JP2010085616A - Substrate for liquid crystal display device - Google Patents

Abstract

A substrate for a liquid crystal display device having a color filter layer and an optically anisotropic layer capable of reducing the number of manufacturing steps is provided.
A substrate for a liquid crystal display device including a substrate, a color filter layer, and an optically anisotropic layer in this order, wherein the color filter layer and the optically anisotropic layer are formed by partition walls formed on the substrate. A substrate for a liquid crystal display device, which is divided into a plurality of regions, and the optically anisotropic layer is provided directly by an ink jet method after the color filter layer is subjected to an alignment treatment.
[Selection] Figure 1

Description

The present invention relates to a substrate for a liquid crystal display device. The present invention particularly relates to a substrate for a liquid crystal display device including a color filter layer and an optically anisotropic layer.

Conventionally, optical compensation films have been used to improve the viewing angle characteristics of liquid crystal display devices. However, in recent years, there are many techniques for achieving viewing angle characteristics improvement using an optically anisotropic layer provided in a liquid crystal cell. It has been developed (for example, Patent Document 1). As one of such embodiments, when an optically anisotropic layer made of a polymerizable liquid crystal compound is formed on a color filter layer on a substrate, an alignment layer is usually provided between the color filter and the optically anisotropic layer. There is a need. When this alignment layer is provided by solid coating, the alignment layer usually adheres to the entire surface of the partition wall (black matrix) present in the color filter. When the optically anisotropic layer is provided by ink jet ejection, it is necessary to perform ink repellent treatment on the partition wall surface, but the ink repellency is lost due to the adhesion of the alignment layer. Such a problem does not occur when the alignment layer is also provided by ink jet droplet deposition, but the process load is larger than that of solid coating.
Patent Documents 2 to 5 disclose attempts to share the function of an alignment film for aligning liquid crystal molecules for driving liquid crystal cells with a color filter.
Japanese Patent Application No. 2007-233376 JP-A-8-76106 JP-A-8-122791 JP-A-9-274105 JP-A-10-104606

An object of the present invention is to provide a substrate for a liquid crystal display device having a color filter layer and an optically anisotropic layer, which can reduce the number of manufacturing steps. In particular, a substrate for a liquid crystal display device including a color filter layer and an optically anisotropic layer provided on the color filter layer by an ink jet method, wherein the alignment is between the color filter layer and the optically anisotropic layer. It is an object to provide a substrate for a liquid crystal display device in which formation of a layer is unnecessary.

As a result of intensive studies, the inventors have succeeded in simultaneously providing the color filter layer with functions as an alignment layer and an optically anisotropic layer, and completed the present invention based on this finding. That is, the present invention provides the following [1] to [11].
[1] A substrate for a liquid crystal display device comprising a substrate, a color filter layer, and an optically anisotropic layer in this order,
The color filter layer and the optically anisotropic layer are divided into a plurality of regions by a partition formed on a substrate, and the optically anisotropic layer is directly rubbed on the color filter layer, A substrate for a liquid crystal display device provided by an inkjet method.

[2] The color filter layer is at least selected from the group consisting of polyimide, polyisoimide, polyesterimide, polyetherimide, polyamideimide, polyamic acid, polyamic acid ester, polyamide, polyamine, polythioamide, polyurethane, polyurea, and polyazomethine. The substrate for a liquid crystal display device according to [1], comprising a layer containing one.
[3] The optically anisotropic layer is a layer formed by applying or drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then heating or irradiating light. The substrate for liquid crystal display device according to [1] or [2].
[4] The substrate for a liquid crystal display device according to [3], wherein the liquid crystalline compound is a rod-like liquid crystalline compound.
[5] The substrate for a liquid crystal display device according to [1] or [4], wherein the reactive group is an ethylenically unsaturated group.

[6] The substrate for a liquid crystal display device according to any one of [1] to [5], wherein a front retardation of the optically anisotropic layer is 40 to 550 nm.
[7] A liquid crystal display device having the substrate for a liquid crystal display device according to any one of [1] to [6].
[8] The liquid crystal display device according to [7], wherein an alignment mode of the liquid crystal display device is any one of TN, VA, IPS, FFS, and OCB.
[9] A method for manufacturing a substrate for a liquid crystal display device,
(1) A step of preparing a substrate on which a partition is formed and including a color filter layer divided into a plurality of regions by the partition;
(2) rubbing the color filter surface; and (3) forming a liquid crystal phase by applying and drying a solution containing a liquid crystal compound having at least one reactive group on the rubbed surface by an ink jet method. A step of forming an optically anisotropic layer that is divided into a plurality of regions by the partition wall by heating or light irradiation.

[10] The method according to [9], wherein the color filter layer includes a copolymer having a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). .

In General Formula (1), Y ¹ represents a methylene group, an ethylene group or an ethenylene group, and X ¹ represents a divalent linking group represented by the following General Formula (3);

In General Formula (2), Y ² represents a methylene group, an ethylene group or an ethenylene group, and X ² represents a divalent linking group represented by the following General Formula (4);

In general formula (3), R ¹ and R ² are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. Represents one group, l and m each independently represents an integer of 0 to 4;

In general formula (4), A represents a cyclic or non-cyclic hydrocarbon group which may be unsubstituted or optionally substituted, provided that A is directly connected to three or more aromatic rings from the same carbon atom. No partial structure, B ² represents a substituted or unsubstituted aryl group or heteroaryl group, L represents a divalent linking group, Q ² represents a reactive group (eg, the reactive group), R ⁴ represents a hydrogen atom, an unsubstituted or optionally substituted cyclic or non-cyclic hydrocarbon group, and n represents an integer of 0 or more.

[11] The method according to [10], wherein the copolymer is end-capped with a compound of the following general formula (5):

In the general formula (5), B ¹ represents a substituted or unsubstituted aryl group or heteroaryl group, Q ¹ represents a reactive group (for example, the reactive group), R ³ represents a hydrogen atom, unsubstituted or arbitrary Represents a cyclic or non-cyclic hydrocarbon group which may be substituted, and k represents an integer of 0 or more.

According to the present invention, there is provided a substrate for a liquid crystal display device including a color filter layer and an optically anisotropic layer which are divided into a plurality of regions by partition walls formed on the substrate, wherein the optically anisotropic layer is the color filter. Provided is a substrate for a liquid crystal display device, which is provided by an ink jet method directly on the orientation treatment of the layer. In the substrate for a liquid crystal display device of the present invention, an optically anisotropic layer composed of polymerizable liquid crystal molecules can be provided on the color filter layer without the need to separately provide an alignment film. Further, by using the composition of the present invention, it is possible to easily produce a fine structure in which a color filter layer and an optically anisotropic layer are laminated, so that the liquid crystal cell is optically compensated for each color. It is possible to design a liquid crystal display device that can be used more easily.

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In this specification, the Re retardation value is calculated based on the following. Re (θ) represents in-plane retardation when the θ-degree sample is inclined with the slow axis as the rotation axis. Re (θ) is measured in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments) by making light of wavelength λ nm incident by the parallel Nicol method. In this specification, λ refers to 611 ± 5 nm, 545 ± 5 nm, 435 ± 5 nm for R, G, and B, respectively, and refers to 550 ± 5 nm unless there is a particular description regarding color.

In this specification, “substantially” for the angle means that the error from the exact angle is within a range of less than ± 5 °. Furthermore, the error from the exact angle is preferably less than 4 °, more preferably less than 3 °. With regard to retardation, “substantially” means that the retardation is within ± 5%. Furthermore, Re is not substantially 0 means that Re is 5 nm or more. In addition, the measurement wavelength of the refractive index indicates an arbitrary wavelength in the visible light region unless otherwise specified. In the present specification, “visible light” refers to light having a wavelength of 400 to 700 nm.

[Alignment layer]
The color filter layer is a layer that also serves as an alignment layer. An alignment layer refers to a layer for forming an optically anisotropic layer without causing alignment failure. The presence / absence of the alignment treatment needs to be selected depending on the situation, but it is generally preferable to perform the alignment treatment. The alignment treatment may be rubbing, photo-alignment, stretching, shrinkage, etc., but is preferably a rubbing treatment widely adopted as a liquid crystal alignment processing step for LCD. As the rubbing treatment, a treatment for obtaining orientation by rubbing the surface of the layer in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like may be performed. In general, it can be carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are averagely planted.

