JP2001019766A - Agent for orienting chiral nematic liquid crystal, color filter of chiral nematic liquid crystal, and formation of color filter of chiral nematic liquid crystal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agent for orienting liquid crystal, good in affinity for chiral nematic liquid crystal, manifesting adequate hydrophilicity and easily orienting the chiral nematic liquid crystal in the horizontal direction, by reacting a specific diamine compound with a tetracarboxylic acid dihydrate. SOLUTION: This agent is composed of a polyimide obtained by reacting a diamine compound shown by the formula (R is an alkyl, alkanoyl or benzoyl) with a tetracarboxylic acid dihydrate, preferably 1,2,3,4- cyclobutanetetracarboxylic acid dihydrate. The diamine compound shown by the formula preferably has an I/O (inorganic/organic) ratio of 0.05 to 1.10. A color filter of chiral nematic liquid crystal can be formed by producing an oriented membrane on a transparent substrate using the above agent, and transferring a photosensitive resin layer containing a chiral nematic liquid-crystal compound to the membrane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal alignment agent, a chiral nematic liquid crystal color filter, and a method for forming the same.

[0002]

2. Description of the Related Art In order to form a color filter using a chiral nematic liquid crystal, it is necessary to orient the chiral nematic liquid crystal horizontally with respect to a substrate. In an alignment film used in a conventional display element, it has been difficult to uniformly and horizontally align a chiral nematic liquid crystal suitable for forming a color filter. Therefore, development of a liquid crystal aligning agent for horizontally aligning a chiral nematic liquid crystal has been desired.

[0003]

The present invention provides a liquid crystal aligning agent comprising a polyimide obtained by reacting a diamine compound represented by the following general formula (I) with tetracarboxylic dianhydride.

[0004]

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Wherein R is an alkyl group, an alkanoyl group,
Or a benzoyl group.

Further, according to the present invention, an alignment film formed of the liquid crystal alignment agent according to claim 1 is provided on a transparent substrate, and a photosensitive resin layer containing a chiral nematic liquid crystal compound is formed on the alignment film. A chiral nematic liquid crystal color filter characterized by the following.

Further, the present invention is characterized in that a photosensitive resin layer containing a chiral nematic liquid crystal compound is transferred onto an alignment film formed of the liquid crystal alignment agent according to claim 1 provided on a transparent substrate. And a method for forming a chiral nematic liquid crystal color filter.

The diamine structure of the polyimide of the present invention has a structure similar to the chiral dopant of the chiral nematic liquid crystal, has a good affinity with the chiral nematic liquid crystal, and has a moderate hydrophilicity. Easy to orient.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a liquid crystal aligning agent comprising a polyimide obtained by reacting a diamine compound represented by the above general formula (I) with tetracarboxylic dianhydride.

Wherein R is an alkyl group, an alkanoyl group,
Or a benzoyl group.

The alkyl group represented by R may be unsubstituted or have a substituent, and the substituent is preferably, for example, a phenyl group, a phenoxy group, an alkoxy group, or an alkanoyloxy group.

The alkyl group represented by R is more preferably an alkyl group having 5 to 20 carbon atoms, for example, hexyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. Group, octadecyl group, 4- (acetyloxy) butyl group, 4- (acetyloxy) hexyl group, 4- (octanoyloxy) butyl group, 4- (octanoyloxy) hexyl group, 4-
(Acryloyloxy) butyl group, 4- (acryloyloxy) hexyl group, 4- (methacryloyloxy) butyl group, and 4- (methacryloyloxy) hexyl group are preferred.

The alkanoyl group represented by R may be unsubstituted or substituted. Examples of the substituent include an alkylphenyl group, an alkoxyphenyl group, an alkylphenoxy group, an alkoxyphenoxy group, and a halogen atom. Atoms are preferred.

The alkanoyl group represented by R is more preferably an alkanoyl group having 5 to 20 carbon atoms, for example, 2-ethylhexanoyl group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, octadecayl group. A noyl group, a cyclohexylcarbonyl group, a p- (butyl) cyclohexylcarbonyl group, a p-methylbenzyl group, a p- (hexyloxy) benzyl group, a p- (octyl) phenoxy group, and a p- (octyloxy) phenoxy group are preferred.

The benzoyl group represented by R may be unsubstituted or may have a substituent, and the substituent is preferably, for example, an alkyl group, an alkoxy group, or an alkanoyloxyalkoxy group.

