JP4472460B2 - Retardation plate - Google Patents

Description

  The present invention relates to a phase difference plate used for a liquid crystal display element or the like.

  At present, a phase difference plate is widely used for a liquid crystal display element. Since the liquid crystal has a refractive anisotropy in which the refractive index varies depending on the direction, the display quality deteriorates when the liquid crystal display element is viewed from an oblique direction. In order to improve such viewing angle dependency, a retardation plate capable of optical compensation is required.

  Examples of the general retardation plate include those using a uniaxially stretched film or liquid crystal. A phase difference plate using liquid crystal has an advantage that the same function can be obtained with a thinness of 1/10 because the anisotropy is larger than that of a uniaxially stretched film, but an alignment film for aligning the liquid crystal is required. Become.

  As this alignment film, a rubbing film or an optical alignment film is generally used. However, the rubbing film has problems such as generation of static electricity and dust and unevenness during large area processing. In addition, the photo-alignment film is useful in that it does not generate static electricity or dust and can control the orientation process quantitatively. However, it requires an exposure process and requires a device cost, and the photoreaction rate is slow. There's a problem.

  On the other hand, Patent Document 1 proposes an alignment film using a dichroic dye exhibiting lyotropic liquid crystallinity. A dichroic dye exhibiting lyotropic liquid crystallinity can be aligned by applying a coating solution containing this dichroic dye using a coating method in which a shearing force acts. It has the advantage that it can be formed.

  Here, since the retardation plate is used to improve the viewing angle dependency, when the retardation plate is incorporated into a liquid crystal display element, the orientation direction of the liquid crystal of the liquid crystal cell or the absorption axis of the polarizing plate The optical axis of the retardation plate is arranged at a specific angle. In order to make such an arrangement, it is necessary to cut the retardation plate to a predetermined size, arrange the optical axis in a predetermined direction, and attach it to a liquid crystal cell or a polarizing plate, which is troublesome. is there. Therefore, for example, there is a demand for an optical axis that forms a specific angle with respect to the long direction of a long film, or a retardation plate that has an optical axis in an oblique direction of a glass substrate.

  When a rubbing film is used as an alignment film in a retardation plate using liquid crystal, it is difficult to rub continuously at an angle with respect to the long direction of the long film. It is difficult to obtain a retardation plate in which liquid crystals are oriented at an angle with respect to the long direction. In addition, when a photo-alignment film is used as the alignment film, it can meet the requirement of liquid crystal alignment with an angle with respect to the long direction of the long film. It is difficult to keep precisely the angle and distance between the irradiation direction and the long film. Furthermore, in an alignment film using a dichroic dye, the liquid crystal alignment can be controlled by the application direction of the coating liquid containing the dichroic dye, but at an angle with respect to the long direction of the long film. It is difficult to apply continuously.

JP 2002-148441 A

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide a phase difference plate using liquid crystal, which can arbitrarily set the alignment direction of the liquid crystal. To do.

In order to achieve the above object, the present invention provides a base material, a resin layer formed on the base material and having a pattern-like concave portion or convex portion, formed on the resin layer, and containing a plate-like molecule. A retardation plate having an alignment layer and a retardation layer formed on the alignment layer and fixing liquid crystal,
The plate molecule provides a retardation plate characterized by forming a column structure in which the normal direction of the plate molecule is aligned in a certain direction of the substrate.

  According to the present invention, an orientation layer having orientation ability can be obtained by orienting the column structure made of plate-like molecules by the recesses of the resin layer, and liquid crystal can be obtained by utilizing the orientation ability of the orientation layer. Is oriented so that a retardation layer can be obtained. As described above, in the present invention, the orientation direction of the liquid crystal can be controlled by appropriately selecting the concave or convex pattern of the resin layer, so that the optical axis of the retardation plate can be arbitrarily set. Is possible. The resin layer is formed by, for example, sandwiching the resin composition between a base material and a recess forming substrate having a convex portion on the surface, curing the resin composition, and peeling the recess forming substrate. Therefore, a desired concave pattern can be easily formed by appropriately selecting the convex pattern of the concave portion forming substrate. Therefore, in the present invention, the orientation direction of the liquid crystal can be controlled by a simple method, and a retardation plate having an optical axis in a desired direction can be easily obtained.

  In the said invention, it is preferable that the said column structure is orientated along the recessed part of the said resin layer. This is because the column structure made up of plate-like molecules is oriented along the recesses of the resin layer, so that the column structure made up of plate-like molecules is easily aligned in a certain direction.

  In the present invention, the plate molecule preferably exhibits lyotropic liquid crystallinity in a solution. Such a plate-like molecule forms a column structure by self-organization in a solution and exhibits lyotropic liquid crystallinity. Therefore, by applying an alignment layer forming coating solution containing this plate-like molecule, This is because a column structure composed of molecules can be easily oriented.

  The present invention also provides a substrate for a liquid crystal display element comprising the above-described retardation plate, a polarizing plate, an electrode layer, and an alignment film.

  In the present invention, since the retardation plate described above is used, the optical axis of the retardation plate can be set at an arbitrary angle. It is possible to paste together without doing. In addition, when the retardation layer and the polarizing plate of the retardation plate are formed on the alignment film side of the substrate of the retardation plate, when the liquid crystal display element is used using the liquid crystal display element substrate of the present invention, Since the retardation layer and the polarizing plate are formed inside the base material, it is not affected by the birefringence of the base material, and the choice of materials used for the base material is widened. The weight can be reduced and the manufacturing cost can be reduced.

  Furthermore, the present invention provides a liquid crystal display element using the above-described retardation plate.

  In the present invention, since the liquid crystal display element has the above-described retardation plate, when the retardation plate is disposed such that the optical axis forms a predetermined angle with respect to the alignment direction of the liquid crystal of the liquid crystal cell, Since the optical axis of the phase difference plate can be set arbitrarily, it is not necessary to cut the phase difference plate to a predetermined size as in the prior art, and a liquid crystal display element with high manufacturing efficiency can be obtained.

In addition, the present invention provides a coating step of applying a curable resin composition on a base material or a recess-forming substrate having a pattern-like convex portion, the base material and the recess-forming substrate, the curable resin composition An arrangement step of stacking objects, a curing step of curing the curable resin composition to make a curable resin, and peeling the recess-forming substrate from the curable resin composition or the curable resin. A resin layer forming step of forming a resin layer by performing a recess forming step of forming a patterned recess,
A coating liquid is formed by applying a coating liquid for forming an alignment layer containing plate-like molecules on the resin layer, and orienting the plate-like molecules so that a column structure is formed by the recesses of the resin layer. An alignment layer forming step of forming an alignment layer by performing a film forming step, a drying step of drying the coating film, and an immobilization step of fixing the alignment state of the plate-like molecules;
A retardation layer forming step of forming a retardation layer by applying a liquid crystal composition on the alignment layer, aligning the liquid crystal with the alignment layer, and fixing the alignment state of the liquid crystal. A method of manufacturing a retardation film is provided.

  In the present invention, an orientation layer having orientation ability is formed by orienting the plate-like molecules by the concave portions of the resin layer, and by aligning the liquid crystal using the orientation ability of the orientation layer. A retardation layer is formed. Furthermore, since the resin layer is formed by duplicating the convex portion of the concave portion forming substrate, in the present invention, by appropriately selecting the pattern of the convex portion of the concave portion forming substrate, It becomes possible to control the alignment direction of the liquid crystal in the retardation layer. For this reason, it is possible to easily manufacture a retardation plate having an optical axis in an arbitrary direction by appropriately selecting the shape of the convex portion of the concave portion forming substrate. Moreover, since a retardation plate having an optical axis in an arbitrary direction can be manufactured in a large amount only by once producing an original plate of such a recess forming substrate, there is an advantage that manufacturing efficiency is improved.

  In the said invention, it is preferable that the method of bridge | crosslinking the said plate-like molecule | numerator is used in the fixing process of the said orientation layer formation process. This is because the orientation of the column structure composed of plate-like molecules is stable and an orientation layer having excellent heat resistance can be formed.

  In the present invention, it is preferable that spray coating, dip coating, an ink jet method, or a flexographic printing method is used in the coating film forming step of the alignment layer forming step. This is because by using such a method, the plate-like molecules can be easily oriented in the recesses of the resin layer.

  According to the present invention, the orientation direction of the liquid crystal can be controlled by appropriately selecting the concave or convex pattern of the resin layer, so that the optical axis of the retardation plate can be set arbitrarily. It becomes. The resin layer is formed by, for example, sandwiching the resin composition between a base material and a recess forming substrate having a convex portion on the surface, curing the resin composition, and peeling the recess forming substrate. Therefore, a desired concave pattern can be easily formed by appropriately selecting the convex pattern of the concave portion forming substrate. As described above, in the present invention, it is possible to control the alignment direction of the liquid crystal by a simple method, and it is possible to easily obtain a retardation plate having an optical axis in a desired direction.

  Hereinafter, the retardation plate of the present invention, a substrate for a liquid crystal display device and a liquid crystal display device using the retardation plate, and a method for producing the retardation plate will be described in detail.

A. Phase difference plate First, the phase difference plate of the present invention will be described.
The retardation plate of the present invention includes a base material, a resin layer formed on the base material and having a patterned concave or convex portion, an alignment layer formed on the resin layer and containing a plate-like molecule, A retardation plate formed on the alignment layer and having a retardation layer formed by immobilizing liquid crystal, wherein the plate molecule has a normal direction of the plate molecule in a certain direction of the substrate. It is characterized by forming a column structure arranged facing.

  The retardation plate of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the retardation plate of the present invention. As shown in FIG. 1, a retardation plate 11 of the present invention is formed on a base material 1, a resin layer 2 formed on the base material 1 and having a pattern-shaped concave portion, and the resin layer 2. It has an alignment layer 3 containing plate-like molecules, and a retardation layer 4 formed on the alignment layer 3 and having a liquid crystal fixed thereon.