[Color filter layer forming composition]
As a composition for forming a color filter layer, at least 1 consisting of the group of polyamine, polyimide, polyisoimide, polyesterimide, polyetherimide, polyamideimide, polyamic acid, polyamic acid ester, polyamide, polythioamide, polyurethane, polyurea, polyazomethine A composition containing at least one selected from the group consisting of polyimide, polyisoimide, polyesterimide, polyetherimide, polyamideimide, polyamic acid, polyamic acid ester and polyamide, more preferably polyimide. , A polyisoimide, a polyesterimide, a polyetherimide, a polyamideimide, and a polyamic acid. In addition, in order to impart solvent resistance after the smoothing layer is formed, the smoothing layer is formed by applying or drying a composition comprising a compound having at least one reactive group, and then heating or irradiating with light. It is preferred that the layer be a layer. The reactive group is not particularly limited, but is preferably an acetylene group, a maleimide group, a nadiimide group, a benzoxazine group, a vinyl group, an epoxy group, a cyanate group, or an isocyanate group, and more preferably an acetylene group.

As the composition for forming a color filter layer, a copolymer having both repeating units represented by the following general formula (1) and the following general formula (2) is particularly preferably used.

Y ¹ in the general formula (1) represents a methylene group, an ethylene group or an ethenylene group, preferably an ethylene group or an ethenylene group, and more preferably an ethylene group. X ¹ represents a divalent linking group represented by the following general formula (3).

In general formula (2), Y ² represents a methylene group, an ethylene group or an ethenylene group, preferably an ethylene group or an ethenylene group, and more preferably an ethylene group. X ² represents a divalent linking group represented by the following general formula (4).

In general formula (3), R ¹ and R ² are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. At least one kind.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom and a chlorine atom are more preferable. As the substituted or unsubstituted alkyl group, an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a trifluoromethyl group is preferable, and a methyl group, an ethyl group, and a trifluoromethyl group are preferable. More preferred. As a substituted or unsubstituted alkoxy group, C1-C8 alkoxy groups, such as an ethoxy group and a methoxy group, are preferable, and a phenoxy group and a methoxy group are more preferable. The substituted or unsubstituted aryl group is preferably a monocyclic or condensed polycyclic aromatic group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, or a p-methoxyphenyl group, and more preferably a phenyl group. R ¹ and R ² are preferably in the ortho position with respect to the linking group connecting the benzenes, and the linking group with the nitrogen atom is in the 3-position or 4-position with respect to the linking group connecting the benzenes. It is preferable to be in the 4th position.
l and m each independently represent an integer of 0 to 4, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and particularly preferably 1.

In general formula (4), A represents a cyclic or non-cyclic hydrocarbon group which may be unsubstituted or optionally substituted. However, the case where three or more aromatic rings are directly connected from the same carbon atom is not included. B ² represents a substituted or unsubstituted aryl group or heteroaryl group. It is preferable that one or both of A and B ² are benzene rings. L represents a divalent linking group, and is preferably a single bond, —OCO—, —COO—, —NRCO—, —CONR—, —NRCOO—, —OCONR—, or —NRCONR—. Q ² represents the reactive group and may be the same as or different from Q ¹ , but is preferably the same. R ⁴ represents a hydrogen atom, an unsubstituted or optionally substituted cyclic or non-cyclic hydrocarbon group, and is preferably a hydrogen atom. n represents an integer of 0 or more, and is preferably 1.

As the composition for forming a color filter layer, it is preferable to use a copolymer which is end-capped with a compound of the following general formula (5).

In General Formula (5), B ¹ represents a substituted or unsubstituted aryl group or heteroaryl group, and is preferably a benzene ring. Q ¹ represents the reactive group. R ³ represents a hydrogen atom, an unsubstituted or optionally substituted cyclic or acyclic hydrocarbon group, and is preferably a hydrogen atom. k represents an integer of 0 or more, and is preferably 1.

Although the especially preferable specific example of the structure of General formula (1) is given to the following, this invention is not limited to this.

In the following, particularly preferred specific examples of the structure excluding X ² in the general formula (2) are listed, but the present invention is not limited thereto.

Although the especially preferable specific example of the structure of X2 in General formula (2) is given to the following, this invention is not limited to this. Moreover, although the reactive group in the following specific examples is an acetylene group as a preferable example, the said reactive group may be said other reactive group.

Although the especially preferable specific example of the structure of General formula (5) is given to the following, this invention is not limited to this.

[Solvent of composition for forming color filter layer]
Examples of solvents used in the production of the smoothing layer include acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, dichloromethane, tetrahydrofuran, pyridine, benzene, hexane, 1,2-dimethoxyethane, N-methyl-2-pyrrolidone. N-methylcaprolactam, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, Propylene glycol-1-monoethyl ether-2-acetate, propylene glycol-n-butyl ether acetate, tripropylene glycol methyl ether Teracetate, 1,3-butanediol diacetate, dipropylene glycol-n-propyl ether acetate, dipropylene glycol mono-n-butyl ether acetate, diethylene glycol monobutyl ether acetate, propylene carbonate, dipropylene glycol monomethyl ether, dipropylene glycol mono -N-butyl ether, diethylene glycol monobutyl ether, cyclohexanone, cyclohexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, 2- (2 -Ethoxypropoxy) propanol, ethylene glycol, dipropylene glycol, N, N-dimethylformamide, N, N-di Examples include methylacetamide, dimethylsulfoxide, dimethylsulfone, hexamethylsulfoxide, methyl acetate, butyl acetate, ethyl lactate, methyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and caprolactam. Of these, two or more organic solvents may be used in combination.

The composition for producing a color filter of the present invention further contains a colorant such as a dye or a pigment. The colorant may be a known colorant (dye or pigment). In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the colored resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly preferably 0.08 μm or less. .
Examples of the known dyes or pigments include those described in paragraph numbers “0107” to “0109” of JP-A-2007-233376.

As the colorant in the present invention, among the above-mentioned colorants, (i) R (red) colored resin composition is C.I. I. Pigment Red 254 is C.I. in (ii) G (green) colored resin composition. I. In the colored resin composition of (iii) B (blue), CI Pigment Green 36 is C.I. I. Pigment Blue 15: 6 is a preferable example. Furthermore, the above pigments may be used in combination.

In the present invention, the combination of the above-described pigments preferably used in combination is C.I. I. In pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment yellow 139 or C.I. I. A combination with Pigment Violet 23; I. In Pigment Green 36, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138 or C.I. I. A combination with CI Pigment Yellow 180, and C.I. I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23 or C.I. I. A combination with Pigment Blue 60 is mentioned.

C. in the pigment when used together in this way. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. The content of Pigment Blue 15: 6 is C.I. I. The pigment red 254 is preferably 80% by mass or more, particularly preferably 90% by mass or more. C. I. The pigment green 36 is preferably 50% by mass or more, particularly preferably 60% by mass or more. C. I. Pigment Blue 15: 6 is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used when dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

The colorant (pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. When the number average particle diameter of the pigment is less than 0.001 μm, the particle surface energy is increased and the particles are easily aggregated, so that it is difficult to disperse the pigment and it is difficult to keep the dispersion state stable. On the other hand, if the number average particle diameter of the pigment exceeds 0.1 μm, the polarization is canceled by the pigment, and the contrast is lowered. In the present specification, “particle size” means the diameter when the electron micrograph image of the particle is a circle of the same area, and “number average particle size” means the above-mentioned particle size for many particles. This means the average value of 100 obtained.

The contrast of the colored pixels can be improved by reducing the particle size of the dispersed pigment. Reduction of the particle size can be achieved by adjusting the dispersion time of the pigment dispersion. For dispersion, the known disperser described above can be used. The dispersion time is preferably 10 to 30 hours, more preferably 18 to 30 hours, and most preferably 24 to 30 hours. When the dispersion time is less than 10 hours, the pigment particle size is large, the polarization due to the pigment is canceled, and the contrast may be lowered. On the other hand, if it exceeds 30 hours, the viscosity of the dispersion liquid increases and application may be difficult. Further, in order to make the difference in contrast between two or more colored pixels within 600, the pigment particle diameter is adjusted to obtain a desired contrast.

The contrast of each colored pixel of the color filter formed from the color filter layer is preferably 2000 or more, more preferably 2800 or more, still more preferably 3000 or more, and most preferably 3400 or more. When the contrast of each colored pixel constituting the color filter is 2000 or less, when an image of a liquid crystal display device having the color pixel is observed, an overall whitish impression is obtained, which is not preferable. Further, the difference in contrast between the colored pixels is preferably within 600, more preferably within 410, still more preferably within 350, and most preferably within 200. If the difference in contrast between the colored pixels is within 600, the amount of light leakage from each colored pixel portion at the time of black display does not differ greatly.

The composition for producing a color filter of the present invention may further contain a monomer or an oligomer. The radically polymerizable monomer or oligomer used is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the colored resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred.

