KR102355232B1 - Polarizer and method for production thereof - Google Patents

Abstract

An object of this invention is to provide a novel polarizer and its manufacturing method.
The present invention is a polarizer in which an alignment layer, a polarizing layer and a protective layer are installed in this order on a transparent substrate,
The polarizing layer,
A step of forming a film from a composition comprising a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent;
removing the solvent from the film;
making the polymerizable liquid crystal compound contained in the film from which the solvent is removed to a smectic liquid crystal state;
A step of polymerizing the polymerizable liquid crystal compound while the polymerizable liquid crystal compound maintains the smectic liquid crystal state
It provides a polarizer manufactured by a manufacturing method comprising a, and a manufacturing method thereof.

Description

A polarizer and its manufacturing method

The present invention relates to a polarizer, a manufacturing method thereof, and the like.

The polarizing element (polarizer) used for a liquid crystal display device contains optical films, such as a protective layer, a polarizing layer, and a transparent substrate. For example, in Patent Document 1, a transparent resin protective layer (protective film), a light absorption anisotropic layer (polarizing film) and a transparent film (transparent substrate) are laminated in this order on a transparent film (transparent substrate), and the light A polarizer is described wherein the absorption anisotropic layer contains a dichroic dye having a specific structure of nematic liquid crystallinity.

[Patent Document 1] Japanese Patent Laid-Open No. 2010-152351

This invention provides a novel polarizer and its manufacturing method.

The present invention includes the following inventions [1] to [14].

[1] A polarizer in which an alignment layer, a polarizing layer and a protective layer are provided in this order on a transparent substrate,

The polarizing layer,

A step of forming a film from a composition comprising a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent;

removing the solvent from the film;

making the polymerizable liquid crystal compound contained in the film from which the solvent is removed to a smectic liquid crystal state;

The polarizer manufactured by the manufacturing method including the process of superposing|polymerizing the said polymerizable liquid crystal compound, maintaining the said smectic liquid crystal state.

[2] The polarizer according to [1], wherein the polarizing layer is a polarizing layer from which a black peak is obtained in X-ray diffraction measurement.

[3] The polarizer according to [1] or [2], wherein the thickness of the polarizing layer is in the range of 0.5 µm to 3 µm.

[4] The polarizer according to any one of [1] to [3], wherein the dichroic dye is an azo dye.

[5] The polarizer according to any one of [1] to [4], wherein the polymerizable liquid crystal compound contains two or more polymerizable smectic liquid crystal compounds.

[6] The protective layer according to any one of [1] to [5], wherein the protective layer is formed from a protective layer composition comprising a polyfunctional acrylate and a solvent, and the solvent is substantially composed of an alcohol solvent and/or an ether solvent. polarizer.

[7] The polarizer according to any one of [1] to [5], wherein the protective layer is formed from a composition for forming a protective layer comprising a polymer or oligomer obtained by polymerization of a polyfunctional acrylate and water.

[8] The polarizer according to any one of [1] to [5], wherein the protective layer is formed from a composition for forming a protective layer comprising a water-soluble polymer and water.

[9] A liquid crystal display device provided with the polarizer according to any one of [1] to [8].

[10] The liquid crystal display device according to [9], wherein the polarizer is disposed inside a liquid crystal cell.

[11] A circularly polarizing plate in which a quarter wave plate is provided on the protective layer of the polarizer according to any one of [1] to [8].

[12] The circularly polarizing plate according to the above [11], wherein the quarter wave plate is a wave plate having a characteristic that the in-plane retardation value with respect to visible light becomes smaller as the wavelength becomes shorter.

[13] An organic EL display device comprising the circularly polarizing plate according to the above [11] or [12] and an organic EL element.

[14] A step (1) of forming an orientation layer on a transparent substrate to form a laminate;

A step (2) of forming a first coating film on the alignment layer by applying a composition containing a polymerizable liquid crystal compound, a dichroic dye and a polymerization initiator on the alignment layer of the laminate;

A first dry film is formed by drying the first coating film formed in the step (2) under conditions in which the polymerizable liquid crystal compound contained in the first coating film does not polymerize, and the polymerization in the first dry film is performed. Step (3) of forming a polarizing layer from the first dry film by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state after the liquid crystal compound is in a smectic liquid crystal state;

On the polarizing layer formed in the step (3), a protective layer composition containing a polyfunctional acrylate and a solvent is applied to form a second coating film on the polarizing layer, and the second coating film is included in the second coating film. The manufacturing method of the polarizer including the process (4) of forming a protective layer from the said 2nd coating film by polymerizing a polyfunctional acrylate.

[15] The method for producing a polarizer according to [14], wherein the solvent contained in the protective layer composition is substantially composed of an alcohol solvent and/or an ether solvent.

[16] A step (1) of forming an orientation layer on a transparent substrate to form a laminate;

A step (2) of forming a first coating film on the alignment layer by applying a composition containing a polymerizable liquid crystal compound, a dichroic dye and a polymerization initiator on the alignment layer of the laminate;

A first dry film is formed by drying the first coating film formed in the step (2) under conditions in which the polymerizable liquid crystal compound contained in the first coating film does not polymerize, and the polymerization in the first dry film is performed. Step (3) of forming a polarizing layer from the first dry film by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state after the liquid crystal compound is in a smectic liquid crystal state;

On the polarizing layer formed in the step (3), a composition for forming a protective layer containing a polymer or oligomer obtained by polymerization of a polyfunctional acrylate and water is applied to form a second coating film on the polarizing layer, The manufacturing method of a polarizer including the process (4) of forming a protective layer from this 2nd coating film by drying this 2nd coating film.

[17] A step (1) of forming an orientation layer on a transparent substrate to form a laminate;

A step (2) of forming a first coating film on the alignment layer by applying a composition containing a polymerizable liquid crystal compound, a dichroic dye and a polymerization initiator on the alignment layer of the laminate;

A first dry film is formed by drying the first coating film formed in the step (2) under conditions in which the polymerizable liquid crystal compound contained in the first coating film does not polymerize, and the polymerization in the first dry film is performed. Step (3) of forming a polarizing layer from the first dry film by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state after the liquid crystal compound is in a smectic liquid crystal state;

A composition for forming a protective layer containing a water-soluble polymer and water is applied on the polarizing layer formed in the step (3) to form a second coating film on the polarizing layer, and drying the second coating film, The manufacturing method of a polarizer including the process (4) of forming a protective layer from a 2nd coating film.

[18] A polarizer manufactured by the manufacturing method according to any one of [14] to [17].

According to the present invention, a polarizer including a novel polarizing layer is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which showed typically the cross-sectional structure of the polarizer of this invention.
2 is a schematic diagram schematically showing a cross-sectional configuration of a liquid crystal display device using the polarizer of the present invention.
3 is a schematic diagram schematically illustrating a layer order of a polarizer of the present invention installed in a liquid crystal display device.
Fig. 4 is a schematic diagram schematically showing the order of layers of a polarizer of the present invention installed in a liquid crystal display device.
5 is a schematic diagram schematically showing a cross-sectional configuration of a liquid crystal display device (in-cell type) using the polarizer of the present invention.
6 is a schematic diagram schematically showing a cross-sectional configuration of an EL display device using the polarizer of the present invention.
Fig. 7 is a schematic diagram schematically showing a method of manufacturing an EL display device using the polarizer of the present invention.
Fig. 8 is a schematic diagram schematically showing the layer order of the polarizer of the present invention provided in an EL display device.
9 is a schematic diagram schematically showing a cross-sectional configuration of an EL display device using the polarizer of the present invention.
10 is a schematic diagram illustrating a projection type liquid crystal display using the polarizer of the present invention.

The polarizer of the present invention (hereinafter referred to as "the present polarizer" in some cases) is provided on a transparent substrate with an alignment layer, a polarizing layer and a protective layer in this order, and the polarizing layer,

A step of forming a coating film from a composition comprising a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent;

removing the solvent from the coating film;

making the polymerizable liquid crystal compound contained in the coating film from which the solvent is removed to a smectic liquid crystal state;

It is manufactured by the manufacturing method including the process of superposing|polymerizing the said polymerizable liquid crystal compound, maintaining the said smectic liquid crystal state.

Preferred embodiment of the manufacturing method of this polarizer is demonstrated, referring drawings as needed. A preferred embodiment of this production method is

Step (1) of forming an orientation layer on a transparent substrate to form a laminate;

Step (2) of forming a first coating film on the alignment layer by coating a composition containing a polymerizable liquid crystal compound, a dichroic dye and a polymerization initiator on the alignment layer of the laminate formed in the step (1) Wow,

A first dry film is formed by drying the first coating film formed in the step (2) under conditions in which the polymerizable liquid crystal compound contained in the first coating film does not polymerize, and the polymerizable film in the first dry film is dried. Step (3) of forming a polarizing layer from the first dry film by placing the liquid crystal compound in a smectic liquid crystal state and then polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state;

On the polarizing layer formed in the step (3), a protective layer composition containing a polyfunctional acrylate and a solvent is applied to form a second coating film on the polarizing layer, and the second coating film contained in the second coating film is applied. The process (4) of forming a protective layer from the said 2nd coating film by polymerizing a polyfunctional acrylate is included. Hereinafter, such a manufacturing method will be described for each process.

<Transparent substrate>

In the manufacturing method of this polarizer, first, a transparent base material is prepared. This transparent base material is a base material which has the transparency of the grade which can transmit light, especially visible light. This transparency means the characteristic that the transmittance|permeability with respect to the light ray over a wavelength of 380 nm - 780 nm becomes 80% or more. Specifically, examples of such a transparent substrate include a glass substrate, a plastic translucent sheet, and a translucent film. Examples of the plastic constituting the translucent sheet or the translucent film include polyolefins such as polyethylene, polypropylene, norbornene polymer; Cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; Polyphenylene sulfide, polyphenylene oxide, etc. are mentioned. Among the above specific examples of the transparent substrate, among the plastic translucent sheet and translucent film, a plastic translucent film, that is, a polymer film is preferable. Among these polymer films, a polymer film (a cellulose ester film or a cyclic olefin resin film) made of a cellulose ester or a cyclic olefin resin is preferable from the viewpoint of being easily available in the market or excellent in transparency. In manufacturing the present polarizer using such a transparent substrate, a supporting substrate or the like is adhered to the transparent substrate from the viewpoint of being able to handle it easily without causing damage such as tearing when transporting or storing the transparent substrate. You can do it. In addition, the thickness of the said transparent base material should just be enough to express the above-mentioned transparency. Moreover, when using a polymer film as a transparent base material, you may provide the function as a retardation film to this polymer film by an extending|stretching process etc. In addition, the case where the function as retardation film is provided to a transparent base material is demonstrated later.

A cellulose-ester film and a cyclic olefin resin film are demonstrated further in detail. Moreover, among these 2 types, when providing a function as retardation film, a cyclic olefin resin film is a preferable thing also from the point which is easy to control the retardation value.

As for the cellulose ester which comprises a cellulose-ester film, at least one part of the hydroxyl groups contained in a cellulose is an acetate esterified thing. A cellulose ester film made of such a cellulose ester can be easily obtained in the market. As a commercially available cellulose ester film (triacetyl cellulose film), For example, "Fuji Tack Film" [Fuji Shashin Film Co., Ltd.]; "KC8UX2M", "KC8UY" and "KC4UY" [Konica Minolta Opt Co., Ltd.] and the like. Such a commercially available cellulose film can be used as a transparent substrate as it is or as necessary, after the surface is subjected to a surface treatment such as an antiglare treatment, a hard coat treatment, an antistatic treatment or an antireflection treatment.

In order to impart retardation to the polymer film, as described above, a method such as stretching the polymer film is followed. Although all of the polymer films which consist of plastics, ie, a thermoplastic resin, can be extended|stretched, a cyclic olefin resin film is preferable at the point of being easy to provide retardation. The cyclic olefin-based resin constituting the cyclic olefin-based resin film is, for example, composed of a polymer or copolymer (cyclic olefin-based resin) of cyclic olefins such as norbornene and polycyclic norbornene-based monomers, and the cyclic olefin-based resin is partially Therefore, it may include a ring-opening part. Moreover, what hydrogenated the cyclic olefin resin containing a ring-opening part may be sufficient. Further, the cyclic olefin-based resin may be, for example, a copolymer of a cyclic olefin and a chain olefin or a vinylated aromatic compound (styrene, etc.) from the viewpoint of not significantly impairing transparency and not significantly increasing hygroscopicity. In addition, in this cyclic olefin resin, a polar group may be introduce|transduced in the molecule|numerator.

When the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound or chain olefin having a vinyl group, examples of the chain olefin include ethylene and propylene, and examples of the vinylated aromatic compound include styrene, α-methylstyrene and alkyl-substituted styrene. etc. Such a copolymer WHEREIN: The content rate of the structural unit derived from a cyclic olefin is 50 mol% or less with respect to all the structural units of a cyclic olefin resin, For example, it is the range of about 15-50 mol%. When the cyclic olefin resin is a terpolymer obtained from a cyclic olefin, a chain olefin, and a vinylated aromatic compound, for example, the content ratio of the structural unit derived from the chain olefin is 5 to all structural units of the cyclic olefin resin. It is about 80 mol%, and the content rate of the structural unit derived from a vinylated aromatic compound is about 5-80 mol%. The cyclic olefin resin of such a terpolymer has the advantage that the usage-amount of an expensive cyclic olefin can be comparatively decreased, when manufacturing this cyclic olefin resin.