  FIG. 2A is a diagram showing a model structure and normal direction of a plate-like molecule used in the present invention, and FIG. 2B is a schematic perspective view of an alignment layer used in the present invention. As shown in FIG. 2 (b), in this alignment layer, the plate-like molecule 13 has a normal direction n of the plate-like molecule 13 facing a certain direction of the substrate 1 along the concave portion of the resin layer 2. A column structure 13 'is formed by arranging, and a plurality of such column structures 13' are arranged to constitute an alignment layer. In the present invention, since the alignment layer is configured by arranging the plate-like molecules 13 in this way, the column axial direction of the plurality of column structures 13 ′ is directed to a certain direction of the substrate 1. Thus, an orientation layer having orientation ability can be obtained.

  When such an alignment layer is formed, a concave portion on the surface of the resin layer is formed by applying an alignment layer forming coating solution containing, for example, a plate-like molecule on the resin layer having a pattern-like concave portion or convex portion. Since the column structure composed of plate-like molecules can be arranged along the direction, the arrangement direction of the column structure can be controlled by appropriately selecting the pattern of the concave portion or convex portion of the resin layer. In addition, since the liquid crystal constituting the retardation layer formed on the alignment layer is aligned according to the alignment direction of this column structure, the phase difference can be determined by appropriately selecting the concave or convex pattern of the resin layer. It is possible to control the alignment direction of the liquid crystal constituting the layer. That is, the optical axis of the phase difference plate can be arbitrarily set.

  In addition, the resin layer having the pattern-like recesses, for example, sandwiches the resin composition between the base material and the substrate for forming recesses having the protrusions on the surface to cure the resin composition, and peels the substrate for forming recesses. Therefore, a desired concave pattern can be easily formed by selecting the convex pattern of the concave portion forming substrate.

  Since the retardation plate of the present invention has such a resin layer and an alignment layer, the alignment direction of the liquid crystal can be controlled by a simple method, and a retardation plate having an optical axis in a desired direction can be easily obtained. Obtainable.

In general, when laminating a retardation plate with a polarizing plate, the optical axis of the retardation plate is arranged to make a specific angle with the absorption axis of the polarizing plate. Since the polymer film is produced by uniaxial stretching, its absorption axis is directed in the longitudinal direction of the long film. Since the retardation plate of the present invention can set the optical axis in a desired direction as described above even when a long film is used as a base material, the absorption axis is the long direction of the long film. Even if it is a case where it bonds with the polarizing plate which faced, it has the advantage that it can bond as it is.
Hereinafter, each component of such a retardation plate will be described.

1. Resin Layer The resin layer used in the present invention has a pattern-like concave portion or convex portion on the surface. The shape of the pattern of such concave portions or convex portions is not particularly limited as long as it is a shape capable of aligning a column structure composed of plate-like molecules to form a layer having orientation ability. Of these, a stripe shape is preferred. This is because a column structure made of plate-like molecules can be easily oriented along the stripe-shaped recess.

  The width of the concave portion varies depending on the type of plate-like molecule to be described later, but is usually in the range of 0.1 μm to 10 μm, more preferably in the range of 0.2 μm to 1 μm, particularly 0.2 μm to It is preferable to be within the range of 0.4 μm. Forming the width of the concave portion narrower than the above range is difficult in terms of manufacturing method, and conversely, if the width of the concave portion is too wide, it may be difficult to arrange the column structure made of plate-like molecules. It is. Here, the width of the concave portion is, for example, the width indicated by a in FIG. 3 and refers to the width of the portion formed in a concave shape.

  Further, the depth of the concave portion is preferably within a range of 0.05 μm to 1 μm, and more preferably within a range of 0.1 μm to 0.2 μm. If the depth of the recess is too shallow, the ability to align the column structure made of plate-like molecules will be low, and if the depth of the recess is too deep, the orientation of the liquid crystal constituting the retardation layer described later may be adversely affected. Because. Here, the depth of the recess is, for example, the depth indicated by b in FIG. 3 and refers to the height from the deepest portion in the recess to the end of the recess.

  Furthermore, when the shape of the pattern of the recesses is a stripe shape, the interval between the recesses varies depending on the type of plate molecule, etc., but usually the interval between the ends of the adjacent recesses and the ends of the recesses, that is, The width is less than or equal to half the wavelength of visible light, preferably in the range of 0.05 μm to 2 μm, more preferably in the range of 0.1 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 0.2 μm. It is difficult in terms of manufacturing method to form the interval between the end of the adjacent recess and the end of the recess smaller than the above range. Conversely, if the interval between the end of the adjacent recess and the end of the recess is too wide, the plate This is because it may be difficult to arrange a column structure composed of molecular molecules. Further, if the distance between the end of the adjacent recess and the end of the recess is a value close to the wavelength of visible light, there is a possibility that problems such as optical coloring may occur due to light diffraction. Here, the space | interval of the edge of an adjacent recessed part and the edge of a recessed part is a space | interval shown by c of FIG. 3, for example.

  Further, the pitch of the recesses is appropriately selected depending on the type of plate-like molecule to be described later and the like, but is usually in the range of 0.1 μm to 10 μm, preferably in the range of 0.2 μm to 1 μm, particularly preferably 0.2. It is preferable to be in the range of 2 μm to 0.4 μm. It is difficult to make the pitch of the recesses narrower than the above range in terms of the manufacturing method, and conversely, if the pitch of the recesses is too wide, it may be difficult to arrange the column structure made of plate-like molecules. It is. Here, the pitch of the recesses is, for example, the pitch indicated by d in FIG. 3 and refers to the distance from the center of the adjacent recesses to the center of the recesses.

  The cross-sectional shape of the concave portion is not particularly limited. For example, the cross-sectional shape may be a rectangle as shown in FIG. 1 or may be another cross-sectional shape such as a trapezoid. This is because the column structure composed of plate-like molecules can be easily oriented.

  Moreover, it is preferable that the resin layer used for this invention consists of curable resin. The resin layer made of a curable resin is prepared by preparing a concave portion forming substrate having a convex portion corresponding to a target concave portion on the surface, and a curable resin composition is interposed between the concave portion forming substrate and a base material described later. It is because a recessed part can be easily formed by pinching and hardening. Moreover, it is because the shape of a recessed part can be stabilized by consisting of curable resin which hardened the curable resin composition.

  Examples of the curable resin composition used in the present invention include an energy ray curable resin composition that is cured by irradiation with energy rays, and a thermosetting resin composition that is cured by heat. In the present invention, an energy beam curable resin composition is particularly preferable. Examples of the energy beam curable resin composition include a UV curable resin composition that is cured by irradiation with ultraviolet rays, and an electron beam curable resin composition that is cured by irradiation with electron beams. A resin composition is preferred. This is because the method of using ultraviolet rays as energy rays is an already established technique and can be easily applied to the present invention.

  The UV curable resin composition is not particularly limited as long as it is cured by irradiation with ultraviolet rays, but the polyfunctional monomer component and / or oligomer component and / or polymer component is cured by photopolymerization. It is preferable.

  Although it does not specifically limit as said polyfunctional monomer component, A polyfunctional acrylate monomer is used suitably. Specifically, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol diacrylate, penta Erythritol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Ruhekisa (meth) acrylate can be exemplified dipentaerythritol penta (meth) acrylate.

  The oligomer component is not particularly limited, and examples thereof include urethane acrylate, epoxy acrylate, polyester acrylate, epoxy, vinyl ether, and polyene / thiol.

  The polymer component is not particularly limited, and examples thereof include a photocrosslinking polymer. Specifically, a polyvinyl cinnamate-based resin that causes a photodimerization reaction can be used.

  Further, as the photopolymerization initiator added to the UV curable resin composition, a photo radical polymerization initiator that can be activated by ultraviolet light, for example, ultraviolet light of 365 nm or less is used. Specifically, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4- Benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloro Acetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin methyl ether, Nzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, naphthalenesulfonyl chloride, quinoline Sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, Adeka N1717, carbon tetrabromide, tribromophenyl sulfone, Examples thereof include a combination of a photoreductive dye such as benzoin peroxide, eosin and methylene blue with a reducing agent such as ascorbic acid or triethanolamine. In this invention, these photoinitiators can be used 1 type or in combination of 2 or more types.

  The content of such a photopolymerization initiator is preferably in the range of 0.5 to 30% by weight, particularly in the range of 1 to 10% by weight in the UV curable resin composition.

  Examples of the solvent that can be used for the UV curable resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; acetone , Ketones such as methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol , Butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethyl Glycol ethers such as lenglycol monomethyl ether and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl Acetic acid esters such as ether acetate and propylene glycol monoethyl ether acetate can be exemplified. Moreover, 1 type (s) or 2 or more types can be mixed and used from these solvents.

  In the present invention, the UV curable resin composition may be applied without adding a solvent. Therefore, the content of such a solvent is preferably in the range of 0 to 99.9% by weight, particularly in the range of 0 to 80% by weight in the UV curable resin composition.

  The reason why the photopolymerization initiator and the solvent are set within the above-described ranges is as follows. In this invention, the resin layer which has a recessed part can be formed by pinching and hardening the said curable resin composition between the base material and the board | substrate for recessed part formation which has a convex part. Therefore, it is preferable that the curable resin composition has a predetermined viscosity so as to enter the gaps between the concaves and convexes of the substrate for forming recesses, and the desired amount of the photopolymerization initiator and the solvent is within the above-described range. It can be set as the curable resin composition which has a viscosity.

