JP2020052411A - Laminate and manufacturing method of the same, polarization plate, liquid crystal display device, and organic el display device - Google Patents

Abstract

To provide a laminate that includes a polarizer and an optical alignment film and is excellent in humidity and heat durability of the polarizer and a manufacturing method of the laminate, and a polarizing plate, a liquid crystal display device, and an organic EL display device including the laminate.SOLUTION: There is provided a laminate that includes a polarizer and an optical alignment film arranged adjacent onto the polarizer, where the optical alignment film is a layer formed by bringing an optical alignment film forming composition directly into contact with a surface of the polarizer, and the optical alignment film forming composition contains a compound A having an optical alignment group and a compound B having a crosslinking group, or a compound C having an optical alignment group and a crosslinking group.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a method for producing the same, a polarizing plate, a liquid crystal display, and an organic EL display.

Various display devices such as a liquid crystal display device and an organic EL display device use a polarizing plate. For example, as a polarizing plate included in a liquid crystal display device, a polarizing plate including a polarizer and an optically anisotropic layer is used in order to realize higher quality image display by optical compensation using a phase difference. I have.
As a polarizing plate, for example, in Patent Document 1, a polarizing film (polarizer) and an optically anisotropic layer formed of liquid crystal molecules are provided, and the optically anisotropic layer has an alignment film on the surface of the polarizer. Disclosed is a polarizing plate provided through the intermediary. That is, a polarizing plate having a polarizer, an alignment film, and an optically anisotropic layer in this order is disclosed.

JP 2004-53770 A

On the other hand, in recent years, display devices (for example, IPS mode liquid crystal display devices) have become thinner, and accordingly, members (for example, polarizing plates) used have been required to be thinner. In view of such a situation, if a thinner polarizer can be used, it can be expected that the display device will be made thinner.
With reference to Patent Document 1, the present inventors tried to produce an alignment film by arranging a layer of the composition for forming an alignment film directly on a thin polarizer and performing a rubbing treatment. It has been found that when a process of pressing and rubbing a rubbing roll is performed to reduce the mechanical strength of the polarizer, problems such as tearing of the polarizer itself or peeling of the alignment film occur.
Therefore, the present inventors have studied using a so-called photo-alignment film that expresses alignment capability by irradiating light as the alignment film.In a laminate including the obtained polarizer and the photo-alignment film, The wet heat durability of the polarizer was not always sufficient, and further improvement was required.

In view of the above circumstances, an object of the present invention is to provide a laminate including a polarizer and a photo-alignment film and having excellent wet heat durability of the polarizer.
Another object of the present invention is to provide a method for producing the laminate, and a polarizing plate, a liquid crystal display, and an organic EL display each including the laminate.

As a result of intensive studies on the problems of the prior art, the present inventors have found that the above problems can be solved by using a composition for forming a photo-alignment film containing a predetermined component.
That is, it has been found that the above-described object can be achieved by the following configuration.

(1) having a polarizer and a photo-alignment film disposed adjacent to the polarizer;
The photo-alignment film is a layer formed by bringing the composition for forming a photo-alignment film into direct contact with the surface of the polarizer,
A laminate, in which the composition for forming a photo-alignment film contains the compound A having a photo-alignment group and the compound B having a cross-linkable group, or contains the compound C having a photo-alignment group and a cross-linkable group. .
(2) The laminate according to (1), wherein the photo-alignable group is a group having a structure that undergoes photodimerization or photoisomerization.
(3) The laminate according to (1) or (2), wherein the photo-alignable group is a group selected from the group consisting of a group having an azobenzene structure and a group having a cinnamoyl structure.
(4) The laminate according to any one of (1) to (3), wherein the crosslinkable group is a photocrosslinkable group.
(5) The photocrosslinkable group contains at least one selected from the group consisting of a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, an epoxy group, an oxetanyl group, and a vinyloxy group. The laminate according to item 1.
(6) The laminate according to any one of (1) to (3), wherein the crosslinkable group is a thermally crosslinkable group.
(7) The group in which the heat crosslinkable group is a hydroxy group, a carboxyl group, an amino group, a thiol group, a methylol group, an alkoxysilane group, an isocyanate group, an acid anhydride group, an epoxy group, an oxetane group, and a boronic acid group. The laminate according to (6), comprising at least one member selected from the group consisting of:
(8) at least one kind selected from the group consisting of a hydroxy group, a carboxyl group, an amino group, and a thiol group; a methylol group, an alkoxysilane group, an isocyanate group, an acid anhydride group, The laminate according to (6) or (7), comprising a group, an oxetane group, and at least one selected from the group consisting of boronic acids.
(9) The laminate according to any one of (1) to (8), further including an optically anisotropic layer containing a liquid crystal compound on a surface of the optical alignment film opposite to the polarizer.
(10) The method for producing a laminate according to any one of (1) to (9),
A composition for forming a photo-alignment film containing a compound A having a photo-alignable group and a compound B having a cross-linkable group, or containing a compound C having a photo-alignable group and a cross-linkable group, Contacting directly with, to form a coating film on the polarizer,
Performing a curing treatment and a photo-alignment treatment on the coating film in any order to form a photo-alignment film.
(11) A polarizing plate comprising the laminate according to any one of (1) to (9).
(12) A liquid crystal display device including the laminate according to any one of (1) to (9).
(13) The liquid crystal display device according to (12), which is in an IPS mode.
(14) An organic EL display device including the laminate according to any one of (1) to (9).

ADVANTAGE OF THE INVENTION According to this invention, the laminated body containing a polarizer and a photo-alignment film and having excellent wet heat durability of a polarizer can be provided.
Further, according to the present invention, it is also possible to provide a method for producing the laminate, and a polarizing plate, a liquid crystal display, and an organic EL display including the laminate.

  Hereinafter, the present invention will be described in detail. The description of the components described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit. In addition, “orthogonal” and “parallel” with respect to an angle mean a range of an exact angle ± 10 °, and “same” and “different” with respect to an angle indicate whether the difference is less than 5 ° Can be determined based on

  In the present invention, the “tilt angle” means an angle formed by the tilted liquid crystal compound with the layer plane, and the maximum angle of the refractive index direction in the refractive index ellipsoid of the liquid crystal compound forms the layer plane. Means angle. Therefore, in the case of a rod-shaped liquid crystal compound having a positive optical anisotropy, the tilt angle means the angle between the major axis direction of the rod-shaped liquid crystal compound, that is, the director direction and the layer plane. In the present invention, the “average tilt angle” means an average value of the tilt angles from the above tilt angle at the upper interface to the lower interface of the optically anisotropic layer. The inclination angle (that is, the inclination of the optically anisotropic layer in the direction in which the refractive index of the optically anisotropic layer is maximum) with respect to the surface of the optically anisotropic layer is measured by an automatic birefringence meter (for example, KOBRA-21ADH, manufactured by Oji Scientific Instruments). ) Can be measured.

In the present specification, Re (λ) and Rth (λ) represent the in-plane retardation and the retardation in the thickness direction at a wavelength λ, respectively. Re (λ) is measured using KOBRA 21ADH or WR (trade name, manufactured by Oji Scientific Instruments) by irradiating light with a wavelength of λ nm in the normal direction of the film.
When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is obtained by using the above Re (λ) with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (in the case where there is no slow axis, the in-plane slow axis). (Any direction is defined as the axis of rotation) With respect to the normal direction of the film, light of wavelength λ nm is incident from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side from each direction, and a total of six points are measured. It is calculated by KOBRA 21ADH or WR based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.

  In the above, in the case of a film having a direction in which the retardation value becomes zero at a certain inclination angle with the in-plane slow axis as a rotation axis from the normal direction, the retardation at an inclination angle larger than the inclination angle The value is calculated in KOBRA 21ADH or WR after changing its sign to negative. In addition, a retardation value is measured from any two inclined directions, with the slow axis as a tilt axis (rotation axis) (when there is no slow axis, an arbitrary direction in the film plane is used as a rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated by the following equations (1) and (2).

  In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from a normal direction. nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the plane perpendicular to nx, and nz represents the refractive index in the direction perpendicular to nx and ny. d represents the thickness of the film.

If the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis (OPTIC AXIS), Rth (λ) is calculated by the following method.
Rth (λ) is obtained by converting the above Re (λ) from −50 ° to + 50 ° with respect to the normal direction of the film, using the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis). The light having a wavelength of λ nm is incident from each inclined direction at 10-degree steps, and 11 points are measured. Based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value, KOBRA 21ADH is measured. Or it is calculated by WR.
In the above measurement, as the assumed value of the average refractive index, a value from a catalog of various optical films or a polymer handbook (JOHN WILEY & SONS, INC) can be used. If the value of the average refractive index is not known, it can be measured with an Abbe refractometer. Examples of average refractive index values of main optical films are as follows: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). By inputting these assumed values of the average refractive index and the film thickness, nx, ny and nz are calculated in KOBRA 21ADH or WR. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

  One of the features of the laminate of the present invention is that a composition for forming a photo-alignment film containing a predetermined component is directly contacted with a polarizer to form a photo-alignment film. The composition for forming a photo-alignment film contains a compound having a crosslinkable group (compound B or C described later). Although the details of the reason why the wet heat durability of the polarizer is improved are unknown, it is considered that the compound having the crosslinkable group has an influence. More specifically, this compound can be bonded to a polarizer via a crosslinkable group, and by improving the adhesion between the photo-alignment film and the polarizer, for example, iodine or the like in the polarizer When the dichroic component is contained, it is considered that the movement of the dichroic component is suppressed, and as a result, the wet heat durability (durability in a wet heat environment) of the polarizer is improved.