Cyclic olefin resin which can manufacture a cyclic olefin resin film can be obtained easily also from a market. As a commercially available cyclic olefin resin, "Topas" [Ticona Corporation (Germany)]; "Aton" [JSR Co., Ltd.]; "ZEONOR" and "ZEONEX" [Nippon Zeon Co., Ltd.]; "Apel" [manufactured by Mitsui Chemicals Co., Ltd.] and the like. Such a cyclic olefin resin can be formed into a film by well-known film forming means, such as the solvent casting method and the melt extrusion method, for example, and it can be set as a film (cyclic olefin resin film). Moreover, the cyclic olefin resin film already marketed in the form of a film can also be used. Examples of such commercially available cyclic olefin resin films include "S Thinner" and "SCA40" (Sekisui Chemical Co., Ltd.); "Zeonoa Film" [Optis Co., Ltd.]; "Aton Film" [JSR Corporation] etc. are mentioned. In addition, all of what is described in " " here is a brand name, and the following is carried out in the same way.

Then, the method of providing retardation to a polymer film is demonstrated briefly. A polymer film can provide retardation property by a well-known extending|stretching method. For example, a winding body in which a polymer film is wound on a roll is prepared, the film is continuously unwound from this winding body, and the unwound film is conveyed to a heating furnace. The set temperature of the heating furnace is in the range from around the glass transition temperature of the plastic constituting the polymer film (°C) to [glass transition temperature + 100] (°C), preferably near the glass transition temperature (°C) to [glass transition temperature] temperature + 50] (°C). In the heating furnace, uniaxial or biaxial thermal stretching is performed by adjusting the conveying direction or tension to incline at an arbitrary angle when stretching in the film advancing direction or in a direction orthogonal to the advancing direction. A draw ratio is the range of about 1.1-6 times normally, Preferably it is the range of about 1.1-3.5 times. Moreover, as a method of extending|stretching in an oblique direction, if it can incline an orientation axis to a desired angle continuously, it will not specifically limit, A well-known extending method can be employ|adopted. As for such an extending|stretching method, the method of Unexamined-Japanese-Patent No. 50-83482 and Unexamined-Japanese-Patent No. 2-113920 is mentioned, for example.

In using as a transparent substrate, the thickness of the polymer film is preferably a thin one from the point of having a weight sufficient for practical handling and from the point of ensuring sufficient transparency, but if it is too thin, the strength decreases, The workability tends to be inferior. Then, the suitable thickness of these films is, for example, about 5 micrometers - 200 micrometers, Preferably it is 20 micrometers - 100 micrometers. When using this polarizer as a circularly polarizing plate mentioned later, when using the display apparatus using this circularly polarizing plate for a mobile use, as for the thickness of a film, about 20 micrometers - 80 micrometers is especially preferable. In addition, when providing retardation property to a film by extending|stretching, the thickness after extending|stretching is determined with the thickness of the film before extending|stretching, or a draw ratio.

<Process (1)>

In step (1), by providing an orientation layer on the transparent base material mentioned above, the laminated board which has a transparent base material and an orientation layer, Preferably, the laminated board on which the transparent base material and orientation layer were laminated|stacked is formed. In addition, when the surface treatment such as hard coat treatment or antiglare treatment is performed on the transparent substrate, an orientation layer may be formed on the surface opposite to the surface treated surface.

<Orientation layer>

It is preferable that the alignment layer is not significantly modified in the process of forming a polarizing layer to be described later. As a method of forming the alignment layer, a method of using an alignment polymer capable of imparting an alignment control force by rubbing (hereinafter referred to as a "rubbing method" in some cases), light capable of imparting an alignment control force by irradiating polarized light A method of using an orientation polymer (hereinafter referred to as "photo-alignment method" in some cases), a method of forming an orientation layer by depositing silicon oxide in all directions on a transparent substrate (transparent substrate surface), and Langmuir - A method of forming an alignment layer by forming a monomolecular film having a long-chain alkyl group using the Broget method (LB method), and the like. Especially, the point which can obtain the orientation layer excellent in orientation uniformity, and the point of the processing time and process cost which the orientation layer formation requires to a rubbing method and a photo-alignment method are preferable. As the alignment layer, solvent resistance to the extent that it does not dissolve in the solvent contained in the composition (composition for forming a polarizing layer to be described later) applied in a subsequent step thereon, heat resistance to heat treatment at the time of forming the polarizing layer such as solvent removal, and a transparent substrate It is preferable to have sufficient adhesiveness with respect to it. In addition, since friction is applied to the coating film for forming the orientation layer when an orientation regulating force is applied to the orientation layer by a rubbing method or the like, the coating film for forming the orientation layer or a compound constituting the orientation layer ( For example, it is preferable if the orientation polymer mentioned later) has a property that does not modify|denature by the said friction etc., or the orientation layer itself does not peel from the transparent base material by the said friction etc. From the point of being able to form such an orientation layer simply, it is preferable to form an orientation layer from the composition containing an orientation polymer or an orientation polymer, or a composition containing a photo-alignment polymer or a photo-alignment polymer.

Hereinafter, the orientation polymer and photo-alignment polymer for orientation layer formation are demonstrated.

Examples of preferred orientation polymers include polyamides having an amide bond in the molecule; gelatins; polyimides having an imide bond in the molecule and polyamic acids as hydrolyzates thereof; polyvinyl alcohol; alkyl-modified polyvinyl alcohol; polyacrylamide; polyoxazole; polyethyleneimine; polystyrene; polyvinylpyrrolidone; Polymers, such as polyacrylic acid and polyacrylic acid ester, are mentioned. These polymers may be used individually or in mixture of two or more types for alignment layer formation, and a copolymer which has multiple types of structural units which comprise these polymers may be used for alignment layer formation. As mentioned above, although the preferable example of an orientation polymer was shown, polyvinyl alcohol is especially preferable as an orientation polymer among these. In addition, depending on the type of these oriented polymers, polycondensation by dehydration polymerization, deamination polymerization, etc., chain polymerization such as radical polymerization, anionic polymerization and cationic polymerization, coordination polymerization, ring-opening polymerization, etc. It can be manufactured easily.

As the photo-alignment polymer, a polymer having a photosensitive structure is used. When a polymer having a photosensitive structure is irradiated with polarized light, the photo-alignment polymer is oriented by isomerization or crosslinking of the photosensitive structure of the irradiated portion, and as a result, an orientation regulating force is imparted to the film made of the photo-alignment polymer to form an alignment layer. Examples of the photosensitive structure include azobenzene structure, maleimide structure, chalcone structure, cinnamic acid structure, 1,2-vinylene structure, 1,2-acetylene structure, spiropyran structure, spirobenzopyran structure, and fulgide structure. and the like. In alignment layer formation, the polymer which has any one photosensitive structure chosen from these may be used independently and may use 2 or more types together. In addition, these photo-alignment polymers are a monomer (monomer) having a photosensitive structure, polycondensation by dehydration polymerization, deamination polymerization, etc., chain polymerization such as radical polymerization, anionic polymerization and cationic polymerization, coordination polymerization, ring-opening polymerization, etc. It can be easily prepared by selecting a known polymerization method. Moreover, it is good also as a copolymer using several types of monomers which have different photosensitive structures.

As a method of forming an orientation layer from an orientation polymer or a photo-alignment polymer, the method of preparing the composition which melt|dissolved the said orientation polymer or the said photo-alignment polymer in a solvent, and using this composition is preferable from the point of the operation being simple. Hereinafter, the composition which can form this orientation layer is called "composition for orientation layer formation" in some cases. If, for example, the composition for forming an alignment layer is applied on a transparent substrate and the solvent is removed from the coating film by heating operation, pressure reduction operation, or the like, the alignment layer can be easily formed on the transparent substrate. Although the solvent used for the composition for orientation layer formation can be suitably selected according to the kind and quantity of the orientation polymer or photo-alignment polymer to be used, Specifically, Water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene, and nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-substituted hydrocarbon solvents, such as chloroform and chlorobenzene, etc. are mentioned. These solvents may be used independently and may be used in combination of multiple types.

Moreover, in order to form an orientation layer, the composition for orientation layer formation marketed can also be used. As a commercially available composition for orientation layer formation, "Sunever" [Nissan Chemical Industries, Ltd.], "Optomer" [JSR Corporation], etc. are mentioned. Use of such a commercially available composition for forming an alignment layer is advantageous in that an alignment layer with little non-uniformity can be formed, and an alignment layer having good environmental resistance and mechanical resistance can be formed.

As a method of forming an alignment layer using the composition for forming an alignment layer, the composition for forming an alignment layer is applied on a transparent substrate and then heat-treated (annealed) to form an alignment layer on the transparent substrate to form a coating film. The thickness of the coating film for orientation layer formation obtained in this way is determined so that the orientation layer obtained after providing an orientation regulating force may become a desired thickness. The thickness of the alignment layer is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm. The thickness of such an orientation layer can be controlled by adjusting the conditions which apply|coat the composition for orientation layer formation.

Moreover, in order to provide an appropriate orientation regulating force with respect to the said coating film for orientation layer formation, and to form an orientation layer, rubbing or polarization irradiation is performed with respect to the said coating film for orientation layer formation. By providing an orientation regulating force, the polymeric liquid crystal compound contained in the coating film for polarizing layer formation (1st coating film) mentioned later can be orientated in a desired direction. In addition, as described later, when a plurality of types of polymerizable liquid crystal compounds are contained in the first coating film, that is, when a polymerizable liquid crystal mixture is contained, the polymerizable liquid crystal mixture is oriented in a desired direction. .

As a method of rubbing the coating film for forming the alignment layer, for example, a rubbing roll on which a rubbing cloth is wound and rotating is prepared, and the laminate in which the coating film (coating film for forming the alignment layer) is formed on a transparent substrate is placed on a stage. The method of making this coating film and the rotating rubbing roll contact by conveying toward the rubbing roll which is mounted and is rotating is mentioned. Moreover, also by irradiating polarized light (preferably polarized light UV) to the coating film for orientation layer (photo-alignment layer) formation, an orientation regulating force may be provided with respect to this coating film. When performing rubbing or polarized light irradiation, if masking is performed, the some area|region (pattern) from which the direction of a slow axis differs can also be formed in this polarizer obtained.

<Process (2)>

In a process (2), a polarizing layer is provided on the orientation layer formed as mentioned above.

The polarizing layer which this polarizer has is formed by the method as mentioned above. It is repeated, but this method will be described. First, a composition containing a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator and a solvent (hereinafter referred to as “a composition for forming a polarizing layer” in some cases) is applied on the alignment layer to form a first coating film, , The first dry film is formed by drying the first coating film to remove the solvent. Then, a polarizing layer is formed by superposing|polymerizing the polymerizable liquid crystal compound in this 1st dry film, maintaining the liquid-crystal state of a smectic phase. In order to polymerize the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state as described above, first, the phase transition temperature of the polymerizable liquid crystal compound to be used is measured, the temperature at which the smectic phase can be maintained is obtained, and then the temperature is lowered below this temperature. What is necessary is just to polymerize the said polymerizable liquid crystal compound under the following temperature conditions, but it is so preferable that the polymerization temperature which polymerizes this polymeric liquid crystal compound is low. In addition, the measurement conditions for this phase transition temperature measurement are demonstrated in the Example of this application.

The thickness of the said polarizing layer is the range of 0.5 micrometer - 10 micrometers normally, and the range of 0.5 micrometer - 3 micrometers is more preferable. Therefore, the thickness of a 1st coating film considers the thickness of the polarizing layer obtained, and it is determined. In addition, the thickness of the said polarizing layer can be calculated|required by the measurement of an interference film thickness meter, a laser microscope, or a needle contact type film thickness meter.

The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is a compound having a polymerizable group and exhibiting liquid crystallinity. The polymerizable group means a group involved in the polymerization reaction of the polymerizable liquid crystal compound.

As said smectic phase, Smectic B phase, Smectic D phase, Smectic E phase, Smectic F phase, Smectic G phase, Smectic H phase, Smectic I phase, Smectic J phase, Smectic K phase and Smectic L-phase. Among them, higher-order smectic phases such as smectic B-phase, smectic F-phase, smectic I-phase, inclined smectic F-phase and inclined smectic I-phase are preferable, and smectic B-phase is more preferable. A polarizing layer with a high degree of alignment order can be formed when the composition for polarizing layer formation in which the liquid crystal phase which a polymeric liquid crystal compound shows can become these liquid crystal phases is used.

Preferred examples of the polymerizable liquid crystal composition include a compound represented by the general formula (1) [hereinafter referred to as “compound (1)” in some cases].

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (1)

In the above formula (1),

X ¹ , X ² and X ³ each independently represent a p-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, ^{at least one of X 1} , X ² and X ³ is a p-phenylene group which may have a substituent.

Y ¹ and Y ² are each independently -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N- ^{, -CR a} =CR ^b -, -C≡ C- or -CR ^a =N-. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² each independently represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group is substituted with -O-, -S- or -NH- it may be good

In compound (1), as described above, ^{at least one of X 1} , X ² and X ³ is a 1,4-phenylene group which may have a substituent, and among these, at least two of them may have a substituent A good p-phenylene group is more preferable.

It is preferable that the said p-phenylene group is unsubstituted. It is preferable that it is a trans-cyclohexane-1,4-diyl group, and, as for the said cyclohexane-1,4-diyl group, it is more preferable that this is also unsubstituted.