The benzoyl group represented by R is more preferably a benzoyl group having 6 to 30 carbon atoms.
p-cyclohexylbenzoyl group, p-decylbenzoyl group, p- (4-butylcyclohexyl) benzoyl group, p-octyloxybenzoyl group, p- (4- (acryloyloxy) butyloxy) benzoyl group, p-
(6- (acryloyloxy) hexyloxy) benzoyl group, p- (4- (methacryloyloxy) butyloxy) benzoyl group and p- (6- (methacryloyloxy) hexyloxy) benzoyl group are preferred.

The diamine used in the present invention has an I / O value of from 0.50 to 1.10, preferably from 0.5 to 1.10.
5 or more and 1.00 or less, more preferably 0.60 or more and 0.1 or less.
90 or less. Here, the I / O value is a parameter indicating a measure of lipophilicity / hydrophilicity of a compound or a substituent, and is referred to as “organic conceptual diagram” (Yoshio Koda, Sankyo Publishing, 1984).
Year) has a detailed explanation. I represents inorganic property, O represents organic property, and the larger the I / O value, the higher the inorganic property. Hereinafter, specific examples of the I / O value will be described.

The I value is -200 for the -NHCO- group and -N
In the case of an HSO ₂ — group, it is 240, and in the case of a —COO— group, it is 85. For example, in the case of —NHCOC ₅ H ₁₁ , the number of carbon atoms is 6, and the O value is 20 × 6 = 120. Since I = 200, the I / O value is about 1.67.

When the I / O value of the diamine is less than 0.50 or greater than 1.10, the chiral nematic liquid crystal is easily oriented perpendicular to the substrate and the chiral nematic liquid crystal is easily repelled.

Examples of the diamine compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[0021]

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The tetracarboxylic dianhydride used in the present invention includes, for example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5- Tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,
4,5,9b-hexahydro-5-tetrahydro-2,
5-dioxo-3-furanyl-naphtho [1,2-c]-
Furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-
1,2-dicarboxylic dianhydride, bicyclo [2.2.
2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and other aliphatic acid dianhydrides; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone Tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalenetetracarboxylic dianhydride, 3,3 ',
4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic acid Dianhydride, 1,2,
3,4-furantetracarboxylic dianhydride, 4,4′-
Bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,
4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′,
4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride,
p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis ( Aromatic tetracarboxylic dianhydrides such as (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride can be mentioned.

Among these, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-
Tricarboxycyclopentylacetic acid dianhydride, 1,3
3a, 4,5,9b-Hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl-naphtho [1,2-
c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.
2.2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentylacetic dianhydride is particularly preferred. These may be used alone or in combination of two or more.

The polyimide used for the liquid crystal aligning agent of the present invention can be obtained by imidizing the above polyamic acid by heating or in the presence of a dehydrating agent and an imidization catalyst. The polyamic acid is obtained by reacting the diamine compound with a tetracarboxylic dianhydride. Such a reaction is usually carried out in an organic solvent at 0 to 150 ° C., preferably at 0 to 1 ° C.
The reaction is performed at a reaction temperature of 00 ° C. The use ratio of the tetracarboxylic dianhydride and the total diamine compound is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group in the diamine compound, More preferably, it is 0.3 to 1.2 equivalent.

Depending on the type of the diamine compound, the tetracarboxylic dianhydride and the reaction conditions, an imide unit may be formed in the resulting polyamic acid in addition to the amic acid unit. In the present invention, if the imide unit is less than 10 mol% in the total amount of 100 mol% of the amic acid unit and the imide unit, it is treated as a polyamic acid.

As the organic solvent, those which can dissolve the polyamic acid produced by the reaction are preferably used.
For example, aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; Phenol solvents such as cresol, xylenol, phenol and halogenated phenol can be preferably mentioned. The amount of the organic solvent used is usually
It is preferable that the total amount of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount of the reaction solution.