The laminate of the present invention has a polarizer and a photo-alignment film disposed adjacent to the polarizer.
Hereinafter, first, a method of manufacturing a laminate will be described in detail, and then, a configuration of the laminate will be described in detail.

<Production method of laminate>
The method for producing a laminate includes a step of forming a coating film on the polarizer by bringing the composition for forming a photo-alignment film into direct contact with the surface of the polarizer (Step 1) and a step of forming a photo-alignment film from the coating film (Step 1). Step 2).
Hereinafter, materials and procedures used for each step will be described in detail.

[Step 1: coating film forming step]
Step 1 is a step of forming a coating film on the polarizer by bringing the composition for forming a photo-alignment film into direct contact with the surface of the polarizer. By performing this step, a coating film (photo-alignment material layer) corresponding to the precursor film of the photo-alignment film is obtained.
Hereinafter, first, the members and materials used in the present step will be described in detail, and then the procedure of the present step will be described in detail.

(Polarizer)
The polarizer may be a member (linear polarizer) having a function of converting light into specific linearly polarized light, and an absorption polarizer can be mainly used.
As the absorption polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a polyene-based polarizer, and the like are used. Iodine-based polarizers and dye-based polarizers include coating polarizers and stretched polarizers, both of which can be applied.Polarized light produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching. Children are preferred.
Above all, from the viewpoint of handleability, polyvinyl alcohol-based resins (at least one selected from the group consisting of polymers containing -CH ₂ -CHOH- as a repeating unit, particularly polyvinyl alcohol and ethylene-vinyl alcohol copolymer, are preferred. Is preferable.
In addition, in addition to the absorption polarizer, reflective polarizers such as a polarizer in which thin films having different birefringence are laminated, a wire grid polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter-wave plate are combined. Polarizers can also be used.
The thickness of the polarizer is not particularly limited, but is preferably 35 μm or less, more preferably 3 to 25 μm, and still more preferably 5 to 20 μm from the viewpoint of reducing the thickness of the image display device.

(Composition for forming photo-alignment film)
The composition for forming a photo-alignment film is a composition used for forming a photo-alignment film, and contains a compound A having a photo-alignment group and a compound B having a cross-linkable group, or Contains a compound C having a functional group and a crosslinkable group. That is, the composition for forming a photo-alignment film contains two types of compounds, a compound A having a photo-alignment group and a compound B having a cross-linkable group, or a compound having a photo-alignment group and a cross-linkable group. Contains one molecule having two types of functional groups C. When compound C is used, the composition for forming a photo-alignment film may further contain compound A and / or compound B together with compound C.

The photo-alignment group contained in the compound A and the compound C is a functional group capable of imparting anisotropy to a film by light irradiation. More specifically, it is a group whose molecular structure can be changed by irradiation with light, for example, plane-polarized light. Typically, irradiation with light, for example, plane-polarized light, results in a photoisomerization reaction, It refers to a group that causes at least one photoreaction selected from a quantification reaction and a photolysis reaction.
Among these photo-alignable groups, a group that causes a photoisomerization reaction (a group having a structure that photoisomerizes) and a group that causes a photodimerization reaction (a group having a structure that photodimerizes) are preferable. Raised groups are more preferred.

The photoisomerization reaction refers to a reaction that causes stereoisomerization and structural isomerization by the action of light. Examples of the substance causing such a photoisomerization reaction include a substance having an azobenzene structure (K. Ichimura et al., Mol. Cryst. Liq. Cryst., 298, 221 (1997)) and a hydrazono-β-ketoester structure. (S. Yamamura et al., Liquid Crystals, vol. 13, No. 2, page 189 (1993)), substances having a stilbene structure (JGVictor and JMTorkelson, Macromolecules, 20,2241 (1987)), and spiropyran Substances having a structure (K. Ichimura et al., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993)) and the like are known.
As the group that causes the photoisomerization reaction, a group that causes a photoisomerization reaction including a C ＝ C bond or an N ＝ N bond is preferable. Examples of such a group include a group having an azobenzene structure (skeleton), Examples include a group having a hydrazono-β-ketoester structure (skeleton), a group having a stilbene structure (skeleton), and a group having a spiropyran structure (skeleton).

The above-mentioned photodimerization reaction refers to a reaction in which an addition reaction occurs between two groups by the action of light, typically forming a ring structure. As a substance causing such photodimerization, for example, a substance having a cinnamic acid structure (M. Schadt et al., J. Appl. Phys., Vol. 31, No. 7, page 2155 (1992)), coumarin Substances having a structure (M. Schadt et al., Nature., Vol. 381, page 212 (1996)), substances having a chalcone structure (Toshihiro Ogawa et al., Proceedings of the Liquid Crystal Symposium, 2AB03 (1997)), benzophenone Substances having a structure (YK Jang et al., SID Int. Symposium Digest, P-53 (1997)) and the like are known.
Examples of the group that causes the photodimerization reaction include a group having a cinnamic acid (cinnamoyl) structure (skeleton), a group having a coumarin structure (skeleton), a group having a chalcone structure (skeleton), and a benzophenone structure (skeleton). And a group having an anthracene structure (skeleton). Among these groups, a group having a cinnamic acid structure and a group having a coumarin structure are preferable, and a group having a cinnamic acid structure is more preferable.

  The number of photo-alignment groups contained in compound A and compound C is not particularly limited, and a plurality of photo-alignment groups may be present. Further, the compound A and the compound C may contain only one kind or plural kinds of photo-alignment groups.

The crosslinkable group contained in the compound B and the compound C is a group that can be crosslinked, and is preferably a group that can be crosslinked (bonded) with the polarizer described above. The crosslinkable groups may react with each other.
The type of the crosslinkable group is not particularly limited, but mainly includes a photocrosslinkable group and a heat crosslinkable group by a crosslinking reaction (curing reaction).
The photocrosslinkable group is a group that is crosslinked by light irradiation, and includes, for example, a radical polymerizable group and a cationic polymerizable group. Suitable examples of the radical polymerizable group include a (meth) acryloyl group. Specific examples of the cationic polymerizable group include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and a vinyloxy group. Of these, an alicyclic ether group and a vinyloxy group are preferred, and an epoxy group, an oxetanyl group, and a vinyloxy group are particularly preferred. Of these, preferred examples of the photocrosslinkable group include a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, an epoxy group, an oxetanyl group, and a vinyloxy group. The (meth) acryloyl group is a concept including both a methacryloyl group and an acryloyl group.
The photo-crosslinkable group does not include the above-described photo-alignment group (for example, a group having a cinnamic acid structure).

  The thermally crosslinkable group is a group that is crosslinked by heat treatment, and examples thereof include a crosslinkable group described in a crosslinker handbook (Shinzo Yamamoto, Tosuke Kaneko: Taiseisha). Among them, amide group, halogen group, hydroxy group, carboxyl group, methylol group, alkoxysilane group, isocyanate group, thiol group, acid anhydride group, epoxy group, oxetane group, boronic acid group, vinyl group, aldehyde group, oxime Groups and the like, preferably a hydroxy group, a carboxyl group, a methylol group, an alkoxysilane group, an isocyanate group, an acid anhydride group, an epoxy group, an oxetane group, a boronic acid group, and the like.More preferably, a methylol group, an epoxy group More preferred.

  In one preferred embodiment of the heat-crosslinkable group, the heat-crosslinkable group is at least one selected from the group consisting of a hydroxy group, a carboxyl group, an amino group, and a thiol group (heat-crosslinkable group A). And an embodiment including at least one selected from the group consisting of a methylol group, an alkoxysilane group, an isocyanate group, an acid anhydride group, an epoxy group, an oxetane group, and a boronic acid (thermally crosslinkable group B). Can be That is, it is preferable that the compound has a thermally crosslinkable group A selected from the above group and a thermally crosslinkable group B selected from the above group as the thermally crosslinkable group contained in the compound. According to the above aspect, the wet heat durability of the polarizer is more excellent.

The number of the crosslinkable groups contained in the compound B and the compound C is not particularly limited, and may be plural. When the compound B and the compound C are low molecular weight compounds as described later, when there are a plurality of crosslinkable groups, the number is preferably 2 to 10, more preferably 4 to 8.
Further, the compound B and the compound C may contain only one kind or plural kinds of crosslinkable groups.