Examples of the substituent optionally included in the p-phenylene group or the cyclohexane-1,4-diyl group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group; cyano group; A halogen atom etc. are mentioned. _{In addition, -CH 2} - constituting the cyclohexanoic acid-1,4-diyl group may be substituted with -O-, -S- or -NR-. R is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

^{Y 1} in compound (1) _{is preferably -CH 2} CH ₂ -, -COO- or a single bond, and Y ² is _{preferably -CH 2} CH ₂ - or -CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. That is, if U ¹ and U ² is a group all polymeric, and more preferably when both a photopolymerizable group. Here, the photopolymerizable group refers to a group capable of participating in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator described later. The use of a polymerizable liquid crystal compound having a photopolymerizable group is also advantageous in that the polymerizable liquid crystal compound can be polymerized under a lower temperature condition.

In the compound (1), ^{the photopolymerizable groups of U 1} and U ² may be different from each other, but it is preferably the same type of group. Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. . Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

Examples of the alkanediyl group represented by V ¹ and V ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group and ico acid-1,20-diyl group; and the like. V ¹ and V ² are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.

* Examples of the substituent optionally included in the alkanediyl group include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted or straight-chain alkanediyl group.

W ¹ and W ² are each independently of the other, preferably a single bond or —O—.

As compound (1), the compound etc. which are represented by any one of Formula (1-1) - Formula (1-21) are mentioned. When the specific example of such compound (1) has a cyclohexane-1,4-diyl group, it is preferable that the cyclohexane-1,4-diyl group is a trans body.

The exemplified compound (1) [polymerizable liquid crystal compound] can be used alone or as a polymerizable liquid crystal mixture in which two or more types are mixed. In addition, components other than the polymerizable liquid crystal compound of the composition for forming a polarizing layer so that the phase transition temperature of the compound (1) is obtained as described above, and the compound (1) can be polymerized under the temperature condition below the phase transition temperature. to adjust As a component which can control such polymerization temperature, the photoinitiator mentioned later, a photosensitizer, a polymerization inhibitor, etc. are mentioned. The polymerization temperature of compound (1) can be controlled by appropriately adjusting the types and amounts thereof. In addition, even when a mixture of two or more compounds (1), that is, a polymerizable liquid crystal mixture is used in the composition for forming a polarizing layer, after the phase transition temperature of the polymerizable liquid crystal mixture is obtained, the same as in the case of the polymerizable liquid crystal compound to control the polymerization temperature.

As the polymerizable liquid crystal compound used in the composition for forming a polarizing layer, among the exemplified compound (1), general formula (1-3), general formula (1-6), general formula (1-7), general formula (1-12), or It is preferably represented by the formula (1-13). All of these compounds (1) polymerize the compound (1) under a temperature condition that easily falls below the phase transition temperature by interaction with the photopolymerization initiator used, that is, while sufficiently maintaining the high-order smectic phase liquid crystal state. can do it More specifically, by interaction with the photopolymerization initiator, these compounds (1) can be polymerized under a temperature condition of 70°C or less, preferably 60°C or less, while sufficiently maintaining the high-order smectic phase liquid crystal state. can

As described above, the polymerizable liquid crystal compound contained in the composition for forming a polarizing layer may be a single species or may be plural, but preferably a plurality of types, and more preferably a plurality of types in the exemplified compound (1). Further, the polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is preferably a polymerizable smectic liquid crystal compound, and preferably contains a plurality of polymerizable smectic liquid crystal compounds. In addition, all of the compounds (1) represented by the aforementioned formulas (1-1) to (1-21) correspond to polymerizable smectic liquid crystal compounds.

70-99.9 mass % is preferable with respect to the solid content of this composition for polarizing layer formation, and, as for the content rate of the polymeric liquid crystal compound in the said composition for polarizing layer formation, 90-99.9 mass % is more preferable. When the content of the polymerizable liquid crystal compound is within the above range, the orientation of the polymerizable liquid crystal compound tends to increase. Here, solid content means the total amount of the component except volatile components, such as a solvent, from the said composition for polarizing layer formation. When using compound (1) as a polymeric liquid crystal compound, what is necessary is just to make the content rate with respect to the said composition for polarizing layer formation of this compound (1) into an above-mentioned range. When multiple types of compound (1) are contained in the said composition for polarizing layer formation, the total content ratio should just be the above-mentioned range.

It is preferable when the said composition for polarizing layer formation contains a leveling agent. This leveling agent has the function of adjusting the fluidity|liquidity of a polymeric liquid crystal compound and making flatter the said 1st coating film obtained by apply|coating the composition for polarizing layer formation more. As said leveling agent, surfactant etc. can be used. At least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component of this leveling agent is more preferable.

As a leveling agent containing a polyacrylate compound as a main component, "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK-358N", "BYK" -361N", "BYK-380", "BYK-381" and "BYK-392" [BYK Chemie Corporation], etc. are mentioned.

As a leveling agent containing a fluorine atom-containing compound as a main component, "Mega Pak R-08", "Mega Pak R-30", "Mega Pak R-90", "Mega Pak F-410", "Mega Pak F-411" ", "Megapack F-443", "Megapack F-445", "Megapack F-470", "Megapack F-471", "Megapack F-477", "Megapack F-479", "Megapack F-482" and "Megapack F-483" [DIC Co., Ltd.]; "Suffron S-381", "Suffron S-382", "Suffron S-383", "Suffron S-393", "Suffron SC-101", "Suffron SC-105", "KH -40" and "SA-100" [AGC Semichemical Co., Ltd.]; "E1830", "E5844" [Daikin Fine Chemical Genkyusho Co., Ltd.]; "Ftop EF301", "Ftop EF303", "Ftop EF351" and "Ftop EF352&quot; (Mitsubishi Materials Co., Ltd.).

When the composition for forming a polarizing layer contains a leveling agent, the content is preferably 0.3 parts by mass or more and 5 parts by mass or less, and more preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound. desirable. It is easy to horizontally orientate a polymeric liquid crystal composition as content of a leveling agent is in an above-described range, and there exists a tendency for the polarizing layer obtained to become further smoother. On the other hand, when content of the leveling agent with respect to a polymeric liquid crystal compound exceeds an above-described range, there exists a tendency for nonuniformity to generate|occur|produce easily in the polarizing layer obtained. Moreover, the said composition for polarizing layer formation may contain 2 or more types of leveling agents.

The composition for forming a polarizing layer contains a dichroic dye. The dichroic dye herein refers to a dye having a property in which the absorbance in the long-axis direction of the molecule differs from the absorbance in the short-axis direction. As long as it has such a property, a dichroic dye in particular will not restrict|limit, A dye may be sufficient and a pigment may be sufficient. A plurality of types of this dye may be used, a plurality of types of pigments may be used, and a dye and a pigment may be combined.

The dichroic dye preferably has a maximum absorption wavelength (λMAX) in the range of 300 nm to 700 nm. As such a dichroic dye, although an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, an anthraquinone dye, etc. are mentioned, for example, Among these, an azo dye is preferable. As an azo dye, a monoazo dye, a bisazo dye, a trisazo dye, a tetrakis azo dye, a stilbenazo dye, etc. are mentioned, Preferably they are a bisazo dye and a trisazo dye.

Examples of the azo dye include a compound represented by the general formula (2) [hereinafter referred to as "compound (2)" in some cases].

A ¹ (-N=NA ² ) _p -N=NA ³ (2)

In the above formula (2),

A ¹ and A ³ each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. A ² represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents the integer of 1-4. p is 2 or more, plural A ² may be the same with each other or may be different.

Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole and benzooxazole. The group obtained by removing two hydrogen atoms from the heterocyclic compound corresponds to a divalent heterocyclic group, and specific examples of the heterocyclic compound are as described above.

Substituents optionally having a phenyl group, a naphthyl group, and a monovalent heterocyclic group for A ¹ and A ³ , and a p-phenylene group, a naphthalene-1,4- ^{diyl group and a divalent heterocyclic group for A 2 include 1 carbon atom} to 4 alkyl groups; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; a C1-C4 fluorinated alkyl group, such as a trifluoromethyl group; cyano group; nitro group; halogen atom; A substituted or unsubstituted amino group such as an amino group, a diethylamino group and a pyrrolidino group (a substituted amino group is an amino group having one or two C1-C6 alkyl groups, or two substituted alkyl groups having 2 to 8 carbon atoms bonded to each other refers to an amino group forming an alkanediyl group of (the unsubstituted amino group is —NH ₂ ). In addition, the specific example of a C1-C6 alkyl group is the same as what was illustrated by the substituent which the phenylene group etc. of compound (1) have arbitrarily.

Among the compounds (2), compounds represented by any one of the following formulas (2-1) to (2-6) are preferable.

In the above formulas (2-1) to (2-6),

B ^{1 to} B ²⁰ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (the definition of a substituted amino group and an unsubstituted amino group is as described above ), a chlorine atom or a trifluoromethyl group.

n1 to n4 each independently represent an integer of 0 to 3.

When n1 is 2 or more, a plurality of B ² may be the same as or different from each other,

When n2 is 2 or more, a plurality of B ⁶ may be the same as or different from each other,

When n3 is 2 or more, a plurality of B ⁹ may be the same as or different from each other,

When n4 is 2 or more, some B ¹⁴ may be mutually same, and may differ from each other.

As such azo dyes, those readily available in the market may be used. Commercially available azo dyes that can be used in the composition for forming a polarizing layer include "NKX2029" and "G205" (manufactured by Hayashibara Seibutsuka Chemicals Kyusho).

As said anthraquinone pigment|dye, the compound represented by General formula (2-7) is preferable.

In the above formula (2-7),

R ¹ to ^{R 8} each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

As said acridine dye, the compound represented by General formula (2-8) is preferable.

In the above formula (2-8),

R ⁹ to ^{R 15} each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

As said oxazone pigment|dye, the compound represented by General formula (2-9) is preferable.

In the above formula (2-9),

R ¹⁶ to ^{R 23} each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

In the above formulas (2-7), (2-8) and (2-9), ^{the alkyl group having 1 to 4 carbon atoms in R x} is a methyl group, an ethyl group, a propyl group, a butyl group, or the like, and has 6 to 4 carbon atoms. Examples of the aryl group of 12 include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.

As said cyanine pigment|dye, the compound represented by Formula (2-10) and the compound represented by Formula (2-11) are preferable.

In the above formula (2-10),

D ¹ and D ² each independently represent a group represented by any one of Formulas (2-10a) to (2-10d).

n5 represents the integer of 1-3.

In the above formula (2-11),

D ³ and D ⁴ each independently represent a group represented by any one of Formulas (2-11a) to (2-11h).

n6 represents the integer of 1-3.

Although content of the dichroic dye in the said composition for polarizing layer formation can be suitably adjusted according to the kind etc. of this dichroic dye, For example, 0.1 mass part or more and 50 mass with respect to a total of 100 mass parts of a polymeric liquid crystal compound. A part is preferable, 0.1 mass part or more and 20 mass parts or less are more preferable, and 0.1 mass part or more and 10 mass parts or less are still more preferable. If the content of the dichroic dye is within this range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable liquid crystal compound while maintaining the high-order smectic phase liquid crystal state. When there is too much content of a dichroic dye, there exists a possibility of inhibiting the orientation of a polymerizable liquid crystal compound. Therefore, a polymeric liquid crystal compound can also determine content of a dichroic dye in the range which can maintain the liquid crystal state of a high-order smectic phase.

The composition for forming the polarizing layer contains a solvent. The solvent can be suitably selected from a preferable solvent in consideration of the solubility of the polymerizable liquid crystal compound to be used, and the like. However, it is preferable that it is an inert solvent which does not significantly impede the progress of the polymerization reaction of the said polymerizable liquid crystal compound. Examples of such solvents include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; and chlorine-containing solvents such as chloroform and chlorobenzene. These solvents may be used independently and may be used in combination of multiple types.

As for content of a solvent, 50-98 mass % is preferable with respect to the total amount of the said composition for polarizing layer formation. In other words, as for solid content in the composition for polarizing layer formation, 2-50 mass % is preferable. If solid content is 2 mass % or more, the dichroism required as a polarizing layer which this polarizer has can be acquired. On the other hand, when this solid content is 50 mass % or less, since the viscosity of the composition for polarizing layer formation becomes low, since the thickness of a polarizing layer becomes substantially uniform, there exists a tendency for this polarizing layer to become non-uniformity less easily. In addition, such a solid content can be determined so that the thickness of the above-mentioned polarizing layer can be formed.

The composition for forming a polarizing layer contains a polymerization initiator. This polymerization initiator is a compound which can initiate the polymerization reaction of a polymeric liquid crystal compound, and a photoinitiator is preferable at the point which can start the said polymerization reaction under lower temperature conditions. Specifically, a compound capable of generating active radicals or acids by the action of light under low temperature conditions (this low temperature refers to a temperature of 70° C. or lower, preferably 60° C. or lower as described above) is used as a photopolymerization initiator do. Among these photoinitiators, those that generate radicals by the action of light are more preferable.

Examples of the photopolymerization initiator include a benzoin compound, a benzophenone compound, an alkylphenone compound, an acylphosphine oxide compound, a triazine compound, an iodonium salt, and a sulfonium salt.

Hereinafter, the specific example of this photoinitiator is given.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butyl) Peroxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone, etc. are mentioned.

As the alkylphenone compound, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethan-1-one, 2 -hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-[ The oligomer of 4-(1-methylvinyl)phenyl]propan-1-one, etc. are mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- (4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) )ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-tri Ajin etc. are mentioned.

As a photoinitiator, what can be obtained easily in a market can also be used. As a commercially available photoinitiator, "Irgacure 907", "Irgacure 184", "Irgacure 651", "Irgacure 819", "Irgacure 250", "Irgacure 369" [Chiba Japan ( main)]; "Sake All BZ", "Shake All Z", "Shake All BEE" [Seiko Chemicals Co., Ltd.]; "kayacure BP100" (Nippon Kayaku Co., Ltd.); "Kayacure UVI-6992" (manufactured by Dow Corporation); "adeca optomer SP-152", "adeca optomer SP-170" [ADEKA Co., Ltd.]; "TAZ-A", "TAZ-PP" (Nippon Siebel Hegner); and "TAZ-104" (Sanwa Chemical).

