KR20130008466A - Polarizer and method for production thereof - Google Patents

Abstract

PURPOSE: A polarizer and a manufacturing method are provided to improve durability. CONSTITUTION: A polarizer installs an orientation layer(3), a polarization layer(4) and a protective layer(7) on a transparent base(2) in order. The polarization layer is manufactured with the following. A membrane is formed from a composite including a polymer liquid crystal compound, a dichromatic pigment, a polymerization initiator, and solvent. The solvent is removed from the membrane. The polymer liquid crystal compound, which is included in the membrane removing the solvent, is maintained as a smectic liquid crystal state. The polymer liquid crystal compound maintained as the smectic liquid crystal state is polymerized.

Description

Polarizer and its manufacturing method {POLARIZER AND METHOD FOR PRODUCTION THEREOF}

This invention relates to a polarizer, its manufacturing method, etc.

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 | stacked in this order on a transparent film (transparent substrate), and this light The polarizer in which the absorption anisotropic layer contains the dichroic dye which has the nematic liquid crystal of a specific structure is described.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2010-152351

This invention provides a novel polarizer and its manufacturing method.

This invention includes invention of the following [1]-[14].

[1] On a transparent substrate, an alignment layer, a polarizing layer, and a protective layer are polarizers provided in this order,

The polarizing layer,

Forming a film from a composition containing a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent;

Removing the solvent from the membrane;

Making the polymeric liquid crystal compound contained in the film | membrane remove | excluding the said solvent into a smect liquid crystal state,

The polarizer manufactured by the manufacturing method containing the process of superposing | polymerizing, maintaining the said polymeric liquid crystal compound in the said liquid crystal liquid state.

[2] The polarizer according to the above [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 the above [1] or [2], wherein the polarizing layer has a thickness 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], in which the polymerizable liquid crystal compound contains two or more kinds of polymerizable smectic liquid crystal compounds.

[6] The protective layer is formed from a protective layer composition containing a polyfunctional acrylate and a solvent, and the solvent is any one of the above-mentioned [1] to [5], which is substantially composed of an alcohol solvent and / or an ether solvent. Polarizer.

[7] The polarizer according to any one of [1] to [5], in which the protective layer is formed from a protective layer-forming composition containing a polymer or oligomer and water obtained by polymerizing a polyfunctional acrylate.

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

[9] A liquid crystal display device comprising 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 provided with a quarter wave plate on the protective layer of the polarizer according to any one of [1] to [8].

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

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

[14] a step (1) of forming an laminated layer by forming an alignment layer on a transparent substrate;

Process (2) which apply | coats the composition containing a polymeric liquid crystal compound, a dichroic dye, and a polymerization initiator on the said orientation layer of the said laminated board, and forms a 1st coating film on the said orientation layer,

A 1st dry film is formed by drying the said 1st coating film formed in the said process (2) on condition that the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize, and the said superposition | polymerization in this 1st dry film Step (3) of forming a polarizing layer from the said 1st dry film by polymerizing the said polymeric liquid crystal compound, after making a crystalline liquid crystal compound into a smect liquid crystal state, and maintaining this smect liquid crystal state,

The protective layer composition containing a polyfunctional acrylate and a solvent is apply | coated on the said polarizing layer formed at the said process (3), the 2nd coating film is formed on the said polarizing layer, and the said containing in this 2nd coating film The manufacturing method of light polarizer containing the process (4) of forming a protective layer from the said 2nd coating film by superposing | polymerizing a polyfunctional acrylate.

[15] The manufacturing method of light polarizer as described in said [14] in which the solvent contained in the said protective layer composition consists essentially of an alcohol solvent and / or an ether solvent.

[16] a step (1) of forming an laminated layer by forming an alignment layer on a transparent substrate;

Process (2) which apply | coats the composition containing a polymeric liquid crystal compound, a dichroic dye, and a polymerization initiator on the said orientation layer of the said laminated board, and forms a 1st coating film on the said orientation layer,

A 1st dry film is formed by drying the said 1st coating film formed in the said process (2) on condition that the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize, and the said superposition | polymerization in this 1st dry film Step (3) of forming a polarizing layer from the said 1st dry film by polymerizing the said polymeric liquid crystal compound, after making a crystalline liquid crystal compound into a smect liquid crystal state, and maintaining this smect liquid crystal state,

On the said polarizing layer formed in the said process (3), the composition for protective layer formation containing the polymer or oligomer obtained by superposing | polymerizing a polyfunctional acrylate, and water is apply | coated, and a 2nd coating film is formed on the said polarizing layer, The manufacturing method of light polarizer containing the process (4) which forms a protective layer from this 2nd coating film by drying this 2nd coating film.

[17] a step (1) of forming an laminated layer by forming an alignment layer on a transparent substrate;

Process (2) which apply | coats the composition containing a polymeric liquid crystal compound, a dichroic dye, and a polymerization initiator on the said orientation layer of the said laminated board, and forms a 1st coating film on the said orientation layer,

A 1st dry film is formed by drying the said 1st coating film formed in the said process (2) on condition that the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize, and the said superposition | polymerization in this 1st dry film Step (3) of forming a polarizing layer from the said 1st dry film by polymerizing the said polymeric liquid crystal compound, after making a crystalline liquid crystal compound into a smect liquid crystal state, and maintaining this smect liquid crystal state,

By apply | coating the composition for protective layer formation containing a water-soluble polymer and water on the said polarizing layer formed at the said process (3), forming a 2nd coating film on the said polarizing layer, and drying this 2nd coating film, The manufacturing method of light polarizer containing the process (4) of forming a protective layer from a 2nd coating film.

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

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

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

As for the polarizer (henceforth "this polarizer" in some cases) of this invention, an orientation layer, a polarizing layer, and a protective layer are provided in this order on a transparent base material, The said polarizing layer,

Forming a coating film from a composition containing a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent;

Removing the solvent from the coating film;

Making the polymeric liquid crystal compound contained in the coating film from which the said solvent was removed into the schematic liquid crystal state,

It is manufactured by the manufacturing method containing the process of superposing | polymerizing, maintaining the said polymeric liquid crystal compound in the said liquid crystal liquid state.

Preferred embodiment of the manufacturing method of this polarizer is described, referring drawings as needed. Preferred embodiment of this manufacturing method is

A step (1) of forming an laminated layer by forming an alignment layer on a transparent substrate,

Process of apply | coating the composition containing a polymeric liquid crystal compound, a dichroic dye, and a polymerization initiator on the said orientation layer of the said laminated board formed in the said process (1), and forming a 1st coating film on the said orientation layer (2) Wow,

The 1st dry film is formed by drying the 1st coating film formed at the said process (2) on the conditions which the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize, and the said polymeric property in this 1st dry film Step (3) of forming a polarizing layer from the said 1st dry film by polymerizing the said polymerizable liquid crystal compound, after making a liquid crystal compound into a smect liquid crystal state, and maintaining this smect liquid crystal state,

The protective layer composition containing a polyfunctional acrylate and a solvent is apply | coated on the said polarizing layer formed at the said process (3), the 2nd coating film is formed on the said polarizing layer, and the said containing in this 2nd coating film The process (4) of forming a protective layer from the said 2nd coating film by superposing | polymerizing a polyfunctional acrylate is included. Hereinafter, such a manufacturing method is demonstrated for every process.

<Transparent substrate>

In the manufacturing method of this polarizer, a transparent base material is prepared first. This transparent base material is a base material which has transparency enough to transmit light, especially visible light. This transparency means the characteristic that the transmittance | permeability with respect to the light ray over wavelength 380nm -780nm becomes 80% or more. Specific examples of such a transparent substrate include a glass substrate, a light-transmissive sheet made of plastic, and a light-transmissive film. Moreover, as a plastic which comprises this translucent sheet and a translucent film, For example, Polyolefin, such as polyethylene, a polypropylene, norbornene-type polymer; Cyclic olefin resins; 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; Polysulfones; Polyether sulfone; Polyether ketones; Polyphenylene sulfide, polyphenylene oxide, etc. are mentioned. In the specific example of the above-mentioned transparent base material, among the plastics transparent sheet and the transparent film, the plastics transparent film, ie, a polymer film, is preferable. Among these polymer films, polymer films (cellulose ester films or cyclic olefin resin films) made of cellulose esters or cyclic olefin resins are preferable from the viewpoint of being easily available on the market or excellent in transparency. In manufacturing this polarizer using such a transparent base material, when carrying or storing this transparent base material, it can be handled easily, without causing damage, such as tearing, A support base material etc. are adhere | attached on the said transparent base material. You may let it do. In addition, the thickness of the said transparent base material should just be a grade which can express transparency mentioned above. In addition, when using a polymer film as a transparent base material, you may give a function as a retardation film to this polymer film by an extending | stretching process. In addition, when providing a function as a retardation film to a transparent base material, it demonstrates later.

A cellulose ester film and a cyclic olefin resin film are demonstrated in more detail. Moreover, in these 2 types, when providing a function as retardation film, a cyclic olefin resin film is also preferable at 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 esterified. The cellulose ester film which consists of such cellulose esters can be obtained easily in a market. As a commercially available cellulose ester film (triacetyl cellulose film), it is "Fuji Tak Film" [Fuji Shashin Film Co., Ltd.]; "KC8UX2M", "KC8UY", and "KC4UY" (Konica Minolta Opt Co., Ltd.). Such a commercially available cellulose film can be used as a transparent base material after performing surface treatment, such as an anti-glare process, a hard coat process, an antistatic process, or an antireflective process, on the surface as it is or as needed.

In order to provide retardation to a polymer film, it is based on the method of extending | stretching the said polymer film as mentioned above. Although all 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 which is easy to provide retardation. The cyclic olefin resin constituting the cyclic olefin resin film is composed of, for example, a polymer or copolymer (cyclic olefin resin) of cyclic olefins such as norbornene or a polycyclic norbornene monomer, and the cyclic olefin resin is partially In addition, you may include the ring-opening part. Moreover, you may hydrogenate cyclic olefin resin containing a ring-opening part. The cyclic olefin resin may be, for example, a copolymer of a cyclic olefin and a linear olefin or a vinylated aromatic compound (styrene or the like), in that it does not significantly impair transparency or does not significantly increase hygroscopicity. Moreover, the polar group may introduce | transduce this cyclic olefin resin in the molecule | numerator.

In the case where the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound or a 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-methyl styrene and alkyl-substituted styrene. And so on. In such a copolymer, the content rate of the structural unit derived from cyclic olefin is 50 mol% or less, for example, about 15-50 mol% with respect to the total structural units of cyclic olefin resin. In the case where the cyclic olefin resin is a ternary copolymer obtained from a cyclic olefin, a chain olefin, and a vinylated aromatic compound, the content ratio of the structural unit derived from the chain olefin is, for example, 5 to 5 based on all the 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 expensive cyclic olefin can be made comparatively small when this cyclic olefin resin is manufactured.

