JP2006267723A - Polymerizable composition, optical anisotropic layer and its manufacturing method, optical compensation element, liquid crystal display device and liquid crystal projector - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical anisotropic layer which optically compensates a liquid crystal layer in black display state with higher accuracy, prevents light leakage at a wide viewing angle and hardly causes secular change, to provide a manufacturing method of the optical anisotropic layer, and to provide a liquid crystal display device and a liquid crystal projector which has a large viewing angle, a high contrast, high image quality and has a long life by using an optical compensation element comprising the optical anisotropic layer. <P>SOLUTION: The polymerizable composition comprises a polymerizable liquid crystal compound and a radical generator which has an absorption peak at a light wavelength of 320 to 380 nm and substantially has no absorption at a light wavelength of ≥420 nm. The optical anisotropic layer formed on a substrate is the optical compensation element using the polymerizable composition. The liquid crystal display device uses the optical compensation element. The liquid crystal projector is provided with a light source, the liquid crystal display device which is irradiated with illumination light from the light source and a projection optical system which images light optically modulated by the liquid crystal display device on a screen. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymerizable composition suitable for an optical compensation element or the like, an optically anisotropic layer and a method for producing the same, an optical compensation element, a liquid crystal display device, and a liquid crystal projector.

In recent years, the use of liquid crystal display devices has been rapidly advanced, and is used in mobile phones, personal computer monitors, televisions, liquid crystal projectors, and the like.
In general, a liquid crystal display device is in a TN (Twisted Nematic) mode, a VA (Vertical Alignment) mode, an IPS (In-Plane Switching) mode, an OCB (Optically Compensatory Bend) mode, an ECB (Electrically Bending mode), or the like. It is a display device that expresses characters and images by operating a liquid crystal and electrically controlling light passing through the liquid crystal to display a difference between light and dark on a screen.

As such a liquid crystal display device, a TFT (Thin Film Transistor) -LCD is generally known, and a TN mode is mainstream as a liquid crystal operation mode of the TFT-LCD. On the other hand, as the application development of liquid crystal display devices progresses in recent years, the demand for higher contrast has increased, and research on VA mode liquid crystal display devices has been actively conducted.
In a TN mode liquid crystal display device, nematic liquid crystal twisted by 90 ° is enclosed between two glass substrates, and a pair of polarizing plates are arranged in crossed Nicols outside the two glasses. When no voltage is applied, the linearly polarized light that has passed through the polarizer on the polarizer side is twisted by 90 ° in the liquid crystal layer and passes through the polarizer on the analyzer side, resulting in white display. In addition, when the voltage is sufficiently applied, the alignment direction of the liquid crystal changes substantially perpendicular to the liquid crystal panel, and the linearly polarized light passing through the polarizer on the polarizer side passes through the liquid crystal layer without changing the polarization state. As a result, the light reaches the polarizing plate on the analyzer side and black is displayed.

  A liquid crystal display device that operates in these display modes has a field of view that display characteristics deteriorate due to a decrease in contrast or a gradation inversion phenomenon in which the brightness is reversed in gradation display when the display screen is viewed from an oblique direction. There is a problem of angular dependence. Such a problem of viewing angle dependency is caused by light leakage even if an attempt is made to display the liquid crystal display device in black, depending on the viewing angle.

Conventionally, the phase difference value of light passing through the liquid crystal layer in the black display state is combined with the phase difference value of the optical anisotropic film, and the liquid crystal layer in the black display state is optically compensated three-dimensionally, Various optical compensation films have been proposed that eliminate light leakage from any direction and improve the problem of viewing angle dependency. For example, the applicant of the present application first comprises a support such as a triacetyl cellulose (TAC) film and an optically anisotropic layer provided thereon, and the optically anisotropic layer has a discotic structural unit. The disc surface of the discotic structural unit is obtained by coating, orienting, and fixing the structure of the coating liquid containing the compound having optical anisotropy composed of the compound and having the discotic structural unit on the support. And an optical compensation film having a hybrid orientation that is inclined with respect to the support surface and in which the angle formed by the disc surface of the discotic structural unit and the support surface changes in the thickness direction of the optically anisotropic layer. (See Patent Document 1).
According to this optical compensation film, since the discotic structural unit of the optically anisotropic layer is arranged so as to be mirror-symmetrical with the liquid crystal layer in the black display state, the support and the discotic structural unit As the optical characteristics of the entire laminate, the liquid crystal layer in the black display state is optically compensated, and light leakage can be prevented in a wide viewing angle.
However, in this case, by using the optical compensation film, the problem of the viewing angle dependency of the liquid crystal display device has been improved and the viewing angle has been successfully expanded. The demand for liquid crystal monitors, liquid crystal projectors, and the like has increased, and there has been a demand for the large-screen liquid crystal monitors, liquid crystal projectors, and the like that have little deterioration in display quality such as fading and color shift even when used for a long period of time. In addition, since the liquid crystal projector integrates light incident on the liquid crystal cell at various angles and is projected on the screen in an enlarged manner, higher contrast is required, and the optical compensation film still has room for improvement. .

Further, conventionally, an optical film having a hybrid-aligned liquid crystal layer is arranged between two polarizing plates arranged so as to sandwich a liquid crystal cell, and the optical film is made of a plastic film having extremely low birefringence. There is known a method for improving the contrast ratio of a liquid crystal projector in which a hybrid-aligned liquid crystal layer is disposed on a base film (see Patent Document 2).
However, in the case of a liquid crystal projector in which a liquid crystal layer having a hybrid orientation is disposed on the base film, the optical compensation film is formed of an organic material such as a polymerizable compound, and the optical compensation film Then, after applying an alignment film coating solution made of an organic polymer, the optical anisotropic layer coating solution is applied by a coating method or the like. In such a coating process, air is filled in the layer of the optical compensation film, so about 21% of oxygen, water, nitrogen oxides and sulfur oxides (for example, sulfite compounds) contained in the air. Molecules such as various solvent gases generated in the coating step adhere (adsorb) to the alignment film of the optically anisotropic layer. For this reason, the obtained optical compensation element gradually deteriorates in quality due to the aging of the optically anisotropic layer and the alignment film due to adverse effects such as adhesion of these attached molecules to the organic material and causing an oxidation reaction. There is a problem that the display quality of the optical compensation element is deteriorated.
In particular, when used in a liquid crystal projector as in the improvement method, the oxidation reaction is accelerated by light irradiation, and the blue channel of the red, green, and blue channels is greatly deteriorated and not only the contrast is lowered. There is a problem that the color balance is obscured.

As these improvement methods, a method is known in which a protective layer is provided on an organic material layer by means of vapor deposition of an inorganic material or application of an organic material to suppress an oxidation reaction (see Patent Documents 3 to 5).
However, in the case of the coating means, the gas barrier property in the light passing direction and the normal direction of each layer can be improved, but the effect from the influence of impurities from the end face of the optical compensation element is lacking, Moreover, it has been insufficient to effectively prevent deterioration over time due to an oxidation reaction of the organic material portion of the optical compensation element, such as inferior production efficiency.

JP-A-8-50206 Republished patent WO01 / 090808 JP-A-6-289227 JP-A-5-27114 JP 2001-91747 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention optically compensates the liquid crystal layer in a black display state with higher accuracy, prevents light leakage at a wide viewing angle, and has an optically anisotropic layer with little deterioration over time, and a manufacturing method thereof, An object of the present invention is to provide a liquid crystal display device and a liquid crystal projector having a high viewing angle, a high contrast, a high image quality and a long life by using the optical compensation element comprising the optically anisotropic layer.

Means for solving the problems are as follows. That is,
<1> A polymerizable composition comprising a polymerizable liquid crystal compound and a radical generator having an absorption peak at 320 to 380 nm and having substantially no absorption at 420 nm or more. is there.
<2> The polymerizable composition according to any one of <1> to <2>, wherein the polymerizable liquid crystal compound includes a discotic liquid crystal compound.
<3> The polymerizable composition according to any one of <1> to <3>, wherein the polymerizable liquid crystal compound includes a rod-like liquid crystal compound.
<4> An optically anisotropic layer comprising the polymerizable composition according to any one of <1> to <3> and formed on a support.
<5> The orientation angle of the polymerizable liquid crystal compound in the orientation state formed by the polymerizable liquid crystal compound is inclined with respect to the thickness direction of the optically anisotropic layer, and is fixed in the inclined state <5 > Is an optically anisotropic layer.
<6> The optically anisotropic layer according to any one of <4> to <5>, wherein the orientation angle of the polymerizable liquid crystal compound is fixed in a hybrid orientation that changes in the thickness direction of the optically anisotropic layer.
<7> The polymerizable composition according to any one of <1> to <3> is applied on at least one surface of a support, and the polymerizable composition is heated to 130 ° C. or higher. This is a method for producing an optically anisotropic layer.
<8> The method for producing an optically anisotropic layer according to <7>, wherein the polymerization of the polymerizable composition is performed only by heating.
<9> A support and an optically anisotropic layer on at least one surface of the support. It is an optical compensation element characterized by being an anisotropic layer.
<10> The optical compensation element according to <9>, wherein the optical compensation element has two optically anisotropic layers and is arranged so that the orientation directions thereof are different.
<11> The optical compensation element according to any one of <9> to <10>, wherein two layers having different orientation directions are provided on one surface of the support.
<12> The optical compensation element according to <9> to <11>, wherein two layers having different orientation directions are provided on both surfaces of the support via a support.
<13> The optical compensation element according to any one of <9> to <12>, having two layers so that the orientation directions are orthogonal to each other.
<14> A liquid crystal element having at least a pair of electrodes and liquid crystal molecules sealed between the electrodes, an optical compensation element disposed on both sides or one side of the liquid crystal element, and opposed to the liquid crystal element and the optical compensation element. The liquid crystal display device is characterized in that the optical compensation element is an optical compensation element according to any one of <9> to <13>.
<15> The liquid crystal display device according to <14>, wherein the liquid crystal element is a twisted nematic type.
<16> A light source, a liquid crystal display device irradiated with illumination light from the light source, and a projection optical system that forms an image of light modulated by the liquid crystal display device on a screen, the liquid crystal display device comprising: A liquid crystal projector according to any one of <14> to <15>.

The polymerizable composition of the present invention comprises a polymerizable liquid crystal compound and a radical generator having an absorption peak at a light wavelength of 320 to 380 nm and substantially no absorption at 420 nm or more.
As a result, it is possible to prevent deterioration of the optically anisotropic layer over time, to make the thickness uniform, to obtain the optical characteristics of the optically anisotropic layer with high accuracy, and to prevent light leakage in a wide viewing angle. Is possible.

  The optically anisotropic layer of the present invention comprises the polymerizable composition of the present invention. As a result, an optically anisotropic layer having a uniform thickness can be manufactured, and the optical characteristics of the optically anisotropic layer can be adjusted to desired characteristics with high accuracy, and light leakage and deterioration over time can be prevented in a wide viewing angle. It becomes possible.

  The liquid crystal display device of the present invention includes at least a pair of electrodes, a liquid crystal element having liquid crystal molecules sealed between the pair of electrodes, an optical compensation element disposed on either one or both sides of the liquid crystal element, A polarizing element disposed opposite to the liquid crystal element and the optical compensation element, and the optical compensation element is the optical compensation element of the present invention. As a result, a liquid crystal display device with high viewing angle, high contrast, high image quality, and little deterioration over time can be provided.

  The liquid crystal projector of the present invention includes a light source, a liquid crystal display device irradiated with illumination light from the light source, and a projection optical system that forms an image of light modulated by the liquid crystal display device on a screen, The liquid crystal device is the liquid crystal display device of the present invention. As a result, it is possible to provide a liquid crystal projector with high viewing angle, high contrast, high image quality and little deterioration over time.

  According to the present invention, the conventional problems can be solved, the liquid crystal layer in the black display state is optically compensated with higher accuracy, light leakage is prevented in a wide viewing angle, and optical anisotropy with little deterioration over time is achieved. By using the layer, a method for manufacturing the layer, and an optical compensation element including the optically anisotropic layer, a liquid crystal display device and a liquid crystal projector having a high viewing angle, a high contrast, a high image quality, and a long life can be provided.

