JP4404606B2 - Polarizer, manufacturing method thereof, optical film, and image display device - Google Patents

Description

  The present invention relates to a polarizer and a method for manufacturing the same. The present invention also relates to a polarizing plate and an optical film using the polarizer. Further, the present invention relates to an image display device such as a polarizing plate, a liquid crystal display device using an optical film, an organic EL display device, a CRT, or a PDP.

  As the polarizer, for example, an iodine-based polarizer obtained by staining polyvinyl alcohol with iodine and having a high transmittance and a high degree of polarization is widely used. However, iodine-based polarizers are excellent in initial performance such as polarization degree and transmittance, but are not sufficient in heat resistance and moisture resistance.

  Also known is a dye-based polarizer obtained by dyeing polyvinyl alcohol with a dichroic dye and stretching it. The dye-based polarizer is superior in heat resistance and moisture resistance to the iodine-based polarizer. However, since the dichroic dye has a lower absorption dichroic ratio than the iodine compound, the dye-based polarizer is inferior in initial performance to the iodine-based polarizer. Therefore, if a dichroic dye can be highly oriented in a dye-based polarizer, an excellent polarizer can be produced.

As a polarizer in which a dichroic dye is aligned, a film obtained by aligning and curing a mixture of a dichroic dye and a curable liquid crystal on a rubbing-treated surface of a substrate (Patent Document 1), a polymerizable dichroic dye An anisotropic film (Patent Document 2) or the like is known in which a copolymer is formed with other polymerizable monomers while maintaining the orientation. However, the dichroic ratio of the polarizer described in the above patent document is not sufficient.
Japanese Patent Laid-Open No. 2001-330726 Japanese Patent Laid-Open No. 2001-133630

  An object of the present invention is to provide a polarizer having a high dichroic ratio using a dichroic dye and a method for producing the same.

  Another object of the present invention is to provide a polarizing plate and an optical film using the polarizer. Furthermore, it aims at providing the image display apparatus using the said polarizer, a polarizing plate, and an optical film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the object can be achieved by the following polarizer and the production method thereof, and have completed the present invention.

That is, the present invention relates to a polarizer having an alignment layer formed using an azo liquid crystalline dichroic dye , wherein the azo liquid crystalline dichroic dye is aligned as a hexatic phase or a crystal phase. and, and, the liquid crystalline dichroic dye, the temperature lowering process in the measurement of differential scanning calorimetry state, and are not not seen crystal transition peak,
The polarizer has the following characteristics (a) and (b):
(A) obtaining at least one diffraction peak in X-ray reflection measurement;
(B) that a Bragg peak is obtained in the X-ray reflectivity measurement;
The present invention relates to a polarizer characterized by comprising:

The polarizer has the following characteristics (a) and / or (b):
(A) obtaining at least one diffraction peak in X-ray reflection measurement;
(B) It is preferable that a Bragg peak is obtained in the X-ray reflectivity measurement.

  The present invention also relates to a polarizing plate in which a transparent protective layer is provided on at least one surface of the polarizer. The present invention also relates to an optical film, wherein at least one of the polarizer and the polarizing plate is laminated. Furthermore, this invention relates to the image display apparatus characterized by using the said polarizer, the said polarizing plate, or the said optical film.

  The polarizer of the present invention has an alignment layer formed with a liquid crystalline dichroic dye, and has a higher order alignment layer than an alignment layer formed with a mixture of a liquid crystal material and a dichroic dye. Can be formed. Moreover, since the polarizer of the present invention is formed of a liquid crystalline dichroic dye, it does not require a stretching operation and is advantageous in production. Further, it is advantageous for reducing the thickness of the alignment layer. Moreover, since it can form directly on a base material, it is not necessary to use an adhesive. Further, the heat shrinkage is smaller than that of a polyvinyl alcohol polarizer. Such a polarizer of the present invention can be arranged, for example, outside or inside a liquid crystal cell substrate in a liquid crystal display device.

  Further, the liquid crystalline dichroic dye used in the polarizer of the present invention does not show a crystal transition peak in the temperature decreasing process in the measurement of the differential scanning calorific value, among the dichroic dyes exhibiting liquid crystallinity. Since such a liquid crystalline dichroic dye does not show a crystal transition peak, the alignment is maintained at a high order even when the alignment is fixed by cooling at a temperature showing a liquid crystal state and then cooling. Can do. Therefore, a polarizer having a high dichroic ratio in which liquid crystalline dichroic dyes are aligned in a high order is obtained. The liquid crystalline dichroic dye has a very high dichroic ratio having an order in the film thickness direction while being -axially oriented after orientation and cooling.

  The polarizer usually has the characteristics (a) and / or the characteristics (b). Characteristic (a) indicates that there is order in the film thickness direction, and characteristic (b) indicates that there is order in the film thickness direction and that the period of the order clearly exists. From the above, it is recognized that those having the characteristics (a) and / or the characteristics (b) are highly ordered.

  In the polarizer of the present invention, it is preferable that the liquid crystalline dichroic dye has a higher alignment order than the smectic phase, that is, a hexatic phase or a crystal phase (that is, a plastic crystal). Crystal phase (plastic crystal phase) includes crystal B phase, crystal E phase in which molecules are perpendicular to the interlayer ordered plane, crystal G phase, crystal H phase, and crystal J phase in which the molecules are inclined with respect to the interlayer ordered plane. Any of crystal K phase may be used.