The content of the polymerization initiator in the composition for forming a polarizing layer can be appropriately adjusted depending on the type and amount of the polymerizable liquid crystal compound contained in the composition for forming a polarizing layer, for example, a total of 100 polymerizable liquid crystal compounds 0.1-30 mass parts is preferable, as for content of the polymerization initiator with respect to mass part, 0.5-10 mass parts is more preferable, 0.5-8 mass parts is still more preferable. If the content of the polymerizable initiator is within this range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable liquid crystal compound.

When the said composition for polarizing layer formation contains a photoinitiator, you may contain the photosensitizer in this composition for polarizing layer formation. As this photosensitizer, For example, xanthone compounds, such as xanthone and thioxanthone (For example, 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, etc.); anthracene compounds such as anthracene and alkoxy group-containing anthracene (eg, dibutoxyanthracene); phenothiazine, rubrene, and the like.

When the composition for polarizing layer formation contains a photoinitiator and a photosensitizer, the polymerization reaction of the polymeric liquid crystal compound contained in this composition for polarizing layer formation can be accelerated|stimulated more. Although the usage-amount of such a photosensitizer can be suitably adjusted according to the kind and amount of the photoinitiator and polymeric liquid crystal compound used together, For example, 0.1-30 mass parts is preferable with respect to a total of 100 mass parts of polymerizable liquid crystal compounds. and 0.5-10 mass parts is more preferable, and 0.5-8 mass parts is still more preferable.

Although it has been described that the polymerization reaction of the polymerizable liquid crystal compound can be accelerated by containing a photosensitizer in the composition for forming a polarizing layer, a polymerization inhibitor is included in the composition for forming a polarizing layer in order to stably advance this polymerization reaction. may be appropriately incorporated. By containing a polymerization inhibitor, the advancing degree of the polymerization reaction of a polymeric liquid crystal compound is controllable.

Examples of the polymerization inhibitor include hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butylcatechol, etc.), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical, and the like. of radical supplements; thiophenols; and β-naphthylamines and β-naphthols.

In the case where the composition for forming a polarizing layer contains a polymerization inhibitor, the content thereof can be appropriately adjusted according to the type and amount of the polymerizable liquid crystal compound to be used, the amount of the photosensitizer used, and the like. For example, 0.1-30 mass parts is preferable, as for content of the polymerization inhibitor with respect to a total of 100 mass parts of a polymeric liquid crystal compound, 0.5-10 mass parts is more preferable, 0.5-8 mass parts is still more preferable. If the content of the polymerization inhibitor is within this range, the polymerizable liquid crystal compound or the polymerizable liquid crystal compound or the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable liquid crystal compound or the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer. The liquid crystal composition can be polymerized while maintaining a good liquid crystal state of the higher-order smectic phase.

The above-described composition for forming a polarizing layer is applied on an alignment layer of a laminate having a transparent substrate and an alignment layer to obtain a first coating film, and the polymerizable liquid crystal compound contained in the first coating film is not polymerized under the condition that A 1st dry film is formed by drying.

As a method (application method) of applying the composition for forming a polarizing layer to the laminate, for example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, a die coating method, a dip coating method, a bar coating method and a spin coating method. In addition, these application|coating methods are applicable also when apply|coating the composition for orientation layer formation on a transparent base material. In addition, application|coating conditions are set so that the thickness of the polarizing layer obtained may become the above-mentioned preferable range.

Then, by drying the said 1st coating film, a solvent is removed from this 1st coating film, and a 1st dry film is formed. At the time of removal of a solvent, volatile components other than the solvent contained in this 1st coating film are also removed together. As the removal method of the solvent, a drying means (drying method) is usually used, and it can perform the natural drying method, the ventilation drying method, the reduced pressure drying method, or combining these. In addition, although any drying method may be used, it is preferable to set drying conditions so that the polymeric liquid crystal compound contained in this 1st coating film may not superpose|polymerize.

<Process (3)>

In step (3), the polarizing layer is formed from the first dry film by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the polymerizable liquid crystal composition contained in the first dry film in a smectic liquid crystal state. to form

<Formation of Polarizing Layer>

In order to make the liquid crystal state of the polymerizable liquid crystal compound contained in the first dry film into a smectic phase (hereinafter referred to as “smectic phase” or “liquid crystal state of smectic phase” in some cases), the first dry film What is necessary is just to heat to an appropriate temperature, in other words, what is necessary is just to heat what consists of a laminated board which has the said 1st dry film to the appropriate temperature calculated|required from the phase transition temperature. Further, in forming the smectic phase, once the liquid crystal state of the polymerizable liquid crystal compound contained in the first dry film is set to a nematic phase (nematic liquid crystal state), the nematic phase is transferred to the smectic phase It is preferable to do In order to form the smectic phase via the nematic phase as described above, for example, the polymerizable liquid crystal compound contained in the first dry film is heated to a temperature higher than the phase transition to the liquid crystal state of the nematic phase, and then the polymerizable liquid crystal compound is The method of cooling to the temperature which shows the liquid-crystal state of a smectic phase is employ|adopted.

In forming the liquid crystal state of a smectic phase via a nematic phase, if the said polarizing layer formation composition contains the above-mentioned leveling agent, it is especially preferable. When the liquid crystal state is formed, if the first dry film contains a leveling agent, the leveling agent tends to flow in the first dry film, so that the polymerizable liquid crystal compound or the polymerizable liquid crystal composition is easily horizontally aligned. have. The temperature for forming the nematic phase and the smectic phase is preferably in the range of not less than the nematic phase transition point and not more than 100° C. higher than the nematic phase transition point, and not less than the nematic phase transition point and 50° C. above the nematic phase transition point. The range below high temperature is more preferable. The heat treatment for orienting a desired liquid crystal phase and the drying treatment of the solvent mentioned above can also be performed simultaneously.

When polymerizing the polymerizable liquid crystal compound, also in order to maintain a good liquid crystal state of the smectic phase, as the polymerizable liquid crystal compound, a polymerizable liquid crystal mixture comprising two or more polymerizable liquid crystal compounds (more preferably, two types) It is preferable to use the composition for forming a polarizing layer comprising the above polymerizable liquid crystal compound (a polymerizable liquid crystal mixture). When the composition for forming a polarizing layer in which the content ratio of each polymerizable liquid crystal compound in the polymerizable liquid crystal composition is adjusted is used, the liquid crystal state of the smectic phase is formed via the nematic phase, and then a supercooled state is temporarily formed. It is possible, and there is an advantage that it is easy to maintain the liquid-crystal state of a high-order smectic phase easily.

Here, after the composition for forming a polarizing layer contains a photopolymerization initiator and the liquid crystal state of the polymerizable liquid crystal compound in the first dry film is made into a smectic phase, the polymerizable liquid crystal is maintained while the liquid crystal state of the smectic phase is maintained. A method of photopolymerizing the compound will be described in detail. In the photopolymerization, as light rays irradiated to the first dry film, the type of the photoinitiator or the polymerizable liquid crystal compound contained in the first dry film (in particular, the type of photopolymerizable group contained in the polymerizable liquid crystal compound) and Depending on the amount, the light selected from the group consisting of visible light, ultraviolet light and laser light or an active electron beam can be used as appropriate. Among these, ultraviolet light is preferable from the point of being easy to control advancing of a polymerization reaction, and the point that what is widely used in the art as an apparatus accompanying photopolymerization can be used. Therefore, it is preferable to select the kind of a polymerizable liquid crystal compound and a photoinitiator contained in the said composition for polarizing layer formation so that it can photopolymerize by ultraviolet light. In addition, when superposing|polymerizing, superposition|polymerization temperature can also be controlled by cooling a 1st dry film by an appropriate cooling means together with ultraviolet light irradiation. If the polymerization of the polymerizable liquid crystal compound can be carried out at a lower temperature by employing such a cooling means, there is also an advantage that a polarizing layer can be appropriately formed even if the above-described transparent substrate or alignment layer having relatively low heat resistance is used. have. Moreover, at the time of photopolymerization, a patterned polarizing layer can also be obtained by masking or developing.

By performing the photopolymerization as described above, the polymerizable liquid crystal compound is polymerized while maintaining the smectic phase, preferably the liquid crystal state of the higher smectic phase as previously exemplified, and a polarizing layer is formed. A polarizing layer obtained by polymerization of a polymerizable liquid crystal compound or polymerizable liquid crystal composition while maintaining a smectic liquid crystal state is a conventional polarizing layer, that is, a polymerizable liquid crystal compound or the like while maintaining a nematic liquid crystal state. Compared with the polarizing layer obtained by superposing|polymerizing, there exists an advantage that polarization|polarized-light performance is much higher.

Moreover, the polarizing layer formed in this way is especially preferable if a black peak is obtained in X-ray-diffraction measurement. As a polarizing layer from which such a black peak is obtained, the polarizing layer which shows the diffraction peak derived from a hexatic phase or a crystal phase is mentioned, for example. In addition, the measurement conditions for such X-ray diffraction measurement include, for example, the conditions described in the Examples of the present application.

<Process (4)>

In the process (4), it is a process of forming a protective layer on the polarizing layer of the laminated board in which the orientation layer and the polarizing layer were provided in this order on the transparent base material obtained in the process (3). When the polarizing layer in the present polarizer is, for example, a polarizing layer formed by polymerizing a polymerizable liquid crystal compound in a liquid crystal state of a higher smectic phase, such as smectic B phase, this polarizing layer is significantly more sensitive to the external environment. It may be altered by factors. By forming the protective layer on the polarizing layer, it is possible to very effectively prevent the deterioration of the polarizing layer.

As step (4),

On the polarizing layer formed in the step (3), the composition 1 for forming a protective layer containing a polyfunctional acrylate and a solvent is applied to form a second coating film on the polarizing layer, and the second coating film is Step (4-1) of forming a protective layer from the second coating film by polymerizing the contained polyfunctional acrylate;

On the polarizing layer formed in the step (3), the composition 2 for forming a protective layer containing a polymer or oligomer obtained by polymerization of a polyfunctional acrylate and water is applied to form a second coating film on the polarizing layer, , step (4-2) of forming a protective layer from this second coating film by drying the second coating film, and

By coating the composition 3 for forming a protective layer containing a water-soluble polymer and water on the polarizing layer formed in the step (3), forming a second coating film on the polarizing layer, and drying the second coating film, Step of forming a protective layer from this second coating film (4-3)

and the like.

On the polarizing layer formed in the step (3), the composition 1 for forming a protective layer containing a polyfunctional acrylate and a solvent is applied to form a second coating film on the polarizing layer, and the second coating film is The method of forming a protective layer from the said 2nd coating film by polymerizing the said polyfunctional acrylate contained is demonstrated. This method of forming a protective layer from the composition 1 for forming a protective layer also has an advantage that the operation is very simple.

<Composition 1 for forming a protective layer>

The composition 1 for forming a protective layer contains a polyfunctional acrylate and a solvent. The polyfunctional acrylate contained in the composition 1 for forming a protective layer is selected from the group consisting of an acrylate group (CH ₂ =CH-CO-) and a methacrylate group (CH ₂ =C(CH ₃ )-CO-). It means a compound which has two or more selected groups in a molecule|numerator and does not have liquid crystallinity like the said compound (1). Preferred polyfunctional acrylates are compounds having 2 to 6 groups in the molecule selected from the group consisting of acrylate groups and methacrylate groups. In addition, polyfunctional acrylates having two such groups are hereinafter referred to as "bifunctional acrylates" and the like depending on the number of these groups, and polyfunctional acrylates having three or more of these groups are referred to as "trifunctional or more polyfunctional acrylates". Functional acrylate" and the like.

In addition, the polyfunctional acrylate contained in the composition 1 for forming a protective layer exhibits a degree of transparency such that the protective layer can transmit light, particularly visible light, when the polyfunctional acrylate is cured to form a protective layer. It is chosen to have In addition, "transparency to the extent that visible light can permeate" here is the same meaning as having demonstrated the transparency of the said transparent base material.

Here, preferred polyfunctional acrylates are exemplified.

Examples of the bifunctional acrylate having two groups in the molecule selected from the group consisting of an acrylate group and a methacrylate group include 1,3-butanediol di(meth)acrylate; 1,3-butanediol (meth)acrylate; 1,6-hexanediol di(meth)acrylate; ethylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate; neopentyl glycol di (meth) acrylate; triethylene glycol di (meth) acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol diacrylate; bis(acryloyloxyethyl)ether of bisphenol A; ethoxylated bisphenol A di(meth)acrylate; propoxylated neopentyl glycol di(meth)acrylate; and ethoxylated neopentyl glycol di(meth)acrylate and 3-methylpentanediol di(meth)acrylate.