Each of the compound A, the compound B, and the compound C may be a low molecular compound or a high molecular compound. A low molecular weight compound means a compound having a molecular weight of 2000 or less, and a high molecular weight compound means a compound having a molecular weight of more than 2000.
When the compounds A to C are polymer compounds, these compounds preferably have a predetermined repeating unit. For example, compound A and compound C preferably have a repeating unit having a photo-alignable group (preferably, a repeating unit represented by the following formula (A1)). (Preferably, a repeating unit represented by the following formula (A2)).
Compound C may have a repeating unit having both a photo-alignable group and a cross-linkable group.

In Formula (A1) and Formula (A2), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
In Formulas (A1) and (A2), L ₁ and L ₂ each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include -O-, -CO-, -NH-, -CO-NH-, -COO-, -O-COO-, an alkylene group, an arylene group, and a heterocyclic group (heteroaryl group). Group) and a divalent linking group selected from a combination thereof.
In the formula (A1), X represents a photo-alignable group. The definition of the photo-alignment group is as described above.
In the formula (A2), Y represents a crosslinkable group. The definition of the crosslinkable group is as described above.

In addition, as an example of the compound C, the compound represented by the following formula (X) described in JP-A-2006-285197 can be exemplified.
In the formula, R ¹ and R ² each independently represent a hydroxy group or a group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, a vinyl group, a vinyloxy group, and a maleimide group. Represents a polymerizable group selected from
X ¹ is when ^{R 1} is a hydroxy group, a single bond, when ^{R 1} is a polymerizable _{^{group, - (A 1 -B 1)}} m - represents a linking group represented by, ^{X 2} is R ^{When 2} is a hydroxy group, it represents a single bond, and when R ² is a polymerizable group, it represents a linking group represented by-(A ² -B ² ) _n- . Here, A ¹ is bonded to R ¹ , A ² is bonded to R ^2, and B ¹ and B ² are each bonded to an adjacent phenylene group. A ¹ and A ² each independently represent a single bond or a divalent hydrocarbon group; B ¹ and B ² each independently represent a single bond, —O—, —CO—O—, —O—CO Represents-, -CO-NH-, -NH-CO-, -NH-CO-O-, or -O-CO-NH-. m and n each independently represent an integer of 0-4. However, when m or n is 2 or more, a plurality of A ¹ , B ¹ , A ² and B ² may be the same or different. However, A ¹ or A ² sandwiched between two B ¹ or B ² is not a single bond. R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a halogenated methyl group, a halogenated methoxy group, a cyano group, a nitro group, -OR ⁷ (where R ⁷ is A lower alkyl group having 1 to 6 carbon atoms, which is substituted with a lower alkyl group having 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or a lower alkoxy group having 1 to 6 carbon atoms); Represents a hydroxyalkyl group, —CONR ⁸ R ⁹ (R ⁸ and R ⁹ each independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms), or a methoxycarbonyl group. However, the carboxyl group may form a salt with the alkali metal.
R ⁵ and R ⁶ each independently represent a carboxyl group, a sulfo group, a nitro group, an amino group, or a hydroxy group. However, the carboxyl group and the sulfo group may form a salt with the alkali metal.

The composition for forming a photo-alignment film may contain components other than the above-mentioned compounds (compounds A to C).
For example, the composition for forming a photo-alignment film may contain a solvent. The type of the solvent is not particularly limited, and includes water and an organic solvent. Examples of the organic solvent include amide solvents (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compound solvents (eg, pyridine), and hydrocarbon solvents (eg, benzene, hexane). ), Alkyl halide solvents (eg, chloroform, dichloromethane), ester solvents (eg, methyl acetate, ethyl acetate, butyl acetate), ketone solvents (eg, acetone, methyl ethyl ketone), ether solvents (eg, tetrahydrofuran, 1) , 2-dimethoxyethane).
When the solvent is contained in the composition for forming a photo-alignment film, the solid content concentration in the composition for forming a photo-alignment film is, from the viewpoint of handleability (such as applicability), relative to the total mass of the composition. 0.1-10 mass% is preferable, and 1-5 mass% is more preferable.
In addition, the solid content intends the component (for example, compounds A-C) which forms a photo-alignment film.

Other components that may be included in the composition for forming a photo-alignment film include a polymerization initiator (radical polymerization initiator or cationic polymerization initiator), a curing agent, and the like.
As will be described later, when the curing treatment is performed by light irradiation treatment, it is preferable to use a photopolymerization initiator having a light absorption wavelength band different from the absorption band derived from the photo-alignment group.

(Process procedure)
In this step, the method is not particularly limited as long as the composition for forming a photo-alignment film can be brought into direct contact with the surface of the polarizer, and a known method is employed. For example, a spin coating method, a roll coating method, a flow coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, a gravure printing method and the like can be mentioned.
The surface of the polarizer to be brought into contact with the composition for forming a photo-alignment film may be only one side or both sides.

After the composition for forming a photo-alignment film is brought into contact with the surface of the polarizer, a drying treatment may be performed, if necessary, to remove volatile components (eg, a solvent). The method of the drying treatment is not particularly limited, and examples thereof include an air drying treatment and a heating treatment.
The thickness of the coating film obtained by the above procedure is not particularly limited, and is appropriately adjusted so that a desired thickness of a photo-alignment film described later is obtained. Above all, 10 nm to 10 μm is preferable, and 20 nm to 1 μm is more preferable, from the viewpoint of the alignment property and handleability of the photo alignment film.

[Step 2: photo-alignment film forming step]
Step 2 is a step of forming a photo-alignment film from the coating film obtained in step 1 above. In addition, as described later, the photo-alignment film refers to an alignment film in which an alignment control force has been developed by light irradiation.
As a procedure for forming such a photo-alignment film, there is a method of performing a curing process and a photo-alignment process on a coating film in random order. More specifically, a curing treatment is performed on the coating film, and then a photo-alignment treatment may be performed. Is also good.
Hereinafter, the procedure of each process will be described in detail.

(Curing treatment)
The curing treatment intends a treatment for reacting the above-mentioned crosslinkable group. By performing this treatment, the reaction between the crosslinkable groups in the coating film and the reaction between the polarizer and the crosslinkable group in the coating film progress. The progress of such a reaction improves the wet heat durability of the polarizer.
For the curing treatment procedure, an optimal treatment is appropriately selected depending on the type of the crosslinkable group. However, when the crosslinkable group is a photocrosslinkable group, a light irradiation treatment (photocuring treatment) is performed, and the crosslinkable group is thermally crosslinked. In the case of an acidic group, a heat treatment (thermosetting treatment) is preferably performed.

The type of light source used in the light irradiation treatment is not particularly limited, but is preferably performed at a wavelength other than the absorption band of the photo-alignment group, specifically, it is preferable to irradiate ultraviolet light of 320 nm or less. It is more preferable to irradiate light having a wavelength of 250 to 300 nm. However, when decomposition of the photo-alignment film is caused by ultraviolet light of 320 nm or less, it may be preferable to perform the polymerization treatment with ultraviolet light of 320 nm or more.
The light to be irradiated is preferably diffused light and non-polarized light in order not to disturb the alignment of the photo-alignable group.
In addition, when irradiating light from the same direction as the photo-alignment treatment described later, an arbitrary wavelength can be used because there is no possibility of disturbing the alignment state of the photo-alignable group.

  The heating temperature in the heat treatment is not particularly limited, and an optimal heating temperature is appropriately selected depending on the type of the heat-crosslinkable group. Usually, the heating temperature is preferably in the range of 40 to 300 ° C and more preferably in the range of 50 to 150 ° C. .

(Photo alignment treatment)
The photo-alignment treatment is a treatment of irradiating the photo-alignable groups contained in the coating film with light to align the photo-alignable groups in a certain direction, thereby imparting a liquid crystal alignment ability.
One method of photo-alignment treatment is to irradiate the coating with polarized light. Irradiation of polarized light may be performed from the normal direction (vertical direction) to the coating film surface, may be performed from an oblique direction to give a pretilt angle, or may be performed in combination. Good. The type of polarized light is not particularly limited, and may be either linearly polarized light or elliptically polarized light. In order to efficiently perform optical alignment, it is preferable to use linearly polarized light having a high extinction ratio.
As another method of the photo-alignment treatment, a method of irradiating the coating film with unpolarized light (unpolarized light) can be mentioned. When irradiating with non-polarized light, irradiate with non-polarized light from a direction oblique to the coating film surface. The incident angle of the non-polarized light at this time is preferably in the range of 10 to 80 ° with respect to the normal to the coating film surface, and considering the uniformity of the irradiation energy on the irradiation surface, the obtained pretilt angle, the alignment efficiency, etc. A range of from 60 to 60 is more preferable, and a range of 45 is most preferable.

In order to obtain polarized light in a light irradiation device, it is necessary to use a polarizing filter or the like, and thus there is a disadvantage that the light intensity applied to the coating film surface is reduced. There is an advantage that a large irradiation intensity can be obtained without requiring a polarizing filter or the like in the device, and the irradiation time for photo-alignment can be shortened.
Further, when a photomask is used when irradiating polarized light, the liquid crystal alignment ability can be generated in the photo alignment film in two or more different directions in a pattern. Specifically, the coating film may be covered with a photomask, and the entire surface may be irradiated with polarized or non-polarized light to give a liquid crystal alignment capability to the exposed portion in a pattern. By repeating this as necessary a plurality of times, liquid crystal alignment ability can be generated in a plurality of directions.

