KR20170133266A - Light absorptive composition - Google Patents

Abstract

Provided is a light absorptive composition which exhibits selective light absorptiveness to short-wavelength visible light around 400 nm, and also shows high solubility in various solvents and/or affinity with materials in members constituting display devices. To this end, the light absorptive composition contains at least two types of selective light absorptive compounds which have the same conjugated structure.

Description

[0001] LIGHT ABSORPTIVE COMPOSITION [0002]

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

Various members such as organic EL elements, display elements such as liquid crystal cells, and optical films such as a polarizing plate and a retardation plate are used for a flat panel display (FPD) such as an organic EL display or a liquid crystal display. Since materials such as an organic EL compound and a liquid crystal compound used in these members are organic substances, deterioration due to ultraviolet (UV) may be a problem. In order to solve such a problem, countermeasures such as the addition of a UV absorber to the protective film of the polarizing plate used in the display device have been made. For example, in Patent Document 1, the deterioration of members is being prevented by adding a UV absorber to the protective film of the polarizing plate used in these display devices.

In addition, in recent years, thickness reduction of optical films has been required while thickness of a display device is progressing, and optical films not having a protective film are also being developed. In such an optical film, it is necessary to blend the components added to the conventional protective film in separate members. For example, the UV absorbing function may be imparted to the pressure-sensitive adhesive layer laminated on the optical film. Patent Document 2 discloses a pressure-sensitive adhesive sheet in which a UV absorbent synthesized from a monomer mixture containing a UV absorbing monomer is applied to one side of the substrate.

Japanese Patent Application Laid-Open No. 2006-308936 Japanese Patent Application Laid-Open No. 2008-56859

The UV absorber absorbs light in the ultraviolet region and prevents deterioration of the member. On the other hand, the UV absorber has photo-selective absorptivity that does not exhibit absorption characteristics with respect to blue light (for example, visible light exceeding 430 nm) .

Further, such a UV absorber requires high affinity with a constituent member and high solubility in a solvent in order to be mounted on a constituent member of a display device such as a pressure-sensitive adhesive or an optical film. If the affinity of the UV absorber is insufficient, for example, when the UV absorber is added to the pressure-sensitive adhesive, the UV absorber bleeds out to deteriorate the adhesive function, and if the solubility in the solvent in the pressure- The UV absorber may not be uniformly dispersed in the member and the light absorbing function may be insufficient. Further, when the UV absorber is added to an optical film such as a retardation film and then stretched by applying heat, the UV absorber bleeds out on the surface of the film, so that the light absorptive function can not be sufficiently expressed. Therefore, in order to use it 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.

Accordingly, it is an object of the present invention to provide a light absorbing composition which exhibits light selective absorptivity for visible light of a short wavelength near 400 nm and high affinity with a material of a constituent member of a display device and / or solubility in various solvents The purpose.

The present invention provides the following preferred embodiments.

 [1] A light absorbing composition comprising at least two kinds of photo-selective absorptive compounds, wherein at least two kinds of the light-selective absorptive compounds have the same conjugated system 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 in the above-mentioned optical selective-absorptive compound having at least two kinds of the same conjugated system structure is 5 nm or less.

 [3] The photodetecting composition according to [1] or [2]

[Chemical Formula 1]

[Wherein,

R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 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 represents a methylene group, a secondary amino group, an oxygen atom or a sulfur atom,

X ¹ and X ² may independently represent an electron attractive group and X ¹ and X ² may be connected to each other to form a ring structure]

Or formula (II):

(2)

[Wherein,

R ¹ , X ¹ and X ² have the same meanings as defined above,

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 when the alkyl group has at least one methylene group, at least one of the methylene groups is a secondary amino group, Sulfur atom, and the aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent]

The light absorbing composition according to the above [1] or [2], which is a photo-selective absorptive compound represented by the following formula (1).

[4] The photo-selective absorptive compound represented by the formula (I) is a compound represented by the formula (I-2):

(3)

[Wherein,

R ¹ is as defined above,

R ⁴ represents a hydrogen atom or an alkyl group having 2 to 50 carbon atoms, and when the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted with an oxygen atom]

(II-2): " (II-2) " represents a photo-selective water absorbent compound represented by the formula

[Chemical Formula 4]

[Wherein R ¹ and R ⁴ are as defined above]

Is a photo-selective absorptive compound represented by the following formula (1).

[5] The photodynamic composition according to any one of [1] to [5], wherein the photodecomposable composition comprises at least two photodecomposing compounds having the same conjugated system structure, wherein the content of the optically- Absorbing composition according to any one of [1] to [4], wherein the ratio of the total amount of the light absorbing agent to the total amount of the light absorbing agent is from 1:10 to 10: 1.

[6] Expression (1), Expression (2) and Expression (3):

? (420) /? (400)? 0.3 (1)

? max? 420 nm (2)

? (400)? 20 (3)

[Wherein,

? 420 represents a gram extinction coefficient at a wavelength of 420 nm,

? 400 represents a gram extinction coefficient at a wavelength of 400 nm,

? max represents the maximum absorption wavelength]

Of the light absorbing composition according to any one of [1] to [5].

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

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

[9] An optical film comprising the polymer composition according to the above [7] or [8].

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

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

[12] the following formulas (4) and (5):

Ap (400)? 0.4 (4)

Ap (420) / Ap (400)? 0.3 (5)

[Wherein,

Ap 400 represents the absorbance of the optical film in the transmission axis direction of the polarizing film at a wavelength of 400 nm,

And Ap (420) represents the absorbance of the optical film in the transmission axis direction of the polarizing film at a wavelength of 420 nm.

Of the laminated polarizing film described in [11].

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

[14] An elliptically polarizing film comprising the optical film described in [9] or [10], a polarizing film, and a retardation film.

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

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

1 is a schematic cross-sectional view showing an example of the layer structure of an optical laminate in one embodiment of the present invention.
2 is a schematic cross-sectional view showing an example of the layer structure of the optical laminate 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, but various modifications can be made without departing from the spirit of the present invention.

The light absorbing composition of the present invention is a composition comprising at least two kinds of photo-selective absorptive compounds, and at least two of the above-described photo-selective absorptive compounds have the same conjugated system structure. Further, in the present invention, the conjugated system structure refers to a molecular structure in which a pi -electric system is a non-electrode material along a molecular chain. The conjugated system structure includes, for example, a structure surrounded by the following square. In the following formulas, the moiety bonded to the conjugated system structure (structure in the range surrounded by the square) is a methylene group. However, unless the conjugated system structure is elongated, such moiety is not limited to the methylene group, And the like.

[Chemical Formula 5]

The number of carbon atoms in the conjugated system structure is preferably 1 to 20, more preferably 2 to 15, still more preferably 3 to 10. When the number of carbon atoms contained in the conjugated system structure is within the above range, the light absorbing composition of the present invention tends not to absorb blue light and tends to exhibit photo-selective absorptivity against visible light of a short wavelength near 400 nm.

In the light absorbing composition of the present invention, at least two kinds of photo-selective absorptive compounds contained in the composition have the same conjugated system structure. Accordingly, when added to the light absorptive composition of the present invention in the pressure-sensitive adhesive sheet, the bleed-out of the photo-selective absorptive compound in the pressure-sensitive adhesive can be suppressed, and at the same time, the pressure-sensitive adhesive function of the pressure-sensitive adhesive is hardly inhibited. Further, since the bleed-out of the photo-selective absorptive compound is suppressed, a pressure-sensitive adhesive sheet having a high concentration of the photo-selective absorptive compound can be incorporated into the pressure-sensitive adhesive and excellent in both thinness and light absorptivity can be obtained. As the thickness of the display device is reduced, the thickness of each member is also required. However, when the thickness of the member is reduced, it is necessary to increase the concentration of the light absorbent incorporated in the member. According to the light absorbing composition of the present invention, since the bleeding-out is suppressed, it is possible to meet the requirement of thinness of the member. In addition, when added to the optical absorbing composition of the present invention in the optical film, the bleed-out of the photo-selective absorptive compound can be suppressed, and at the same time the optical function can be inhibited from being inhibited. Further, in the present invention, as long as at least two kinds of photo-selective absorptive compounds contained in the light absorbent composition have the same conjugated system structure, other photo-selective absorptive compounds having a conjugated system structure different from the conjugated system structure are included You can.

In a preferred embodiment of the present invention, the conjugated system structure of any one kind of photo-selective absorptive compound is the same as the conjugated system structure of at least one kind of photo-selective absorptive compound. That is, when a photo-selective absorptive compound A having a conjugated system structure a is contained in the composition, another photo-selective absorptive compound B having the same conjugated system structure a is also included in the composition. In addition, when the photo-selective absorptive compound C having the conjugated system structure b is further contained in the composition, it is preferable that the photo-absorptive compound D having the conjugated system structure b is further included in the composition. That is, when four kinds of photo-selective absorptive compounds A to D are contained in the light absorbing composition of the present invention, for example, it is preferable that only one kind of photo-selective absorptive compound has no other conjugated system structure Do. In this case, the bleed-out of the light-selective absorptive compound from the constituent members (optical film, pressure-sensitive adhesive, etc.) of the display device can be further suppressed and the inhibition of the optical function of the optical film and / have.

The difference between the maximum value and the minimum value of the maximum absorption wavelength (hereinafter also referred to as "? Max ") in the at least two kinds of photo-selective absorptive compounds having the same conjugated system structure contained in the light absorptive composition of the present invention is preferably Is not more than 5 nm, more preferably not more than 4 nm, further preferably not more than 3 nm, particularly preferably not more than 2 nm, for example, not more than 1 nm. The fact that the difference between the maximum value and the minimum value of? Max is 5 nm or less means that the structure of each photo-selective absorptive compound having the same conjugate system structure is close (having a similar structure). It is possible to further suppress the bleed-out of the photo-selective absorptive compound from the constituent members of the display device and to further improve the light absorptive composition which is superior in the photo-selective absorptive property when the difference between the maximum value and the minimum value of? Max of the photo- Can be obtained. The lower limit of the difference between the maximum value and the minimum value of? Max of the photo-selective absorptive compound is, for example, 0 nm or more.

In one embodiment of the present invention, from the standpoint of exhibiting high photo-selective absorptivity, the photo-selective absorptive compound has the formula (I):

[Chemical Formula 6]

[Wherein,

R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 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 amino group, an oxygen atom or a sulfur atom,

X ¹ and X ² may independently represent an electron attractive group and X ¹ and X ² may be connected to each other to form a ring structure]

Or formula (II):

(7)

[Wherein,

R ¹ , X ¹ and X ² have the same meanings as defined above,

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 when the alkyl group has at least one methylene group, at least one of the methylene groups is a secondary amino group, Sulfur atom, and the aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent]

Is a photo-selective absorptive compound. 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 the same or different You can.

In the formulas (I) and (II), R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 10 carbon atoms, Represents an alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Here, 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 such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, An isopropoxy group, and a polypropylene glycol group.

In the formulas (I) and (II), X ¹ and X ² independently represent an electron-withdrawing group. Examples of the electron-withdrawing group include -CN (cyano group), -NO ₂ (nitro group), a halogen atom, an alkyl group substituted with a halogen atom, -Y ¹ -R ^{4 wherein} R ⁴ is a hydrogen atom, When the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted with an oxygen atom, a substituent may be bonded to the carbon atom on the alkyl group, Y ¹ (Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group), or a group represented by -O-, -CO-, -COO-, -OCO-, -NR ⁶ CO- or -CONR ⁷ - ). X ¹ and X ² may be connected to each other to form a ring structure. The ring structure includes, for example, a ring structure having 4 to 8 atomic rings, and a ring structure having 5 atomic or 6-member rings is preferable And examples thereof include a meldrum acid structure, a barbituric acid structure, a dimedon structure, and the like.

The alkyl group having 2 to 50 carbon atoms in R ⁴ has preferably 3 or more carbon atoms, more preferably 6 or more carbon atoms, from the viewpoint of affinity with the material of the constituent members of the display device and / or solubility in various solvents. Or more. It is preferably 40 or less, more preferably 30 or less, and further preferably 12 or less. The number of carbon atoms is preferably from 2 to 40 (for example, from 2 to 20), more preferably from 3 to 40 (for example, from 3 to 18), and still more preferably from 3 to 30 , 3 to 16), and particularly preferably 6 to 12 (for example, 6 to 14).

In the case where the 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, propoxy group, 2- And a methoxyethoxymethyl group. Further, polyethylene glycol groups such as diethylene glycol group and triethylene glycol group, and polypropylene glycols such as dipropylene glycol group and tripropylene glycol group are also exemplified.