The cyclic olefin resin which can manufacture a cyclic olefin resin film can be obtained easily from a market. As cyclic olefin resin marketed, it is "Topas" [Ticona company (Germany)]; "Aton" [JSR Corporation]; "ZEONOR" and "ZEONEX" (Nihon Xeon Corporation); "Apel" (made by Mitsui Chemicals, Inc.), etc. are mentioned. Such cyclic olefin resin can be formed into a film (cyclic olefin resin film), for example by well-known film forming means, such as a solvent casting method and a melt-extrusion method. Moreover, the cyclic olefin resin film already marketed in the form of a film can also be used. As such a commercially available cyclic olefin resin film, "S thinner" and "SCA40" (Sekisui Chemical Co., Ltd.); "Zeonoa film" [Optis Co., Ltd.]; "Aton film" [JSR Corporation] etc. are mentioned. In addition, all here described in "" is a brand name, and the following is also the same.

Then, the method to give retardation property to a polymer film is demonstrated easily. A polymer film can provide retardation by a well-known extending | stretching method. For example, the winding body by which the polymer film is wound up by the roll is prepared, the film is unwound continuously from this winding body, and the unwinded film is conveyed by a heating furnace. The setting temperature of a heating furnace is the range of the glass transition temperature vicinity (degreeC)-[glass transition temperature +100] (degreeC) of the plastic which comprises a polymer film, Preferably, the glass transition temperature near (degreeC)-[glass transition Temperature + 50] (° C). In the said heating furnace, when extending | stretching to the advancing direction of a film or the direction orthogonal to a advancing direction, a conveyance direction and a tension are adjusted, it inclines at arbitrary angles, and a 1 or 2 axis | shaft thermal stretching process is performed. A draw ratio is a range of about 1.1 to 6 times normally, Preferably it is a range of about 1.1 to 3.5 times. Moreover, as a method of extending | stretching in a diagonal direction as long as it can continuously incline an orientation axis | shaft to a desired angle, it will not specifically limit, A well-known extending | stretching method can be employ | adopted. Examples of such stretching methods include methods described in Japanese Patent Laid-Open No. 50-83482 and Japanese Patent Laid-Open No. 2-113920.

In using it as a transparent base material, the thickness of a polymer film is the weight of the grade which can be practically handled, and the point which can ensure sufficient transparency, although thinner is preferable, when it is too thin, intensity | strength falls, The workability tends to be inferior. Therefore, the suitable thickness of these films is about 5 micrometers-about 200 micrometers, for example, Preferably they are 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 mobile uses, about 20 micrometers-about 80 micrometers are especially preferable for the thickness of a film. In addition, when providing retardation to a film by extending | stretching, the thickness after extending | stretching is determined according to the thickness and the draw ratio of the film before extending | stretching.

<Step (1)>

In the step (1), by providing the alignment layer on the above-mentioned transparent substrate, a laminate having a transparent substrate and an alignment layer, preferably a laminate having a transparent substrate and an alignment layer laminated thereon is formed. Moreover, when surface treatments, such as a hard-coat process and an antiglare process, are given to this transparent base material, what is necessary is just to form an orientation layer in the surface on the opposite side with respect to this surface-treated surface.

<Orientation layer>

It is preferable that the said orientation layer does not remarkably change in the formation process of the polarizing layer mentioned later. As a method of forming an orientation layer, the method of using the orientation polymer which can provide an orientation regulation force by rubbing (henceforth a "rubbing method"), and the light which can provide an orientation regulation force by irradiating polarized light Method of using an oriented polymer (hereinafter sometimes referred to as "optical alignment method"), a method of forming an alignment layer by depositing silicon oxide on a transparent substrate (transparent substrate surface) in all directions, and Langmuir And a method of forming an alignment layer by forming a monomolecular film having a long chain alkyl group using the brozet method (LB method). Especially, the rubbing method and the photo-alignment method are preferable at the point which can obtain the orientation layer excellent in orientation uniformity, and the processing time and processing cost which are required for formation of an orientation layer. As an orientation layer, the heat resistance and the transparent base material with respect to the heat processing at the time of polarizing layer formation, such as solvent resistance and solvent removal of the grade which are not melt | dissolved in the solvent contained in the composition (composition for polarizing layer formation mentioned later) apply | coated on it. It is preferable to have sufficient adhesiveness with respect to. In addition, when an orientation regulation force is provided by the rubbing method etc., since the friction is added to the coating film for orientation layer formation, the compound which comprises the said alignment layer formation coating film or the said orientation layer ( For example, it is preferable that the orientation polymer mentioned later) denatures by friction or the like, or the orientation layer itself does not peel off from the transparent substrate due to the friction or the like. From the point which can easily form such an alignment layer, it is preferable to form an alignment layer from the composition containing an oriented polymer or an orientation polymer, or the composition containing a photo-alignment polymer or a photo-alignment polymer.

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

Preferred oriented polymers include polyamides having amide bonds in the molecule; Gelatins; Polyamic acid having an imide bond in a molecule thereof and a polyamic acid which is a hydrolyzate thereof; Polyvinyl alcohol; Alkyl modified polyvinyl alcohol; Polyacrylamides; Polyoxazoles; Polyethylene imine; polystyrene; Polyvinylpyrrolidone; Polymers, such as polyacrylic acid and polyacrylic acid ester, are mentioned. These polymers may be used alone or in combination of two or more thereof to form the alignment layer, or a copolymer having a plurality of kinds of structural units constituting these polymers may be used for the formation of the alignment layer. As mentioned above, although the suitable example of an orientation polymer was shown, polyvinyl alcohol is especially preferable as an orientation polymer among these. Moreover, according to the kind, these orientation polymers are polycondensation by dehydration polymerization, deamine polymerization, etc., and by well-known polymerization methods, such as chain polymerization, coordination polymerization, ring-opening polymerization, such as radical polymerization, anionic polymerization, and cationic polymerization, etc. It can be manufactured easily.

As the photo-alignment polymer, a polymer having a photosensitive structure is used. When polarized light is irradiated to a polymer having a photosensitive structure, the photoalignable polymer is oriented by isomerizing or crosslinking the irradiated portion, and as a result, an alignment regulating force is applied to a film made of the photoalignable polymer to form an alignment layer. Examples of the photosensitive structure include azobenzene structure, maleimide structure, calcon structure, cinnamic acid structure, 1,2-vinylene structure, 1,2-acetylene structure, spiropyran structure, spirobenzopyran structure and pulgide structure. Etc. can be mentioned. The polymer which has any photosensitive structure chosen from these may be used independently in the formation of an orientation layer, and may be used together 2 or more types. Moreover, these photo-orientation polymers are used for polycondensation of the monomer (monomer) which has a photosensitive structure, such as polycondensation by dehydration polymerization, deamine polymerization, chain polymerization, such as radical polymerization, anion polymerization, and cationic polymerization, coordination polymerization, ring-opening polymerization, etc. It can manufacture easily by selecting a well-known polymerization method. Moreover, you may make a copolymer using the some kind of monomer which has a different photosensitive structure.

As a method of forming an orientation layer from an orientation polymer or a photo-alignment polymer, the method which uses the composition which prepared the composition which melt | dissolved the said orientation polymer or the said photo-alignment polymer in the solvent, and uses this composition is preferable at the point that the operation is easy. Hereinafter, the composition which can form this orientation layer is called "a composition for orientation layer formation" as the case may be. If the composition for orientation layer formation is apply | coated on a transparent base material, for example, and a solvent is removed from the coating film by a heating operation, a pressure reduction operation, etc., an alignment layer can be easily provided on this transparent base material. 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 and photo-alignment polymer to be used, Specifically; 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; Nitrile solvents, such as aromatic hydrocarbon solvents, such as toluene and xylene, and 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.

In addition, a commercially available composition for forming an alignment layer may be used to form an alignment layer. Examples of the commercially available composition for forming an alignment layer include "Sun Ever" [Nissan Kagaku Kogyo Co., Ltd.], "Optomer" [JSR Corporation], and the like. Using such a commercially available composition for forming an alignment layer is advantageous in that an alignment layer with less unevenness 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 coated on a transparent substrate, and then heat treated (annealed) to form an alignment layer on the transparent substrate. A coating film is formed. The thickness of the coating film for orientation layer formation obtained in this way is determined so that the orientation layer obtained after giving an orientation regulation force may be desired thickness. The thickness of this alignment layer is 10 nm-10000 nm, for example, Preferably it is 10 nm-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 a suitable orientation control force with respect to the coating film for orientation layer formation, and to form an orientation layer, rubbing or polarized light irradiation is performed with respect to the coating film for orientation layer formation. By providing an orientation regulation force, the polymeric liquid crystal compound contained in the coating film (1st coating film) for polarizing layer formation mentioned later can be oriented in a desired direction. As described later, when the plurality of polymerizable liquid crystal compounds are included in the first coating film, that is, when the polymerizable liquid crystal mixture is contained, the polymerizable liquid crystal mixture is oriented in the desired direction. .

As a method of rubbing the coating film for forming the alignment layer, for example, a rubbing roll in which a rubbing cloth is wound and rotated is prepared, and a laminate in which the coating film (coating film for forming an alignment layer) is formed on a transparent substrate is placed on a stage. The conveyance of the coating film and the rotating rubbing roll is carried out by conveying it toward the rotating rubbing roll. Moreover, also when irradiating polarization | polarized-light (preferably polarization UV) to the coating film for orientation layer (photoalignment layer) formation, an orientation regulation force may be provided with respect to this coating film. When masking is performed at the time of rubbing or polarizing irradiation, a plurality of regions (patterns) different in the direction of the slow axis may be formed in the present polarizer obtained.

<Step (2)>

In 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. Although repeated, this method is explained. First, the composition containing a polymeric liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent (henceforth "a composition for polarizing layer formation") is apply | coated on the said orientation layer, and a 1st coating film is formed The first coating film is dried to form a first dry film by removing the solvent. Thereafter, the polarizing layer is formed by polymerizing the polymerizable liquid crystal compound in the first dry film while maintaining the liquid crystal state of the smear phase. Thus, in order to superpose | polymerize a polymeric liquid crystal compound, maintaining the smectic liquid crystal state, after measuring the phase transition temperature of the polymeric liquid crystal compound to be used, and obtaining the temperature which can maintain a smetic phase, it is less than this temperature. Although what is necessary is just to superpose | polymerize the said polymeric liquid crystal compound under the temperature conditions to make, the polymerization temperature which superposes | polymerizes this polymeric liquid crystal compound is so preferable that it is low. In addition, the measurement conditions of 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 is determined in consideration of the thickness of the polarizing layer obtained. 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 film thickness meter.

The polymeric liquid crystal compound contained in the said composition for polarizing layer formation is a compound which has a polymeric group and shows liquid crystallinity. A polymerizable group means the group which participates in the polymerization reaction of a polymeric liquid crystal compound.

As the above-mentioned Smetic phase, Smetic B phase, Smetic D phase, Smetic E phase, Smetic F phase, Smetic G phase, Smetic H phase, Smetic I phase, Smetic J phase, Smetic K phase And smectic L phase. Among them, higher-order smectic phases such as the smear B phase, the smear F phase, the smear I phase, the inclined smear F phase and the inclined smect I phase are preferable, and the smear B phase is more preferable. When the liquid crystal phase represented by a polymerizable liquid crystal compound uses the composition for polarizing layer formation which can become these liquid crystal phases, a polarizing layer with high orientation order degree can be formed.

