JP2009244670A - Method of manufacturing retardation substrate - Google Patents

Abstract

There is provided a method capable of easily and high-quality manufacturing a retardation substrate having an optical compensation capability capable of solving a phase difference problem caused when performing multicolor display by a liquid crystal display device.
In manufacturing a retardation substrate including a substrate and a liquid crystal fixing layer formed on one side of the substrate and corresponding to first to third display pixels, (a) the substrate An alignment layer made of a compound that can be decomposed by light is formed thereon, (b) the alignment layer is rubbed to provide alignment ability, and (c) the first to third displays are applied to the alignment layer. Light irradiation is performed at different doses for each region corresponding to the pixel, and the alignment layer in the light-irradiated region is photolyzed to reduce the alignment regulating force. (D) Thermotropic liquid crystal properties are provided on the alignment layer. And a solution containing a liquid crystal compound exhibiting photopolymerizability and / or photocrosslinkability is applied to form liquid crystal fixing layers having different degrees of orientation in each region in accordance with the regulating force of the lower alignment film.
[Selection] Figure 2

Description

  The present invention relates to a method for manufacturing a retardation substrate used in a liquid crystal display device and other display devices.

  In recent years, liquid crystal display devices have been evaluated for space saving and light weight due to their thinness, power saving, and the like, and recently, they are rapidly spreading to portable devices and television applications. A liquid crystal display device can perform multicolor display by providing a color filter substrate in the panel configuration, and generally performs RGB three-color display or six-color display in which RGB pixels for reflection are added thereto. Is.

  For example, a liquid crystal display device for portable devices may employ a reflective type or a transflective type liquid crystal display device in which a reflective part is formed in part in order to ensure visibility even under strong outdoor light in the daytime. Many. In such a case, in order to effectively utilize the reflected light, a λ / 4 retardation film, a λ / 2 retardation film, or the like is incorporated in the liquid crystal panel configuration as a member that forms part of the absorption-type circularly polarizing plate. .

  On the other hand, in a liquid crystal display device for television use, a retardation film is often incorporated in a liquid crystal panel configuration together with a linear polarizing plate for the purpose of improving visibility in all directions.

  However, since such retardation films usually have the same retardation value in the plane, when the liquid crystal display device in which the retardation film is incorporated is colored by the color filter substrate, each color passes through the display area. Due to the difference in wavelength range, a problem that appropriate phase difference control becomes difficult occurs.

  For example, in a reflective or transflective liquid crystal display device for portable devices, a retardation film having a retardation amount of λ / 4 (about 138 nm) in a substantially green wavelength region (center wavelength around 550 nm) is a linear polarizing plate. When combined and used as a circularly polarizing plate, the blue wavelength range (center wavelength around 450 nm) is more than λ / 4, and the red wavelength range (center wavelength around 630 nm) is insufficient relative to λ / 4. In the display pixel, complete circularly polarized light cannot be obtained.

  In addition, when a retardation film is designed so that the phase difference is compensated for one of the three RGB colors (wavelength region) in a liquid crystal display device for television applications, etc., the compensation is made for the other colors (wavelength region). Often there will be an imperfection. The following factors can be cited as the cause.

  (A) The liquid crystal of the cell does not necessarily have the same retardation value in the entire wavelength region, (B) many of the color pigments used in the color filter have optical anisotropy, (C ) Furthermore, since the degree is different depending on the type of pigment, the phase difference varies depending on the red, green, and blue pixels.

  To solve this problem, (1) a method of solving the problem by optical compensation using a retardation plate outside the liquid crystal cell, and (2) optical compensation by providing a retardation layer inside the liquid crystal cell. There are known ways to solve the problem.

  Patent Document 1 is an example of (1). In Patent Document 1, a phase difference plate is provided separately from the color filter substrate, and “the phase difference plate distributes three regions having different phase differences corresponding to the three basic color pixels forming the color display”. ing. However, in this method, since a distance is generated between the color filter substrate and the retardation substrate, it is difficult to accurately perform optical compensation particularly for display in an oblique direction.

  As an example of (2), a phase difference element having a phase difference amount corresponding to a display pixel of three colors has been devised by forming a polymerization type liquid crystal material having different film thicknesses or different types. (For example, refer to Patent Document 2).

  In addition, the thickness of the light transmissive pattern of the color filter layer is formed to be different for each color, and a retardation control layer (such as a liquid crystalline polymer) is formed thereon, and the total thickness of the color filter layer and the retardation control layer A color filter having a phase difference control layer in which a phase difference amount is provided so as to correspond to display pixels of three colors by laminating so as to be constant has been devised (for example, see Patent Document 3).

  Further, the thickness of the light transmissive pattern of the color filter layer is formed to be different not only in each color but also in the transmission part / reflection part, and the step of the color filter layer is flattened thereon and the orientation direction is made different. By laminating a retardation layer (liquid crystal polymer, etc.), a liquid crystal display device having no retardation at the transmission part and having a retardation at the reflection part and an appropriate value (each λ / 4) for each color has been devised. (For example, see Patent Document 4).

  However, it can be said that these conventional methods are unsuitable for easily and sufficiently solving the phase difference problem.

  For example, in Patent Document 2, as a means for varying the thickness of the retardation layer for each region, a polymerization type liquid crystal material is formed, and this is exposed to radiation such as ultraviolet rays by changing the irradiation amount for each region. A method of developing with an organic solvent is shown. However, in this method, particularly when uncured components remain in the thin film, the final film thickness greatly depends on the development conditions. Therefore, the desired film thickness can be stably adjusted by controlling the dose during exposure. It is very difficult to get. Further, when patterning different types of polymerizable liquid crystal materials using a photolithography method, a printing method, or the like, a process is required for each type, and thus the manufacturing process becomes complicated.

  In Patent Document 3, since the thickness of the retardation layer is determined by the thickness of the color filter layer serving as a base, the difficulty in the deposition process of the retardation layer is somewhat eliminated. However, this time, it becomes necessary to strictly control the film thickness of the color filter layer, and there is a problem that the design of the color filter is limited or the difficulty of the manufacturing process of the color filter is increased. In the first place, it is not so easy to form a retardation layer on a color filter layer having a thickness difference so that the total thickness of the retardation layer and the color filter layer is kept uniform.