A substituent may be bonded to the carbon atom on the alkyl group of R < ^{4 &} gt ;. 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, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, Alkyl group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, A sulfamoyl group, and an N, N-dialkyl sulfamoyl group having 2 to 12 carbon atoms.

When R ⁴ is an alkyl group having 2 to 50 carbon atoms, it is more preferable that R ⁴ is an alkyl group having a branched structure, from the viewpoint of affinity with a hydrophobic substance and solubility in a hydrophobic solvent.

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

[Chemical Formula 8]

X ¹ and X ² are each independently selected from the group consisting of -CN (cyano group), -NO ₂ (nitro group, and the like) in view of the light selective absorptivity and the affinity with the material of the constituent members of the display device and / group), a halogen atom, or -Y ¹ -R ⁴ of the Y ¹ is preferably a -CO-, -COO-, or -OCO-, and, -CN (cyano group), or -Y ¹ -R ⁴ of Y ¹ is more preferably -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, and preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, 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, Represents a hydrogen atom.

In formula (I), A ¹ represents a methylene group, a secondary amino group, an oxygen atom or a sulfur atom. The secondary amino group is a substituent represented by the general formula -NR ⁵ -, and R ⁵ is, for example, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, An alicyclic hydrocarbon group or an aromatic hydrocarbon group. A ¹ preferably represents a methylene group or an oxygen atom from the viewpoint of exhibiting high photo-selective absorptivity.

In 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 groups may be substituted with a secondary amino group, an oxygen atom, or a sulfur atom, and the aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent. Examples of the alkyl group represented by A ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, . Examples of the substituent that the aromatic hydrocarbon group and 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. The 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 a pyridyl group, a quinolyl group, a thiophene group, an imidazolyl group, an oxazolyl group, a pyrrolyl group, a thiazolyl group , And furanyl group. From the viewpoint of ease of production, A ² is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

When the light absorbing composition of the present invention contains at least two compounds represented by the above formula (I), R ¹ to R ³ , X ¹ , X ^2, and A ¹ in the formula (I) And 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 or more compounds represented by the above formula (I), from the viewpoint of further enhancing the photo-selective absorptivity of the light absorbing composition of the present invention, 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 compounds represented by the above formula (II), R ¹ , X ¹ , X ² and A ² in the formula (II) representing each compound may be different 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 compounds represented by the above formula (II), from the viewpoint of further enhancing the photo-selective absorbability of the light absorbing composition of the present invention, R ¹ , X ¹ and A ² in formula (II) representing each compound are the same and X ² is different.

Examples of the photo-selective absorptive compound represented by the formula (I) include compounds represented by the following formulas.

[Chemical Formula 9]

[Chemical formula 10]

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

The photo-selective absorptive compound represented by the formula (I) has a photo-selective absorptive property and is excellent in affinity with the material of the constituent members of the display device and / or solubility in various solvents. Is preferably a photo-selective absorptive compound.

(11)

In the formula (I-2), R ¹ and R ⁴ have the same meanings as defined above.

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

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

The photo-selective absorptive compound represented by the formula (II) is preferably a photo-selective absorptive compound represented by the following formula (II-2) from the viewpoints of photo-selective absorptivity and ease of production.

[Chemical Formula 16]

Wherein R ¹ and R ⁴ have the same meanings as defined above.

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

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

Examples of the photo-selective absorptive compound represented by the formula (II) include compounds represented by the following formulas.

[Chemical Formula 22]

The compound represented by the above formula (I-2) can be obtained by, for example, using 2-methylpyrroline as a methylating agent to give a 1,2-dimethylpyrrolinium salt, followed by N, N'-diphenylformamidine Lt; / RTI > Finally, it can be prepared by reacting an active methylene compound in the presence of acetic anhydride and an amine catalyst. The compound represented by the above formula (I) or (I-1-2) can be produced by the same method as the compound represented by the above formula (I-2). The compounds represented by formulas (II) and (II-2) can be obtained by reacting 3-formylindole with an active methylene compound (Knoevenagel reaction), and an amine catalyst may be used in combination for the reaction. When R ¹ in the formulas (II) and (II-2) is an alkyl group having 1 to 10 carbon atoms, the alkyl halide is reacted with 3-formylindole in the presence of a base catalyst and then reacted with an active methylene compound Can be produced. Commercially available compounds may also be used.

When at least two kinds of photo-selective absorptive compounds having the same conjugated system structure and contained in the light absorptive composition of the present invention are compounds _cmax in which the content of the photo-absorptive composition in the light absorptive composition is the maximum, the ratio of the total amount of the content of content and the other light-absorbent compounds selected of compound _cmax ([compound content of _cmax]: [the total amount of content of the other light absorbent selected compound]) is preferably 1:10 to 10:01, More preferably from 1: 8 to 8: 1, more preferably from 1: 6 to 6: 1, particularly preferably from 1: 5 to 5: 1, particularly preferably from 1: 4 to 4: : 3 to 3: 1, for example 1: 2 to 2: 1. When the ratio is within the above range, the bleed-out of the photo-selective absorptive compound is suppressed, making it difficult to inhibit the adhesive function as an adhesive and the optical function as an optical film.

The light absorbing composition is excellent in affinity with components of a display device (for example, a pressure-sensitive adhesive, an optical film, etc.) and / or solubility in various solvents. If the solubility in solvents constituting the pressure-sensitive adhesive coating liquid is excellent, a photo-selective absorptive compound can be uniformly dispersed in the pressure-sensitive adhesive sheet, so that a pressure-sensitive adhesive having excellent light absorptivity can be obtained. Examples of such solvents include alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, 1-butanol, 2-butanol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether An ester solvent such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone, propylene glycol monomethyl ether acetate and ethyl lactate; acetone, 2-butanone, cyclopentanone, cyclohexanone, methyl amyl Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene, xylene and mesitylene; nitrile solvents such as acetonitrile; ketones such as tetrahydrofuran, dimethoxyethane, 1,4-dioxane and the like, and chlorinated hydrocarbon solvents such as dichloromethane, chloroform and chlorobenzene.

Such solvents include hydrophilic solvents and hydrophobic solvents. For example, the alcohol solvent may be different depending on the number of carbon atoms, but is generally a solvent having hydrophilicity. On the other hand, aliphatic hydrocarbon solvents such as pentane, hexane and heptane are generally hydrophobic solvents. From the viewpoint of widening the selectivity of the solvent, it is preferable that the light absorbing composition is soluble in a hydrophilic solvent or a hydrophobic solvent, and that the light absorbing composition is soluble in a hydrophilic solvent and a hydrophobic solvent, that is, Do.

The light absorbing composition of the present invention is particularly excellent in affinity with a pressure-sensitive adhesive, an optical film and the like. If the affinity with the polymer (particularly acrylic resin) constituting the pressure-sensitive adhesive is excellent, bleeding-out of the photo-selective absorptive compound from the pressure-sensitive adhesive sheet can be suppressed and it is difficult to inhibit the adhesive function of the pressure-sensitive adhesive sheet. It is preferable that the light absorbing composition of the present invention is used in combination with a polymer constituting the optical film (in particular, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, , Polyvinylidene fluoride / polymethyl methacrylate, acetyl cellulose, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride), the bleed-out of the optical selective-absorptive compound from the optical film is suppressed It is difficult to inhibit the optical function of the optical film. Further, when the affinity with the polymer (particularly, triacetyl cellulose or cycloolefin polymer) constituting the protective film is excellent, the bleed-out of the photo-selective absorptive compound from the protective film can be suppressed.

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

? (420) /? (400)? 0.3 (1)

In the formula (1),? (420) represents the gram extinction coefficient of the light absorbing composition at a wavelength of 420 nm, and? (400) represents the gram extinction coefficient of the light absorbing composition at a wavelength of 400 nm. The value of? (420) /? (400) represents the absorption intensity (grazing extinction coefficient) at a wavelength of 400 nm to the absorption intensity (grazing extinction coefficient) at a wavelength of 420 nm, As compared with the absorption in the wavelength region near 420 nm, there is a specific absorption in the wavelength region near 400 nm, indicating that it has photo selective absorptivity. The smaller the value, the less yellowish the compound becomes.

When the light absorbing composition satisfies the above formula (1), it is difficult to absorb light having a wavelength of 420 nm while absorbing light having a wavelength of 400 nm, and it is difficult to absorb blue visible light. , It is possible to provide a light absorber which is difficult to inhibit good color expression. Further, in the case of an optical laminate including such a light absorbing composition, it is preferable that a member constituting the optical laminate (for example, an optical film such as a retardation film, a display element such as an organic EL element or a liquid crystal display element) It is possible to suppress deterioration in performance due to visible light (that is, light near a wavelength of 400 nm). The value of? (420) /? (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, Particularly preferably 0.1 or less, and very preferably 0.05 or less, for example, 0.03 or less. The lower limit value is not particularly limited, but is preferably 0.005 or more from the viewpoint of maintaining the absorption ability near 400 nm by the above-described light absorbing composition. In one preferred embodiment of the present invention, the value of? (420) /? (400) is 0.01 to 0.17.

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

? max? 420 nm (2)

? (400)? 20 (3)

In the formula (2),? Max represents the maximum absorption wavelength of the light absorbing composition. In the formula (3),? (400) represents the gram extinction coefficient of the light absorbing composition at a wavelength of 400 nm, and the unit of the gram extinction coefficient is defined as? / (G?

When the above formulas (2) and (3) are satisfied, it can be said that the maximum absorption of the light absorbing composition exists on the shorter wavelength side than 420 nm, and also exhibits a high absorption toward the wavelength of 400 nm. When the light absorbing composition satisfies this formula, members such as an optical film containing such a composition hardly affect the display characteristics and can have high light resistance. In the present invention, the maximum absorption? Max of the light absorbing composition is more preferably 410 nm or less, further preferably 400 nm or less. The maximum absorption? Max of the light absorbing composition is, for example, 370 nm or more.

When the above-mentioned light absorbing composition satisfies the above formula (3), the light absorbing composition has a high light absorbing property. Therefore, even if the light absorbing composition contained in the member constituting the optical laminate is small, It is difficult to deteriorate the adhesive function, and when the light-absorbing composition is contained in the protective film, it is difficult to hinder the optical function of the protective film. The value of epsilon 400 is preferably at least 20 [l / (g · cm)], more preferably at least 30 [l / (g · cm)] and more preferably at most 40 [ (G · cm)] or more, still more preferably 50 [l / (g · cm)] or more, particularly preferably 80 )] Or more. Further, the value of? (400) is usually 300 [liter / (g · cm)] or less.

In another embodiment of the present invention, there is provided a polymer composition containing the light absorbing composition and a polymer (hereinafter also referred to as " the polymer composition of the present invention "). By using the polymer composition, various members (for example, a pressure-sensitive adhesive sheet, a protective film, a polarizing film, a retardation film and a front plate) constituting the optical laminate can be obtained. Since such an optical laminate contains the above-described light absorbing composition having excellent light selective absorptivity, it is difficult to absorb blue visible light, and therefore it is difficult to inhibit good color expression. The performance of the display element or the optical film as the constituent member of the display device may be deteriorated not only by ultraviolet rays but also by visible light in the short wavelength range, that is, near 400 nm wavelength. However, It is possible to suppress the deterioration of short wavelength components due to visible light.

The thickness of the optical film of the present invention is not particularly limited, but is preferably 18 占 퐉 or less, more preferably 13 占 퐉 or less, and even more preferably 8 占 퐉 or less. When the thickness of the optical film is not more than the upper limit value, bleeding-out is unlikely to occur even if the concentration of the light absorbing composition contained in the optical film is high. Thus, it is easy to obtain a thin optical laminate, Function (for example, the retardation function of the retardation film, the adhesive function of the adhesive sheet) can be exhibited. The lower limit value of the thickness of the optical film of the present invention is not particularly limited, but is preferably 0.1 占 퐉 or more, more preferably 1 占 퐉 or more, and further preferably 2 占 퐉 or more. If the thickness of the optical film is not more than the upper limit value, it is preferable from the viewpoint of thinning. The thickness of the optical film can be measured by, for example, a laser microscope or an ellipsometer.