(Polymerizable composition)
The polymerizable composition of the present invention includes a polymerizable liquid crystal compound, a radical generator having an absorption peak at a wavelength of light of 320 to 380 nm and substantially no absorption at 420 nm or more, and as necessary. It contains other selected components.

-Polymerizable liquid crystal compound-
The polymerizable liquid crystal compound is not particularly limited as long as it has a functional group so that it can be polymerized or cross-linked to a compound that can be aligned to form a liquid crystal state. You can choose. As the form of the compound, a polymerizable liquid crystal compound containing a rod-like liquid crystal compound, a discotic liquid crystal compound, a banana-like liquid crystal compound and the like is preferable, and a polymerizable liquid crystal compound containing a discotic liquid crystal compound is more preferable. Moreover, the polymerizable liquid crystal compound containing the liquid crystal compound can contain other components appropriately selected as necessary.

  The polymerizable liquid crystal compound including the rod-like liquid crystal compound is not particularly limited and can be appropriately selected depending on the purpose. For example, the alignment state of the rod-like liquid crystal compound can be fixed using a polymer binder. Examples thereof include polymerizable liquid crystal compounds and polymerizable liquid crystal compounds having a polymerizable group that can fix the alignment state of the liquid crystal compound by polymerization. Among these, preferred are the polymerizable liquid crystal compounds having a polymerizable group.

  The rod-like liquid crystal compound (rod-like liquid crystal molecule) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoate esters , Cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, alkenylcyclohexylbenzonitriles and the like.

  Examples of the polymerizable liquid crystal compound containing the rod-like liquid crystal compound include a polymer liquid crystal compound obtained by polymerizing a rod-like liquid crystal compound having a low-molecular polymerizable group represented by the following structural formula (1).

However, in the structural formula (1), Q ¹ and Q ² each represent a polymerizable group, and L ¹ , L ² , L ³ and L ⁴ each represent a single bond or a divalent linking group, At least one of L ² and L ³ represents —O—CO—O—. A ¹ and A ² each independently represent a spacer group having 2 to 20 carbon atoms. M represents a mesogenic group.

  The polymerizable liquid crystal compound including the discotic liquid crystalline compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the alignment state of the discotic liquid crystalline compound is fixed using a polymer binder. Polymerizable liquid crystal compounds, and polymerizable liquid crystal compounds having a polymerizable group capable of fixing the alignment state of the discotic liquid crystalline compound by polymerization, and the like. Among these, the polymerizable compounds having a polymerizable group are mentioned. A liquid crystal compound is preferable.

  Examples of the polymerizable liquid crystal compound having a polymerizable group include a structure in which a linking group is introduced between a discotic core and a polymerizable group. Specific examples of the polymerizable liquid crystal compound include compounds represented by the following structural formula (2).

In the structural formula (2), D represents a discotic core, L represents a divalent linking group, and P represents a polymerizable group. Moreover, n is an integer of 4-12. Further, the combination of a plurality of divalent linking groups L and polymerizable groups P may be a combination of different divalent linking groups and polymerizable groups, but the same combination is preferred. As the disk-shaped core D, two or more kinds can be used in combination.

  In the structural formula (2), specific examples of the disk-shaped core D include disk-shaped cores represented by the following structural formulas (D1) to (D15).

  In the structural formula (2), the divalent linking group L is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an alkylene group, an alkenylene group, an arylene group, —CO—, —NH -, -O-, -S-, combinations thereof and the like are preferable, alkylene group, alkenylene group, arylene group, -CO-, -NH-, -O-, -S-, and a divalent group selected from these More preferred is a divalent linking group in which at least two of the above groups are combined, and an alkylene group, alkenylene group, arylene group, -CO-, -O-, or at least two divalent groups selected from these are combined. A divalent linking group is particularly preferred.

  The number of carbon atoms of the alkylene group is preferably 1-12. The number of carbon atoms of the alkenylene group is preferably 2-12. The number of carbon atoms in the arylene group is preferably 6-10. The alkylene group, the alkenylene group, and the arylene group may have a substituent such as an alkyl group, a halogen atom, a cyano, an alkoxy group, or an acyloxy group.

Examples of the divalent linking group L include -AL-CO-O-AL-, -AL-CO-O-AL-O-, -AL-CO-O-AL-O-AL-, and -AL. -CO-O-AL-O-CO-, -CO-AR-O-AL-, -CO-AR-O-AL-O-, -CO-AR-O-AL-O-CO-, -CO -NH-AL-, -NH-AL-O-, -NH-AL-O-CO-, -O-AL-, -O-AL-O-, -O-AL-O-CO-, -O -AL-O-CO-NH-AL-, -O-AL-S-AL-, -O-CO-AL-AR-O-AL-O-CO-, -O-CO-AR-O-AL -CO-, -O-CO-AR-O-AL-O-CO-, -O-CO-AR-O-AL-O-AL-O-CO-, -O-CO-AR-O-AL -O-AL-O-AL-OC -, - S-AL -, - S-AL-O -, - S-AL-O-CO -, - S-AL-S-AL -, - S-AR-AL-, and the like.
However, in the specific example of the divalent linking group L, the left side is bonded to the discotic core D, and the right side is bonded to the polymerizable group P. AL represents an alkylene group or an alkenylene group, and AR represents an arylene group.

  In the structural formula (2), the polymerizable group P is not particularly limited and may be appropriately selected depending on the kind of the polymerization reaction, and is preferably an unsaturated polymerizable group or an epoxy group, and is ethylenically unsaturated. A polymerizable group is more preferable. Specific examples of the polymerizable group P include polymerizable groups represented by the following structural formulas (P1) to (P18).

However, in the polymerizable groups represented by the structural formulas (P1) to (P18), n represents an integer of 4 to 12, and is a value determined by the type of the disk-shaped core D.
As for these polymerizable liquid crystal compounds, for example, JP-A-9-104656, JP-A-11-92220, JP-A 2000-34251, JP-A 2000-44507, JP-A 2000-44517. JP-A-2000-86589 can be exemplified.

-Other components contained in the polymerizable liquid crystal compound-
There is no restriction | limiting in particular as another component contained in the said polymeric liquid crystal compound, According to the objective, it can select suitably.

―Radical generator―
The radical generator is necessary when preparing a polymerizable composition using radical polymerization. However, if it remains in the polymerizable composition, when irradiated with light, an unexpected radical reaction is excited to promote decomposition of the polymerizable composition. That is, when the radical generator is present in the optically anisotropic layer, when light is applied, the light energy is absorbed by the organic component, the atomic vibration energy is increased, and the organic component is activated and released. Radicals are generated and affect oxidation and other reactions. Further, when heated by absorbing light and converting it into heat, the thermal energy of atoms in the optically anisotropic layer is increased and activated, and an oxidation reaction is likely to occur. One method for overcoming this concern is to completely remove the radical generator from the optically anisotropic layer. However, since it is indispensable when producing a polymerizable composition, a difficult point such as a restriction on the production process is increased.
Also, when used in a liquid crystal projector that is irradiated with light at high illuminance, the oxidation reaction is accelerated, and the red, green, and blue channels used as the three primary colors of light have the shortest wavelength and the strongest energy. In blue light, an undesirable deterioration phenomenon such as an oxidation reaction is easily promoted as compared with the other two colors, so that the blue channel is greatly deteriorated and not only the contrast is lowered but also the color balance is degraded.
Focusing on the fact that the degradation is increased by the blue channel light, a compound that is insensitive to the light incident on the optically anisotropic layer is used as the radical generator. Even if it remains in the optically anisotropic layer, it does not generate radicals when irradiated with light, so it has a function of suppressing the generation of radicals by light irradiation of the optically anisotropic layer and improving durability (light resistance). .

The radical generator is not particularly limited as long as it has an absorption peak at a wavelength of 320 to 380 nm and substantially no absorption at 420 nm or more, and is appropriately selected according to the purpose. Can do. By selecting such an absorption wavelength, the influence of blue light passing through the optically anisotropic layer can be reduced as much as possible. Here, “substantially no absorption at 420 nm or more” means that the absorption peak of the radical generator having an absorption peak at 320 to 380 nm is less than one thousandth. Examples of the radical generator as such a polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure-651, manufactured by Ciba Geigy), tribromomethylphenylsulfone, azobis Isobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile (V-65: Wako Pure Chemical Industries), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70: Wako Pure Chemical Industries), polyethylene glycol unit-containing polymer azo polymerization initiator (VPE-0201: Wako Pure Chemical Industries), etc. Among these, 2,2-dimethoxy-1,2-diphenylethane -1-On (Irgacure-651, manufactured by Ciba Geigy) and azobisisobutyronitrile (AIBN) are preferable.
In the photopolymerization system, a sensitizer may be added to promote polymerization, but it is not preferable to add a sensitizer having absorption at 420 nm or more for the purpose of the present invention.

The addition amount of the radical generator is preferably 0.02 to 5.0% by mass, more preferably 0.05 to 1.0% by mass with respect to the solid content of the polymerizable composition, and 0.05 to 0.2% by mass is particularly preferable.
When the addition amount is less than 0.02% by mass, the radical polymerization reaction of the polymerizable liquid crystal compound is not sufficient, and the durability may not be improved. In some cases, the hardness of the compound does not increase and a suitable polymerizable composition cannot be obtained.

-Other components contained in the polymerizable composition-
The other components contained in the polymerizable composition are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a thermal crosslinking agent that accelerates the polymerization reaction of the polymerizable composition. .

The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability For example, an epoxy resin compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used within a range that does not adversely affect the like.
Examples of the epoxy resin compound include a bixylenol type or biphenol type epoxy resin (“YX4000; manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton (“TEPIC; Nissan”). Chemical Industries, "Araldite PT810; Ciba Specialty Chemicals, etc.), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy Resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type Poxy resin, glycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032, EXA-4750, EXA-4700; large Nippon Ink Chemical Co., Ltd. ”), epoxy resins having a dicyclopentadiene skeleton (“ HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals ”etc.), glycidyl methacrylate copolymer epoxy resin (“ CP -50S, CP-50M; manufactured by NOF Corporation, etc.), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like, but is not limited thereto. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, oxetane groups and novolak resins , Poly (p-hydroxystyrene), cardo-type bisphe And ether compounds with hydroxyl groups, such as siloles, calixarenes, calixresorcinarenes, silsesquioxanes, and the like, as well as unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. And a copolymer thereof.

Moreover, in order to accelerate the thermosetting of the epoxy resin compound or the oxetane compound, for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole and 2-ethylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the oxetane compound is a curing catalyst, or any compound that can accelerate the reaction between the epoxy resin compound and the oxetane compound and a carboxyl group. May be.
Solid content in the said photosensitive composition solid content of the said epoxy resin, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; bifunctional isocyanates, trimethylolpropane, pentalysitol, glycerin, etc. An alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Cyclic trimers, such as preparative and derivatives thereof; and the like.

Furthermore, for the purpose of improving the storage stability of the optically anisotropic layer of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include isopropanol, tert. Alcohols such as butanol; lactams such as ε-caprolactam; phenol, cresol, p-tert. -Butylphenol, p-sec. -Butylphenol, p-sec. -Phenols such as amylphenol, p-octylphenol, p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime, Active methylene compounds such as cyclohexanone oxime; and the like. In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, etc.). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethoxymethylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

According to the polymerizable composition of the present invention, an optically anisotropic layer having a uniform thickness can be obtained, and the optical characteristics of the optically anisotropic layer can be set to desired characteristics with high accuracy, and a wide field of view. It becomes possible to prevent light leakage at the corners.
Moreover, since the said polymeric composition is excellent in patterning property, when producing an optically anisotropic layer using the inkjet method etc., a predetermined shape and an optical characteristic are obtained with high precision, for example.
Therefore, for example, an optical compensation film having a fine optical anisotropic layer pattern having predetermined optical characteristics corresponding to each pixel of RGB in a full-color liquid crystal display device is obtained. According to the optical compensation film, , For each RGB pixel in the liquid crystal display device, the phase difference value of the light passing through the liquid crystal layer and the phase difference value of the optical compensation film are arbitrarily combined, and the liquid crystal layer in the black display state is three-dimensionally, In addition, optical compensation is performed for each pixel to eliminate light leakage from any direction and to improve the problem of viewing angle dependency. In addition, secular changes such as fading and color shift can be reduced even when used for a long period of time, and durability can be improved.