As a preferable polymeric liquid crystal composition, the compound represented by General formula (1) [Hereinafter, a "compound (1)" is mentioned in some cases) is mentioned, for example.

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 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 independently of one another are -CH ₂ CH _2- , -CH ₂ O-, -COO-, -OCOO-, 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 independently of each other represent a single bond, -O-, -S-, -COO- or -OCOO-.

V <^1> and V <^2> represent the C1-C20 alkanediyl group which may have a substituent independently of each other, -CH <_2> which comprises this alkanediyl group is substituted by -O-, -S-, or -NH- You may be.

In the 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, but two or more of these may have a substituent. It is more preferable if it is a good p-phenylene group.

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

As a substituent which said p-phenylene group or the said cyclohexane-1, 4-diyl group arbitrarily has, C1-C4 alkyl groups, such as a methyl group, an ethyl group, and a butyl group; Cyano group; 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 a C1-C6 alkyl group or a phenyl group.

Y ¹ of 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, and preferably a polymerizable group. That is, both U ¹ and U ² are preferable as long as it is a polymerizable group, and it is more preferable if they are all photopolymerizable groups. Here, a photopolymerizable group means group which can participate in a polymerization reaction by the active radical, the acid, etc. which generate | occur | produced from the photoinitiator mentioned later. Use of the polymerizable liquid crystal compound having a photopolymerizable group is also advantageous in that the polymerizable liquid crystal compound can be polymerized under lower temperature conditions.

In compound (1), although the photopolymerizable groups of U <^1> and U <^2> may mutually differ, it is preferable that they are the same kind of group. Examples of the photopolymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group and the like. . Especially, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group, and oxetanyl group are preferable, and acryloyloxy group is more preferable.

As the alkanediyl group of V ¹ and V ² , a methylene group, an ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5- 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 eco And acid-1,20-diyl groups. V <^1> and V <^2> , Preferably they are a C2-C12 alkanediyl group, More preferably, they are a C6-C12 alkanediyl group.

Although the cyano group, a halogen atom, etc. are mentioned as a substituent which the said alkanediyl group arbitrarily contains, It is preferable that the said alkanediyl group is unsubstituted, and it is more preferable that it is unsubstituted and linear alkanediyl group.

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

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

Illustrated Compound (1) [Polymerizable Liquid Crystal Compound] can be used as a polymerizable liquid crystal mixture in which one or two or more kinds are mixed. Furthermore, as mentioned above, components other than the polymerizable liquid crystal compound of the composition for polarizing layer formation are obtained so that the phase transition temperature of the compound (1) can be obtained and the compound (1) can be polymerized under a temperature condition below the phase transition temperature. Adjust it. As a component which can control such polymerization temperature, the photoinitiator, the photosensitizer, the polymerization inhibitor, etc. which are mentioned later are mentioned. The polymerization temperature of compound (1) can be controlled by suitably adjusting these types and amounts. In addition, even when using the mixture of 2 or more types of compound (1), ie, a polymeric liquid crystal mixture, in the composition for polarizing layer formation, after obtaining the phase transition temperature of this polymeric liquid crystal mixture, it is the same as that of the polymeric liquid crystal compound. To control the polymerization temperature.

As a polymeric liquid crystal compound used for the composition for polarizing layer formation, Among the illustrated compound (1), General formula (1-3), general formula (1-6), general formula (1-7), general formula (1-12), or It is preferable to represent with General formula (1-13). These compounds (1) superpose | polymerize the said compound (1) under the temperature conditions which are less than the phase transition temperature easily by interaction with the photoinitiator which is used all, ie, fully maintaining the liquid crystal state of higher smetic phase. You can. More specifically, these compounds (1) may be polymerized by interaction with a photopolymerization initiator while maintaining a high degree of liquid crystal state of a high degree of smectic phase under a temperature condition of 70 ° C. or lower, preferably 60 ° C. or lower. Can be.

As described above, the polymerizable liquid crystal compound contained in the composition for forming a polarizing layer may be a single species or a plurality of species, but a plurality of species are preferable, and a plurality of species of the compound (1) illustrated are more preferable. Moreover, the polymeric liquid crystal compound is preferable, and, as for the polymeric liquid crystal compound contained in this polarizing layer formation composition, it is preferable to contain two or more types of polymeric smear liquid crystal compounds. In addition, the compound (1) represented by the above-mentioned general formula (1-1)-general formula (1-21) all correspond to a polymeric smect liquid crystal compound.

70-99.9 mass% is preferable with respect to 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. There exists a tendency for the orientation of a polymeric liquid crystal compound to become high that the content rate of the said polymeric liquid crystal compound exists in the said range. Here, solid content means the total amount of components remove | excluding 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 the said range. When several types of compound (1) is contained in the said composition for polarizing layer formation, the total content ratio should just be the said range.

It is preferable that the said composition for polarizing layer formation contains a leveling agent. This leveling agent has a function which adjusts the fluidity | liquidity of a polymeric liquid crystal compound, and makes the said 1st coating film obtained by apply | coating the composition for polarizing layer formation more flat. As said leveling agent, surfactant etc. can be used. The leveling agent is more preferably one or more selected from the group consisting of a leveling agent mainly containing a polyacrylate compound and a leveling agent mainly containing a fluorine atom-containing compound.

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].

As a leveling agent containing a fluorine atom-containing compound as a main component, "Megapack R-08", "Megapack R-30", "Megapack R-90", "Megapack F-410", and "Megapack F-411" Mega Pack F-443, Mega Pack F-445 Mega Pack F-470 Mega Pack F-471 Mega Pack F-477 Mega Pack F-479 "Megapack F-482" and "Megapack F-483" [DIC Corporation]; "Surfron S-381", "Surfron S-382", "Surfron S-383", "Surfron S-393", "Surfron SC-101", "Surfron SC-105", "KH -40 "and" SA-100 "[AGC Seiko Chemical Co., Ltd.]; "E1830", "E5844" [Daikin Fine Chemical Gensho Co., Ltd.]; "F-top EF301", "F-top EF303", "F-top EF351", and "F-top EF352" [Mitsubishi Material Denshi Kasei Co., Ltd.] etc. are mentioned.

When it contains a leveling agent in the said composition for polarizing layer formation, 0.3 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of polymeric liquid crystal compounds, and 0.5 mass part or more and 3 mass parts or less are furthermore. desirable. When content of a leveling agent exists in the said range, it is easy to horizontally align a polymeric liquid crystal composition, and there exists a tendency for the polarizing layer obtained to become even more smooth. On the other hand, when content of the leveling agent with respect to a polymeric liquid crystal compound exceeds the said range, there exists a tendency for a nonuniformity to arise easily in the polarizing layer obtained. Moreover, the said composition for polarizing layer formation may contain two or more types of leveling agents.

The composition for forming a polarizing layer contains a dichroic dye. The dichroic dye as used herein refers to a dye having a property in which the absorbance in the major axis direction of the molecule and the absorbance in the minor axis direction are different. If it has such a property, a dichroic dye will not be restrict | limited in particular, A dye may be sufficient and a pigment may be sufficient. Two or more types of this dye may be used, two or more types of pigment may be used, and a dye and a pigment may be combined.

It is preferable that the said dichroic dye has maximum absorption wavelength ((lambda) MAX) in the range of 300 nm-700 nm. As such a dichroic dye, an acridine pigment, an oxazine pigment, a cyanine pigment, a naphthalene pigment, an azo pigment, an anthraquinone pigment, etc. are mentioned, for example, Azo pigment is especially preferable. As an azo dye, a monoazo pigment | dye, a bis azo pigment | dye, a tris azo pigment | dye, a tetrakis azo pigment | dye, a stilbenazo pigment | dye, etc. are mentioned, Preferably, it is a bis azo pigment | dye and a tris azo pigment | dye.

As an azo pigment | dye, the compound represented by General formula (2) (henceforth called "compound (2)") is mentioned, for example.

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 the p-phenylene group which may have a substituent, the naphthalene-1, 4-diyl group which may have a substituent, or the bivalent heterocyclic group which may have a substituent. p represents the integer of 1-4. When p is 2 or more, some A <^2> may mutually be same or different.

Examples of the monovalent heterocyclic group include groups in which one hydrogen atom is removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole and benzoxazole. The group which removed two hydrogen atoms from the heterocyclic compound corresponds to a bivalent heterocyclic group, and the specific example of such a heterocyclic compound is as above-mentioned.

As a substituent which a phenyl group, a naphthyl group, and a monovalent heterocyclic group in A <^1> and A <^3> and a p-phenylene group, a naphthalene-1, 4- diyl group, and a bivalent heterocyclic group in A <^2> arbitrarily have, C1 is 1 An alkyl group of -4; Alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group and butoxy group; C1-C4 alkyl fluoride groups, such as a trifluoromethyl group; Cyano group; A nitro group; A 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 alkyl groups having 1 to 6 carbon atoms, or two substituted alkyl groups which are bonded to each other and have 2 to 8 carbon atoms) It means of the amino group which forms an alkanediyl group. unsubstituted amino group may be mentioned being -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 of compound (1) etc. have arbitrarily.

Among the compounds (2), compounds represented by any one of the following general 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 (a definition of a substituted amino group and an unsubstituted amino group is described above. And chlorine atom or trifluoromethyl group.

n1-n4 represent the integer of 0-3 independently of each other.

If more than n1 is 2, a plurality of B ² which may be the same or different, bonded to each other to different,

When n2 is two or more, some B <^6> may mutually be same or different,

When n3 is two or more, some B <^9> may mutually be same or different,

When n4 is two or more, some B <^14> may mutually be same or different.

You may use such an azo dye which can be easily obtained in a market. Commercially available azo dyes which can be used for the composition for forming a polarizing layer include "NKX2029" and "G205" (manufactured by Hayashibara Seibutsu Chemical Co., Ltd.).

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 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 pigment, 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 formulas (2-7), (2-8) and (2-9), the alkyl group having 1 to 4 carbon atoms of R ^x is a methyl group, an ethyl group, a propyl group, a butyl group, or the like. As an aryl group of 12, they are a phenyl group, toluyl group, xylyl group, a naphthyl group, etc.

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

In the above formula (2-10),

D ¹ and D ² independently of one another represent a group represented by 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 independently of one another 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 adjusted suitably according to the kind of this dichroic dye, etc., For example, with respect to a total of 100 mass parts of a polymeric liquid crystal compound, it is 0.1 mass part or more and 50 mass parts Part or less is preferable, 0.1 mass part or more and 20 mass parts or less are more preferable, 0.1 mass part or more and 10 mass parts or less are further more preferable. When content of a dichroic dye is in this range, the said polymeric liquid crystal compound can be polymerized, without disturbing the orientation of a polymeric liquid crystal compound, maintaining the high-order smectic liquid crystal state. When there is too much content of a dichroic dye, there exists a possibility that the orientation of a polymeric liquid crystal compound may be inhibited. Therefore, content of a dichroic dye can also be determined in the range which a polymeric liquid crystal compound can maintain the high-order smectic liquid crystal state.