  The thickness of the resin layer varies depending on the type of the retardation plate of the present invention, but the thickness of the recess is usually 1 μm or less, preferably 0.2 μm or less. This is because if the thickness of the recess is too thick, the retardation plate of the present invention may become heavy. Further, considering the thickness reduction of the retardation plate, the thickness of the recess is preferably thin. However, since it is difficult to form a too thin one, the thickness of the recess is usually 0.1 μm or more. Here, the thickness of the recess is, for example, the thickness of the portion where the recess as shown by e in FIG. 3 is formed.

  Since the resin layer used in the present invention has depressions or projections formed on the surface thereof, the resin layer surface has high water repellency, and the column structure made of plate-like molecules may not be sufficiently oriented. Since the alignment layer in the present invention is formed by applying an alignment layer forming coating solution on the resin layer, the surface of the resin layer is preferably hydrophilic. In this case, a hydrophilic layer may be provided on the resin layer, or the surface of the resin layer may be subjected to a hydrophilic treatment. Examples of the hydrophilic layer include a silica film formed by a sol-gel method of tetraethoxysilane. Moreover, as a method of surface-treating the surface of the resin layer so as to be hydrophilic, a hydrophilic surface treatment by plasma treatment using argon, water, or the like can be given.

2. Next, the alignment layer used in the present invention will be described. The alignment layer used in the present invention is a layer formed on the resin layer and containing plate-like molecules. Further, the plate-like molecules contained in the alignment layer form a column structure in which the normal direction of the plate-like molecules is arranged in a certain direction of the substrate. Since the liquid crystal is aligned by the interaction between the column structure composed of the plate-like molecules and the liquid crystal constituting the retardation layer described later, the alignment layer has an alignment ability for controlling the liquid crystal alignment. Moreover, by aligning such a column structure along the concave portion of the resin layer, the column structure can be easily aligned in a certain direction.

  The plate-like molecule used in the present invention forms a column structure in which the normal direction of the plate-like molecule is arranged in a certain direction of the substrate.

  Here, the plate-like molecule means a molecule having at least a plurality of aromatic ring structures and having a core portion of the molecule arranged in a planar shape.

  Such a plate-like molecule is not particularly limited as long as it can form a column structure by arranging in a columnar shape. Examples of the plate-like molecule forming the column structure include a plate-like molecule having a hydrophilic group such as a sulfonic acid group or a plate-like molecule having a hydrophobic group such as a long-chain alkyl group. Among these, it is preferable to use a plate molecule having a hydrophilic group. This is because the plate-like molecule having a hydrophilic group has a small hydrophilic group and the distance between adjacent column structures is short, so that the column structures can be easily arranged. Moreover, it is because an immobilization process becomes easy by neutralizing hydrophilic parts, such as a sulfonic acid group, and making it hardly soluble or insoluble in water. Examples of the hydrophilic group include a sulfonic acid group such as a sulfonic acid group, a sodium sulfonate group, an ammonium sulfonate group, a lithium sulfonate group, and a potassium sulfonate group, a carboxyl group, a sodium carboxylate group, and a carboxylic acid. Examples thereof include carboxylic acid-based hydrophilic groups such as ammonium group, lithium carboxylate group, and potassium carboxylate group, hydroxyl groups, and amino groups. Among these, a sulfonic acid-based hydrophilic group is preferable.

  In addition, it can be confirmed by measuring using a X-ray-diffraction apparatus that a plate-shaped molecule | numerator forms the column structure.

  Among the above, the plate-like molecules used in the present invention preferably form a column structure in a solution and exhibit lyotropic liquid crystallinity. This is because a plate-like molecule exhibiting lyotropic liquid crystallinity in a solution has a high self-organizing power. For example, by applying a coating liquid for forming an alignment layer containing a plate-like molecule exhibiting lyotropic liquid crystallinity in a solution, the column structure can be easily aligned using self-organization of the plate-like molecule.

  Examples of the plate-like molecule exhibiting lyotropic liquid crystallinity in such a solution include a plate-like molecule exhibiting lyotropic liquid crystallinity in an aqueous solution, or a plate-like molecule exhibiting lyotropic liquid crystallinity in an organic solvent. The type of the solution differs depending on the substituent of the plate molecule, and when the plate molecule has a hydrophilic group such as a sulfonic acid group, an aqueous solution is used, and a hydrophobic property such as a long chain alkyl group. When it has a group, an organic solvent is used. In the present invention, it is particularly preferable to use a plate-like molecule that forms a column structure in an aqueous solution and exhibits lyotropic liquid crystallinity. Such a plate-like molecule forms a column structure by self-organization in an aqueous solution and exhibits lyotropic liquid crystallinity. Therefore, by applying an alignment layer-forming coating liquid containing this plate-like molecule, the column structure This is because can be easily oriented. Furthermore, because the plate-like molecule is water-soluble, an immobilization process for immobilizing the column structure is facilitated.

  Specific examples of the plate-like molecule that forms a column structure in the aqueous solution and exhibits lyotropic liquid crystallinity include substances represented by the following chemical formula.

The alkyl group in each chemical formula is preferably one having 1 to 4 carbon atoms. The halogen in each chemical formula is preferably Cl or Br. Further, as the cation in the above ^{formula, H +, Li +, Na} +, K +, Cs + or _NH ^{4 +} and the like. These substances can be used alone or in combination of two or more.

  As the plate-like molecule used in the present invention, among the above substances, substances represented by the above chemical formulas I to V are preferably used.

  The plate-like molecules are not limited to those showing lyotropic liquid crystal properties as described above, and may be those showing thermotropic liquid crystal properties.

  Furthermore, the alignment layer used in the present invention may contain a liquid crystal material in addition to the above plate-like molecules. For example, even if the column structure made of plate-like molecules is difficult to align along the recesses of the resin layer, by aligning the liquid crystal material along the recesses, the column made of plate-like molecules along the alignment direction of the liquid crystal material This is because the structure can be oriented. As the liquid crystal material, a liquid crystal material that can be generally used for an alignment layer can be used. The liquid crystal composition of the liquid crystal material and the plate-like molecule may exhibit lyotropic liquid crystallinity or thermotropic liquid crystallinity, but usually exhibits thermotropic liquid crystallinity. Is used.

  The thickness of the alignment layer used in the present invention varies depending on the required properties of the retardation plate of the present invention, but is usually preferably in the range of 10 nm to 1000 nm, more preferably in the range of 20 nm to 500 nm, More preferably within the range of 50 nm to 300 nm. If the alignment layer is too thin, the alignment of the liquid crystal may not be sufficiently controlled. On the other hand, if the alignment layer is too thick, the alignment may be disturbed near the surface, which is not preferable in terms of cost.

  Further, the transmittance of the alignment layer is preferably 80% or more in the visible light region, and more preferably 90% or more. The transmittance is a value measured at a distance of 40 cm using a spectrum photometer (SR-3 manufactured by Topcon).

  Such an alignment layer is formed by forming a column structure composed of the plate-like molecules in the alignment layer-forming coating solution containing the plate-like molecules, and applying the alignment layer-forming coating solution. It can be formed on the resin layer while maintaining the column structure. In addition, since the formation method of an orientation layer is demonstrated in detail by the term of the "D. manufacturing method of phase difference plate" mentioned later, description here is abbreviate | omitted.

3. Next, the retardation layer used in the present invention will be described. The retardation layer used in the present invention is formed by fixing a liquid crystal. This liquid crystal is aligned by interacting with the column structure composed of the plate-like molecules of the alignment layer described above, and the column structure composed of the plate-like molecules extends along the recesses of the resin layer as described above. Since it is oriented, in the present invention, the orientation direction of the liquid crystal can be arbitrarily set by appropriately selecting the pattern of the concave portion or convex portion of the resin layer. In addition, since the optical axis of the retardation plate faces the alignment direction of the liquid crystal, in the present invention, a retardation plate having desired optical characteristics can be easily provided at a low cost.

  The retardation layer used in the present invention is formed by fixing liquid crystal, and is formed by fixing the alignment state of liquid crystal. The liquid crystal used for the retardation layer is not particularly limited as long as it is a material exhibiting liquid crystallinity at a predetermined temperature. Further, it may be a polymer liquid crystal material having no polymerizability, or may be a polymerizable liquid crystal material.

  As the polymerizable liquid crystal material, any of a polymerizable liquid crystal monomer, a polymerizable liquid crystal oligomer, and a polymerizable liquid crystal polymer can be used. On the other hand, as a polymer liquid crystal material having no polymerizability, since the alignment state of the liquid crystal needs to be constant at the storage or use temperature of the retardation plate, the liquid crystal material having a relatively high temperature that becomes a relatively isotropic phase Are preferably used.

  In the present invention, it is particularly preferable to use a polymerizable liquid crystal material. As described later, the polymerizable liquid crystal material can be polymerized by irradiation with an active irradiation ray or the like to fix the alignment state, so that the liquid crystal can be easily aligned at a low temperature, and This is because the orientation state is fixed during use, so that it can be used regardless of the use conditions such as temperature.

  Among the polymerizable liquid crystal materials, a polymerizable liquid crystal monomer is preferably used. This is because the polymerizable liquid crystal monomer can be easily aligned because it can be aligned at a lower temperature than the polymerizable liquid crystal oligomer and the polymerizable liquid crystal polymer and has high sensitivity at the time of alignment. . As such a polymerizable liquid crystal monomer, those generally used for retardation plates can be used.

  Furthermore, the liquid crystal property of the liquid crystal used in the present invention is not particularly limited, and examples thereof include nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and discotic liquid crystal.

  Examples of the polymerizable liquid crystal monomer exhibiting nematic liquid crystallinity include compounds represented by the following chemical formula.

  In the above chemical formula (1), X is hydrogen, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, alkyloxy having 1 to 20 carbons, alkyloxycarbonyl having 1 to 20 carbons, formyl, carbon It represents an alkylcarbonyl having 1 to 20 carbon atoms, an alkylcarbonyloxy having 1 to 20 carbon atoms, halogen, cyano or nitro. M represents an integer in the range of 2-20.