(Optically anisotropic layer)
The optically anisotropic layer of the present invention is formed from a polymerizable composition containing at least the polymerizable liquid crystal compound and the polymerization initiator, and further containing other components as necessary.
It is preferable that the polymerizable liquid crystal compound is in an aligned state when the polymerizable composition is applied onto a support during layer formation. There is no restriction | limiting in particular as this orientation state, According to the objective, it can select suitably. This alignment state may be fixed by polymerizing or crosslinking the polymerizable liquid crystal compound, and may not exhibit a liquid crystal state in the optically anisotropic layer.
Here, in the present invention, the alignment state refers to a long axis direction, a plate-like molecule, if the compound (molecule) constituting the liquid crystal state is a natural axis resulting from the molecular shape, that is, a rod-like molecule such as a rod. If the natural axis is set in the normal direction of the plate, the average directions of the natural axes of the molecules constituting the liquid crystal state included in the microscopic area of interest are substantially aligned, that is, the liquid crystal state is This refers to the orientation state of the constituent molecules.

  Further, in the present invention, when in this orientation state, the average direction of the natural axis of the liquid crystalline compound in the microscopic area of interest and the stacking direction of the optical compensation element (normal line at the interface between the optically anisotropic layer and the support) The angle formed with the direction) is referred to as the orientation angle, and the component obtained by projecting the average direction of the natural axes onto the interface is referred to as the orientation direction.

As the alignment state, the liquid crystal compound has a state in which the alignment angle is inclined, that is, the alignment angle is not uniformly parallel or perpendicular to the thickness direction of the optical compensation layer. Preferable examples include those having a hybrid orientation in which the orientation angle continuously changes in the thickness direction between the upper surface and the lower surface of the optically anisotropic layer.
The orientation angle in the hybrid orientation is preferably adjusted so as to continuously change in the range of 20 ° ± 20 ° to 65 ° ± 25 ° from the orientation film side to the air interface side.
As the alignment state determined by the alignment angle and the alignment direction of the polymerizable liquid crystal compound, it is preferable that the alignment angle and the alignment method are adjusted so that the liquid crystal layer in a black display state and a mirror surface target.
Here, the orientation angle near the orientation film side of the polymerizable liquid crystal compound in the optically anisotropic layer, the orientation angle on the air interface side, and the average orientation angle are obtained by using an ellipsometer (M-150, manufactured by JASCO Corporation). It is a value calculated from the refractive index ellipsoid model assuming a refractive index ellipsoid model from the measured retardation.
In addition, as a method of calculating the orientation angle from the retardation, it is also possible to calculate by an approach described in Design Concepts of Discrete Negative Birefringence Compensation Films SID98 DIGEST. The measurement direction of the retardation in calculating the orientation angle is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the retardation in the normal direction of the optically anisotropic layer (Re0 ), Retardation in the −40 ° direction with respect to the normal direction (Re-40) and retardation in the + 40 ° direction (Re40).
The measurements of Re0, Re-40, and Re40 are values obtained by changing the observation angle in each of the measurement directions using the ellipsometer.

There is no restriction | limiting in particular as another structure with which the said optically anisotropic layer is equipped, According to the objective, it can select suitably, The alignment film for orientating the said polymeric liquid crystal compound is mentioned suitably. It is preferable that the polymerizable liquid crystal compound is laminated on the alignment film by coating or the like.
The alignment film is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an alignment film made of a rubbed organic compound (polymer), an alignment film having a microgroup, a Langmuir-Blodgett method (LB film) alignment film in which organic compounds such as ω-triconic acid, dioctadecyldimethylammonium chloride, methyl stearylate are accumulated, alignment film in which inorganic compounds are obliquely deposited, alignment by electric field, magnetic field or light irradiation Examples thereof include an alignment film having a function, and an alignment film made of the rubbed organic compound is preferable.
There is no restriction | limiting in particular as said rubbing process, According to the objective, it can select suitably, For example, the process which rubs the surface of the film | membrane which consists of the said organic compound several times in a fixed direction with paper or cloth is mentioned.

The type of the organic compound is not particularly limited and can be determined according to the alignment state (particularly the alignment angle) of the liquid crystalline compound. For example, in order to align the liquid crystalline compound horizontally, Examples thereof include polymers for alignment films that do not reduce surface energy.
As specific examples of the alignment film polymer, when the liquid crystalline compound is aligned in a direction orthogonal to the rubbing treatment direction, modified polyvinyl alcohol (see JP 2002-62427 A), acrylic acid-based polymer Preferable examples include copolymers (see JP-A-2002-98836) polyimide, polyamic acid (see JP-A-2002-268068), and the like.

The alignment film preferably has a reactive group for the purpose of improving adhesion to the polymerizable liquid crystal compound and the support. There is no restriction | limiting in particular as said reactive group, According to the objective, it can select suitably, For example, what introduce | transduced the reactive group into the side chain of the repeating unit of the said polymer for alignment films, The said polymer for alignment films In which a substituent of a cyclic group is introduced.
The alignment film that forms a chemical bond with the polymerizable liquid crystal compound and the support by the reactive group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-9-152509 It is also possible to use the alignment film described in the publication.
There is no restriction | limiting in particular as thickness of the said alignment film, According to the objective, it can select suitably, 0.01-5 micrometers is preferable and 0.05-2 micrometers is more preferable.

(Method for producing optically anisotropic layer)
The method for producing an optically anisotropic layer of the present invention includes a step of applying the polymerizable composition of the present invention on at least one surface of a support and heating the polymerizable composition to 130 ° C. or higher. And further includes other steps as necessary.

As the support, those similar to the optical compensation element described later can be used.
There is no restriction | limiting in particular as a coating method on the said support body (or alignment film) of the said coating liquid, According to the objective, it can select suitably, For example, extrusion coating method, direct gravure coating method, reverse gravure coating Publicly known methods such as a method, a die coating method, and a spin coating method.

As the method for producing the optically anisotropic layer, the polymerizable liquid crystal compound is aligned using the alignment film, and then the liquid crystalline molecules are fixed in the aligned state to form the optically anisotropic layer. Then, only the optically anisotropic layer may be transferred onto a support such as a polymer film. According to such a manufacturing method, it is not necessary to consider the influence of birefringence by the alignment film, and the liquid crystal layer in the black display state can be optically compensated with higher accuracy.

(Optical compensation element)
The optical compensation element of the present invention comprises an optically anisotropic layer on at least one surface of a support, the optically anisotropic layer has the optically anisotropic layer of the present invention, and If necessary, it has other layers.

-Support-
The support is not particularly limited as long as it is transparent so as to transmit at least 50% with respect to the wavelength of light to be used, and can be appropriately selected according to the purpose. For example, white plate glass, blue plate glass, quartz Examples thereof include glass, sapphire glass, and organic polymer film.
The organic polymer film is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyolefins such as polyarylate-based, polyester-based, polycarbonate-based and norbornene-based polymers, polyether-based, and polysulfin. 1 type or 2 types or more selected from polymer groups such as poly (meth) acrylic acid esters such as poly (meth) acrylates such as cellulose, polysulfone, polyethersulfone, cellulose ester such as cellulose acetate and cellulose diacetate, and polymethyl methacrylate Examples include combinations.

Specific examples of the organic polymer film include a polycarbonate copolymer, a polyester copolymer, a polyester carbonate copolymer, and a polyarylate copolymer, and a polycarbonate copolymer is more preferable.
The polycarbonate copolymer is preferably a polycarbonate copolymer having a fluorene skeleton, and is obtained by reacting a bisphenol with a carbonate ester-forming compound such as phosgene or diphenyl carbonate from the viewpoint of transparency, heat resistance, and productivity. Polycarbonate copolymers are particularly preferred.
As content of the fluorene skeleton which the said polycarbonate copolymer has, 1-99 mol% is preferable. As the polycarbonate copolymer, it is also possible to use repeating units described in WO 00/26705 pamphlet.
Among these, the glass which consists of said various inorganic material can be used suitably from a viewpoint of the smoothness of a surface.
There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, 0.1 micrometer or more is preferable, and the upper limit of thickness is substantially 0.5-1.5 mm.

-Other layers-
The other layers are not particularly limited and may be appropriately selected depending on the purpose. For example, an additional optically anisotropic layer having a negative uniaxial refractive index ellipsoidal optical layer, a protective layer, and a reflective layer. Examples include a prevention layer.
The additional optically anisotropic layer has a function of eliminating, for example, the influence of the incident angle of light and the influence of the liquid crystal at the center of the cell in the TN type liquid crystal cell, and may be formed as another layer. it can.

There is no restriction | limiting in particular as a raw material of the said additional optically anisotropic layer, According to the objective, it can select suitably, For example, various raw materials, such as an organic material and an inorganic material, etc. are mentioned.
As the organic material, for example, a material in which birefringence is generated by stretching a plastic film and orienting molecules is known. In this case, the material used as the support may have a function as a birefringent layer. For example, a film obtained by stretching a film of triacetyl cellulose is well known as a support for an optical compensation film.
Examples of the inorganic material include a plurality of layers in which a plurality of inorganic materials having different refractive indexes are periodically stacked with the normal direction of the support as a stacking direction, and the refractive index in the stacking direction is periodically changed. Preferred examples include a structure having a periodic structure multilayer film in which the period of refractive index change is shorter than the wavelength of light in the visible light region. Among these, it is particularly preferable that the periodic structure multilayer film is composed of two layers of two kinds of inorganic materials.
The structure of the additional optically anisotropic layer is not particularly limited as long as it is formed of an inorganic material and has optical characteristics of a negative uniaxial refractive index ellipsoid, and may be appropriately selected according to the purpose. For example, with a normal direction of the support as a stacking direction, a plurality of inorganic materials having different refractive indexes are periodically stacked, and a plurality of layers having a periodic structure in which the refractive index in the stacking direction changes periodically Preferred is a structure composed of a film, and the period of the refractive index change is shorter than the wavelength of light in the visible light region. Among these, the periodic structure multilayer film is composed of two layers of two inorganic materials. Particularly preferred.

Such an additional optically anisotropic layer is equivalent to a medium having a uniform refractive index in the stacking direction of the multilayer film, that is, in the normal direction of the support. Due to the occurrence of anisotropy called refraction, it has the optical characteristics of a negative refractive index ellipsoid that is not uniaxially inclined.
The period of the periodic structure multilayer film is not particularly limited as long as it is shorter than the wavelength of light in the visible light region, and can be appropriately selected from the visible light region according to the purpose. The visible light region means a wavelength region of 400 to 700 nm, unless otherwise specified. Therefore, it is preferable that the period of the periodic structure is appropriately selected within a range of 400 to 700 nm.
Further, as the refractive index in the visible light region of the periodic structure multilayer film, when the multilayer film is composed of a plurality of layers, the difference between the maximum value and the minimum value of the refractive index is preferably 0.5 or more. In the case of consisting of different types of layers, the refractive index difference of each layer is preferably 0.5 or more.
Here, the refractive index is a value measured at a wavelength of 550 nm, unless otherwise specified.
There is no restriction | limiting in particular as the number of layers in the multilayer film of the said additional optically anisotropic layer, According to the objective, it can select suitably.

There is no restriction | limiting in particular as the material of the said periodic structure multilayer film which comprises the said additional optically anisotropic layer, It can select suitably according to the objective, The combination of the several material suitably selected from an oxide film Is preferable, and a combination of a SiO ₂ layer and a TiO ₂ layer is more preferable.
Therefore, the additional optically anisotropic layer can be prepared with high accuracy and ease by appropriately selecting the material, film thickness, number of layers, period of refractive index change, and the like of the periodic structure multilayer film. It becomes possible to do.

  As retardation of these additional optically anisotropic layers, the retardation Rth represented by the following formula 1 is preferably 40 to 200 nm, and more preferably 50 to 150 nm.

<Formula 1>
Rth = {(nx + ny) / 2−nz} × d
However, in Equation 1, nx, ny, and nz are refractions in the X, Y, and Z axis directions orthogonal to each other in the additional optically anisotropic layer when the normal direction of the support is the Z axis. Represents each rate. D represents the thickness of the optically anisotropic layer.