The said composition for polarizing layer formation contains a solvent. This solvent can consider a solubility of the polymeric liquid crystal compound to be used, etc., and can select a suitable thing suitably. However, it is preferable that it is an inert solvent which does not significantly inhibit the progress of the polymerization reaction of the said polymeric liquid crystal compound. As such a solvent, 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; Chlorine-containing solvents, such as chloroform and chlorobenzene, etc. are mentioned. 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. When solid content is 2 mass% or more, the dichroism required as a polarizing layer which this polarizer has can be obtained. 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, there exists a tendency for the nonuniformity to arise in this polarizing layer easily because the thickness of a polarizing layer becomes substantially uniform. In addition, such solid content can be determined so that the thickness of the polarizing layer mentioned above can be formed.

The composition for forming a polarizing layer contains a polymerization initiator. The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound, and a photopolymerization initiator is preferable in that the polymerization reaction can be started under lower temperature conditions. Specifically, a compound capable of generating an active radical or an acid by the action of light is used as a photopolymerization initiator under low temperature (this low temperature refers to a temperature of 70 ° C. or lower, preferably 60 ° C. or lower, as described above). do. Among these photoinitiators, it is more preferable to generate radicals by the action of light.

As said photoinitiator, a benzoin compound, a benzophenone compound, an alkylphenone compound, an acylphosphine oxide compound, a triazine compound, an iodonium salt, a sulfonium salt, etc. are mentioned, for example.

Hereinafter, the specific example of this photoinitiator is given.

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butyl Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 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- [ And oligomers of 4- (1-methylvinyl) phenyl] propan-1-one.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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 Azine and the like.

The photoinitiator can also use what is easily obtained on the market. Commercially available photopolymerization initiators include "Ilgacure 907", "Ilcure 184", "Ilcure 651", "Ilcure cure 819", "Ilcure cure 250", "Ilcure cure 369" [Chiba Japan ( week)]; "Shakeol BZ", "Shakeol Z", "Shakeol BEE" [Seiko Kagaku Co., Ltd.]; "Kayacure BP100" [Nihon Kayaku Co., Ltd.]; "Kayakure UVI-6992" (manufactured by Dausa); "Adecaoptomer SP-152", "adecaoptomer SP-170" [ADEKA]; "TAZ-A", "TAZ-PP" (Nippon Seibel Hegner); And "TAZ-104" (Sanwa Chemical Co., Ltd.).

Although content of the polymerization initiator in the said composition for polarizing layer formation can be adjusted suitably according to the kind and quantity of the polymerizable liquid crystal compound contained in this composition for polarizing layer formation, For example, the sum total of 100 is a polymeric liquid crystal compound. 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 more preferable. When content of a polymeric initiator is in this range, since it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal compound, the said polymeric liquid crystal compound can be superposed | polymerized, maintaining the liquid crystal state of a higher order smectic phase.

When the said composition for polarizing layer formation contains a photoinitiator, this composition for polarizing layer formation may contain the photosensitizer. 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 an alkoxy group-containing anthracene (eg, dibutoxyanthracene, etc.); 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 promoted more. Although the usage-amount of such a photosensitizer can be suitably adjusted according to the kind and quantity of the photoinitiator and polymeric liquid crystal compound used together, 0.1-30 mass parts is preferable with respect to a total of 100 mass parts of a polymeric liquid crystal compound, for example. 0.5-10 mass parts is more preferable, and 0.5-8 mass parts is more preferable.

Although it was demonstrated that the polymerization reaction of a polymeric liquid crystal compound can be promoted by containing a photosensitizer in the said composition for polarizing layer formation, in order to advance this polymerization reaction stably, the said composition for polarizing layer formation is a polymerization inhibitor. It can also be contained suitably. By containing a polymerization inhibitor, the progress of the polymerization reaction of a polymeric liquid crystal compound can be controlled.

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-piperidinyloxyradical, and the like. Radical supplements; Thiophenols; (beta) -naphthylamine, (beta) -naphthol, etc. are mentioned.

When making the composition for polarizing layer formation contain a polymerization inhibitor, the content can be suitably adjusted according to the kind of polymerizable liquid crystal compound to be used, the quantity, the usage-amount of a photosensitizer, etc. For example, as for content of the polymerization inhibitor with respect to a total of 100 mass parts of a polymeric liquid crystal compound, 0.1-30 mass parts is preferable, 0.5-10 mass parts is more preferable, 0.5-8 mass parts is more preferable. When content of a polymerization inhibitor exists in this range, since it can superpose | polymerize without disturbing the orientation of the polymeric liquid crystal compound or polymeric liquid crystal composition contained in the said composition for polarizing layer formation, the said polymeric liquid crystal compound or polymerizable property The liquid crystal composition can be polymerized while maintaining a liquid crystal state of a higher order smectic phase well.

The composition for polarizing layer formation demonstrated above is apply | coated on the orientation layer of the laminated board provided with a transparent base material and an orientation layer, and a 1st coating film is obtained on condition that the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize. By drying, a first dry film is formed.

As a method (coating method) of apply | coating the said composition for polarizing layer formation to the said laminated board, for example, an extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP coating method, the diecoat method, the dipcoat method, the barcoat method And a spin coat 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.

Subsequently, 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 a method of removing a solvent, a drying means (drying method) is usually used, and it can be performed by a natural drying method, a ventilation drying method or a vacuum drying method, or a combination thereof. In addition, although the drying method may use any, it is preferable to set drying conditions so that the polymeric liquid crystal compound contained in this 1st coating film may not superpose | polymerize.

<Step (3)>

In the 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 the smect liquid crystal state. Form.

<Formation of Polarizing Layer>

In order to make the liquid crystal state of the polymeric liquid crystal compound contained in a said 1st dry film into a smectic phase (henceforth a "smetic phase" or a "smetic phase liquid crystal state"), the said 1st dry film What is necessary is just to heat at an appropriate temperature, In other words, what is necessary is just to heat what consists of the laminated board which has the said 1st dry film to the suitable temperature calculated | required from the phase transition temperature. Moreover, in forming a smear phase, once the liquid crystal state of the polymeric liquid crystal compound contained in this 1st dry film is made into a nematic phase (nematic liquid crystal state), this nematic phase is transferred to a smear phase If it is preferable. Thus, in order to form a smetic phase via a nematic phase, for example, the polymerizable liquid crystal compound included in the first dry film is heated above a temperature at which phase transitions into a liquid crystal state of the nematic phase, and then the polymerizable liquid crystal compound is The method of cooling to the temperature which shows a liquid crystalline state of a smectic phase is employ | adopted.

In forming the liquid crystal state of a smectic phase via a nematic phase, it is especially preferable if the said composition for polarizing layer formation contains the above-mentioned leveling agent. When forming a liquid crystal state, if a leveling agent is contained in the said 1st dry film, the advantage that a leveling agent will flow easily in this 1st dry film, and a polymeric liquid crystal compound or a polymeric liquid crystal composition will become easy to horizontally align, have. As a temperature at the time of forming a nematic phase and a smectic phase, the range of the temperature below 100 degreeC higher than the nematic phase transition point and also the nematic phase transition point is preferable, and it is 50 degreeC above the nematic phase transition point and the nematic phase transition point. The range below the high temperature is more preferable. The heat treatment for orienting a desired liquid crystal phase and the drying treatment of the solvent described above can also be performed at the same time.

When polymerizing the polymerizable liquid crystal compound, a polymerizable liquid crystal mixture composed of two or more polymerizable liquid crystal compounds is more preferable as the polymerizable liquid crystal compound in order to maintain the smectic liquid crystal state satisfactorily. It is preferable to use the composition for polarizing layer formation containing the polymeric liquid crystal mixture which consists of the above-mentioned polymeric smear liquid crystal compounds). When using the composition for polarizing layer formation which adjusted the content ratio of each polymeric liquid crystal compound in the said polymeric liquid crystal composition, after forming a liquid crystalline state via a nematic phase, a supercooled state is formed temporarily. It is possible to achieve this, and there is an advantage that it is easy to easily maintain the liquid crystal state of the higher order smectic phase.

Here, after containing a photoinitiator in the said composition for polarizing layer formation, making the liquid crystal state of the polymeric liquid crystal compound in a 1st dry film into a smetic phase, the said polymeric liquid crystal is maintained, maintaining this liquid crystalline state. The method of photopolymerizing a compound is explained in full detail. In photopolymerization, as a light ray irradiated to a 1st dry film, the kind of photoinitiator contained in this 1st dry film, or the kind of polymeric liquid crystal compound (especially the kind of photopolymerizable group which this polymeric liquid crystal compound has), and According to the quantity, it can carry out suitably with the light and active electron beam chosen from the group which consists of visible light, an ultraviolet light, and a laser light. Among these, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction, and that a device widely used in the art can be used as a device for photopolymerization. Therefore, it is preferable to select the kind of the polymeric liquid crystal compound and the photoinitiator contained in the said polarizing layer formation composition so that photopolymerization may be carried out by ultraviolet light. Moreover, when superposing | polymerizing, superposition | polymerization temperature can also be controlled by cooling a 1st dry film with suitable cooling means with ultraviolet light irradiation. If the polymerization of the polymerizable liquid crystal compound can be carried out at a lower temperature by the use of such cooling means, the advantage that the polarizing layer can be appropriately formed even if the transparent base material and the alignment layer described above are relatively low in heat resistance is used. have. Moreover, when photopolymerizing, the patterned polarizing layer can also be obtained by masking, image development, etc.

By performing photopolymerization as mentioned above, the said polymerizable liquid crystal compound superposes | polymerizes, maintaining the liquid crystal state of the smetic phase, Preferably the higher smetic phase as already illustrated, and a polarizing layer is formed. The polarizing layer obtained by superposing | polymerizing, with a polymeric liquid crystal compound or a polymeric liquid crystal composition holding the smectic liquid crystal state is a conventional polarizing layer, ie, maintaining a liquid crystal state of a nematic phase, etc. Compared with the polarizing layer obtained by superposing | polymerizing, there exists an advantage that polarization 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 of such an X-ray-diffraction measurement can mention the conditions etc. which were described in the Example of this application, for example.

<Step (4)>

In 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 by process (3). When the polarizing layer in the present polarizer is a polarizing layer formed by polymerizing a polymerizable liquid crystal compound in a liquid crystal state of higher order such as, for example, Smetic B phase, the polarizing layer is remarkably It may be altered by a factor. By forming a protective layer on a polarizing layer, the deterioration of such a polarizing layer can be prevented very effectively.

As the step (4),

On the said polarizing layer formed in the said process (3), the composition 1 for protective layer formation containing a polyfunctional acrylate and a solvent is apply | coated, a 2nd coating film is formed on the said polarizing layer, Step (4-1) of forming a protective layer from the said 2nd coating film by polymerizing the polyfunctional acrylate contained,

On the polarizing layer formed at the said process (3), the composition 2 for protective layer formation containing the polymer or oligomer obtained by superposing | polymerizing a polyfunctional acrylate, and water is apply | coated, and a 2nd coating film is formed on the said polarizing layer, , Step (4-2) of forming a protective layer from this second coating film by drying this second coating film, and

By apply | coating the composition 3 for protective layer formation containing a water-soluble polymer and water on the said polarizing layer formed at the said process (3), forming a 2nd coating film on the said polarizing layer, and drying this 2nd coating film, Process of forming protective layer from this 2nd coating film (4-3)

And the like.