Examples of the cationic polymerizable monomer or oligomer used in the color filter layer include cyclic ethers, cyclic formals, acetals, vinyl alkyl ethers, compounds containing thiirane groups, bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins. And epoxy compounds such as epoxidized unsaturated fatty acid and epoxidized polybutadiene. Examples of such monomers or oligomers include compounds described in Hiroaki Kakiuchi's “New Epoxy Resin” Shoshodo (published in 1985), “Epoxy Resin” published by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (1969), etc. Other trifunctional glycidyl ethers (trimethylol ethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), tetra- or higher functional glycidyl ethers (sorbitol tetraglycidyl ether, Pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc.) trifunctional or higher cycloaliphatic epoxy (Epolide GT-) 01, Epolede GT-401, EHPE (manufactured by Daicel Chemical Industries, Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc., trifunctional or more oxetanes (OX-SQ, PNOX-1009 (above, Tojo) Synthetic Co., Ltd.) and the like.

In addition, the monomer or oligomer demonstrated above may be contained in the optically anisotropic layer.

When the composition for producing a color filter of the present invention is cured with light or the like, it may further contain a photopolymerization initiator. Examples of the photopolymerization initiator or photopolymerization initiator system used in the color filter layer include a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660 and US Pat. No. 2,448,828. Acyloin ether compounds, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinones described in US Pat. Nos. 3,046,127 and 2,951,758 Compound, a combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound and a trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, Trihalomethyl described in US Pat. No. 4,239,850 Triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example. The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

Cationic polymerization initiators include aryl diazonium salts of Lewis acids such as etrafluoroborate and hexafluorophosphenol, double salts such as diaryl iodonium salts and triarylsulfonium luster, benzyl silyl ether, o-nitrobenzyl silyl ether, triphenyl ( Examples thereof include a mixed system of a silanol-generating silane compound such as (t-butyl) peroxysilane and an aluminum complex such as tris (ethylacetoacetate) aluminum. The content of the cationic polymerization initiator based on the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

In the present invention, these photopolymerization initiators may be used in combination with two or more different photoreaction mechanisms.

The composition for producing a color filter may further contain a binder in order to control film physical properties. As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. As disclosed in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. Can be mentioned.

Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid, and other monomers can be used. Mention may be made of multi-component copolymers. These binders having a polar group may be used singly or may be used in the state of a composition used in combination with an ordinary film-forming polymer.
As content in the dark color composition of a binder, 20-50 mass% is preferable with respect to the total solid (mass) of a layer or a composition, and 24-45 mass% is more preferable.

In the present specification, “contrast of colored pixels” means a contrast that is individually evaluated for each color of R, G, and B constituting the color filter. The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. Note that the polarizing plate used for contrast measurement is the same as the polarizing plate used for the liquid crystal display device using the color filter.

In the composition for producing a color filter, it is preferable to contain an appropriate surfactant from the viewpoint of effectively preventing display unevenness (color unevenness due to film thickness variation). As the surfactant, reference can be made to the descriptions of [0095] to [0105] of JP-A-2007-121986.

The composition can also contain a solvent, and as the solvent, water, alcohols, ketones, etc., refer to the solvent described in “New Edition Solvent Pocket Book (edited by Organic Synthetic Science Association, published by Ohmsha)”, The mass in the composition is preferably 50% or less, more preferably 30% or less.
The composition of the present invention in a solution state is, for example, ejected onto a substrate or the like by an ink jet method as described in JP-A-2008-76690, and then removed (dried) from water or a polar organic solvent. A layer can be formed.

The dried layer can be cured by heating or light irradiation, preferably by heating. The heating temperature may be about 120 ° C to 260 ° C, preferably 150 ° C to 250 ° C, more preferably 180 ° C to 230 ° C. The heat treatment time is not particularly limited, but is preferably 1 minute to 5 hours, more preferably 3 minutes to 3 hours, and particularly preferably 5 minutes to 2 hours.

Moreover, X-rays, electron beams, ultraviolet rays, visible rays, or infrared rays (heat rays) are used as the irradiation light in the light irradiation, and it is particularly preferable to use ultraviolet rays. The wavelength of the ultraviolet light is preferably 400 nm or less, and more preferably 180 to 360 nm. As the light source, a low-pressure mercury lamp, a high-pressure discharge lamp, or a short arc discharge lamp is preferably used. It is preferable to irradiate the layer with light aligned in a single direction as much as possible. This “single direction” means a single direction in the film plane (direction in which the direction of light is projected onto the film plane), and includes a direction horizontal or perpendicular to the film plane. It is also preferable to heat and cure after light irradiation. The heat treatment may be performed by heating at about 120 ° C. to 260 ° C., preferably 150 ° C. to 250 ° C., more preferably 180 ° C. to 230 ° C. The heat treatment time is not particularly limited, but is preferably 1 minute to 5 hours, more preferably 3 minutes to 3 hours, and particularly preferably 5 minutes to 2 hours.
The thickness of the formed layer is preferably 1 to 8 μm, and particularly preferably 2 to 6 μm.

[Partition wall]
The partition wall only needs to form a fine region (for example, each pixel region) on the substrate. It is preferable that the partition walls have a light-shielding property because they can be used as a black matrix (hereinafter, the partition walls that also function as a black matrix are referred to as “light-shielding partition walls”), and the configuration and manufacturing method can be simplified.
Regarding the formation of the partition wall, reference can be made to the description of [0133] to [0176] of JP-A-2007-233376.

[Liquid crystal display substrate]
The substrate for a liquid crystal display device of the present invention has a color filter layer and an optically anisotropic layer for compensating the viewing angle of the liquid crystal cell. The optically anisotropic layer may be a patterned optically anisotropic layer including a region divided by partition walls. For example, depending on the hue of the color filter layer disposed below (substrate side) (for example, for each of R, G, and B colors), the optical characteristics are optimal for compensating the viewing angle of the liquid crystal cell. It is preferable. Such a substrate for a liquid crystal display device may be used for either one of a pair of substrates of a liquid crystal cell, or may be used for both.

[Method of manufacturing substrate for liquid crystal display device]
An example of a method for manufacturing a substrate for a liquid crystal display device is an example of using a substrate on which a partition wall is formed, in which a part of a color filter layer and an optically anisotropic layer are formed in a portion (fine region) formed from the partition wall. An example in which a laminated structure including partial regions is formed will be described with reference to FIG.

First, partition walls are formed on the substrate 11. The partition is not particularly limited, but typically a black matrix formed from a negative black matrix resist material can be used. A black matrix 12 (partition) of a dot pattern may be formed by photolithography using a negative black matrix resist material, and a plurality of fine regions a separated by the partition 12 may be formed (FIG. 1A). In the formation of the black matrix 12, there is no particular limitation on the forming material and the forming process, and any method other than a method using a photolithography method using a resist material may be used as long as a matrix pattern can be formed. Further, the pattern of the black matrix 12 is not limited to a dot pattern, and the arrangement of the color filters to be formed is not particularly limited. For example, any of dot arrangement, stripe arrangement, mosaic arrangement, delta arrangement, and the like may be used.

The black matrix 12 is preferably subjected to plasma treatment with a gas containing F atoms (CF ₄ or the like) after pattern formation, and its surface is subjected to ink repellent treatment. In addition to the plasma treatment, the black matrix 12 may be made to contain an ink repellant in the black matrix material, or the black matrix may be formed from a material that exhibits ink repellency with respect to the glass substrate 11. May be.

Next, the ink is discharged for the first time with the color filter ink liquid 13 'to the fine region a separated by the black matrix 12 subjected to the ink repellent treatment if desired (FIG. 1B), and this is dried. By performing processing such as exposure and polarization exposure as necessary, a partial region 13 of the color filter is formed (FIG. 1C).

A rubbing process is performed on a partial region 13 of the color filter formed in this way, and a fluid 14 ′ such as a solution that develops optical anisotropy is discharged using an ink jet apparatus to enter the fine region a. A layer made of the fluid is formed (FIG. 1D). The fluid preferably contains at least one liquid crystalline compound, and is preferably prepared so as to form a liquid crystal phase after drying. A dispersion liquid in which a part or all of a material such as a liquid crystal compound is dispersed may be used as long as it can be ejected by ink jetting, but a solution is preferable. After the discharge of the solution is completed, the solution layer is dried to form a liquid crystal phase and exposed to form a partial region 14 of the optically anisotropic layer (FIG. 1E). In order to form the liquid crystal phase, heating may be performed as necessary, and in that case, a heating device may be used.

There are no particular restrictions on the ejection conditions of the ink or the like when forming the partial region 13 of the color filter and the partial region 14 of the optically anisotropic layer. In the case where the viscosity of the ink is high, it is preferable from the viewpoint of ejection stability that the ink is ejected at a lower temperature at room temperature or under heating (for example, 20 to 70 ° C.). It is preferable to keep the temperature of the ink or the like as constant as possible because the viscosity variation of the ink or the like greatly affects the droplet size and the droplet ejection speed as it is and causes image quality degradation.