Also in Patent Document 4, the problem associated with flattening by providing a step in the color filter layer and laminating a retardation film thereon is the same as in Patent Document 3. In addition, the alignment direction of the retardation layer may be changed by a method of forming an alignment film having different alignment directions between the reflection part and the transmission part by photo-alignment treatment, or by the mask rubbing with different alignment directions between the reflection part and the transmission part. A method of forming an alignment film is shown. However, in order to perform the photo-alignment treatment, it is necessary to perform polarization exposure or non-polarization parallel light oblique exposure, which causes a significant increase in the price of the exposure apparatus. In mask rubbing, a process involving physical contact must be performed a plurality of times, and a reduction in yield is inevitable.
Japanese Patent No. 3687862 JP 2004-191832 A JP 2005-24919 A JP 2006-85130 A

  The present invention has been made to solve the above-described problems, and easily and with high quality, a retardation substrate having an optical compensation capability that can eliminate the phase difference problem that occurs when performing multicolor display with a liquid crystal display device. It aims to provide a possible method.

  A configuration of the present invention for solving the above-described problems will be described below.

  The invention according to claim 1 is to manufacture a retardation substrate including a substrate and a liquid crystal fixing layer formed on one side of the substrate and corresponding to the first to third display pixels. (A) Applying a solution containing a compound having orientation and decomposable by light on the substrate to form an alignment layer; and (b) rubbing the alignment layer to provide alignment ability. And (c) irradiating the alignment layer with light with a different dose for each of the regions corresponding to the first to third display pixels, and photolyzing the alignment layer in the irradiated region. (D) applying a solution containing a thermotropic liquid crystal property and a liquid crystal compound exhibiting photopolymerizability and / or photocrosslinkability on the alignment layer, and forming a lower alignment film Liquids with different degrees of orientation depending on the region's regulatory power A retardation substrate manufacturing method which comprises a step of forming an immobilized layer.

  The invention according to claim 2 is the method for manufacturing a retardation substrate according to claim 1, wherein a color filter layer is formed on the substrate before the step (a) is performed.

  According to a third aspect of the present invention, the color filter layer is formed on the liquid crystal immobilization layer after performing the step (d), and the method of manufacturing a retardation substrate according to the first aspect of the present invention. It is.

  According to the present invention, it is possible to reliably form liquid crystal fixed layers having different phase differences for each color, and to make the phase difference close to zero in a region where no phase difference is required. Further, according to the present invention, it is not necessary to make the film thicknesses of the liquid crystal immobilization layer and other layers different, and the process can be facilitated.

  Hereinafter, the present invention will be described in detail.

  The retardation substrate of the present invention has a liquid crystal immobilization layer having a different phase difference due to a different degree of orientation for each of the first to third display pixels.

  The substrate having the liquid crystal fixing layer may be a color filter substrate or a TFT substrate. Further, the liquid crystal fixing layer itself can be used as a self-holding type retardation substrate and retardation film. Examples of the material for the substrate include glass, plastic, and a film base material.

  Hereinafter, a description will be given of a retardation substrate in which a liquid crystal fixing layer is formed on a color filter layer on which first to third display pixels are formed.

  FIG. 1 is a perspective view showing a part of a retardation substrate according to an embodiment of the present invention. FIG. 2 is a sectional view of this retardation substrate. Red, green, and blue color filter layers 12R, 12G, and 12B are formed on one surface of the glass substrate 11, respectively. An alignment layer is formed on the color filter layers 12R, 12G, and 12B. The alignment layers 13R, 13G, and 13B corresponding to the red, green, and blue display pixels have different alignment capabilities. A liquid crystal fixing layer (retardation layer) is formed on the alignment layer. The liquid crystal fixing layers 14R, 14G, and 14B corresponding to the display pixels of red, green, and blue have different degrees of alignment of the liquid crystal compounds according to the alignment ability of the alignment layers 13R, 13G, and 13B.

  That is, as shown in FIG. 2, in each of the liquid crystal fixed layers 14R, 14G, and 14B, the liquid crystal compound LC is polymerized and / or crosslinked and fixed in a state where the degree of alignment is different. For example, the red pixel portion (14R) is almost completely oriented, and the birefringence is most strongly expressed. The green pixel portion (14G) has a lower degree of orientation than the red pixel portion (14R), and its birefringence is relatively weak. The blue pixel portion (14B) has a lower degree of orientation than the green pixel portion (14G) and has the weakest birefringence. The degree of orientation as described above can be estimated from the change in birefringence. When the degree of alignment of the liquid crystal compounds in the liquid crystal fixing layers 14R, 14G, and 14B is different, the birefringence of each display pixel is different, and the phase difference amount is also different.

  In the retardation substrate shown in FIGS. 1 and 2, the liquid crystal immobilization layer is laminated on the color filter layer, but the liquid crystal immobilization layer may be provided below the color filter layer. When the liquid crystal immobilization layer is provided under the color filter layer, the order may be glass substrate / liquid crystal immobilization layer / black separation wall / colored composition layer, or glass substrate / black separation wall / liquid crystal immobilization layer. / The order of the colored composition layer may be used. On the other hand, the liquid crystal fixing layer may be provided on the counter substrate (usually the TFT substrate) without providing the liquid crystal fixing layer in the color filter layer. In addition, a liquid crystal fixing layer may be provided on the color filter substrate, and a liquid crystal fixing layer may be provided on the counter substrate.

  In the present invention, the “degree of orientation” of the liquid crystal compound describes the orientation in each in-plane region, and does not necessarily mean that the degree of orientation is constant in the thickness direction. For example, in a certain region, the alignment may be more uniform near the lower surface, or near non-orientation near the upper surface. In this case, “degree of orientation” indicates an average degree of orientation in the thickness direction.