The reaction temperature when the obtained polyamic acid is imidized by heating is usually from 60 to 250 ° C., preferably from 100 to 170 ° C. When the reaction temperature is lower than 60 ° C., the progress of the reaction is delayed, and when it exceeds 250 ° C., the molecular weight of the polyimide may be largely reduced. The reaction for imidization in the presence of a dehydrating agent and an imidization catalyst can be performed in the above-mentioned organic solvent. The reaction temperature is usually 0 to 180 ° C, preferably 60 to 150 ° C. Acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. As the imidation catalyst, for example, pyridine,
Tertiary amines such as collidine, lutidine, and triethylamine can be used, but are not limited thereto. The amount of the dehydrating agent used is preferably 1.6 to 20 mol per 1 mol of the corresponding polyamic acid repeating unit. The amount of the imidization catalyst used is preferably 0.5 to 10 mol per 1 mol of the dehydrating agent used.

It is not necessary that all of the amic acid units of the polyamic acid be imidized in the polyimide. The polyimide only needs to be imidized at 10 to 100 mol% of the portion.

The organic solvent may be used in combination with poor solvents such as alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons to such an extent that the resulting polyimide does not precipitate. it can. Examples of such poor solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether,
Ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichloro Benzene, hexane, heptane, octane, benzene,
Examples thereof include toluene and xylene.

The liquid crystal aligning agent of the present invention may contain the following functional silane-containing compound for the purpose of further improving the adhesion between the coating film formed and the substrate. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl -3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxyisylyl-1 , 4,7-Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-
Trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-
Examples include aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, and the like, and further disclosed in JP-A-63-291922.
A reaction product of a tetracarboxylic dianhydride and an amino group-containing silane compound described in Japanese Patent Application Laid-Open Publication No. H11-15064 can be used.

The liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention can be produced, for example, by the following method. First, the liquid crystal aligning agent of the present invention is applied on the transparent conductive film side of the substrate provided with the transparent conductive film by a roll coater method, a spinner method, a printing method, or the like, and is applied at 80 to 250 ° C, preferably 120 to 200 ° C. Heat at a temperature to form a coating. This coating film has a thickness of usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm. The formed coating film is subjected to a rubbing treatment with a roll around which a cloth made of a synthetic fiber such as nylon is wound, thereby forming a liquid crystal alignment film.

As the substrate, for example, a transparent substrate made of glass, such as float glass or soda glass, or a plastic film, such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or polycarbonate, can be used. As the transparent conductive film, a NESA film made of SnO ₂ , In ₂ O ₃ —Sn
An ITO film made of O ₂ or the like can be used, and a photo-etching method, a method using a mask in advance, or the like is used for patterning these transparent conductive films. In applying the liquid crystal alignment agent, a functional silane-containing compound, titanate, or the like may be applied on the substrate and the transparent conductive film in advance to further improve the adhesion between the substrate and the transparent conductive film. it can.

In the present invention, a photosensitive resin layer is provided on the alignment film formed as described above. To provide a photosensitive resin layer on the alignment film, a photosensitive transfer material is used. The photosensitive transfer material is obtained by providing a photosensitive resin layer on a temporary support that is peeled off and removed at the time of forming a color filter.

The temporary support that can be used in the present invention is not particularly limited as long as it is a resin film having a uniform thickness, and a known resin film can be appropriately selected and used as long as strength and durability are satisfied. . Specifically, for example, polyester film (among others, PET), polyethylene film,
A polypropylene film and the like.