The type of light applied in the photo-alignment treatment is not particularly limited, and light having an optimal wavelength is selected according to the absorption band of the photo-alignment group. For example, ultraviolet light including light having a wavelength of 150 nm to 800 nm and Visible light can be used, and light having a wavelength of 350 nm to 500 nm is preferably used.
Examples of the light source of the irradiation light include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and an ultraviolet laser such as KrF and ArF.
In addition, linearly polarized light can be obtained by passing light from a light source through a polarizing filter or a polarizing prism such as a Glan-Thompson or a Glan-Teller. Irrespective of whether polarized light or non-polarized light is used, it is particularly preferable that the irradiated light be substantially parallel light.

But not dose specifically limited in the light alignment treatment, can efficiently impart liquid crystal alignment capability, in that the manufacturing cost is excellent, preferably ^{0.1~3000mJ / cm 2, 1~1000mJ / cm} 2 is more preferable.

<Laminate>
Through the steps described above, a laminate having a polarizer and a photo-alignment film disposed adjacent to the polarizer is obtained. Since the polarizer and the photo-alignment film are in direct contact with each other, the laminate of the present invention can be used for a thin display device.
The definition of the polarizer included in the laminate is as described above.
As described above, the photo-alignment film contained in the laminate is a film having a liquid crystal alignment ability containing a compound having a group (photo-alignment group) that generates liquid crystal alignment ability by absorbing light. In the photo-alignment film, the photo-alignment groups are arranged in a certain direction by the above-described photo-alignment treatment.
The thickness of the photo-alignment film is not particularly limited, and is appropriately adjusted so that a desired thickness of the photo-alignment film described later is obtained. Above all, 10 nm to 10 μm is preferable, and 20 nm to 1 μm is more preferable, from the viewpoint of the alignment property and handleability of the photo alignment film.
As described above, the crosslinkable group contained in the compound B and the compound C reacts during the curing treatment and is almost inactivated, but may partially remain in the photo-alignment film.

The laminate may include a layer other than the polarizer and the photo-alignment film. For example, an optically anisotropic layer is disposed on the photo-alignment film (on the surface opposite to the polarizer). You may.
Hereinafter, the optically anisotropic layer will be described in detail.

(Optically anisotropic layer)
The optically anisotropic layer is a layer that causes a phase difference in light passing through this layer. The optically anisotropic layer preferably contains a liquid crystal compound. In the optically anisotropic layer, the liquid crystal compound is preferably fixed in a state of being oriented in a certain direction.
The type of liquid crystal compound is not particularly limited, but can be classified into a rod type (rod liquid crystal compound) and a disk type (disk liquid crystal compound; discotic liquid crystal compound) according to the shape. Furthermore, there are low molecular type and high molecular type respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (polymer physics / phase transition dynamics, Masao Doi, page 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used. Two or more rod-shaped liquid crystal compounds, two or more disc-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disc-shaped liquid crystal compound may be used.
As the rod-like liquid crystal compound, for example, those described in claims 1 of JP-T-11-513019 or paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used. In particular, an optically anisotropic layer exhibiting a smectic phase is preferable because the panel contrast of a display device including the laminate of the present invention is more excellent. As the discotic liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 are preferably used. But not limited to these.

The optically anisotropic layer is more preferably formed using a liquid crystal compound having a polymerizable group (a rod-shaped liquid crystal compound or a disc-shaped liquid crystal compound), since a change in optical characteristics such as a change in temperature and a change in humidity can be reduced. The liquid crystal compound may be a mixture of two or more kinds, and in that case, it is preferable that at least one has two or more polymerizable groups.
That is, the optically anisotropic layer is preferably a layer formed by fixing a rod-shaped liquid crystal compound or a disc-shaped liquid crystal compound having a polymerizable group by polymerization or the like. There is no need to show sex.
The type of the polymerizable group contained in the rod-shaped liquid crystal compound or the disc-shaped liquid crystal compound is not particularly limited, and a functional group capable of performing an addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable. More specifically, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group and the like are preferable, and a (meth) acryloyl group is more preferable.

The method for forming the optically anisotropic layer is not particularly limited, and may be a known method.
For example, a composition for an optically anisotropic layer containing a liquid crystal compound having a polymerizable group (hereinafter, also simply referred to as “composition”) is applied on a photo-alignment film to form a coating film, and the resulting coating is obtained. By subjecting the film to a curing treatment (irradiation with ultraviolet light (light irradiation treatment) or heat treatment), an optically anisotropic layer can be produced.
The composition can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method).

The composition may contain components other than the liquid crystal compound described above.
For example, the composition may include a polymerization initiator. The polymerization initiator used is selected according to the type of the polymerization reaction, and includes, for example, a thermal polymerization initiator and a photopolymerization initiator. For example, examples of the photopolymerization initiator include an α-carbonyl compound, an acyloin ether, an α-hydrocarbon-substituted aromatic acyloin compound, a polynuclear quinone compound, or a combination of a triarylimidazole dimer and p-aminophenyl ketone. Is mentioned.

  Further, the composition may contain a polymerizable monomer from the viewpoint of the uniformity of the coating film and the strength of the film. Examples of the polymerizable monomer include radically polymerizable and cationically polymerizable compounds. Preferably, it is a polyfunctional radical polymerizable monomer, which is copolymerizable with the above-mentioned polymerizable group-containing liquid crystal compound. For example, those described in paragraphs [0018] to [0020] of JP-A-2002-296423 are exemplified.

  Further, the composition may contain a surfactant in view of uniformity of the coating film and strength of the film. Examples of the surfactant include conventionally known compounds, and a fluorine compound is particularly preferable. Specifically, for example, compounds described in paragraphs [0028] to [0056] of JP-A-2001-330725 and compounds described in paragraphs [0069] to [0126] of Japanese Patent Application No. 2003-295212 are disclosed. Is mentioned.

  The composition may contain a solvent, and an organic solvent is preferably used. Examples of the organic solvent include an organic solvent that may be contained in the composition for forming a photo-alignment film described above.

  The composition also includes various alignment agents such as a vertical alignment agent such as a polarization interface side vertical alignment agent, an air interface side vertical alignment agent, a horizontal alignment accelerator such as a polarizer interface side horizontal alignment agent, and an air interface side horizontal alignment agent. May be included. These alignment control agents are alignment control agents capable of horizontally controlling the alignment of the rod-shaped liquid crystal compound on the polarizer interface side or air interface side, and are also alignment control agents capable of controlling the disk-shaped liquid crystal compound vertically. Known compounds are appropriately used as these alignment controlling agents. For example, as a vertical aligning agent on the polarizer interface side of the discotic liquid crystal compound, paragraphs [0079] to [0104] of JP-A-2012-215704. And the air interface side vertical alignment agent include the compounds described in paragraphs [0106] to [0113] of JP-A-2012-215704, the contents of which are incorporated herein by reference. It is.

  Further, in addition to the above components, the composition may contain an adhesion improver, a plasticizer, a polymer, and the like.

The thickness of the optically anisotropic layer varies depending on the material used and the retardation value to be set, but is preferably from 0.1 to 15 μm, more preferably from 0.2 to 10 μm, and preferably from 0.3 to 10 μm. More preferably, it is 8 μm.
The preferred range of the in-plane retardation Re (550) of the optically anisotropic layer at a wavelength of 550 nm varies depending on the application.
For example, when a polarizing plate including an optically anisotropic layer is manufactured as a λ / 4 plate used for a circularly polarizing plate or the like, the optically anisotropic layer is formed to have a retardation region having a retardation of about λ / 4. Has a Re (550) of preferably 10 to 200 nm, more preferably 110 to 180 nm, further preferably 115 to 170 nm, and particularly preferably 120 to 160 nm. In this case, Rth (550) is not particularly limited, but in the case of the A plate, the range of the Nz coefficient expressed as (Rth / Re) +0.5 satisfies 0.8 to 1.2. It is preferably 1.0, and most preferably 1.0.
In the case of manufacturing as a λ / 2 plate, Re (550) is preferably from 220 to 325 nm, and more preferably from 250 to 300 nm, in order to obtain a retardation region having a retardation of about λ / 2. More preferred. In this case, Rth (550) is not particularly limited, but in the case of the A plate, the range of the Nz coefficient expressed as (Rth / Re) +0.5 satisfies 0.8 to 1.2. It is preferably 1.0, and most preferably 1.0.
When a laminate combined with a positive C plate is used as a λ / 2 plate, the optimum value differs depending on the physical properties of the combined C plate. For example, 100 nm ≦ Re (550) ≦ 180 nm is preferable, and 100 nm ≦ Re. (550) ≦ 150 nm is more preferred, and 120 nm ≦ Re (550) ≦ 140 nm is even more preferred. The preferable range of the retardation Rth (550 nm) in the thickness direction at a wavelength of 550 nm of the optically anisotropic layer also varies depending on the application. For example, 30 nm ≦ Rth (550) ≦ 100 nm is preferable, and 40 nm ≦ Rth (550) ≦. 90 nm is more preferred, and 50 nm ≦ Rth (550) ≦ 80 nm is even more preferred.