In another embodiment of the present invention, a pressure-sensitive adhesive comprising the polymer composition and an optical film (also referred to as " the optical film of the present invention ") are also provided. In the present invention, examples of the optical film include a polarizing film, a retardation film, a protective film, a pressure-sensitive adhesive sheet, and a front plate. These optical films and pressure-sensitive adhesives can be cited as members constituting the optical laminate. In the present invention, the optical laminate refers to a laminate including the optical film of the present invention, and includes a laminated polarizing film, laminated phase difference film and elliptically polarizing film to be described later.

Here, for the optical laminate, examples of several suitable layer structures are shown in the sectional schematic diagrams in Figs. 1 and 2. Fig. In the example shown in Fig. 1, a first protective film 4 having a surface treatment layer 2 is adhered to one surface of a polarizing film 1 on the surface opposite to the surface treatment layer 2 And the second protective film 3 is adhered to the other surface of the polarizing film 1 to constitute the polarizing plate 10. [ A pressure sensitive adhesive sheet 20 is formed on the outside of the second protective film 3 constituting the polarizing plate 10 to constitute a polarizing plate 15 having a pressure sensitive adhesive. The surface of the pressure-sensitive adhesive sheet 20 opposite to the polarizing plate 10 is bonded to the image display element 30 to form the optical laminated body 40. Such an optical laminate can be used in an image display apparatus. It is also preferable that the member including the light absorbing composition of the present invention is disposed on the viewer side of an image display element such as an optical film or an organic EL element which is easily deteriorated. By this arrangement, it is possible to suppress deterioration of the function of the member, which is liable to be deteriorated.

In the example shown in Fig. 2, the first protective film 4, which may have the surface treatment layer 2, is adhered to one surface of the polarizing film 1 on the surface opposite to the surface treatment layer 2 The second protective film 3 is bonded to the other surface of the polarizing film 1 and the retardation film 7 is adhered to the outside of the second protective film 3 through the interlayer adhesive 6, Thereby constituting a polarizing plate 10. A pressure sensitive adhesive sheet 20 is formed on the outer side of the retardation film 7 constituting the polarizing plate 10 to constitute a polarizing plate 15 with a pressure sensitive adhesive. The surface of the pressure-sensitive adhesive sheet 20 opposite to the retardation film 7 is bonded to the image display element 30 to form the optical laminate 40. [

In these examples, the first protective film 4 and the second protective film 3 are generally composed of a triacetylcellulose film or a polycycloolefin, but they may also be composed of the following transparent resin films. The surface treatment layer that can be formed on the surface of the first protective film 4 may be a hard coat layer, an antiglare layer, an antireflection layer, or an antistatic layer. It is also possible to form a plurality of these layers.

As in the example shown in Fig. 2, in the case of laminating the retardation film 7 in the polarizing plate 10, a 1/4 wavelength plate can be mentioned as a suitable example of the retardation film 7 in the case of a small and medium-sized liquid crystal display device . In this case, it is common that the absorption axis of the polarizing film 1 and the slow axis of the retardation film 7, which is a 1/4 wavelength plate, are arranged to intersect at almost 45 degrees. However, depending on the characteristics of the image display element 30 The angle may be shifted to some extent from 45 degrees. On the other hand, in the case of a large-sized liquid crystal display device such as a television, a phase difference film having various retardation values is used in accordance with the characteristics of the image display element 30 for the purpose of compensating the retardation of the image display element 30 and the viewing angle. In this case, it is general that the absorption axis of the polarizing film 1 and the slow axis of the retardation film 7 are arranged to be almost orthogonal or substantially parallel. When the retardation film 7 is constituted by a 1/4 wavelength plate, a uniaxial or biaxially stretched film is suitably used. When the retardation film 7 is formed for purposes of phase difference compensation or viewing angle compensation of the image display element 30, besides monoaxially or biaxially stretched film, besides monoaxial or biaxial stretching, A film obtained by applying a retardation-developing substance such as liquid crystal on a supporting film and orientation-fixed on the supporting film may be used as the retardation film 7, which is called an optical compensation film.

Likewise, when the retardation film 7 in the configuration of the polarizing plate 10 is bonded through the interlaminar adhesive 6 as in the example shown in Fig. 2, it is customary to use a general acrylic adhesive for the interlaminar adhesive 6 However, it is also possible to use a pressure-sensitive adhesive or pressure-sensitive adhesive sheet composed of the polymer composition of the present invention. In the case where the absorption axis of the polarizing film 1 and the slow axis of the retardation film 7 are arranged so as to be almost orthogonal or almost parallel to each other as in the above-described large liquid crystal display device, Roll-to-roll lamination can be performed when the laminate 1 and the retardation film 7 are laminated through the interlaminar adhesive 6.

The pressure-sensitive adhesive film on which the pressure-sensitive adhesive sheet is formed on the retardation film can be formed into an optical laminate by bonding the pressure-sensitive adhesive sheet to an image display element, and the polarizing plate may be bonded to the retardation film side.

Here, a polarizing film (also referred to as a " polarizer ") is an optical film having a function of emitting polarized light to incident light such as natural light. The polarizing plate includes a linearly polarizing plate that absorbs linearly polarized light having a vibration plane in any direction incident on the polarizing plate and transmits linearly polarized light having a vibration plane orthogonal thereto and a linearly polarizing plate having a straight line having a vibration surface in any direction A polarized light separating film having a property of reflecting polarized light and transmitting linearly polarized light having a vibration plane orthogonal thereto, and an elliptically polarizing plate obtained by laminating a polarizing plate and a retardation film to be described later. As a preferable example of a polarizing plate, particularly a linear polarizing plate (sometimes referred to as a polarizer or a polarizer film), a monoaxially stretched polyvinyl alcohol resin film in which a dichroic dye such as iodine or a dichroic dye is adsorbed and oriented . A coating type thin film polarizing film may also be used. As the coating type thin film polarizing film, for example, those exemplified in JP-A-2012-58381, JP-A-2013-37115, WO-A-2012/147633 and WO-A-2014/091921 can be used have. The thickness of the polarizer is not particularly limited, but is usually 0.5 to 35 mu m.

The retardation film is an optical film exhibiting optical anisotropy, and includes, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polymethacrylate, polyimide, polyolefin, polycycloolefin (norbornene or tetracyclo Polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride / polymethyl methacrylate, liquid crystal polyester, acetylcellulose, ethylene-vinyl acetate copolymer saponite, polyvinyl chloride, etc. And a stretched film obtained by stretching a polymer film made of a polymer of about 1.01 to 6 times. Among them, a polymer film in which a polycarbonate film or a polycycloolefin film is uniaxially or biaxially stretched is preferable. In one embodiment of the present invention, a phase difference film can be obtained by forming the polymer and the composition comprising the light absorbing composition of the present invention into a film, and then uniaxially or biaxially stretching the obtained film. A film exhibiting optical anisotropy by application and orientation of a polymerizable liquid crystal compound can also be used as a retardation film.

Further, a protective film adhered to these optical films can also be used as an optical film. As the protective film, a transparent resin film is used. As the transparent resin, for example, an acetylcellulose resin represented by triacetylcellulose or diacetylcellulose, a methacrylic resin represented by polymethylmethacrylate, a poly Ester resins, polyolefin resins, polycarbonate resins, polyether ether ketone resins, and polysulfone resins. The resin constituting the protective film may be blended with a UV absorber such as a salicylic ester compound, a benzophenone compound, a benzotriazole compound, a triazine compound, a cyanoacrylate compound or a nickel complex salt compound. In this case, , Deterioration of the display device can be suitably suppressed by the synergistic effect with the effect of the light absorbing composition of the present invention. As the protective film, an acetylcellulose-based resin film such as a triacetylcellulose film is suitably used.

Among the optical films described above, a linear polarizer is often used in a state in which a protective film is attached to one side or both sides of a polarizing film made of a polarizing film, for example, a polyvinyl alcohol-based resin. The above-mentioned elliptically polarizing plate is a laminate of a linearly polarizing plate and a retardation film. In many cases, however, the polarizing plate is also in a state where a protective film is adhered to one surface or both surfaces of the polarizing plate.

The protective film is a film used for the purpose of protecting the surface of an optical film or the like to be protected from scratches or contamination. 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 polyfluoroethylene; polyesters such as polyethylene naphthalate, polyethylene terephthalate, Polyamides such as nylon 6 and nylon 6,6, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, Vinyl alcohol copolymers, polyvinyl alcohols, and vinylon; cellulose polymers such as cellulose acetate triacetate, cellulose diacetate, cellophane and triacetyl cellulose; polymers such as polymethyl methacrylate, ethyl polymethacrylate, ethyl polyacrylate, poly Acrylic polymer such as butyl acrylate, etc. In addition, , There may be mentioned polycarbonate, polyarylate, polyimide, polyurethane or the like.

The pressure-sensitive adhesive sheet is a sheet made of a pressure-sensitive adhesive. The pressure-sensitive adhesive is a reagent for bonding a member such as the optical film to another member. The polymer constituting the pressure-sensitive adhesive is not particularly limited, and examples thereof include poly (meth) acrylate (acrylic resin), silicone polymer, polyurethane, and rubber. These polymers may be used alone or in combination. Of these, it is preferable to employ an acrylic resin as the polymer in that the functionality can be easily imparted to the pressure-sensitive adhesive by selecting the kind of the monomer to be introduced into the polymer. Further, (meth) acrylate means acrylate and / or methacrylate.

By using the polymer composition of the present invention, the members constituting the optical laminate can be obtained. For example, in one embodiment of the present invention, there can be provided a pressure-sensitive adhesive sheet, a protective film, a retardation film, a polarizing film, a front plate and the like, which are composed of a polymer composition comprising the light- have.

The polymer contained in the polymer composition is preferably an acrylic resin [poly (meth) acrylate], a polyurethane, a polyester, a polycarbonate, a polycycloolefin or the like, from the viewpoint of suitably preparing a member constituting the optical laminate Olefin, and triacetyl cellulose.

The adhesive function of the pressure-sensitive adhesive sheet may be impaired when the UV absorber is blended with the pressure-sensitive adhesive sheet (particularly when the pressure-sensitive adhesive sheet is blended at a high concentration). However, the pressure-sensitive adhesive sheet composed of the polymer composition of the present invention, It is possible to suppress the bleed-out from the pressure-sensitive adhesive sheet and to exhibit stable light absorbency over a long period of time. In the display device using the pressure-sensitive adhesive sheet, it is not necessary to dispose a separate member having a light-absorbing function, so that the display device can be made thinner and lighter.

In one embodiment of the present invention, the polymer composition may contain a crosslinking agent, if necessary, in addition to the polymer and the light absorbing composition. The crosslinking agent is, for example, a compound which reacts with a constituent unit derived from a hydroxyl group or a polar functional group-containing monomer, particularly in poly (meth) acrylate, and crosslinks the poly (meth) acrylate. Specific examples thereof include isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds and the like. Among them, the isocyanate compound, the epoxy compound and the aziridine compound have at least two functional groups in the molecule which can react with the hydroxyl group and optionally the polar functional group in the poly (meth) acrylate (A).

In the polymer composition, the content of the light absorbing composition (preferably the total amount of the photo-selective absorptive compound contained in the light absorbing composition) relative to 100 parts by mass of the polymer (solid content) is preferably 1 to 15 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. If the content of the light absorbing composition is less than the above lower limit value, the amount of light absorbed increases, and the amount of light absorbed in the member constituting the optical laminate (for example, an optical film such as a retardation film or an image display element such as an organic EL element) Deterioration due to visible light of short wavelength can be suppressed. When the content of the light absorbing composition is not more than the upper limit value, when the polymer composition is used as a pressure-sensitive adhesive, the pressure-sensitive adhesive function can be sufficiently exhibited and it is difficult to further inhibit the optical function as an optical film obtained using the polymer composition. Further, the above-mentioned light absorbing composition is excellent in solubility in various solvents. Therefore, even if the content is high (for example, the light absorbing composition (preferably, the light absorbing composition The total amount of the photo-selective-absorptive compound contained) 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) Out can be suppressed and it becomes difficult to inhibit the adhesive function as the pressure-sensitive adhesive and the optical function as the optical film.