As a trifunctional or more hexafunctional polyfunctional acrylate having 3 to 6 groups selected from the group consisting of an acrylate group and a methacrylate group in a molecule,

trimethylolpropane tri(meth)acrylate; pentaerythritol tri (meth) acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; ethoxylated trimethylolpropane tri(meth)acrylate; propoxylated trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate; tripentaerythritol tetra(meth)acrylate; tripentaerythritol penta (meth) acrylate; tripentaerythritol hexa (meth) acrylate; tripentaerythritol hepta (meth) acrylate; tripentaerythritol octa (meth) acrylate;

a reaction product of pentaerythritol tri(meth)acrylate and an acid anhydride; a reaction product of dipentaerythritol penta (meth)acrylate and an acid anhydride;

a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride;

caprolactone-modified trimethylolpropane tri(meth)acrylate; caprolactone-modified pentaerythritol tri(meth)acrylate; caprolactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; caprolactone-modified pentaerythritol tetra(meth)acrylate; caprolactone-modified dipentaerythritol penta (meth) acrylate; caprolactone-modified dipentaerythritol hexa(meth)acrylate; caprolactone-modified tripentaerythritol tetra(meth)acrylate; caprolactone-modified tripentaerythritol penta (meth) acrylate; caprolactone-modified tripentaerythritol hexa(meth)acrylate; caprolactone-modified tripentaerythritol hepta (meth) acrylate; caprolactone-modified tripentaerythritol octa (meth) acrylate; reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride; A reaction product of caprolactone-modified dipentaerythritol penta(meth)acrylate and an acid anhydride, caprolactone-modified tripentaerythritol hepta(meth)acrylate, an acid anhydride, etc. are mentioned. In addition, in the specific example of the polyfunctional acrylate shown here, (meth)acrylate means an acrylate or a methacrylate. Note that caprolactone-modified caprolactone means that a ring-opened product or a ring-opened polymer of caprolactone is introduced between the alcohol-derived moiety and (meth)acryloyloxy group of the (meth)acrylate compound.

In order to obtain a protective layer with a large surface hardness, it is preferable to use a polyfunctional acrylate more than trifunctional among the specific examples of the polyfunctional acrylate, and it is particularly preferable to use a hexafunctional acrylate. In addition, the composition 1 for forming a protective layer may contain one type of polyfunctional acrylate or may contain a plurality of types of polyfunctional acrylates.

In addition, from the viewpoint of the printability of the composition 1 for forming a protective layer and the adhesiveness of the obtained protective layer, the composition 1 for forming a protective layer may contain a binder resin.

As this binder resin, the copolymer etc. of 1 or more types of monomer chosen from the group which consists of an unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and this monomer and another monomer copolymerizable are illustrated.

Specific examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Unsaturated mono[(meth)acryloyloxyalkyl of divalent or higher polyhydric carboxylic acid, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] ]esters; and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid. The unsaturated carboxylic acid anhydride refers to the anhydride of the unsaturated carboxylic acid shown here. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable as said monomer for binder resin manufacture. These acrylic acid, methacrylic acid and maleic anhydride have good polymerization reactivity when copolymerized with various other monomers, have high glass transition temperature (Tg) and mechanical properties of the resulting binder resin, and are preferably used because of no tackiness. . In addition, when manufacturing binder resin, single type may be used for the monomer chosen from the group which consists of an unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and multiple types may be used for it.

As another monomer copolymerizable with a monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides,

(meth)acrylic acid alkylesters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate and tert-butyl (meth)acrylate;

Cyclohexyl(meth)acrylate, 2-methylcyclohexyl(meth)acrylate, tricyclo[5.2.1.02,6]decan-8-yl(meth)acrylate (as a common name in the art, dicyclopentanyl (meth)acrylic acid cyclic alkylesters such as (meth)acrylate), dicyclopentanyloxyethyl (meth)acrylate, and isoboronyl (meth)acrylate;

Cyclohexylacrylate, 2-methylcyclohexylacrylate, tricyclo[5.2.1.02,6]decan-8-ylacrylate (commonly known in the art as dicyclopentanylacrylate), dicyclopentaoxy acrylic acid cyclic alkyl esters such as ethyl acrylate and isoboronyl acrylate;

(meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate;

*Dicarboxylic acid diesters, such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Bicyclo[2.2.1]hepto-2-ene, 5-methylbicyclo[2.2.1]hepto-2-ene, 5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxybi Cyclo[2.2.1]hepto-2-ene, 5-carboxybicyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5-(2 '-Hydroxyethyl)bicyclo[2.2.1]hepto-2-ene, 5-methoxybicyclo[2.2.1]hepto-2-ene, 5-ethoxybicyclo[2.2.1]hepto-2-ene , 5,6-dihydroxybicyclo[2.2.1]hepto-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene, 5,6-di(hydroxymethyl) Bicyclo[2.2.1]hepto-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2-ene, 5,6-dimethoxybicyclo[2.2. 1]hepto-2-ene, 5,6-diethoxybicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5- Hydroxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-ethylbicyclo[2.2 .1]hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hepto-2-ene , 5-Carboxy-6-ethylbicyclo[2.2.1]hepto-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride (hymic acid anhydride), 5-tert- Butoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hepto -2-ene, 5,6-di(tert-butoxycarbonyl)bicyclo[2.2.1]hepto-2-ene and 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1 ] Bicyclo unsaturated compounds such as hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutylate, N-succinimidyl dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene; and the like.

Examples of the solvent contained in the composition 1 for forming a protective layer include those exemplified as the solvent contained in the composition for forming a polarizing layer. Among these, the solvent contained in the composition 1 for forming a protective layer preferably contains a solvent selected from the group consisting of an alcohol solvent and an ether solvent, and more preferably a solvent substantially composed of an alcohol solvent and/or an ether solvent. . Here, "a solvent consisting substantially of an alcohol solvent and/or an ether solvent" means that it contains almost no solvent other than the alcohol solvent, contains almost no solvent other than the ether solvent, and the alcohol solvent and the ether It is one of the things which hardly contain solvents other than a solvent. However, the solvent substantially composed of an alcohol solvent and/or an ether solvent may contain unexpectedly contained moisture or the like, as long as it is in a trace amount sufficient to form a protective layer. As described above, the alcohol solvent includes methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether. Examples of the ether solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Among these, as the solvent contained in the composition for forming a polarizing layer, ethanol, isopropyl alcohol, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, and a plurality of types of mixed solvents selected from these are more preferable.

When the solvent contained in the composition 1 for forming a protective layer is substantially composed of an alcohol solvent and/or an ether solvent, when the composition 1 for forming a protective layer is applied on the polarizing layer, the alignment state of the polarizing layer is The protective layer can be formed while maintaining this orientation state so as not to be significantly damaged. In this regard, if the solvent contained in the composition 1 for forming a protective layer is substantially composed of an alcohol solvent and/or an ether solvent, the present polarizer can be produced stably. Moreover, the method of forming a protective layer using the composition 1 for protective layer formation in this way is advantageous also from the point that the operation is simple. The content of the solvent contained in the composition 1 for forming a protective layer may be determined in consideration of the applicability when the composition 1 for forming a protective layer is applied on the polarizing layer. It is preferable that content of a solvent is 10-80 mass parts with respect to 100 mass parts of total amounts, and it is more preferable in it being 20-60 mass parts.

When forming a protective layer from the composition 1 for protective layer formation, it is necessary to polymerize and harden the polyfunctional acrylate contained in this composition 1 for protective layer formation. Also in the polymerization of this polyfunctional acrylate, the photopolymerization as described in the polymerization of the polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is preferable. The photopolymerization of the polyfunctional acrylate can be performed by irradiating visible light or ultraviolet rays to the second dry film formed on the polarizing layer by the composition 1 for forming a protective layer. In addition, in order to efficiently photopolymerize the polyfunctional acrylate, it is preferable that the composition 1 for forming a protective layer contains a photopolymerization initiator. As this photoinitiator, the thing similar to what was illustrated as a photoinitiator contained in the said composition for polarizing layer formation is illustrated.

Hereinafter, the operation of forming the protective layer will be briefly described.

In order to form the protective layer, first, the composition 1 for forming the protective layer is applied on the polarizing layer to form a second coating film. The coating method of the composition 1 for forming a protective layer is, for example, the same as that described as a method of applying the composition for forming a polarizing layer.

Next, a solvent (preferably an alcohol solvent and/or an ether solvent) is removed from the second coating film obtained by applying on the polarizing layer to obtain a second dry film. The same method as illustrated as a drying method of forming the said 1st dry film from the said 1st coating film is employable for this drying degree as well. In the process of drying the second dry film, it is necessary to prevent mixing of an unpolymerized polymerizable liquid crystal compound from the polarizing layer into the second dry film during drying. As temperature conditions for this, the range of about 0 degreeC - about 60 degreeC is preferable, and the range of about 20 degreeC - about 50 degreeC is more preferable. When the solvent contained in the composition 1 for forming a protective layer is the solvent described as more preferable, the second coating film can be dried according to such suitable temperature conditions. In addition, in order to dry in such a temperature range, depending on the kind of solvent contained in the said composition 1 for protective layer formation, you may hold|maintain the 2nd coating film under appropriate reduced-pressure conditions.

The present inventors have found that when the composition 1 for forming a protective layer substantially comprising an alcohol solvent and/or an ether solvent as a solvent is applied on the polarizing layer, the properties of the polarizing layer are not impaired. Therefore, when the protective layer is formed on the polarizing layer using the composition 1 for forming a protective layer, the deterioration of the polarizing layer of the present polarizer over time can be well prevented by the protective layer, and the protective layer It can be prevented favorably from impairing the property of a polarizing layer at the time of formation. Such an effect cannot be immediately discovered by manufacture of the conventional polarizer, It is based on the original knowledge of this inventor.

On the polarizing layer formed in the step (3), the composition 2 for forming a protective layer containing a polymer or oligomer obtained by polymerization of a polyfunctional acrylate and water is applied to form a second coating film on the polarizing layer, By drying this 2nd coating film, the method of forming a protective layer from this 2nd coating film is demonstrated. This method of forming a protective layer from the composition 2 for forming a protective layer also has an advantage that the operation is very simple.

<Composition 2 for forming a protective layer>

The composition 2 for forming a protective layer contains a polymer or oligomer obtained by polymerizing a polyfunctional acrylate, and water. As a polymer or oligomer obtained by polymerizing a polyfunctional acrylate, an aliphatic urethane acrylate etc. are mentioned, for example.

The content of water contained in the composition 2 for forming a protective layer may be determined in consideration of applicability when the composition 2 for forming a protective layer is applied on a polarizing layer, for example, the total amount of the composition 2 for forming a protective layer is 100 mass It is preferable in it being 50-99 mass parts with respect to content of water, and it is still more preferable in it being 60-95 mass parts.

Hereinafter, the operation of forming the protective layer will be briefly described.

In order to form a protective layer, first, the composition 2 for forming a protective layer is applied on the polarizing layer to form a second coating film. The coating method of the composition 2 for forming a protective layer is the same as described as a method of applying the composition for forming a polarizing layer, for example.

Next, water is removed from the second coating film to obtain a protective layer. The same method as what was illustrated as a drying method of the said 1st coating film can be employ|adopted for such drying. As temperature conditions, the range of about 0 degreeC - about 100 degreeC is preferable, and the range of about 20 degreeC - about 80 degreeC is more preferable.

By coating the composition 3 for forming a protective layer containing a water-soluble polymer and water on the polarizing layer formed in the step (3), forming a second coating film on the polarizing layer, and drying the second coating film, The method of forming a protective layer from this 2nd coating film is demonstrated. The method of forming a protective layer from such a composition for protective layer formation also has the advantage that the operation is very simple.

<Composition 3 for forming a protective layer>

The composition 3 for forming a protective layer contains a water-soluble polymer and water. Examples of the water-soluble polymer include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, etc., and preferably polyvinyl alcohol. have.

The content of water contained in the composition 3 for forming a protective layer may be determined in consideration of the applicability when the composition 3 for forming a protective layer is applied on a polarizing layer. For example, the total amount of the composition 3 for forming a protective layer 3 is 100 mass It is preferable in it being 50-99 mass parts with respect to content of water, and it is still more preferable in it being 60-95 mass parts.

Hereinafter, the operation of forming the protective layer will be briefly described.

In order to form the protective layer, first, the composition 3 for forming a protective layer is applied on the polarizing layer to form a second coating film. The coating method of this composition 3 for forming a protective layer is the same as described as a method of applying the composition for forming a polarizing layer, for example.

Next, water is removed from the second coating film to obtain a protective layer. The same method as what was illustrated as a drying method of the said 1st coating film can be employ|adopted for such drying. As temperature conditions, the range of about 0 degreeC - about 100 degreeC is preferable, and the range of about 20 degreeC - about 80 degreeC is more preferable.

The thickness of the protective layer can be appropriately adjusted depending on the type of the polarizing layer protected by the protective layer. As for the measurement of such a thickness, the thing similar to what was demonstrated as a measuring method of the said polarizing layer thickness is employ|adopted.

<This polarizer>

By providing a protective layer, this polarizer obtained by the manufacturing method including process (1) - process (4) is excellent not only in the abrasion resistance and solvent resistance of the surface of a polarizing layer, but also the heat resistance and heat-and-moisture resistance of this polarizer itself. It is advantageous over the conventional polarizer from the point of being excellent. Moreover, in embodiment of the manufacturing method of this polarizer including process (1) - process (4), the said 1st dry film of process (3) is this 1st dry film under the temperature condition of 25±10 degreeC. Various modifications are possible within the range in which the polymerizable liquid crystal compound or the polymerizable liquid crystal composition contained in the polymerizable liquid crystal composition is polymerized while maintaining the smectic liquid crystal state. For example, when forming or preparing a laminate of the transparent substrate and the orientation layer in the step (1), the transparent substrate itself having orientation characteristics may be used, and a retardation film is further laminated in addition to the orientation layer, and the transparent substrate It can also be set as the structure provided on it in order of an orientation layer, a polarizing layer, retardation layer, and a protective layer. In addition, in the protective layer formed in the step (4), a bead-shaped resin having a different refractive index from a UV absorber, an antistatic agent, or a component of the protective layer may be mixed. However, since it is advantageous if the composition for forming a protective layer used in the formation of the protective layer is substantially composed of an alcohol solvent and/or an ether solvent as a solvent, or water, a composition for forming a protective layer made of such a solvent is used in the process It is preferable that (4) can be implemented.