As one of preferred embodiments of the optically anisotropic layer, the polymerizable rod-shaped liquid crystal compound has an optically anisotropic layer in which the state in which the smectic phase is expressed, or the polymerizable rod-shaped liquid crystal compound shows a smectic phase and a nematic phase, An optically anisotropic layer in which a state in which a nematic phase is expressed is fixed is exemplified.
In the optically anisotropic layer, the molecules of the liquid crystal compound are fixed in a state of a smectic phase or a nematic phase in a homogeneous alignment (horizontal alignment) or a substantially horizontal tilt alignment in which the liquid crystal compound has a tilt angle of 10 ° or less. Is preferred. The above-mentioned inclination angle intends that the angle between the maximum direction of the refractive index and the layer plane is 10 ° or less, preferably 3 ° or less, particularly preferably 1 ° or less. The lower limit of the angle between the maximum direction of the refractive index and the layer plane is not particularly limited as long as it is 0 ° or more.

The optically anisotropic layer can be produced by fixing a smectic liquid crystal. When a smectic liquid crystal is used, the smectic liquid crystal is first (horizontally) horizontally aligned and then fixed by polymerization, photocrosslinking or thermal crosslinking.
Smectic liquid crystals can be more preferably used in applications requiring a relatively large retardation of 100 nm or more, since the scattered polarization of the optically anisotropic layer due to alignment fluctuations is small. The smectic phase is not particularly limited, and may be SmA, SmB, SmC or a higher order phase.
Whether the liquid crystal compound is fixed in the state of the smectic phase can be confirmed by observation using an X-ray diffraction pattern. If fixed in the state of the smectic phase, an X-ray diffraction pattern derived from the layer order is observed, so that the fixed state can be determined. The optically anisotropic layer of the present invention may be a layer in which a smectic liquid crystal is fixed in a state showing a nematic phase. Whether the liquid crystal compound is fixed in the nematic phase can be confirmed by observation using an X-ray diffraction pattern. If the phase is fixed in the nematic phase, no sharp peak on the low angle side due to layer formation is observed, and only a broad halo peak on the wide angle side is observed. Is possible.
Note that, in the present invention, as long as desired characteristics can be obtained, use of an optically anisotropic layer in which an alignment state is fixed by using a liquid crystal compound that expresses only a nematic phase is not hindered.

(Use of optically anisotropic layer)
The optically anisotropic layer of the present invention can be preferably used for various applications. For example, an optical compensation film for optically compensating a liquid crystal cell, a broadband λ / 4 plate for preventing reflection of external light in an organic EL display device, or a retardation plate such as a λ / 2 plate or a λ / 4 plate. Useful as
Further, as the optically anisotropic layer, an A plate or a quasi-A plate having a low contrast and a high contrast can be obtained. In particular, since an A plate or a quasi-A plate having reverse wavelength dispersion is obtained, it can be preferably used as a broadband λ / 4 plate of an organic EL display device or an optical compensation film of a liquid crystal display device.
Particularly, as the optically anisotropic layer, an A plate or a quasi-A plate with a suppressed tilt angle can be obtained. It can also be preferably used as an optical compensation film.

In the present specification, an optically anisotropic layer having a low tilt angle (low tilt angle) of 10 ° or less, particularly 1 ° or less is a uniaxial birefringent layer having a slow axis substantially in a plane. Consider
As an example of an embodiment of the optically anisotropic layer, Re (450), Re (550) and Re (650) which are retardation values measured at wavelengths of 450 nm, 550 nm and 650 nm are represented by the following formulas (1) to (3). ) Which satisfies the above condition.
Formula (1) 100 ≦ Re (550) ≦ 180 nm
Formula (2) 0.70 ≦ Re (450) / Re (550) ≦ 0.95
Formula (3) 1.00 ≦ Re (650) / Re (550) ≦ 1.30
Note that the in-plane slow axis of the optically anisotropic layer is preferably orthogonal to the absorption axis of the polarizer.

Further, the optically anisotropic layer is laminated with a positive C plate in which Rth (550), which is a retardation value in the thickness direction measured at a wavelength of 550 nm, satisfies the following formula (4). For example, as an IPS-type optical compensation film or a half-wave plate, it is possible to significantly improve color change and light leakage in oblique directions.
Formula (4): −180 ≦ Rth (550) ≦ −10

<Polarizing plate>
The present invention also relates to a polarizing plate including the above laminate.
As an embodiment of the polarizing plate of the present invention, for example, an embodiment in which an optically anisotropic layer is laminated on the surface of the photo-alignment film in the laminate opposite to the polarizer side, or the light in the laminate is Embodiment in which an optically anisotropic layer is laminated on the surface of the alignment film opposite to the polarizer side, and a protective film is laminated on the surface of the polarizer in the laminate opposite to the optical alignment film side. Is mentioned.
The structure of the protective film is not particularly limited, and may be, for example, a transparent support or a hard coat layer, or a laminate of the transparent support and the hard coat layer.
As the hard coat layer, a known layer can be used, and for example, a layer obtained by polymerizing and curing a polyfunctional monomer may be used.
Further, as the transparent support, a known transparent support can be used.For example, as a material for forming the transparent support, cellulose, cyclic olefin, acryl, polycarbonate, polyester, polyvinyl alcohol used for optical materials such as The materials used are preferably used. One preferred example of the protective film is a cellulose acylate film such as a triacetyl cellulose film.

<Liquid crystal display device>
The present invention also relates to a liquid crystal display device including the above laminate.
Generally, a liquid crystal display device has a liquid crystal cell and two polarizing plates disposed on both sides of the liquid crystal cell, and the liquid crystal cell carries liquid crystal between two electrode substrates. Further, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.
The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode, and more preferably in IPS mode. An IPS mode using photo-alignment is particularly preferred.
The orientation angle of the rod-like liquid crystal compound used in the liquid crystal cell with respect to the optically anisotropic layer is preferably 1 ° or less.

<Organic EL display device>
The present invention also relates to an organic EL display device including the laminate of the present invention.
In an organic EL display device, for example, a laminate (the optical alignment film is located on the optically anisotropic layer side in the laminate), an optically anisotropic layer, and an organic EL panel are provided in this order. Just do it.

  An organic EL panel is a member in which a light-emitting layer or a plurality of organic compound thin films including a light-emitting layer is formed between a pair of electrodes of an anode and a cathode. In addition to the light-emitting layer, a hole injection layer, a hole transport layer, and an electron injection layer are provided. , An electron transport layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.

  The anode supplies holes to the hole-injection layer, the hole-transport layer, the light-emitting layer, and the like. A metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), metals such as gold, silver, chromium, and nickel, and metals and conductive metal oxides. Mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, and the like. It is an oxide, and ITO is particularly preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

  Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.

<Example 1>
(Preparation of protective film)
The following composition was put into a mixing tank and stirred to dissolve each component, thereby preparing a core layer cellulose acylate dope 1.
――――――――――――――――――――――――――――――――――――――
Cellulose acetate having a degree of acetyl substitution of 2.88 100 parts by mass Ester oligomer (compound 1-1) 10 parts by mass Durability improver (compound 1-2) 4 parts by mass UV absorber (compound 1-3) 3 parts by mass methylene chloride (First solvent) 438 parts by mass Methanol (second solvent) 65 parts by mass ―――――――――――――――――――――――――――――――― ―――――

(Preparation of outer layer cellulose acylate dope 1)
10 parts by mass of the following matting agent dispersion liquid 1 was added to 190 parts by mass of the above-mentioned core layer cellulose acylate dope, whereby an outer layer cellulose acylate dope 1 was prepared.
――――――――――――――――――――――――――――――――――――――
Silica particles having an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by weight Methylene chloride (first solvent) 76 parts by weight Methanol (second solvent) 11 parts by weight Core layer cellulose acylate dope 1 1 part by weight ――――――――――――――――――――――――――――――――――――――

(Preparation of cellulose acylate film)
The above-mentioned core layer cellulose acylate dope 1 and three outer layer cellulose acylate dopes 1 on both sides thereof were simultaneously cast from a casting port onto a drum at 20 ° C. The film is peeled off with the solvent content being approximately 20% by mass, and both ends in the width direction of the film are fixed with tenter clips, and while the residual solvent is 3 to 15% by mass, the film is stretched 1.2 times in the horizontal direction. Dried. Thereafter, the cellulose acylate film having a thickness of 25 μm was produced by transporting between rolls of the heat treatment apparatus, and the resultant was used as the polarizing plate protective film 01.