There is no restriction | limiting in particular as the number of layers in the multilayer film of the said additional optically anisotropic layer, According to the objective, it can select suitably.
The thickness of the additional optically anisotropic layer is preferably one that satisfies the retardation, specifically 20 to 300 μm, more preferably 40 to 200 μm, and 50 to 150 μm. It is particularly preferred.
The support itself may have the function of the additional optically anisotropic layer. In the case where a material such as triacetyl cellulose stretched on the support is used and the function is achieved only by the retardation, the additional optically anisotropic layer may not be provided. On the other hand, when an optically isotropic material such as glass is used for the support, the additional optically anisotropic layer can be suitably used. In this case, the thickness in the case of an optically anisotropic layer other than the additional optically anisotropic layer may have a function as a protective film or a support. Can do.
In addition, a layer in which layers having different refractive indexes as described above are alternately stacked can be given a function as an antireflection layer by appropriately selecting each layer configuration from the viewpoint of optical film thickness. In the case of this antireflection layer, not only an inorganic material but also an organic material or a material obtained by adding an inorganic material to an organic material is used as a material constituting a layer having a different refractive index as long as the optical film thickness design condition is satisfied. be able to.

The protective layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cellulose esters such as cellulose acetate, cellulose acetate butyrate, and cellulose propionate, polycarbonate, polyolefin, polystyrene, polyester, and the like. Is mentioned.
Specific examples of the protective layer include polyolefins such as cellulose triacetate, ZEONEX, ZEONOR (both manufactured by Nippon Zeon Co., Ltd.), and ARTON (manufactured by JSR Co., Ltd.).
Further, non-birefringent optical resin materials described in JP-A-8-110402 and JP-A-11-293116 can also be used.
Although there is no restriction | limiting in particular as an orientation axis (slow axis) direction of the said protective layer, It is preferable that the orientation axis of the said protective layer is parallel to a longitudinal direction from the simplicity on work operation. Further, the angle between the slow axis (alignment axis) of the protective layer and the absorption axis (stretching axis) of the polarizing film is not particularly limited, and can be appropriately set according to the purpose of the polarizing plate. When the polarizing film is produced using the width direction uniaxial stretching type tenter stretching machine, the slow axis (alignment axis) of the protective layer and the absorption axis (stretching axis) direction of the polarizing film are substantially the same. Will be orthogonal.
There is no restriction | limiting in particular as retardation of the said protective layer, According to the objective, it can select suitably, For example, 10 nm or less is preferable in measurement wavelength 632.8nm, and 5 nm or less is more preferable.
In the case of using the cellulose acetate, the retardation is preferably less than 3 nm, more preferably 2 nm or less, for the purpose of reducing the change in retardation due to environmental temperature and humidity.

  The material and structure of the antireflection layer is not particularly limited as long as it reduces the reflectance and increases the transmittance, and can be appropriately selected according to the purpose. A known AR film (Anti Reflection) Coat Film).

<Structure of optical compensation element>
There is no restriction | limiting in particular as a structure of the said optical compensation element, According to the objective, it can select suitably, For example, the optical compensation element of the 1st-8th structure shown below is mentioned suitably.

(Optical compensation element having the first structure)
FIG. 1 is a cross-sectional view of an optical compensation element according to the first structure.
The optical compensation element according to the first structure includes the first optical anisotropic layer made of the additional optical anisotropic layer on one surface of the support, and the other surface of the present invention. Two second optically anisotropic layers made of an optically anisotropic layer and having different orientation directions are provided. That is, as shown in FIG. 1, the optical compensation element 10 according to the first structure has an alignment film 4A, a second optical anisotropic layer 3A, an alignment film 4B, a first film on one surface of the support 1. The optically anisotropic layer 3B and the antireflection layer 5B are laminated so that the antireflection layer 5B is disposed on the outermost surface, and the first optically anisotropic layer is formed on the other surface of the support 1. 2. The antireflection layer 5A is laminated so that the antireflection layer 5A is disposed on the outermost surface.
The first optically anisotropic layer 2 is a periodic structure laminate of a TiO ₂ layer 2A and a SiO ₂ layer 2B, and each layer has a thickness of about 15 nm. The first optical anisotropic layer 2 can also have an antireflection function by using such a periodic structure laminate.
Moreover, it is preferable that the directions of rubbing treatment of the alignment film 4A and the alignment film 4B differ by 90 °. By providing the alignment film 4A and the alignment film 4B, the alignment directions of the liquid crystal compounds included in the polymerizable liquid crystal compounds in the second anisotropic layers 3A and 3B are aligned in directions different by 90 °. Is possible.

(Optical compensation element having the second structure)
FIG. 2 is a cross-sectional view showing an example of an optical compensation element according to the second structure.
The optical compensation element according to the second structure includes the first optical anisotropic layer and the second anisotropic layer in this order on at least one surface of the support.
That is, as shown in FIG. 2, the optical compensation element 20 according to the second structure has the first optical anisotropic layer 22, the alignment film 24, and the second optical difference on one surface of the support 21. The isotropic layer 23 and the antireflection layer 25B are laminated in this order so that the antireflection layer 25B is disposed on the outermost surface, and the antireflection layer 25A is laminated on the other surface of the support 21. is there.
The structure of the first optical anisotropic layer 22 can be the same structure as that of the first optical anisotropic layer 2 in the optical compensation element 10 according to the first structure.
Also, two optical compensation elements 20 according to the second structure can be laminated. In this case, it is preferable that the direction of rubbing treatment of the alignment film in each optical compensation element is different by 90 °.
As shown in the optical compensation element 20 according to the second structure, the mode in which each layer is arranged on one surface of the support depends on the material and combination constituting each layer, but generally has good handling, Manufacturing is also easy.

(Optical compensation element of the third structure)
FIG. 3 is a cross-sectional view showing an example of an optical compensation element according to the third structure.
The optical compensation element according to the third structure is formed by providing two second anisotropic layers having different orientation directions on one surface of the support.
That is, as shown in FIG. 3, the optical compensation element 30 according to the third structure has the first optical anisotropic layer 32, the alignment film 34A, and the second optical difference on one surface of the support 31. The isotropic layer 33A, the alignment film 34B, the second optically anisotropic layer 33B, and the antireflection layer 35B are laminated in this order so that the antireflection layer 35B is disposed on the outermost surface. The antireflection layer 35A is laminated on the surface.
The structure of the first optically anisotropic layer 32 can be the same as that of the first optically anisotropic layer 2 in the optical compensation element 10 according to the first structure.
Further, it is preferable that the rubbing treatment directions of the alignment film 34A and the alignment film 34B are different by 90 °. By providing such alignment films 34A and 34B, the alignment direction of the liquid crystal compound contained in the polymerizable liquid crystal compound in the second anisotropic layers 33A and 33B can be aligned in a direction different by 90 °. Become.

(Fourth structure optical compensation element)
FIG. 4 is a cross-sectional view showing an example of an optical compensation element according to the fourth structure.
The optical compensation element according to the fourth structure is formed by providing the two second anisotropic layers having different orientation directions via the support.
That is, as shown in FIG. 4, the optical compensation element 40 according to the fourth structure has the first optical anisotropic layer 42, the alignment film 44A, and the second optical difference on one surface of the support 41. The isotropic layer 43A and the antireflection layer 45B are laminated in this order so that the antireflection layer 45B is disposed on the outermost surface, and the orientation film 44B and the second optical anisotropy are formed on the other surface of the support 41. The layer 43B and the antireflection layer 45A are laminated so as to be arranged in this order.
The structure of the first optical anisotropic layer 42 can be the same structure as that of the first optical anisotropic layer 2 in the optical compensation element 10 according to the first structure.
In addition, it is preferable that the rubbing treatment directions of the alignment film 44A and the alignment film 44B are different by 90 °. By providing such alignment films 44A and 44B, it is possible to align the alignment direction of the liquid crystalline compound contained in the polymerizable liquid crystal compound in the second anisotropic layers 43A and 43B in directions different by 90 °. It becomes.

(5th structure optical compensation element)
FIG. 5 is a cross-sectional view showing an example of an optical compensation element according to the fifth structure.
The optical compensation element according to the fifth structure comprises the first optical anisotropic layer and the second anisotropic layer on at least one surface of the support.
That is, as shown in FIG. 5, the optical compensation element 50 according to the fifth structure has an alignment film 54, a second optical anisotropic layer 53, and a first optical difference on one surface of a support 51. The isotropic layer 52 and the antireflection layer 55B are laminated in this order so that the antireflection layer 55B is disposed on the outermost surface, and the antireflection layer 55A is laminated on the other surface of the support 51. is there.
The structure of the first optical anisotropic layer 52 can be the same structure as that of the first optical anisotropic layer 2 in the optical compensation element 10 according to the first structure.
In addition, two optical compensation elements 50 according to the fifth structure can be stacked. In this case, it is preferable that the direction of rubbing treatment of the alignment film in each optical compensation element is different by 90 °.

(Sixth structure optical compensation element)
FIG. 6 is a cross-sectional view showing an example of an optical compensation element according to the sixth structure.
The optical compensation element according to the sixth structure includes the two second anisotropic layers having different orientation directions. That is, as shown in FIG. 6, the optical compensation element 60 according to the sixth structure has an alignment film 64A, a second optical anisotropic layer 63A, an alignment film 64B, a first film on one surface of a support 61. The second optically anisotropic layer 63B, the first optically anisotropic layer 62, and the antireflection layer 65B are laminated in this order so that the antireflection layer 65B is disposed on the outermost surface. The antireflection layer 65A is laminated on the surface.
The structure of the first optical anisotropic layer 62 can be the same structure as that of the first optical anisotropic layer 2 in the optical compensation element 10 according to the first structure.
In addition, it is preferable that the rubbing treatment directions of the alignment film 64A and the alignment film 64B differ by 90 °. By providing the alignment film 64A and the alignment film 64B, the alignment direction of the liquid crystal compound contained in the polymerizable liquid crystal compound in the second anisotropic layer 63A and the second anisotropic layer 63B is 90. It is possible to align in different directions.

(7th structure optical compensation element)
FIG. 7 is a cross-sectional view showing an example of an optical compensation element according to the seventh structure.
The optical compensation element according to the seventh structure is provided with the two second anisotropic layers having different orientation directions via the support.
That is, as shown in FIG. 7, the optical compensation element 70 according to the seventh structure has an alignment film 74A, a second optical anisotropic layer 73A, and a first optical difference on one surface of a support 71. The isotropic layer 72 and the antireflection layer 75B are laminated in this order so that the antireflection layer 75B is disposed on the outermost surface. The alignment film 74B and the second optical anisotropy are formed on the other surface of the support 71. The layer 73B, the first optical anisotropic layer 72, and the antireflection layer 75A are laminated in this order so that the antireflection layer 75A is disposed on the outermost surface.
The structure of the first optical anisotropic layer 72 can be the same structure as that of the first optical anisotropic layer 2 in the optical compensation element 10 according to the first structure. Further, it is sufficient that at least one first optical anisotropic layer 72 is provided, and any one of the first optical anisotropic layers 72 can be omitted.
Further, it is preferable that the rubbing treatment directions of the alignment film 74A and the alignment film 74B differ by 90 °. By providing such alignment films 74A and 74B, it is possible to align the alignment direction of the liquid crystalline compound contained in the polymerizable liquid crystal compound in the second anisotropic layers 73A and 73B in directions different by 90 °. It becomes.

(Eighth structure optical compensation element)
FIG. 8 is a cross-sectional view showing an example of an optical compensation element according to the eighth structure.
An optical compensation element according to an eighth structure includes the first optical anisotropic layer on one surface of the support and the second optical anisotropic layer on the other surface. .
That is, as shown in FIG. 8, the optical compensation element 80 according to the eighth structure includes an alignment film 84, a second optical anisotropic layer 83, and an antireflection layer 85B on one surface of the support 81. The antireflection layer 85B is laminated so as to be disposed on the outermost surface in order, and the first optical anisotropic layer 82 and the antireflection layer 85A are arranged on the other surface of the support 81 in this order. 85A is laminated so as to be disposed on the outermost surface.
The structure of the first optical anisotropic layer 82 can be the same structure as the first optical anisotropic layer 2 in the optical compensation element 10 according to the first structure.
Further, two optical compensation elements 80 according to the eighth structure can be used by being laminated. In this case, it is preferable that the direction of rubbing treatment of the alignment film in each optical compensation element is different by 90 °.