  Moreover, as a polymerizable liquid crystal monomer which shows cholesteric liquid crystallinity, the compound shown by the above-mentioned chemical formula (1) or the compound shown by the following chemical formula is mentioned, for example.

  Furthermore, as a polymerizable liquid crystal material exhibiting discotic liquid crystallinity, for example, a triphenylene-based discotic liquid crystal that can be polymerized as used for forming a WV film (trade name, manufactured by Fuji Photo Film Co., Ltd.), or Examples thereof include compounds represented by the following chemical formula.

  In the present invention, among the above, the compound represented by the chemical formula (1) is preferably used. The compound represented by the chemical formula (1) exhibits nematic liquid crystallinity as described above, and exhibits cholesteric liquid crystallinity. In the chemical formula (1), X is preferably an alkyloxycarbonyl having 1 to 20 carbon atoms, methyl or chlorine, and particularly preferably methyl.

  The retardation layer in the present invention may contain a photopolymerization initiator as necessary. This is because, for example, when a polymerizable liquid crystal material is polymerized by ultraviolet (UV) irradiation, a photopolymerization initiator is usually used to accelerate the polymerization. As the photopolymerization initiator, those generally used for polymerizing a polymerizable liquid crystal material are used. Moreover, it is also possible to add a sensitizer other than a photoinitiator in the range which does not impair the objective of this invention.

  The thickness of the retardation layer used in the present invention may be determined according to the required optical anisotropy, but is usually in the range of 0.1 μm to 10 μm and in the range of 0.3 μm to 6 μm. It is preferable. This is because if the retardation layer is too thick, an optical anisotropy more than necessary occurs, and if it is too thin, the predetermined optical anisotropy may not be obtained.

4). Next, the substrate used in the present invention will be described. The base material used for this invention may be comprised only from the board | substrate, and may be comprised from the board | substrate and the functional layer. Hereinafter, each structure of such a base material is demonstrated.

(1) Substrate The substrate used in the present invention is not particularly limited as long as it is generally used for a phase difference plate. For example, it is flexible such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plate, etc. A transparent rigid material having no flexibility, or a transparent flexible material having flexibility such as a transparent resin film and an optical resin plate can be used.

  Moreover, as a board | substrate used for this invention, a elongate board | substrate may be sufficient and a web-like board | substrate may be sufficient, but it is preferable that it is a elongate board | substrate. In the present invention, a retardation plate having an optical axis that forms a specific angle with respect to the longitudinal direction of the substrate can be used, and thus a polarizing plate with an absorption axis oriented in the longitudinal direction of the substrate; This is because it has an advantage that it can be bonded as it is.

  Furthermore, it is preferable to use a long transparent flexible material among the long substrates. This is because a phase difference plate can be continuously produced through a roll-to-roll process, and a phase difference plate with high production efficiency can be obtained. Examples of such a long transparent flexible material include transparent resin films such as polycarbonate, polyethylene terephthalate, polyethylene naphthalate, diacetyl cellulose, triacetyl cellulose, and polypropylene.

  In the present invention, a TAC (triacetyl cellulose) film is particularly preferable. This is because the TAC film is excellent in optical properties such as high transparency and less retardation, and versatility.

(2) Functional layer In the present invention, a functional layer may be formed on the substrate. The functional layer used in the present invention is not particularly limited as long as it is generally used for a liquid crystal display element, and examples thereof include a color filter layer.

  The color filter layer is not particularly limited as long as it is generally used as a color filter layer of a liquid crystal display element, and a layer using a pigment or a resin can be used. A black matrix may be formed between the colors.

(3) Others In the present invention, the base material may be subjected to a surface treatment in order to improve the adhesion between the base material and the resin layer. Specifically, glow discharge treatment, corona discharge treatment, UV treatment, saponification treatment, or the like can be used. Moreover, you may form a primer layer on a base material. Further, a primer layer (barrier layer) may be provided for the purpose of protecting the substrate from the curable resin. Examples of such a primer layer include silane-based and titanium-based coupling agents.

5). Retardation Plate The thickness of the retardation plate of the present invention is appropriately selected depending on the use and type of the retardation plate, and can usually be in the range of 50 μm to 500 μm.

B. Next, the substrate for a liquid crystal display element of the present invention will be described.
The substrate for a liquid crystal display element of the present invention is characterized by having the above-mentioned retardation plate, a polarizing plate, an electrode layer, and an alignment film.

  The substrate for a liquid crystal display element of the present invention will be described with reference to the drawings. FIG. 4 is a schematic sectional view showing an example of the substrate for a liquid crystal display element of the present invention. As shown in FIG. 4, the substrate for a liquid crystal display element of the present invention includes a base material 1, a resin layer 2 formed on the base material 1, an alignment layer 3 formed on the resin layer 2, and the alignment On the phase difference plate 11 having the phase difference layer 4 formed on the layer 3, the polarizing plate 5 formed on the substrate 1 of the phase difference plate 11, and the phase difference layer 4 of the phase difference plate 11 The electrode layer 6 is formed and the alignment film 7 is formed on the electrode layer 6.

  In a general liquid crystal display element, polarizing plates are attached to both sides of a liquid crystal cell, and one polarizing plate is used by being attached to a retardation plate. As described above, the retardation plate is usually bonded to the polarizing plate. However, since the retardation plate is used to improve the viewing angle dependency of the liquid crystal display element, the optical axis of the retardation plate is The liquid crystal cell needs to be arranged at a specific angle with the scanning line direction of the liquid crystal cell and the absorption axis of the polarizing plate. Therefore, when pasting together with a polarizing plate, it has to arrange | position so that the optical axis of a phase difference plate may turn into a predetermined direction with respect to the absorption axis of a polarizing plate. For example, when a long retardation plate and a long polarizing plate are to be bonded together, the absorption axis of the polarizing plate formed by impregnating iodine in a uniaxially stretched PVA film faces the long direction of the film. Therefore, in order to achieve the above-described arrangement, a retardation plate having an optical axis that forms a specific angle with respect to the longitudinal direction of the film is required. In addition, conventionally, either the retardation plate or the polarizing plate must be cut into a predetermined size, and the optical axis of the retardation plate and the absorption axis of the polarizing plate must be arranged in a predetermined direction and bonded together, There was a problem that it took time and effort.

  In the present invention, since the above-described retardation plate is used, the optical axis of the retardation plate can be set to an arbitrary angle, so that it is bonded to a polarizing plate whose absorption axis is in the longitudinal direction of the film. Even if it is a case, it is possible to bond as it is, without cut | disconnecting to a predetermined dimension.

  In the present invention, when the retardation layer and the polarizing plate of the retardation plate are formed on the alignment film side with respect to the base material of the retardation plate, the liquid crystal display element is used with the liquid crystal display element substrate of the present invention. In this case, since the retardation layer and the polarizing plate are formed inside the base material, it is not affected by the birefringence of the base material, and the choice of materials used for the base material is widened. Thinning and weight reduction can be achieved, and further, manufacturing costs can be reduced.

  Hereinafter, each configuration of the liquid crystal display element substrate will be described. The base material, the resin layer, the alignment layer, the retardation layer, and the retardation plate are the same as those described in the above-mentioned section “A. Retardation plate”, and thus description thereof is omitted here.

1. Alignment film The alignment film used in the present invention is for aligning liquid crystals when the liquid crystal display element substrate of the present invention is used, and is formed on the outermost surface of the liquid crystal display element substrate. Is.

  The alignment film used in the present invention is not particularly limited as long as the liquid crystal can be aligned. For example, a rubbing film, a photo alignment film, or the like can be used. The formation position of this alignment film is not particularly limited as long as it is the outermost surface of the substrate for a liquid crystal display element. For example, as shown in FIG. 4, the side where the retardation layer 4 of the retardation plate 11 is provided. Although not shown, it may be the outermost surface on the side where the base material of the retardation plate is provided, but considering the influence of the birefringence of the base material, the alignment film has a retardation. It is preferably formed on the outermost surface on the side where the retardation layer of the plate is provided.

2. Electrode layer The electrode layer used in the present invention is not particularly limited as long as it is generally used as an electrode layer of a liquid crystal display element. For example, indium oxide, tin oxide, indium tin oxide (ITO), etc. Transparent electrodes, and metal electrodes such as chromium and aluminum.

  The electrode layer may be formed between the alignment film and the retardation plate substrate, and between the resin layer and the alignment layer or between the alignment layer and the retardation layer. It is not particularly limited. For example, when the alignment film is formed on the phase difference layer side of the phase difference plate, the electrode layer is formed between the phase difference layer 4 and the alignment film 7 of the phase difference plate 11 as shown in FIG. Further, although not shown, it may be between the base material of the retardation plate and the resin layer. Moreover, when a base material has a board | substrate and a functional layer, the electrode layer may be formed between the board | substrate and the functional layer. On the other hand, when the alignment film is formed on the substrate side of the retardation plate, the electrode layer may be formed between the substrate and the alignment film of the retardation plate, and the substrate is a substrate. And the functional layer may be provided between the substrate and the functional layer.

3. Polarizing plate The polarizing plate used in the present invention transmits only light polarized in the alignment direction of the liquid crystal molecules of the liquid crystal cell when the incident light is linearly polarized and the liquid crystal display element substrate of the present invention is used in the liquid crystal display element. It has the function to do. The polarizing plate used in the present invention is not particularly limited as long as it transmits only a specific direction in the wave of light, and a polarizing plate generally used for a liquid crystal display element can be used. .

