test]

Put the laminated optical film into a thermostatic bath (manufactured by Espec Co., Ltd .: model PL-3KT), and leave it for 250 hours and 500 hours under dry conditions at a temperature of 85 ° C, and then visually observe the appearance of the laminated optical film. The evaluation criteria described above are evaluated. The results are shown in Table 10.

[Evaluation Criteria for Heat Resistance Test]

A: In the sample after 500 hours, almost no change in appearance such as floating, peeling, foaming, and crystal precipitation was observed.

B: In the sample after 250 hours, almost no change in appearance such as floating, peeling, foaming, and crystal precipitation was observed.

C: In the sample after 250 hours, a change in appearance such as floating, peeling, foaming, crystal precipitation, etc. was noticeable.

[Damp and heat resistance test]

Put the laminated optical film in a thermostatic bath (manufactured by Espec Co., Ltd .: model PH-4KT), and leave the laminated optical film at a temperature of 60 ° C and a relative humidity of 90% for 250 hours and 500 hours, and then visually observe the appearance of the laminated optical film. Based on the evaluation criteria described below. The results are shown in Table 10.

[Evaluation Criteria for Humidity and Heat Resistance Test]

A: In the sample after 500 hours, almost no change in appearance such as floating, peeling, foaming, and crystal precipitation was observed.

B: In the sample after 250 hours, almost no change in appearance such as floating, peeling, foaming, and crystal precipitation was observed.

C: In the sample after 250 hours, changes in appearance such as floating, peeling, foaming, and crystal precipitation were noticeable.

[Heat Shock (HS) Test]

The laminated optical film was put into a hot and cold punching device (manufactured by Espec Co., Ltd .: model TSA-71L-A), and the temperature was reduced to -40 ° C after heating to 70 ° C, and then the temperature was increased to 70 ° C as one process. The cycle (30 minutes) was repeated for 50 cycles and 100 cycles, and then the appearance state of the laminated optical film was visually observed. The evaluation was performed according to the evaluation criteria described below. The results are shown in Table 10.

[Evaluation Criteria for Thermal Shock Test]

A: In the sample after 100 cycles, almost no change in appearance such as floating, peeling, foaming, and crystal precipitation was observed.

B: In the sample after 50 cycles, almost no change in appearance such as floating, peeling, foaming, and crystal precipitation was observed.

C: In the sample after 50 cycles, changes in appearance such as floating, peeling, foaming, crystal precipitation, etc. were noticeable.

It can be seen that the optical films of Examples 22 to 42 have high absorption characteristics at a wavelength of 400 nm compared to Reference Examples 4 to 6, so that ΔRe (450) and ΔRe (550) of the retardation film can be suppressed.

Claims (15)

    A light-absorbing composition containing at least two kinds of light-selective absorbing compounds, wherein the at least two kinds of light-selective absorbing compounds have the same conjugated structure.         The light-absorbing composition according to item 1 of the scope of patent application, wherein the difference between the maximum value and the minimum value of the maximum absorption wavelength of the at least two light-selective absorbing compounds having the same conjugated structure is 5 nm or less .     The light-absorbing composition according to item 1 or 2 of the scope of patent application, wherein the at least two light-selective absorbing compounds are those represented by the following formula (I) or formula (II): In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. When the alkyl group has at least one methylene group, at least one of the methylene group may be substituted by an oxygen atom or a sulfur atom. R ² and R ³ independently of each other represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a methylene group, a secondary amine group, an oxygen atom, or a sulfur atom, X ¹ and X ² independently represent an electron attracting group, and X ¹ and X ² can be connected to each other to form a ring structure; Formula (II): In the formula, R ¹ , X ¹ , and X ² have the same definitions as the foregoing, and A ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, or an aromatic heterocyclic group, wherein the alkyl group has at least In the case of one methylene group, at least one of the methylene groups may be substituted with a secondary amine group, an oxygen atom, and a sulfur atom, and the aromatic hydrocarbon group and the aromatic heterocyclic group may have a substituent. The light-selective absorbing composition according to item 3 of the scope of the patent application, wherein the light-selective absorbing compound represented by the aforementioned formula (I) is represented by the following formula (I-2): In the formula, R ¹ has the same definition as the foregoing, and R ⁴ represents a hydrogen atom or an alkyl group having 2 to 50 carbon atoms. When the alkyl group has at least one methylene group, at least one of the methylene groups can be oxygenated. Atomic substitution; the light-selective absorbing compound represented by the aforementioned formula (II) is represented by the formula (II-2): In the formula, R ¹ and R ⁴ have the same definitions as the foregoing.     The light-absorbing composition according to any one of claims 1 to 4, in which at least two kinds of light-selective absorbing compounds having the same conjugated system structure are contained in the light-absorbing composition. The ratio of the content of the light-selective absorbing compound with the largest content in the light-absorbing composition to the content of other light-selective absorbing compounds is 1:10 to 10: 1.         The light-absorbing composition according to any one of claims 1 to 5 of the scope of patent application, which satisfies the following formulae (1), (2), and (3): ε (420) / ε (400) ≦ 0.3 (1) λ max ≦ 420nm (2) ε (400) ≧ 20 (3) In the formula, ε (420) represents the gram absorption coefficient at a wavelength of 420nm, ε (400) represents the gram absorption coefficient at a wavelength of 400nm, λ max represents the maximum absorption wavelength.         A polymer composition includes the light-absorbing composition described in any one of claims 1 to 6 and a polymer.         The polymer composition according to item 7 of the scope of patent application, wherein the content of the light-absorbing composition is 1 to 15 parts by mass based on 100 parts by mass of the polymer.         An optical film is composed of the polymer composition described in item 7 or 8 of the scope of patent application.         The optical film according to item 9 of the scope of patent application has a thickness of 0.1 to 18 μm.         A laminated polarizing film comprises an optical film and a polarizing film according to item 9 or 10 of the scope of patent application.         The laminated polarizing film described in item 11 of the scope of the patent application satisfies the following formulas (4) and (5): Ap (400) ≧ 0.4 (4) Ap (420) / Ap (400) ≦ 0.3 (5 In the formula, Ap (400) represents the absorbance of the optical film in the direction of the transmission axis of the polarizing film at a wavelength of 400 nm, and Ap (420) represents the absorbance of the optical film in the direction of the transmission axis of the polarizing film at the wavelength of 420 nm.         A laminated retardation film comprises an optical film and a retardation film as described in item 9 or 10 of the scope of patent application.         An elliptical polarizing film comprises an optical film, a polarizing film, and a retardation film as described in item 9 or 10 of the scope of patent application.         A display device includes the film according to any one of claims 9 to 14 of the scope of patent application.