  In the optical compensation element, the optical characteristics of the first optical anisotropic layers 2, 22, 32, 42, 52, 62, 72, and 82 are determined by the periodic structure pitch of the periodic structure laminate made of an inorganic material. Therefore, it is possible to prevent problems of optical non-uniformity such as refractive index variation and haze value decrease in the surface of the polymer film due to residual stress generated when the polymer film is uniaxially stretched to obtain predetermined optical characteristics. It is possible to increase the optical uniformity in the plane of the first optical anisotropic layer. Therefore, the optical compensation element can optically compensate the liquid crystal layer in the black display state with higher accuracy.

In addition, the first optically anisotropic layer 2, 22, 32, 42, 52, 62, 72, 82 can control the in-plane thickness within a range of several tens of nm, and can realize high smoothness. It is possible to increase the optical uniformity in the plane of the first optical anisotropic layer. Therefore, the liquid crystal layer in the black display state can be optically compensated with higher accuracy, light leakage can be reduced, and the occurrence of streaky irregularities can be prevented.
Further, the first optically anisotropic layer 2, 22, 32, 42, 52, 62, 72, 82 does not expand or contract even when used for a long time in a high temperature / high humidity environment.
As a whole, the optical compensation element as described above can minimize the change in optical characteristics over a long period of time, and the durability is remarkably improved.

  In particular, in the optical compensation elements having the first to third structures, the first optical anisotropy capable of in-plane thickness control in the range of several tens of nanometers on the supports 1, 21 and 31. Layers 2, 22, and 32 are provided. For this reason, the first optically anisotropic layers 2, 22, and 32 can prevent in-plane thickness unevenness with high accuracy, and the first optically anisotropic layer having a highly smooth surface can be used. Can be obtained. Since the second optical anisotropic layers 3, 23, 33 are laminated on the first optical anisotropic layers 2, 22, 32 having such a high smooth surface, the second optical anisotropic layers are stacked. It becomes possible to prevent orientation defects in the plane of the isotropic layers 3, 23, 33. For this reason, an optical compensation element that optically compensates the liquid crystal layer in the black display state with higher accuracy and prevents light leakage at a wide viewing angle can be realized, and a large-screen liquid crystal monitor or liquid crystal that requires a wide viewing angle. By using the optical compensation element in a projector or the like, a liquid crystal display device and a liquid crystal projector with high image quality and high contrast can be realized. In addition, secular changes such as fading and color shift can be reduced even when used for a long period of time, and durability can be improved.

(Liquid crystal display device)
The liquid crystal display device of the present invention includes a liquid crystal element having at least a pair of electrodes and a liquid crystal compound sealed between the pair of electrodes, an optical compensation element disposed on either one or both sides of the liquid crystal element, And a polarizing element disposed opposite to the liquid crystal element and the optical compensation element, and further includes other configurations as necessary. The optical compensation element of the present invention is used as the optical compensation element.
The display mode of the liquid crystal element is not particularly limited and can be appropriately selected according to the purpose. For example, a TN (Twisted Nematic) mode, a VA (Vertical Alignment) mode, an IPS (In-Plane Switching) mode, An OCB (Optically Compensatory Bend) mode, an ECB (Electrically Controlled Birefringence) mode, and the like can be given. Among these, the TN mode is preferable because it has a high contrast ratio.

<Method of manufacturing optical compensation element>
There is no restriction | limiting in particular as a manufacturing method of the said optical compensation element, According to the objective, it can select suitably, For example, the 1st optical anisotropic layer formation process, the alignment film formation process, 2nd optical Examples of the manufacturing method include an anisotropic layer forming step, a heat treatment step, a second optically anisotropic layer polymerization curing step, an antireflection layer forming step, and other layer forming steps.

Hereinafter, each forming process will be described.
-First optical anisotropic layer formation process-
The first optically anisotropic layer forming step is not particularly limited as long as it satisfies the optical characteristics, and can be appropriately selected according to the purpose. For example, the first optically anisotropic layer forming step may be performed on the support. A step of stacking a plurality of layers having different refractive indexes in a regular order with a normal direction as a stacking direction, and forming a periodic structure stacked body having a repeating structure (repeating repeating units); Preferably mentioned.
The material of the periodic structure laminate is not particularly limited as long as it is an inorganic material, and can be appropriately selected according to the purpose. It is preferable to use a combination of a material having a high refractive index or a material having a low refractive index.
The material having a high refractive index is preferably TiO ₂ , ZrO ₂ or the like, and the material having a low refractive index is preferably SiO ₂ or MgF ₂ . These may be used individually by 1 type and may use 2 or more types together.
Specifically, it is preferably selected from a combination of materials in which the difference in refractive index between the maximum value and the minimum value of the refractive index in the visible light region is 0.5 or more, and a plurality of materials appropriately selected from oxides more preferably a combination of, SiO ₂ combinations (refractive index n = 1.4870-1.5442) and TiO ₂ (refractive index n = 2.583-2.741) is particularly preferred.
The number of layers constituting the repetitive structure is not particularly limited as long as it is a plurality of layers having different refractive indexes, but is preferably formed of two or more layers of two kinds of inorganic materials. More preferably, SiO ₂ and TiO ₂ are alternately deposited on the support using a sputtering apparatus under reduced pressure to form a periodic structure laminate composed of several tens of layers.
The optical thickness of the repeating unit, that is, the thickness in the stacking direction of the repeating structure in the periodic structure stacked body is preferably formed to be thinner than the wavelength of light in the visible light region. Λ / 100 to λ / 5 is preferable, λ / 50 to λ / 5 is more preferable, and λ / 30 to λ / 10 is particularly preferable. Each layer is preferably thin, but the number of laminations increases to obtain the required total thickness. Therefore, when determining the number of laminations of each layer, desired optical characteristics and layers of the first optical anisotropic layer In consideration of coloring problems due to mutual interference, it is preferable that the thickness of each layer be optimized from the material, refractive index, thickness ratio, total thickness, etc. of each layer. For example, it is preferable to select and form within a range of 400 to 700 nm.
There is no restriction | limiting in particular as thickness of the said 1st optically anisotropic layer, According to the objective, it can select suitably, For example, it is preferable to form so that it may become 100-1500 micrometers.

―Alignment film formation process―
The one alignment film forming step is a step of forming a film having a function of determining an alignment direction of the liquid crystalline compound in the second optical anisotropic layer on the first optical anisotropic layer. .
The material of the alignment film is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the alignment film made of an organic compound (polymer) subjected to rubbing treatment, the alignment film having a microgroup, Langmuir-Bro Alignment film in which organic compounds such as ω-triconic acid, dioctadecyldimethylammonium chloride, methyl stearylate are accumulated by jet method (LB film), alignment film in which inorganic compounds are obliquely deposited, electric field, magnetic field, light irradiation, etc. An alignment film that generates an alignment function by the above-described method is preferable, and an alignment film made of the rubbed organic compound is preferable.
There is no restriction | limiting in particular as said rubbing process, According to the objective, it can select suitably, For example, the process which rubs the surface of the film | membrane which consists of the said organic compound several times in a fixed direction with paper or cloth is mentioned.

The type of the organic compound is not particularly limited, and can be determined according to the alignment state (particularly the alignment angle) of the liquid crystalline compound. For example, in order to align the liquid crystalline compound horizontally, Examples thereof include polymers for alignment films that are effective in reducing the surface energy.
Specific examples of the alignment film polymer include modified polyvinyl alcohol, acrylic acid copolymer, polyimide, and polyamic acid when the liquid crystalline compound is aligned in a direction orthogonal to the rubbing treatment direction. A polyimide having excellent orientation is more preferable.
There is no restriction | limiting in particular as thickness of the said alignment film, According to the objective, it can select suitably, 0.01-5 micrometers is preferable and 0.02-2 micrometers is more preferable.

-Second optical anisotropic layer forming step-
The first second optically anisotropic layer forming step is a step of forming an optically anisotropic layer using at least a polymerizable liquid crystal compound on the alignment film.
A solution of a polymerizable compound containing the liquid crystal compound is applied onto the alignment film to form a coating layer. As the coating method, it can be formed by a coating method such as a wire bar coating method, a gravure coating method, a micro gravure method or a die coating method. The micro gravure method and the gravure method are preferable from the viewpoint of eliminating drying unevenness by minimizing the wet coating amount, and the forward gravure from the viewpoint of the uniformity of the thickness in the width direction and the uniformity of the thickness in the longitudinal direction over the time of application. The method is more preferred.
There is no restriction | limiting in particular as said polymeric compound, According to the objective, it can select suitably, For example, it is preferable to use the polymeric liquid crystal compound containing the liquid crystalline compound which made the orientation state fixable, rod-like liquid crystalline A polymerizable liquid crystal compound containing a liquid crystal compound such as a compound, a discotic liquid crystal compound, or a banana liquid crystal compound is more preferred, and a polymerizable liquid crystal compound containing a discotic liquid crystal compound is particularly preferred.
The polymerizable composition may contain the radical generator and other components appropriately selected as necessary. Examples of other components include a polymerization initiator for initiating a polymerization reaction of the polymerizable composition, a solvent for preparing a coating liquid for the polymerizable composition, and the like.

―Heat treatment process―
The heat treatment step is a step of heating the second optically anisotropic layer to make the orientation uniform, aging, and maintaining it.
The coating layer is heated at 60 to 120 ° C. to volatilize and dry the solvent. After drying the solvent, the heating temperature is controlled in the range of 85 to 180 ° C. or until the liquid crystal shows the ND layer in order to ripen the orientation of the polymerization compound containing the liquid crystal compound, and the amount of energy that the curing reaction is sufficiently performed. The polymer compound is polymerized by irradiating the ultraviolet ray, and the orientation of the polymer compound containing the liquid crystal compound is fixed to obtain an optically anisotropic layer.

-Second optical anisotropic layer polymerization curing process-
The second optical anisotropic layer polymerization curing step is a step of polymerizing and curing the second optical anisotropic layer while maintaining the transition temperature.
The polymerization and curing step of the second optically anisotropic layer with matured orientation is not particularly limited as long as the orientation of the liquid crystal layer can be fixed, and can be appropriately selected according to the purpose. For example, what performs a hardening reaction by irradiating the active ray for photopolymerization is mentioned. As an active ray for photopolymerization, an electron beam, an ultraviolet ray, a visible ray, an infrared ray (heat ray) or the like can be appropriately selected and used as necessary. In general, an ultraviolet ray is preferably used. Examples of ultraviolet light sources include low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), and short arc discharge lamps (extra-high pressure mercury lamps, xenon lamps, mercury xenon). Lamp). Further, in the present invention, in consideration of the absorption wavelength characteristic of the polymerization initiator, it may be formed only by polymerization by heat without performing irradiation with light such as ultraviolet rays.
The following compounds can be used in combination as the polymerization initiator depending on the polymerizable functional group.
Examples of the compound include azobis compounds, peroxides, hydroperoxides, redox catalysts, and the like, for example, potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, 2,4-dichloro. Benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) hydrochloride or benzophenones, acetophenones, benzoins, thioxanthone And the like. Details thereof are described in “Ultraviolet Curing System” General Technical Center, pages 63 to 147, 1989, and the like.

In consideration of thermal polymerization, the aforementioned 2,2′-azobis (2,4-dimethylvaleronitrile (V-65: Wako Pure Chemical Industries), 2,2′-azobis (4-methoxy-2) Peroxide-based and azo-based polymerization initiators such as 1,4-dimethylvaleronitrile (V-70: Wako Pure Chemical Industries), polyethylene glycol unit-containing polymer azo polymerization initiator (VPE-0201: Wako Pure Chemical Industries) In addition to these polymerization initiators, the above-mentioned thermal crosslinking agent may be added to accelerate the polymerization reaction.
In addition, when performing a curing reaction using a radical reaction, in order to avoid a delay in the polymerization reaction due to the presence of oxygen in the air, irradiation with the active ray under a nitrogen atmosphere or the like shortens the reaction time. This is preferable in that it can be cured with a small amount of light.