  In the present invention, the type of alignment of the liquid crystal compound to be immobilized is not particularly limited. For example, a positive A plate obtained by homogeneous alignment in which rod-shaped liquid crystals are aligned so as to be horizontal in the plane, a positive C plate obtained by homeotropic alignment in which rod-shaped liquid crystals are aligned so as to be perpendicular to the surface, in-plane A negative C plate obtained by cholesteric alignment that is horizontally and spirally wound, a negative A plate obtained by homeotropic alignment in which the disc-like liquid crystal is aligned so as to be perpendicular to the surface, and the disc-like liquid crystal is in-plane Examples include, but are not limited to, a positive C plate obtained by homogeneous orientation aligned so as to be horizontal. In addition, any orientation that can exist in the present invention, such as a biaxial type (positive A plate / negative C plate composite) in which the rod-like liquid crystal is horizontal in the plane and has a spiral azimuth angle is deflected Can be applied.

  In the retardation substrate of the present invention, a part of the region may be optically substantially isotropic by fixing the liquid crystal compound in a non-oriented state. The liquid crystal immobilization layer substantially functions as a transparent thin film because there is substantially no phase difference.

  Since the retardation substrate of the present invention is intended to control the phase difference to a desired value by making the birefringence of the liquid crystal fixing layer different for each region, the region having a separate phase difference amount. However, it is not necessary to change the thickness of the liquid crystal fixing layer. Therefore, the film thickness of the liquid crystal fixing layer in the plurality of regions can be made substantially the same, that is, the film thickness can be made equal throughout the retardation layer. Of course, the film thickness of the liquid crystal fixing layer may be different for each region.

  Various methods for forming the retardation substrate of the present invention are conceivable. First, the color filter layer can be formed using an existing method. As described above, the color filter layer may be provided on the substrate, or may be provided on the liquid crystal fixing layer provided on the substrate.

  Hereinafter, as an example, a case where a colored composition in which a pigment is dispersed in a pigment carrier is formed in a predetermined region of each color and cured to form pixels will be described.

  As a pigment contained in a coloring composition, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. The pigment preferably has high color developability and high heat resistance, particularly high heat decomposition resistance, and an organic pigment is usually used. Hereinafter, specific examples of organic pigments that can be used in the colored composition are indicated by color index numbers.

  Examples of the organic pigment of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 179, 184, 185, Red pigments such as 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279 can be used. As the organic pigment of the red coloring composition, a mixture of a red pigment and a yellow pigment may be used. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182, 185, 187, 188, 193, 194, 199, 198, 213, 214, etc. can be used.

  Examples of the organic pigment of the green coloring composition include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. As the organic pigment of the green coloring composition, a mixture of a green pigment and a yellow pigment may be used. As the yellow pigment, the same pigments as exemplified for the red coloring composition can be used.

  Examples of the organic pigment of the blue coloring composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. As an organic pigment of the blue coloring composition, a mixture of a blue pigment and a purple pigment may be used. Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can be used.

  Examples of inorganic pigments include yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, and other metal oxide powders, metal sulfide powders, and metal powders. Etc. can be used. Inorganic pigments are used in combination with organic pigments in order to achieve good coatability, sensitivity, developability and the like while balancing chroma and lightness.

  For coloring, the coloring composition may contain a dye as long as the heat resistance is not lowered.

  The pigment carrier contained in the coloring composition is for dispersing the pigment. As the pigment carrier, a transparent resin, a precursor thereof, and a mixture thereof can be used. The transparent resin means a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm that is a visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin. The precursor of the transparent resin includes a monomer and an oligomer that are cured by radiation irradiation to form a transparent resin. These can be used alone or in admixture of two or more.

  The pigment carrier is used in an amount of 30 to 700 parts by mass, preferably 60 to 450 parts by mass with respect to 100 parts by mass of the pigment. When a mixture of a transparent resin and its precursor is used as a pigment carrier, the amount of the transparent resin in the coloring composition is 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the pigment. Used in. The precursor of the transparent resin is used in an amount of 10 to 300 parts by mass, preferably 10 to 200 parts by mass with respect to 100 parts by mass of the pigment.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

  Examples of the photosensitive resin include a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, and an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into a linear polymer by reacting a compound or cinnamic acid can be used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is used as a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. It is also possible to use a resin half-esterified by.

  Monomers and oligomers that are precursors of transparent resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate and methacrylate esters such as acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, and epoxy (meth) acrylate ; (Meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

  When the colored composition is cured by irradiation with ultraviolet rays or the like, for example, a photopolymerization initiator is added to the colored composition.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Acetophenone photopolymerization initiators such as butan-1-one; benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid Benzophenone photopolymerization initiators such as methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone photopolymerization initiators such as 4-diisopropylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) ) -S-triazine, 2 4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1) -Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine And triazine photopolymerization initiators; borate photopolymerization initiators; carbazole photopolymerization initiators; imidazole photopolymerization initiators and the like. A photoinitiator can be used individually or in mixture of 2 or more types.

  The photopolymerization initiator is used in an amount of 5 to 200 parts by mass, preferably 10 to 150 parts by mass with respect to 100 parts by mass of the pigment.

  A sensitizer may be used together with the photopolymerization initiator. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like. The sensitizer is used in an amount of 0.1 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.

  The coloring composition may contain a chain transfer agent such as a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol groups. As polyfunctional thiols, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate tris ( 2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) Such as 4,6-dimercapto -s- triazine. Polyfunctional thiols can be used alone or in admixture of two or more. The polyfunctional thiol is used in an amount of 0.2 to 150 parts by mass, preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the pigment.

  You may make a coloring composition contain a solvent. If a solvent is used, the dispersibility of the pigment in the pigment carrier can be improved, and each color display pixel can be easily formed by setting the dry film thickness of the colored composition applied on the substrate to 0.2 to 5 μm. It becomes like this.

  Solvents include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents. These can be used alone or in admixture of two or more. The solvent is used in an amount of 800 to 4000 parts by mass, preferably 1000 to 2500 parts by mass with respect to 100 parts by mass of the pigment.