  The polarizer of the present invention has an alignment layer formed using a liquid crystalline dichroic dye in which no crystal transition peak is observed in the temperature lowering process in the measurement of differential scanning calorimetry. The measurement of the differential scanning calorific value of the liquid crystalline dichroic dye is performed in detail by the method described in the examples. Examples of the liquid crystalline dichroic dye having the above characteristics include LSR-406 manufactured by Mitsubishi Chemical Corporation, which is an azo liquid crystalline dichroic dye. The phase transition temperature is measured by observation with a polarizing microscope using a hot stage and DSC (differential scanning calorimeter) measurement.

  As the liquid crystalline dichroic dye, those having a polymerizable functional group can be used. When the liquid crystalline dichroic dye has a polymerizable functional group, the durability can be improved by a curing treatment after cooling. Examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group, an epoxy group, and a vinyl ether group. Curing of the polymerizable functional group can be performed by irradiating actinic rays such as ultraviolet rays or electron beams. When ultraviolet rays are used, a photopolymerization initiator is blended. In the case of an electron beam, no initiator is required. The photoinitiator is not particularly limited as long as it does not absorb in the visible light region after curing, and a general-purpose photoinitiator can be used. As the photopolymerization initiator, when the polymerizable functional group is a (meth) acryloyl group, for example, Irgacure 907, 184, 651, 369, 819, etc. manufactured by Ciba Specialty Chemicals, etc. Can be illustrated. When the polymerizable functional group is an epoxy group or a vinyl ether group, a photocationic initiator is used. The addition amount of the photopolymerization initiator is added to such an extent that the orientation of the liquid crystalline dichroic dye is not disturbed. Usually, about 0.5-30 weight part is preferable with respect to 100 weight part of liquid crystalline dichroic dye, and 1-10 weight part is especially preferable.

  In forming the alignment layer, other dichroic dyes can be used in combination with the liquid crystalline dichroic dye as required.

  The polarizer of the present invention is performed by orienting the material containing the liquid crystalline dichroic dye at a temperature at which the liquid crystalline dichroic dye exhibits a liquid crystal state, and then cooling to fix the orientation. be able to.

  The alignment of the material containing the liquid crystalline dichroic dye is performed by applying the above to a substrate on which an alignment film is formed, if desired, and heating to a temperature at which the liquid crystalline dichroic dye exhibits a liquid crystal state.

  Examples of the substrate include a glass plate, a sheet-like or film-like plastic substrate, and the like. The thickness of the substrate is usually about 10 to 1000 μm.

  The plastic substrate is not particularly limited as long as it does not change depending on the formation temperature of the alignment film to be formed. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, and cellulose polymers such as diacetyl cellulose and triacetyl cellulose. , Polycarbonate polymers, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene and acrylonitrile / styrene copolymers, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and olefins such as ethylene / propylene copolymers Polymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyethersulfurs Transparent polymers such as vinyl polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, acrylate polymers, polyoxymethylene polymers, epoxy polymers, etc. Examples thereof include a film made of a polymer blend.

  Of the plastic substrates, a plastic film made of a polymer having a triacetyl cellulose or norbornene structure has excellent optical characteristics. Specific examples of the polymer having a norbornene structure include ZEONOR (trade name, manufactured by ZEON CORPORATION), ZEONEX (trade name, manufactured by ZEON CORPORATION), Arton (trade name, manufactured by JSR Corporation). Is exemplified. Since these have very small optical anisotropy, the alignment layer formed by the liquid crystalline dichroic dye formed thereon is used as it is for a liquid crystal display device as a polarizer without being transferred to another plastic substrate. be able to.

  In the case of forming an alignment layer with the liquid crystalline dichroic dye on a plastic substrate or an opaque substrate having optical anisotropy, a film having a triacetyl cellulose or norbornene structure after the formation of the alignment layer, etc. The alignment layer can be transferred directly onto a transparent plastic substrate having a small optical anisotropy or via an adhesive or an adhesive and used as a polarizer.

When a plastic substrate having a small optical anisotropy is used, a substrate in which an alignment film is formed on the substrate is used. Examples of alignment films include those obtained by rubbing a polymer thin film such as polyvinyl alcohol and polyimide, those obtained by obliquely depositing SiO _x or In ₂ O ₃ / SnO ₂ , and thin films such as polytetrafluoroethylene formed by a friction transfer method. Various alignment films such as a photo-alignment film are preferably used. A material containing a liquid crystalline dichroic dye is applied onto the alignment film to form an alignment layer. Note that when a substrate having a large optical anisotropy is used, it is not particularly necessary to form an alignment film on the substrate.

  As a method for coating the material containing the liquid crystalline dichroic dye on the substrate, a solution coating method using a solution in which the material is dissolved in a solvent or a melt coating method by melting the material at a liquid crystal temperature or higher. The method of crafting is raised. Among these, the method of coating a solution on a substrate by a solution coating method is preferable.

  The solvent used in preparing the solution varies depending on the type of liquid crystalline dichroic dye, alignment film, and substrate, and cannot be determined unconditionally. Halogenated hydrocarbons such as chlorobenzene; phenols such as phenol and parachlorophenol; aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, 1,2-dimethoxybenzene; other, acetone, ethyl acetate, tert-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, 2-pyrrole Emissions, N- methyl-2-pyrrolidone, pyridine, triethylamine, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, can be used acetonitrile, butyronitrile, carbon disulfide and the like. The concentration of the solution depends on the solubility of the liquid crystal dichroic dye used and the thickness of the alignment layer of the final liquid crystal dichroic dye. % By weight, preferably 0.5 to 20% by weight.