  The formation position of the polarizing plate is not particularly limited as long as it is a position other than between the resin layer and the alignment layer or between the alignment layer and the retardation layer. For example, when the alignment film is formed on the retardation layer side of the retardation plate, the polarizing plate may be formed outside the substrate 1 of the retardation plate 11 as shown in FIG. Although not shown, it may be between the substrate of the retardation plate and the resin layer, or between the retardation layer of the retardation plate and the alignment film. In the case where the substrate has a substrate and a functional layer, a polarizing plate may be formed between the substrate and the functional layer. On the other hand, when the alignment film is formed on the substrate side of the retardation plate, the polarizing plate may be formed on the outside of the retardation layer of the retardation plate, It may be formed between the resin layer and may be formed between the base material of the retardation plate and the alignment film. Moreover, when a base material has a board | substrate and a functional layer, as above-mentioned, the polarizing plate may be formed between the board | substrate and the functional layer.

  In the present invention, either the polarizing plate or the retardation layer may be disposed on the side close to the alignment film, but the retardation layer is formed on the side close to the alignment film in consideration of the optical compensation effect. It is preferable. Moreover, when the influence by the birefringence of a base material is considered, it is preferable that the polarizing plate is formed in the orientation film side rather than the base material. Furthermore, in consideration of the refractive index at the interface of the layers, the polarizing plate is preferably disposed so as to be in contact with the retardation layer.

C. Next, the liquid crystal display element of the present invention will be described.
The liquid crystal display element of the present invention is characterized by using the above-described retardation plate.

  In the present invention, since the liquid crystal display element has the above-described retardation plate, when the retardation plate is arranged so that the optical axis forms a predetermined angle with respect to the scanning line direction of the liquid crystal cell, the retardation is set. Since the optical axis of the plate can be arbitrarily set, it is not necessary to cut the retardation plate to a predetermined size as in the prior art, and a liquid crystal display element with high manufacturing efficiency can be obtained.

  The liquid crystal display element of the present invention is not particularly limited as long as the liquid crystal cell and the retardation plate are laminated. Moreover, as a liquid crystal cell, what is generally used for a liquid crystal display element can be used.

  Moreover, in this invention, it is preferable that a liquid crystal display element uses the liquid crystal display element substrate mentioned above. In the liquid crystal display element substrate, when the retardation layer and the polarizing plate of the retardation plate are formed closer to the alignment film than the base material of the retardation plate, that is, in the liquid crystal display element of the present invention, When a retardation layer and a polarizing plate are formed on the inside of the substrate, since it is not affected by the birefringence of the base material, the choice of materials used for the base material is widened, so the liquid crystal display element can be made thinner and lighter. It is because it can plan. This also leads to a reduction in manufacturing costs.

D. Next, a method for producing a retardation plate of the present invention will be described.
The method for producing a retardation plate of the present invention includes a coating step of applying a curable resin composition on a substrate or a substrate for forming a recess having a pattern-shaped projection, the substrate and the substrate for forming a recess, Arrangement step of sandwiching the curable resin composition, a curing step of curing the curable resin composition to obtain a curable resin, and forming the recess from the curable resin composition or the curable resin A resin layer forming step of forming a resin layer by performing a recess forming step of peeling a substrate to form a patterned recess,
A coating liquid is formed by applying a coating liquid for forming an alignment layer containing plate-like molecules on the resin layer, and orienting the plate-like molecules so that a column structure is formed by the recesses of the resin layer. An alignment layer forming step of forming an alignment layer by performing a film forming step, a drying step of drying the coating film, and an immobilization step of fixing the alignment state of the plate-like molecules;
A retardation layer forming step of forming a retardation layer by applying a liquid crystal composition on the alignment layer, aligning the liquid crystal with the alignment layer, and fixing the alignment state of the liquid crystal.

  A method for producing a retardation plate of the present invention will be described with reference to the drawings. FIG. 5 is a process diagram showing an example of a method for producing a retardation plate of the present invention. As shown in FIG. 5, in the method for producing a retardation plate of the present invention, first, a curable resin composition 22 is applied onto a substrate 1 (FIG. 5A, an application step), and the substrate 1 and The recess-forming substrate 25 having pattern-like convex portions is overlapped with the curable resin composition 22 interposed therebetween, and the curable resin composition 22 is cured by irradiating energy 26 (FIG. 5B, placement step). And curing step). Furthermore, the resin layer 2 having a patterned recess is formed by peeling the recess forming substrate 25 (FIG. 5C, recess forming step). In this way, the resin layer forming step is performed.

  Next, an alignment layer-forming coating solution 23 containing plate-like molecules is applied onto the resin layer 2, and the plate-like molecules are oriented so that a column structure is formed by the recesses of the resin layer 2. (FIG. 5D, coating film forming step). Furthermore, a drying process for drying the coating film is performed, and a hydrophobic treatment liquid 27 is applied on the dried coating film 23 'to perform a hydrophobic treatment, thereby fixing the orientation state of the plate molecules (FIG. 5). (E) Immobilization step). Next, the hydrophobic layer is washed and dried to form the alignment layer 3 (FIG. 5 (f)). In this way, the alignment layer forming step is performed.

  Finally, the liquid crystal composition 24 is applied onto the alignment layer 3, and the liquid crystal is aligned by the alignment layer 3 by performing an alignment treatment so that the liquid crystal in the liquid crystal composition 24 becomes a liquid crystal phase (FIG. 5G). ). Furthermore, the phase difference layer 4 is formed by irradiating the ultraviolet rays 28 to polymerize the liquid crystal and fixing the alignment state (FIG. 5H). In this way, the retardation layer forming step is performed.

  In the present invention, an alignment layer having alignment ability is formed by orienting a column structure made of plate-like molecules by the recesses of the resin layer, and the liquid crystal is produced by utilizing the alignment ability of the alignment layer. The retardation layer is formed by the orientation. Furthermore, since the resin layer is formed by duplicating the convex portion of the concave portion forming substrate, in the present invention, by appropriately selecting the shape of the convex portion of the concave portion forming substrate, It becomes possible to control the alignment direction of the liquid crystal in the retardation layer. Therefore, it is possible to easily manufacture a retardation plate having an optical axis in an arbitrary direction by appropriately selecting the shape of the convex portion of the concave portion forming substrate. Therefore, a retardation plate in which liquid crystals are aligned so as to form a specific angle with respect to the longitudinal direction of the long transparent resin film, or a retardation plate in which liquid crystals are aligned in an oblique direction of a web-like glass substrate is provided. It can be easily manufactured. Moreover, since a retardation plate having an optical axis in an arbitrary direction can be manufactured in a large amount only by once producing an original plate of such a recess forming substrate, there is an advantage that manufacturing efficiency is improved.

In addition, when a long film is used as a substrate, the retardation plate manufactured according to the present invention can set the optical axis in a desired direction as described above, and therefore the absorption axis is a long film. There is an advantage that it can be bonded as it is when it is bonded to a polarizing plate oriented in the long direction. Further, when a web-like base material is used, a retardation plate having an optical axis in an oblique direction of the web-like base material can be manufactured. Without being cut into dimensions, it can be directly bonded to the polarizing plate.
Hereinafter, each process of the manufacturing method of such a phase difference plate is demonstrated.

1. Resin Layer Forming Step The resin layer forming step in the present invention comprises a coating step of applying a curable resin composition on a substrate or a substrate for forming a recess having a pattern-like projection, and the substrate and the recess forming step. An arrangement step of stacking the substrates with the curable resin composition interposed therebetween, a curing step of curing the curable resin composition to obtain a curable resin, and the curable resin composition or the curable resin from the above A recess forming step of peeling the recess forming substrate to form a patterned recess.
Hereinafter, each process of such a resin layer formation process is demonstrated.

(1) Application | coating process In the resin layer formation process in this invention, the application | coating process which apply | coats curable resin composition on the base material or the board | substrate for recessed formation which has a pattern-shaped convex part first is performed.
Hereinafter, the method for applying the recess forming substrate and the curable resin composition used in this step will be described.

(Substrate forming substrate)
First, the recess forming substrate used in this step will be described. The substrate for forming recesses used in this step has a pattern-like protrusion on the surface. Moreover, this convex part is formed so that it may become symmetrical with respect to the concave part of the target resin layer.

  The shape of the convex portion of the concave portion forming substrate used in the present invention is not particularly limited as long as the concave portion of the target resin layer can be formed. In addition, since the width | variety, height, shape, pattern, etc. of a convex part respond | correspond to the recessed part of the resin layer mentioned above, description here is abbreviate | omitted.

  Further, the concave portion forming substrate may be a flexible substrate such as a resin film, or may be a non-flexible substrate such as glass. In the present invention, since the recess forming substrate is used repeatedly, a material having a predetermined strength is preferably used. Specific examples include glass, ceramic, metal, and plastic. Such a material is appropriately selected depending on a method for forming a convex portion described later. Furthermore, the said recessed part formation board | substrate is suitably selected with the irradiation method of the energy at the time of hardening the curable resin composition in the hardening process mentioned later. That is, when irradiating energy rays from the concave portion forming substrate side, it is necessary to be a transparent material, but when irradiating energy rays from the base material side, it is not particularly limited to transparent materials. Absent.

  The concave portion forming substrate may be moved by the concave / convex cylindrical drum, and the concave portion forming substrate itself constitutes the concave / convex cylindrical drum, that is, a convex portion is formed on the surface of the concave / convex cylindrical drum. It may be. It is because a recessed part can be continuously replicated on a base material and a manufacturing efficiency improves by passing through a roll to roll process. In addition, it is possible to manufacture a large amount of retardation plates having an optical axis in an arbitrary direction only by once producing an original plate of such a recess forming substrate, and therefore, the manufacturing efficiency can be further improved.

  As a method for forming such a convex portion, for example, a method of patterning glass or a resin film, a method of applying a photosensitive resin layer or the like on the surface of glass or the like, and a method of patterning the photosensitive resin layer, or the like is used. Can do. As the patterning method, a general method can be used, and examples thereof include a photolithography method, a sputtering method, and a mechanical cutting method. Furthermore, an oblique vapor deposition method, a rubbing method, etc. can also be used.