  The coloring composition includes one or more pigments, together with the photopolymerization initiator as necessary, in a pigment carrier and an organic solvent, and various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. It can be used by being finely dispersed. The coloring composition containing two or more kinds of pigments can be produced by mixing finely dispersed pigments in a pigment carrier and an organic solvent separately. When the pigment is dispersed in the pigment carrier and the organic solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative may be used. The dispersion aid improves the dispersibility of the pigment and suppresses reaggregation of the pigment after dispersion. Therefore, when a coloring composition in which a pigment is dispersed in a pigment carrier and an organic solvent using a dispersion aid is used, a color filter having excellent transparency can be obtained.

  The dispersing aid is used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment.

  The resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersibility of the pigment in the pigment carrier. . Resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid partial amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkyls Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides formed by the reaction of poly (lower alkylene imines) and polyesters having free carboxyl groups and their Oil-based dispersants such as salts; water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin or water-soluble polymer Compound; polyesters, modified polyacrylates, an ethylene oxide / propylene oxide adduct, and the like phosphoric ester. These can be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include alkylbetaines such as betaine acetate and amphoteric surfactants such as alkylimidazolines. These can be used alone or in admixture of two or more.

  The coloring composition may contain a pigment derivative. A pigment derivative is a compound in which a substituent is introduced into an organic pigment. The pigment derivative preferably has a hue close to that of the pigment to be used, but a pigment having a different hue may be used as long as the addition amount is small. In addition to the compound generally called a pigment | dye, the organic pigment | dye shall also contain light yellow aromatic polycyclic compounds, such as a naphthalene type compound and an anthraquinone type compound which are not generally called a pigment | dye. Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. You can use what you have. In particular, a pigment derivative having a basic group has a large effect of enhancing the dispersibility of the pigment. These can be used alone or in admixture of two or more.

  A storage stabilizer may be added to the coloring composition in order to increase the stability over time of the viscosity. Storage stabilizers include benzyltrimethyl chloride; quaternary ammonium chlorides such as diethylhydroxyamine; organic acids such as lactic acid and oxalic acid and their methyl ethers; t-butylpyrocatechol; organic phosphines such as tetraethylphosphine and tetraphenylphosphine; And phosphites. These can be used alone or in admixture of two or more. The storage stabilizer is used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the pigment.

  In order to improve the adhesion to the substrate, an adhesion improver such as a silane coupling agent may be added to the coloring composition.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane; (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane; β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N- β- (aminoethyl ) -Γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ -Aminosilanes such as aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. These can be used alone or in admixture of two or more. The silane coupling agent is used in an amount of 0.01 to 100 parts by mass with respect to 100 parts by mass of the pigment.

  The coloring composition can be prepared in the form of a gravure offset printing ink, a waterless offset printing ink, a silk screen printing ink, an ink jet printing ink, or a solvent development type or alkali development type coloring resist. The colored resist is obtained by dispersing a dye in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and an organic solvent.

  The pigment is used in an amount of 5 to 70% by mass, preferably 20 to 50% by mass, based on the total solid content of the coloring composition (100% by mass). The remaining solid content of the coloring composition is substantially composed of a resin binder constituting the pigment carrier.

  Before using the colored composition for film formation, means such as centrifugation, sintered filter, membrane filter, etc. are used to measure coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0. It is preferable to remove coarse particles of 5 μm or more and mixed dust.

  Each of the colored layers can be formed on the substrate by a printing method or a photolithography method. As the substrate, glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the substrate in order to drive the element after forming the panel. The liquid crystal immobilization layer according to the present invention may be formed on the substrate.

  Regarding the formation of display pixels of each color by the printing method, patterning can be performed simply by repeating printing and drying of the coloring composition prepared as printing ink as described above. For this reason, the printing method is excellent in mass productivity at low cost. Moreover, with the recent development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. When using the printing method, the composition of the coloring composition is designed so that the coloring composition does not dry and solidify on the printing plate or blanket. In the printing method, it is also important to optimize the fluidity of the coloring composition in the printing press. For this reason, you may adjust the viscosity by adding a dispersing agent and extender to a coloring composition.

  Each of the colored layers may be formed using a photolithography method. When using the photolithography method, first, a colored composition prepared as a solvent developing type or alkali developing type colored resist is applied on a substrate by a method such as spray coating, spin coating, slit coating, roll coating or the like. This coating film is formed so that the dry film thickness is, for example, 0.2 to 10 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like is used. Drying of the coating film can be omitted. Ultraviolet exposure is performed through a photomask having a predetermined pattern provided in contact or non-contact with the coating film. Thereafter, the coating film is immersed in the developer or the developer is sprayed onto the coating film, and the soluble portion is removed from the coating film to form a desired pattern. Similar operations are repeated for display pixels of other colors. A color filter layer is obtained as described above. In this method, heat treatment may be performed as necessary in order to promote polymerization of the colored resist. According to the photolithography method, the color filter layer can be formed with higher accuracy than the printing method.

  In the development, an aqueous solution such as sodium carbonate or sodium hydroxide can be used as the alkaline developer. Alternatively, an organic alkali such as dimethylbenzylamine or triethanolamine can be used as the alkali developer. You may add additives, such as an antifoamer and surfactant, to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the ultraviolet exposure sensitivity, the following processing may be added. That is, after the colored resist coating film is dried, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film. The latter film prevents the polymerization in the coating film of the colored resist from being inhibited by oxygen, so that higher exposure sensitivity can be achieved.

  The color filter layer may be formed by other methods. For example, it may be formed using an ink jet method, an electrodeposition method, or a transfer method. When forming a color filter layer by the ink jet method, a light-shielding separation wall is formed on the substrate in advance, and ink is ejected from the nozzle toward the area partitioned by the light-shielding separation wall. Each colored layer is obtained. When forming a color filter layer by an electrodeposition method, a transparent conductive film is formed in advance on a substrate, and the colored composition is deposited on the transparent conductive film by electrophoresis of colloidal particles made of the colored composition. Each colored layer is obtained. When the transfer method is used, a color filter layer is formed in advance on the surface of the peelable transfer base sheet, and the color filter layer is transferred from the base sheet onto the substrate.