―Anti-reflection layer formation process―
The antireflection layer forming step is a step of forming an antireflection layer on the cured second optically anisotropic layer. For example, in the case of forming with an inorganic material, a method of forming on the second optically anisotropic layer by a vapor deposition method or in the case of an organic material by a coating method can be mentioned.
The deposition method is not particularly limited and may be appropriately selected depending on the purpose. For example, the CVD or evaporation in which a sample is placed in a gas source atmosphere and a layer is formed on the sample surface by a chemical reaction. And PVD formed by attaching a raw material in the form of particles to a sample by sputtering.
Among these, PVD physically produced by sputtering under reduced pressure using a sputtering target formed of a metal that is a material of the antireflection layer is more preferable.
The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, the coating method can be formed by a coating method such as a wire bar coating method, a gravure coating method, a micro gravure method, or a die coating method. . The micro gravure method and the gravure method are preferable from the viewpoint of eliminating drying unevenness by minimizing the wet coating amount, and the forward gravure from the viewpoint of the uniformity of the thickness in the width direction and the uniformity of the thickness in the longitudinal direction over the time of application. The method is more preferred.

-Other layer formation process-
The other layer forming steps include the first optical anisotropic layer forming step, the alignment film forming step, the second optical anisotropic layer forming step, the heat treatment step, and the second optical anisotropic layer polymerization curing. Each process up to the process is repeated at least once in this order to form a second optical anisotropy that forms a second optical anisotropic layer having a different orientation direction from the previously formed second optical anisotropic layer. A layer formation process is mentioned.
Before or after the antireflection layer forming step, other layers can be appropriately selected, and examples thereof include a forming step of a protective layer, an antiglare layer, an antifouling layer, an antistatic layer, and the like.

--Protective layer formation process--
The protective layer forming step is a step of forming a protective layer, and is not particularly limited and can be appropriately selected depending on the purpose. After the optically anisotropic layer is polymerized and cured and the orientation of the liquid crystal layer is fixed, a step of laminating on the second optically anisotropic layer is preferable. The protective layer is a layer that improves the durability by blocking the second optical anisotropic layer made of an organic material from an oxidation reaction, and is preferably laminated on the second optical anisotropic layer. is there.

The method for laminating the protective layer is not particularly limited and may be appropriately selected depending on the purpose. In the case of an organic material, a protective layer forming solution is prepared and the second optically anisotropic layer is formed. The method of laminating by applying to is preferred.
The application method is not particularly limited, and examples thereof include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, and a spin coating method.
In the case of an inorganic material, the vapor deposition method which laminate | stacks by vapor-depositing material is mentioned suitably.
The vapor deposition method is not particularly limited and may be appropriately selected depending on the purpose. For example, a chemical vapor deposition method in which a sample is placed in an atmosphere of a gas source and a thin film is formed on the sample surface by a chemical reaction. (CVD: Chemical Vapor Deposition) or physical vapor deposition (PVD: Physical Vapor Deposition), in which a raw material in the form of particles is attached to a sample by evaporation or sputtering.
Among these, PVD that is physically manufactured by sputtering using a sputtering target formed of a metal that is a material of the protective layer under reduced pressure is more preferable.

(Liquid crystal display device)
The liquid crystal display device of the present invention includes at least a pair of electrodes and a liquid crystal element having liquid crystal molecules sealed between the electrodes, an optically anisotropic layer disposed on both sides or one side of the liquid crystal element, the liquid crystal element, A polarizing element disposed opposite to the optically anisotropic layer, and further provided with other components as necessary, and using the optically anisotropic layer of the present invention as the optically anisotropic layer. .

  The display mode of the liquid crystal element is not particularly limited and can be appropriately selected according to the purpose. For example, a TN (Twisted Nematic) mode, a VA (Vertical Alignment) mode, an IPS (In-Plane Switching) mode, An OCB (Optically Compensatory Bend) mode, an ECB (Electrically Controlled Birefringence) mode, and the like can be given. Among these, the TN mode is preferable because it has a high contrast ratio.

9 to 12 are schematic configuration diagrams of the liquid crystal display device of the present invention.
In order to facilitate understanding in these drawings, the schematic configuration of the liquid crystal display device shown in each drawing shows a mode in which light from a light source is incident from the lower side of the drawing and is emitted toward the upper side of the drawing. For those including two components of the second optically anisotropic layer, the upper direction of the drawing is referred to as “upper side” and the lower direction of the drawing is referred to as “lower side”. .
As shown in FIG. 9, the liquid crystal display device 100 includes a pair of an upper polarizing element 101 (analyzer) and a lower polarizing element 116 (polarizer) in which absorption axes 102 and 115 are substantially orthogonal and opposed to each other in crossed Nicols. The phase difference plate 108 disposed between the upper and lower polarizing elements 101 and 116, and a liquid crystal element 114 (liquid crystal cell).
In place of the upper and lower polarizing elements 101 and 116, a polarizing beam splitter such as a Glan-Thompson prism may be used as a polarizing element so as to be opposed to the liquid crystal element 114.

  In the liquid crystal element 114, an upper substrate 109 made of a glass substrate and a lower substrate 113 are arranged to face each other, and for example, a nematic liquid crystal 111 is sealed between the upper substrate 109 and the lower substrate 113. On the opposing surfaces of the upper substrate 109 and the lower substrate 113, pixel electrodes (not shown), circuit elements (thin film transistors), and the like are formed. Upper and lower alignment films (not shown) are formed on opposing surfaces of the upper substrate 109 and the lower substrate 113 that are in contact with the nematic liquid crystal 111. A rubbing process is performed on the surface of the alignment film in contact with the nematic liquid crystal 111 in order to align the alignment direction of the liquid crystal molecules. For example, in the case of a TN mode liquid crystal display device, the rubbing directions 110 and 112 in the upper and lower alignment films are substantially orthogonal to each other as the direction of the groove (rubbing direction) carved by the rubbing treatment.

  FIG. 10 shows an alignment state of liquid crystal molecules in a normal state where no voltage is applied to the liquid crystal element 114. The nematic liquid crystals 111 on the upper substrate 109 and the lower substrate 113 are arranged in substantially the same direction as the rubbing directions 110 and 112 by the action of the rubbing treatment applied to the alignment film (not shown). Since the rubbing directions 110 and 112 are orthogonal to each other, the molecules of the nematic liquid crystal 111 are in a state where the major axis of the liquid crystal molecules is twisted by 90 ° as it goes from the upper substrate 109 to the lower substrate 113. Arranged.

The polarizing element preferably has a light transmittance of 0.001% or less when the polarizing element is arranged in a crossed Nicol state, where the light transmittance when the polarizing element is arranged in parallel Nicols is 100%. .
The upper polarizing element 101 (analyzer) and the lower polarizing element 116 (polarizer) have at least a polarizing film, and further have other configurations as necessary.

The polarizing film is not particularly limited and may be appropriately selected depending on the intended purpose. And a film obtained by adsorbing a dichroic substance such as iodine, azo-based, anthraquinone-based, and tetrazine-based dichroic dyes on the resulting film, and then subjecting the film to stretching orientation.
The stretching orientation treatment is not particularly limited and may be appropriately selected depending on the purpose. A width direction uniaxial stretching type tenter stretching machine in which the absorption axis of the polarizing film is substantially perpendicular to the longitudinal direction. Preferably mentioned. Such a width direction uniaxial stretching type tenter stretching machine has an advantage that foreign matter hardly enters during bonding.
As the stretching orientation treatment, a stretching method described in JP-A No. 2002-131548 can be used.

There is no restriction | limiting in particular as said other structure, According to the objective, it can select suitably, The protective layer, antireflection layer, glare-proofing layer, etc. which are provided in the single side | surface or both surfaces of the said polarizing film are mentioned.
The upper and lower polarizing elements 101 and 116 are structured such that a polarizing plate having the protective layer on at least one surface of the polarizing film and a liquid crystal element 114 as a support are integrated with one surface of the optical compensation element. Suitable examples include those having the polarizing film.
The protective layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cellulose esters such as cellulose acetate, cellulose acetate butyrate, and cellulose propionate, polycarbonate, polyolefin, polystyrene, polyester, and the like. Is mentioned.
Specific examples of the protective layer include polyolefins such as cellulose triacetate, ZEONEX, ZEONOR (both manufactured by Nippon Zeon Co., Ltd.), and ARTON (manufactured by JSR Co., Ltd.).
Further, non-birefringent optical resin materials described in JP-A-8-110402 and JP-A-11-293116 can also be used.
Although there is no restriction | limiting in particular as an orientation axis (slow axis) direction of the said protective layer, It is preferable that the orientation axis of the said protective layer is parallel to a longitudinal direction from the simplicity on work operation. Further, the angle between the slow axis (alignment axis) of the protective layer and the absorption axis (stretching axis) of the polarizing film is not particularly limited, and can be appropriately set according to the purpose of the polarizing plate. When the polarizing film is produced using the width direction uniaxial stretching type tenter stretching machine, the slow axis (alignment axis) of the protective layer and the absorption axis (stretching axis) direction of the polarizing film are substantially the same. Will be orthogonal.
There is no restriction | limiting in particular as retardation of the said protective layer, According to the objective, it can select suitably, For example, 10 nm or less is preferable in measurement wavelength 632.8nm, and 5 nm or less is more preferable.
In the case of using the cellulose acetate, the retardation is preferably less than 3 nm, more preferably 2 nm or less, for the purpose of reducing the change in retardation due to environmental temperature and humidity.

The method for producing the polarizing plate is not particularly limited and may be appropriately selected according to the purpose. The polarizing plate is continuously formed so that the longitudinal direction thereof is coincident with the long polarizing film supplied in a roll form. It is preferable that they are bonded together.
Moreover, it is preferable that the polarizing film and the polarizing plate are fixed to the optical compensation element from the viewpoints of preventing displacement of the optical axis and preventing entry of foreign matters such as dust.
There is no restriction | limiting in particular as said antireflection layer, According to the objective, it can select suitably, For example, optical interference layers, such as a coating layer of a fluorine-type polymer, a multilayer metal vapor deposition layer, etc. are mentioned.
Is the optical properties and durability (short-term, long-term storage stability) of the upper and lower polarizing elements 101, 116 equivalent to commercially available super high contrast products (for example, HLC2-5618 manufactured by Sanlitz Co., Ltd.)? It is preferable to have more performance.

The optical compensation element 108 uses the optical compensation element of the present invention.
As the optical compensation element, when the white display transmittance of the liquid crystal display device 100 in a state incorporated in the liquid crystal display device 100 is Vw and the black display transmittance is Vb, the white display on the front surface of the liquid crystal display device 100 is performed. The ratio between the transmittance Vw and the black display transmittance Vb, that is, the contrast ratio Vw: Vb is preferably 100: 1 or more, more preferably 200: 1 or more, and further preferably 300: 1 or more.
Further, in all azimuth angle directions inclined by 60 ° from the normal direction on the display surface of the liquid crystal display device 100, the maximum value of the black display transmittance is preferably 10% or less, more preferably 5% or less with respect to Vw. By using such an optical compensation element, it is possible to realize a liquid crystal display device having a wide viewing angle with high contrast and no gradation inversion.
Further, in order to accurately compensate a liquid crystal element having a large residual twist component, the optical compensation element is disposed between a pair of polarizing elements disposed in crossed Nicols, and the normal direction of the optical compensation element is used as a rotation axis. There is no direction in which the liquid crystal display device extinguishes when the optical compensation element is rotated, and the light transmittance is preferably 0.01% or more in all directions.

The optical compensation element 108 is disposed between the upper polarizing element 101 and the liquid crystal element 114, and includes a first optical anisotropic layer 107, an upper second optical anisotropic layer 103, and a lower second optical anisotropic layer. 105.
Each of the optically anisotropic layers constituting the optical compensation element 108 includes a rubbing direction 104 of the alignment film in the upper second optically anisotropic layer 103 and a rubbing direction 110 of the upper alignment film in the upper substrate 109 of the liquid crystal element 114. The rubbing direction 106 of the alignment film in the lower second optically anisotropic layer 105 and the rubbing direction 112 of the lower alignment film in the lower substrate 132 of the liquid crystal element 114 are arranged so that the angle formed by The angle formed by is arranged to be 180 °.
The relationship between the second optically anisotropic layer and the rubbing direction of the alignment film in the substrate of the liquid crystal element may be replaced, and the rubbing direction 106 of the alignment film in the lower second optically anisotropic layer 105; The angle formed between the upper alignment film of the upper substrate 109 of the liquid crystal element 114 and the rubbing direction 110 of the upper alignment film is 180 °, the rubbing direction 104 of the alignment film in the upper second optical anisotropic layer 103, and the liquid crystal element 114 The angle formed with the rubbing direction 112 of the lower alignment film on the lower substrate 113 may be 180 °.
The first optically anisotropic layer 107 is preferably provided so as to be on the liquid crystal element 114 side.