As mentioned above, although this polarizer was demonstrated centering around the case of the form of the laminated body of a transparent base material / orientation layer / polarizing layer / protective layer, layers other than these may be laminated|stacked on this polarizer. As already explained, this polarizer may be further equipped with retardation film, and may further be equipped with the antireflection layer or the brightness improving film. Moreover, it can also be combined with a quarter wave plate and it can also be set as a circularly polarizing plate. It is preferable that the quarter-wave plate used when manufacturing a circularly polarizing plate has the characteristic that the in-plane retardation value with respect to visible light becomes small as a wavelength becomes short.

<Use of this polarizer>

This polarizer can be used for various display devices. A display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. As the display device, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (such as a field emission display device (FED), a surface field emission display device) device (SED)], electronic paper (display device using electronic ink or an electrophoretic element, plasma display device, projection display device (eg, a grating light valve (GLV) display device, a display device having a digital micromirror device (DMD)) and piezoelectric ceramic displays, etc. The liquid crystal display includes all of a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct view liquid crystal display, and a projection liquid crystal display. The display device may be a display device that displays a two-dimensional image or a stereoscopic display device that displays a three-dimensional image.

The present polarizer can be particularly effectively used for a display device of an organic electroluminescence (EL) display device or an inorganic electroluminescence (EL) display device.

1 is a schematic diagram schematically showing the simplest cross-sectional configuration of the present polarizer. An alignment layer 3, a polarizing layer 4, and a protective layer 7 are laminated in this order from the transparent substrate 2, and the polarizing layer 4 is in a matrix 5 in which a polymerizable liquid crystal compound is polymerized. The dichroic dye 6 is dispersed.

2 and 5 are schematic diagrams schematically showing the cross-sectional configuration of a liquid crystal display device (hereinafter, sometimes referred to as “the present liquid crystal display device”) 10 using the present polarizer. The liquid crystal layer 17 is sandwiched between the two substrates 14a and 14b.

4 and 7 are schematic diagrams schematically showing the cross-sectional configuration of an EL display device using the present polarizer (hereinafter referred to as "the present EL display device" in some cases).

8 is a schematic diagram schematically showing the configuration of a projection type liquid crystal display device using the present polarizer.

First, the present liquid crystal display device shown in FIG. 2 will be described.

The present polarizer is preferably disposed on the light incident side with respect to the liquid crystal layer. A color filter 15 is disposed on the liquid crystal layer 17 side of the substrate 14a. The color filter 15 is arranged at a position opposite to the pixel electrode 22 with the liquid crystal layer 17 interposed therebetween, and the black matrix 20 is arranged at a position facing the boundary between the pixel electrodes. The transparent electrode 16 is disposed on the liquid crystal layer 17 side so as to cover the color filter 15 and the black matrix 20 . Further, an overcoat layer (not shown) may be provided between the color filter 15 and the transparent electrode 16 .

On the liquid crystal layer 17 side of the substrate 14b, the thin film transistor 21 and the pixel electrode 22 are regularly arranged. The pixel electrode 22 is disposed at a position opposite to the color filter 15 with the liquid crystal layer 17 interposed therebetween. An interlayer insulating film 18 having a connection hole (not shown) is disposed between the thin film transistor 21 and the pixel electrode 22 .

As the substrate 14a and the substrate 14b, a glass substrate and a plastic substrate are used. As for such a glass substrate and a plastic substrate, the thing of the same material as what was illustrated as a transparent base material of this polarizer can be employ|adopted. When manufacturing the color filter 15 and the thin film transistor 21 formed on a board|substrate, when the process of heating to high temperature is required, a glass substrate or a quartz board|substrate is preferable.

As for the thin film transistor, an optimal one can be employ|adopted according to the material of the board|substrate 14b. Examples of the thin film transistor 21 include a high-temperature polysilicon transistor formed on a quartz substrate, a low-temperature polysilicon transistor formed on a glass substrate, and an amorphous silicon transistor formed on a glass substrate or a plastic substrate. In order to further reduce the size of the present liquid crystal display device, a driver IC may be formed on the substrate 14b.

A liquid crystal layer 17 is disposed between the transparent electrode 16 and the pixel electrode 22 . A spacer 23 is disposed in the liquid crystal layer 17 to keep the distance between the substrate 14a and the substrate 14b constant. In addition, although shown as a columnar spacer in FIG. 2, this spacer is not limited to columnar shape, As long as the distance between the board|substrate 14a and the board|substrate 14b can be kept constant, the shape is arbitrary.

Among the layers formed on the substrate 14a and the substrate 14b, an alignment layer for aligning the liquid crystal in a desired direction may be disposed on the surface in contact with the liquid crystal layer 17, respectively. In addition, the present polarizer may be arranged inside the liquid crystal cell, that is, the present polarizer may be arranged on the side in contact with the liquid crystal layer 17 . This format is hereinafter referred to as an "in-cell format". Details of this in-cell format will be described later.

Each member includes a substrate 14a, a color filter 15 and a black matrix 20 , a transparent electrode 16 , a liquid crystal layer 17 , a pixel electrode 22 , an interlayer insulating film 18 , and a thin film transistor 21 . and the substrate 14b.

* Among the substrates 14a and 14b with the liquid crystal layer 17 interposed therebetween, a polarizer 12a and a polarizer 12b are provided outside the substrate 14b, and at least one of these polarizers (1) is.

Moreover, it is preferable that retardation layers (for example, a quarter wave plate or an optical compensation film) 13a, 13b are laminated|stacked. By disposing the polarizer 12b among the two polarizers, the function of converting incident light into linearly polarized light can be provided to the liquid crystal display device 10 . In addition, the retardation layer 13a and the retardation layer 13b may not be arrange|positioned depending on the structure of a liquid crystal display device, or the kind of liquid crystal compound contained in the liquid crystal layer 17, and this polarizer 1 A polarizing film may be further provided on the light emission side (outside).

It is preferable if the antireflection film 11 for preventing the reflection of external light is arrange|positioned on the outer side of this polarizer 1 (in the case where the polarizing film is further provided in this polarizer 1).

As described above, the present polarizer 1 can be used for the polarizer 12a or the polarizer 12b of the liquid crystal display device 10 of FIG. 2 . By providing this polarizer 1 to the polarizer 12a and/or the polarizer 12b, there exists an effect that thickness reduction of this liquid crystal display device 10 can be achieved.

When this polarizer 1 is used for the polarizer 12a or the polarizer 12b, the lamination|stacking order is not specifically limited. This will be described with reference to enlarged views of portions A and B surrounded by dotted lines in FIG. 2 .

3 is an enlarged schematic cross-sectional view of a portion A of FIG. 2 . 3A1 shows, when the present polarizer 1 is used as the polarizer 12a, the protective layer 7, the polarizing layer 4, the alignment layer 3 and the transparent substrate from the retardation layer 13a side ( It shows that this polarizer 1 is provided so that 2) may be arrange|positioned in this order. In addition, in FIG. 3(A2), from the retardation layer 13a side, the transparent base material 2, the orientation layer 3, the polarizing layer 4, and the protective layer 7 are arrange|positioned in this order, this polarizer It indicates that (1) is installed.

4 is an enlarged schematic view of a portion B of FIG. 2 . 4(B2) shows a protective layer 7, a polarizing layer 4, an orientation layer 3, and a transparent base material 2 from the retardation film 13b side when this polarizer is used as the polarizer 12b. The present polarizer 1 is installed so that is arranged in this order.

A backlight unit 19 serving as a light emitting source is disposed outside the polarizer 12b. The backlight unit 19 includes a light source, a light guide, a reflection plate, a diffusion sheet, and a viewing angle adjustment sheet. Examples of the light source include electroluminescence, a cold cathode tube, a hot cathode tube, a light emitting diode (LED), a laser light source, and a mercury lamp. In addition, the type of the present polarizer can be selected according to the characteristics of the light source.

When the present liquid crystal display device 10 is a transmissive liquid crystal display device, the white light generated from the light source in the backlight unit 19 is incident on the light guide, and the path is changed by the reflecting plate and is diffused in the diffusion sheet. The diffused light enters the polarizer 12b from the backlight unit 19 after being adjusted to have a desired directivity by the viewing angle adjustment sheet.

Of the non-polarized incident light, only one linearly polarized light passes through the polarizer 12b of the liquid crystal panel. The linearly polarized light is converted into circularly polarized light or elliptically polarized light by the retardation layer 13b, and passes through the substrate 14b, the pixel electrode 22, and the like in sequence to reach the liquid crystal layer 17.

Here, the alignment state of liquid crystal molecules included in the liquid crystal layer 17 is changed depending on the presence or absence of a potential difference between the pixel electrode 22 and the opposing transparent electrode 16 , so that the luminance of the light emitted from the liquid crystal display device 10 is increased. Controlled. When the liquid crystal layer 17 is in an alignment state that transmits polarized light as it is, the polarized light passes through the liquid crystal layer 17 and the transparent electrode 16 , and light in a specific wavelength range passes through the color filter 15 , When it reaches the polarizer 12a and passes through the antireflection film 11 further, the liquid crystal display device displays the color determined by the color filter the brightest.

Conversely, when the liquid crystal layer 17 is in an alignment state that converts and transmits polarized light, the light transmitted through the liquid crystal layer 17 , the transparent electrode 16 , and the color filter 15 is absorbed by the polarizer 12a. Thereby, this pixel displays black. In the intermediate alignment state between these two states, since the luminance of the light emitted from the liquid crystal display device 10 is also intermediate between the above-mentioned two, this pixel displays an intermediate color.

When this liquid crystal display device 10 is a transflective liquid crystal display device, it is preferable to use what further laminated|stacked the 1/4 wave plate on the protective layer side of this polarizer. At this time, the pixel electrode 22 has a transmissive part made of a transparent material and a reflective part made of a material that reflects light, and an image is displayed on the transmissive part in the same manner as in the above-described transmissive liquid crystal display device. On the other hand, in the reflection unit, external light is incident on the liquid crystal display device from the direction of the antireflection film 11, and circularly polarized light transmitted through the present polarizer by the action of a quarter-wave plate further provided in the main polarizer is converted into the liquid crystal layer 17. It passes through and is reflected by the pixel electrode 22 and used for display.

Next, an in-cell type suitable liquid crystal display device (this liquid crystal display device 24 ) using the present polarizer 1 will be described with reference to FIG. 5 .

In the present liquid crystal display device 24 , an antireflection film 11 , a substrate 14a , a polarizer 12a , a retardation layer 13a , a color filter 15 and a black matrix 20 , a transparent electrode 16 , a liquid crystal The layer 17, the pixel electrode 22, the interlayer insulating film 18 and the thin film transistor 21, the retardation layer 13b, the polarizer 12b, the substrate 14b and the backlight unit 19 are stacked in this order, In this configuration, the present polarizer 1 is preferably used as the polarizer 12a. In this structure, this polarizer 1 is arrange|positioned in this order of the transparent base material 2, the orientation layer 3, the polarizing layer 4, and the protective layer 7 from the antireflection film 11 side. In this liquid crystal display device 24 provided with the present polarizer with such a configuration, a function of converting incident light into linearly polarized light is provided. In addition, similarly to the present liquid crystal display device 10 , the retardation layer 13a and the retardation layer 13b may not be disposed depending on the type of the liquid crystal compound contained in the liquid crystal layer 17 .

Next, the present EL display device using the present polarizer will be described with reference to Figs.

In the EL display device 30 , an organic functional layer 36 serving as a light emitting source and a cathode electrode 37 are laminated on a substrate 33 on which a pixel electrode 35 is formed. On the opposite side to the organic functional layer 36 with the substrate 33 interposed therebetween, the retardation plate 32 and the polarizing plate 31 are arranged, and the present polarizer 1 is used as the polarizing plate 31 . By applying a positive voltage to the pixel electrode 35 and a negative voltage to the cathode electrode 37 to apply a direct current between the pixel electrode 35 and the cathode electrode 37 , the organic functional layer 36 emits light. The organic functional layer 36, which is a light emitting source, includes an electron transport layer, a light emitting layer, a hole transport layer, and the like. Light emitted from the organic functional layer 36 passes through the pixel electrode 35 , the interlayer insulating film 34 , the substrate 33 , the retardation plate 32 , and the polarizer 31 (this polarizer 1 ). Although the organic electroluminescent display which has the organic functional layer 36 is demonstrated, you may apply also to the inorganic electroluminescent display which has an inorganic functional layer.

In manufacturing the present EL display device 30 , first, a thin film transistor 40 is formed in a desired shape on a substrate 33 . Then, an interlayer insulating film 34 is formed, and then the pixel electrode 35 is formed and patterned by sputtering. Thereafter, an organic functional layer 36 is laminated.

Then, the polarizer 31 (this polarizer 1) is provided on the surface opposite to the surface on which the thin film transistor 40 is provided of the board|substrate 33. As shown in FIG. It is preferable to provide the retardation layer 32 between the polarizer 31 and the substrate 33, and it is more preferable if the retardation layer 32 is made of a quarter wave plate. In order to provide the retardation layer 32, a laminate 45 in which the polarizer 31 (the present polarizer 1) and the retardation layer 32 are laminated is prepared in advance, and the laminate 45 is applied to the substrate 33 ) to be joined. The outline|summary of the manufacturing method using this laminated body 45 is shown in FIG.

When this polarizer 1 is used for the polarizer 31, the lamination|stacking order is not specifically limited. This will be described with reference to an enlarged view of a portion C surrounded by a dotted line in FIG. 4 .