When the polymer composition of the present invention is a pressure-sensitive adhesive composition constituting a pressure-sensitive adhesive sheet, in a preferred embodiment of the present invention,

(A) Based on the total amount of the solid components of the acrylic resin (polymer)

(A-1) a compound represented by the following formula (A-1):

(23)

50 to 99.9 mass% of a (meth) acrylic acid ester monomer represented by the following formula

(A-2) 0.1 to 50% by mass of an unsaturated monomer having a polar functional group,

An acrylic resin having a weight average molecular weight of 500,000 to 2,000,000, and

(B) 0.01 to 10 parts by mass of a crosslinking agent

Lt; / RTI >

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

Specific examples of the (meth) acrylic acid ester monomer (A-1) (hereinafter sometimes referred to as "monomer (A-1)") represented by the above formula (A-1) include methyl acrylate, ethyl acrylate, Propyl acrylate, n-butyl acrylate, n-octyl acrylate and lauryl acrylate; branched alkyl acrylates such as isobutyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate; Linear methyl methacrylate alkyl esters such as methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate and lauryl methacrylate; Acrylic acid ester having an aromatic group such as phenyl acrylate and benzyl acrylate; acrylates such as 2-phenoxy acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Methacrylate, such as the 2-phenoxy ethyl acrylate, phenoxy esters, methacrylic acid phenyl ester, methacrylic acid, benzyl ester, and methacrylic acid esters having an aromatic group and the like. These may be used alone or in combination of a plurality of species. Among them, n-butyl acrylate is preferable from the viewpoint of stickiness.

Examples of the polar functional group in the unsaturated monomer (A-2) having a polar functional group (hereinafter also referred to as "monomer (A-2)") include a free carboxyl group, a hydroxyl group, an amino group, And the like. The monomer (A-2) is preferably a (meth) acrylic acid-based compound having a polar functional group. Examples thereof include unsaturated monomers having a free carboxyl group such as acrylic acid, methacrylic acid, and? -Carboxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Unsaturated monomers having a hydroxyl group such as 2- or 3-chloro-2-hydroxypropyl, and diethylene glycol mono (meth) acrylate; acryloylmorpholine, vinylcaprolactam, N- (Meth) acrylate, glycidyl (meth) acrylate, and 2,5-di (meth) acrylate, Unsaturated monomers having a heterocyclic group such as hydrofluorene and hydrofuran; and unsaturated monomers having an amino group different from heterocyclic rings such as N, N-dimethylaminoethyl (meth) acrylate. These monomers (A-2) may be used alone or in a plurality of different types.

Among them, it is preferable that the unsaturated monomer having a hydroxyl group is contained as one of the monomers (A-2) constituting the acrylic resin (A) from the viewpoint of increasing the adhesive force of the pressure-sensitive adhesive composition and further improving durability.

An acrylic resin having a monomer (A-1) and a monomer (A-2) as a constitutional unit (hereinafter sometimes referred to as "acrylic resin (A)") Preferably 50 to 99.9% by mass, more preferably 70 to 99.9% by mass, based on 100% by mass of the component (A-1). The content of the constituent unit derived from the monomer (A-2) is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass. When the ratio of the monomer (A-1) to the monomer (A-2) is within the above range, a pressure-sensitive adhesive composition having excellent workability can be provided.

Although the acrylic resin (A) contains, as a constituent component, a monomer other than the monomer (A-1) and the monomer (A-2) (hereinafter sometimes referred to as "monomer (A-3) do. Examples of other monomers include (meth) acrylate esters having an alicyclic structure in the molecule, styrene monomers, vinyl monomers, monomers having a plurality of (meth) acryloyl groups in the molecule, (meth) acrylamide derivatives And the like.

The alicyclic structure is a cycloparaffin structure having a carbon number of usually 5 or more, preferably 5 to 7 or so. Specific examples of the acrylic ester having an alicyclic structure include acrylic acid esters such as isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, Cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, , Cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, cyclohexylphenyl methacrylate, and the like.

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

Examples of the vinyl-based monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate, vinyl halides such as vinyl chloride and vinyl bromide, vinylidene halides such as vinylidene chloride ; Nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; and acrylonitrile and methacrylonitrile.

Examples of the monomer having plural (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate such as ethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tripropylene glycol di Monomers having three (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate, and the like.

Examples of the (meth) acrylamide derivatives include N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl Amide, 5-hydroxypentyl (meth) acrylamide, 6-hydroxyhexyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (Meth) acrylamide, N- [2- (2-oxo-1-imidazolidinyl) ethyl] (Meth) acrylamide, 2-acryloylamino-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 acrylic resin (A) which can be used in the pressure-sensitive adhesive composition of the present invention, the constitutional unit derived from the monomer (A-3) is usually 0 To 20 parts by mass, and preferably from 0 to 10 parts by mass.

In one embodiment of the present invention, the pressure-sensitive adhesive composition may contain one or more kinds of the acrylic resin (A).

The acrylic resin (A) preferably has a weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) of preferably 500,000 to 2,000,000, more preferably 600,000 to 1,800,000, It is between 700,000 and 170,000. If the weight average molecular weight in terms of the standard polystyrene is 500,000 or more, the adhesiveness under high temperature and high humidity is improved and the possibility of peeling or peeling between the glass substrate (image display element) and the pressure sensitive adhesive sheet tends to decrease, It is preferable since the property tends to be improved. If the weight average molecular weight is not more than 2,000,000, even if the size of the optical film changes when the pressure-sensitive adhesive sheet is stuck to an optical film or the like, the pressure-sensitive adhesive sheet follows and changes in size, There is no difference between the brightness of the periphery of the device and the brightness of the center portion, which tends to suppress the white coloring and the 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 by various known methods such as solution polymerization, emulsion polymerization, bulk polymerization and suspension polymerization, for example. In the production of the acrylic resin, a polymerization initiator is usually used. The polymerization initiator is used in an amount of 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of all the monomers used in the production of the acrylic resin.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, and the like are used. As the photo polymerization initiator, for example, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like can be given. As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane- (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxy valeronitrile), dimethyl- Azo compounds such as azobis (2-methylpropionate), 2,2'-azobis (2-hydroxymethylpropionitrile), and the like; lauryl peroxide, tert- butyl hydroperoxide, benzoyl peroxide , tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxy pivalate, 5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide; and the like. A redox-type initiator using a peroxide and a reducing agent in combination may also be used as a polymerization initiator.

As the method for producing the acrylic resin (A), a solution polymerization method is preferable among the methods shown above. A specific example of the solution polymerization method will be described. A desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added in a nitrogen atmosphere, and the solution polymerization is carried out at about 40 to 90 ° C, preferably about 50 to 80 ° C for 3 to 15 hours , And the like. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during polymerization, or may be added in a state dissolved in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as propyl alcohol and isopropyl alcohol, aliphatic alcohols such as acetone, 2-butanone, And ketones such as methyl isobutyl ketone.

The pressure-sensitive adhesive composition may contain, in addition to the acrylic resin (A), an acrylic resin different from the acrylic resin (A). As such an acrylic resin, for example, a resin containing a constituent unit derived from a (meth) acrylate ester as a main component (for example, polymethyl (meth) acrylate) and having a weight average molecular weight in the range of 50,000 to 300,000 And the like.

When the pressure-sensitive 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 preferably 50 parts by mass or less based on 100 parts by mass of the acrylic resin (A) And more preferably 30 parts by mass or less.

The acrylic resin contained in the pressure-sensitive adhesive composition (in the case of combining two or more kinds thereof, the mixture thereof) is preferably a solution obtained by dissolving the acrylic resin in ethyl acetate and adjusting the solid content concentration to 20% by mass at 20 캜 or less at 25 캜, To 7 Pa · s. If the viscosity at this time is 20 Pa s or less, the adhesiveness under high temperature and high humidity is improved, the possibility of floating or peeling between the display element and the pressure sensitive adhesive sheet tends to be lowered, and furthermore, Therefore, it is desirable. The viscosity can be measured by a Brookfield viscometer.

As the crosslinking agent in the pressure-sensitive adhesive composition, for example, a compound which reacts with a constituent unit derived from an unsaturated monomer having a particularly polar functional group in the acrylic resin (A) and crosslinks the acrylic resin (A) is used. Specific examples thereof include isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds and the like. Among them, the isocyanate compound, the epoxy compound and the aziridine compound have at least two functional groups capable of reacting with the polar functional group in the acrylic resin (A) in the molecule.

The isocyanate compound is a compound having at least two isocyanato groups (-NCO) in the molecule and includes, for example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. It is also possible to use an adduct in which an isocyanate compound is reacted with a polyol such as glycerol or trimethylolpropane, or an isocyanate compound in the form of a dimer, a trimer or the like, or a crosslinking agent used in a pressure-sensitive adhesive. Two or more isocyanate compounds may be mixed and used.

The epoxy compound is a compound having at least two epoxy groups in the molecule, and examples thereof include bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, Glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, N, N-diglycidyl aniline, N, N, N ', N'-tetraglycidyl -m-xylene diamine, and 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane. Two or more kinds of epoxy compounds may be mixed and used.

The aziridine compound is a compound having at least two skeletons of a nitrogen atom and a triple ring composed of two carbon atoms, which is also called ethyleneimine, in the molecule. For example, diphenylmethane-4,4'-bis (1 Aziridine carboxamide), toluene-2,4-bis (1-aziridine carboxamide), triethylene melamine, isophthaloylbis-1- (2-methyl aziridine), tris- Hexamethylene-1,6-bis (1-aziridine carboxamide), trimethylolpropane-tri-? -Aziridinylpropionate, tetramethylolmethane-tri-? -Aziridinyl Propionate and the like.

Examples of the metal chelate compound include compounds for adding acetylacetone or ethyl acetoacetate to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium .

Among these cross-linking agents, an isocyanate-based compound, particularly xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, or an isocyanate-based compound thereof is reacted with a polyol such as glycerol or trimethylolpropane, A dimer, a trimer or the like, a mixture of these isocyanate compounds, and the like are preferably used. Suitable isocyanate compounds include tolylene diisocyanate, an adduct obtained by reacting tolylene diisocyanate with a polyol, a dimer of tolylene diisocyanate, a trimer of tolylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate, , A dimer of hexamethylene diisocyanate, and a trimer of hexamethylene diisocyanate. These may be used alone or in combination of two or more.

In the present invention, the pressure-sensitive adhesive composition is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the acrylic resin (100 parts by mass in total when two or more kinds of acrylic resins are contained) 0.01 to 0.08 part by mass, more preferably 0.01 to 0.06 part by mass of a crosslinking agent. When the amount of the crosslinking agent is 0.01 part by mass or more, the durability of the pressure-sensitive adhesive sheet tends to be improved, and if it is 10 parts by mass or less, white coloration when applied to a liquid crystal display device, .

Further, in the present invention, the pressure-sensitive adhesive composition preferably contains a silane-based compound, and in particular, it is preferable that a silane-based compound is contained in the acrylic resin before the crosslinking agent is blended. Since the silane-based compound improves the adhesion to glass, the adhesion between the display element sandwiched by the glass substrate and the pressure-sensitive adhesive sheet can be improved by including the silane-based compound.

Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, -Mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxy Dimethylsilane, and the like. These may be used alone or in combination of two or more.

The silane-based compound may be a silicone oligomer type. Examples of the silicone oligomer in the form of a (monomer) oligomer include the following.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer , 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer, and the like;

Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, mercaptomethyltriethoxysilane copolymer, A mercapto methyl group-containing copolymer such as a methoxy silane-tetraethoxy silane copolymer;

3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane copolymer Tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane- 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxy Copolymers containing methacryloyloxypropyl groups, such as silane-tetraethoxysilane copolymers;

3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane- 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, Copolymers containing acryloyloxypropyl groups, such as polymers;

Vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer Polymers,

Vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, vinylmethyldiethoxysilane-tetraethoxysilane copolymer Vinyl group-containing copolymers such as polymers;

3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3- Aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltrimethoxysilane- Methyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, and the like, amino group-containing copolymers and the like.

The blending amount of the silane compound in the pressure-sensitive adhesive composition is usually about 0.01 to 10 parts by mass, preferably 0.01 (parts by mass), more preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the solid content of the acrylic resin To 5 parts by mass. When the amount of the silane-based compound relative to 100 parts by mass of the solid content of the acrylic resin is 0.01 part by mass or more, adhesion between the pressure-sensitive adhesive sheet and the display element is improved. When the amount is less than 10 parts by mass, the silane-based compound tends to be inhibited from bleeding out from the pressure-sensitive adhesive sheet.