  The thickness of the alignment layer formed by the liquid crystalline dichroic dye is selected so that the single transmittance is 30% or more. If the thickness of the alignment layer is too thick, the alignment order and transmittance will decrease, and if it is too thin, the degree of polarization will decrease. Specifically, 0.05 μm to 5 μm, preferably 0.1 μm to 2 μm is desirable. In addition, if there is variation in the thickness of the alignment layer, the optical characteristics as a polarizer vary, so it is desirable to apply as uniformly as possible.

  As a method for applying a solution prepared by adjusting the above material to a desired concentration using the above-mentioned solvent on a substrate, for example, a spin coating method, a bar coating method, a gravure coating method, a lip coating method, or the like can be employed. . After coating, the solvent is removed, and a layer containing a liquid crystalline dichroic dye is formed on the substrate. The conditions for removing the solvent are not particularly limited, as long as the solvent can be removed generally and the layer having the liquid crystalline dichroic dye does not flow or flow down. Usually, the solvent is removed by drying at room temperature, drying in a drying furnace, heating on a hot plate, or the like.

  Next, the layer having the liquid crystalline dichroic dye formed on the substrate is heated to be aligned in a liquid crystal state. As a heating method, it can carry out by the method similar to said drying method. The heat treatment temperature varies depending on the liquid crystalline dichroic dye to be used and the type of the substrate, and thus cannot be determined unconditionally, but is usually in the range of about 60 to 300 ° C, preferably 70 to 200 ° C. Further, the heating time varies depending on the heating temperature and the type of liquid crystalline dichroic dye to be used and the substrate and cannot be determined unconditionally. However, it is usually selected in the range of about 5 seconds to 1 hour, preferably 10 seconds to 10 minutes. When it is shorter than 5 seconds, there is a possibility that the layer having the liquid crystalline dichroic dye does not sufficiently transition to the liquid crystal state.

  After the heating, it is cooled to fix the orientation of the liquid crystalline dichroic dye. If the cooling rate at the time of cooling is too slow, fine crystals may be deposited and the dichroic ratio may be lowered. Therefore, the cooling rate is preferably 1 ° C./second or more. The cooling rate is preferably 5 ° C./second or more, more preferably 10 ° C./second or more. As the cooling means, forced cooling such as air cooling or water cooling is preferably used. Note that there is no particular problem if the cooling rate is too high. The cooling rate can be controlled by the cooling capacity of the apparatus.

When the liquid crystalline dichroic dye has a polymerizable functional group, it is then irradiated with actinic rays. The ultraviolet irradiation conditions are preferably in an inert gas atmosphere in order to sufficiently promote the reaction. Usually, a high-pressure mercury ultraviolet lamp having an illuminance of 80 to 160 mW / cm ² is typically used. Different types of lamps such as metahalide UV lamps and incandescent tubes can also be used. In order to prevent the surface temperature of the dichroic dye layer from being increased when irradiated with ultraviolet rays, the temperature is adjusted as appropriate by, for example, a cold mirror, water cooling or other cooling treatment, or increasing the line speed. The electron beam irradiation is desirably performed in an inert gas atmosphere. As for the irradiation amount, if the amount is too small, sufficient crosslinking does not proceed and the heat resistance may be inferior. If the amount is too large, the dichroic dye or the substrate may be destroyed, which is not preferable from the viewpoint of quality. Therefore, although it differs depending on the system, irradiation of 1 to 200 Mrad / cm ² is preferable.

  In order to protect the alignment layer formed of the liquid crystalline dichroic dye, the alignment layer can be overcoated in the heating step, the cooling step, and the like. The overcoat resin is not particularly limited as long as it does not disturb the orientation of the orientation layer.

  The alignment layer formed with the liquid crystalline dichroic dye thus obtained is used as a polarizer. The alignment layer formed of the liquid crystalline dichroic dye may be peeled off from the substrate, or may be used as it is as an alignment layer formed on the substrate without being peeled off.

  Since the polarizer obtained by the present invention has the same function as an existing absorption polarizing plate, it can be used without any change to various application fields using the absorption polarizing plate.

  The obtained polarizer can be made into a polarizing plate provided with a transparent protective layer on at least one surface thereof according to a conventional method. The transparent protective layer can be provided as a polymer coating layer, a film laminate layer, or the like. As the transparent polymer or film material for forming the transparent protective layer, an appropriate transparent material can be used, but a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property and the like is preferably used. Examples of the material for forming the transparent protective layer include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as cellulose diacetate and cellulose triacetate, acrylic polymers such as polymethyl methacrylate, polystyrene, acrylonitrile, Examples thereof include styrene polymers such as styrene copolymers (AS resins), polycarbonate polymers, and the like. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Polymer blends and the like are also examples of the polymer that forms the transparent protective layer.

  Moreover, the polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, and (B) a substitution in the side chain And / or a resin composition containing an unsubstituted phenyl and a thermoplastic resin having a nitrile group. A specific example is a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of the resin composition or the like can be used.

  The transparent protective layer that can be particularly preferably used in terms of polarization characteristics and durability is a triacetyl cellulose film whose surface is saponified with alkali or the like. The thickness of the transparent protective layer is arbitrary, but is generally 500 μm or less, more preferably 1 to 300 μm, and particularly preferably 5 to 300 μm for the purpose of reducing the thickness of the polarizing plate. In addition, when providing a transparent protective layer on both sides of a polarizer, the transparent protective film which consists of a polymer etc. which are different in the front and back can be used.