  FIG. 11 shows an arrangement state of liquid crystal molecules in a black display state, that is, in a state where a voltage is applied to the liquid crystal element 114, in the TN mode liquid crystal display device. When a voltage is applied to the liquid crystal element 114, the alignment state of the liquid crystal molecules changes so that the liquid crystal molecules rise, that is, the major axis of the liquid crystal molecules is perpendicular to the light incident surface. Ideally, it is desirable that all the liquid crystal molecules in the liquid crystal element 114 when a voltage is applied are parallel to the light incident surface, but in practice, as shown in FIG. The liquid crystal molecules in the liquid crystal element 114 are gradually in a state where the major axis of the liquid crystal molecules rises from the upper substrate 109 and the lower substrate 113 toward the central region of the liquid crystal element 114. Accordingly, the liquid crystal molecules in the vicinity of the interface between the upper substrate 109 and the lower substrate 113 are in a tilted arrangement state in which the major axis of the liquid crystal molecules is not parallel to the light incident surface even when a voltage is applied. Thus, the presence of liquid crystal molecules tilted with respect to the light incident surface may cause light leakage depending on the viewing angle without being in a black display state.

Further, nematic liquid crystal used in a TN mode liquid crystal display device is generally a rod-like liquid crystal and exhibits optically positive uniaxiality. For this reason, even when the liquid crystal molecules exist in the central region of the liquid crystal element 114 and are completely upright, when the liquid crystal display device 100 is viewed from an oblique direction, birefringence is manifested. This may cause light leakage without being displayed.
Therefore, with respect to the alignment state of the liquid crystal in the liquid crystal element 114 near the interface between the upper substrate 109 and the lower substrate 113 in the black display state, the alignment of the liquid crystal molecules included in the second optical anisotropic layers 103 and 105 The state is mirror-symmetrical and optically compensates for the occurrence of birefringence in the interface region on the upper substrate 109 and lower substrate 113 side. The liquid crystal display element 114 in a black display state as a whole is three-dimensionally arranged by being optically compensated by the first optical anisotropic layer 107 having an optical characteristic of a negative refractive index ellipsoid that is not inclined. Thus, optical compensation can be performed to prevent light leakage at a wide viewing angle.

Further, the optical compensation element 108 can be provided on the lower surface of the liquid crystal element 114 as shown in FIG. 11, and further can be provided as 108a and 108b on the upper and lower surfaces of the liquid crystal element 114 as shown in FIG. . Note that in the case of disposing the liquid crystal element on the upper and lower surfaces, either the first optical anisotropic layer 107a or 107b can be omitted, and in the case where the first optical anisotropic layer is provided for each, 107a. , 107b, the total retardation value.
As the optical compensation element 108, the support (not shown) provided in the optical compensation element 108 can be the upper substrate 109 and the lower substrate 113 of the liquid crystal element 114. In this case, the first optical anisotropic layer 107 a or 107 b shown in FIG. 12 is directly formed on the upper substrate 109 and the lower substrate 113.

(LCD projector)
The liquid crystal projector of the present invention is a liquid crystal projector that displays an image by irradiating the liquid crystal display device with illumination light from a light source and forming an image on the screen by the projection optical system using light modulated by the liquid crystal display device. The liquid crystal display device uses the liquid crystal display device of the present invention.
The liquid crystal projector is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a screen projection type front projector and a rear projection television. The liquid crystal display device used for the liquid crystal projector is not particularly limited and may be appropriately selected depending on the intended purpose. Suitable examples include a transmissive liquid crystal display device and a reflective liquid crystal display device.

FIG. 13 is an external view showing an example of a rear type liquid crystal projector.
As shown in FIG. 13, the liquid crystal projector 200 is provided with a diffusion transmission type screen 203 on the front surface of the housing 202, and an image projected on the back surface is observed from the front surface side of the screen 203. A projection unit 300 is incorporated inside the housing 202, and a projection image projected by the projection unit 300 is reflected by the mirrors 206 and 207 and formed on the back surface of the screen 203. In the liquid crystal projector 200, a tuner circuit (not shown), a well-known circuit unit for reproducing a video signal and an audio signal, and the like are disposed inside the housing 202.
The projection unit 300 incorporates a liquid crystal display device (not shown) as image display means. The liquid crystal display device displays the reproduced image of the video signal, so that the image can be displayed on the screen 203.

FIG. 14 is a configuration diagram illustrating an example of the projection unit 300.
As shown in FIG. 14, the projection unit 300 includes three transmissive liquid crystal elements 311R, 311G, and 311B, and can perform full-color image projection.
Light emitted from the light source 312 passes through a filter 313 that cuts ultraviolet rays and infrared rays to become white light including red light, green light, and blue light, and illumination light from the light source 312 to the liquid crystal elements 311R, G, and B. It enters the glass rod 314 along the axis. The light incident surface of the glass rod 314 is located near the focal position of the parabolic mirror used in the light source 312, and the light from the light source 312 efficiently enters the glass rod 314.

A relay lens 315 is disposed on the exit surface of the glass rod 314, and the white light emitted from the glass rod 314 becomes parallel light by the relay lens 315 and the subsequent collimator lens 316 and enters the mirror 317.
The white light reflected by the mirror 317 is divided into two light beams by a dichroic mirror 318R that transmits only red light, and the transmitted red light is reflected by the mirror 319 to illuminate the liquid crystal element 311R from the back.
Further, the green light and the blue light reflected by the dichroic mirror 318R are further divided into two light beams by the dichroic mirror 318G that reflects only the green light. The green light reflected by the dichroic mirror 318G illuminates the liquid crystal element 311G from the back side. The blue light transmitted through the dichroic mirror 318G is reflected by the mirrors 318B and 320, and illuminates the liquid crystal element 311B from the back.

  Each of the liquid crystal elements 311R, 311G, 311B is composed of a TN mode liquid crystal element, and each liquid crystal element displays a density pattern image of a red image, a green image, and a blue image constituting a full color image. The A synthesis prism 324 is arranged so that the center is optically equidistant from these liquid crystal elements 311R, 311G, and 311B, and a projection lens 325 is provided to face the emission surface of the synthesis prism 324. Yes. The combining prism 324 includes two dichroic surfaces 324a and 324b inside, and combines the red light transmitted through the liquid crystal element 311R, the green light transmitted through the liquid crystal element 311G, and the blue light transmitted through the liquid crystal element 311B. To enter the projection lens 325.

  A projection lens 325 is provided on the projection optical axis from the center of the exit surface of each of the liquid crystal elements 311R, 311G, 311B, through the center of the combining prism 324 and the projection lens 325 to the center of the screen 3. The projection lens 325 is disposed such that the object-side focal plane coincides with the exit surfaces of the liquid crystal elements 311R, 311G, and 311B, and the image-plane focal plane coincides with the screen 3. Therefore, the full color image synthesized by the synthesis prism 324 is formed on the screen 303.

Polarizing plates 326R, 326G, and 326B are provided on the illumination light incident surfaces of the liquid crystal elements 311R, 311G, and 311B, respectively. Further, optical compensation elements 327R, 327G, and 327B and polarizing plates 328R, 328G, and 328B are provided on the emission surface side of each liquid crystal element. The polarizing plates 326R, 326G, and 326B on the incident surface side and the polarizing plates 328R, 328G, and 328B on the outgoing surface side are arranged in a crossed Nicol arrangement. The polarizing plate on the incident surface side is a polarizer, and the polarizing plate on the outgoing surface side. Acts as an analyzer.
The liquid crystal display device of the present invention includes liquid crystal elements 311R, 311G, 311B, polarizing plates 326R, 326G, 326B, 328R, 328G, 328B, and optical compensation elements 327R, 327G, 327B.
In addition, although the liquid crystal element provided for each color channel, the action of the polarizing plate and the optical compensation element respectively provided on both sides thereof are different based on each color light, the basic action is substantially common. Therefore, the operation will be described below using the red channel.

  The red illumination light reflected by the mirror 319 becomes linearly polarized light by the polarizing plate 326R on the incident surface side and enters the liquid crystal element 311R. In the normally white mode, a signal voltage is applied to the pixel of the TN mode liquid crystal used in the liquid crystal element 311R in order to display black of a red image. At this time, the liquid crystal molecules contained in the liquid crystal layer take various orientations, and even if the red illumination light becomes a parallel light flux and enters the liquid crystal element 311R, the liquid crystal layer exhibits optical rotation and birefringence. The light emitted from the emission surface of the liquid crystal element 311R does not become completely linearly polarized light, and generally elliptically polarized image light is emitted, causing light leakage from the analyzer-side polarizing plate 328R, which is sufficient. I can't get black. Even in the normally black mode, the black level does not become sufficiently black due to a slight inclination of the liquid crystal molecules.

In addition, in the state where black display is desired, if the light passing through the liquid crystal molecules in the liquid crystal element is included obliquely, the image light modulated by the liquid crystal layer has a slightly optical phase different from the linearly polarized light. Becomes elliptically polarized light different from each other, light leakage occurs from the analyzer-side polarizing plate 328R, and sufficient black cannot be obtained.
The liquid crystal projector of the present invention uses the liquid crystal display device of the present invention provided with the optical compensation element of the present invention. The optical compensation element 327R can optically compensate the liquid crystal layer in the black display state with higher accuracy, and can prevent light leakage in a wide viewing angle.
Therefore, the liquid crystal projector of the present invention can obtain a high viewing angle, high contrast, and high image quality.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
As described below, a polymerizable composition coating solution and an alignment film coating solution were prepared, an optical compensation element was manufactured, and a liquid crystal display device was manufactured.

<Preparation of polymerizable composition coating solution>
A polymerizable composition coating solution having the following composition was prepared.
―――――――――――――――――――――――――――――――――――――――
-Discotic liquid crystal compound represented by the following structural formula (3) ... 4.00 g
・ Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 0.27g
・ Cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co., Ltd.) ... 0.04g
・ Cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co., Ltd.) …… 0.01g
-Photopolymerization initiator (Irgacure-651, manufactured by Ciba Geigy) ... 0.12 g
・ Solvent (mixed solution of 4.5 g of 1-methoxy-2-propanol acetate, 9.0 g of ethyl ethoxypropionate and 1.5 g of ethyl lactate) ... 15.00 g
―――――――――――――――――――――――――――――――――――――――

<Preparation of alignment film coating solution>
An alignment film coating solution having the following composition was prepared.
――――――――――――――――――――――――――――――――――――――――
・ Modified polyvinyl alcohol represented by the following structural formula (4) 20 g
・ Water (solvent) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 360g
・ Methanol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 120g
・ Glutaraldehyde (crosslinking agent) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1g
――――――――――――――――――――――――――――――――――――――――

<Production of optical compensation element>
An optical compensation element similar to the first structure shown in FIG. 1 was produced by the following method.
As shown in FIG. 1, in the optical compensation element 10 according to the first structure, the first optical anisotropic layer 2 and the antireflection layer 5A are laminated in this order on one surface of the support 1, An optical compensation element in which an alignment film 4A, a second optical anisotropic layer 3A, an alignment film 4B, a second optical anisotropic layer 3B, and an antireflection layer 5B are laminated in this order on the other surface of the support 1 It is.

-Production of first optically anisotropic layer-
As a support 1, a glass substrate is used, and SiO ₂ and TiO ₂ are alternately deposited on the glass substrate by using a sputtering apparatus under reduced pressure, and each layer is 26 layers, for a total of 52 layers. A first optically anisotropic layer 2 comprising: The total thickness of the manufactured first optical anisotropic layer was 760 nm and Rth = 200 nm.

―Preparation of antireflection layer―
On the surface of the obtained second optically anisotropic layer 2, SiO ₂ and TiO ₂ were alternately deposited using a sputtering apparatus under reduced pressure to form an antireflection layer 5A. The thickness of the formed antireflection layer 5A was 0.24 μm.