The pressure-sensitive adhesive composition may further contain a crosslinking catalyst, an antistatic agent, an antioxidant, a weather stabilizer, a tackifier, a plasticizer, a softening agent, 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-tert-butyl-4-methylphenol), 3,9-bis [2- [3- Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) phenol-based antioxidants such as tert-butyl-4,4'-butylidenedi-m-cresol, triisodecyl phosphite, tris (4-nonylphenyl) phosphorous acid, 2,2'-methylenebis Di-tert-butylphenyl) 2-ethylhexyl, tris (2,4-di-tert-butylphenyl) phosphate and the like, ditridecyl 3,3'-thiobisopropionate, bis [3- (Dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl, bis [3- Bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl Sulfuric acid antioxidant such as 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, Bis (2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl), butane-1,2,3,4-tetracarboxylic acid tetrakis , 6-pentamethyl-4-piperidinyl), and the like.

It is also useful to blend an ultraviolet curable compound in the pressure-sensitive adhesive composition and cure the pressure-sensitive adhesive sheet by irradiating ultraviolet rays after forming the pressure-sensitive adhesive sheet to obtain a harder pressure-sensitive adhesive sheet. In particular, when a crosslinking catalyst is blended with a crosslinking agent in a pressure-sensitive adhesive composition, it is possible to prepare the pressure-sensitive adhesive sheet for a short period of aging. In the obtained optical laminate, peeling or peeling occurs between the polarizing plate, It is possible to inhibit foaming or the like from occurring in the inside, and also to improve the workability. Examples of the crosslinking catalyst include, for example, hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin and melamine resin Amine-based compounds, and the like. When an amine compound is added to the pressure-sensitive adhesive composition as a crosslinking catalyst, an isocyanate compound is suitable as the crosslinking agent

The respective components constituting the pressure-sensitive adhesive may be constituted of a pressure-sensitive adhesive composition in a state dissolved in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc .; ethyl acetate, butyl acetate, ethylene Ester solvents such as acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl ethyl ketone, methyl ethyl ketone, Aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorinated hydrocarbons such as chloroform, chlorobenzene and the like. Among them, 2-butanone, methyl isobutyl ketone and the like are preferable from the viewpoints of solubility and environmental load reduction of each component.

The pressure-sensitive adhesive sheet can be prepared, for example, by applying the pressure-sensitive adhesive composition as described above to an organic solvent solution and applying the pressure-sensitive adhesive composition on a film or layer (for example, a polarizing plate or a protective film) to be laminated by a die coater or a gravure coater , Followed by drying. It is also possible to form a sheet-like pressure-sensitive adhesive on a release film-treated plastic film (referred to as a separator film) by transferring the sheet-like pressure-sensitive adhesive onto a film or layer to be laminated.

In another embodiment of the present invention, an optical film of the present invention and a laminated polarizing film (also referred to as " laminated polarizing film of the present invention ") comprising a polarizing film are provided. Here, the polarizing film is an optical film having a function of emitting polarized light to incident light such as natural light. The polarizing film includes a linear polarizing film having a property of absorbing linearly polarized light having a vibration plane in any direction incident on the film surface and transmitting linearly polarized light having a vibration plane orthogonal thereto, A polarized light separating film having a property of reflecting linearly polarized light and transmitting linearly polarized light having a vibration plane perpendicular to the polarized light, and an elliptically polarizing plate in which a polarizing film and a retardation film described later are laminated. As a suitable example of a polarizing film, particularly a linear polarizing film (sometimes referred to as a polarizer), a monoaxially stretched polyvinyl alcohol based resin film or a polymer of a polymerizable liquid crystal compound is provided with a dichroic dye such as iodine or a dichroic dye Adsorption-oriented. The laminated polarizing film is a laminated optical film comprising a polarizing film and an optical film of the present invention, for example, a pressure-sensitive adhesive sheet, a protective film, a retardation film and the like. A laminated optical film comprising a polarizing film and a pressure-sensitive adhesive sheet, in particular, a laminated optical film in which a pressure-sensitive adhesive sheet is laminated on a polarizing film, is also referred to as a polarizing plate having a pressure-sensitive adhesive.

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

Ap (400)? 0.4 (4)

In Equation (4), Ap (400) represents the absorbance of the polarizing film in the transmission axis direction at a wavelength of 400 nm. The larger the value of Ap (400), the higher the absorption at 400 nm. If this value is less than 0.4, the absorption at 400 nm is weak and the sufficiently high light resistance . 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, further preferably 0.8 or more, still more preferably 1 or more, particularly preferably Preferably 1.2 or more, particularly preferably 1.5 or more, and very preferably 1.8 or more, for example, 2 or more. The upper limit of the value of Ap (400) is not particularly limited, but is preferably 5 or less from the viewpoint of suppressing the bleed-out 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, Ap (420) represents the absorbance in the transmission axis direction of the polarizing film at a wavelength of 420 nm Absorbance. The value of Ap (420) / Ap (400) represents the absorption intensity at a wavelength of 400 nm with respect to the absorption intensity at 420 nm. As this value is smaller, the absorption at the wavelength range around 420 nm It shows that there is a specific absorption in the wavelength region near 400 nm. The smaller the value is, the smaller the yellowish color and the transparent laminated polarizing film tends to be obtained.

When the laminated polarizing film satisfies the formula (5), it is difficult to absorb light having a wavelength of 420 nm and absorb light having a wavelength of 400 nm, and at the same time, it is difficult to absorb blue visible light, The blue light-cutting function can be achieved. When such a laminated polarizing film is mounted on the optical laminate, it is preferable that a member constituting the optical laminate (for example, an optical film such as a retardation film, a display element such as an organic EL element or a liquid crystal display element) That is, light having a wavelength of about 400 nm) can be suppressed from deteriorating. The value of Ap (420) / Ap (400) in the laminated polarizing film is preferably 0.25 or less, more preferably 0.2 or less, further preferably 0.15 or less, for example, 0.1 or less. Although the lower limit value thereof is not particularly limited, it is preferably 0.01 or more from the viewpoint of maintaining the absorption ability near 400 nm in the laminated polarizing film. In one preferred embodiment of the present invention, the value of Ap (420) / Ap (400) is 0.05 to 0.15.

In another embodiment of the present invention, a laminated phase difference film (also referred to as " the laminated phase difference film of the present invention ") comprising the optical film and the phase difference film of the present invention is provided. Here, the retardation film is an optical film exhibiting optical anisotropy, for example, a film of polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polycycloolefin, polystyrene, polysulfone, A stretched film obtained by stretching a polymer film comprising polyvinylidene fluoride / polymethyl methacrylate, acetyl cellulose, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc. to a degree of 1.01 to 6 times. Among them, a polymer film in which a polycarbonate film or a cycloolefin-based resin film is uniaxially or biaxially stretched is preferable. In the case where the optical laminate of the present invention includes a retardation film, it is preferable to include a retardation film exhibiting optical anisotropy by coating / orientation of the polymerizable liquid crystal compound from the viewpoint of thinness.

The laminated retardation film is a laminated optical film comprising a retardation film and an optical film of the present invention, for example, a pressure-sensitive adhesive sheet, a protective film, a polarizing film and the like. An elliptically polarizing film (also referred to as " elliptically polarizing film of the present invention ") comprising an optical film, a polarizing film and a retardation film of the present invention is also provided. The elliptically polarizing film is a laminated optical film comprising a retardation film, a polarizing film and an optical film of the present invention. Further, a laminated optical film including a retardation film and a pressure-sensitive adhesive sheet, in particular, a laminated optical film in which a pressure-sensitive adhesive sheet is laminated on a retardation film is also referred to as a pressure-sensitive adhesive-attached retardation film.

In the laminated retardation film of the present invention, it is preferable that the following formula (6) is satisfied.

100 nm? Re (550)? 170 nm (6)

By having the optical property represented by the formula (6), the laminated retardation film of the present invention can function as a 1/4 wavelength plate. Further, in the laminated retardation film of the present invention, Re (550) = 137.5 nm is theoretically preferable, but preferably satisfies the following formula (6-1) as a range in which good display characteristics can be obtained.

130 nm? Re (550)? 150 nm (6-1)

In the laminated retardation film of the present invention, it is preferable that the retardation film has a reverse wavelength dispersion property. The inverse wavelength dispersion is an optical characteristic in which the in-plane retardation value at a short wavelength is larger than the in-plane retardation value at a long wavelength, and preferably the retardation film satisfies the following expressions (7) and (8). In addition, Re (?) Represents the in-plane retardation value for the light of the wavelength? Nm.

Re (450) / Re (550)? 1 (7)

1? Re (630) / Re (550) (8)

In the laminated retardation film of the present invention, when the retardation film has an inverse wavelength dispersion property, it is preferable because coloring at the time of black display in a display device is reduced. In the above formula (7), 0.82? Re (450) / Re (550) < / = 0.93.

In the laminated retardation film of the present invention, the retardation film is preferably a layer comprising a polymer in an aligned state of a polymerizable liquid crystal compound (hereinafter may be referred to as an " optically anisotropic layer " The polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable functional group, particularly a photopolymerizable functional group. The photopolymerizable functional group means a group capable of participating in the polymerization reaction by an active radical or an acid generated from the photopolymerization initiator. Examples of the photopolymerizable functional group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxyllanyl group, oxetanyl group, . Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The liquid crystal property may be either a thermotropic liquid crystal or a lyotropic liquid crystal, but a thermotropic liquid crystal is preferable in that a dense film thickness control is possible. Further, as the phase ordered structure in the thermotropic liquid crystal, nematic liquid crystal or smectic liquid crystal may be used.

In the present invention, the polymerizable liquid crystal compound is particularly preferably a structure represented by the following formula (III) in that it exhibits the above-mentioned reverse wavelength dispersion property.

≪ EMI ID =

In the formula (III), Ar represents a divalent aromatic group, and the divalent aromatic group includes 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 is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, And the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom.

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

k and l each independently represent an integer of 0 to 3, and satisfy a relationship of 1 < = k + l. Here, when 2? K + 1, B ¹ and B ² , G ¹ and G ² may be mutually the same or different.

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

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

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

In addition, at least one of G ¹ and G ² in which a plurality presence of a divalent preferably aliphatic hydrocarbon group, and further, L ^1, or at least one of G ¹ and G ² that bind to the L ² is a divalent aliphatic hydrocarbon Is more preferable.

L ¹ and L ² are each independently preferably a single bond, -O-, -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCO-, -N═N-, -CR ^a = CR ^b -, or -C? C-. Wherein 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 and more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, or -OCO-.

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

k and l are preferably in the range of 2? k + 1? 6, preferably in the range of k + 1 = 4, more preferably in the range of k = 2 and 1 = 2 from the viewpoint of expression of reverse wavelength dispersion. When k = 2 and l = 2, a symmetrical structure is preferable.

E ¹ and E ² each independently represent 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, an acryloyloxy group, a methacryloyloxy group, , And an oxetanyl group. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

It is preferable that Ar has an aromatic heterocyclic ring. Examples of the aromatic heterocyclic ring include furan ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and phenanthrol And the like. Among them, those having a thiazole ring, a benzothiazole ring, or a benzofuran ring are preferable, and it is more preferable to have a benzothiazole group. When Ar contains a nitrogen atom, the nitrogen atom preferably has a pi electron.

In the formula (III), the total number N _pi of the? Electrons contained in the bivalent aromatic group represented by Ar is preferably 10 or more, more preferably 14 or more, and further preferably 18 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.

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

(25)

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, a sialoalkyl group having 1 to 12 carbon atoms, A nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 12 carbon atoms , An N-alkylamino group having 1 to 12 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 12 carbon atoms or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms .

Q ¹ , Q ² and Q ³ each independently represent -CR ^{2 '} R ^3' -, -S-, -NH-, -NR ^{2 '} -, -CO- or -O-, and R ^2' And R ^{3 '} each independently represent 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 for Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, And a phenyl group is more preferable. Examples of the aromatic heterocyclic group include an aromatic heterocyclic group having 4 to 20 carbon atoms including at least one hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group; A furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ , Y ² and Y ³ each independently may be a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic ring. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic cyclic ring group. The polycyclic aromatic heterocyclic group means a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring group.

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

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

Among the formulas (Ar-1) to (Ar-20), the formulas (Ar-6) and (Ar-7) are preferable from the viewpoint of stability of molecules.

In the formulas (Ar-14) to (Ar-20), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . 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 pyrin ring and a pyrrolidine ring. The aromatic heterocyclic group may have a substituent. Y ¹ , together with the nitrogen atom and Z ^{0 to} which it is bonded, may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic ring which may be substituted as described above.