The inkjet head (hereinafter also simply referred to as a head) used in the method for manufacturing a substrate for a liquid crystal display device is not particularly limited, and various known ones can be used. Continuous type and dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the composition can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of injection is 5 to 25 mPa · s, and to control the composition temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

Each region 14 in the optically anisotropic layer may be formed using fluids such as the same type of solution, and each has an optimal optical anisotropy, for example, depending on the hue of the color filter layer 13. It may be formed using fluids such as solutions containing different materials and / or different blending amounts so as to express. When using a different solution or the like depending on the hue of the color filter layer when forming the partial region 14 of the optically anisotropic layer, the respective solutions may be discharged and then dried simultaneously. You may perform the process of discharge and drying for every seed | species. Also, when forming the partial region 13 of the color filter layer, for example, after all ink liquids for forming the R layer, the G layer, and the B layer are discharged, drying may be performed simultaneously. You may perform the process of discharge and drying for every seed | species. Further, the color of the color filter is not necessarily limited to the three colors of red, green, and blue, and may be a multi-primary color filter.

In this manner, for example, R, G, and B ink liquids are ejected and dried for each region corresponding to each pixel of the substrate and separated by the black matrix 12, and then a predetermined optical anisotropic property is further formed thereon. The fluid prepared so as to exhibit the property can be discharged and dried to form a pattern layer including a color filter pattern and an optically anisotropic layer pattern in each region. A color filter layer is formed by the plurality of color filter patterns and a part of the partition walls, and an optical anisotropic layer is formed by the plurality of optical anisotropic layer patterns and a part of the partition walls. A transparent electrode layer and / or an alignment layer may be formed on the optically anisotropic layer. For example, as described in JP-A Nos. 11-248921 and 3255107, a base is formed by overlapping colored resin compositions forming a color filter, a transparent electrode is formed thereon, and further required Accordingly, it is preferable from the viewpoint of cost reduction that the spacers are formed by overlapping the protrusions for split orientation.

A liquid crystal device substrate manufactured as described above and another liquid crystal display device substrate as a counter substrate are prepared and bonded together. Furthermore, a liquid crystal layer can be formed by injecting a liquid crystal material into the vacant wall between these opposing surfaces to form a liquid crystal cell. The first substrate is preferably disposed with the surface on which the optically anisotropic layer and the color filter layer are formed facing inward, that is, with the opposing surface. Thereafter, a polarizing plate, an optical compensation film, and the like can be attached to the outer surfaces of both substrates, respectively, to produce a liquid crystal display device.

By manufacturing the substrate for a liquid crystal device of the present invention by an inkjet method, the substrate can be manufactured with a small number of steps without complicating the structure. That is, when the ink liquid for forming the color filter layer and the fluid for forming the optically anisotropic layer, and the black matrix as the partition walls are first formed at the predetermined positions, the first matrix on the first substrate is formed. An optically anisotropic layer and a color filter layer can be accurately formed in a predetermined region.

FIG. 2 shows a schematic cross-sectional view of an example of a substrate that can be used in the liquid crystal display device of the present invention.
The liquid crystal cell substrate shown in FIG. 2A has a pattern-like shape in which a black matrix 22 is formed as a partition on a transparent substrate 21 and is discharged by an inkjet method into a fine region separated by the partition. A color filter layer 23 and an optically anisotropic layer 27 are formed. Furthermore, the transparent electrode layer 25 and the alignment layer 26 are provided thereon. FIG. 2 shows an embodiment in which the color filter layers 23 of R, G, and B are formed. As is often seen recently, a color filter layer composed of layers of R, G, B, and W (white) is formed. May be. The first optical anisotropic layer 27 is divided into r, g, and b regions, and has optimum retardation characteristics for the hues of the R, G, and B filter layers 23, respectively.

Furthermore, as shown in FIG. 2B, the optically anisotropic layer may be divided into a second optically anisotropic layer 24 and a patterned optically anisotropic layer 27. In the case of dividing into two, the solid optical anisotropic layer 24 may be formed on the same color filter side substrate side as the patterned optical anisotropic layer 27, or it is formed on the counter substrate side although not shown. May be. In general, a drive electrode such as a TFT array is generally arranged on the counter substrate side, and may be formed at any position on the counter substrate. However, in the case of an active drive type having a TFT, optical anisotropy is provided. The heat resistance of the conductive layer is preferably higher than that of the silicon layer.

[Liquid Crystal Display]
FIG. 3 is a schematic sectional view of an example of the liquid crystal display device of the present invention.
3 (a) and 3 (b) use the substrates of FIGS. 2 (a) and 2 (b) as upper substrates, respectively, and a glass substrate 21 having a transparent electrode layer 25 with TFT 32 and an alignment layer 26 thereon. Is a liquid crystal display device having a liquid crystal cell 37 with a liquid crystal 31 interposed therebetween. On both sides of the liquid crystal cell 37, a polarizing plate 36 made of a polarizing layer 33 sandwiched between protective layers 34 and 35 made of a cellulose acetate (TAC) film or the like is disposed. The protective layer 35 on the liquid crystal cell side may be a polymer film such as a TAC film that satisfies optical characteristics as an optical compensation sheet, or may be made of the same polymer film as the protective layer 34. Although not shown in the drawing, in the aspect of the reflective liquid crystal display device, only one polarizing plate is required on the observation side, and a reflective film is provided on the back surface of the liquid crystal cell or on the inner surface of the lower substrate of the liquid crystal cell. Of course, a front light can be provided on the liquid crystal cell observation side. Further, a transflective type in which a transmissive portion and a reflective portion are provided in one pixel of the display device is also possible. The display mode of the present liquid crystal display device is not particularly limited, and can be used for all transmissive and reflective liquid crystal display devices. In particular, the present invention is effective for the VA mode where color viewing angle characteristics are desired to be improved.

Hereinafter, although this aspect demonstrates in detail about the material used for preparation, a preparation method, etc., this invention is not limited to this aspect. Other embodiments can also be produced with reference to the following description and conventionally known methods.

[substrate]
In the liquid crystal display device, the substrate on which the color filter layer and the optically anisotropic layer are provided is not particularly limited, and substrates made of various materials conventionally used as substrates for liquid crystal cells can be used. For example, a metallic support, a metal bonded support, glass, ceramic, synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

[Optically anisotropic layer]
The optically anisotropic layer (which may be referred to as the first optically anisotropic layer in the present specification) provided on the color filter layer formed from the composition for producing a color filter of the present invention is at least one kind of liquid crystallinity. It is desirable that the composition containing the compound is an optically anisotropic layer formed by forming a liquid crystal phase and then curing it by irradiating with ultraviolet rays. Moreover, in order to harden | cure by ultraviolet irradiation, it is preferable that the said composition contains a radical polymerization initiator and / or a cationic polymerization initiator. The compound containing a polymerizable group having reactivity with the polymerization initiator itself has liquid crystallinity, or does not impair the liquid crystallinity of the liquid crystalline compound that forms an optically anisotropic layer upon addition. It is preferable that it is an added amount that is not impaired. The addition amount is preferably 0.1 to 50% by mass, more preferably 1.0 to 30% by mass, based on the solid content of the coating solution.

As described above, the optically anisotropic layer functions as an optically anisotropic layer that compensates the viewing angle of the liquid crystal cell. Of course, the optically anisotropic layer alone may have sufficient viewing angle compensation ability, or may be an embodiment satisfying optical characteristics required for viewing angle compensation in combination with other layers. The birefringence of the first optically anisotropic layer is not particularly limited, but preferably functions as the optically anisotropic layer of the A-plate.

In general, liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type based on their shapes. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In this embodiment, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a disk-like liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. It is more preferable to use a rod-like liquid crystal compound or a disk-like liquid crystal compound having a reactive group, since at least one of the reactive groups in one liquid crystal molecule can be formed. Is more preferably 2 or more. The liquid crystalline compound may be a mixture of two or more, and in that case, at least one preferably has two or more reactive groups. The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and further preferably 1 to 4 μm.

Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. The polymer liquid crystalline compound is a polymer compound obtained by polymerizing a rod-like liquid crystalline compound having a low molecular reactive group. The rod-like liquid crystal compound having a low-molecular reactive group that is particularly preferably used is a rod-like liquid crystal compound represented by the following general formula (I).

Formula (I): Q ¹ -L ¹ -A ¹ -L ³ -ML ⁴ -A ² -L ² -Q ²
Wherein, Q ¹ and Q ² respectively represent a reactive group, the L ^1, L ^2, L ³ and L ⁴ respectively represent a single bond or a divalent linking group, L ³ and At least one of L ⁴ is preferably —O— or O—CO—O—. A ¹ and A ² each independently represent a spacer group having 2 to 20 carbon atoms. M represents a mesogenic group.