(Preparation of polarizing plate 01)
1) Saponification of Film The produced polarizing plate protective film 01 was immersed in a 4.5 mol / L aqueous sodium hydroxide solution (saponified solution) adjusted to 37 ° C. for 1 minute, and then the film was washed with water. After being immersed in a 0.05 mol / L sulfuric acid aqueous solution for 30 seconds, it was further passed through a washing bath. Then, draining with an air knife was repeated three times, and after dropping water, the resultant was retained in a drying zone at 70 ° C. for 15 seconds and dried to produce a saponified polarizing plate protective film 01.
2) Production of Polarizer According to Example 1 of JP-A-2001-141926, a peripheral speed difference was given between two pairs of nip rolls, and the film was stretched in the longitudinal direction to prepare a polarizer having a width of 1330 mm and a thickness of 15 μm. The polarizer produced in this manner was designated as Polarizer 1.
3) Lamination The polarizer 1 thus obtained and the saponified polarizing plate protective film 01 were bonded to each other using a 3% by mass aqueous solution of PVA (PVA-117H, manufactured by Kuraray Co., Ltd.) as an adhesive. The polarizing plate 01 with a single-sided protective film (hereinafter, also simply referred to as the polarizing plate 01) is adhered by roll-to-roll so that the polarizing axis (absorption axis) of No. 1 is perpendicular to the longitudinal direction of the saponified polarizing plate protective film 01. ) Was prepared.

[Preparation of Photo Alignment Film A]
On the polarizer in the polarizing plate 01, a composition for forming a photo-alignment film A having the following composition was applied using a wire bar. Next, the obtained coating film was dried with hot air at 100 ° C. for 120 seconds, and light was applied to the coating film using a 300 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under air. Irradiation was performed (corresponding to light curing treatment).
Next, the light-cured coating film is irradiated with ultraviolet rays in a direction perpendicular to the coating film surface using a 160 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) in air. Then, a photo-alignment treatment was performed to prepare a photo-alignment film A. At this time, exposure was performed by setting a wire grid polarizer (Moxtek, ProFlux PPL02) so that it was parallel to the coating surface, and the transmission axis of the wire grid polarizer and the absorption axis of the polarizer were parallel. Was. The illuminance of the ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 380 nm to 320 nm), and the irradiation amount was 1000 mJ / cm ² in the UV-A region.
────────────────────────────────────
Composition of composition for forming photo-alignment film A────────────────────────────────────
The following photo-alignment material (a) 2 parts by mass The following adhesion improver 1 1 part by mass 97 parts by mass of chloroform ─────────

Material for photo alignment:

<Example 2>
[Preparation of Photo Alignment Film B]
After applying a composition for forming a photo-alignment film B having the following composition on the polarizer in the polarizing plate 01 using a spin coater, baking is performed on a hot plate at a temperature of 100 ° C. for 60 seconds (thermal curing treatment). To form a coating film having a thickness of 0.2 μm.
This coating film was irradiated with linearly polarized light of 300 to 400 nm from the direction perpendicular to the coating film surface, and was subjected to a photo-alignment treatment to produce a photo-alignment film B.
────────────────────────────────────
Composition of composition for forming photo-alignment film B────────────────────────────────────
CIN5 (see below) 0.99 parts by mass P2 (see below) 5.96 parts by mass hexamethoxymethyl melamine 1.24 parts by mass p-toluenesulfonic acid-hydrate 0.022 parts by mass propylene glycol monomethyl ether 57.01 Parts by mass

CIN5:
P2:

<Example 3>
[Preparation of Photo-Alignment Film C]
The composition for forming a photo-alignment film C having the following composition is applied on the polarizer in the polarizing plate 01 by a die coating method, and then is flowed in a dryer adjusted to 100 ° C. for 2 minutes to evaporate the solvent and evaporate the composition. The article was heat cured. As a result, a coating film having a thickness of 200 nm was formed.
The coating film was irradiated with polarized ultraviolet light through a wire grid to perform a photo-alignment treatment, thereby obtaining a photo-alignment layer C. At this time, as the ultraviolet irradiation device, "H bulb" (manufactured by Fusion) was used. The wavelength of the polarized ultraviolet light was 313 nm, and the integrated light amount was 40 mJ / cm ² .
────────────────────────────────────
Composition of composition for forming photo-alignment film CＣ
100 parts by mass of a photo-alignment material (trade name: ROP-103, manufactured by Lorick Co., Ltd.) (the photo-alignment material has both a photo-alignment group (photo-dimerization group) and a thermo-crosslinkable group)
Methyl ethyl ketone 900 parts by mass

<Example 4>
[Preparation of Photo-Alignment Film D]
A composition for forming a photo-alignment film D having the following composition was applied to the polarizer in the polarizing plate 01 using a bar coater, and then baked in an oven at 100 ° C. for 2 minutes (thermal curing treatment). A coating film having a thickness of 100 nm was formed.
This coating film was irradiated with polarized ultraviolet rays 10 mJ / cm ² including a 313 nm bright line from the vertical direction using a Hg-Xe lamp and a Glan-Taylor prism to the coating film surface to perform a photo-alignment treatment. Film D was prepared.
───────────────────────────────────
Composition of composition for forming photo-alignment film D───────────────────────────────────
Polyorganosiloxane (PA-5) (see below) 80 parts by mass poly (meth) acrylate (PB-5) (see below) 20 parts by mass tris (acetylacetonate) aluminum 10 parts by mass (aluminum chelate A (W), Kawaken Fine Chemical)
Tri (p-tolyl) silanol 40 parts by mass n-butyl acetate 70 parts by mass cyclohexanone 20 parts by mass ethyl acetoacetate 5 parts by mass propylene glycol monomethyl ether acetate 5 parts by mass ────────────────────

(Synthesis of polyorganosiloxane (POS-3))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 70.5 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol and triethylamine 8.8 g was charged and mixed at room temperature. Next, 70.5 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 2 hours while stirring under reflux. The operation of concentrating the reaction solution and diluting with butyl acetate was repeated twice to remove triethylamine and water, thereby obtaining a polymer solution containing polyorganosiloxane (POS-3).

(Synthesis of polyorganosiloxane (PA-5))
In a 100 mL three-necked flask, 9.3 g of polyorganosiloxane (POS-3), cinnamic acid derivative (C-4), light ester HOMS (manufactured by Kyoeisha Chemical), 26 g of methyl isobutyl ketone, and 0.93 g of tetrabutylammonium bromide were placed. It stirred and stirred at 80 degreeC for 12 hours. After the completion of the reaction, the reaction mixture was diluted with 100 g of butyl acetate and washed three times with water. The operation of concentrating this solution and diluting it with butyl acetate was repeated twice to finally obtain a solution containing a polyorganosiloxane (PA-5) having a photo-alignment group.
The amounts of (C-4) and light ester HOMS used were adjusted so that the amounts introduced into the epoxy group in the polyorganosiloxane (POS-3) were 40 mol% and 10 mol%, respectively.

(Synthesis of poly (meth) acrylate (PB-5))
100 parts by mass of the following poly (meth) acrylate (PB-2), 20 parts by mass of an acryloyl group-containing carboxylic acid (Aronix M-5300, manufactured by Toagosei), 10 parts by mass of tetrabutylammonium bromide as a catalyst, and propylene as a solvent 150 parts by mass of glycol monomethyl ether acetate was charged and stirred at 90 ° C. for 12 hours under a nitrogen atmosphere. After the completion of the reaction, the mixture was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate and washed three times with water. The operation of concentrating this solution and diluting it with butyl acetate was repeated twice to finally obtain a polymer solution containing poly (meth) acrylate (PB-5).

<Example 5>
[Preparation of Photo-Alignment Film E]
The composition for forming a photo-alignment film E having the following composition is applied on the polarizer in the polarizing plate 01 by bar coating, and then heated at 60 ° C. for 1 minute (thermal curing treatment) to remove the solvent. A film was formed.
Next, the coating film was irradiated with 10 mJ / cm ² of linearly polarized ultraviolet light having a wavelength near 313 nm from a direction of 90 ° to the coating film surface from an ultra-high pressure mercury lamp to perform a photo-alignment treatment. A photo-alignment film E of about 0.2 μm was produced.
────────────────────────────────────
Composition of composition for forming photo-alignment film E────────────────────────────────────
Photo-alignable polymer (i3-1) 0.125 parts by mass Polymer (ii1-1) 0.04 parts by mass p-toluenesulfonic acid hydrate 0.005 parts by mass 1-methoxy-2-propanol 3 parts by mass ──────────────────────────────────

<Example 6>
[Preparation of Photo-Alignment Film F]
The composition for forming a photo-alignment film F having the following composition was applied onto the polarizer in the polarizing plate 01 using a spin coater, and then dried at 100 ° C. for 3 minutes to form a coating film.
Next, a linearly polarized and parallel light of visible ultraviolet light (wavelength: 313 nm, irradiation intensity: 8 mW / cm ² ) was applied to the ultra-high pressure mercury lamp through a wavelength cut filter, a hand pass filter, and a polarizing filter. Irradiation was performed on the surface obliquely at an angle of 45 degrees to perform a photo-alignment treatment, thereby producing a photo-alignment film F. The irradiation amount was 100 mJ / cm ² .
───────────────────────────────────
Composition of composition for forming photo-alignment film F───────────────────────────────────
1 part by weight of DiCin-10 2 parts by weight of the following adhesion improver 97 parts by weight of cyclopentanone ─────

Solution 1 was prepared by dissolving 1 part by mass of a compound represented by the following formula in 10 parts by mass of ethyl methyl ketone. To this solution 1, 0.01 parts by mass of azobisisobutyronitrile (AIBN) was added, and the mixture was heated and refluxed for 2 days under a nitrogen atmosphere to obtain a solution 2. Next, the solution 2 was dropped and stirred into 60 parts by mass of methanol, and the precipitated solid was filtered. The obtained solid was dissolved in 5 parts by mass of tetrahydrofuran (THF), dropped and stirred in 120 parts by mass of ice-cooled hexane, and the precipitated solid was filtered. The obtained solid was dissolved in THF, dropped and stirred in 120 parts by mass of ice-cooled methanol, and the precipitated solid was filtered. DiCin-10 was obtained by dissolving the obtained solid in THF and drying in vacuum.