  Next, a method for forming the alignment layer will be described. In the present invention, an alignment layer is formed by applying a solution containing a compound that has alignment properties and can be decomposed by light, and the alignment layer is rubbed to impart alignment ability. For example, after applying and drying materials such as polyvinyl alcohol and soluble polyimide to be the alignment layer, the surface is rubbed to impart alignment ability.

  Thereafter, the alignment layer is irradiated with light at different doses for the regions corresponding to the red, green, and blue display pixels, and the alignment layer in the light-irradiated region is photodecomposed to reduce the alignment regulation power. . In a region irradiated with a sufficient amount of light to decompose the alignment layer, the alignment regulating force generated by rubbing is substantially zero, that is, a non-aligned region. In a region irradiated with a smaller amount of light, the alignment regulating force is weakened according to the amount of light irradiation. The alignment regulating force in the region not irradiated with light is maintained as it is.

  Radiation such as ultraviolet rays, electron beams, visible rays, and infrared rays can be used for light irradiation of the alignment layer. In the present invention, “light” means one or more of the radiations, and expressions such as “decompose by light” and “photolysis” also have characteristics relating to one or more of the radiations. means.

  Spin coating, slit coating, letterpress printing, screen printing, flat plate printing, reversal printing, gravure printing, other printing methods, and these printing methods combined with the offset method for alignment layer coating The ink jet method, bar coating method, etc. can be applied.

  The rubbing treatment can employ a treatment method widely adopted as a liquid crystal alignment treatment step. That is, a method of imparting orientation ability by rubbing the surface of the orientation layer in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. In general, rubbing is performed several times using a cloth in which fibers having uniform length and thickness are planted on average.

  Next, a method for forming a liquid crystal fixing layer in the present invention will be described. Although various methods can be used, a coating solution containing a liquid crystal compound that exhibits thermotropic liquid crystallinity and photopolymerizability and / or photocrosslinkability is applied on the substrate, and exposure and heating are used in combination. A method of curing is simple.

  In addition to the liquid crystal compound and the solvent, this coating liquid is a chiral agent, photopolymerization initiator, thermal polymerization initiator, sensitizer, chain transfer agent, polyfunctional monomer and / or oligomer, resin, surfactant, storage stabilizer. In addition, components such as an adhesion improver can be added as long as liquid crystallinity is not impaired.

  Examples of thermotropic liquid crystals include alkylcyanobiphenyl, alkoxybiphenyl, alkylterphenyl, phenylcyclohexane, biphenylcyclohexane, phenylbicyclohexane, pyrimidine, cyclohexanecarboxylic acid ester, halogenated cyanophenol ester, alkylbenzoic acid ester, alkylcyanotolane. Dialkoxytolane, alkylalkoxytolane, alkylcyclohexyltoluene, alkylbicyclohexane, cyclohexylphenylethylene, alkylcyclohexylcyclohexene, alkylbenzaldehyde azine, alkenylbenzaldehyde azine, phenylnaphthalene, phenyltetrahydronaphthalene, phenyldecahydronaphthalene, and derivatives thereof, As well as these Acrylate compounds.

  As the photopolymerization initiator, sensitizer, chain transfer agent, polyfunctional monomer and / or oligomer, resin, surfactant, storage stabilizer, and adhesion improver, the same ones as exemplified for the coloring composition are used. can do. As the solvent, the same solvents as those exemplified for the coloring composition can be used.

  Next, the coating liquid is applied onto the substrate and dried to form a thin film containing a liquid crystal compound. For the application of the coating solution, a method similar to that described for the application of the alignment layer can be applied. Thereafter, the thin film containing the liquid crystal compound is exposed in a predetermined pattern. As a result, the liquid crystal compound is fixed in the region irradiated with light while maintaining different alignment states depending on the alignment regulating force of the alignment layer, and the region not irradiated with light remains unreacted.

  For this exposure, radiation such as ultraviolet rays, electron beams, visible rays, infrared rays, X-rays, and gamma rays can be used. In the present invention, “light” means one or more of the radiations, and expressions such as “polymerization by light” and “photopolymerization” are also characteristics relating to one or more of the radiations. Means.

  Next, the substrate is heated to a temperature higher than the phase transition temperature of the liquid crystal compound to the isotropic phase. As a result, a region of the liquid crystal compound that has not been exposed transitions to an isotropic phase. In this case, by making the alignment layer in the lower layer of the region that has not been exposed to a non-orientable region, a non-alignment state in which the phase difference is as close to zero as possible can be obtained. The exposed region is in a state in which the liquid crystal compound is fixed while maintaining the alignment state expressed according to the alignment regulating force of the lower alignment layer.

  Examples of the present invention will be described below.

  In the following examples, all operations for handling photosensitive materials were performed under a yellow or red lamp in order to prevent unwanted exposure of the materials.

  First, the production of the alkali development type coloring composition used for forming the color filter layer, the preparation of the acrylic resin solution and the pigment dispersion used for the production, and the salt milling treatment pigment used for the preparation of the pigment dispersion Manufacturing will be described.

<Preparation of acrylic resin solution 1>
Into the reaction vessel, 370 parts by mass of cyclohexanone was charged and heated to 80 ° C. while supplying nitrogen gas to the vessel. While maintaining the temperature of the liquid in the container at this temperature, a mixture of the following monomer and thermal polymerization initiator was dropped into the container over 1 hour to cause a polymerization reaction.

Methacrylic acid 20.0 parts by weight Methyl methacrylate 10.0 parts by weight n-Butyl methacrylate 55.0 parts by weight 2-Hydroxyethyl methacrylate 15.0 parts by weight 2,2′-azobisisobutyronitrile 4.0 parts by weight Dropping After completion, the reaction was continued at 80 ° C. for a further 3 hours. Thereafter, a solution prepared by dissolving 1.0 part by mass of azobisisobutyronitrile in 50 parts by mass of cyclohexanone was added to the liquid in the container, and the reaction was continued at 80 ° C. for another 1 hour to obtain an acrylic resin solution. Got. The weight average molecular weight of this acrylic resin was about 40,000.