Hereinafter, the rod-like liquid crystal compound having a reactive group represented by the general formula (I) will be described in more detail. In the formula, Q ¹ and Q ² are each independently a reactive group. The polymerization reaction of the reactive group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the reactive group is preferably a reactive group capable of an addition polymerization reaction or a condensation polymerization reaction. Examples of reactive groups are shown below.

Examples of the divalent linking group represented by L ¹ , L ² , L ³ and L ⁴ include —O—, —S—, —CO—, —NR ² —, —CO—O—, and —O—CO. —O—, —CO—NR ² —, —NR ² —CO—, —O—CO—, —O—CO—NR ² —, —NR ² —CO—O—, and NR ² —CO—NR ^2. A divalent linking group selected from the group consisting of-is preferred. R ² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In this case, at least one of L ³ and L ⁴ is preferably —O— or O—CO—O— (carbonate group). In the formula (I), Q ¹ -L ¹ and Q ² -L ² -are CH ₂ ═CH—CO—O—, CH ₂ ═C (CH ₃ ) —CO—O—, and CH ₂ ═C ( Cl) -CO-O-CO- O- are _{preferable, CH 2 = CH-CO-} O- is most preferable.

A ¹ and A ² represent spacer groups having 2 to 20 carbon atoms. An aliphatic group having 2 to 12 carbon atoms is preferable, and an alkylene group is particularly preferable. The spacer group is preferably chain-like and may contain oxygen atoms or sulfur atoms that are not adjacent to each other. The spacer group may have a substituent and may be substituted with a halogen atom (fluorine, chlorine, bromine), a cyano group, a methyl group, or an ethyl group.

Examples of the mesogenic group represented by M include all known mesogenic groups. In particular, a group represented by the following general formula (II) is preferable.
Formula (II): - (- W 1 -L 5) n-W 2 -
In the formula, W ¹ and W ² each independently represent a divalent cycloaliphatic group, a divalent aromatic group or a divalent heterocyclic group, L ⁵ represents a single bond or a linking group, and Specific examples of the group include specific examples of groups represented by L ^{1 to} L ⁴ in the formula (I), —CH ₂ —O—, and O—CH ₂ —. n represents 1, 2 or 3.

W ¹ and W ² include 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, pyridazine-3,6-diyl . In the case of 1,4-cyclohexanediyl, there are trans isomers and cis isomers, but either isomer may be used, and a mixture in any proportion may be used. More preferably, it is a trans form. W ¹ and W ² may each have a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, etc.), and an alkoxy group having 1 to 10 carbon atoms. (Methoxy group, ethoxy group, etc.), C1-10 acyl group (formyl group, acetyl group, etc.), C1-10 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), carbon atom Examples thereof include an acyloxy group having 1 to 10 (acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like.

Preferred examples of the basic skeleton of the mesogenic group represented by the general formula (II) are shown below. These may be substituted with the above substituents.

Examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto. The compound represented by the general formula (I) can be synthesized by the method described in JP-T-11-513019.

The optically anisotropic layer is formed by applying a fluid containing a liquid crystal compound (for example, a solution of a liquid crystal compound) in an area separated by a black matrix by an ink jet method to obtain an alignment state exhibiting a desired liquid crystal phase. Thereafter, the layer is preferably a layer prepared by fixing the alignment state by irradiation with heat or ionizing radiation.

When a rod-like liquid crystal compound having a reactive group is used as the liquid crystal compound, it may be fixed in any alignment state of horizontal alignment, tilt alignment, hybrid alignment, and twist alignment. In this specification, the horizontal orientation means an orientation having an inclination angle with a horizontal plane of less than 10 degrees.

As another aspect, there is an aspect in which a discotic liquid crystal is used for the second optical anisotropic layer. The optically anisotropic layer is preferably a layer of a low molecular weight liquid crystal discotic compound such as a monomer or a polymer layer obtained by polymerization (curing) of a polymerizable liquid crystal discotic compound. Examples of the discotic (discotic) compound include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physicslett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, page 2655 (1994), and azacrown-based and phenylacetylene-based macrocycles. The above discotic (discotic) compounds generally have a discotic mother nucleus at the center of the molecule, and groups (L) such as linear alkyl groups, alkoxy groups, and substituted benzoyloxy groups are radially substituted. In other words, it has liquid crystallinity and generally includes a so-called discotic liquid crystal. However, when such an aggregate of molecules is uniformly oriented, it exhibits negative uniaxiality, but is not limited to this description. Further, in the present invention, it is not necessary that the final product is formed from a discotic compound, for example, the low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light or the like, resulting in high molecular weight and loss of liquid crystallinity.

In the present invention, it is preferable to use a discotic liquid crystalline compound represented by the following general formula (III).
Formula (III): D (-LP) _n
In the formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.
In the formula (III), preferred specific examples of the discotic core (D), the divalent linking group (L) and the polymerizable group (P) are (D1) described in JP-A No. 2001-4837, respectively. To (D15), (L1) to (L25), (P1) to (P18), and the disk-shaped core (D), divalent linking group (L) and polymerizable group ( The contents regarding P) can be preferably applied here.
Preferable examples of the discotic compound include compounds described in [0045] to [0055] of JP-A-2007-121986.

  In the case of laminating two or more optically anisotropic layers made of a liquid crystalline compound, the combination of liquid crystalline compounds is not particularly limited, and a laminate of layers made of all discotic liquid crystalline compounds, all made of rod-like liquid crystalline compounds. It may be a laminate of layers composed of a layer, a layer composed of a discotic liquid crystalline compound and a layer composed of a rod-shaped liquid crystalline compound. The combination of the alignment states of the layers is not particularly limited, and optically anisotropic layers having the same alignment state may be stacked, or optically anisotropic layers having different alignment states may be stacked.

The first optically anisotropic layer (first optically anisotropic layer) is preferably a positive A plate. A uniaxial birefringent layer having an optical axis in the plane and having a refractive index of the slow axis larger than the refractive index in the thickness direction is referred to as a positive A plate. The positive A plate can be realized by horizontal alignment of rod-like liquid crystals.

The first optically anisotropic layer is preferably formed by applying a coating liquid containing a liquid crystalline compound and the following polymerization initiator and other additives by an inkjet method. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, dichloromethane, tetrahydrofuran, pyridine, benzene, hexane, 1,2-dimethoxyethane, N-methyl-2-pyrrolidone, cyclohexanone, cyclohexanol, propylene glycol- 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, 1,3-butanediol diacetate, N, N-dimethylformamide, dimethyl sulfoxide, methyl acetate, butyl acetate, ethyl lactate, Examples include methyl lactate and caprolactam. Two or more organic solvents may be used in combination.

[Fixation of alignment state of liquid crystalline composition]
The aligned liquid crystalline composition is fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into the liquid crystalline composition. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No. 4,221,970).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. Light irradiation for the polymerization of the liquid crystalline compound is preferably performed using ultraviolet rays. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under a nitrogen atmosphere or under heating conditions.

The optical characteristics of the first optically anisotropic layer are preferably adjusted to optical characteristics that are optimal for viewing angle compensation when R light, G light, and B light are incident. That is, when the color filter layer is colored red and used for forming the R layer of the color filter, the optical characteristics of the optical anisotropic layer are optimally adjusted for viewing angle compensation when R light is incident, When colored green, the optical properties of the optically anisotropic layer are optimally adjusted for viewing angle compensation when G light is incident, and when colored blue, the optical properties of the optically anisotropic layer Is preferably optimally adjusted for viewing angle compensation when B light is incident. The optical characteristics of the optically anisotropic layer are adjusted to a preferable range depending on, for example, the type of liquid crystalline compound, the type or addition amount of the alignment control agent, the rubbing treatment condition of the color filter layer, the film thickness, or the polarization irradiation condition. Can do.

[Horizontal alignment control agent]
In the composition for forming the optically anisotropic layer, compounds represented by general formulas (1) to (3) described in [0068] to [0072] of JP-A-2007-121986 and the following general formula By containing at least one fluorine-containing homopolymer or copolymer using the monomer (4), the molecules of the liquid crystal compound can be substantially horizontally aligned.

In the formula, R represents a hydrogen atom or a methyl group, X represents an oxygen atom or a sulfur atom, Z represents a hydrogen atom or a fluorine atom, m is an integer of 1 to 6, and n is an integer of 1 to 12. Represents. In addition to the fluorine-containing polymer containing the general formula (4), the compounds described in JP-A-2005-206638 and JP-A-2006-91205 can be used as the unevenness improving polymer in coating as a horizontal alignment agent. Are also described in the specification.
The addition amount of the horizontal alignment agent is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass of the mass of the liquid crystal compound. In addition, the compounds represented by the general formulas (1) to (4) may be used alone or in combination of two or more.