<Example 7>
[Preparation of Photo-Alignment Film G]
The composition for forming a photo-alignment film G having the following composition was applied on a polarizer in the polarizing plate 01 with a wire bar. The obtained coating film was dried with hot air at 100 ° C. for 120 seconds, and irradiated with light using a 300 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under air.
Next, the obtained coating film was irradiated with ultraviolet rays from the vertical direction of the coating film surface using a 160 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under air. An alignment treatment was performed to produce a photo-alignment film G. At this time, exposure was performed by setting a wire grid polarizer (Moxtek, ProFlux PPL02) so that it was parallel to the coating surface, and the transmission axis of the wire grid polarizer and the absorption axis of the polarizer were parallel. Was. The illuminance of the ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 380 nm to 320 nm), and the irradiation amount was 1000 mJ / cm ² in the UV-A region.
───────────────────────────────────
Composition of composition for forming photo-alignment film G───────────────────────────────────
The following materials for photo alignment 2 parts by mass 98 parts by mass of chloroform

Material for photo alignment:

[Comparative Example 2]
<Preparation of alignment film H>
On the polarizer in the polarizing plate 01, a composition for forming an alignment film H having the following composition was continuously applied using a # 8 wire bar. The coating film was dried with hot air at 60 ° C. for 60 seconds, and further with hot air at 100 ° C. for 120 seconds to form an alignment film H, and then subjected to a rubbing treatment. Partial peeling was confirmed at the interface between the polarizer and the alignment film by the rubbing treatment.
The alignment film H did not contain a photo-alignment group.
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Composition of composition for forming alignment film H───────────────────────────────────
The following modified polyvinyl alcohol 2.4 parts by mass Isopropyl alcohol 1.6 parts by mass Methanol 36 parts by mass Water 60 parts by mass ─────────

[Comparative Example 3]
<Preparation of Photo-Alignment Film I>
On the polarizer in the polarizing plate 01, a composition for forming a photo-alignment film I having the following composition was applied using a wire bar. The coating film was dried with hot air at 100 ° C. for 120 seconds, and irradiated with light using a 300 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under air.
Next, the obtained coating film was irradiated with ultraviolet rays in the direction perpendicular to the coating film surface using a 160 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) in air. Then, a photo-alignment treatment was performed to produce a photo-alignment film I. At this time, exposure was performed by setting a wire grid polarizer (Moxtek, ProFlux PPL02) so that it was parallel to the coating surface, and the transmission axis of the wire grid polarizer and the absorption axis of the polarizer were parallel. Was. The illuminance of the ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 380 nm to 320 nm), and the irradiation amount was 1000 mJ / cm ² in the UV-A region.
The composition for forming a photo-alignment film I did not contain a compound having a crosslinkable group.
───────────────────────────────────
Composition of composition for forming photo-alignment film I───────────────────────────────────
The following materials for photo alignment 2 parts by mass 98 parts by mass of chloroform
Material for photo alignment:

<Preparation of Optically Anisotropic Layer (Part 1)>
An optically anisotropic layer A or an optically anisotropic layer B was produced on each of the alignment films produced in the above Examples and Comparative Examples according to the following procedure. The types of the optically anisotropic layers disposed on each alignment film are shown in a table described later.

(Preparation of Optically Anisotropic Layer A)
The following composition A for optically anisotropic layer was produced. This composition was applied to the surface of a slide glass and observed with a polarizing microscope while heating. As a result, the phase transition temperature of the smectic A phase-nematic phase was 82 ° C.
───────────────────────────────────
Composition of composition A for optically anisotropic layer───────────────────────────────────
Smectic liquid crystal compound Sm-1 85 parts by weight Rod compound RL-1 15 parts by weight Photopolymerization initiator 3.0 parts by weight (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Fluorine-containing compound A 0.8 parts by weight Methyl ethyl ketone 588 parts by weight
Smectic liquid crystal compound Sm-1
Rod compound RL-1
Fluorine-containing compound A

The composition A for an optically anisotropic layer was applied on the photo-alignment film using a bar coater. Subsequently, the film was heated and aged at a film surface temperature of 100 ° C. for 60 seconds, cooled to 70 ° C., and then cooled to a temperature of 1000 mJ / cm ² in air using a 70 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). The optically anisotropic layer was formed by irradiating ultraviolet rays to fix the alignment state. In the formed optically anisotropic layer, the rod-like liquid crystal compound was oriented such that the slow axis direction was orthogonal to the polarized light irradiation direction. At this time, the thickness of the optically anisotropic layer was 0.8 μm. Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments), the dependence of Re on the light incident angle and the inclination angle of the optical axis (that is, the refractive index of the optically anisotropic layer is maximized) (Inclination with respect to the surface of the optically anisotropic layer). The results are shown in a table below.
Note that the polarized light irradiation direction is the direction of the plane of vibration of polarized light.

(Preparation of Optically Anisotropic Layer B)
The following composition B for optically anisotropic layers was produced. This composition was applied to the surface of a slide glass and observed with a polarizing microscope while heating. As a result, a clear smectic A phase was provided from 148 ° C., and the phase changed to a nematic phase at 183 ° C., and the isotropic phase transition temperature was 255 ° C.
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Composition of composition B for optically anisotropic layer───────────────────────────────────
100 parts by mass of smectic liquid crystal compound Sm-21 3.0 parts by mass of photopolymerization initiator 3.0 parts by mass (Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.)
0.8 parts by mass of the fluorine compound A chloroform 990 parts by mass
Smectic liquid crystal compound Sm-21; II-2-2

The composition B for an optically anisotropic layer was applied on the photo-alignment film using a bar coater. The film was heated and aged at a film surface temperature of 150 ° C. for 60 seconds, and then irradiated with 1000 mJ / cm ² ultraviolet light using a 70 mW / cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) in air. The optically anisotropic layer B was formed by fixing the orientation state. In the formed optically anisotropic layer B, the rod-like liquid crystal compound Sm-21 was oriented such that the slow axis direction was orthogonal to the polarized light irradiation direction. At this time, the thickness of the optically anisotropic layer was 2 μm. Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments), the dependence of Re on the light incident angle and the inclination angle of the optical axis were measured. The results are shown in a table below.

<Preparation of Optically Anisotropic Layer (Part 2)>
On the optically anisotropic layer A or the optically anisotropic layer B produced above, an optically anisotropic layer C was further produced according to the following procedure, and using the laminate produced in each of Examples and Comparative Examples. A polarizing plate including an optically anisotropic layer was produced.

The modified polyvinyl alcohol was changed to commercially available unmodified polyvinyl alcohol PVA103 (manufactured by Kuraray Co., Ltd.), and an alignment film was formed on the temporary support for formation in the same procedure as in Comparative Example 2.
The following composition K for an optically anisotropic layer was coated on this alignment film, aged at 60 ° C. for 60 seconds, and then air-cooled metal halide lamp of 70 mW / cm ² under air (Eye Graphics Co., Ltd.) The polymerizable rod-shaped liquid crystal compound was vertically aligned by irradiating ultraviolet rays of 1000 mJ / cm ² using the above method to fix the alignment state, thereby producing an optically anisotropic layer C (positive C plate). . Rth was -115 nm at a wavelength of 550 nm.

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Composition of Composition K for Optically Anisotropic Layer───────────────────────────────────
80 parts by weight of liquid crystal compound B01 20 parts by weight of liquid crystal compound B02 20 parts by weight of liquid crystal compound for vertical alignment (S01) 1 part by weight of vertical alignment agent (S02) 0.5 part by weight of ethylene oxide modified trimethylolpropane triacrylate (V # 360, Osaka Organic) 8 mass parts Irgacure 907 (manufactured by BASF) 3 mass parts Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 1 mass part B03 0.4 mass parts methyl ethyl ketone 170 mass parts cyclohexanone 30 mass parts ───────────────────────────────

  On the optically anisotropic layer A or the optically anisotropic layer B produced above, the optically anisotropic layer C (positive C plate) was bonded using an adhesive. After the lamination, the temporary support for formation was peeled off to prepare a polarizing plate having an optically anisotropic layer disposed on the laminate of the present invention.