The optically anisotropic layer is formed by curing a composition containing the polymerizable liquid crystal compound (also referred to as " composition for forming optically anisotropic layer ") by, for example, light irradiation. The composition for forming an optically anisotropic layer may contain various additives. Examples of the additives include the polymerization initiator, polymerization inhibitor, photosensitizer and leveling agent. The total content of the polymerizable liquid crystal compound in 100 parts by mass of the solid content of the optically anisotropic layer-forming composition is usually 70 parts by mass to 99.5 parts by mass, preferably 80 parts by mass to 99 parts by mass, Is 80 parts by mass to 94 parts by mass, and more preferably 80 parts by mass to 90 parts by mass. When the total content is within the above range, orientation of the obtained optically anisotropic layer tends to be enhanced. Here, the solid content refers to the total amount of components excluding the solvent from the composition.

In another embodiment of the present invention, a display device provided with any one of the optical film, the laminated polarizing film, the laminated retardation film, and the elliptically polarizing film may be provided. Such a display device is provided with a member containing the light absorbing composition, so that it is possible to suppress deterioration of an optical film and a display element such as a retardation film, and to be able to exhibit a blue light cut function. In addition, since the light absorbing composition is excellent in light selective absorptivity for light having a wavelength of around 400 nm, it is difficult to absorb light near a wavelength of 430 nm which is blue light, and an image display device can exhibit a good color representation.

Example

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

≪ Gel permeation chromatography measurement >

In the following examples, the weight average molecular weight and the number average molecular weight were measured by gel permeation chromatography (hereinafter referred to as GPC) apparatus (GPC-8120, manufactured by Tosoh Corporation) (Total of 5) were placed in series in a column, and one column of "TSK gel XL (manufactured by Tosoh Corporation)" and one "Shodex GPC KF-802 (manufactured by Showa Denko K.K.)" were connected in series and tetrahydrofuran At a sample concentration of 5 mg / ml, a sample introduction amount of 100 占 퐇, a temperature of 40 占 폚, and a flow rate of 1 ml / min, and calculated by standard polystyrene conversion.

≪ Preparation of acrylic resin &

An acrylic resin (a) and an acrylic resin (b) were prepared according to the compositions shown in Table 1 by the following methods.

[Polymerization Example 1] Preparation of acrylic resin (a)

A reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with 81.8 parts of ethyl acetate as a solvent, 70.4 parts of butyl acrylate as monomer (A-1), 20.0 parts of methyl acrylate, and 8.0 parts of 2-phenoxyethyl acrylate , 1.0 part of 2-hydroxyethyl acrylate as a monomer (A-2) and 0.6 part of acrylic acid were charged, and the air inside the apparatus was replaced with nitrogen gas to raise the internal temperature to 55 DEG C while leaving oxygen free. Thereafter, a total amount of a solution obtained by dissolving 0.14 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. After the addition of the polymerization initiator, the reaction was continued for 1 hour at this temperature, and then ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts / hr while keeping the internal temperature at 54 to 56 ° C to adjust the concentration of the acrylic resin to 35% , The addition of ethyl acetate was stopped and the temperature was maintained at this temperature for 12 hours from the start of addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%, and an ethyl acetate solution of an acrylic resin was prepared. The obtained acrylic resin had a weight average molecular weight Mw of 142,000 and a Mw / Mn of 5.2 as measured by GPC in terms of polystyrene. This was used as the acrylic resin (a).

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

A mixed solution of 81.8 parts of ethyl acetate as a solvent, 96.0 parts of butyl acrylate as the monomer (A-1) and 4.0 parts of acrylic acid as the monomer (A-2) was charged in a reaction vessel equipped with a stirrer, a thermometer, , And the inside temperature was raised to 55 캜 while oxygen was removed by replacing air in the apparatus with nitrogen gas. Thereafter, a total amount of a solution obtained by dissolving 0.14 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. Ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts / hr while the internal temperature was maintained at 54 to 56 DEG C, and the concentration of the acrylic resin was 35% The addition of ethyl acetate was stopped and the temperature was maintained at this temperature for 12 hours from the start of the addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%, and an ethyl acetate solution of an acrylic resin was prepared. The obtained acrylic resin had a weight average molecular weight Mw of 756,000 and a Mw / Mn of 4.1 as measured by GPC in terms of polystyrene. This was used as the acrylic resin (b).

≪ Preparation of pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet &

(a) Preparation of pressure-sensitive adhesive composition

A pressure-sensitive adhesive composition was prepared by mixing an acrylic resin (a), a photo-selective absorptive compound (ultraviolet absorber), a crosslinking agent and a silane-based compound as follows.

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

 [Crosslinking agent]

- Colonate L: Trimethylol propane of tolylene diisocyanate An ethyl acetate solution (solid content concentration 75%) of the duct body, manufactured by Nippon Polyurethane Co., Ltd.

Takenate D-110N: ethyl acetate solution (solid concentration 75%) of trimethylolpropane adduct of xylylenediisocyanate, manufactured by Mitsui Chemicals, Inc. (hereinafter abbreviated as "D110N"),

 [Silane compound]

KBM-403: 3-glycidoxypropyltrimethoxysilane, liquid, manufactured by Shin-Etsu Chemical Co., Ltd.

 [Photo-selective absorptive compound]

≪ Synthesis of photo-selective water absorbent compound >

(Synthesis Example 1)

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In a 200 ml-four-necked flask equipped with a Dimros cooling tube and a thermometer, 10 g of an intermediate 1 powder synthesized with reference to the patent document (Japanese Patent Application Laid-Open No. 2011-184414) in a nitrogen atmosphere, 10 g of anhydrous acetic acid , 2.5 g of morpholine (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 g of 2-propyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer . The inner temperature was raised to 72 캜 and stirred for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solvent was distilled off using this separator. To the resulting concentrate, a mixed solution of 17 g of methanol and 3 g of water was added to obtain crystals. The crystals were dried under reduced pressure at 40 DEG C to obtain 2.0 g of Compound (1) as a yellow powder. The yield was 70%.

As a result of measurement of maximum absorption wavelength (? Max) using a spectrophotometer UV-3150 (Shimadzu Corporation),? Max = 389 nm (in 2-butanone) and? g · cm) and? (420) /? (400) was 0.0251.

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

(Synthesis Example 2)

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3 g of an intermediate 2 powder (Wako Pure Chemical Industries, Ltd.) and 2-ethoxyethyl cyanoacetate (commercially available from Tokyo Chemical Industry Co., Ltd.) were added to a 200 ml-four-necked flask equipped with a stirrer, (Manufactured by Wako Pure Chemical Industries, Ltd.) and 12 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer. After raising the inner temperature to 75 캜, 1.1 g of pyridine (Wako Pure Chemical Industries, Ltd.) was added dropwise and stirred for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solvent was distilled off using this separator. To the obtained concentrate, 20 g of toluene and 30 g of a 4.1% by mass hydrochloric acid aqueous solution were added, and the toluene solution was separated and separated. Further, 40 g of water was added to the toluene solution, and liquid separation was carried out. Toluene was distilled off using this distributor to obtain crystals. The crystals were dried under reduced pressure at 40 캜 to obtain 3.5 g of a compound (2) as a yellow powder. The yield was 73%.

The maximum absorption wavelength (? Max) was measured using a spectrophotometer UV-3150 (Shimadzu Corporation). As a result,? Max = 386 nm (in 2-butanone) and? g · cm) and? (420) /? (400) was 0.165.

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

(Synthesis Example 3)

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In a 200 ml-four-necked flask equipped with a thermocouple cooling tube and a thermometer, 10 g of the intermediate 3 powder synthesized with reference to the patent document (JP-A-2014-194508) in a nitrogen atmosphere, 10 g of acetic anhydride , 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.) were charged, Lt; / RTI > 4.7 g of N, N-diisopropylethylamine (hereinafter abbreviated as DIPEA, hereinafter abbreviated as "DIPEA") was added dropwise from the dropping funnel over 1 hour at an internal temperature of 25 ° C. After completion of dropwise addition, And kept warm for 2 hours. After the completion of the reaction, acetonitrile was removed using a decompression diverter, toluene was added to the obtained oil, and insoluble components produced were removed by filtration. The filtrate was concentrated using a decompression separator again, and the concentrated solution was purified by column chromatography (silica gel) and recrystallized from toluene to obtain the target product. The crystals were dried under reduced pressure at 60 DEG C to obtain 5.2 g of a compound (3) as a yellow powder. The yield was 65%.

As a result of measurement of the absorption maximum wavelength (? Max) using a spectrophotometer UV-3150 (Shimadzu Corporation),? Max = 389 nm (in 2-butanone) and? g · cm) and? (420) /? (400) was 0.0153.

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

(Synthesis Example 4)

[Chemical Formula 29]

In a 200 ml-four-necked flask equipped with a thermocouple cooling tube and a thermometer, 10 g of the intermediate 3 powder synthesized with reference to the patent document (JP-A-2014-194508) in a nitrogen atmosphere, 10 g of acetic anhydride , 6.9 g of 2-ethylhexyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer. 4.5 g of DIPEA (manufactured by TOKYO CHEMICAL INDUSTRIES CO., LTD.) Was added dropwise from the dropping funnel over 1 hour at an internal temperature of 25 DEG C, and the temperature was further kept at 25 DEG C for 2 hours. After completion of the reaction, acetonitrile was removed using a reduced pressure separator and purification was conducted by column chromatography (silica gel), and the effluent containing the compound (4) was removed using a vacuum decomposer , And yellow crystals were obtained. The crystals were dried under reduced pressure at 60 DEG C to obtain 4.6 g of a compound (4) as a yellow powder. The yield was 50%.

The maximum absorption wavelength (? Max) was measured using a spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). As a result,? Max = 389 nm (in 2-butanone) and? Cm), and the value of? (420) /? (400) was 0.013.

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

(Synthesis Example 5)

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2.0 g of cyanoacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3 g of triethylene glycol monomethyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were placed in a 200 ml-four-necked flask equipped with a stirrer, , 0.2 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer. The inner temperature was raised to 110 캜 and stirred for 3 hours. After completion of the reaction, 40 g of water was added to the toluene solution, and liquid separation was carried out. Toluene was distilled off from the toluene solution obtained using this disperser to obtain 4.7 g of Intermediate 4 as an oil phase liquid. The yield was 86%.

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2.0 g of Intermediate 2 (manufactured by Wako Pure Chemical Industries, Ltd.), 2.6 g of Intermediate 4, and 0.5 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 200 ml-four-necked flask equipped with a stirrer, Ltd.) was added and stirred with a magnetic stirrer. The internal temperature was raised to 75 캜 and 0.7 g of piperidine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise from the dropping funnel over one hour. After completion of the dropwise addition, the internal temperature was further maintained at 75 캜 for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solvent was distilled off using this separator. To the obtained concentrate was added 10 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 g of water, and the ethyl acetate solution was subjected to liquid separation. Ethyl acetate was distilled off from the ethyl acetate solution obtained using this disperser to obtain 3.6 g of a compound (5) as an oil phase liquid. The yield was 93%.

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

(Synthesis Example 6)

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3.0 g of an intermediate 2 powder (manufactured by Wako Pure Chemical Industries, Ltd.) and 2-ethylhexyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd., Japan) in a nitrogen-atmosphere flask equipped with a thermometer, (Manufactured by Wako Pure Chemical Industries, Ltd.), and 12 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer. The inner temperature was raised to 75 DEG C and the temperature was maintained for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crystals were filtered. The crystals were washed with 10 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), and further the crystals were dried under reduced pressure at 40 ° C to obtain 4.3 g of a compound (6) as a yellow powder. The yield was 81%.

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

(Synthesis Example 7)

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10 g of the intermediate 3 powder, 2.9 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), 2 g of isobutyl cyanoacetate (manufactured by Wako Pure Chemical Industries, Ltd.) (Manufactured by HASUNG KOGYO CO., LTD.) And 30 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer. 3.7 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise from the dropping funnel over 1 hour at an internal temperature of 25 占 폚, and the temperature was further kept at 25 占 폚 for 2 hours. After completion of the reaction, an acetonitrile solution was added dropwise to 150 g of cold water, and the precipitated crystals were filtered. The crystals were washed with a mixed solution of 2 g of water and 10 g of acetonitrile, and the crystals were further washed with 10 g of heptane. The washed crystal was dried under reduced pressure at 70 캜 to obtain 5.2 g of a compound (7) as a yellow powder. The yield was 84%.

As a result of measurement of the absorption maximum wavelength (? Max) using a spectrophotometer UV-3150 (Shimadzu Corporation),? Max = 389 nm (in 2-butanone) and? g 占 ㎝ m) and? (420) /? (400) was 0.0092.