6 is an enlarged cross-sectional view schematically illustrating a portion C of FIG. 4 . 6C1 shows, when the present polarizer 1 is used as the polarizer 31, the transparent substrate 2, the alignment layer 3, the polarizing layer 4 and the protective layer from the retardation layer 32 side. It shows that this polarizer 1 is provided so that (7) may be arrange|positioned in this order. In addition, in FIG. 6C2, from the retardation layer 32 side, the polarizer ( 1) indicates that it is installed.

Next, members other than the polarizer of the present EL display device will be briefly described.

Examples of the substrate 33 include ceramic substrates such as sapphire glass substrates, quartz glass substrates, soda glass substrates, and alumina; metal substrates such as copper; A plastic substrate etc. are mentioned. Although not shown, a thermally conductive film may be formed on the substrate 33 . Examples of the thermally conductive film include a diamond thin film (DLC, etc.). When the pixel electrode 35 is of a reflective type, light is emitted in a direction opposite to that of the substrate 33 . Therefore, not only transparent materials, but also non-transmissive materials such as stainless steel can be used. The board|substrate may be formed singly, and may be formed as a laminated board by bonding several board|substrates with an adhesive agent. In addition, these board|substrates are not limited to a plate-shaped thing, A film may be sufficient as them.

As the thin film transistor 40, for example, a polycrystalline silicon transistor or the like may be used. The thin film transistor 40 is provided at the end of the pixel electrode 35 and has a size of about 10 μm to 30 μm. In addition, the size of the pixel electrode 35 is about 20 μm×20 μm to 300 μm×300 μm.

A wiring electrode of the thin film transistor 40 is provided on the substrate 33 . The wiring electrode has a low resistance and is electrically connected to the pixel electrode 35 and has a function of suppressing the resistance value to be low. In general, the wiring electrode is composed of Al, Al, transition metals (except Ti), Ti Or one containing any one type or two or more types of titanium nitride (TiN) is used.

An interlayer insulating layer 34 is provided between the thin film transistor 40 and the pixel electrode 35 . The interlayer insulating film 34 is formed _{by sputtering or vacuum deposition of an inorganic material such as silicon oxide such as SiO 2} or silicon nitride, a silicon oxide layer formed by SOG (spin on glass), photoresist, polyimide, and Any one may be sufficient as long as it has insulation, such as a coating film of resin-type materials, such as an acrylic resin.

Ribs 41 are formed on the interlayer insulating film 34 . The ribs 41 are disposed at the periphery of the pixel electrode 35 (between adjacent pixels). As a material of the rib 41, an acrylic resin, polyimide resin, etc. are mentioned. The thickness of the rib 41 is preferably 1.0 µm or more and 3.5 µm or less, and more preferably 1.5 µm or more and 2.5 µm or less.

Next, the EL element comprising the pixel electrode 35 as a transparent electrode, the organic functional layer 36 as the light emission source, and the cathode electrode 37 will be described. The organic functional layer 36 has at least one hole transporting layer and a light emitting layer, respectively, and sequentially has, for example, an electron injection transport layer, a light emitting layer, a hole transport layer, and a hole injection layer.

Examples of the pixel electrode 35 include ITO (tin-doped indium oxide), IZO (zinc-doped indium oxide), IGZO, ZnO, SnO _{2 ,} and In ₂ O ₃ , and ITO and IZO are particularly preferable. The thickness of the pixel electrode 35 may be at least a certain thickness capable of sufficiently performing hole injection, and is preferably set to be about 10 nm to 500 nm.

The pixel electrode 35 can be formed by a vapor deposition method (preferably a sputtering method). The sputtering gas is not particularly limited, and an inert gas such as Ar, He, Ne, Kr or Xe, or a mixed gas thereof may be used.

As a constituent material of the cathode electrode 37, for example, a metal element such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn and Zr may be used. In order to improve the operational stability of the , it is preferable to use a two-component or three-component alloy system selected from the exemplified metal elements. Examples of the alloy system include Ag·Mg (Ag: 1 to 20 at%), Al·Li (Li: 0.3 to 14 at%), In·Mg (Mg: 50 to 80 at%), and Al·Ca (Ca: 5-20 at%) etc. are preferable.

The cathode electrode 37 is formed by a vapor deposition method, a sputtering method, or the like. The thickness of the cathode electrode 37 is preferably 0.1 nm or more, preferably 1 nm to 500 nm or more.

The hole injection layer has a function of facilitating injection of holes from the pixel electrode 35, and the hole transport layer has a function of transporting holes and blocking electrons, and is also called a charge injection layer or a charge transport layer.

The thickness of the light emitting layer, the combined thickness of the hole injection layer and the hole transport layer, and the thickness of the electron injection and transport layer are not particularly limited and vary depending on the formation method, but are preferably set to about 5 nm to 100 nm. Various organic compounds can be used for a positive hole injection layer and a positive hole transport layer. A vacuum deposition method can be used for formation of a hole injection/transport layer, a light emitting layer, and an electron injection/transport layer from the point which can form a homogeneous thin film.

As the organic functional layer 36 serving as a light emission source, light emission (fluorescence) from singlet excitons is used, light emission from triplet excitons (phosphorescence) is used, light emission from singlet excitons (fluorescence) is used, and triplet excitons use light emission (fluorescence). Those that use light emission (phosphorescence) from excitons, those that are formed of organic substances, those that are formed of organic substances and those that are inorganic, those that contain high molecular weight materials, low molecular weight materials, high molecular materials and low molecular materials, etc. is available. However, it is not limited to this, The organic functional layer 36 using various well-known things for EL elements can be used for this EL display device 30. As shown in FIG.

A desiccant 38 is disposed in the space between the cathode electrode 37 and the sealing lid 39 . This is because the organic functional layer 36 is weak against humidity. The desiccant 38 absorbs moisture to prevent deterioration of the organic functional layer 36 .

8 is a schematic diagram showing a cross-sectional configuration of another embodiment of the present EL display device 30. As shown in FIG. This EL display device 30 has a sealing structure using a thin film encapsulation film 41, and can obtain emitted light also from the opposite surface of the array substrate.

As the thin film encapsulation film 41, it is preferable to use a DLC film in which DLC (diamond carbon) is deposited on a film of an electrolytic capacitor. A DLC film|membrane has the characteristic that water permeability is very bad, and moisture-proof performance is high. Alternatively, a DLC film or the like may be formed by directly vapor-depositing it on the surface of the cathode electrode 37 . In addition, the thin film encapsulation film 41 may be formed by laminating a resin thin film and a metal thin film in multiple layers.

As described above, the novel polarizer (the present polarizer) according to the present invention and the novel display device (the present liquid crystal display device and the present EL display device) provided with the present polarizer are provided.

Finally, a projection type liquid crystal display device using the present polarizer 1 will be described.

8 is a schematic diagram showing a projection type liquid crystal display device using the present polarizer 1 .

As the polarizing film 142 and/or the polarizing film 143 of this projection type liquid crystal display device, the present polarizer 1 is used.

The light bundle emitted from the light source (eg, high-pressure mercury lamp) 111 as the light-emitting source is first the first lens array 112 , the second lens array 113 , the polarization conversion element 114 , and the superposition lens 115 . By passing through the , uniformity and polarization of the luminance in the cross-section of the semi-ray bundle are performed.

Specifically, the light bundle emitted from the light source 111 is divided into a plurality of minute light bundles by the first lens array 112 in which the minute lenses 112a are formed in a matrix form. The second lens array 113 and the superposition lens 115 are provided so that each of the divided light bundles illuminates the entire three liquid crystal panels 140R, 140G, and 140B to be illuminated, so that each liquid crystal panel is incident The lateral surface has an almost uniform roughness as a whole.

The polarization conversion element 114 is constituted by a polarization beam splitter array, and is disposed between the second lens array 113 and the superposition lens 115 . Accordingly, the random polarization from the light source is converted into polarized light having a specific polarization direction in advance, and the light loss in the incident-side polarizer, which will be described later, is reduced to improve the luminance of the screen.

As described above, the luminance uniformed and polarized light is sequentially red channel, green channel, It is separated into a blue channel and is incident on the liquid crystal panels 140R, 140G, and 140B, respectively.

In the liquid crystal panels 140R, 140G, and 140B, the polarizer film 142 of the present invention is arranged on the incident side, and the polarizer film 143 of the present invention is arranged on the emission side, respectively.

The polarizing film 142 and the polarizing film 143 arranged in each of the RGB optical paths are arranged so that their respective absorption axes are orthogonal to each other. Each liquid crystal panel 140R, 140G, 140B arranged in each optical path has a function of converting the polarization state controlled for each pixel by an image signal into a light quantity.

This polarizer 1 is useful as a polarizing film excellent in durability in any optical path of a blue channel, a green channel, and a red channel by selecting the kind of dichroic dye suitable for a corresponding channel.

An optical image created by transmitting incident light at different transmittances for each pixel according to image data of the liquid crystal panels 140R, 140G, and 140B is synthesized by a cross dichroic prism 150 and a screen 180 by a projection lens 170 ) is projected on a larger scale.

Examples of the electronic paper include those represented by molecules such as optical anisotropy and dye molecular orientation, those represented by particles such as electrophoresis, particle migration, particle rotation, and phase change, those represented by moving one end of the film, molecules There are those displayed by the color development/phase change of More specifically, microcapsule type electrophoresis, horizontal movement type electrophoresis, vertical movement type electrophoresis, spherical twist ball, magnetic twist ball, circumferential twist ball method, charged toner, electron powder fluid, magnetophoretic type, magnetic thermal type, electrophoresis Electrowetting, light scattering (transparency/cloudy change), cholesteric liquid crystal/photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, dichroic dye/liquid crystal dispersion type, movable film, leuco dye Decolorization, photochromic, electrochromic, electrodeposition, flexible organic EL, etc. are mentioned. The electronic paper may be used not only for personal use of texts and images, but also for advertisement display (signage) or the like. According to the optical film of the present invention, the thickness of the electronic paper can be made thin.

As a stereoscopic display device, for example, a method of arranging different retardation films alternately as in the micropole system has been proposed (Japanese Patent Application Laid-Open No. 2002-85983), but when the optical film of the present invention is used as a polarizing film, printing, Since patterning is easy by inkjet, photolithography, etc., the manufacturing process of a display apparatus can be shortened and retardation film becomes unnecessary.

Example

Hereinafter, the present invention will be described in more detail by way of Examples. Unless otherwise specified, "%" and "part" in the examples are mass% and parts by mass.

In this Example, the following polymerizable liquid crystal compound was used.

Compound (1-6) [Compound represented by the following formula (1-6)]

Compound (1-6) is described in Lub et al. Recl. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).

[Measurement of phase transition temperature]

The phase transition temperature of compound (1-6) was confirmed by determining the phase transition temperature of the film made of compound (1-6). The operation is as follows.

A film made of compound (1-6) was formed on the glass substrate on which the alignment film was formed, and the phase transition temperature was confirmed by observation of the texture with a polarizing microscope (BX-51, manufactured by Olympus) while heating. The film made of compound (1-6), after raising the temperature to 120 °C, when the temperature is lowered, a phase change to the nematic phase at 112 °C, a phase change to the smectic A phase at 110 °C, and to the smectic B phase at 94 °C It was confirmed that there was a phase change.

Compound (1-7) [Compound represented by the following formula (1-7)]

Compound (1-7) was synthesized with reference to the synthesis of compound (1-6) described above.

[Measurement of phase transition temperature]

The phase transition temperature of compound (1-7) was confirmed in the same manner as the measurement of the phase transition temperature of compound (1-6). Compound (1-7) undergoes a phase change to a nematic phase at 133° C., a smectic A phase at 118° C., and a smectic B phase at 78° C. confirmed that.

Example 1

[Preparation of a composition for forming a polarizing layer]

By mixing the following components and stirring at 80° C. for 1 hour, a composition for forming a polarizing layer was obtained.

polymerizable liquid crystal compounds; 50 parts of compound (1-6)

50 parts of compound (1-7)

dichroic pigment; 2.5 parts of azo dye (NKX2029; manufactured by Hayashibara Seibutsukagakugenkyusho)

polymerization initiator;

6 parts of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Ilgacure 369; manufactured by Chiba Specialty Chemicals)

leveling agent;

1.2 parts of polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

solvent; 250 parts of cyclopentanone

[Measurement of phase transition temperature]

As in the case of compound (1-6) and compound (1-7), the phase transition temperature of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer prepared as described above was determined. This polymerizable liquid crystal composition, after raising the temperature to 120°C, undergoes a phase change at 112°C to the nematic phase, a phase change to the smectic A phase at 104°C, and a phase change to the smectic B phase at 78°C during the temperature decrease. Confirmed.

[Production and evaluation of this polarizer]

1. Formation of alignment layer

A glass substrate was used as the transparent substrate.

On the glass substrate, a 2% by mass aqueous solution (composition for alignment layer formation) of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied by spin coating and dried. Then, a film having a thickness of 100 nm was formed. Then, the orientation layer was formed by performing a rubbing process on the surface of the obtained film|membrane. The rubbing treatment was performed using a semi-automatic rubbing device (trade name: LQ-008 type, manufactured by Joyoko KK), and with a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Kako, Ltd.), press-in amount 0.15 mm , rotation speed of 500 rpm, and 16.7 mm/s conditions. By this rubbing process, the laminated body 1 in which the orientation layer was formed on the glass substrate was obtained.