On the said polarizing layer formed in the said process (3), the composition 1 for protective layer formation containing a polyfunctional acrylate and a solvent is apply | coated, a 2nd coating film is formed on the said polarizing layer, The method of forming a protective layer from the said 2nd coating film by polymerizing the polyfunctional acrylate contained is demonstrated. The method of forming a protective layer from such a protective layer formation composition 1 also has the advantage that the operation is very simple.

<Composition 1 for forming a protective layer>

The said composition 1 for protective layer formation contains a polyfunctional acrylate and a solvent. The polyfunctional acrylate contained in the protective layer-forming composition 1 is from the group consisting of an acrylate group (CH ₂ = CH-CO-) and a methacrylate group (CH ₂ = C (CH ₃ ) -CO-). It means the compound which has two or more groups selected 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, the polyfunctional acrylate etc. which have two such groups are called "bifunctional acrylate" etc. hereafter according to the number of these groups, and the polyfunctional acrylate which has three or more such groups is "multifunctional or more trifunctional". Functional acrylate ”and the like.

In addition, when the polyfunctional acrylate contained in this protective layer formation composition 1 hardens | cures this polyfunctional acrylate and it is set as a protective layer, transparency to such an extent that such a protective layer can permeate | transmit light, especially visible light, Having is chosen. In addition, "transparency enough to transmit visible light" here is the same meaning as what was demonstrated about the transparency of the said transparent base material.

Here, preferable polyfunctional acrylate is illustrated.

As a bifunctional acrylate which has two groups selected from the group which consists of an acrylate group and a methacrylate group in a molecule | numerator, 1, 3- butanediol di (meth) acrylate; 1,3-butanediol (meth) acrylate; 1,6-hexanedioldi (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 neopentylglycol di (meth) acrylates; Ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

As a trifunctional or more than trifunctional polyfunctional acrylate which has 3-6 groups selected from the group which consists of an acrylate group and a methacrylate group in a molecule | numerator,

Trimethylolpropane tri (meth) acrylate; Pentaerythritol tri (meth) acrylate; Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; Ethoxylated trimethylolpropane tri (meth) acrylate; Propoxylated trimethylolpropanetri (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; Tripentaerythritolhepta (meth) acrylate; Tripentaerythritol octa (meth) acrylate;

Reactants of pentaerythritol tri (meth) acrylate with acid anhydride; Reactant of dipentaerythritol penta (meth) acrylate with an acid anhydride;

A reaction product of tripentaerythritol hepta (meth) acrylate with 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 tripentaerythritolhepta (meth) acrylate; Caprolactone modified tripentaerythritol octa (meth) acrylate; A reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate with an acid anhydride; The reaction product of caprolactone modified dipentaerythritol penta (meth) acrylate and an acid anhydride, a 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. In addition, a caprolactone modification means that the ring-opening body or ring-opening polymer of caprolactone is introduce | transduced between the alcohol-derived site | part of a (meth) acrylate compound, and a (meth) acryloyloxy group.

In order to obtain a protective layer with a large surface hardness, it is preferable to use a trifunctional or more than trifunctional acrylate among the specific examples of the polyfunctional acrylate mentioned above, and it is especially preferable to use a hexafunctional acrylate. Moreover, the said composition 1 for protective layer formation may contain 1 type of polyfunctional acrylates, and may contain multiple types of polyfunctional acrylates.

Moreover, the binder resin may be contained in the said composition 1 for protective layer formation from the point of the printability of the composition 1 for protective layer formation, or the adhesiveness of the protective layer obtained.

As this binder resin, the copolymer etc. of 1 or more types of monomers chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the other monomer copolymerizable with this monomer 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 a divalent or higher polyhydric carboxylic acid such as monosuccinic acid [2- (meth) acryloyloxyethyl] and monophthalic acid [2- (meth) acryloyloxyethyl] ] Esters; and unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid. An unsaturated carboxylic anhydride corresponds to the anhydride of the unsaturated carboxylic acid shown here. Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable as the monomer for producing the binder resin. These acrylic acid, methacrylic acid, and maleic anhydride are preferably used because they have good polymerization reactivity when copolymerized with various other monomers, have a high glass transition temperature (Tg) and mechanical properties of the resulting binder resin, and are not tacky. . In addition, when manufacturing binder resin, the monomer chosen from the group which consists of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride may use a single species, and may use multiple types.

As another monomer copolymerizable with the monomer chosen from the group which consists of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride,

(Meth) acrylic acid alkyl esters 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 (in the art, conventionally known as dicyclopentanyl (Meth) acrylic-acid cyclic alkylesters, such as (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isoboroyl (meth) acrylate;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.02,6] decane-8-yl acrylate (common name in the art as dicyclopentanyl acrylate), dicyclopentaoxy Acrylic cyclic alkyl esters such as ethyl acrylate and isoboroyl 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-cyclohexyloxy Cycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2 .1] bicyclo unsaturated compounds, such as hepto-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, 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, 2,3-dimethyl-1,3-butadiene, and the like.

The solvent contained in the said composition for protective layer formation 1 is the same as what was illustrated as a solvent contained in the said composition for polarizing layer formation, etc., for example. Among these, the solvent contained in the said composition 1 for protective layer formation should just contain the solvent chosen from the group which consists of an alcohol solvent and an ether solvent, and it is still more preferable if it consists essentially 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 little solvent other than the alcohol solvent is contained, little solvent other than the ether solvent is contained, the alcohol solvent and the ether. It is any one of solvents other than a solvent being hardly contained. However, in the solvent which consists of an alcohol solvent and / or an ether solvent substantially, moisture etc. which were unexpectedly contained may be contained as long as it is a trace amount sufficient to form a protective layer. As mentioned above, methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether, etc. are mentioned as mentioned above. Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. are mentioned as said ether solvent. Among these, as the solvent contained in the composition for forming a polarizing layer, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and a plurality of mixed solvents selected from these are more preferable.

When the solvent contained in the said protective layer forming composition 1 consists essentially of an alcohol solvent and / or an ether solvent, when the said protective layer forming composition 1 is apply | coated on a polarizing layer, the orientation state of a polarizing layer will become The protective layer can be formed while maintaining this orientation state so as not to be remarkably damaged. In this respect, the present polarizer can be stably produced as long as the solvent contained in the protective layer-forming composition 1 consists essentially of an alcohol solvent and / or an ether solvent. Moreover, the method of forming a protective layer using the composition 1 for protective layer formation in this way is also advantageous at the point that the operation is easy. In addition, what is necessary is just to determine content of the solvent contained in the composition 1 for protective layer formation considering the applicability | paintability at the time of apply | coating this composition 1 for protective layer formation on a polarizing layer, For example, of this composition 1 for protective layer formation It is preferable in it being content of 10-80 mass parts with respect to 100 mass parts of total amounts, and 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 superpose | polymerize and harden the polyfunctional acrylate contained in this composition 1 for protective layer formation. Also in the superposition | polymerization of this polyfunctional acrylate, photopolymerization as demonstrated in superposition | polymerization of the polymeric liquid crystal compound contained in the said composition for polarizing layer formation is preferable. Photopolymerization of the said polyfunctional acrylate can be performed by irradiating visible light or an ultraviolet-ray to the 2nd dry film formed on the said polarizing layer by the said composition 1 for protective layer formation. In addition, in order to perform photopolymerization of polyfunctional acrylate efficiently, it is preferable to contain the photoinitiator in the said composition 1 for protective layer formation. As this photoinitiator, the thing similar to what was illustrated as a photoinitiator to be contained in the said composition for polarizing layer formation is illustrated.

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

In order to form a protective layer, first, the said composition 1 for protective layer formation is apply | coated on the said polarizing layer, and a 2nd coating film is formed. The application method of the composition 1 for protective layer formation is the same as what was demonstrated as a method of apply | coating the said composition for polarizing layer formation, for example.

Next, a solvent (preferably an alcohol solvent and / or an ether solvent) is removed from the 2nd coating film obtained by apply | coating on a polarizing layer, and a 2nd dry film is obtained. Such drying can also employ | adopt the method similar to what was illustrated as a drying method of forming the said 1st dry film from the said 1st coating film. In the process of drying the said 2nd dry film, it is necessary to prevent the unpolymerized polymerizable liquid crystal compound from mixing in the said polarizing layer in a 2nd dry film during drying. As temperature conditions for that, 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 said composition 1 for protective layer formation is a solvent demonstrated as more preferable, a 2nd coating film can be dried in accordance with such suitable temperature conditions. In addition, in order to perform drying 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 a 2nd coating film under suitable pressure reduction conditions.

When the composition 1 for protective layer formation which consists of an alcohol solvent and / or an ether solvent substantially as a solvent is apply | coated on the said polarizing layer, this inventor discovered that the property of this polarizing layer is not impaired. Therefore, when the protective layer is formed on the polarizing layer using the composition 1 for forming the protective layer, not only the protective layer can prevent the deterioration over time of the polarizing layer of the present polarizer, but also the protective layer. It is possible to satisfactorily prevent damaging the properties of the polarizing layer at the time of formation. Such an effect cannot be immediately found in the production of a conventional polarizer and is based on the inventor's original knowledge.

On the polarizing layer formed at the said process (3), the composition 2 for protective layer formation containing the polymer or oligomer obtained by superposing | polymerizing a polyfunctional acrylate, and water is apply | coated, and a 2nd coating film is formed on the said polarizing layer, The method of forming a protective layer from this 2nd coating film by drying this 2nd coating film is demonstrated. The method of forming a protective layer from the composition 2 for protective layer formation also has the advantage that the operation is very simple.

<Composition 2 for forming a protective layer>

The said composition 2 for protective layer formation contains the polymer or oligomer obtained by superposing | polymerizing a polyfunctional acrylate, and water. As a polymer or oligomer obtained by superposing | polymerizing a polyfunctional acrylate, aliphatic urethane acrylate etc. are mentioned, for example.

Although content of the water contained in the composition 2 for protective layer formation should just be considered in consideration of the applicability | paintability at the time of apply | coating this composition 2 for protective layer formation on a polarizing layer, For example, the total amount of this composition 2 for protective layer formation 100 mass It is preferable in it being content of 50-99 mass parts with respect to a part, and more preferable in it being 60-95 mass parts.

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

In order to form a protective layer, first, the said composition 2 for protective layer formation is apply | coated on the said polarizing layer, and a 2nd coating film is formed. The application method of the composition 2 for protective layer formation is the same as what was demonstrated as a method of apply | coating the said composition for polarizing layer formation, for example.

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

By apply | coating the composition 3 for protective layer formation containing a water-soluble polymer and water on the said polarizing layer formed at the said process (3), forming a 2nd coating film on the said polarizing layer, and drying this 2nd 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 protective layer formation composition also has the advantage that the operation is very simple.

<Composition 3 for Protective Layer Formation>

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

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

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

In order to form a protective layer, first, the said composition 3 for protective layer formation is apply | coated on the said polarizing layer, and a 2nd coating film is formed. The application | coating method of such a protective layer formation composition 3 is the same as what was demonstrated as a method of apply | coating the said composition for polarizing layer formation, for example.