<Various evaluations>
[Wet heat durability evaluation]
In the present invention, the orthogonal transmittance CT of a polarizing plate (a polarizing plate in which an optically anisotropic layer is disposed on a laminate) is measured using an automatic polarizing film measuring device VAP-7070 manufactured by JASCO Corporation as follows. It was measured at a wavelength of 410 nm by the method.
Two samples (5 cm × 5 cm) in which the polarizing plate of the present invention was attached to glass via an adhesive were produced. At this time, the polarizing plate protective film is attached so that the side of the protective film is opposite to the glass (air interface side). The cross transmittance measurement was performed by setting the glass side of the sample toward the light source. Each of the two samples was measured, and the average value was defined as the cross transmittance CT.
Thereafter, each polarizing plate was stored over time under the aging conditions described below, and then the cross transmittance CT was measured in the same manner. The change in the cross transmittance CT before and after the lapse of time was determined, and this was evaluated as the polarizing plate durability according to the following criteria. Note that "A" or "B" is desirable in practical use.
The relative humidity in an environment without humidity control was in the range of 0 to 20% RH.
−Aging conditions−
Evaluation criteria for 500 hours in an environment of 60 ° C. and a relative humidity of 95% RH:
A: Change in cross transmittance CT before and after aging is less than 0.6% B: Change in cross transmittance CT before and after aging is 0.6 to 1.0%
C: Change in cross transmittance CT before and after aging exceeds 1.0%

[Adhesion]
Using the equally spaced spacers having a guide, cuts were made at 1 mm intervals with a cutter knife on the photo-alignment films of the laminates obtained in the examples and comparative examples to form a 10 × 10 lattice pattern. Subsequently, a cellophane tape was placed on the lattice pattern and tightly adhered, and then the cellophane tape was peeled off. The cut portion of the photo-alignment film after peeling off the cellophane tape was observed. Excellent (“A”) when the number of grids where the photo-alignment film is peeled along the cut line or at the point where the photo-alignment film intersects is not confirmed with respect to the total number of grid patterns. ) And less than 15% were judged as having good adhesion ("B"), and more than 15% were judged as having poor adhesion ("C").

[Evaluation of solvent resistance]
Each of the composition for forming a photo-alignment film or the composition for forming an alignment film used in each of the examples and the comparative examples was applied to a silicon wafer by using a spin coater, and then subjected to a predetermined curing treatment to obtain a film having a film thickness of 0. A cured film of 2 μm was formed. In addition, as the curing treatment, when the crosslinkable group in the compound contained in the composition is a heat crosslinkable group, baking is performed on a hot plate at a thermosetting temperature of 130 ° C. for 60 seconds, and the crosslinkable group becomes photocrosslinkable. In the case of a base, the coating film was irradiated with light using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 300 mW / cm ² in air.
The film thickness was measured using F20 manufactured by FILMETRICS. After the cured film was immersed in cyclohexanone (CHN) for 60 seconds, it was dried at a temperature of 100 ° C. for 60 seconds, and the film thickness was measured. “A” indicates no change in film thickness after immersion in CHN, and “B” indicates a decrease in film thickness after immersion in CHN.

[Film hardness]
A photo-alignment film was produced in the same manner as in each example and comparative example except that a glass substrate was used instead of the polarizing plate 01. About this photo alignment film, the film hardness was measured with the pencil scratch tester for coating films. When the pencil hardness measurement result is 3H or more, the film hardness is judged to be excellent ("A"). When the pencil hardness measurement result is less than 3H or more, the film hardness is judged to be good ("B"). Was determined to be defective ("C").

<Production of liquid crystal display device>
The polarizing plate on the viewing side was peeled off from a liquid crystal cell of an iPad (using a photo-alignment film, manufactured by Apple) and used as an IPS mode liquid crystal cell using a photo-alignment film. The pre-tilt angle in the liquid crystal cell was 0 °.
Instead of the peeled polarizing plate, a polarizing plate in which an optically anisotropic layer was disposed on the laminates prepared in the above Examples and Comparative Examples was bonded to a liquid crystal cell to produce a liquid crystal display device. At this time, when observed from a direction perpendicular to the surface of the liquid crystal cell substrate, the substrates were bonded so that the absorption axis of the polarizer was orthogonal to the optical axis of the liquid crystal layer in the liquid crystal cell. Further, the polarizing plate was set so that the optically anisotropic layer was on the side opposite to the backlight side.
Comparative Example 1 corresponds to a mode in which a liquid crystal display device was manufactured using the polarizing plate 01 as the polarizing plate.

  The display performance was measured using a commercially available liquid crystal viewing angle and chromaticity characteristic measuring device Ezcom (manufactured by ELDIM), and the backlight used a commercially available liquid crystal display device iPad (manufactured by Apple). The liquid crystal cell to which the polarizing plate was attached was placed and measured so that the optically anisotropic layer was on the side opposite to the backlight side. The results are summarized in the following table.

[Panel contrast (panel CR)]
Using the above liquid crystal display device, the luminance (Yw) of the panel in white display from the vertical direction and the luminance (Yb) of the panel in black display from the vertical direction were measured, and the luminance in the vertical direction with respect to the panel was measured. The contrast ratio (Yw / Yb) was calculated and used as the front contrast, which was evaluated according to the following criteria.
A: Front contrast is 95% or more with respect to Comparative Example 1 B: Front contrast is 85% or more and less than 95% with respect to Comparative Example 1 C: Front contrast is 75% or more and less than 85% with respect to Comparative Example 1 D: Front contrast is less than 75% of Comparative Example 1

[Diagonal light leakage (diagonal light leakage)]
A value (luminance max) obtained by averaging the maximum values of the black luminance (Cd / m ² ) in the upward direction (azimuth angles of 0 to 180 ° in 5 ° increments) and in the downward directions (azimuth angles of 180 to 360 ° in 5 ° increments). ) Was calculated.
The smaller the numerical value, the smaller the light leakage of black display, and the evaluation was made on the following four grades A to D.
A: 1 or less B: more than 1 and 2 or less C: more than 2 and 5 or less D: more than 5

In Table 1, the “type” column of the “optically anisotropic layer” column indicates whether the optically anisotropic layer A or the optically anisotropic layer B was used.
In Examples and Comparative Examples, the in-plane slow axis of the optically anisotropic layer A or B was orthogonal to the absorption axis of the polarizer.

As can be seen from Table 1 above, it was confirmed that the laminate of the present invention had excellent wet heat durability. In addition, it was also excellent in various effects (for example, adhesion, solvent resistance, film hardness, panel CR, oblique light leakage).
On the other hand, in the laminates of Comparative Examples 2 and 3, which did not satisfy the predetermined requirements, the desired effects could not be obtained.

Claims (14)

Polarizer, having a photo-alignment film disposed adjacent to the polarizer,
The photo-alignment film is a layer formed by bringing the composition for forming a photo-alignment film into direct contact with the surface of the polarizer,
The composition for forming a photo-alignment film, comprising a compound A having a photo-alignment group and a compound B having a cross-linkable group, or a compound comprising a compound C having a photo-alignment group and a cross-linkable group. body.   The laminate according to claim 1, wherein the photo-alignable group is a group having a structure that undergoes photodimerization or photoisomerization.   The laminate according to claim 1, wherein the photo-alignment group is a group selected from the group consisting of a group having an azobenzene structure and a group having a cinnamoyl structure.   The laminate according to any one of claims 1 to 3, wherein the crosslinkable group is a photocrosslinkable group.   The photocrosslinkable group includes at least one selected from the group consisting of a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, an epoxy group, an oxetanyl group, and a vinyloxy group. Laminate.   The laminate according to any one of claims 1 to 3, wherein the crosslinkable group is a thermally crosslinkable group.   The heat crosslinkable group is selected from the group consisting of a hydroxy group, a carboxyl group, an amino group, a thiol group, a methylol group, an alkoxysilane group, an isocyanate group, an acid anhydride group, an epoxy group, an oxetane group, and a boronic acid group. The laminate according to claim 6, comprising at least one of the following.   The heat crosslinkable group is a hydroxy group, a carboxyl group, an amino group, and at least one selected from the group consisting of a thiol group, and a methylol group, an alkoxysilane group, an isocyanate group, an acid anhydride group, an epoxy group, The laminate according to claim 6, comprising an oxetane group and at least one selected from the group consisting of boronic acids.   The laminate according to any one of claims 1 to 8, further comprising an optically anisotropic layer containing a liquid crystal compound on a surface of the optical alignment film opposite to the polarizer. It is a manufacturing method of the layered product according to any one of claims 1 to 9,
A composition for forming a photo-alignment film containing a compound A having a photo-alignable group and a compound B having a cross-linkable group, or containing a compound C having a photo-alignable group and a cross-linkable group, Contacting directly with, to form a coating film on the polarizer,
Performing a curing treatment and a photo-alignment treatment on the coating film in any order to form a photo-alignment film.   A polarizing plate comprising the laminate according to claim 1.   A liquid crystal display device comprising the laminate according to claim 1.   13. The liquid crystal display device according to claim 12, wherein the liquid crystal display device is in an IPS mode.   An organic EL display device comprising the laminate according to claim 1.