  Moreover, it is preferable that a transparent protective film has as little color as possible. Therefore, Rth = [(nx + ny) / 2−nz] · d (where nx and ny are the main refractive index in the plane of the film, nz is the refractive index in the film thickness direction, and d is the film thickness). A protective film having a retardation value in the film thickness direction of −90 nm to +75 nm is preferably used. By using a film having a thickness direction retardation value (Rth) of −90 nm to +75 nm, the coloring (optical coloring) of the polarizing plate caused by the protective film can be almost eliminated. The thickness direction retardation value (Rth) is more preferably −80 nm to +60 nm, and particularly preferably −70 nm to +45 nm.

  The surface of the transparent protective film to which the polarizer is not adhered may be subjected to a hard coat layer, an antireflection treatment, an antisticking treatment, or a treatment for diffusion or antiglare.

  The hard coat treatment is applied for the purpose of preventing scratches on the surface of the polarizing plate. For example, a transparent protective film with a cured film excellent in hardness, sliding properties, etc. by an appropriate ultraviolet curable resin such as acrylic or silicone is used. It can be formed by a method of adding to the surface of the film. The antireflection treatment is performed for the purpose of preventing reflection of external light on the surface of the polarizing plate, and can be achieved by forming an antireflection film or the like according to the conventional art. Further, the anti-sticking treatment is performed for the purpose of preventing adhesion with an adjacent layer.

  The anti-glare treatment is applied for the purpose of preventing the outside light from being reflected on the surface of the polarizing plate and obstructing the visibility of the light transmitted through the polarizing plate. For example, the surface is roughened by a sandblasting method or an embossing method. It can be formed by imparting a fine concavo-convex structure to the surface of the transparent protective film by an appropriate method such as a blending method of transparent particles. The fine particles to be included in the formation of the surface fine concavo-convex structure are, for example, conductive materials made of silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide or the like having an average particle size of 0.5 to 50 μm. In some cases, transparent fine particles such as inorganic fine particles, organic fine particles composed of a crosslinked or uncrosslinked polymer, and the like are used. When forming a surface fine uneven structure, the amount of fine particles used is generally about 2 to 50 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the transparent resin forming the surface fine uneven structure. The antiglare layer may also serve as a diffusion layer (viewing angle expanding function or the like) for diffusing the light transmitted through the polarizing plate to expand the viewing angle.

  The antireflection layer, antisticking layer, diffusing layer, antiglare layer and the like can be provided on the transparent protective film itself, or can be provided separately from the transparent protective layer as an optical layer.

  An adhesive is used for the adhesion treatment between the polarizer and the transparent protective film. Examples of the adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, and water-based polyesters. The said adhesive agent is normally used as an adhesive agent which consists of aqueous solution, and contains 0.5 to 60 weight% of solid content normally.

  The polarizing plate of the present invention is produced by bonding the transparent protective film and the polarizer using the adhesive. The adhesive may be applied to either the transparent protective film or the polarizer, or to both. After bonding, a drying step is performed to form an adhesive layer composed of a coating dry layer. Bonding of a polarizer and a transparent protective film can be performed with a roll laminator or the like. The thickness of the adhesive layer is not particularly limited, but is usually about 0.1 to 5 μm.

  The polarizing plate of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a phase difference plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or more optical layers that may be used can be used. In particular, a reflective polarizing plate or a semi-transmissive polarizing plate in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing plate of the present invention, an elliptical polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on the polarizing plate. A wide viewing angle polarizing plate obtained by further laminating a viewing angle compensation film on a plate or a polarizing plate, or a polarizing plate obtained by further laminating a brightness enhancement film on the polarizing plate is preferable.

  A reflective polarizing plate is a polarizing plate provided with a reflective layer, and is used to form a liquid crystal display device or the like that reflects incident light from the viewing side (display side). Such a light source can be omitted, and the liquid crystal display device can be easily thinned. The reflective polarizing plate can be formed by an appropriate method such as a method in which a reflective layer made of metal or the like is attached to one surface of the polarizing plate via a transparent protective layer or the like as necessary.

  Specific examples of the reflective polarizing plate include those in which a reflective layer is formed by attaching a foil or a vapor deposition film made of a reflective metal such as aluminum on one side of a transparent protective film matted as necessary. Moreover, the transparent protective film contains fine particles so as to have a surface fine concavo-convex structure and a reflective layer having a fine concavo-convex structure thereon. The reflective layer having the fine concavo-convex structure has an advantage that incident light is diffused by irregular reflection to prevent directivity and glaring appearance and to suppress unevenness in brightness and darkness. The transparent protective film containing fine particles also has an advantage that incident light and its reflected light are diffused when passing through it, and light and dark unevenness can be further suppressed. The reflective layer of the fine concavo-convex structure reflecting the surface fine concavo-convex structure of the transparent protective film is formed by transparent the metal by an appropriate method such as a vapor deposition method such as a vacuum vapor deposition method, an ion plating method, a sputtering method, or a plating method. It can be performed by a method of directly attaching to the surface of the protective layer.

  Instead of the method of directly applying the reflecting plate to the transparent protective film of the polarizing plate, the reflecting plate can be used as a reflecting sheet provided with a reflecting layer on an appropriate film according to the transparent film. Since the reflective layer is usually made of metal, the usage form in which the reflective surface is covered with a transparent protective film, a polarizing plate or the like is used to prevent the reflectance from being lowered due to oxidation, and thus to maintain the initial reflectance for a long time. In addition, it is more preferable to avoid a separate attachment of the protective layer.