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

Although the thickness of a protective layer can be suitably adjusted according to the kind etc. of the polarizing layer protected by a protective layer, it is preferable in it being the range of 0.1 micrometer-30 micrometers, for example, and more preferable in the range of 1 micrometer-5 micrometers. The measurement of such thickness is also employ | adopted as what was demonstrated as the measuring method of the thickness of the said polarizing layer.

<Bone polarizer>

This polarizer obtained by the manufacturing method including a process (1)-a process (4) is not only excellent in the scratch resistance and solvent resistance of the surface of a polarizing layer by providing a protective layer, but also the heat resistance and moisture-heat resistance of this polarizer itself. This is advantageous from the conventional polarizer in that it is excellent. Moreover, embodiment of the manufacturing method of this polarizer containing a process (1) thru | or (4), this 1st dry film is made into the said 1st dry film of a process (3) under the temperature conditions of 25 +/- 10 degreeC. Various deformation | transformation is possible in the range which does not change the aspect to superpose | polymerize, with the said polymeric liquid crystal compound or polymeric liquid crystal composition contained in the maintaining the smect liquid crystal state. For example, when forming or preparing the laminated board of the transparent base material and an orientation layer of a process (1), this transparent base material itself may use what has an orientation characteristic, In addition to an orientation layer, retardation film is further laminated | stacked, and a transparent base material It can also be set as the structure provided in the order of an orientation layer, a polarizing layer, a retardation layer, and a protective layer on it. Moreover, the bead-shaped resin from which a refractive index and a component of a ultraviolet absorber, an antistatic agent, or a protective layer differ in the protective layer formed in process (4) can also be mixed. However, since it is advantageous if the said composition for protective layer formation used in formation of a protective layer is what consists of an alcohol solvent and / or an ether solvent substantially as a solvent, or water, it is a process using the composition for protective layer formation of such a solvent. It is preferable that (4) can be implemented.

As mentioned above, although this polarizer was demonstrated centering on the case 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 described above, the polarizer may further include a retardation film, or may further include an antireflection layer or a brightness enhancement film. Moreover, it can also be set as a circularly polarizing plate in combination with a quarter wave plate. It is preferable that the quarter wave plate used when manufacturing a circularly polarizing plate has the characteristic that an in-plane phase difference 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. The 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 electro luminescence (EL) display device, an inorganic electro luminescence (EL) display device, an electron emission display device (for example, an electric field emission display device (FED), a surface field emission display) Device (SED)], electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device [for example, display device having a grating light valve (GLV) display device, a digital micro mirror device (DMD)]) And piezoelectric ceramic displays, etc. The liquid crystal display device includes all of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, a projection liquid crystal display device, and the like. The display device may be a display device for displaying a two-dimensional image, or a stereoscopic display device for displaying a three-dimensional image.

Especially this polarizer can be used especially effectively for the display apparatus of an organic electroluminescent (EL) display apparatus or an inorganic electro luminescence (EL) display apparatus.

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

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

4 and 7 are schematic diagrams schematically showing a cross-sectional structure of an EL display device (hereinafter, referred to as a "main EL display device") using the present polarizer.

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 shown in FIG. 2 will be described.

It is preferable that this polarizer is arrange | positioned with respect to a light incident side with respect to a liquid crystal layer. The color filter 15 is arranged on the liquid crystal layer 17 side of the substrate 14a. The color filter 15 is disposed at a position facing the pixel electrode 22 with the liquid crystal layer 17 therebetween, and the black matrix 20 is disposed 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. In addition, an overcoat layer (not shown) may be provided between the color filter 15 and the transparent electrode 16.

The thin film transistor 21 and the pixel electrode 22 are regularly arranged on the liquid crystal layer 17 side of the substrate 14b. The pixel electrode 22 is disposed at a position facing the color filter 15 with the liquid crystal layer 17 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 board | substrate 14a and the board | substrate 14b, a glass substrate and a plastic substrate are used. As 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 needed, a glass substrate or a quartz board | substrate is preferable.

As the thin film transistor, an optimal one can be adopted depending on the material of the substrate 14b. As the thin film transistor 21, there may be mentioned a high temperature polysilicon transistor formed on a quartz substrate, a low temperature polysilicon transistor formed on a glass substrate, an amorphous silicon transistor formed on a glass substrate or a plastic substrate. In order to further reduce the size of the liquid crystal display device, a driver IC may be formed on the substrate 14b.

The liquid crystal layer 17 is disposed between the transparent electrode 16 and the pixel electrode 22. In the liquid crystal layer 17, spacers 23 are disposed in order 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 a columnar shape, If the distance between the board | substrate 14a and the board | substrate 14b can be kept constant, the shape is arbitrary.

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

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

The polarizer 12a and the polarizer 12b are provided in the outer side of the board | substrate 14b among the board | substrate 14a and 14b which sandwiched this liquid crystal layer 17, and one or more of these saw the polarizer ( 1).

Moreover, it is preferable that retardation layers (for example, 1/4 wavelength plate and optical compensation film) 13a, 13b are laminated | stacked. By arrange | positioning the polarizer 12b among two polarizers, the function which converts incident light into linearly polarized light can be given to this liquid crystal display device 10. The retardation layer 13a and the retardation layer 13b may not be disposed depending on the structure of the liquid crystal display device and the type of liquid crystal compound included in the liquid crystal layer 17. You may provide a polarizing film further on the light emission side (outer side).

It is preferable that the antireflection film 11 for preventing reflection of external light is disposed outside the present polarizer 1 (when the polarizer film is further provided on the present polarizer 1).

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

3 is an enlarged schematic cross-sectional view of a portion A of FIG. 2. 3A shows the protective layer 7, the polarizing layer 4, the alignment layer 3, and the transparent substrate (from the phase difference layer 13a side when the polarizer 1 is used as the polarizer 12a). This polarizer 1 is provided so that 2) is arrange | positioned in this order. 3 (A2) shows the present polarizer so that the transparent base material 2, the alignment layer 3, the polarizing layer 4 and the protective layer 7 are arranged in this order from the phase difference layer 13a side. (1) is provided.

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

The backlight unit 19 which is a light emitting source is arrange | positioned outside the polarizer 12b. The backlight unit 19 includes a light source, a light guide, a reflecting plate, a diffusion sheet, and a viewing angle adjustment sheet. As a light source, electroluminescent, a cold cathode tube, a hot cathode tube, a light emitting diode (LED), a laser light source, a mercury lamp, etc. are mentioned. Moreover, the kind of polarizer which can be seen according to the characteristic of such a light source can be selected.

In the case where the 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 enters the light guide, and the path is changed by the reflecting plate and diffused in the diffusion sheet. The diffused light enters the polarizer 12b from the backlight unit 19 after being adjusted to have the desired directivity by the viewing angle adjusting sheet.

Of the unpolarized 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 or elliptically polarized light by the phase difference layer 13b, and sequentially passes through the substrate 14b, the pixel electrode 22, and the like to reach the liquid crystal layer 17. FIG.

Here, the alignment state of the liquid crystal molecules included in the liquid crystal layer 17 is changed by the presence or absence of a potential difference between the pixel electrode 22 and the opposing transparent electrode 16, so that the luminance of 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 of a specific wavelength range passes through the color filter 15. When the polarizer 12a is reached and further passes through the anti-reflection film 11, the liquid crystal display displays the color determined by the color filter brightest.

On the contrary, when the liquid crystal layer 17 is in an alignment state in which the polarized light is converted and transmitted, light transmitted through the liquid crystal layer 17, the transparent electrode 16, and the color filter 15 is absorbed by the polarizer 12a. As a result, this pixel displays black. In the intermediate alignment state of these two states, since the luminance of the light emitted from the liquid crystal display device 10 also becomes the middle of the above, this pixel displays the intermediate color.

When this liquid crystal display device 10 is a semi-transmissive liquid crystal display device, it is preferable to use what laminated | stacked the 1/4 wavelength plate further on the protective layer side of this polarizer. At this time, the pixel electrode 22 has a transmissive portion formed of a transparent material and a reflecting portion formed of a material that reflects light, and the transmissive portion displays an image in the same manner as the above-described transmissive liquid crystal display device. On the other hand, in the reflecting portion, external light is incident on the liquid crystal display device from the direction of the anti-reflection film 11, and the circularly polarized light that has passed through the polarizer by the action of the quarter-wave plate provided in the present polarizer is 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 liquid crystal display device 24, the antireflection film 11, the substrate 14a, the polarizer 12a, the phase difference layer 13a, the color filter 15, the black matrix 20, the transparent electrode 16, and the 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 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 the order of the transparent base material 2, the orientation layer 3, the polarizing layer 4, and the protective layer 7 from the anti-reflection film 11 side. In this liquid crystal display device 24 equipped with the present polarizer in such a configuration, a function of making incident light into linearly polarized light is provided. In addition, similarly to the liquid crystal display device 10, the retardation layer 13a and the retardation layer 13b may not be disposed depending on the type of liquid crystal compound included in the liquid crystal layer 17.

Next, the present EL display device using the present polarizer will be described with reference to FIGS. 4 and 7.

In the EL display device 30, the organic functional layer 36 and the cathode electrode 37 serving as light emitting sources are stacked on the substrate 33 on which the pixel electrode 35 is formed. The retardation plate 32 and the polarizing plate 31 are arrange | positioned on the opposite side to the organic functional layer 36 through the board | substrate 33, and this polarizer 1 used as this polarizing plate 31 is used. The organic functional layer 36 emits light 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 which is a light emitting source is composed of an electron transporting layer, a light emitting layer, a hole transporting 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 electroluminescence display which has the organic functional layer 36 is demonstrated, you may apply also to the inorganic electroluminescence display which has an inorganic functional layer.

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

Then, the polarizer 31 (this polarizer 1) is provided in the surface opposite to the surface in which the thin film transistor 40 of the board | substrate 33 is provided. It is preferable to provide a retardation layer 32 between the polarizer 31 and the substrate 33, and this retardation layer 32 is more preferable if it consists of a quarter wave plate. In order to provide the phase difference layer 32, the laminated body 45 in which the polarizer 31 (this polarizer 1) and the phase difference layer 32 were laminated | stacked is prepared previously, and this laminated body 45 is board | substrate 33 It is good to join. The outline of the manufacturing method using this laminated body 45 is shown in FIG.

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

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

Next, members other than the polarizer of this EL display apparatus are demonstrated briefly.

As the board | substrate 33, Ceramic substrates, such as a sapphire glass substrate, a quartz glass substrate, a soda glass substrate, and alumina; Metal substrates such as copper; Plastic substrates; Although not shown, a thermal conductive film may be formed on the substrate 33. As a thermal conductive film, a diamond thin film (DLC etc.) etc. are mentioned. When the pixel electrode 35 is a reflective type, light is emitted in a direction opposite to the substrate 33. Therefore, not only a transparent material but also a non-transparent material, such as stainless, can be used. The substrate may be formed singly or may be formed as a laminated substrate by bonding a plurality of substrates with an adhesive. In addition, these board | substrates are not limited to being plate-shaped, A film may be sufficient.