(Coating method of curable resin composition)
In this step, the curable resin composition may be applied on a base material or may be applied on a recess forming substrate. Further, the base material and the recess forming substrate may be fixed with a predetermined gap, and the curable resin composition may be poured and applied between them.

  Examples of the method for applying the curable resin composition include spin coating, roll coating, printing, dip coating, curtain coating (die coating), and the like.

  The film thickness of the applied curable resin composition is preferably in the range of 0.1 to 30 μm, and more preferably in the range of 0.2 to 10 μm. This is because if the film thickness is too thinner than the above range, the recesses may not be sufficiently replicated in the curable resin composition. Moreover, it is because the retardation plate manufactured by this invention may become heavy when a film thickness is too thick. Further, when the substrate is a film, there is a possibility that a problem that the coated surface is easily curled may occur.

  Moreover, it may apply | coat by the method mentioned above, controlling application quantity so that the said curable resin composition may become a desired film thickness, and after apply | coating, you may remove an excess curable resin composition. Examples of a method for removing excess curable resin composition include a method for removing using a roller, a method for scraping using a doctor, and the like. Moreover, the process of removing such an excessive curable resin composition may be performed after an application | coating process, and may be performed after the arrangement | positioning process mentioned later.

  In addition, since it is the same as that of what was described in the term of the above-mentioned "A. phase difference plate" about a base material and curable resin composition, description here is abbreviate | omitted.

(2) Arrangement Step Next, the arrangement step of the resin layer forming step in the present invention will be described. The disposing step in the present invention is a step of overlapping the base material and the concave portion forming substrate with the curable resin composition interposed therebetween.

  The method for arranging the substrate and the recess forming substrate is not particularly limited as long as the applied curable resin composition is arranged so as to be in contact with the substrate and the recess forming substrate. It is preferable to arrange so as to be in close contact with the substrate. This is because the resin layer made of the curable resin obtained by curing the curable resin composition is formed on the substrate, and therefore, the curable resin composition is preferably in close contact with the substrate. Moreover, it is preferable that the said base material and the said board | substrate for recessed part formation are arrange | positioned with a gap | interval so that a curable resin composition may become the target film thickness.

  Moreover, in order to improve the adhesiveness of the said base material and the said curable resin composition, it is preferable to surface-treat to a base material. Specifically, glow discharge treatment, corona discharge treatment, UV treatment, saponification treatment, or the like can be used. Moreover, you may form a primer layer on a base material. Further, a primer layer (barrier layer) may be provided for the purpose of protecting the substrate from the curable resin. Examples of such a primer layer include silane-based and titanium-based coupling agents.

(3) Curing step In the resin layer forming step in the present invention, a curing step is performed in which the curable resin composition is cured to obtain a curable resin.

  Examples of the curing method of the curable resin composition include a method of irradiating energy rays, a method of heating, and the like. In the present invention, it is preferable to use a method of irradiating energy rays. The energy rays referred to in the present invention indicate energy rays capable of causing polymerization with respect to monomers and polymers contained in the curable resin composition.

  The energy ray is not particularly limited as long as it is an energy ray capable of polymerizing the curable resin composition, but usually ultraviolet light or visible light is used from the viewpoint of the ease of equipment and the like. Irradiation light having a wavelength of 150 to 500 nm, preferably 250 to 450 nm, and more preferably 300 to 400 nm is used.

  In the present invention, a method of irradiating ultraviolet rays (UV) as energy rays is a preferable method. This is because the method using UV as the actinic radiation is an already established technique, and therefore it is easy to apply to the present invention including the photopolymerization initiator to be used.

  As the light source of this irradiation light, low pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high pressure discharge lamp (high pressure mercury lamp, metal halide lamp), short arc discharge lamp (super high pressure mercury lamp, xenon lamp, mercury xenon) Lamp). In particular, the use of metal halide lamps, xenon lamps, high-pressure mercury lamps, etc. is recommended. The irradiation intensity is appropriately adjusted according to the composition of the curable resin composition and the amount of photopolymerization initiator.

  Moreover, as a film thickness of curable resin obtained by hardening | curing curable resin composition, it is preferable to exist in the range of 0.1-30 micrometers, especially in the range of 0.2-10 micrometers. This is because if the film thickness is too thick, the retardation plate produced according to the present invention may become heavy. Moreover, it is because toughness is inferior when a film thickness is too thin.

  In the present invention, the curing step may be performed after the coating step, after the placement step, or during the recess formation step. That is, the curable resin composition is applied on a substrate or a substrate for forming recesses and then cured (after the application step, the first aspect), and the substrate and the substrate for forming recesses are stacked with the curable resin composition interposed therebetween. In either case of curing after placing together (second mode after placement step) or curing after peeling the substrate for forming recesses from the curable resin composition (third mode during the recess forming step) It may be done at. Hereinafter, each aspect will be described.

(First aspect)
In this invention, the 1st aspect of a hardening process apply | coats a curable resin composition on the base material or the board | substrate for recessed formation, irradiates energy, hardens the said curable resin composition, and is obtained by hardening. The base material and the concave portion forming substrate are arranged so as to overlap each other with the curable resin sandwiched therebetween, and the concave portion forming substrate is peeled from the curable resin to form the concave portion.

  At this time, the irradiation direction of the energy rays for curing the curable resin composition may be from the substrate or the concave portion forming substrate side or from the curable resin composition side. However, when a curable resin composition is applied onto a substrate or a substrate for forming recesses and irradiated from the substrate or substrate for forming recesses, the substrate or substrate for forming recesses needs to be a transparent material.

  In addition, when the curable resin composition is applied and cured on the base material, the concave portion forming substrate is placed on the surface of the curable resin obtained by curing, and the concave portion is duplicated. The curable resin needs to have a predetermined viscosity. Therefore, it is preferable not to completely cure the curable resin composition, and after the recess forming substrate is disposed on the surface of the curable resin, or after the recess forming substrate is peeled from the curable resin, it may be cured again. Good.

(Second aspect)
In the present invention, in the second aspect of the curing step, the curable resin composition is applied onto a substrate or a recess forming substrate, and the substrate and the recess forming substrate are overlapped with the curable resin composition interposed therebetween. The curable resin composition is cured by irradiating with energy, and the substrate for forming recesses is peeled from the curable resin obtained by curing to form the recesses.

  At this time, the irradiation direction of the energy rays for curing the curable resin composition may be from the recess forming substrate side or from the base material side. However, when irradiating from the base material side, the base material needs to be a transparent material, and when irradiating from the concave portion forming substrate side, the concave portion forming substrate needs to be a transparent material.

(Third aspect)
In this invention, the 3rd aspect of a hardening process apply | coats curable resin composition on the base material or the board | substrate for recessed part formation, and laminate | stacks the base material and the board | substrate for recessed part formation on both sides of the said curable resin composition. And disposing the substrate for forming recesses from the curable resin composition, irradiating energy to cure the curable resin composition, and forming recesses.

  At this time, the irradiation direction of the energy ray for curing the curable resin composition may be from the curable resin composition side or from the substrate side. However, when irradiating from the base material side, the base material needs to be a transparent material.

  In addition, since the curable resin composition is cured after peeling the recess forming substrate from the curable resin composition, the curable resin composition needs to maintain the recess even after peeling the recess forming substrate. There is. Therefore, the curable resin composition may have a semi-cured state in advance before peeling the recess forming substrate from the curable resin composition so that the curable resin composition has a predetermined viscosity.

(4) Concave formation process In the resin layer formation process in this invention, the concavity formation process which peels the said board | substrate for recessed part formation from the said curable resin composition or the said curable resin, and forms a pattern-shaped recessed part is performed. .

  As a method of peeling the concave portion forming substrate from the curable resin composition or the curable resin, the curable resin composition or the curable resin is peeled off from the concave portion forming substrate and is in close contact with the base material, and the concave portion is formed. If it is formed, it will not specifically limit.

  Further, in the present invention, the recess forming substrate is moved by the concave and convex cylindrical drum, and the base material is moved by the base cylindrical drum, and the curable resin composition or the curable resin is moved on the two cylindrical drums. By overlapping the base material and the concave portion forming substrate across the substrate, peeling the concave portion forming substrate from the curable resin composition or the curable resin, and continuously replicating the concave portion on the base material, A resin layer having a recess may be formed. Furthermore, the concave-convex forming substrate may be a concave-convex cylindrical drum. This is because by passing through the roll-to-roll process, the concave portions can be continuously replicated on the base material, and the production efficiency is improved. Moreover, it is because a retardation plate having an optical axis in an arbitrary direction can be produced in a large amount only by once producing an original plate of such a recess forming substrate.

(5) Others In the present invention, it is preferable that after the resin layer forming step, a hydrophilic treatment step for hydrophilizing the resin layer surface having the recesses is performed. Usually, when the above-described resin layer forming step is performed, the surface of the formed resin layer has high water repellency, and the plate-like molecules may not be sufficiently oriented. The hydrophilic treatment method is the same as that described in the section of the resin layer of “A. Retardation plate” described above, and a description thereof will be omitted here.

2. Alignment layer formation process Next, the alignment layer formation process in this invention is demonstrated. In the alignment layer forming step in the present invention, an alignment layer-forming coating solution containing plate-like molecules is applied on the resin layer so that the column structure is formed by the concave portions of the resin layer. It has a coating film forming process for forming a coating film by orientation, a drying process for drying the coating film, and an immobilizing process for fixing the orientation of the plate-like molecules. Each step in the forming step will be described.

(1) Coating film forming step In the alignment layer forming step in the present invention, first, an alignment layer forming coating solution containing a plate-like molecule is applied on the resin layer, and the plate-like shape is formed by the recesses of the resin layer. A coating film forming step is performed in which molecules are aligned so as to form a column structure to form a coating film.