These films have good transparency when used in such a manner that they are exposed through a temporary support.
That is, those having good transmittance with respect to the wavelength of the exposure light are preferable, and an antistatic layer is provided to prevent adhesion of dust due to peeling charging at the time of removal, or the temporary support itself has an antistatic property. Is preferred. That is, a conductive layer is provided on at least one surface of the temporary support to reduce the surface electrical resistance to 10 ¹³ Ω or less, or the temporary support itself is given conductivity to reduce the surface electrical resistance to 10 ¹³ Ω. It is preferable to set the following. In order to impart conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method in which metal oxide fine particles and an antistatic agent are kneaded is suitable. As the metal oxide, at least one crystalline metal oxide selected from zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, molybdenum oxide, and / or Or fine particles of the composite oxide. Examples of the antistatic agent include, for example, an alkyl phosphate-based anionic surfactant (for example, Electrostripper A of Kao Soap Co., Ltd., Eleanon No. 19 of Daiichi Kogyo Seiyaku Co., Ltd.).
And betaine (for example, Amogen K of Daiichi Kogyo Seiyaku Co., Ltd.) as amphoteric surfactant, and polyoxyethylene fatty acid ester (for example, Nitsan of Nippon Oil & Fats Co., Ltd.) as a nonionic surfactant. Nonionic L, etc.), polyoxyethylene alkyl ethers (for example, Emulgen 106, 120, 147, 420 of Kao Soap Co., Ltd.)
220, 905, 910, Nitsan Nonion E of Nippon Yushi Co., Ltd.) are useful. Other nonionic surfactants include polyoxyethylene alkylphenol ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines. When a conductive layer is provided on the support, the conductive layer can be appropriately selected from known ones. In particular, as the conductive material, ZnO, TiO ₂ , SnO ₂ , Al
_The method of containing at least one kind of crystalline metal oxide selected from ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, and MoO ₃ , and / or fine particles of a composite oxide thereof,
It is preferable because it shows conductivity that is not affected by humidity. The volume resistivity of the fine particles of the crystalline metal oxide or its composite oxide is 1
0 ⁷ Ω · cm or less, preferably 10 ⁵ Ω · cm or less.
cm or less. Further, the particle size is preferably 0.01 to 0.7 μm, particularly preferably 0.02 to 0.5 μm. A method for producing fine particles of a conductive crystalline metal oxide and its composite oxide is disclosed in
No. 6,143,430. Briefly describing them, first, a method in which metal oxide fine particles are produced by firing and heat-treated in the presence of a heteroatom for improving conductivity, A method of coexisting heteroatoms for improving conductivity when producing metal oxide fine particles by firing; and thirdly, reducing oxygen concentration in the atmosphere when producing metal fine particles by firing to reduce oxygen defects. It is a method to introduce. Examples of including heteroatoms include Al and In for ZnO, Nb and Ta for TiO ₂ , and Sn and the like.
For O ₂ , Sb, Nb, a halogen element and the like can be mentioned. The addition amount of the hetero atom is preferably in the range of 0.01 to 30 mol%, particularly preferably 0.1 to 10 mol%.
The amount of the conductive particles used is preferably 0.05 to 20 g / m ² ,
0.1 to 10 g / m ² is particularly preferred. The thickness of the conductive layer is preferably about 20 to 100 μm.

The thickness of the temporary support is preferably 150 μm or less from the viewpoints of heat conduction when the photosensitive resin layer is transferred to the substrate by heating and followability with the underlayer. The thickness is preferably 20 μm or more from the viewpoint of handleability during film formation.

When the photosensitive transfer material has a structure in which the photosensitive resin layer is provided directly on the temporary support, the surface of the temporary support may be subjected to a rubbing treatment.

The photosensitive transfer material is provided with a photosensitive resin layer on the temporary support. In order to improve the ability to follow the substrate when the photosensitive resin layer is transferred to the substrate by heating, the temporary support is used. It is preferable to provide a thermoplastic resin layer between the resin and the photosensitive resin layer. In particular, when sequentially forming filters of a plurality of hues, the thermoplastic resin layer functions as a cushion layer, which is preferable because characteristics of an interface between hues of the filter can be improved.

The thermoplastic resin layer has a glass transition temperature (T
g) is composed of one or more thermoplastic polymers having a temperature of 80 ° C. or lower, and if necessary, a plasticizer may be added to the thermoplastic photomolecules.

The thermoplastic resin that can be used for the thermoplastic resin layer is selected in relation to the resin of the photosensitive resin layer. For example, polyethylene, polypropylene, acrylic resin, methacrylic resin, polyester, polyamide, polyurethane, Polycarbonate, polystyrene, ethylene-vinyl acetate copolymer resin, ethylene-acrylate copolymer resin, vinyl chloride resin, vinylidene chloride resin,
Chlorinated polyethylene, chlorinated polypropylene, chlorinated rubbers, polyvinyl butyral, polyvinyl acetal,
Examples include polyvinylpyrrolidone, polyethylenenoside, phenolic resins, cellulose derivatives, polyvinyl alcohol derivatives, latexes, and mixtures thereof.

The thickness of the thermoplastic resin layer is not particularly limited, but is usually preferably 6 μm or more from the viewpoint of effectively exhibiting the cushioning property, and is preferably 100 μm or less, more preferably 50 μm from the viewpoint of handling properties. The following is preferred.