[Liquid Crystal Display]
By using the substrate for a liquid crystal display device of the present invention, a liquid crystal display device having a wide viewing angle can be provided.
The present invention can be used for liquid crystal display devices in various display modes such as TN, IPS, FFS, FLC, OCB, STN, VA and HAN modes. Among them, it is suitable for a VA mode liquid crystal display device.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Preparation of partition wall forming composition K-1)
K pigment dispersion 1 and propylene glycol monomethyl ether acetate are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. 2 °) at the top. After the addition, the partition wall-forming coating solution K-1 was prepared by stirring at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes.
────────────────────────────────── ――――――
Partition wall coating liquid K-1 composition (%)
────────────────────────────────── ――――――
K pigment dispersion 1 12.13
Propylene glycol monomethyl ether acetate 14.39
Methyl ethyl ketone 34.16
Cyclohexanone 8.55
Binder solution 1 23.26
Monomer solution 1 7.17
2,4-Bis (trichloromethyl) -6- [4′-N, N-bis (ethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine 0.27
Phenothiazine 0.006
Surfactant solution 1 0.058
────────────────────────────────── ――――――

────────────────────────────────── ――――――
K pigment dispersion 1 composition (%)
────────────────────────────────── ――――――
Carbon black (Nipex 35, manufactured by Degussa) 13.10
Dispersant 1 (DI-1) 0.65
Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72
Propylene glycol monomethyl ether acetate 79.53
────────────────────────────────── ――――――

────────────────────────────────── ――――――
Binder solution 1 (%)
────────────────────────────────── ――――――
Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000) 27.00
Propylene glycol monomethyl ether acetate 73.00
────────────────────────────────── ――――――

────────────────────────────────── ――――――
Monomer solution 1 (%)
────────────────────────────────── ――――――
KAYARAD DPHA (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd.) 76.00
Propylene glycol monomethyl ether acetate 24.00
────────────────────────────────── ――――――

────────────────────────────────── ――――――
Surfactant solution 1 (%)
────────────────────────────────── ――――――
Surfactant 1 (SU-1) 30.00
Methyl ethyl ketone 70.00
────────────────────────────────── ――――――

(Preparation of developer KOH-1)
A KOH developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) containing a nonionic surfactant was diluted 100 times to prepare a developer KOH-1.

(Preparation of colored coating liquid R-1 for red pixel portion)
After preparing the following composition, after premixing, using a motor mill M-50 (manufactured by Eiger Japan), zirconia beads with a diameter of 0.65 mm were used at a filling rate of 80%, and dispersed at a peripheral speed of 9 m / s for 25 hours. R pigment dispersion 1 was prepared. In addition, it was 49 nm as a result of measuring a number average particle diameter using Nikkiso Co., Ltd. nano track UPA-EX150.
────────────────────────────────── ――――――
R pigment dispersion 1 composition (%)
────────────────────────────────── ――――――
Red pigment C.I. I. P. R. 177 (Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.) 17.5
Dispersant 1 (DI-1) 2.5
1,3-butanediol diacetate 80.0
────────────────────────────────── ――――――

After preparing the following composition, R pigment dispersion 2 was prepared in the same manner as R pigment dispersion 1. The number average particle diameter was measured and found to be 49 nm.
────────────────────────────────── ――――――
R pigment dispersion 2 composition (%)
────────────────────────────────── ――――――
Red pigment C.I. I. P. R. 254 (Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) 17.5
Dispersant 1 (DI-1) 2.5
1,3-butanediol diacetate 80.0
────────────────────────────────── ――――――

The R pigment dispersion 1 and the R pigment dispersion 2 are weighed, and the following compositions excluding the above two are added in order from the top while stirring at 25 ° C. After the addition, the mixture was stirred at 25 ° C. for 30 minutes to prepare a red pixel portion colored coating solution R-1.
────────────────────────────────── ――――――
Colored coating liquid R-1 composition for red pixel part (%)
────────────────────────────────── ――――――
R pigment dispersion 1 46.38
R pigment dispersion 2 3.57
1,3-butanediol diacetate 28.54
Polyimide (SM-1-1) 21.40
Surfactant 1 (SU-1) 0.11
────────────────────────────────── ――――――

（レッド画素部用着色塗布液Ｒ−２の調製）
Ｒ用顔料分散液１、Ｒ用顔料分散液２をはかり取り、２５℃で撹拌しながら、上記２種を除く下記の組成物を上から順に添加する。添加後、２５℃で３０分間撹拌して、レッド画素部用着色塗布液Ｒ−２を調製した。
──────────────────────────────────――――――
レッド画素部用着色塗布液Ｒ−２組成（％）
──────────────────────────────────――――――
Ｒ顔料分散液１ ４６．３８
Ｒ顔料分散液２ ３．５７
１，３−ブタンジオールジアセテート ２８．５４
ＫＡＹＡＲＡＤ ＤＰＨＡ（日本化薬株式会社製） ２１．４０
界面活性剤１（ＳＵ−1） ０．１１
──────────────────────────────────――――――

(Preparation of coloring application liquid R-2 for red pixel part)
The R pigment dispersion 1 and the R pigment dispersion 2 are weighed, and the following compositions excluding the above two are added in order from the top while stirring at 25 ° C. After the addition, the mixture was stirred at 25 ° C. for 30 minutes to prepare a red pixel portion colored coating solution R-2.
────────────────────────────────── ――――――
Colored coating liquid R-2 composition for red pixel part (%)
────────────────────────────────── ――――――
R pigment dispersion 1 46.38
R pigment dispersion 2 3.57
1,3-butanediol diacetate 28.54
KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 21.40
Surfactant 1 (SU-1) 0.11
────────────────────────────────── ――――――

(Preparation of colored coating solution G-1 for green pixel portion)
After preparing the following composition, G pigment dispersion 1 was prepared in the same manner as R pigment dispersion 1. The number average particle diameter was measured and found to be 50 nm.
────────────────────────────────── ――――――
G pigment dispersion 1 composition (%)
────────────────────────────────── ――――――
Green pigment C.I. I. Pigment Green 36 (Rionol Green 6YK, manufactured by Toyo Ink Manufacturing Co., Ltd.) 17.5
Dispersant 1 (DI-1) 2.5
1,3-butanediol diacetate 80.0
────────────────────────────────── ――――――

After preparing the following composition, G pigment dispersion 2 was prepared in the same manner as G pigment dispersion 1. The number average particle diameter was measured and found to be 50 nm.
────────────────────────────────── ――――――
G pigment dispersion 2 composition (%)
────────────────────────────────── ――――――
Yellow pigment C.I. I. P. Y. 150 (Bayplast Yellow 5GN 01, manufactured by Bayer Corporation) 17.5
Dispersant 1 (DI-1) 2.5
1,3-butanediol diacetate 80.0
────────────────────────────────── ――――――

Weigh out the pigment dispersion 1 for G and the pigment dispersion 2 for G, and add the following compositions in order from the top with stirring at 25 ° C., except for the above two types. After the addition, the mixture was stirred at 25 ° C. for 30 minutes to prepare a green pixel portion colored coating solution G-1.
────────────────────────────────── ――――――
Colored coating liquid G-1 composition for green pixel part (%)
────────────────────────────────── ――――――
G pigment dispersion 1 46.38
G pigment dispersion 2 3.57
1,3-butanediol diacetate 28.54
Polyimide (SM-1-1) 21.40
Surfactant 1 (SU-1) 0.11
────────────────────────────────── ――――――

(Preparation of green pixel portion coating solution G-2)
Weigh out the pigment dispersion 1 for G and the pigment dispersion 2 for G, and add the following compositions in order from the top with stirring at 25 ° C., except for the above two types. After the addition, the mixture was stirred at 25 ° C. for 30 minutes to prepare a green pixel portion colored coating solution G-2.
────────────────────────────────── ――――――
Colored coating liquid G-2 composition for green pixel part (%)
────────────────────────────────── ――――――
G pigment dispersion 1 46.38
G pigment dispersion 2 3.57
1,3-butanediol diacetate 28.54
KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 21.40
Surfactant 1 (SU-1) 0.11
────────────────────────────────── ――――――

(Preparation of colored coating solution B-1 for blue pixel portion)
After preparing the following composition, a pigment dispersion 2 for B was prepared in the same manner as the pigment dispersion 1 for R. The number average particle diameter was measured and found to be 44 nm.
────────────────────────────────── ――――――
B pigment dispersion 1 composition (%)
────────────────────────────────── ――――――
Blue pigment C.I. I. P. B. 15: 6 (Rionol Blue ES, manufactured by Toyo Ink Manufacturing Co., Ltd.) 17.5
Dispersant 2 (EFKA6745, manufactured by EFKA) 2.5
1,3-butanediol diacetate 80.0
────────────────────────────────── ――――――