  The coating liquid for forming an alignment layer used in the present invention contains a plate-like molecule, and this plate-like molecule is dispersed or dissolved in a solvent. The plate-like molecules are the same as those described in the section of the alignment layer of “A. Retardation plate” described above, and thus the description thereof is omitted here.

  The solvent used for the alignment layer-forming coating solution is appropriately selected depending on the substituent introduced into the plate molecule described above. For example, when a hydrophilic group such as a sulfonic acid group is introduced, water is used as the solvent. On the other hand, when a hydrophobic group such as a long-chain alkyl group is introduced, an organic solvent is used. A common thing can be used as such an organic solvent. Moreover, the said coating liquid for alignment layer formation may contain various additives, such as surfactant, such as polyethyleneglycol, as needed.

  In addition, the alignment layer-forming coating solution used in the present invention is preferably an aqueous solution among the above. This is because, as the plate-like molecule used in the present invention, one that forms a column structure, has a hydrophilic group, and exhibits lyotropic liquid crystallinity in an aqueous solution is preferably used.

  The method for applying the alignment layer-forming coating solution is not particularly limited as long as the normal direction of the plate-like molecules can be aligned in a certain direction. It is preferable that the shear stress is not applied. If a method that requires shear stress is used, it may be difficult to align the normal direction of the plate molecules in the coating direction so that the normal directions of the plate molecules are aligned along the concave portion of the resin layer. Because there is. Examples of the application method in which shear stress is not applied include spray coating, dip coating, an ink jet method, a flexographic printing method, and the like. Among these, an ink jet method is preferably used.

(2) Drying step Next, in the alignment layer forming step in the present invention, a drying step of drying the coating film formed in the coating film forming step is performed. The drying step in the present invention is a step of drying the solvent contained in the alignment layer forming coating solution. In the present invention, by providing this drying step, an immobilization step described later is smoothly performed.

  The drying method used in the present invention is not particularly limited as long as it does not destroy the column structure composed of plate-like molecules or deform the pattern of the recesses of the resin layer. The methods used for drying, such as heat drying, room temperature drying, freeze drying, far infrared drying, and the like can be used.

(3) Immobilization step In the alignment layer forming step in the present invention, an immobilization step of fixing the alignment state of the plate-like molecules is performed. In the present invention, by performing such an immobilization step, the alignment layer can be imparted with water resistance, and the column structure composed of plate-like molecules is not disturbed by moisture in the air, and the phase difference described later. In the layer forming step, the liquid crystal can have excellent alignment stability.

  As a method for fixing the orientation state of the plate molecules used in the present invention, a method of crosslinking the plate molecules can be used. The method for crosslinking the plate molecule differs depending on the substituent introduced into the plate molecule.

  When the plate-like molecule has a hydrophilic group such as a sulfonic acid group, a crosslinking method for hydrophobizing the hydrophilic group is used. When the hydrophilic group of the plate molecule is hydrophobized, a cross-link is formed between adjacent plate molecules, and the orientation state of the plate molecule is fixed. When the above plate-like molecules exhibit lyotropic liquid crystallinity in an aqueous solution, unless such a hydrophobizing treatment is performed, the water resistance is poor, the orientation state is likely to be disturbed due to moisture in the air, etc. There is a case.

  The hydrophobizing solution used for the hydrophobizing treatment is not particularly limited as long as the hydrophilic group can be hydrophobized, and it varies depending on the hydrophilic group of the plate molecule used. However, it is preferable that a bridge can be formed between adjacent plate molecules. As such a hydrophobizing treatment liquid, for example, an aqueous solution of a salt of a divalent metal such as magnesium, calcium, barium or the like can be used. Specific examples include an aqueous barium chloride solution, an aqueous magnesium chloride solution, and an aqueous calcium chloride solution.

The mechanism by which adjacent plate molecules are cross-linked is as follows. For example, when the plate molecule has an SO ₃ Na group and is hydrophobized using an aqueous barium chloride solution, SO ₃ ions of the SO ₃ Na group of the plate molecule and Ba ions in the aqueous barium chloride solution By bonding, the adjacent plate-like molecules are cross-linked and the orientation state is fixed. In other words, in the state where the normal direction of the plate molecules is aligned in a certain direction, the adjacent plate molecules are cross-linked, so that the column structure is fixed.

  Further, the method for the hydrophobizing treatment is not particularly limited as long as it is a method capable of hydrophobizing the hydrophilic substituent, and after the alignment layer forming coating solution is dried, the hydrophobizing treatment is performed. Examples thereof include a method of applying a liquid and a method of immersing in the hydrophobizing treatment liquid. After the application or immersion of the hydrophobizing solution, the alignment layer can be formed by washing and drying.

  On the other hand, when the plate molecule has a hydrophobic group such as a long chain alkyl group, for example, a polymerizable group is introduced into the core portion of the plate molecule or a part of the alkyl side chain to polymerize the polymerizable group. Thus, a cross-linking method is used in which the plate-like molecules are cross-linked in a linear or network form to fix the alignment state.

  Further, when the alignment layer forming coating solution contains the liquid crystal material described above, the alignment state of the plate-like molecules can be fixed by polymerizing the liquid crystal material. In this case, the liquid crystal material needs to have a polymerizable group.

3. Retardation layer forming step Next, the retardation layer forming step in the present invention will be described. The phase layer forming step in the present invention is a step of forming a retardation layer by applying a liquid crystal composition on the alignment layer, aligning the liquid crystal with the alignment layer, and fixing the alignment state of the liquid crystal. .

  The liquid crystal composition used in the present invention contains the liquid crystal described in the section of the retardation layer of “A. Retardation plate” described above. Moreover, when apply | coating the said liquid-crystal composition on an orientation layer, you may melt | dissolve and use a liquid-crystal composition, and you may melt | dissolve and use a liquid-crystal composition in a solvent.

  The solvent used for dissolving the liquid crystal composition is not particularly limited as long as it can dissolve the liquid crystal described above and does not inhibit the alignment ability of the alignment layer. For example, hydrocarbons such as benzene, toluene, xylene, n-butylbenzene, diethylbenzene and tetralin; ethers such as methoxybenzene, 1,2-dimethoxybenzene and diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2 Ketones such as 1,4-pentanedione; esters such as ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone; 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl Amide solvents such as acetamide; t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethyleneglycol Alcohols such as hexylene glycol, phenols, phenols such as phenol and parachlorophenol, and one or more cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and ethylene glycol monomethyl ether acetate can be used. .

  In addition, the use of a single type of solvent may result in insufficient solubility of the liquid crystal or the like, and the alignment layer may be eroded as described above. Therefore, this inconvenience can be avoided. Of these solvents, hydrocarbons and glycol monoether acetate solvents are preferred as the sole solvent, and mixed solvents of ethers or ketones and glycol solvents are preferred as the mixed solvent. It is. The concentration of the solution in which the liquid crystal composition is dissolved in a solvent depends on the solubility of the liquid crystal and the thickness of the target retardation layer, but cannot be defined unconditionally, but is usually 0.1 to 40% by weight, preferably Is prepared in the range of 1 to 20% by weight. If the concentration of the solution is too low, it may be difficult to align the liquid crystal. Conversely, if the concentration of the solution is too high, the viscosity of the solution will increase and it may be difficult to form a uniform coating film. is there.

  Furthermore, the following compounds can be added to the liquid crystal composition as long as the object of the present invention is not impaired. Examples of compounds that can be added include polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; A polyurethane (meth) acrylate obtained by reacting a compound having two isocyanate groups with each other and then reacting the reaction product with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak Type epoxy resins, polycarboxylic acid polyglycidyl esters, polyol polyglycidyl ethers, aliphatic or cycloaliphatic epoxy resins, amine epoxy resins, triphenolmethane type epoxy resins, dihydroxybenzene type epoxy resins and the like (meth) Acry Photopolymerizable compound in epoxy (meth) acrylate obtained by reacting an acid; photopolymerizable liquid crystal compound having an acryl group or methacryl group and the like. The amount of these compounds added to the liquid crystal composition is selected in such a range that the object of the present invention is not impaired. By adding these compounds, the curability of the liquid crystal is improved, the mechanical strength of the obtained retardation layer is increased, and the stability is improved.

  Examples of the method for applying such a liquid crystal composition include spin coating, roll coating, printing, dipping and lifting, curtain coating (die coating), casting, bar coating, blade coating, and spray coating. , Gravure coating method, reverse coating method, extrusion coating method and the like.

  In the present invention, in addition to the method of forming a coating film by applying the liquid crystal composition on the alignment layer as described above, for example, a method of previously forming a dry film and laminating the film on the alignment layer. It is also possible to take In the present invention, among them, a method in which the liquid crystal composition is dissolved in a solvent, applied onto the alignment layer, and the solvent is dried is preferably used. This is because such a method is simpler in process than other methods.

  Examples of the solvent drying method include methods generally used for solvent drying, such as vacuum drying or heat drying, and a combination of these.

  In the present invention, as described above, after the liquid crystal composition is applied on the alignment layer and dried, the liquid crystal in the liquid crystal composition is aligned by the alignment layer. The alignment treatment of the liquid crystal is usually performed by a method of performing a heat treatment below the NI transition point. Here, the NI transition point indicates the temperature at which the liquid crystal phase transitions to the isotropic phase.

  In the present invention, after the liquid crystal is aligned, the alignment state of the liquid crystal is fixed. The process for fixing the alignment state of the liquid crystal is performed by a different method depending on the liquid crystal used. Specifically, there are a case where the liquid crystal is a polymerizable liquid crystal material and a case where the liquid crystal is a polymer liquid crystal material having no polymerizability. Hereinafter, the case of a polymerizable liquid crystal material and the case of a polymer liquid crystal material having no polymerizability will be described separately.