2. Formation of a polarizing layer

On the alignment layer of the laminate 1, the composition for forming a polarizing layer is applied by spin coating, dried by heating on a hot plate at 120° C. for 3 minutes, and then rapidly 70° C. (smectic phase when temperature is lowered). temperature)) to form a first dry film on the alignment layer. Such a first dry film WHEREIN: The liquid crystal state of the polymeric liquid crystal compound contained was Smectic B phase. Then, using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.), the first dried film is irradiated with ultraviolet rays at an exposure amount of 2400 mJ/cm 2 (based on 365 nm) to dry this first The polymerizable liquid crystal compound contained in the film was polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal composition, and a polarizing layer was formed from the first dry film to obtain a laminate (2). The thickness of the polarizing layer at this time was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), and as a result, it was 1.8 µm.

3. X-ray diffraction measurement

About the polarizing layer of the obtained laminated body 2, X-ray-diffraction measurement was performed using the X-ray-diffraction apparatus X'Pert PRO MPD (made by Spectrice Corporation). Using Cu as a target, X-rays generated under the condition of an X-ray tube current of 40 mA and an X-ray tube voltage of 45 kV are passed through a fixed divergence slit 1/2° in the rubbing direction (preliminarily obtain the rubbing direction of the alignment layer under the polarization layer) ) and scanning in 2θ = 0.01671° steps in the scanning range of 2θ = 4.0 to 40.0°, and measuring results, a sharp diffraction peak (FWHM) = about 0.187° near 2θ = 20.22° ( black peak) was obtained. Moreover, the same result was obtained also in the incidence from the rubbing perpendicular|vertical direction. The order period (d) calculated from the peak position was about 4.39 angstroms, and it was found that a structure reflecting a higher-order smectic phase was formed.

4. Manufacture of this polarizer by forming a protective layer

On the polarizing layer of the laminate 2, 50 parts of dipentaerythritol hexaacrylate (Aronix M-403 polyfunctional acrylate manufactured by Toagosei Co., Ltd.), an acrylate resin (Evecryl 4858 Daicel UCB Co., Ltd.) (manufactured) 50 parts, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Ilgacure 907; manufactured by Chiba Specialty Chemicals) 3 parts dissolved in 250 parts of isopropanol ( The composition for forming a protective layer) was applied by a spin coating method, dried by heating on a hot plate at 50° C. for 1 minute, and then ultraviolet rays using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.) The present polarizer (hereinafter referred to as "the present polarizer A") was manufactured by forming a protective layer on the said polarizing layer by irradiating with an exposure amount of 400 mJ/cm<2> (365 nm standard). The protective layer at this time was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), and as a result, it was 2.8 µm.

5. Measurement of dichroic ratio

In order to confirm the usefulness of this polarizer, the dichroic ratio was measured as follows.

^{The absorbance (A 1} ) in the transmission axis direction and the absorbance (A ² ) in the absorption axis direction at the maximum absorption wavelength are set in a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with a folder with a polarizer. Measurements were made by the double beam method using one device. In this folder, on the reference side, a mesh that cuts the amount of light by 50% was installed. From the measured values of the absorbance (A ¹ ) in the transmission axis direction and the absorbance (A ² ) in the absorption axis direction, the ratio (A ² /A ¹ ) was calculated and set as the dichroic ratio. A result is shown in a table. It can be said that it is useful as a polarizing film, so that a dichroic ratio is high. Table 1 shows the measurement results of the dichroic ratio.

Example 2

The same experiment as in Example 1 was conducted except that the dichroic dye was changed from an azo dye (NKX2029; manufactured by Hayashibara Seibuts Chemicals, Ltd.) to an azo dye (G205; manufactured by Hayashibara, Ltd.), and the present polarizer (hereinafter, " This polarizer B") was manufactured. The phase transition behavior of the polymerizable liquid crystal composition at this time is, after raising the temperature to 120 ° C., during the temperature decrease, the phase change to the nematic phase at 112 ° C., the phase change to the smectic A phase at 105 ° C., and the smectic B at 77 ° C. It was confirmed that the phase change to the phase. Table 1 shows the dichroic ratio measurement results of the obtained present polarizer.

Example 3

The same experiment as in Example 1 was performed except that the solvent contained in the composition for protective layer formation was changed from isopropanol to ethanol, and the present polarizer (hereinafter referred to as "this polarizer C") was manufactured. Table 1 shows the dichroic ratio measurement result of the produced polarizer.

Example 4

The same experiment as in Example 1 was conducted except that the solvent contained in the composition for forming a protective layer was changed from isopropanol to propylene glycol monomethyl ether acetate, and the present polarizer (hereinafter referred to as “the present polarizer D”) was manufactured. Table 1 shows the dichroic ratio measurement result of the produced polarizer.

Example 5

The same experiment as in Example 1 was conducted except that the solvent contained in the composition for forming a protective layer was changed from isopropanol to propylene glycol monomethyl ether, and the present polarizer (hereinafter referred to as “the present polarizer E”) was manufactured. Table 1 shows the dichroic ratio measurement result of the produced polarizer.

Example 6

On the protective layer of the present polarizer A obtained in Example 1, a TAC (triacetyl cellulose) film was bonded through an adhesive layer formed of a pressure-sensitive adhesive (PSA). Table 1 shows the dichroic ratio measurement results of the thus-obtained structure (hereinafter referred to as "the present polarizer A+TAC").

Example 7

On the protective layer of the present polarizer B obtained in Example 2, a TAC (triacetyl cellulose) film was bonded through an adhesive layer formed of a pressure-sensitive adhesive (PSA). Table 1 shows the dichroic ratio measurement results of the thus-obtained structure (hereinafter referred to as "the present polarizer B+TAC").

Example 8

On the polarizing layer produced in the same manner as in Example 1, the surface was activated by corona treatment, and a 10% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) The present polarizer (hereinafter referred to as "the present polarizer F") was manufactured by coating by the spin coating method and heating and drying for 1 minute on an 80 degreeC hotplate, and forming a protective layer on this polarizing layer. Table 1 shows the dichroic ratio measurement result of the produced polarizer.

Example 9

On the polarizing layer produced in the same manner as in Example 1, a solution (UCECOAT7655, manufactured by Daicel Cytec Co., Ltd.) in which the surface was activated and an aliphatic urethane acrylate resin was dispersed by corona treatment was applied to the spin coating method. This polarizer (henceforth "this polarizer G") was manufactured by apply|coating with this and making it heat-dry for 1 minute on a 60 degreeC hotplate, and forming a protective layer on this polarizing layer. Table 1 shows the dichroic ratio measurement result of the produced polarizer.

Example 10

On the protective layer of the present polarizer A obtained in Example 8, a TAC (triacetyl cellulose) film was bonded through an adhesive layer formed of a pressure-sensitive adhesive (PSA). Table 1 shows the dichroic ratio measurement results of the thus-obtained structure (hereinafter referred to as "the present polarizer F+TAC").

Example 11

On the protective layer of the present polarizer A obtained in Example 9, a TAC (triacetyl cellulose) film was bonded through an adhesive layer formed of a pressure-sensitive adhesive (PSA). Table 1 shows the dichroic ratio measurement results of the thus-obtained structure (hereinafter referred to as "the present polarizer G+TAC").

(※)

IPA: isopropanol

ETA: ethanol

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

evaluation example

1. Durability test

As a durability test of this polarizer, the following time-dependent change test was done.

The main polarizer obtained in Examples 1 to 2 and the structures obtained in Examples 6 to 7 and 10 (main polarizer A+TAC, main polarizer B+TAC, or main polarizer F+TAC) were placed in a Hitachi thermostat (trade name: EC-15HHP, Hitachikucho Systems Co., Ltd.) [Conditions: dry bulb temperature 60°C, humidity 90% RH, or 85°C humidity 0%], the absorbance was measured after 100 hours, and the dichroic ratio was determined. In this way, the dichroic ratio is measured again after the lapse of 100 hours, and the case where the initial dichroic ratio and the dichroic ratio hardly change after the elapse is "g" (good), and the case where the dichroic ratio is deteriorated is "b" (bad). It was judged as 2 level. A result is shown in Table 2.

2. Content test

When using this polarizer in a liquid crystal cell, ie, using it for the liquid crystal display device of an in-cell system, it is necessary to provide a PI (polyimide) alignment film on the protective layer of this polarizer. An NMP (N-methyl-2-pyrrolidone) solution is often used for this PI alignment film formation. That is, the solvent resistance with respect to NMP is calculated|required of this polarizer. Therefore, NMP was dripped on the surface of these protective layers, and after holding for 5 minutes, it wiped and evaluated whether the protective layer was dissolved. As for the evaluation result, the case where dissolution by NMP was not seen was judged as "g" (good), and the case where dissolution by NMP was seen was determined to be 2 levels of "b" (bad). A result is shown in Table 3.

*The polarizer of this invention is very useful in manufacturing a liquid crystal display device, an (organic) EL display device, and a projection type liquid crystal display device.

1: Polarizer of the present invention (this polarizer)
2: Transparent substrate
3: alignment layer
4: Polarization layer
5: Matrix
6: Dichroic pigment
7: protective layer
10: liquid crystal display
11: anti-reflection film
12a, 12b: polarizing film
13a, 13b: retardation layer
14a, 14b: substrate
15: color filter
16: transparent electrode
17: liquid crystal layer
18: interlayer insulating film
19: backlight unit
20: Black Matrix
21: thin film transistor
22: pixel electrode
23: spacer
24: liquid crystal display device
30: EL display device
31: polarizer
32: retardation layer
33: substrate
34: interlayer insulating film
35: pixel electrode
36: light emitting layer
37: cathode electrode
38: desiccant
39: bag lid
40: thin film transistor
41: rib
42: thin film encapsulation film
44: EL display device
111: light source
112: first lens array
112a: lens
113: second lens array
114: polarization conversion element
115: superposition lens
121, 123, 132: dichroic mirror
122: reflection mirror
140R, 140G, 140B: liquid crystal panel
142, 143: polarizing film
150: cross dichroic prism
170: projection lens
180: screen

Claims (12)

It is a polarizer in which an alignment layer, a polarizing layer and a protective layer are installed in this order on a transparent substrate,
The polarizing layer is formed by polymerization of a polymerizable liquid crystal compound having an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group or an oxetanyl group as a polymerizable group, and is a dichroic in a matrix in a smectic liquid crystal state. A layer in which the sex pigment is dispersed,
The dichroic dye is an azo dye, and is a compound represented by the following formula (2),
A ¹ (-N=NA ² ) _p -N=NA ³ (2)
[In formula (2),
A ¹ and A ³ each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. A ² represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents the integer of 1-4. When p is 2 or more, a plurality of A ² may be the same as or different from each other.]
The protective layer includes a water-soluble polymer, and the water-soluble polymer is polyvinyl alcohol. The said polymerizable liquid crystal compound according to Claim 1, Formula (1)
U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (1)
[In formula (1),
X ¹ , X ² and X ³ each independently represent a p-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, X ¹ , At ^{least one of X 2} and X ³ is a p-phenylene group which may have a substituent.
Y ¹ and Y ² are each independently -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N- ^{, -CR a} =CR ^b -, -C≡ C- or -CR ^a =N-.
R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
U ¹ represents a hydrogen atom, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, or an oxetanyl group.
U ² represents an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, or an oxetanyl group.
W ¹ and W ² each independently represent a single bond, -O-, -S-, -COO- or -OCOO-.
V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group is -O-, -S- or -NH- It may be substituted.]
A polarizer that is a polymerizable liquid crystal compound represented by . The polarizer according to claim 1 or 2, wherein the polarizing layer is a polarizing layer from which a black peak is obtained in X-ray diffraction measurement. The polarizer according to claim 1 or 2, wherein the thickness of the polarizing layer is in the range of 0.5 µm to 3 µm. delete The polarizer according to claim 1 or 2, wherein the polymerizable liquid crystal compound contains two or more polymerizable smectic liquid crystal compounds. The polarizer according to claim 1 or 2, wherein the protective layer is formed from a composition for forming a protective layer comprising a water-soluble polymer and water. The liquid crystal display device in which the polarizer of Claim 1 or 2 is arrange|positioned inside a liquid crystal cell. A circularly polarizing plate in which a quarter wave plate is provided on the protective layer of the polarizer according to claim 1 or 2 . The circular polarizing plate according to claim 9, wherein the quarter wave plate is a wave plate having a characteristic that an in-plane retardation value with respect to visible light decreases as the wavelength becomes shorter. An organic EL display device comprising the circularly polarizing plate according to claim 9 and an organic EL element. Step (1) of forming an orientation layer on a transparent substrate to form a laminate;
On the alignment layer of the laminate, a polymerizable liquid crystal compound having an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group or an oxetanyl group as a polymerizable group, a dichroic dye and a polymerization initiator are contained A step (2) of applying one composition to form a first coating film on the alignment layer;
Here, the dichroic dye is an azo dye, and is a compound represented by the following formula (2),
A ¹ (-N=NA ² ) _p -N=NA ³ (2)
[In formula (2),
A ¹ and A ³ each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. A ² represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents the integer of 1-4. When p is 2 or more, a plurality of A ² may be the same as or different from each other.]
A first dry film is formed by drying the first coating film formed in the step (2) under conditions in which the polymerizable liquid crystal compound contained in the first coating film does not polymerize, and the polymerization in the first dry film is performed. Step (3) of forming a polarizing layer from the first dry film by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state after making the liquid crystal compound into a smectic liquid crystal state;
On the polarizing layer formed in the step (3), a protective layer composition containing polyvinyl alcohol and water is applied to form a second coating film on the polarizing layer, and the water-soluble polymer contained in the second coating film The manufacturing method of the polarizer which has the process (4) of forming a protective layer from the said 2nd coating film by drying.

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