When the photosensitive resin layer is provided directly on the thermoplastic resin layer, the thermoplastic resin layer is preferably made of a material which is not dissolved by a solvent for coating the photosensitive resin layer when the photosensitive resin layer is formed. Specifically, a water-soluble polymer material, for example, a mixture of polyethylene glycol with polyvinyl alcohol, a methyl vinyl ether-maleic anhydride copolymer,
Polyvinyl butyral and the like are preferred.

Further, an intermediate layer can be further provided between the thermoplastic resin layer and the photosensitive resin layer. This intermediate layer is provided to prevent the effect of the plasticizer and the solvent of the thermoplastic resin layer on the photosensitive resin layer,
The intermediate layer is preferably selected from a material that is dispersed or dissolved in water or an aqueous alkaline solution and has low oxygen permeability. Examples of the water-soluble polymer constituting the intermediate layer include polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polyvinyl butyral, and water-soluble nylon (which can be removed by washing with water). The thickness is about 0.1 to 5 μm
Is preferably within the range. As the intermediate layer, those described in paragraph [0011] of JP-A-5-173320 can be suitably used. When such a configuration is used, after the transfer material is transferred onto the present support (substrate), when the temporary support is peeled off, the thermoplastic resin layer remains on the temporary support together with the photosensitive resin layer. .

When a separation layer made of a material having only a slight permeability to oxygen is employed as the intermediate layer, if the temporary support is peeled off after the transfer of the transfer material, the peeling is performed. This occurs at the interface between the thermoplastic resin layer and the intermediate layer, and the temporary support and the thermoplastic resin layer are separated and removed.

The material forming the separation layer is preferably a material exhibiting low oxygen permeability and dispersing or dissolving in water or an aqueous alkali solution, and can be appropriately selected from known materials. For example, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers described in JP-A-46-2121 and JP-B-56-40824.
Consists of water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like. Group of water-soluble salts, styrene /
Maleic acid copolymers and maleate resins.

Of these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferred. The polyvinyl alcohol preferably has a saponification ratio of 80% or more, and the content of polyvinylpyrrolidone is preferably 1% by weight to 75% by weight of the solid content of the separation layer. If it is less than 1% by weight, sufficient adhesion to the photosensitive resin layer cannot be obtained,
If it exceeds 75% by weight, the separation layer will dissolve during application of the photosensitive resin layer coating solution to be applied thereon, and the separation layer cannot be formed. The thickness of the separation layer is very thin, about 0.1 to 5
μm, especially 0.5 to 2 μm. If it is less than about 0.5 μm, oxygen permeability is too high, and if it exceeds about 5 μm, it takes too much time during development or removal of the separation layer. Details of such an intermediate layer having the function of the separation layer are described in Japanese Patent Application Laid-Open No. 5-72724, which was previously proposed by the present applicant.

When an intermediate layer is provided,
Although a photosensitive resin layer is provided, it is preferable from the viewpoint of uniform orientation that the surface is subjected to an orientation treatment by rubbing or the like after the formation of the intermediate layer.

Next, the photosensitive resin layer that will eventually form the color filter layer will be described. The photosensitive resin layer of the present invention preferably contains a chiral nematic liquid crystal compound, and preferably contains a photopolymerizable compound from the viewpoint of the stability of the formed filter layer. The chiral nematic liquid crystal compound and the photopolymerizable compound may be one compound such as a polymerizable liquid crystal compound having both properties in the same molecule.

In order to control the physical properties of the photosensitive resin layer,
A chiral compound, a photopolymerization initiator, a binder and the like can be contained as long as the effects of the present invention are not impaired.

In the present invention, the chiral nematic liquid crystal compound can be selected from a liquid crystal compound exhibiting Δn = 0.10 to 0.40, a polymer liquid crystal compound, a polymerizable liquid crystal material and the like. The so-called liquid crystal compound having a steroid skeleton is included in this.

Hereinafter, specific examples of the chiral nematic liquid crystal compound that can be used in the present invention will be shown, but the invention is not limited thereto.

The following is an example of a liquid crystal compound, which is used in combination with a photopolymerizable compound.

[0053]

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[0054]

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[0055]

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The following are examples of the polymer liquid crystal compound. Since this compound is a liquid crystal compound and has a photopolymerizable functional group in a molecule, the compound alone can constitute a filter layer.

[0057]

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In the above formula, n represents an integer of 3 or more.

In each of the above exemplified compounds, those in which the bonding group is changed to the following structure can also be preferably applied.