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

(Synthesis Example 8)

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In a 200 ml-four-necked flask equipped with a thermocouple cooling tube and a thermometer, 6.3 g of cyanoacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-n-octyl-1-dodecanol (Manufactured by Wako Pure Chemical Industries, Ltd.) (20 g), p-toluenesulfonic acid monohydrate (Wako Pure Chemical Industries, Ltd.) (0.6 g) and toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer Respectively. The inner temperature was raised to 110 캜 and stirred for 3 hours. After completion of the reaction, 100 g of water was added to the toluene solution, and liquid separation was carried out. Toluene was distilled off from the toluene solution obtained using this distributor to obtain 22 g of Intermediate 5 as a liquid. The yield was 90%.

(35)

6 g of the intermediate 3 powder, 1.8 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), 6.3 g of Intermediate 5, and 0.1 g of acetone (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 200 ml- 18 g of nitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred with a magnetic stirrer. 3.7 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise from the dropping funnel over 1 hour at an internal temperature of 25 占 폚, and the temperature was further kept at 25 占 폚 for 2 hours. After completion of the reaction, an acetonitrile solution was added dropwise to 90 g of cold water, and the precipitated crystals were filtered. The crystals were washed with a mixed solution of 2 g of water and 10 g of acetonitrile, and the crystals were further washed with 10 g of heptane. The washed crystals were dried under reduced pressure at 70 캜 to obtain 6.5 g of a compound (8) as a yellow powder. The yield was 92%.

The maximum absorption wavelength (? Max) was measured using a spectrophotometer UV-3150 (Shimadzu Corporation). As a result,? Max = 389 nm (in 2-butanone) and? g · cm) and? (420) /? (400) was 0.0121.

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

(Synthesis Example 9)

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14 g of cyanoacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2 g of 2-ethyl-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd. ), 1.4 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 75 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and stirred with a magnetic stirrer. The inner temperature was raised to 110 캜 and stirred for 3 hours. After completion of the reaction, 100 g of water was added to the toluene solution, and liquid separation was carried out. Toluene was distilled off from the toluene solution obtained using this disperser to obtain 22 g of Intermediate 6 as a liquid. The yield was 90%.

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10 g of the intermediate 3 powder, 2.9 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), 4.8 g of Intermediate 6, and 4.8 g of acetoacetic acid in a nitrogen-atmosphere flask were placed in a 200 ml- 30 g of nitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred with a magnetic stirrer. 3.7 g of DIPEA (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise from the dropping funnel over 1 hour at an internal temperature of 25 占 폚, and the temperature was further kept at 25 占 폚 for 2 hours. After completion of the reaction, an acetonitrile solution was added dropwise to 150 g of cold water, and the precipitated crystals were filtered. The crystals were washed with a mixed solution of 2 g of water and 10 g of acetonitrile, and the crystals were further washed with 10 g of heptane. The washed crystals were dried under reduced pressure at 70 ° C to obtain 5.7 g of Compound (9) as a yellow powder. The yield was 84%.

As a result of measurement of maximum absorption wavelength (? Max) using a spectrophotometer UV-3150 (Shimadzu Corporation),? Max = 389 nm (in 2-butanone) and? g · cm) and? (420) /? (400) was 0.0090.

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

(a-1) Production Example 1: Preparation of pressure-sensitive adhesive composition (1)

0.50 parts by mass of a crosslinking agent (colonate L) and 0.50 parts by mass of a silane compound (KBM-403) were added to 100 parts by mass of a solid content of the acrylic resin (a). Then, 2-butanone was added so that the solid concentration became 14%, and the mixture was stirred with a stirrer (Three One Motor, Yamato Scientific Co., Ltd.) at 300 rpm for 30 minutes to prepare a pressure-sensitive adhesive composition (1).

(a-2) Production Examples 2 to 27: Preparation of pressure-sensitive adhesive compositions (2) to (27)

0.50 parts by mass of a crosslinking agent (colonate L) and 0.50 parts by mass of a silane compound (KBM-403) were added to 100 parts by mass of a solid content of the acrylic resin (a) (9)) were compounded in amounts shown in Table 3. Then, 2-butanone was added so that the solid concentration became 14 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.) Respectively.

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

(a-3) Production Example 28: Preparation of pressure-sensitive adhesive composition (28)

0.50 parts by mass of a crosslinking agent (Colonate L) and 0.50 parts by mass of a silane compound (KBM-403) were added to 100 parts by mass of a solid content of the acrylic resin (b). Then, 2-butanone was added so that the solid 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 a pressure-sensitive adhesive composition (28).

(a-4) Production Examples 29 to 52: Preparation of pressure-sensitive adhesive compositions (29) to (52)

0.50 parts by mass of a crosslinking agent (colonate L) and 0.50 parts by mass of a silane compound (KBM-403) were added to 100 parts by mass of a solid content of the acrylic resin (b) . Then, 2-butanone was added so that the solid concentration became 14%, and the mixture was stirred and mixed at 300 rpm for 30 minutes using a stirrer (Three One Motor, Yamato Scientific Co., Ltd.), and the pressure-sensitive adhesive compositions (29) to Lt; / RTI >

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

(b-1) Reference Example 1

The pressure-sensitive adhesive composition (1) prepared in Preparation Example 1 was applied to the release-treated surface of a polyethylene terephthalate film subjected to releasing treatment (SP-PLR382050 manufactured by Lintec Corp., hereinafter abbreviated as "separator" Of 10 mu m using an applicator, and dried at 100 DEG C for 1 minute to prepare a pressure-sensitive adhesive sheet (R1).

The optical property of the obtained pressure-sensitive adhesive sheet (R1) was measured by a spectrophotometer (UV-3150; manufactured by Shimadzu Corporation). The results are shown in Table 7. In the table, T (400) represents the transmittance (%) at a wavelength of 400 nm and T (420) represents the transmittance (%) at a wavelength of 420 nm.

(b-2) Reference Example 2

The pressure-sensitive adhesive composition (1) prepared in Preparation Example 1 was applied to the release-treated surface of the separator using an applicator so that the thickness of the pressure-sensitive adhesive layer after drying became 5 占 퐉 and dried at 100 占 폚 for 1 minute to obtain a pressure- . The optical properties of the resulting pressure-sensitive adhesive sheet (R2) were measured in the same manner as in Reference Example 1. The results are shown in Table 7.

(b-3) Comparative Examples 1 to 17

The pressure-sensitive adhesive sheets (C1) to (C) of Comparative Examples 1 to 17 were prepared in the same manner as in Reference Example 1, except that the pressure-sensitive adhesive compositions (2) to (18) (C17). Optical properties of the obtained pressure-sensitive adhesive sheets (C1) to (C17) were measured in the same manner as in Reference Example 1. [ The results are shown in Table 7.

(b-4) Examples 1 to 9

The pressure-sensitive adhesive sheets (E1) to (E1) were prepared in the same manner as in Reference Example 1, except that the pressure-sensitive adhesive compositions (19) to (27) (E9), respectively. Optical properties of the resulting pressure-sensitive 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

The pressure-sensitive adhesive sheets (E10) to (23) of Examples 10 to 14 were obtained in the same manner as in Reference Example 2, except that the pressure-sensitive adhesive compositions (19) to E14), respectively. Optical properties of the obtained pressure-sensitive 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

A pressure-sensitive adhesive sheet (R3) of Reference Example 3 was produced in the same manner as in Reference Example 1, except that the pressure-sensitive adhesive composition (28) prepared in Preparation Example 28 was used. The optical property of the obtained pressure-sensitive adhesive sheet (R 3) was measured by the same method as in Reference Example 1. The results are shown in Table 8.

(b-7) Comparative Examples 18 to 34

(C18) to (C34) of Comparative Examples 18 to 34 were prepared in the same manner as in Reference Example 1, using the pressure-sensitive adhesive compositions (29) to (45) prepared in Production Examples 29 to 45, respectively. Optical properties of the obtained pressure-sensitive adhesive sheets (C18) to (C34) were measured in the same manner as in Reference Example 1. [ The results are shown in Table 8.

(b-8) Examples 15 to 21

(E15) to (E21) of Examples 15 to 21 were prepared in the same manner as in Reference Example 1, using the pressure-sensitive adhesive compositions (46) to (52) prepared in Production Examples 46 to 52, respectively. Optical properties of the resulting pressure-sensitive 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 pressure-sensitive adhesive sheet &

[40 ° C heating test (in Table 7 and 8, "heating" is indicated)

The pressure-sensitive adhesive sheet was put in a thermostatic chamber (manufactured by Espec Co., Ltd., model PL-3KT), and each of the pressure-sensitive adhesive sheets was allowed to stand for 7 days and 30 days under a drying condition at a temperature of 40 ° C. , And the evaluation was carried out according to the following evaluation criteria. The results are shown in Tables 7 and 8.

[Evaluation Criteria of 40 ° C Heating Test]

A: Almost no change in appearance such as crystal precipitation was observed in the sample after 30 days.

B: Almost no change in appearance such as crystal precipitation was observed in the sample after 7 days.

C: Appearance change such as crystal precipitation is remarkably confirmed in the sample after 7 days.

[-15 [deg.] C cooling test (indicated as " cooling " in Tables 7 and 8)

The above pressure-sensitive adhesive sheet was placed in a thermostatic chamber and allowed to stand for 7 days and 30 days under a drying condition of a temperature of -15 DEG C, and then the appearance of the pressure-sensitive adhesive sheet was visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 7 and 8.

[Evaluation Criteria of -15 ° C Cooling Test]

A: Almost no change in appearance such as crystal precipitation was observed in the sample after 30 days.

B: Almost no change in appearance such as crystal precipitation was observed in the sample after 7 days.

C: Appearance change such as crystal precipitation is remarkably confirmed in the sample after 7 days.

≪ Production of laminated optical film &

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

Cycloolefin polymer (COP) film: ZF-14 manufactured by Nippon Zeon Co., Ltd.

Corona disposal device: AGF-B10 manufactured by Kasuga Electric Co., Ltd.

Condition of corona treatment: Using the above corona treatment apparatus, the test was conducted once under the conditions of 0.3 kW of output power and 3 m / min of treatment speed

Polarizing UV irradiation device: SPOT CURE SP-7 with a polarizer unit manufactured by Ushio Electric Co., Ltd.

· Laser microscope: LEXT manufactured by Olympus Corporation

· High pressure mercury lamp: UniCure VB-15201BY-A manufactured by Ushio Electric Co., Ltd.

Measurement of in-plane retardation value: Measured using a birefringence measurement device (KOBRA-WR manufactured by Oji Measurement Instruments Co., Ltd.)

Measurement of Film Thickness of Orientation Film: Measured using an ellipsometer M-220 manufactured by Nippon Bunko KK

A composition containing a photo-alignment film, a composition containing a polymerizable liquid crystal compound A, and a polarizer were used for the preparation of an optically anisotropic layer and a laminate.

≪ Preparation of Composition for Photo Orientated Film Formation &

5 parts of the photo-orientable material of the following structure and 95 parts of cyclopentanone (solvent) were mixed, and the obtained mixture was stirred at 80 占 폚 for 1 hour to obtain a composition for forming a photo alignment film.

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≪ Preparation of composition containing polymerizable liquid crystal compound A >

A polymerizable liquid crystal compound A having the following structure and the following polymerization initiator, a leveling agent and a solvent were mixed as a component to obtain a composition containing the polymerizable liquid crystal compound A. The polymerizable liquid crystal compound A was synthesized by the method described in JP-A-2010-31223. The maximum absorption wavelength? Max (LC) of the polymerizable liquid crystal compound A was 350 nm.

Polymerizable liquid crystal compound A (12.0 parts):

[Chemical Formula 39]

Polymerization initiator (0.72 part): 2-Dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; Ciba Specialty Chemicals)

Leveling agent (0.12 part): Polyacrylate compound (BYK-361N, manufactured by BYK-Chemie)

Solvent (100 parts): Cyclopentanone

≪ Production of polarizing plate &

A polyvinyl alcohol film having a thickness of 30 占 퐉 (average degree of polymerization of about 2400 and a degree of saponification of 99.9 mol% or more) was uniaxially stretched by about 4 times by dry stretching and maintained at 40 占 폚 for 40 seconds And then dipped 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 an aqueous boric acid solution having a weight ratio of potassium iodide / boric acid / water of 11.0 / 6.2 / 100 at 70 ° C for 120 seconds. Subsequently, the film was washed with pure water at 8 캜 for 15 seconds, then dried at 60 캜 for 50 seconds and then at 75 캜 for 20 seconds while maintaining the tension at 300 N, and the polyvinyl alcohol film was adsorbed and oriented Thereby obtaining a polarizer having a thickness of 12 占 퐉.