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 its size is about 10 μm to 30 μm. The size of the pixel electrode 35 is about 20 μm × 20 μm to 300 μm × 300 μm.

Wiring electrodes of the thin film transistor 40 are provided on the substrate 33. The wiring electrode has a low resistance and has a function of electrically connecting with the pixel electrode 35 to suppress the resistance value. Generally, the wiring electrode includes Al, Al, and a transition metal (except Ti), Ti Or those containing any one or two or more of titanium nitride (TiN) are used.

An interlayer insulating film 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 inorganic materials such as silicon oxide and silicon nitride such as SiO ₂ , a silicon oxide layer formed of SOG (spin-on-glass), photoresist, polyimide, and As long as it has insulation, such as a coating film of resin materials, such as an acrylic resin, any may be sufficient.

The ribs 41 are formed on the interlayer insulating film 34. The rib 41 is disposed in the peripheral portion (between adjacent pixels) of the pixel electrode 35. As a material of the rib 41, an acrylic resin, a polyimide resin, etc. are mentioned. The thickness of the ribs 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, an EL element composed of a pixel electrode 35 serving as a transparent electrode, an organic functional layer 36 serving as a light emitting source, and a cathode electrode 37 will be described. The organic functional layer 36 has one or more hole transporting layers and light emitting layers, respectively, and has, for example, an electron injection transporting layer, a light emitting layer, a hole transporting layer and a hole injection layer sequentially.

Examples of the pixel electrode 35 include ITO (tin-doped indium oxide), IZO (zinc-doped indium oxide), IGZO, ZnO, SnO ₂ , In ₂ O ₃ , and the like, but ITO and IZO are particularly preferable. The thickness of the pixel electrode 35 should just have a thickness more than fixed which can fully perform hole injection, and it is preferable to set it as about 10 nm-500 nm.

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

As the constituent material of the cathode electrode 37, metal elements 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, it is preferable to use a two- or three-component alloy system selected from the illustrated 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 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 a function of disturbing electrons, and is also called a charge injection layer or a charge transport layer.

The thickness of the light emitting layer, the thickness of the hole injecting layer and the hole transporting layer, and the thickness of the electron injecting transporting layer are not particularly limited and vary depending on the forming method, but are preferably about 5 nm to 100 nm. Various organic compounds can be used for the hole injection layer and the hole transport layer. The vacuum evaporation method can be used for formation of a homogeneous thin film for formation of a hole injection transport layer, a light emitting layer, and an electron injection transport layer.

As the organic functional layer 36 as a light emitting source, it is possible to use light emission from the singlet excitons (fluorescence), to use light emission from the triplet excitons (phosphorescence), to use light emission from the singlet excitons (fluorescence) and to triplet. Comprising using light emission from phosphorus (phosphorescence), formed by organic matter, including those formed by organic matter and those formed by inorganic matter, comprising polymeric materials, low molecular materials, polymer materials and low molecular materials, and the like Can be used. However, the present invention is not limited to this, and the organic functional layer 36 using various known materials for the EL element can be used for the present EL display device 30.

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 in humidity. Moisture is absorbed by the desiccant 38 to prevent deterioration of the organic functional layer 36.

8 is a schematic view showing a cross-sectional structure of another embodiment of the EL display device 30. This EL display device 30 has an encapsulation structure using the thin film encapsulation film 41, and output light can also be obtained from the opposite side of the array substrate.

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

As mentioned above, the novel polarizer (this polarizer) which concerns on this invention, and the novel display apparatus (this liquid crystal display device and this EL display device) provided with this polarizer are provided.

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

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

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

The bundle of rays emitted from the light source (for example, a high-pressure mercury lamp) 111 that is a light emitting source is, first, the first lens array 112, the second lens array 113, the polarization converting element 114, and the overlapping lens 115. By passing through, uniformity and polarization of luminance in the half-ray bundle cross section 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. The second lens array 113 and the overlapping lens 115 are provided so that each of the divided light beam bundles irradiates all three liquid crystal panels 140R, 140G, and 140B to be illuminated, and therefore, each liquid crystal panel incident The side surface is almost uniform in roughness.

The polarization converting element 114 is constituted by a polarization beam splitter array and is disposed between the second lens array 113 and the overlapping lens 115. As a result, the random polarization from the light source is converted into a polarization having a specific polarization direction in advance, and a light amount loss in the incident-side polarizer to be described later is reduced to improve the brightness of the screen.

As described above, the light uniformed and polarized by the dichroic mirrors 121, 123, and 132 for separating the three primary colors of RGB via the reflection mirror 122 are sequentially red, green, They are separated into blue channels and are incident on the liquid crystal panels 140R, 140G, and 140B, respectively.

The polarizer film 142 of this invention is arrange | positioned at the incidence side, and the polarizer film 143 of this invention is respectively arrange | positioned at the liquid crystal panel 140R, 140G, 140B.

The polarizing film 142 and the polarizing film 143 arrange | positioned at each RGB optical path are arrange | positioned so that each absorption axis may orthogonally cross. Each liquid crystal panel 140R, 140G, 140B arrange | positioned at each optical path has a function which converts the polarization state controlled for every pixel by the image signal into the quantity of light.

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

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

Examples of electronic paper include those represented by molecules such as optical anisotropy and dye molecule orientation, those represented by particles such as electrophoresis, particle movement, particle rotation, and phase change, those represented by movement of one end of the film, molecules And those indicated by the color development / phase change of the molecules, those indicated by the light absorption of molecules, and those displayed by self-luminescence in combination with electrons and holes. More specifically, microcapsule type electrophoresis, horizontal moving type electrophoresis, vertical moving type electrophoresis, spherical twist ball, magnetic twist ball, circumferential twist ball method, charging toner, electropowder fluid, magnetophoretic type, magnetic thermosensitive type, electrophoresis Wetting (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 Chrominance, photochromic, electrochromic, electrodeposition, flexible organic EL, and the like. The electronic paper may be used not only for text and images individually but also for advertisement display (signage) and the like. According to the optical film of this invention, the thickness of an electronic paper can be made thin.

As the three-dimensional display device, a method of arranging different phase difference films alternately like the micropole method has been proposed (Japanese Patent Laid-Open No. 2002-185983). However, 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 a retardation film is unnecessary.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example are the mass% and a mass part, unless it mentions specially.

In the present Example, the following polymeric liquid crystal compound was used.

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

Compound (1-6) is described by Lub et al. Recl. Trav. Chim. Synthesis was carried out 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 finding the phase transition temperature of the film | membrane which consists of compound (1-6). The operation is as follows.

On the glass substrate in which the oriented film was formed, the film | membrane which consists of a compound (1-6) was formed, and the phase transition temperature was confirmed by the texture observation by a polarizing microscope (BX-51, Olympus company), heating. After heating up to 120 degreeC, the film | membrane of compound (1-6) phase-transforms into a nematic phase at 112 degreeC, phase-transforms into a Smematic A phase at 110 degreeC, and a Smetic B phase at 94 degreeC. It was confirmed that the phase change.

Compound (1-7) [Compound represented by the following general 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 similarly to the phase transition temperature measurement of compound (1-6). After heating up to 140 degreeC, the compound (1-7) phase-transforms into nematic phase at 133 degreeC, phase-transforms into the Smetic A phase at 118 degreeC, and phase-transforms to Smetic B phase at 78 degreeC. It was confirmed.

Example 1

[Preparation of Composition for Polarizing Layer Formation]

The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a composition for forming a polarizing layer.

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

50 parts of compound (1-7)

Dichroic dyes; Azo pigments (NKX2029; manufactured by Hayashibara Seibutsu Chemical Co., Ltd.) 2.5 parts

A polymerization initiator;

6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (a monocure 369; the Chiba Specialty Chemicals company make)

Leveling agents;

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

solvent; 250 parts cyclopentanone

[Measurement of Phase Transition Temperature]

As in the case of the compound (1-6) and the 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. After heating up to 120 degreeC, this polymeric liquid crystal composition phase-transformed into the nematic phase at 112 degreeC, phase-transformed to the Smematic A phase at 104 degreeC, and phase-transformed to the Smetic B phase at 78 degreeC. Confirmed.

[Production and Evaluation of This Polarizer]

1. Formation of alignment layer

A glass substrate was used as a transparent base material.

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

2. Formation of Polarizing Layer

After apply | coating the said composition for polarizing layer formation by the spin coat method on the orientation layer of the laminated body 1, and heat-drying for 3 minutes on a 120 degreeC hotplate, it is 70 degreeC rapidly (at the time of temperature drop, a smectic phase) It was cooled to below) to form a first dry film on the alignment layer. In this 1st dry film, the liquid crystal state of the polymeric liquid crystal compound contained was a Smetic B phase. Subsequently, this 1st drying is performed by irradiating an ultraviolet-ray to a 1st dry film by exposure amount 2400mJ / cm <2> (365 nm standard) using UV irradiation apparatus (SPOT CURE SP-7; Ushio Denki Co., Ltd. product). The polymerizable liquid crystal compound contained in the film was polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal composition, a polarizing layer was formed from the first dry film to obtain a laminate (2). It was 1.8 micrometers when the thickness of the polarizing layer at this time was measured with the laser microscope (OLS3000 by Olympus Corporation).

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 SPECTLESS Co., Ltd.). Using Cu as a target, determine the rubbing direction (preferably the rubbing direction of the alignment layer under the polarizing layer) through the fixed divergence slit 1/2 ° for the X-ray generated under the condition of 40 mA of X-ray tube current and 45 kV of X-ray tube voltage. ), And the measurement was performed by scanning in 2θ = 0.01671 ° steps in the scan range 2θ = 4.0 to 40.0 °, and as a result, a sharp diffraction peak having a peak half width (FWHM) of about 0.187 ° around 2θ = 20.22 ° Black peak). Moreover, the equivalent result was obtained also in incidence from the rubbing vertical direction. The order period (d) determined from the peak position was about 4.39 Hz, and it was found that a structure reflecting a higher order smectic phase was formed.

4. Production of the present polarizer by forming a protective layer

On the polarizing layer of the laminate 2, 50 parts of dipentaerythritol hexaacrylate (polyfunctional acrylate manufactured by Aronix M-403 Toagosei Co., Ltd.), acrylate resin (Ebecryl 4858 Daicel UCB Co., Ltd.) 50 parts, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholino propane- 1-one (Ilgacure 907; Chiba Specialty Chemicals Co., Ltd.) solution which melt | dissolved 3 parts of isopropanol 250 parts ( The protective layer-forming composition) was applied by a spin coat method and dried on a hot plate at 50 ° C. for 1 minute, followed by ultraviolet rays using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.). This light polarizer (henceforth "this polarizer A") was manufactured by irradiating at 400 mJ / cm <2> (365 nm reference | standard) of exposure amounts, and forming a protective layer on the said polarizing layer. It was 2.8 micrometers when the protective layer at this time was measured by the laser microscope (OLS3000 by Olympus Co., Ltd.).