(1) Polymerizable liquid crystal material In the present invention, the alignment treatment of the polymerizable liquid crystal material is performed by a method of irradiating the coating film made of the polymerizable liquid crystal material with actinic radiation that activates the polymerization. .

  The active radiation as used in the field of this invention means the radiation which has the capability to cause superposition | polymerization with respect to polymeric material, If necessary, the photoinitiator may be contained in polymeric material. The photopolymerization initiator is the same as that described in the section of the retardation layer of “A. Retardation plate” described above, and a description thereof is omitted here.

  The actinic radiation is not particularly limited as long as it is a radiation capable of polymerizing the polymerizable liquid crystal material, but usually ultraviolet light or visible light is used from the viewpoint of the ease of the apparatus, and the wavelength. Irradiating light of 150 to 500 nm, preferably 250 to 450 nm, more preferably 300 to 400 nm is used.

  In the present invention, there is a method in which ultraviolet rays (UV) are irradiated as active radiation to a polymerizable liquid crystal material in which a photopolymerization initiator generates radicals by ultraviolet rays (UV) and the polymerizable liquid crystal material undergoes radical polymerization. It can be said that this is a preferred method. This is because the method using UV as the actinic radiation is an already established technique, and therefore it is easy to apply to the present invention including the photopolymerization initiator to be used.

  As the light source of this irradiation light, low pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high pressure discharge lamp (high pressure mercury lamp, metal halide lamp), short arc discharge lamp (super high pressure mercury lamp, xenon lamp, mercury xenon) Lamp). Among these, use of a metal halide lamp, a xenon lamp, a high-pressure mercury lamp, etc. is recommended. The irradiation intensity is appropriately adjusted according to the composition of the polymerizable liquid crystal material and the amount of photopolymerization initiator.

  Such immobilization treatment by irradiation with actinic radiation may be performed under a temperature condition where the polymerizable liquid crystal material becomes a liquid crystal phase, or may be performed at a temperature lower than the temperature where the polymerizable liquid crystal material becomes a liquid crystal phase. This is because the alignment state of the polymerizable liquid crystal material once in the liquid crystal phase is not disturbed suddenly even if the temperature is lowered thereafter.

(2) Polymer liquid crystal material having no polymerizability In the present invention, in the case of using a polymer liquid crystal material having no polymerizability, the alignment state is fixed from the temperature at which the liquid crystal phase is treated, It is carried out by a method of reducing the temperature to a solid phase. By aligning the polymer liquid crystal material with the alignment layer and lowering the treatment temperature to a temperature at which it becomes a glass state in this state, a retardation layer can be obtained.

4). Others A substrate for a liquid crystal display element can be produced using the method for producing a retardation plate of the present invention. For example, a retardation plate forming step of forming a retardation plate by the above-described retardation plate manufacturing method, an electrode layer forming step of forming an electrode layer on the retardation plate, and an alignment film on the electrode layer By performing the alignment film forming step to be performed, a substrate for a liquid crystal display element can be manufactured.

  The electrode layer can be formed by a vapor deposition method such as a CVD method, a sputtering method, or an ion plating method. In addition, as a method for forming the alignment film, a general method for forming an alignment film can be used, and examples thereof include a rubbing process and a photo-alignment process.

  The other points of the liquid crystal display element substrate are the same as those described in the above-mentioned “B. Liquid crystal display element substrate”, and thus the description thereof is omitted here.

  Moreover, a liquid crystal display element can also be manufactured using the manufacturing method of the phase difference plate of this invention. In this case, it is preferable to use the above-described method for manufacturing a substrate for a liquid crystal display element. A liquid crystal display element is manufactured by arranging the liquid crystal display element substrate and a counter substrate having an electrode layer and an alignment film on a base material so that the alignment films face each other and forming a liquid crystal layer therebetween. can do.

  For example, beads are dispersed as spacers on the alignment film of the liquid crystal display element substrate, a sealing agent is applied to the periphery, and the liquid crystal display element substrate and the counter substrate are bonded so that the alignment films face each other. Crimp. Then, the liquid crystal is heated from the injection port using the capillary effect and injected in an isotropic or nematic phase, and the injection port is sealed with an ultraviolet curable resin or the like. Thereafter, the liquid crystal is gradually cooled to be aligned. Furthermore, a liquid crystal display element can be obtained by bonding a polarizing plate to the outside of the liquid crystal display element substrate and the counter substrate.

  In addition, this invention is not limited to the said embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described with reference to examples.

[Example]
(Formation of resin layer)
On the washed glass substrate with ITO, 0.1 wt% silane coupling agent dissolved in ethanol was applied using a spinner and dried to form a 10 nm anchor layer. On this anchor layer, a UV-curable acrylate resin composition having the following composition was applied, and a polycarbonate recess-forming substrate on which a desired pattern-shaped projection was formed was pressed, and a pressure of 100 kg / cm ² was applied for 1 minute. While pressing, the UV curable acrylate resin composition was cured by irradiating with about 100 mJ / cm ² of ultraviolet rays. Further, the recess-forming substrate was peeled off, and 3000 mJ / cm ² of ultraviolet rays were irradiated to completely cure the UV curable acrylate resin composition, thereby forming a patterned recess. The pattern-like recesses had a recess width: 0.2 μm, a protrusion width: 0.2 μm, a pitch: 0.4 μm, and a depth: 0.2 μm, and had a stripe pattern. Thereby, a resin layer was formed.

<UV curable acrylate resin composition>
-Gosselak UV-7500B (made by Nippon Kayaku Co., Ltd.) 40 parts by weight-1,6-hexanediol acrylate (made by Nippon Kayaku Co., Ltd.) 35 parts by weight-Pentaerythritol acrylate (made by Toagosei Co., Ltd.) 21 parts by weight 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals) 2 parts by weight • Benzophenone (Nippon Kayaku Co., Ltd.) 2 parts by weight

(Formation of alignment layer)
An ink containing a plate-like molecule having dichroism (manufactured by Optiva, product name: N015) was applied onto the well-washed resin layer using an inkjet and dried, and then a 15% barium chloride aqueous solution. For about 1 second. Further, this was washed and dried again to form an alignment layer having a thickness of 0.3 μm.

(Formation of retardation layer)
A powder obtained by mixing a polymerizable liquid crystal material having the following nematic liquid crystal properties and a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name: IRG907) in a ratio of 100: 5 (weight ratio), A liquid crystal composition was prepared by dissolving in toluene at 30% by weight. This liquid crystal composition was applied onto the alignment layer using a bar coat. Further, after the solvent was evaporated, an alignment treatment was performed at 80 ° C. for 3 minutes to align the liquid crystal, and ultraviolet rays were irradiated to polymerize the liquid crystal, thereby forming a retardation layer. When the optical axis of the retardation layer was measured, it was parallel along the stripe-shaped recess.

<Polymerizable liquid crystal material exhibiting nematic liquid crystal properties>
A polymerizable liquid crystal monomer represented by the following chemical formula, having a polymerizable functional group at the terminal, and exhibiting nematic liquid crystallinity within a range of 50 ° C. to 100 ° C. was used.

It is a schematic sectional drawing which shows an example of the phase difference plate of this invention. It is explanatory drawing for demonstrating the plate-shaped molecule | numerator used for this invention. It is explanatory drawing for demonstrating the recessed part of the resin layer used for this invention. It is a schematic sectional drawing which shows an example of the board | substrate for liquid crystal display elements of this invention. It is process drawing which shows an example of the manufacturing method of the phase difference plate of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Resin layer 3 ... Orientation layer 4 ... Phase difference layer 5 ... Polarizing plate 6 ... Electrode layer 7 ... Orientation film 11 ... Phase difference plate 13 ... Plate-like molecule | numerator 13 '... Column structure n ... Normal direction

Claims (7)

A base material, a resin layer formed on the base material and having a patterned concave or convex portion, an alignment layer formed on the resin layer and containing plate-like molecules, and formed on the alignment layer A retardation plate having a retardation layer formed by fixing liquid crystal,
The plate-like molecule forms a column structure in which the normal direction of the plate-like molecule is arranged in a certain direction of the substrate ,
The phase difference plate is characterized in that the column structure is oriented along a concave portion of the resin layer . The retardation plate according to claim 1, wherein the plate-like molecule exhibits lyotropic liquid crystallinity in a solution. A liquid crystal display device substrate comprising the retardation plate according to claim 1 , a polarizing plate, an electrode layer, and an alignment film. The liquid crystal display element characterized by using a phase difference plate according to any of claims to claim 1 or claim 2. A coating step of applying a curable resin composition on a substrate or a recess forming substrate having a pattern-like convex portion, and the substrate and the recess forming substrate are overlapped with the curable resin composition interposed therebetween. A placement step, a curing step for curing the curable resin composition to form a curable resin, and a pattern-shaped recess formed by peeling the recess-forming substrate from the curable resin composition or the curable resin. A resin layer forming step of forming a resin layer by performing a concave portion forming step;
A coating solution is formed by applying a coating liquid for forming an alignment layer containing plate-like molecules on the resin layer, and orienting the plate-like molecules so that a column structure is formed by the recesses of the resin layer. An alignment layer forming step of forming an alignment layer by performing a film forming step, a drying step of drying the coating film, and an immobilization step of fixing the alignment state of the plate-like molecules;
The liquid crystal composition was applied onto the alignment layer, wherein to align the liquid crystal by the alignment layer, have a phase difference layer forming step of forming a retardation layer by fixing the alignment state of the liquid crystal,
The column structure is oriented along the concave portion of the resin layer . The method for producing a retardation plate according to claim 5 , wherein a method of crosslinking the plate-like molecules is used in the fixing step of the alignment layer forming step. The method for producing a retardation plate according to claim 5 or 6 , wherein spray coating, dip coating, an ink jet method, or a flexographic printing method is used in the coating film forming step of the alignment layer forming step.

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