[0060]

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The photosensitive resin layer of the present invention preferably contains isomanide, catechin, isosorbide, fencon, carvone or a chiral compound exemplified below from the viewpoint of improving the hue and color purity of the liquid crystal compound.

[0062]

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[0063]

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The chiral compound is preferably added in an amount of 0.5 to 50% by weight based on the liquid crystal compound.

The photosensitive resin layer according to the present invention contains a photopolymerizable compound. Representative examples of the photopolymerizable compound include polyfunctional photopolymerizable monomers and oligomers, and preferably include polyfunctional monomers such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.

Hereinafter, examples of the polymerizable monomer that can be used in the present invention will be described, but the present invention is not limited thereto.

[0067]

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The photosensitive resin layer may contain a binder, a surfactant, a thermal polymerization inhibitor, a thickener, a dye,
Pigments, UV absorbers, gelling agents, solvents and the like can be added as appropriate.

The binder to be added for stabilizing the layer is not particularly limited. When a binder containing an alkali-soluble acid group as a copolymer component is added as a binder, the binder may be added in the developing step of the photosensitive resin layer. And alkali development becomes possible. In this case, preferably, the acid value is 50 to 300.
A mg KOH / g alkali-soluble binder is used.
Examples of the acid group contained include acrylic acid, methacrylic acid, and maleic anhydride.

Examples of the polymerization inhibitor added for improving the storage stability include hydroquinones and phenothiazines, and preferably 0.01 to 1% by weight based on the compound having a polymerizable group. Is done.

The thickness of the photosensitive resin layer is appropriately determined depending on the desired thickness of the filter layer.
It is preferably about 0.5 to 10 μm. If the thickness is too thin, there is a problem that defects easily occur due to the influence of dust and the like, and it is difficult to control the development.
There are problems such as an increase in cost, and both are not preferable.

Since the photosensitive transfer material having such a structure has a liquid crystal compound in the photosensitive resin layer, a colored layer having high transparency and color purity can be formed. It is preferably used.

Next, a method for manufacturing the color filter of the present invention will be described. The production method of the present invention comprises, as described above, a photosensitive resin layer of a photosensitive transfer material having a photosensitive resin layer containing a chiral nematic liquid crystal compound provided on a temporary support, and a filter for forming a color filter. The method includes a step of bringing the substrate into close contact with the substrate and transferring the substrate. This manufacturing method will be sequentially described in detail for each process.

First, a coating solution containing the liquid crystal aligning agent of the present invention is applied to an appropriate filter substrate 14 (usually, a thermosetting resin such as glass or epoxy resin is used from the viewpoint of heat resistance and dimensional stability). The alignment film 15 is provided by coating. FIG.
After rubbing the surface of the alignment film 15 as shown in (I), the cover film of the photosensitive transfer material 10 is removed, and the photosensitive resin layer 12 is brought into close contact with the alignment film 15 and heated.
Crimping (Fig. 1 (II)).

Next, as shown in FIG.
And the transfer material 10 are laminated, and the whole is heated in a state of being in close contact with the liquid crystal compound to orient the liquid crystal compound to obtain a desired hue on the photosensitive resin layer 12. In either case, the hue that has been heated and oriented is maintained regardless of whether the temperature is kept as it is or if it is allowed to cool to room temperature. Further, as shown in FIG. 1 (IV), predetermined exposure is performed via the mask pattern 16 from the temporary support 11 side of the laminate. By this exposure, inside the photosensitive resin layer 12,
Only the exposed part is cured. After the exposure, the temporary support 11 is peeled off (FIG. 1 (V)), and then the developing process is performed. Development is
Peeling development or wet development using an alkaline aqueous solution or solvent may be used. Unnecessary portions of the photosensitive resin layer 12 are removed by the development, and as shown in FIG. 1 (VI), a colored filter layer 17 is formed in a portion according to a predetermined mask pattern. In this way, a monochromatic filter layer 17 having a desired hue is formed on the substrate 14.

A multicolor filter can be easily formed by selecting photosensitive resin layer materials having different hues by controlling the type of liquid crystal compound and the temperature conditions at the time of heating alignment, and repeating the above steps. . In particular, if a photosensitive transfer material provided with a thermoplastic resin layer having excellent cushioning properties between the temporary support and the photosensitive resin layer is used, even when a filter of a plurality of colors is formed, it is formed first. Since the step due to the thickness of the filter layer can be effectively absorbed, even if there is a preceding pattern on the substrate, it is possible to perform good transfer with no bubbles remaining, and it is possible to more easily form a high quality color filter pixel pattern. it can.