An aqueous adhesive was injected between the obtained polarizer and a cycloolefin polymer film (COP, ZF-4 without UV absorption property, manufactured by Nippon Zeon Co., Ltd., 30 m), and the resultant was bonded with a nip roll. The obtained conjugate was dried at 60 占 폚 for 2 minutes while maintaining the tension at 430 N / m to obtain a 42 占 퐉 polarizing plate having a cycloolefin film as a protective film on one side. The water-based adhesive was prepared by mixing 3 parts of a carboxyl group-modified polyvinyl alcohol (Kurarapoval KL318, manufactured by Kuraray Co., Ltd.) and 3 parts of a water-soluble polyamide epoxy resin (Sumirez resin 650, Concentration: 30% aqueous solution).

The polarization degree Py and the unit transmissivity Ty of the obtained polarizing plate were measured as follows.

The single transmittance T1 in the transmission axis direction and the single transmittance T2 in the absorption axis direction were measured by a double beam method using a device in which a polarizer attached folder was set in a spectrophotometer (UV-3150; Shimadzu Corporation) In a wavelength range of 380 to 680 nm. The following formula (p) and (q) are used to calculate the simple transmittance and the degree of polarization at each wavelength, and the visual sensitivity correction is carried out by using the two-view visual field (C light source) of JIS Z8701, Ty and visual sensitivity correction polarization degree Py were calculated. As a result, an absorption type polarizing plate having a visibility-corrected single-unit transmittance Ty of 43.0% and a visual sensitivity correction polarization degree Py of 99.99% was obtained.

(%) = {(T1 + T2) / 2} x 100 (p)

The polarization degree Py (%) = {(T1 - T2) / (T1 + T2)} 100 (q)

≪ Preparation of optically anisotropic layer &

(COF, ZF-14 manufactured by Nippon Zeon Co., Ltd.) was treated once with a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) under the conditions of an output of 0.3 kW and a treatment rate of 3 m / min Respectively. The composition for forming a photo alignment film was coated on a corona-treated surface by a bar coater and dried at 80 DEG C for 1 minute. Using a polarizing UV irradiation device (SPOT CURE SP-7, manufactured by Ushio Electric Co., Ltd.), 100 mJ / Polarized UV exposure was carried out at an integrated light quantity. The film thickness of the resulting alignment film was measured by an ellipsometer, and found to be 100 nm.

Subsequently, a coating liquid composed of a composition containing the polymerizable liquid crystal compound A prepared first was coated on the alignment film using a bar coater and dried at 120 DEG C for 1 minute. Thereafter, a high pressure mercury lamp (UniCure VB-15201BY-A (Phase difference film) by irradiating ultraviolet rays from the surface side coated with the coating liquid (total amount of light at a wavelength of 313 nm: 500 mJ / cm 2) under a nitrogen atmosphere Was obtained. The film thickness of the resulting optically anisotropic layer was measured by a laser microscope and found to be 2 탆.

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

The pressure-sensitive adhesive sheet (E1) prepared in Example 1 was laminated on the optically anisotropic layer side of the optical film, the separator of the pressure-sensitive adhesive sheet (E1) was removed, and the polarizer was laminated on the surface of the pressure- Respectively. Thereafter, the polarizing plate and the optically anisotropic layer were treated with a pressure of 0.3 kW and a processing speed of 3 m / min using a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) 19). At this time, the circularly polarizing plate was formed by laminating the polarizing plate so that the relationship between the slow axis of the optically anisotropic layer and the absorption axis of the polarizing plate was 45 °. Thereafter, the COP film as the base of the optical film was peeled off to obtain a laminated optical film (circularly polarizing plate) 1 on which the optically anisotropic layer was transferred to the polarizing plate. The thickness of the obtained laminated optical film 1 was 64 占 퐉.

In order to measure the optical characteristics of the laminated optical film 1, a sample for measurement was prepared by transferring it to glass. The retardation value of the sample of 450 nm in wavelength, 550 nm in wavelength and 630 nm in wavelength was measured by a birefringence measurement device (KOBRA-WR; Oji Instruments Co., Ltd.), and the transmittance of the wavelength 400 nm and the wavelength 420 nm was measured with a spectrophotometer UV-3150; manufactured by Shimadzu Corporation). Further, measurement was made by arranging a polarization prism on the light source side to obtain completely linearly polarized light, and irradiating the linearly polarized light to the measurement sample. At this time, linearly polarized light is incident parallel to the transmission axis of the polarizing plate side of the laminated optical film 1 (circularly polarizing plate 1), whereby the absorbance Ap (400) of the laminated optical film at the wavelength 400 nm in the transmission axis direction of the polarizing plate, , And the absorbance Ap (420) of the laminated optical film at a wavelength of 420 nm in the transmission axis direction of the polarizing plate was measured. The results are shown in Table 9. Further, the laminated optical film 1 had all of the optical characteristics represented by the following formulas (4) to (8).

Ap (400)? 0.4 (4)

Ap (420) / Ap (400)? 0.3 (5)

100 nm? Re (550)? 170 nm (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 pressure-sensitive adhesive sheet described in Table 9 below, a laminated optical film ( Circular polarizer). The optical properties of the resulting laminated optical film (circular polarizer) were measured by the same method as in Example 22. [

≪ Evaluation of laminated optical film &

The optical durability test, the heat resistance test, the wet heat resistance test and the internal heat shock test were carried out on the above-prepared laminated optical film. Each test was carried out according to the following method.

[Optical durability test]

A laminated optical film was placed in a Sunshine Weatherometer (manufactured by Suga Test Instruments Co., Ltd., model number SUNSHINE WEATHER METER S80) and irradiated for 100 hours. Then, the retardation value Re (?) Of a wavelength of 450 nm, a wavelength of 550 nm and a wavelength of 630 nm was measured. From the change of the retardation value before and after the optical durability test, evaluation was carried out according to the following criteria. The results are shown in Table 10.

[Evaluation Criteria of Optical Durability Test]

A: Change in retardation value before and after optical durability test When? Re (?) Is less than 5

B: Change in retardation value before and after optical durability test When? Re (?) Is 5 or more and less than 10

C: Change in retardation value before and after optical durability test When? Re (?) Is 10 or more

 [Heat resistance test]

The laminated optical film was put in a thermostatic chamber (manufactured by Espec Co., Ltd., Model No. PL-3KT) and allowed to stand for 250 hours and 500 hours under a drying condition at a temperature of 85 캜. Thereafter, the appearance state of the laminated optical film was visually observed, The evaluation was carried out in accordance with the evaluation criteria of. The results are shown in Table 10.

[Evaluation Criteria of Heat Resistance Test]

A: Almost no change in appearance such as peeling, peeling, foaming and crystal precipitation is observed in the sample after 500 hours.

B: Almost no change in appearance such as peeling, peeling, foaming and crystal precipitation is observed in the sample after 250 hours.

C: Appearance changes such as peeling, peeling, foaming, crystal precipitation, etc. are remarkably confirmed in the sample after 250 hours.

[Heat Resistance Test]

The laminated optical film was put in a thermostatic chamber (manufactured by Espec Co., Ltd., model number PH-4KT) and allowed to stand at a temperature of 60 DEG C and a relative humidity of 90% for 250 hours and 500 hours, respectively. , And the evaluation was carried out according to the following evaluation criteria. The results are shown in Table 10.

[Evaluation Criteria of Humidity Heat Test]

A: Almost no change in appearance such as peeling, peeling, foaming and crystal precipitation is observed in the sample after 500 hours.

B: Almost no change in appearance such as peeling, peeling, foaming and crystal precipitation is observed in the sample after 250 hours.

C: Appearance changes such as peeling, peeling, foaming, crystal precipitation, etc. are remarkably confirmed in the sample after 250 hours.

[Heat Shock (HS) Test]

The process of charging the laminated optical film into a cold / heat shock apparatus (manufactured by Espec Co., Ltd., Model No. TSA-71L-A), lowering the temperature from 70 DEG C to -40 DEG C, Minute), and after repeating this for 50 cycles and 100 cycles, the appearance state of the laminated optical film was visually observed. The evaluation was carried out according to the following evaluation criteria. The results are shown in Table 10.

[Evaluation Criteria of Heat Shock Test]

A: Almost no change in appearance such as peeling, peeling, foaming and crystal precipitation is observed in the sample after 100 cycles.

B: Samples after 50 cycles showed almost no change in appearance such as peeling, peeling, foaming and crystal precipitation.

C: Appearance changes such as peeling, peeling, foaming and crystal precipitation are remarkably confirmed in the sample after 50 cycles.

It was found that the optical films of Examples 22 to 42 had a high absorption characteristic at a wavelength of 400 nm and thus suppressed? R e (450) and? R e (550) of the retardation film as compared with Reference Examples 4 to 6.

1: polarizing film
2: Surface treatment layer
3: Second protective film
4: first protective film
6: Interlayer adhesive
7: retardation film
10: polarizer
15: Polarizer with adhesive
20: Adhesive sheet
30: Image display element (glass substrate)
40: Optical laminate

Claims (15)

A light absorbing composition comprising at least two kinds of photo-selective absorptive compounds, wherein at least two kinds of the light-selective absorptive compounds have the same conjugated system structure. The method according to claim 1,
Wherein the difference between the maximum value and the minimum value of the maximum absorption wavelength in the photo-selective-absorptive compound having at least two kinds of the same conjugated system structure is 5 nm or less. 3. The method according to claim 1 or 2,
At least two of the above-mentioned photo-selective absorbent compounds are represented by formula (I):
(40)

[Wherein,
R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 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 represents a methylene group, a secondary amino group, an oxygen atom or a sulfur atom,
X ¹ and X ² may independently represent an electron attractive group and X ¹ and X ² may be connected to each other to form a ring structure]
Or formula (II):
(41)

[Wherein,
R ¹ , X ¹ and X ² have the same meanings as defined above,
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 when the alkyl group has at least one methylene group, at least one of the methylene groups is a secondary amino group, Sulfur atom, and the aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent]
Is a photo-selective absorptive compound. The method of claim 3,
The light-selective absorptive compound represented by the above formula (I) has the formula (I-2):
(42)

[Wherein,
R ¹ is as defined above,
R ⁴ represents a hydrogen atom or an alkyl group having 2 to 50 carbon atoms, and when the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted with an oxygen atom]
(II-2): " (II-2) " represents a photo-selective water absorbent compound represented by the formula
(43)

[Wherein R ¹ and R ⁴ are as defined above]
Is a photo-selective absorptive compound. 5. The method according to any one of claims 1 to 4,
In the photo-absorptive composition having at least two kinds of the optically-selective absorptive compounds having the same conjugate system structure contained in the above-mentioned light-absorbent composition, the total amount of the optically-selected water-absorbent compound Wherein the ratio is 1:10 to 10: 1. 6. The method according to any one of claims 1 to 5,
Equations (1), (2) and (3):
? (420) /? (400)? 0.3 (1)
? max? 420 nm (2)
? (400)? 20 (3)
[Wherein,
? 420 represents a gram extinction coefficient at a wavelength of 420 nm,
? 400 represents a gram extinction coefficient at a wavelength of 400 nm,
? max represents the maximum absorption wavelength]
Of the light absorbing composition. A polymer composition containing the light absorbing composition according to any one of claims 1 to 6 and a polymer. 8. The method of claim 7,
Wherein the content of the light absorbing composition relative to 100 parts by mass of the polymer is 1 to 15 parts by mass. An optical film comprising the polymer composition according to claim 7 or 8. 10. The method of claim 9,
And a thickness of 0.1 to 18 탆. 11. A laminated polarizing film comprising the optical film according to claim 9 or 10 and a polarizing film. 12. The method of claim 11,
The following formulas (4) and (5)
Ap (400)? 0.4 (4)
Ap (420) / Ap (400)? 0.3 (5)
[Wherein,
Ap 400 represents the absorbance of the optical film in the transmission axis direction of the polarizing film at a wavelength of 400 nm,
And Ap (420) represents the absorbance of the optical film in the transmission axis direction of the polarizing film at a wavelength of 420 nm.
Of the laminated polarizing film. 11. A laminated retardation film comprising the optical film according to claim 9 or 10 and a retardation film. An elliptically polarizing film comprising the optical film according to claim 9 or 10, a polarizing film, and a retardation film. A display device comprising the film according to any one of claims 9 to 14.

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