-Fabrication of alignment film-
Next, 100 ml / m ² of the obtained alignment film coating solution is dropped on the surface of the glass substrate opposite to the first optically anisotropic layer 2 and spin-coated under the condition of 1000 rpm. Thereafter, the alignment film coating solution was dried with hot air at 100 ° C. for 3 minutes to prepare an alignment film having a thickness of 600 nm. Next, a rubbing process was performed on the surface of the formed alignment film to prepare an alignment film 4A that is aligned in a predetermined alignment direction.

-Production of second optically anisotropic layer-
The obtained polymerizable liquid crystal compound coating solution 100 ml / m ² is dropped on the surface of the alignment film 4A and spin-coated under the condition of 1500 rpm. Thereafter, the polymerizable liquid crystal compound was aligned by heating in a constant temperature zone of 130 ° C. for 5 minutes. Thereafter, the polymerizable liquid crystal compound was polymerized by UV irradiation with an irradiation energy of 300 mJ / cm ² using a high pressure mercury lamp, and the alignment state of the liquid crystal compound was fixed. Then, it stood to cool to room temperature, and produced the 2nd optically anisotropic layer 3A.
In the formed second optically anisotropic layer 3A, the discotic liquid crystal compound has an angle (orientation angle) formed by a vertical axis normal to the disc surface and a normal to the glass substrate of 10 ° to 62 °. From the glass substrate side toward the air interface side, the discotic liquid crystal compound was hybrid aligned. The orientation angle of the discotic liquid crystal compound is measured by using an ellipsometer (M-150, manufactured by JASCO Corporation) to measure the retardation while changing the observation angle. Was calculated by the method described in “Design Concepts of the Discrete Negative Birefringence Compensation Films SID98 DIGEST”.
On the surface of the second optically anisotropic layer 3A, an alignment film 4B was further laminated so that the alignment direction was substantially orthogonal to the alignment film 4A. Then, the second optical anisotropic layer 3B was formed on the surface of the alignment film 4B by the same method as the second optical anisotropic layer 3A.
The materials, blending amounts, and the like of the alignment film 4B and the second optical anisotropic layer 3B are the same as those of the alignment film 4A and the second optical anisotropic layer 3A.

  In the obtained second optically anisotropic layer 3B, the discotic liquid crystal compound has an angle (orientation angle) between the disc surface and the glass substrate of 12 ° to 65 ° from the air interface from the glass substrate side. The disk-like liquid crystal compound was hybrid aligned. The obtained optical second optically anisotropic layer 3B was a uniform layer free from defects such as schlieren.

―Preparation of antireflection layer―
On the surface of the obtained second optically anisotropic layer 3B, SiO ₂ and TiO ₂ were alternately deposited using a sputtering apparatus under reduced pressure to produce an antireflection layer 5B. The thickness of the produced antireflection layer 6 was 0.24 μm.

<Production of liquid crystal display device>
The manufactured optical compensation element 10 was superposed on a normally white mode TN mode liquid crystal element of white display 1.5V and black display 3V to manufacture a liquid crystal display device.

(Example 2)
In the same manner as in Example 1, except that 0.12 g of “photopolymerization initiator (Irgacure-651, manufactured by Ciba Gaiky Corporation)” was replaced with “0.19 g of tripromomethylphenylsulfone”. A liquid crystal display device of Example 2 was produced.

(Example 3)
In Example 1, except that “photopolymerization initiator (Irgacure-651, manufactured by Ciba-Gaiky) 0.12 g” was replaced with “azobisisobutyronitrile (AIBN: manufactured by Aldrich) 0.08 g”. A liquid crystal display device of Example 3 was produced in the same manner as Example 1.

Example 4
In Example 1, the liquid crystal display device of Example 4 was produced in the same manner as Example 1 except that the alignment film coating solution was an alignment film coating solution having the following composition.

-Composition of alignment film coating solution-
―――――――――――――――――――――――――――――――――――――――
・ Sun Ever 150 (Nissan Chemical Co., Ltd.) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 20g
-Thinner for polyimide (Nissan Chemical Co., Ltd.) 20g
―――――――――――――――――――――――――――――――――――――――

(Example 5)
A liquid crystal display device of Example 5 was produced in the same manner as in Example 1 except that instead of polymerization by ultraviolet irradiation in Example 1, heat curing was performed at 150 ° C. for 1 hour without performing ultraviolet irradiation.

(Comparative Example 1)
In Example 1, ““ photopolymerization initiator (Irgacure-651, manufactured by Ciba-Gaiky) 0.12 g ”has absorption even at a wavelength of 420 nm or more“ “photopolymerization initiator (Irgacure-651, manufactured by Ciba-Gaykey)” 0. A liquid crystal display device of Comparative Example 1 was produced in the same manner as in Example 1 except that “.13 g” was used.

(Examples 1-5 and Comparative Example 1)
<Evaluation of contrast of liquid crystal display device>
About the liquid crystal display device in Examples 1-5 and the comparative example 1, the contrast in the place of the elevation angle of 20 degrees and the azimuth | direction angle of 450 degrees from the front of the display surface was measured using the conoscope (made by Autronic-Melcher). Here, as the contrast, a contrast (white display illuminance / black display illuminance) calculated from white display illuminance, black display illuminance, and a ratio thereof was measured. The measurement results are shown in Table 1.

(Examples 6 to 10 and Comparative Example 2)
<Production of liquid crystal projector>
Three liquid crystal display devices of Examples 6 to 10 and Comparative Example 2 are mounted on a commercially available TN type liquid crystal projector for each of RGB colors, and the liquid crystal projectors of Examples 6 to 10 and Comparative Example 2 are mounted. Was made.

<Evaluation of contrast of LCD projector>
About the obtained liquid crystal projector, the contrast (white display illuminance / black display illuminance) calculated from the white display illuminance, the black display illuminance and the ratio thereof on the screen set at a distance of 3 m from the projection lens was measured.

―Evaluation method of usage (forced test) ―
The liquid crystal display devices (Examples 1 to 5 and Comparative Example 1) and liquid crystal projectors (Examples 6 to 10 and Comparative Example 2) are used under the respective acceleration conditions of 96 hours using a light source equivalent to 200 million lux of white light. Time (forced test) was performed and the contrast was evaluated. The measurement results are shown in Table 2.

From the results of Table 1, it can be seen that the contrast of the liquid crystal display devices of Examples 1 to 5 is not deteriorated as compared with the liquid crystal display device of Comparative Example 1.

In addition, the liquid crystal display device prepared in Example 1 and Comparative Example 1 is prepared, and the light source is changed from white light to a light source with limited wavelengths of red, green, and blue, and white light equivalent to 200 million lux is used. The time of use (forced test) was performed under each acceleration condition of 96 hours.
As a result, in the liquid crystal display device prepared in Example 1, the red, green, and blue light sources each showed the same deterioration tendency, whereas in the liquid crystal display device prepared in one comparative example, red, green, While the compulsory test result with the light source of the blue light source was almost the same, the test result of the blue light source was reduced to about 40% as compared with the result of the red and green light sources.

From the results of Table 2, it can be seen that the contrast of the liquid crystal projectors of Examples 6 to 10 is not deteriorated as compared with the liquid crystal projector of Comparative Example 2.

  The polymerizable composition of the present invention, an optically anisotropic layer using the polymerizable composition, an optical compensation element having the optically anisotropic layer, and a liquid crystal display device comprising the optical compensation element are a mobile phone, It can be suitably used for personal computer monitors, televisions, liquid crystal projectors, and the like.

FIG. 1 is a cross-sectional view showing an example of the optical compensation element having the first structure. FIG. 2 is a cross-sectional view showing an example of the optical compensation element having the second structure. FIG. 3 is a cross-sectional view showing an example of the optical compensation element having the third structure. FIG. 4 is a cross-sectional view showing an example of an optical compensation element having a fourth structure. FIG. 5 is a cross-sectional view showing an example of the optical compensation element having the fifth structure. FIG. 6 is a cross-sectional view showing an example of an optical compensation element having a sixth structure. FIG. 7 is a cross-sectional view showing an example of an optical compensation element having a seventh structure. FIG. 8 is a sectional view showing an example of an optical compensation element having an eighth structure. FIG. 9 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 10 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 11 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 12 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 13 is an external view showing an example of a rear type liquid crystal projector. FIG. 14 is a configuration diagram illustrating an example of a projection unit.

Explanation of symbols

1, 2, 31, 41, 51, 61, 71, 81... Support 2, 22, 32, 42, 52, 62, 72, 82... First optical anisotropic layer 3, 23, 33, 43, 53, 63, 73, 83 ... Second optical anisotropic layer 4, 24, 34, 44, 54, 64, 74, 84 ... Alignment film 5, 25, 35, 45, 55, 65, 75, 85... Antireflection layer 10, 20, 30, 40, 50, 60, 70, 80... Optical compensation element 100.・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Liquid crystal display device 101 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Upper polarizing plate 102 ・ ・ ・ ・ ・ ・... upper polarizing plate absorption axis 103 ... upper second optically anisotropic layer 104 ... ... Upper second light The rubbing direction at the time of producing the anisotropic layer 105 ... the lower second optically anisotropic layer 106 ...・ ・ Rubbing direction at the time of preparation of the lower second optically anisotropic layer 107...・ ・ ・ ・ ・ ・ Optical compensation element 109 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Liquid crystal cell upper substrate 110 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Upper substrate liquid crystal alignment Rubbing direction 111 ... nematic liquid crystal (liquid crystal layer)
112 ·····························································································································・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Liquid crystal element 115 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Absorption axis of lower polarizing plate 116・ ・ Lower side polarizing plate 200 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Liquid crystal projector 300 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Projection unit

Claims (16)

  A polymerizable composition comprising a polymerizable liquid crystal compound and a radical generator having an absorption peak at a light wavelength of 320 to 380 nm and having substantially no absorption at 420 nm or more.   The polymerizable composition according to claim 1, wherein the polymerizable liquid crystal compound contains a discotic liquid crystal compound.   The polymerizable composition according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound contains a rod-like liquid crystal compound.   An optically anisotropic layer comprising the polymerizable composition according to any one of claims 1 to 3 and formed on a support.   The alignment angle of the polymerizable liquid crystal compound in the alignment state formed by the polymerizable liquid crystal compound is inclined with respect to the thickness direction of the optically anisotropic layer, and is fixed in the inclined state. Optically anisotropic layer.   The optically anisotropic layer according to any one of claims 4 to 5, wherein the orientation angle of the polymerizable liquid crystal compound is fixed in a hybrid orientation that changes in the thickness direction of the optically anisotropic layer.   An optically anisotropic layer, wherein the polymerizable composition according to any one of claims 1 to 3 is applied onto at least one surface of a support, and the polymerizable composition is heated to 130 ° C or higher. Manufacturing method.   The method for producing an optically anisotropic layer according to claim 7, wherein the polymerization of the polymerizable composition is performed only by heating.   A support and an optically anisotropic layer on at least one surface of the support, wherein the optically anisotropic layer is the optically anisotropic layer according to any one of claims 5 to 7. An optical compensation element.   The optical compensation element according to claim 9, wherein the optical compensation element has two optically anisotropic layers and is arranged so that the orientation directions thereof are different.   The optical compensation element according to claim 9, wherein two layers having different orientation directions are provided on one surface of the support.   The optical compensation element according to claim 9, wherein two layers having different orientation directions are provided on both surfaces of the support via a support.   The optical compensation element according to claim 9, comprising two layers so that the alignment directions are orthogonal to each other.   A liquid crystal element having at least a pair of electrodes and liquid crystal molecules sealed between the electrodes, an optical compensation element disposed on both sides or one side of the liquid crystal element, and a polarizing element disposed opposite to the liquid crystal element and the optical compensation element A liquid crystal display device, wherein the optical compensation element is the optical compensation element according to claim 9.   The liquid crystal display device according to claim 14, wherein the liquid crystal element is a twisted nematic type. 15. The liquid crystal display device comprising: a light source; a liquid crystal display device irradiated with illumination light from the light source; and a projection optical system that forms an image of light modulated by the liquid crystal display device on a screen. 16. A liquid crystal projector according to any one of items 1 to 15.