After preparing the following composition, a pigment dispersion 2 for B was prepared in the same manner as the pigment dispersion 1 for R. The number average particle diameter was measured and found to be 44 nm.
────────────────────────────────── ――――――
B pigment dispersion 2 composition (%)
────────────────────────────────── ――――――
Blue pigment C.I. I. P. B. 15: 6 (Rionol Blue ES, manufactured by Toyo Ink Manufacturing Co., Ltd.) 16.5
Violet pigment C.I. I. P. V. 23 (Hostaperm Violet RL-NF, manufactured by Clariant Japan KK) 1.0
Dispersant 3 (Disparon DA-725, manufactured by Enomoto Kasei Co., Ltd.) 2.5
1,3-butanediol diacetate 80.0
────────────────────────────────── ――――――

Weigh out the pigment dispersion 1 for B and the pigment dispersion 2 for B, and add the following compositions in order from the top except the above two while stirring at 25 ° C. After the addition, the mixture was stirred at 25 ° C. for 30 minutes to prepare a blue pixel portion colored coating solution B-1.
────────────────────────────────── ――――――
Blue pixel part coloring coating solution B-1 composition (%)
────────────────────────────────── ――――――
B pigment dispersion 1 46.38
B pigment dispersion 2 3.57
1,3-butanediol diacetate 28.54
Polyimide (SM-1-1) 21.40
Surfactant 1 (SU-1) 0.11
────────────────────────────────── ――――――

(Preparation of blue pixel part coating solution B-2)
────────────────────────────────── ――――――
Color composition for blue pixel part B-2 (%)
────────────────────────────────── ――――――
B pigment dispersion 1 46.38
B pigment dispersion 2 3.57
1,3-butanediol diacetate 28.54
KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 21.40
Surfactant 1 (SU-1) 0.11
────────────────────────────────── ――――――

(Preparation of optical anisotropic layer coating liquid LC-R for red pixel portion)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a red pixel portion optically anisotropic layer coating liquid LC-R.
Here, LC-1 is Tetrahedron Lett. Synthesized according to the method described in Journal, Vol. 43, page 6793 (2002). LC-2 was synthesized by the method described in EP1388538A1, page21.
────────────────────────────────── ――――――
Composition of LC-R (%) for optically anisotropic layer coating for red pixel
────────────────────────────────── ――――――
Bar-shaped liquid crystal (Paliocolor LC242, manufactured by BASF Japan) 28.62
Chiral agent (Paliocolor LC756, manufactured by BASF Japan) 3.40
4,4′-Azoxydianisole 0.52
Horizontal alignment agent (LC-1) 0.10
Photopolymerization initiator (LC-2) 1.36
Methyl ethyl ketone 66.00
────────────────────────────────── ――――――

(Preparation of coating liquid LC-G for green pixel portion optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as an optically anisotropic layer coating liquid LC-G for a green pixel portion.
────────────────────────────────── ――――――
Optical anisotropic layer coating liquid LC-G composition for green pixel part (%)
────────────────────────────────── ――――――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 28.38
Chiral agent (Paliocolor LC756, BASF Japan) 3.34
4,4′-Azoxydianisole 0.27
Horizontal alignment agent (LC-1) 0.10
Photopolymerization initiator (LC-2) 1.34
Methyl ethyl ketone 66.57
────────────────────────────────── ――――――

(Preparation of optical anisotropic layer coating liquid LC-B for blue pixel portion)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm, and used as an optical anisotropic layer coating liquid LC-B for a blue pixel portion.
────────────────────────────────── ――――――
LC-B composition (%) for optically anisotropic layer coating liquid for blue pixels
────────────────────────────────── ――――――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 28.72
Chiral agent (Paliocolor LC756, BASF Japan) 3.36
4,4′-Azoxydianisole 0.03
Horizontal alignment agent (LC-1) 0.10
Photopolymerization initiator (LC-2) 1.34
Methyl ethyl ketone 66.45
────────────────────────────────── ――――――

<Example 1>
(Formation of partition walls)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state. After cooling the substrate and adjusting the temperature to 23 ° C., the partition wall-forming coating solution K-1 was applied with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Applied. Subsequently, a part of the solvent was dried with VCD (vacuum drying apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds, and prebaked at 120 ° C. for 3 minutes.

With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) that has an ultra-high pressure mercury lamp, the exposure mask surface and the dark color photosensitive film with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the layers K1 was set to 200 μm, and pattern exposure was performed with an exposure amount of 600 mJ / cm ² to a partition wall width of 20 μm and a space width of 100 μm.

Next, after spraying pure water with a shower nozzle to uniformly wet the surface, the developer KOH-1 was shower-developed at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post-exposure was performed from above at an exposure amount of 4000 mJ / cm ^{2 in} the atmosphere. After heating at 240 ° C. for 50 minutes, a stripe-shaped partition wall having an opening with a thickness of 5.0 μm, an optical density of 4.0, and a width of 100 μm was obtained.

(Partition partition ink repellent treatment)
The substrate on which the partition wall was formed was subjected to plasma treatment for 30 seconds at a pressure of 40 Pa and an RF power of 50 W while flowing CF4 gas at 80 sccm using a cathode coupling type parallel plate type plasma processing apparatus to make the partition wall ink-repellent. went.

(Formation of pixel part)
Using the ink jet apparatus shown in FIG. 4, the red pixel portion colored coating solution R-1, the green pixel portion colored coating solution G-1, and the blue pixel portion colored coating solution B-1 were respectively ejected into the partition walls. Then, it was heated and dried on a hot plate at 100 ° C. for 2 minutes, and then baked in a 230 ° C. oven for 30 minutes to produce a color filter substrate having a thickness of 2.0 μm.
Here, the head unit 100 of the inkjet apparatus includes three SX-3s manufactured by Dimatix as three-color inkjet heads, and the ejection control apparatus 200 uses a dedicated piezo drive circuit and a dedicated stage control circuit. SX-3 is an on-demand type piezo-drive head, and 128 nozzles are arranged in one head at intervals of 508 μm. When driving the piezo, the central value of the voltage is 50 V, the pulse width is 8 microseconds, and the nozzles are set so that the difference in the discharge amount from each nozzle is within 2% by the above-mentioned flight shape observation and discharge amount measurement. Each voltage was adjusted. Piezo has a driving frequency of 10 KHz for continuous droplet ejection, the center value of the discharge amount is 8 ng / droplet, and 33 droplets and 264 ng droplets have been deposited.

The substrate table 400 on which the substrate manufactured in the above process is placed is an aluminum plate placed on a dedicated automatic two-dimensional moving stage, and is fixed to the moving stage. The distance between the head and the substrate was adjusted to 500 μm, and the time from when the piezo of the head was driven until ink droplets were formed and landed on the substrate was about 63 μs. The size of the pixels on the substrate is 300 μm in the X direction and 100 μm in the Y direction. By tilting the head 53.8 degrees with respect to the X direction, the apparent nozzle interval in the Y direction becomes 300 μm. It was adjusted. The substrate was moved at a constant speed of 8.2 cm / sec and ejected into a 270 μm section of the pixel in the X direction.

(Formation of optically anisotropic layer)
After rubbing the surface of the color filter substrate, the optical anisotropic layer coating liquid LC-R for the red pixel portion and the optical anisotropic layer for the green pixel portion are formed in the partition using the inkjet apparatus shown in FIG. The coating liquid LC-G and the blue pixel part optically anisotropic layer coating liquid LC-B were each deposited and dried at a film surface temperature of 95 ° C. for 2 minutes to obtain a liquid crystal phase. Using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under the following nitrogen atmosphere, the illumination axis is 200 mW / cm ² and the irradiation is performed so that the transmission axis of the polarizing plate is in the TD direction of the transparent support. A substrate for a liquid crystal display device of Example 1 was obtained by irradiating an ultraviolet ray having an amount of 200 mJ / cm ² .
The film thickness of the optically anisotropic layer after irradiation with ultraviolet rays was 2.80 μm for the red pixel portion, 2.75 μm for the green pixel portion, and 2.30 μm for the blue pixel portion.

<Comparative Example 1>
When forming the pixel portion, the red pixel portion coloring coating solution R-1, the green pixel portion coloring coating solution G-1, and the blue pixel portion coloring coating solution B-1 are used instead of the red pixel portion coloring coating solution R-1. A color filter substrate was produced in the same manner as in Example 1 except that R-2, the green pixel portion colored coating solution G-2, and the blue pixel portion colored coating solution B-2 were used.
Next, a polyimide material coating solution (Nissan Chemical Industry Co., Ltd., RN-1199A) is applied onto the color filter substrate, dried and baked at 230 ° C. for 1 hour, and the film thickness after baking is an alignment layer of 50 nm. Formed.
Finally, an optically anisotropic layer was formed on each of the RGB pixels in the same manner as in Example 1, and a liquid crystal display device substrate of Comparative Example 1 was obtained.