  The semi-transmissive polarizing plate can be obtained by using a semi-transmissive reflective layer such as a half mirror that reflects and transmits light with the reflective layer. A transflective polarizing plate is usually provided on the back side of a liquid crystal cell, and displays an image by reflecting incident light from the viewing side (display side) when a liquid crystal display device is used in a relatively bright atmosphere. In a relatively dark atmosphere, a liquid crystal display device or the like that displays an image using a built-in light source such as a backlight built in the back side of the transflective polarizing plate can be formed. In other words, the transflective polarizing plate is useful for forming a liquid crystal display device of a type that can save energy of using a light source such as a backlight in a bright atmosphere and can be used with a built-in light source even in a relatively dark atmosphere. It is.

  An elliptically polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on a polarizing plate will be described. A phase difference plate or the like is used when changing linearly polarized light to elliptically polarized light or circularly polarized light, changing elliptically polarized light or circularly polarized light to linearly polarized light, or changing the polarization direction of linearly polarized light. In particular, a so-called 1/4 wavelength plate (also referred to as a λ / 4 plate) is used as a retardation plate that changes linearly polarized light into circularly polarized light or changes circularly polarized light into linearly polarized light. A 1/2 wave plate (also referred to as a λ / 2 plate) is usually used to change the polarization direction of linearly polarized light.

  The elliptically polarizing plate is effectively used for black and white display without the above color by compensating (preventing) the coloration (blue or yellow) generated by the birefringence of the liquid crystal layer of the super twist nematic (STN) type liquid crystal display device. It is done. Further, the one in which the three-dimensional refractive index is controlled is preferable because it can compensate (prevent) coloring that occurs when the screen of the liquid crystal display device is viewed from an oblique direction. The circularly polarizing plate is effectively used, for example, when adjusting the color tone of an image of a reflective liquid crystal display device in which an image is displayed in color, and also has an antireflection function. Specific examples of the retardation plate include a birefringent film obtained by stretching a film made of an appropriate polymer such as polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene, other polyolefins, polyarylate, and polyamide. And an alignment film of a liquid crystal polymer, and an alignment layer of a liquid crystal polymer supported by a film. The retardation plate may have an appropriate retardation according to the purpose of use, such as those for the purpose of compensating for various wavelength plates or birefringence of liquid crystal layers, compensation of viewing angle, and the like. What laminated | stacked a phase difference plate and controlled optical characteristics, such as phase difference, etc. may be used.

  The elliptical polarizing plate and the reflective elliptical polarizing plate are obtained by laminating a polarizing plate or a reflective polarizing plate and a retardation plate in an appropriate combination. Such an elliptically polarizing plate or the like can also be formed by sequentially laminating them sequentially in the manufacturing process of the liquid crystal display device so as to be a combination of a (reflective) polarizing plate and a retardation plate. An optical film such as a polarizing plate has an advantage that it can improve the production efficiency of a liquid crystal display device and the like because of excellent quality stability and lamination workability.

  The viewing angle compensation film is a film for widening the viewing angle so that an image can be seen relatively clearly even when the screen of the liquid crystal display device is viewed from a slightly oblique direction rather than perpendicular to the screen. As such a viewing angle compensation phase difference plate, for example, a retardation film, an alignment film such as a liquid crystal polymer, or an alignment layer such as a liquid crystal polymer supported on a transparent substrate is used. A normal retardation plate uses a birefringent polymer film uniaxially stretched in the plane direction, whereas a retardation plate used as a viewing angle compensation film stretches biaxially in the plane direction. Birefringent polymer film, biaxially stretched film such as polymer with birefringence with a controlled refractive index in the thickness direction that is uniaxially stretched in the plane direction and stretched in the thickness direction, etc. Used. Examples of the inclined alignment film include a film obtained by bonding a heat shrink film to a polymer film and stretching or / and shrinking the polymer film under the action of the contraction force by heating, and a film obtained by obliquely aligning a liquid crystal polymer. Can be mentioned. The raw material polymer for the phase difference plate is the same as the polymer described in the previous phase difference plate, preventing coloration due to a change in the viewing angle based on the phase difference by the liquid crystal cell and expanding the viewing angle for good visual recognition. An appropriate one for the purpose can be used.

  In addition, from the viewpoint of achieving a wide viewing angle with good visibility, an optically compensated phase difference in which an optically anisotropic layer composed of a liquid crystal polymer alignment layer, particularly a discotic liquid crystal polymer gradient alignment layer, is supported by a triacetylcellulose film. A plate can be preferably used.

  A polarizing plate obtained by bonding a polarizing plate and a brightness enhancement film is usually provided on the back side of a liquid crystal cell. The brightness enhancement film reflects a linearly polarized light with a predetermined polarization axis or a circularly polarized light in a predetermined direction when natural light is incident due to a backlight such as a liquid crystal display device or reflection from the back side, and transmits other light. In addition, a polarizing plate in which a brightness enhancement film is laminated with a polarizing plate allows light from a light source such as a backlight to enter to obtain transmitted light in a predetermined polarization state, and reflects light without transmitting the light other than the predetermined polarization state. The The light reflected on the surface of the brightness enhancement film is further inverted through a reflective layer or the like provided behind the brightness enhancement film and re-incident on the brightness enhancement film, and part or all of the light is transmitted as light having a predetermined polarization state. Luminance can be improved by increasing the amount of light transmitted through the enhancement film and increasing the amount of light that can be used for liquid crystal display image display or the like by supplying polarized light that is difficult to be absorbed by the polarizer. That is, when light is incident through the polarizer from the back side of the liquid crystal cell without using a brightness enhancement film, light having a polarization direction that does not coincide with the polarization axis of the polarizer is almost polarized. It is absorbed by the polarizer and does not pass through the polarizer. That is, although depending on the characteristics of the polarizer used, approximately 50% of the light is absorbed by the polarizer, and the amount of light that can be used for liquid crystal image display or the like is reduced accordingly, resulting in a dark image. The brightness enhancement film allows light having a polarization direction that is absorbed by the polarizer to be reflected once by the brightness enhancement film without being incident on the polarizer, and further inverted through a reflective layer provided on the rear side thereof. Repeatedly re-enter the brightness enhancement film, and the brightness enhancement film transmits only polarized light whose polarization direction is such that the polarization direction of light reflected and inverted between the two can pass through the polarizer. Therefore, light such as a backlight can be efficiently used for displaying an image on the liquid crystal display device, and the screen can be brightened.