5. Measurement of dichroic ratio

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

The absorbance of the transmission axis direction of the maximum absorption wavelength (A ¹⁾ and the absorbance (A ²⁾ of the absorption axis direction, and a spectrophotometer (Shimadzu manufactured by three directors kyusyo whether or producing UV-3150) set the the polarizer attached to the folder It measured by the double beam method using one apparatus. In this folder, the reference side provided a mesh which cuts the amount of light by 50%. The ratio A ² / A ¹ was calculated from the values of the measured absorbance A ¹ in the transmission axis direction and the absorbance A ^{2 in the} absorption axis direction to be a dichroic ratio. The results are shown in the 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 ratios.

Example 2

The same experiment as in Example 1 was carried out except that the dichroic dye was changed from an azo dye (NKX2029; manufactured by Hayashibara Seibutsu Chemical Co., Ltd.) to an azo dye (G205; manufactured by Hayashibara Seibutsu Chemical Co., Ltd.). This polarizer B ") was manufactured. The phase transition behavior of the polymerizable liquid crystal composition at this time is elevated to 120 ° C., and then, when the temperature is lowered, phase transitions to a nematic phase at 112 ° C., phase transition to a Smetic A phase at 105 ° C., and Smetic B at 77 ° C. It was confirmed that the phase change to phase. Table 1 shows the dichroic ratio measurement results of the obtained present polarizer.

Example 3

Except having changed the solvent contained in the composition for protective layer formation into isopropanol from ethanol, the same experiment as Example 1 was performed and the present polarizer (henceforth "this polarizer C") was manufactured. Table 1 shows the dichroic ratio measurement results of the produced polarizers.

Example 4

The same experiment as in Example 1 was carried out except that the solvent contained in the protective layer-forming composition was changed from isopropanol to propylene glycol monomethyl ether acetate to prepare a present polarizer (hereinafter referred to as "the present polarizer D"). Table 1 shows the dichroic ratio measurement results of the produced polarizers.

Example 5

Except having changed the solvent contained in the composition for protective layer formation into propylene glycol monomethyl ether from isopropanol, the same experiment as Example 1 was performed and the present polarizer (henceforth "this polarizer E") was manufactured. Table 1 shows the dichroic ratio measurement results of the produced polarizers.

Example 6

On the protective layer of this polarizer A obtained in Example 1, the TAC (triacetylcellulose) film was bonded through the adhesion layer formed of pressure-sensitive adhesive (PSA). The dichroic ratio measurement result of the structure (henceforth "this polarizer A + TAC") obtained in this way is shown in Table 1. FIG.

Example 7

On the protective layer of this polarizer B obtained in Example 2, the TAC (triacetylcellulose) film was bonded through the adhesion layer formed of pressure-sensitive adhesive (PSA). The dichroic ratio measurement result of the structure (henceforth "this polarizer B + TAC") obtained in this way is shown in Table 1. FIG.

Example 8

10 mass% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, the Wako Pure Chemical Industries, Ltd. make) was activated by performing a corona treatment on the polarizing layer produced like Example 1 The present polarizer (hereinafter, referred to as "the present polarizer F") was produced by forming a protective layer on this polarizing layer by apply | coating by the spin coat method and heat-drying for 1 minute on 80 degreeC hotplate. Table 1 shows the dichroic ratio measurement results of the produced polarizers.

Example 9

On the polarizing layer produced in the same manner as in Example 1, the surface was activated by corona treatment, and a solution (UCECOAT7655, manufactured by Daicel Cytec Co., Ltd.) in which an aliphatic urethane acrylate resin was dispersed was subjected to spin coating. The present polarizer (hereinafter, referred to as "the present polarizer G") was produced by forming a protective layer on this polarizing layer by apply | coating and heat-drying for 1 minute on a 60 degreeC hotplate. Table 1 shows the dichroic ratio measurement results of the produced polarizers.

Example 10

On the protective layer of this polarizer A obtained in Example 8, the TAC (triacetylcellulose) film was bonded through the adhesion layer formed of pressure-sensitive adhesive (PSA). The dichroic ratio measurement result of the structure (henceforth "this polarizer F + TAC") obtained in this way is shown in Table 1. FIG.

Example 11

On the protective layer of this polarizer A obtained in Example 9, the TAC (triacetylcellulose) film was bonded through the adhesion layer formed of pressure-sensitive adhesive (PSA). The dichroic ratio measurement result of the structure (henceforth "this polarizer G + TAC") obtained in this way is shown in Table 1. FIG.

(※)

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-varying test was performed.

The present polarizer obtained in Examples 1 to 2 and the structure obtained in Examples 6 to 7 and 10 (main polarizer A + TAC, main polarizer B + TAC or main polarizer F + TAC) were manufactured using a Hitachi thermostat (brand name: EC-15HHP, Hitachi Kucho System Co., Ltd. (Condition: Dry bulb temperature 60 ° C humidity 90% RH, or 85 ° C humidity 0%), and absorbance after 100 hours was measured to determine the dichroic ratio. In this manner, the dichroic ratio is measured again after 100 hours, and the case where the initial dichroic ratio and the dichroic ratio after elapse is hardly changed to "g" (good) and deteriorates to "b" (bad). 2 levels were determined. The results are shown in Table 2.

2. Solvent test

When using this polarizer in a liquid crystal cell, ie, using it for the in-cell type liquid crystal display device, it is necessary to provide a PI (polyimide) aligning film on the protective layer of this polarizer. NMP (N-methyl-2-pyrrolidone) solution is used for this PI alignment film formation in many cases. That is, this polarizer requires solvent resistance to NMP. Therefore, after NMP was dripped on the surface of these protective layers, and hold | maintained for 5 minutes, it wiped and evaluated whether the protective layer melt | dissolved. The evaluation result determined the case where dissolution by NMP was not seen as "g" (good) and when the dissolution by NMP was seen as 2 levels of "b" (bad). The results are 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 (this polarizer) of this invention
2: transparent substrate
3: alignment layer
4: polarizing 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: phase difference layer
33: substrate
34: interlayer insulation 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: reflective mirror
140R, 140G, 140B: Liquid Crystal Panel
142 and 143: polarizing film
150: cross dichroic prism
170: projection lens
180: screen

Claims (18)

On a transparent base material, an orientation layer, a polarizing layer, and a protective layer are polarizers installed in this order,
The polarizing layer,
Forming a film from a composition containing a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent;
Removing the solvent from the membrane;
Making the polymeric liquid crystal compound contained in the film | membrane remove | excluding the said solvent into a smect liquid crystal state,
The polarizer manufactured by the manufacturing method containing the process of superposing | polymerizing, maintaining the said polymeric liquid crystal compound in the said liquid crystal liquid state. The polarizer of Claim 1 whose said polarizing layer is a polarizing layer from which a black peak is obtained in X-ray diffraction measurement. The polarizer of Claim 1 or 2 whose thickness of the said polarizing layer is the range of 0.5 micrometer-3 micrometers. The polarizer according to any one of claims 1 to 3, wherein the dichroic dye is an azo dye. The polarizer of any one of Claims 1-4 in which the said polymerizable liquid crystal compound contains 2 or more types of polymerizable smectic liquid crystal compounds. The polarizer according to any one of claims 1 to 5, wherein the protective layer is formed from a protective layer composition containing a polyfunctional acrylate and a solvent, and the solvent substantially consists of an alcohol solvent and / or an ether solvent. The polarizer according to any one of claims 1 to 5, wherein the protective layer is formed from a protective layer-forming composition containing water or a polymer or oligomer obtained by polymerizing a polyfunctional acrylate. The polarizer according to any one of claims 1 to 5, wherein the protective layer is formed from a protective layer-forming composition containing a water-soluble polymer and water. The liquid crystal display device provided with the polarizer of any one of Claims 1-8. The liquid crystal display device according to claim 9, wherein the polarizer is disposed inside a liquid crystal cell. The circularly polarizing plate which provided the 1/4 wavelength plate on the said protective layer of the polarizer of any one of Claims 1-8. 12. The circular polarizing plate according to claim 11, wherein the quarter wave plate is a wave plate having characteristics in which the in-plane retardation value with respect to visible light decreases as the wavelength becomes shorter. The organic electroluminescence display provided with the circularly-polarizing plate of Claim 11 or 12, and organic electroluminescent element. A step (1) of forming an laminated layer by forming an alignment layer on a transparent substrate,
Process (2) which apply | coats the composition containing a polymeric liquid crystal compound, a dichroic dye, and a polymerization initiator on the said orientation layer of the said laminated board, and forms a 1st coating film on the said orientation layer,
A 1st dry film is formed by drying the said 1st coating film formed in the said process (2) on condition that the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize, and the said superposition | polymerization in this 1st dry film Step (3) of forming a polarizing layer from the said 1st dry film by polymerizing the said polymeric liquid crystal compound, after making a crystalline liquid crystal compound into a smect liquid crystal state, and maintaining this smect liquid crystal state,
The protective layer composition containing a polyfunctional acrylate and a solvent is apply | coated on the said polarizing layer formed at the said process (3), the 2nd coating film is formed on the said polarizing layer, and the said containing in this 2nd coating film Process of forming protective layer from said 2nd coating film by polymerizing polyfunctional acrylate (4)
Method of manufacturing a polarizer comprising a. The manufacturing method of the polarizer of Claim 14 in which the solvent contained in the said protective layer composition contains an alcohol solvent and / or an ether solvent. A step (1) of forming an laminated layer by forming an alignment layer on a transparent substrate,
Process (2) which apply | coats the composition containing a polymeric liquid crystal compound, a dichroic dye, and a polymerization initiator on the said orientation layer of the said laminated board, and forms a 1st coating film on the said orientation layer,
A 1st dry film is formed by drying the said 1st coating film formed in the said process (2) on condition that the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize, and the said superposition | polymerization in this 1st dry film Step (3) of forming a polarizing layer from the said 1st dry film by polymerizing the said polymeric liquid crystal compound, after making a crystalline liquid crystal compound into a smect liquid crystal state, and maintaining this smect liquid crystal state,
On the said polarizing layer formed in the said process (3), the composition for protective layer formation containing the polymer or oligomer obtained by superposing | polymerizing a polyfunctional acrylate, and water is apply | coated, and a 2nd coating film is formed on the said polarizing layer, Process of forming a protective layer from this 2nd coating film by drying this 2nd coating film (4)
Method of manufacturing a polarizer comprising a. A step (1) of forming an laminated layer by forming an alignment layer on a transparent substrate,
Process (2) which apply | coats the composition containing a polymeric liquid crystal compound, a dichroic dye, and a polymerization initiator on the said orientation layer of the said laminated board, and forms a 1st coating film on the said orientation layer,
The 1st dry film is formed by drying the said 1st coating film formed at the said process (2) on the conditions which the said polymeric liquid crystal compound contained in this 1st coating film does not superpose | polymerize, and this polymerization in this 1st dry film Step (3) of forming a polarizing layer from this 1st dry film by polymerizing the said polymerizable liquid crystal compound, after making a crystalline liquid crystal compound into a smect liquid crystal state, and maintaining this smect liquid crystal state,
By apply | coating the composition for protective layer formation containing a water-soluble polymer and water on the said polarizing layer formed at the said process (3), forming a 2nd coating film on the said polarizing layer, and drying this 2nd coating film, Process of forming protective layer from 2nd coating film (4)
Method of manufacturing a polarizer comprising a. The polarizer manufactured by the manufacturing method in any one of Claims 14-17.

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