(Evaluation of light leakage of optically anisotropic layer)
The substrates for liquid crystal display devices of Example 1 and Comparative Example 1 were observed and evaluated using a polarizing microscope. Here, the polarizing plate of the polarizing microscope was observed in a crossed Nicol state, and the liquid crystal display substrate was observed in a state aligned with the extinction axis. Table 1 shows the evaluation results.

(Production of phase difference measurement substrate)
The phase difference measurement of the optically anisotropic layer of the present invention was substituted by measuring what was formed with the same film thickness on the glass substrate with a polyimide layer.
The alkali-free glass substrate was washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower and with pure water shower, and heated at 100 ° C. for 2 minutes with a substrate preheating device. Then, the polyimide material coating liquid (Nissan Chemical Industry Co., Ltd. make, RN-1199A) was apply | coated, dried, and baked at 230 degreeC for 1 hour, and the glass substrate with a polyimide layer was obtained. The film thickness after firing was 50 nm.

Next, the surface of the glass substrate with a polyimide layer is rubbed, and the optically anisotropic layer coating liquid LC-R for red pixel portion is applied and dried at a film surface temperature of 95 ° C. for 2 minutes to obtain a liquid crystal phase state. Using a 160 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under a nitrogen atmosphere with an oxygen concentration of 0.3% or less, the illuminance is such that the transmission axis of the polarizing plate is in the TD direction of the transparent support. Irradiation with ultraviolet rays of 200 mW / cm ² and an irradiation amount of 200 mJ / cm ² yielded a retardation measurement substrate R having an optically anisotropic layer thickness of 2.80 μm.
The optical anisotropy is the same as that for the phase difference measurement substrate R except that the optically anisotropic layer coating liquid LC-G for green pixel portion and the optically anisotropic layer coating liquid LC-B for blue pixel portion are used. A phase difference measurement substrate G having a layer thickness of 2.75 μm and a phase difference measurement substrate B having an optical anisotropic layer thickness of 2.30 μm were obtained.

(Phase difference measurement)
Retardation Re (40) when the sample is tilted by ± 40 degrees with the front axis Re (0) at the arbitrary wavelength λ and the slow axis as the rotation axis by the parallel Nicol method using a fiber type spectrometer. (-40) was measured. Here, for R, G, and B, λ was 611 nm, 545 nm, and 435 nm, respectively. For the retardation of the optically anisotropic layer of the present invention, only the retardation of the optically anisotropic layer was obtained by calibrating with the transmittance data of the substrate without the optically anisotropic layer measured in advance. Table 2 shows the phase difference measurement results of the phase difference measurement substrate of Example 2.

(Production of VA mode liquid crystal display device)
<Example 5>
A transparent electrode film was formed by sputtering of ITO on a glass substrate provided with a liquid crystal display substrate of Example 1 and a TFT layer serving as a counter substrate, and a polyimide alignment film was provided thereon. A sealant of epoxy resin containing spacer particles is printed at a position corresponding to the outer frame of the black matrix provided around the pixel group of the color filter, and 10 kg of the liquid crystal display substrate and the counter substrate of Example 2 is printed. Bonding was performed at a pressure of / cm. Subsequently, it heat-processed at 150 degreeC for 90 minutes, the sealing agent was hardened, and the laminated body of two glass substrates was obtained. This glass substrate laminate was deaerated under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates to obtain a VA mode liquid crystal cell. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of this VA mode liquid crystal cell. As a cold-cathode tube backlight for a color liquid crystal display device, a phosphor obtained by mixing BaMg ₂ Al ₁₆ O ₂₇ : Eu, Mn and LaPO ₄ : Ce, Tb at a mass ratio of 50:50 is green (G), Y ₂ O ₃ : Eu was red (R) and BaMgAl ₁₀ O ₁₇ : Eu was blue (B) to produce a white three-wavelength fluorescent lamp having an arbitrary color tone. The VA mode liquid crystal cell provided with the polarizing plate was placed on the backlight, and the VA mode liquid crystal display device of Example 3 was obtained.

<Comparative Example 3>
A VA mode liquid crystal display device of Comparative Example 2 was obtained in the same manner as in Example 3 except that the substrate for liquid crystal display device of Comparative Example 1 was used.

(Visual evaluation of VA mode liquid crystal display)
Table 3 shows the visual evaluation results of the VA mode liquid crystal display devices of Example 5, Example 6, Comparative Example 3, and Comparative Example 4.

It is a schematic diagram which shows an example of the flow of the manufacturing method of the board | substrate for liquid crystal display devices. It is a schematic sectional drawing of an example of the board | substrate for liquid crystal display devices. It is a schematic sectional drawing of an example of a liquid crystal display device. It is a figure which shows the inkjet apparatus used in the Example.

Explanation of symbols

11 Transparent substrate 12 Black matrix
13 Partial region of color filter layer 14 Partial region of optically anisotropic layer 21 Substrate 22 Black matrix (partition)
23 Color filter layer 24 Solid optically anisotropic layer (second optically anisotropic layer)
25 Transparent electrode layer 26 Alignment layer 27 Patterning optical anisotropic layer (first optical anisotropic layer)
31 Liquid crystal 32 TFT
33 Polarizing layer 34 Cellulose acetate film (polarizing plate protective film)
35 Cellulose acetate film or optical compensation sheet 36 Polarizing plate 37 Liquid crystal cell 100 Inkjet head unit 200 Discharge control device 300 Substrate 400 Substrate stand 500 Head maintenance station

Claims (11)

A substrate for a liquid crystal display device including a substrate, a color filter layer, and an optically anisotropic layer in this order,
The color filter layer and the optically anisotropic layer are divided into a plurality of regions by a partition formed on a substrate, and the optically anisotropic layer is directly rubbed on the color filter layer, A substrate for a liquid crystal display device provided by an inkjet method. The color filter layer includes at least one selected from the group consisting of polyimide, polyisoimide, polyesterimide, polyetherimide, polyamideimide, polyamic acid, polyamic acid ester, polyamide, polyamine, polythioamide, polyurethane, polyurea, and polyazomethine. The substrate for a liquid crystal display device according to claim 1, comprising a layer containing the liquid crystal display device. The optically anisotropic layer is a layer formed by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then heating or irradiating with light. 2. The substrate for a liquid crystal display device according to 2. The liquid crystal display substrate according to claim 3, wherein the liquid crystal compound is a rod-like liquid crystal compound. The substrate for a liquid crystal display device according to claim 3, wherein the reactive group is an ethylenically unsaturated group. 6. The substrate for a liquid crystal display device according to claim 1, wherein a front retardation of the optically anisotropic layer is 40 to 550 nm. The liquid crystal display device which has a board | substrate for liquid crystal display devices as described in any one of Claims 1-6. The liquid crystal display device according to claim 7, wherein an alignment mode of the liquid crystal display device is any one of TN, VA, IPS, FFS, and OCB. A method for manufacturing a substrate for a liquid crystal display device, comprising:
(1) A step of preparing a substrate on which a partition is formed and including a color filter layer divided into a plurality of regions by the partition;
(2) rubbing the color filter surface; and (3) forming a liquid crystal phase by applying and drying a solution containing a liquid crystal compound having at least one reactive group on the rubbed surface by an ink jet method. A step of forming an optically anisotropic layer that is divided into a plurality of regions by the partition wall by heating or light irradiation. The method according to claim 9, wherein the color filter layer includes a copolymer having a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2).

In General Formula (1), Y ¹ represents a methylene group, an ethylene group or an ethenylene group, and X ¹ represents a divalent linking group represented by the following General Formula (3);

In General Formula (2), Y ² represents a methylene group, an ethylene group or an ethenylene group, and X ² represents a divalent linking group represented by the following General Formula (4);

In general formula (3), R ¹ and R ² are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group. Represents one group, l and m each independently represents an integer of 0 to 4;

In general formula (4), A represents a cyclic or non-cyclic hydrocarbon group which may be unsubstituted or optionally substituted, provided that A is directly connected to three or more aromatic rings from the same carbon atom. B ² represents a substituted or unsubstituted aryl group or heteroaryl group, L represents a divalent linking group, Q ² represents a reactive group, R ⁴ represents a hydrogen atom, unsubstituted Alternatively, an optionally substituted cyclic or acyclic hydrocarbon group is represented, and n represents an integer of 0 or more. The method according to claim 10, wherein the copolymer is end-capped with a compound of the following general formula (5):

In General Formula (5), B ¹ represents a substituted or unsubstituted aryl group or heteroaryl group, Q ¹ represents a reactive group, and R ³ represents a hydrogen atom, unsubstituted or optionally substituted. A cyclic or acyclic hydrocarbon group is represented, and k represents an integer of 0 or more.

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