  A diffusion plate may be provided between the brightness enhancement film and the reflective layer. The polarized light reflected by the brightness enhancement film is directed to the reflective layer or the like, but the installed diffuser plate uniformly diffuses the light passing therethrough and simultaneously cancels the polarized state and becomes a non-polarized state. That is, the diffuser plate returns the polarized light to the original natural light state. The light in the non-polarized state, that is, the natural light state is directed toward the reflection layer and the like, reflected through the reflection layer and the like, and again passes through the diffusion plate and reenters the brightness enhancement film. Thus, while maintaining the brightness of the display screen by providing a diffuser plate that returns polarized light to the original natural light state between the brightness enhancement film and the reflective layer, etc., the brightness unevenness of the display screen is reduced at the same time, A uniform and bright screen can be provided. By providing such a diffuser plate, it is considered that the first incident light has a moderate increase in the number of repetitions of reflection, and in combination with the diffusion function of the diffuser plate, a uniform bright display screen can be provided.

  The brightness enhancement film has a characteristic of transmitting linearly polarized light having a predetermined polarization axis and reflecting other light, such as a multilayer thin film of dielectric material or a multilayer laminate of thin film films having different refractive index anisotropies. Such as an alignment film of a cholesteric liquid crystal polymer or an alignment liquid crystal layer supported on a film substrate, which reflects either left-handed or right-handed circularly polarized light and transmits other light. Appropriate things such as a thing can be used.

  Therefore, in the brightness enhancement film of the type that transmits linearly polarized light having the predetermined polarization axis as described above, the transmitted light is incident on the polarizing plate with the polarization axis aligned as it is, thereby efficiently transmitting while suppressing absorption loss due to the polarizing plate. Can be made. On the other hand, in a brightness enhancement film of a type that emits circularly polarized light such as a cholesteric liquid crystal layer, it can be incident on a polarizer as it is, but from the viewpoint of suppressing absorption loss, the circularly polarized light is linearly polarized through a retardation plate. It is preferable to make it enter into a polarizing plate. Note that circularly polarized light can be converted to linearly polarized light by using a quarter wave plate as the retardation plate.

  A retardation plate that functions as a quarter-wave plate in a wide wavelength range such as a visible light region exhibits, for example, a retardation layer that functions as a quarter-wave plate for light-color light having a wavelength of 550 nm and other retardation characteristics. It can be obtained by a method of superposing a retardation layer, for example, a retardation layer functioning as a half-wave plate. Therefore, the retardation plate disposed between the polarizing plate and the brightness enhancement film may be composed of one or more retardation layers.

  In addition, the cholesteric liquid crystal layer can also be obtained by reflecting circularly polarized light in a wide wavelength range such as a visible light region by combining two or more layers having different reflection wavelengths and having an overlapping structure. Based on this, transmitted circularly polarized light in a wide wavelength range can be obtained.

  Further, the polarizing plate may be formed by laminating a polarizing plate and two or more optical layers as in the above-described polarization separation type polarizing plate. Therefore, a reflective elliptical polarizing plate or a semi-transmissive elliptical polarizing plate in which the above-mentioned reflective polarizing plate or transflective polarizing plate and a retardation plate are combined may be used.

Optical film above described optical layer laminated to the polarizing plate may be formed by a method in which laminating is separately carried out sequentially in manufacturing process of a liquid crystal display etc., ash of an optical film in advance stacked, quality There is an advantage that the manufacturing process of the liquid crystal display device and the like can be improved. For the lamination, an appropriate adhesive means such as an adhesive layer can be used. When adhering the polarizing plate and other optical films, their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.

  An adhesive layer for adhering to other members such as a liquid crystal cell may be provided on the polarizing plate described above or an optical film in which at least one polarizing plate is laminated. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected. Can be used. In particular, those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.

  In addition to the above, in terms of prevention of foaming and peeling phenomena due to moisture absorption, deterioration of optical properties and liquid crystal cell warpage due to differences in thermal expansion, etc., as well as formability of liquid crystal display devices with high quality and excellent durability An adhesive layer having a low moisture absorption rate and excellent heat resistance is preferred.

  The adhesive layer is, for example, natural or synthetic resins, in particular, tackifier resins, fillers or pigments made of glass fibers, glass beads, metal powders, other inorganic powders, colorants, antioxidants, etc. It may contain an additive to be added to the adhesive layer. Moreover, the adhesion layer etc. which contain microparticles | fine-particles and show light diffusibility may be sufficient.

  Attachment of the adhesive layer to one or both sides of the polarizing plate or the optical film can be performed by an appropriate method. For example, a pressure sensitive adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a suitable solvent alone or a mixture such as toluene and ethyl acetate is prepared. A method in which it is directly attached on a polarizing plate or an optical film by an appropriate development method such as a casting method or a coating method, or an adhesive layer is formed on a separator according to the above, and this is applied to a polarizing plate or an optical film. The method of moving up is mentioned.