  After cooling to room temperature, about 2 g of the previous resin solution was sampled. This sample was dried by heating at 180 ° C. for 20 minutes, and the mass of the nonvolatile content was measured. Based on the measurement results, cyclohexanone was added to the previous resin solution so that the concentration of the nonvolatile content was 20% by mass. The acrylic resin solution 1 was prepared as described above.

<Preparation of acrylic resin solution 2>
Into the reaction vessel, 370 parts by mass of cyclohexanone was charged and heated to 80 ° C. while supplying nitrogen gas to the vessel. While maintaining the temperature of the liquid in the container at this temperature, a mixture of the following monomer and thermal polymerization initiator was dropped into the container over 1 hour to cause a polymerization reaction.

Methacrylic acid 20.0 parts by weight Methyl methacrylate 10.0 parts by weight n-butyl methacrylate 35.0 parts by weight 2-hydroxyethyl methacrylate 15.0 parts by weight 2,2′-azobisisobutyronitrile 4.0 parts by weight 20.0 parts by mass of milphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.)
After completion of the addition, the reaction was continued at 80 ° C. for a further 3 hours. Thereafter, a solution prepared by dissolving 1.0 part by mass of azobisisobutyronitrile in 50 parts by mass of cyclohexanone was added to the liquid in the container, and the reaction was continued at 80 ° C. for another 1 hour to obtain an acrylic resin solution. Got. The weight average molecular weight of this acrylic resin was about 40,000.

  After cooling to room temperature, about 2 g of the previous resin solution was sampled. This sample was dried by heating at 180 ° C. for 20 minutes, and the mass of the nonvolatile content was measured. Based on the measurement results, cyclohexanone was added to the previous resin solution so that the concentration of the nonvolatile content was 20% by mass. As described above, an acrylic resin solution 2 was prepared.

<Preparation of acrylic resin solution 3>
The reaction vessel was charged with 560 parts by mass of cyclohexanone, and heated to 80 ° C. while supplying nitrogen gas to the vessel. While maintaining the temperature of the liquid in the container at this temperature, a mixture of the following monomer and thermal polymerization initiator was dropped into the container over 1 hour to cause a polymerization reaction.

Methacrylic acid 34.0 parts by weight Methyl methacrylate 23.0 parts by weight n-butyl methacrylate 45.0 parts by weight 2-hydroxyethyl methacrylate 70.5 parts by weight 2,2′-azobisisobutyronitrile 8.0 parts by weight After completion, the reaction was continued at 100 ° C. for a further 3 hours. Thereafter, a solution prepared by dissolving 1.0 part by mass of azobisisobutyronitrile in 55 parts by mass of cyclohexanone was added to the liquid in the container, and the reaction was continued at 80 ° C. for another 1 hour to obtain a copolymer solution. Got.

  Next, a mixture of the following compounds was added dropwise to 338 parts by mass of the obtained copolymer solution at 70 ° C. over 3 hours.

2-Methacryloyl ethyl isocyanate 32.0 parts by mass Dibutyltin laurate 0.4 parts by mass Cyclohexanone 120.0 parts by mass After cooling to room temperature, about 2 g of the previous resin solution was sampled. This sample was dried by heating at 180 ° C. for 20 minutes, and the mass of the nonvolatile content was measured. Based on the measurement results, cyclohexanone was added to the previous resin solution so that the concentration of the nonvolatile content was 20% by mass. As described above, an acrylic resin solution 3 was prepared. The weight average molecular weight of the obtained acrylic resin was 20000, and the double bond equivalent was 470.

<Preparation of acrylic resin solution 4>
The reaction vessel was charged with 560 parts by mass of cyclohexanone, and heated to 80 ° C. while supplying nitrogen gas to the vessel. While maintaining the temperature of the liquid in the container at this temperature, a mixture of the following monomer and thermal polymerization initiator was dropped into the container over 1 hour to cause a polymerization reaction.

Methacrylic acid 34.0 parts by weight Methyl methacrylate 23.0 parts by weight n-butyl methacrylate 25.0 parts by weight 2-hydroxyethyl methacrylate 70.5 parts by weight 2,2′-azobisisobutyronitrile 8.0 parts by weight 20.0 parts by mass of milphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.)
After completion of the dropwise addition, the reaction was continued at 100 ° C. for a further 3 hours. Thereafter, a solution prepared by dissolving 1.0 part by mass of azobisisobutyronitrile in 55 parts by mass of cyclohexanone was added to the liquid in the container, and the reaction was continued at 80 ° C. for another 1 hour to obtain a copolymer solution. Got.

  Next, a mixture of the following compounds was added dropwise to 338 parts by mass of the obtained copolymer solution at 70 ° C. over 3 hours.

2-Methacryloyl ethyl isocyanate 32.0 parts by mass Dibutyltin laurate 0.4 parts by mass Cyclohexanone 120.0 parts by mass After cooling to room temperature, about 2 g of the previous resin solution was sampled. This sample was dried by heating at 180 ° C. for 20 minutes, and the mass of the nonvolatile content was measured. Based on the measurement results, cyclohexanone was added to the previous resin solution so that the concentration of the nonvolatile content was 20% by mass. As described above, an acrylic resin solution 4 was prepared. The weight average molecular weight of the obtained acrylic resin was 20000, and the double bond equivalent was 470.

<Manufacture of red salt milled pigment>
200 parts by weight of a red pigment (CI pigment red 254, “Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals Co., Ltd.), 1400 parts by weight of sodium chloride, and 360 parts by weight of diethylene glycol were added to 1 gallon kneader made of stainless steel. (Inoue Mfg. Co., Ltd.) was prepared and kneaded at 80 ° C. for 6 hours. Next, this kneaded material was put into 8 liters of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. Filtration of this slurry and washing of the filter cake with water were repeated to remove sodium chloride and diethylene glycol from the pigment. Then, the filter cake was dried at 85 ° C. for a whole day and night to obtain 190 parts by mass of “PR254 treated pigment”.