Further, the color filter obtained by the production method of the present invention comprises a filter layer comprising a photosensitive resin layer containing a chiral nematic liquid crystal compound on a filter substrate (support). Excellent purity,
It has excellent characteristics of having a filter layer having a uniform thickness.

According to the method of the present invention, a liquid crystal layer (photosensitive resin layer) uniformly formed in advance on a temporary support is transferred, so that a filter layer having excellent characteristics is formed on an arbitrary filter substrate. can do. That is, according to this method, a uniform filter layer can be easily formed even on a substrate that is not a plane such as an aspect.

[0079]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Example 1) <Preparation of photosensitive transfer sheet> On a polyethylene terephthalate base film having a thickness of 75 µm, each coating solution prepared according to the following formulation was applied as a coating solution for a photosensitive resin layer using a spin coater. The coating film was dried in an oven at 100 ° C. for 2 minutes, and a 12 μm-thick polypropylene film was laminated as a cover film on the photosensitive resin layer at room temperature, and the photosensitivity for red, green, and blue pixels was obtained. Transfer sheets were obtained respectively. Coating solution for photosensitive resin layer for red pixel Compound (a) 87% by weight Compound (b) 5% by weight Dipentaerythritol hexaacrylate 5% by weight 2,4-trichloromethyl- (4'-methoxy 3% by weight styryl) -6 -Triazine green pixel photosensitive resin layer coating solution compound (a) 86% by weight compound (b) 6% by weight dipentaerythritol hexaacrylate 5% by weight 2,4-trichloromethyl- (4'-methoxy 3% by weight styryl) -6-triazine Blue pixel photosensitive resin layer coating solution Compound (a) 85% by weight Compound (b) 7% by weight Dipentaerythritol hexaacrylate 5% by weight 2,4-Trichloromethyl- (4'-methoxy 3% by weight Styryl) -6-triazine

[0080]

Embedded image

<Preparation of Glass Substrate with Alignment Film>
22. 5-tricarboxycyclopentylacetic acid dianhydride
42 g (100.0 mmol) of synthesized compound (I-1) 0.74 g (1.0 mmol) and p-phenylenediamine 10.71 g (99.0 mmol) were added to N
-Methyl-2-pyrrolidone dissolved in 304.83 g,
The reaction was performed at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol, causing the reaction product to precipitate. Thereafter, the reaction product is washed with methanol,
At 25 ° C. for 15 hours.
5 g were obtained.

10.00 g of the obtained polyamic acid Ia
To 190 g of N-methyl-2-pyrrolidone, 4.75 g
Was added to a mixture of pyridine and 6.13 g of acetic anhydride, and an imidization reaction was performed at 120 ° C. for 4 hours. Then
The reaction mixture was poured into a large excess of methanol to precipitate a reaction product, thereby obtaining 6.55 g of an imidized polymer IIa.

The obtained polymer IIa was dissolved in γ-butyrolactone to form a solution having a solid content of 4% by weight, and this solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent solution. This solution was applied on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner so as to have a thickness of 800 μm, and the coating film was dried at 180 ° C. for 1 hour. By a rubbing machine having a roll in which a nylon cloth is wound around this coating film, the roll bristle foot press length is 0.6 mm, the number of rotations of the roll is 500 rpm,
Rubbing treatment was performed at a stage moving speed of 1 cm / sec to obtain a glass substrate with an alignment film. <Formation of color filter> The cover film was removed from the photosensitive transfer sheet for red pixels, and the laminate was overlapped so that the orientation film surface of the glass substrate with the orientation film was in contact with the photosensitive resin layer of the photosensitive transfer sheet. First Laminator 8B-550-8 manufactured by Laminator Co., Ltd.
Using 0), lamination was performed under a pressure of ² kg / m ² , a roller temperature of 130 ° C., and a feeding condition of 0.2 m / min.

Subsequently, the photosensitive transfer sheets are laminated.
The glass substrate is kept on a hot plate at 120 ° C
At the temperature of 5 minutes to develop the color of the photosensitive resin layer.
Aligner MAP-1200L (Dainippon Screen)
Using a photomask for red pixels.
Ultra-high pressure mercury lamp (500W / cm) to the photosensitive resin layer
Exposure was performed for 25 seconds from a distance of 60 cm (irradiation energy
Ghee; 100mJ / cm ^Two).