  The pressure-sensitive adhesive layer can be provided on one side or both sides of a polarizing plate or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as the adhesion layers of a different composition, a kind, thickness, etc. in the front and back of a polarizing plate or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 5 to 200 μm, particularly preferably 10 to 100 μm.

  On the exposed surface of the adhesive layer, a separator is temporarily attached and covered for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, a suitable thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foam sheet, metal foil, laminate thereof, and the like, silicone type or Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as a long mirror alkyl type, fluorine type or molybdenum sulfide, can be used.

  In the present invention, the polarizer, transparent protective film, optical film, and the like that form the polarizing plate described above, and each layer such as an adhesive layer include, for example, salicylic acid ester compounds, benzophenol compounds, benzotriazole compounds, and cyanoacrylates. It may be a compound having an ultraviolet absorbing ability by a method such as a method of treating with an ultraviolet absorber such as a compound based on nickel or a nickel complex salt compound.

  The polarizing plate or the optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing plate or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing plate or optical film by invention, and it can apply according to the former. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.

  An appropriate liquid crystal display device such as a liquid crystal display device in which a polarizing plate or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the polarizing plate or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell. When providing a polarizing plate or an optical film on both sides, they may be the same or different. Further, when forming a liquid crystal display device, for example, a single layer or a suitable part such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.

  Next, an organic electroluminescence device (organic EL display device) will be described. In general, in an organic EL display device, a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitter (organic electroluminescent light emitter). Here, the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Alternatively, a structure having various combinations such as a laminate of such a light emitting layer and an electron injection layer composed of a perylene derivative or the like, or a laminate of these hole injection layer, light emitting layer, and electron injection layer is known. It has been.

  In organic EL display devices, holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the phosphor material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state. The mechanism of recombination in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.

  In an organic EL display device, in order to extract light emitted from the organic light emitting layer, at least one of the electrodes must be transparent, and a transparent electrode usually formed of a transparent conductor such as indium tin oxide (ITO) is used as an anode. It is used as. On the other hand, in order to facilitate electron injection and increase luminous efficiency, it is important to use a material having a small work function for the cathode, and usually metal electrodes such as Mg—Ag and Al—Li are used.

  In the organic EL display device having such a configuration, the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate. The display surface of the organic EL display device looks like a mirror surface.

  In an organic EL display device comprising an organic electroluminescent light emitting device comprising a transparent electrode on the surface side of an organic light emitting layer that emits light upon application of a voltage and a metal electrode on the back side of the organic light emitting layer, the surface of the transparent electrode While providing a polarizing plate on the side, a retardation plate can be provided between the transparent electrode and the polarizing plate.

  Since the retardation plate and the polarizing plate have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action. In particular, the mirror surface of the metal electrode can be completely shielded by configuring the retardation plate with a quarter-wave plate and adjusting the angle between the polarization direction of the polarizing plate and the retardation plate to π / 4. .

  That is, only the linearly polarized light component of the external light incident on the organic EL display device is transmitted by the polarizing plate. This linearly polarized light becomes generally elliptically polarized light by the retardation plate, but becomes circularly polarized light especially when the retardation plate is a quarter-wave plate and the angle between the polarization direction of the polarizing plate and the retardation plate is π / 4. .

  This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, is reflected by the metal electrode, is again transmitted through the organic thin film, the transparent electrode, and the transparent substrate, and becomes linearly polarized light again on the retardation plate. And since this linearly polarized light is orthogonal to the polarization direction of a polarizing plate, it cannot permeate | transmit a polarizing plate. As a result, the mirror surface of the metal electrode can be completely shielded.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following, “parts” means parts by weight.

(Differential scanning calorimetry (DSC) measurement)
A differential scanning calorimeter (220 CU manufactured by Seiko Instruments Inc.) was used. Under a nitrogen atmosphere (30 ml / min), the differential scanning calorific value in the temperature lowering process from 220 ° C. to 0 ° C. at a cooling rate of 10 ° C./min was measured. The sample was weighed 3.1 mg in an aluminum open container, and three aluminum plates (about 15 mg) were used as a reference.

Example 1
(Liquid crystalline dichroic dye)
LSR-406 (manufactured by Mitsubishi Chemical Corporation) was used as the liquid crystalline dichroic dye.
The phase transition temperature (° C.) at the time of temperature increase was Cr 110 N 207 I.
The phase transition temperature (° C.) at the time of temperature decrease was Cr <45 N 201 I.
FIG. 1 shows the differential scanning calorific value of the liquid crystalline dichroic dye during the temperature lowering process. As shown in FIG. 1, a transition peak from the isotropic phase to the liquid crystal phase was observed at 188.6 ° C., but a crystal transition peak from the liquid crystal phase to the crystal phase was not detected.

(Production of polarizer)
LSR-406 was dissolved in 1,1,2,2-tetrachloroethane to obtain a solution having a concentration of 3% by weight. The solution was applied to a rubbing alignment film of polyvinyl alcohol provided on a substrate (triacetylcellulose film) at 2000 rpm 2 sec. Then, spin coating was performed so that the dry film thickness was 0.3 μm. Next, the film was aligned by heating at 130 ° C. for 2 minutes, and then cooled at 10 ° C./second to fix the alignment to obtain a polarizer.

(Evaluation)
The obtained polarizer was subjected to X-ray reflection (X-ray diffraction) measurement and X-ray reflectivity measurement.