<Manufacture of green salt milled pigment>
In the same manner as described for the red salt milled pigment, except that a green pigment (CI pigment green 36, “Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.) was used instead of the red pigment. , “PG36 treated pigment” was obtained.

<Manufacture of yellow salt milled pigment>
In the same manner as described for the red salt milled pigment except that a yellow pigment (CI pigment yellow 138, “Lionol Yellow 1030” manufactured by Toyo Ink Co., Ltd.) was used instead of the red pigment. , “P.Y.138 treated pigment” was obtained.

<Manufacture of blue salt milled pigment>
A method similar to that described for the red salt milled pigment except that a blue pigment (CI pigment blue 15: 6, “Heliogen Blue L-6700F” manufactured by BASF) was used instead of the red pigment. As a result, “P.B.15: 6 treated pigment” was obtained.

<Manufacture of purple salt milled pigment>
A method similar to that described for the red salt milled pigment except that a purple pigment (CI pigment violet 23, “Lionogen Violet R6200” manufactured by Toyo Ink Co., Ltd.) was used instead of the red pigment. As a result, “P.V.23 treated pigment” was obtained.

<Preparation of red pigment dispersion>
The following materials were stirred to prepare a uniform mixture. This mixture was subjected to treatment for 10 hours using an Eiger mill to uniformly disperse the solid content in the liquid. Here, zirconia beads having a diameter of 0.5 mm were used as the grinding medium. Thereafter, this dispersion was filtered to obtain a red pigment dispersion. For this filtration, a filter capable of separating particles having a diameter of 1.0 μm or more from the liquid phase was used.

P. R. 254 treated pigment 8.0 parts by weight Dispersing aid (“Solspers 20000” manufactured by Avicia) 1.0 part by weight Acrylic resin solution 1 40.0 parts by weight Cyclohexanone 51.0 parts by weight <Preparation of Green Pigment Dispersion>
The following materials were stirred to prepare a uniform mixture. This mixture was subjected to treatment for 10 hours using an Eiger mill to uniformly disperse the solid content in the liquid. Here, zirconia beads having a diameter of 0.5 mm were used as the grinding medium. Thereafter, this dispersion was filtered to obtain a green pigment dispersion. For this filtration, a filter capable of separating particles having a diameter of 1.0 μm or more from the liquid phase was used.

P. G. 36 treated pigments 8.0 parts by weight Dispersing aid ("Solspers 20000" manufactured by Avicia) 1.0 parts by weight Acrylic resin solution 1 40.0 parts by weight Cyclohexanone 51.0 parts by weight <Preparation of yellow pigment dispersion>
The following materials were stirred to prepare a uniform mixture. This mixture was subjected to treatment for 10 hours using an Eiger mill to uniformly disperse the solid content in the liquid. Here, zirconia beads having a diameter of 0.5 mm were used as the grinding medium. Thereafter, this dispersion was filtered to obtain a yellow pigment dispersion. For this filtration, a filter capable of separating particles having a diameter of 1.0 μm or more from the liquid phase was used.

P. Y. 138 treated pigment 8.0 parts by weight Dispersing aid (“Solspers 20000” manufactured by Avicia) 1.0 part by weight Acrylic resin solution 1 40.0 parts by weight Cyclohexanone 51.0 parts by weight <Preparation of blue pigment dispersion>
The following materials were stirred to prepare a uniform mixture. This mixture was subjected to treatment for 10 hours using an Eiger mill to uniformly disperse the solid content in the liquid. Here, zirconia beads having a diameter of 0.5 mm were used as the grinding medium. Thereafter, this dispersion was filtered to obtain a blue pigment dispersion. For this filtration, a filter capable of separating particles having a diameter of 1.0 μm or more from the liquid phase was used.

P. B. 15: 6 treated pigment 8.0 parts by weight Dispersing aid ("BYK111" manufactured by Big Chemie) 1.0 part by weight Acrylic resin solution 2 40.0 parts by weight Cyclohexanone 51.0 parts by weight <Preparation of purple pigment dispersion>
The following materials were stirred to prepare a uniform mixture. This mixture was subjected to treatment for 10 hours using an Eiger mill to uniformly disperse the solid content in the liquid. Here, zirconia beads having a diameter of 0.5 mm were used as the grinding medium. Thereafter, this dispersion was filtered to obtain a purple pigment dispersion. For this filtration, a filter capable of separating particles having a diameter of 1.0 μm or more from the liquid phase was used.

P. V. 23 treated pigments 8.0 parts by weight Dispersing aid ("BYK111" manufactured by Big Chemie) 1.0 parts by weight Acrylic resin solution 2 40.0 parts by weight Cyclohexanone 51.0 parts by weight <Production of red colored composition>
The following materials were stirred to prepare a uniform mixture. This mixture was filtered to obtain an alkali developing type red coloring composition. For this filtration, a filter capable of separating particles having a diameter of 0.6 μm or more from the liquid phase was used.

Red pigment dispersion 50.0 parts by weight Acrylic resin solution 3 10.0 parts by weight Trimethylolpropane triacrylate 3.0 parts by weight (Shin Nakamura Chemical Co., Ltd. “NK ester ATMPT”)
1.8 parts by mass of photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts by mass Cyclohexanone 10.0 parts by mass <Manufacture of green coloring composition>
The following materials were stirred to prepare a uniform mixture. This mixture was filtered to obtain an alkali developing type green coloring composition. For this filtration, a filter capable of separating particles having a diameter of 0.6 μm or more from the liquid phase was used.

Green pigment dispersion 30.0 parts by weight Yellow pigment dispersion 20.0 parts by weight Acrylic resin solution 3 10.0 parts by weight Trimethylolpropane triacrylate 3.0 parts by weight (Shin Nakamura Chemical Co., Ltd. “NK ESTER ATMPT”)
1.8 parts by mass of photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts by mass Cyclohexanone 10.0 parts by mass <Production of blue coloring composition>
The following materials were stirred to prepare a uniform mixture. The mixture was filtered to obtain an alkali developing type blue coloring composition. For this filtration, a filter capable of separating particles having a diameter of 0.6 μm or more from the liquid phase was used.