After the exposure, the substrate was cooled to room temperature. Subsequently, the temporary support of polyethylene terephthalate was peeled off at the interface with the photosensitive resin layer, and the temporary support was removed.

Thereafter, the photosensitive resin layer was developed with methanol to remove unexposed portions, thereby obtaining a red pixel pattern on a glass substrate provided with an alignment film. Further, this photosensitive resin layer was baked in an oven at 220 ° C. for 20 minutes in order to further cure the pixel pattern.

Subsequently, the cover film was removed from the green pixel photosensitive transfer sheet, and the surface of the glass substrate with the red pixel pattern on which the pixel pattern was provided and the photosensitive resin layer of the green pixel photosensitive transfer sheet were removed. As in the case of using the photosensitive transfer sheet for red pixels, pressurization of ² kg / m ² , 130
At a roller temperature of 0.2 ° C. and a feed condition of 0.2 m / min. The glass substrate is held on a hot plate at a temperature of 120 ° C. for 5 minutes to develop the color of the photosensitive resin layer. Then, the alignment is performed by an aligner through a green pixel photomask, and an ultra-high pressure mercury lamp ( (500 W / cm), the photosensitive resin layer was exposed for 25 seconds from a distance of 60 cm (irradiation energy; 100 mJ / cm ² ). Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the photosensitive resin layer, and the temporary support was removed.

Thereafter, the photosensitive resin layer was developed with methanol to remove unexposed portions, thereby obtaining a green pixel pattern on a glass substrate having a red pixel pattern. To further cure the pixel pattern, the photosensitive resin layer was baked in an oven at 220 ° C. for 20 minutes.

Next, using the photosensitive transfer sheet for blue pixels, the blue photosensitive transfer sheet is similarly laminated on a glass substrate having red and green pixel patterns, and color development processing, pattern exposure, removal of the temporary support, and development are performed. Baking the photosensitive resin layer in an oven at 220 ° C. for 2 hours,
A color filter substrate provided with green and blue pixel patterns was obtained. (Comparative Example 1) An alignment film and, consequently, a color filter were prepared in the same manner as in Example 1 except that the diamine part in Example 1 was changed to one having the following structure.

[0090]

Embedded image

The selective reflection of the color filters of Example 1 and Comparative Example 1 was evaluated by measuring the reflection spectrum by a usual spectrum measuring method. As a result, in the example, the chiral nematic liquid crystal was oriented horizontally with respect to the substrate, whereas in the comparative example, the chiral nematic liquid crystal was oriented vertically with respect to the substrate, resulting in poor selective reflection.

[0092]

According to the present invention, a chiral nematic liquid crystal can be horizontally oriented.

[Brief description of the drawings]

FIGS. 1 (I) to (VI) are schematic diagrams showing a process of manufacturing a color filter.

[Explanation of symbols]

 Reference Signs List 10 photosensitive transfer material 11 temporary support 12 photosensitive resin layer 14 filter substrate (substrate) 15 alignment film

Continued on front page F-term (reference) 2H090 HB08Y HB09Y HB10Y HC05 KA04 LA15 MB01 4J043 PA02 PC066 PC116 QB15 QB26 RA05 RA06 SA06 SA47 SA63 SA72 SA77 SB01 TA22 TB01 UA041 UA042 UA121 UA621 UA632 VA051 VA102 XA16 XA25 XA25

Claims (3)

[Claims] 1. A liquid crystal aligning agent comprising a polyimide obtained by reacting a diamine compound represented by the following general formula (I) with tetracarboxylic dianhydride. Embedded image [Wherein, R represents an alkyl group, an alkanoyl group, or a benzoyl group] 2. An alignment film formed of the liquid crystal alignment agent according to claim 1 on a transparent substrate, and a photosensitive resin layer containing a chiral nematic liquid crystal compound is formed on the alignment film. Chiral nematic liquid crystal color filter. 3. A chiral nematic, wherein a photosensitive resin layer containing a chiral nematic liquid crystal compound is transferred onto an alignment film formed of the liquid crystal alignment agent according to claim 1 provided on a transparent substrate. A method for forming a liquid crystal color filter.