  For the X-ray reflection measurement, an enclosed tube X-ray generator (manufactured by Rigaku Corporation) with a copper target was used. X-rays from an X-ray generator are incident on a sample through a slit having a divergence angle of 1/6 deg, and the detector is scanned 2θ with respect to the incident angle θ, which is measured by a symmetric reflection method by so-called θ-2θ scanning. I did it. Ni filter was used for monochromatic X-rays. The scanning of the sample and the detector was performed in the range of θ = 1 to 12.5 deg with a pitch of 0.005 deg. The detection time at each θ was 3 seconds. The detector used was a scintillation counter using NaI as a scintillator.

  The X-ray reflectivity measurement is the same as the above X-ray diffraction, but the incident X-rays were narrowed with a 0.05 mm slit in order to perform measurement from a lower angle of incidence. The range of θ-2θ scanning was 0.3 to 3.5 deg. The scanning pitch was 0.005 deg. The detection time at each θ was 10 seconds. A graphite crystal monochromator placed in front of the detector was used for monochromatic X-rays.

  The result of X-ray reflection (X-ray diffraction) measurement is shown in FIG. 2, and the result of X-ray reflectometry is shown in FIG. From FIG. 2, the presence of a diffraction peak of X-ray reflection (X-ray diffraction) measurement is recognized. From FIG. 3, the Bragg peak obtained from the X-ray reflectivity measurement is recognized. From these results, it can be seen that the alignment layer (polarizer) has an order in the thickness direction. This alignment layer is recognized to be a hexatic phase or a crystal phase because it is aligned in the horizontal direction and ordered in the thickness direction. The order period determined from the position of the Bragg peak was 1.43 nm.

  FIG. 4 shows the absorbance anisotropy when linearly polarized light is incident in a direction perpendicular or parallel to the orientation direction of the obtained polarizer. Linearly polarized light was obtained by placing a Gran Taylor prism on the incident side. An ultraviolet-visible spectrophotometer V-560 manufactured by JASCO Corporation was used as the absorbance measurement apparatus. From FIG. 4, it was found that the obtained dichroic ratio (DR) = 21 at the maximum absorption wavelength λmax = 480 nm. The dichroic ratio (DR) is absorbance (parallel) / absorbance (orthogonal).

  The spectrum of the single transmittance, parallel transmittance, and orthogonal transmittance of the obtained polarizer is shown in FIG. The properties as a polarizer were as extremely high as a single transmittance of 40.7% and a polarization degree of 98.3% at λmax. A UV-visible spectrophotometer V-560 manufactured by JASCO Corporation was used as a measuring device for single transmittance, parallel transmittance, and orthogonal transmittance.

Comparative Example 1
(Liquid crystalline dichroic dye)
LSR-516 (manufactured by Mitsubishi Chemical Corporation) was used as the liquid crystalline dichroic dye.
The phase transition temperature (° C.) at the time of temperature increase was Cr 143 N 214 I.
The phase transition temperature (° C.) when the temperature was lowered was Cr 73 N.

(Production of polarizer)
In Example 1, a polarizer was obtained in the same manner as in Example 1 except that LSR-516 was used instead of LSR-406 and the heating temperature was 163 ° C.

(Evaluation)
The obtained polarizer was subjected to X-ray reflection (X-ray diffraction) measurement and X-ray reflectivity measurement in the same manner as in Example 1. As a result, no diffraction peak in X-ray reflection (X-ray diffraction) measurement was observed, and no Bragg peak was observed in X-ray reflectance measurement. The obtained dichroic ratio (DR) = 11 at the maximum absorption wavelength λmax = 450 nm. The characteristics as a polarizer were a single transmittance of 38% and a polarization degree of 94% at λmax.

FIG. 3 is a diagram showing the differential scanning calorific value of the liquid crystalline dichroic dye used in Example 1. FIG. 3 is a diagram showing the results of X-ray reflection (X-ray diffraction) measurement of the polarizer obtained in Example 1. It is a figure which shows the result of the X-ray reflectivity measurement X-ray reflection (X-ray diffraction) measurement of the polarizer obtained in Example 1. FIG. 4 is a graph showing the absorbance in the orthogonal and parallel directions of the polarizer obtained in Example 1. FIG. 3 is a diagram showing the transmittance and the degree of polarization of the polarizer obtained in Example 1.

Claims (6)

A polarizer having an alignment layer formed using an azo liquid crystal dichroic dye , wherein the azo liquid crystal dichroic dye is aligned as a hexatic phase or a crystal phase, and the liquid crystalline dichroic dye, the temperature lowering process in the measurement of differential scanning calorimetry state, and are not not seen crystal transition peak,
The polarizer has the following characteristics (a) and (b):
(A) obtaining at least one diffraction peak in X-ray reflection measurement;
(B) that a Bragg peak is obtained in the X-ray reflectivity measurement;
Polarizer and having a. After aligning a material containing an azo liquid crystalline dichroic dye that does not show a crystal transition peak in the temperature-falling process in differential scanning calorimetry, at a temperature at which the liquid crystalline dichroic dye exhibits a liquid crystal state. the method of the polarizer according to claim 1, further comprising a step of fixing the orientation by cooling. The method for producing a polarizer according to claim 2 , wherein the cooling is performed at a rate of 1 ° C./second or more. The polarizing plate which provided the transparent protective layer in the at least single side | surface of the polarizer of Claim 1 . Optical film polarizing plate of the polarizer or claim 4, wherein according to claim 1, characterized in that it is laminated at least one. Polarizer of claim 1, wherein the image display device comprising the optical film of the polarizing plate or claim 5, wherein according to claim 4 wherein is used.

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