Blue pigment dispersion 45.0 parts by mass Purple pigment dispersion 5.0 parts by mass Acrylic resin solution 4 10.0 parts by mass Trimethylolpropane triacrylate 3.0 parts by mass (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
1.8 parts by mass of photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts by mass Cyclohexanone 10.0 parts by mass Using a spin coater, the above-mentioned red colored composition is adjusted to a dry film thickness of 1.0 μm. It apply | coated on the glass plate. The glass plate used here is optically isotropic. Subsequently, the coating film was dried by heating at 70 ° C. for 20 minutes using a clean oven. After the substrate was cooled to room temperature, the coating film was irradiated with ultraviolet rays through a photomask. An ultra-high pressure mercury lamp was used as the ultraviolet light source. Next, this coating film was subjected to spray development using a sodium carbonate aqueous solution at 23 ° C. Thereafter, the coating film was washed with ion exchanged water and allowed to air dry. Furthermore, the coating film was baked at 230 ° C. for 30 minutes using a clean oven. As described above, a red colored layer was formed on the substrate.

  Next, a green colored layer was further formed on the substrate on which the red colored layer was formed by the same method as described for the red colored composition except that the green colored composition was used instead of the red colored composition. . Thereafter, the blue colored layer was formed on the substrate on which the red colored layer and the green colored layer were formed in the same manner as described for the red colored composition except that the blue colored composition was used instead of the red colored composition. Further formed. As described above, a color filter layer was obtained.

The laminate of the color filter layer and the glass plate were measured in-plane direction retardation R _e. As a result, the retardation for light of wavelength 630nm of the portion corresponding to the red coloring layer R _e, retardation R _e for the light of wavelength 550nm of the portion corresponding to the green coloring _layer, and corresponding to the blue coloring layer retardation R _e for the light of wavelength 450nm portions were both zero.

  Next, an alignment film material (“SE-1410” manufactured by Nissan Chemical Industries, Ltd.) was applied onto the color filter layer using a spin coater so that the dry film thickness was 0.1 μm. Subsequently, the coating film was dried by heating for 1 minute at 90 ° C. using a hot plate. Subsequently, the coating film was baked at 230 ° C. for 40 minutes using a clean oven. Further, the coating film was rubbed in one direction parallel to the main surface to obtain an alignment film.

Next, each of the regions corresponding to the red colored layer, the green colored layer, and the blue colored layer in the alignment film is irradiated with ultraviolet rays through a photomask, and the alignment layer in the light irradiated region is photolyzed and aligned. Reduced regulatory power. A low-pressure mercury lamp was used as the ultraviolet light source. Exposure of the region corresponding to the red coloring layer and 0 mJ / cm ^2, the exposure amount of the region corresponding to the green coloring layer and 15 mJ / cm ^2, the exposure amount of the region corresponding to the blue coloring layer and 20 mJ / cm ² did.

  Next, the following materials were stirred to prepare a uniform mixture. This mixture was filtered to obtain a coating solution. For this filtration, a filter capable of separating particles having a diameter of 0.6 μm or more from the liquid phase was used.

Horizontal alignment polymerizable liquid crystal 39.7 parts by mass (“Palocolor LC 242” manufactured by BASF Japan Ltd.)
Photopolymerization initiator 0.3 part by mass (“Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 6.0 parts by mass ("BYK111" 2% cyclohexanone solution manufactured by BYK Chemie)
154.0 parts by mass of cyclohexanone This coating solution was applied onto the alignment film using a spin coater so that the dry film thickness was 1.6 μm. Subsequently, the coating film was dried by heating at 90 ° C. for 2 minutes using a hot plate. As described above, a liquid crystal material layer was formed on the alignment film.

  Next, pattern exposure was performed on the liquid crystal material layer. Thereafter, the liquid crystal material layer was baked at 230 ° C. for 40 minutes using a clean oven to obtain a liquid crystal immobilization layer. A retardation substrate was manufactured as described above.

This retardation substrate was measured in-plane direction retardation R _e. As a result, the retardation _{R e} for the light of wavelength 630nm of the portion corresponding to the red coloring layer was 161 nm. Retardation _{R e} for the light of wavelength 550nm of the portion corresponding to the green coloring layer was 136 nm. Retardation _{R e} for the light of wavelength 450nm of the portion corresponding to the blue coloring layer was 112 nm.

The perspective view of the retardation board | substrate which concerns on this invention. Sectional drawing of the retardation board | substrate which concerns on this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Glass substrate, 12R ... Red color filter layer, 12G ... Green color filter layer, 12B ... Blue color filter layer, 13B, 13G, 13B ... Orientation layer, 14B, 14G, 14B ... Liquid crystal fixed layer.

Claims (3)

In manufacturing a retardation substrate including a substrate and a liquid crystal fixing layer formed on one side of the substrate and corresponding to the first to third display pixels,
(A) applying a solution containing a compound having orientation and decomposable by light on the substrate to form an orientation layer;
(B) rubbing the alignment layer to impart alignment ability;
(C) The alignment layer is irradiated with light at a different irradiation amount for each of the regions corresponding to the first to third display pixels, and the alignment layer in the light-irradiated region is photodecomposed to exert an alignment regulating force. Reducing the process;
(D) A solution containing a liquid crystal compound exhibiting thermotropic liquid crystallinity and photopolymerizability and / or photocrosslinkability is applied on the alignment layer, and the degree of alignment according to the regulating force of the lower alignment film Forming a liquid crystal immobilization layer different for each region. A method for manufacturing a retardation substrate.   The method for producing a retardation substrate according to claim 1, wherein a color filter layer is formed on the substrate before the step (a) is performed.   The method for producing a retardation substrate according to claim 1, wherein a color filter layer is formed on the liquid crystal immobilization layer after performing the step (d).

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