JP2000193983A - Resin composition for spacer, substrate for liquid crystal display device and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a substrate for a liquid crystal display device in which a spacer formed is hardly collapsed by incorporating metal oxide ultrafine particles and/or metal alkoxides. SOLUTION: The spacer formed on a substrate for a liquid crystal display device contains metal oxide ultrafine particles and/or metal alkoxides. As for the metal oxide ultrafine particles, particles of SiO2, TiO2, Sb2O5, ZrO2, Al2O3, Nb2O5, MnO2, PbO, Bi2O3, SnO2, HfO2, Nd2O3 or the like can be used and one kind of these or combination of two or more kinds can be used. As for the metal alkoxides, Si(OCH2CH3)4, Ti(OCH(CH3)2)4, Hf(OCH2CH2CH2CH3)4, Ta(OC2 H5)5, Zr(OCH2CH2CH2CH3)4, Ba(OC2H5)2 or the like can be used, and one kind of these or combination of two or more kinds can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a spacer formed on a substrate for a liquid crystal display, a substrate for a liquid crystal display having a spacer, and a liquid crystal display comprising the substrate.

[0002]

2. Description of the Related Art Conventionally, a liquid crystal display device generally uses plastic beads, glass beads or glass as a spacer between two liquid crystal display substrates in order to maintain the thickness (cell gap) of a liquid crystal layer. It is used with fiber in between.

FIG. 3 is a schematic view of a conventional liquid crystal display device using a bead-shaped spacer, in which a black matrix 4 ', a blue pixel 1', a red pixel 2 ', and a green pixel 3' are formed. Further, an alignment film 7 is formed on the glass substrate 5'a on which the electrode layer 6'a and the alignment film 7 are formed, and an alignment film 7 is formed on the glass substrate 5 on which the electrode layer 6'b and the thin film transistor 9 are formed. Injected,
The inlet is sealed with a sealant 8, and the distance between the glass substrates is maintained by a bead-shaped spacer 11.
In a liquid crystal display device using such a bead-shaped spacer such as a plastic bead, the position of the spacer cannot be arbitrarily determined because the spacer is disposed by spraying. The spacer also exists in the light-transmitting portion (excluding the screen). In that case, by scattering and transmission of light by the spacer,
There is a problem that the display quality of the liquid crystal display device is reduced.
Further, a phenomenon may occur in which the spacers are not uniformly dispersed in the liquid crystal display device and are partially biased. When such a phenomenon occurs, the display quality of the portion where the spacers are gathered is degraded, and there is also a problem in maintaining the cell gap accurately. Therefore, a step of uniformly dispersing the spacers is required, and it is necessary to control the particle size distribution of the spacers with high precision. Therefore, a simple and stable method for producing a spacer is desired.

To solve these problems, Japanese Patent Application Laid-Open No.
In Japanese Patent No. 40324, JP-A-63-82405, JP-A-4-93924, and JP-A-5-196946, a structure in which two or three color pixels of a color filter are stacked is formed and used as a spacer. It has been proposed to use.

Japanese Patent Application Laid-Open No. 7-318950 proposes a liquid crystal display device in which a single layer of resin is separately formed on a color filter and used as a spacer.

[0006]

However, in the liquid crystal display devices obtained by using these disclosed techniques, there is a problem that the spacer is crushed and does not function effectively as a spacer.

[0007] Further, with an increase in the aperture ratio of the liquid crystal display device and the high integration of the substrate facing the spacer, there is an increasing demand for reducing the size of the spacer. Further, since the liquid crystal alignment around the spacer is easily disturbed, there is a high demand to reduce the number of spacers. However, the crushing of the spacer is likely to occur particularly when the size of the spacer is small or when the number of spacers is small.

Accordingly, an object of the present invention is to provide a substrate for a liquid crystal display device in which formed spacers are hard to be crushed, to improve the productivity of the liquid crystal display device and to improve the display quality.

[0009]

An object of the present invention is to provide a spacer formed on a substrate for a liquid crystal display device,
This can be achieved by a resin composition for a spacer characterized by containing ultrafine metal oxide particles and / or metal alkoxide.

[0010]

The resin composition for a spacer according to the present invention contains ultrafine metal oxide particles and / or (b) a metal alkoxide in order to prevent crushing.

In the present invention, specific examples of (a) ultrafine metal oxide particles include SiO ₂ , TiO ₂ , Sb ₂ O ₅ , Z
rO ₂ , Al ₂ O ₃ , Nb ₂ O ₅ , MnO ₂ , PbO, Bi ₂
O ₃ , SnO ₂ , HfO ₂ , Nd ₂ O _{3 and the} like can be mentioned, and of these, one kind or a combination of two or more kinds can be used. However, the present invention is not limited to the above-described metal oxide ultrafine particles, and any metal oxide ultrafine particles having an effect of preventing spacer crushing can be used. Above all, in view of storage stability, versatility, cost and dispersibility of the resin composition, SiO ₂ , TiO ₂ , Sb ₂ O ₅ , ZrO ₂ , Al ₂ O ₃
Are preferred. Further, considering the versatility and ease of use of the material, SiO ₂ , TiO ₂ , and Sb ₂ O ₅ are more preferable.

The metal oxide fine particles are contained not only in the resin composition of the present invention but also as ultrafine metal oxide particles after being formed on the substrate.

When a spacer is obtained by patterning, the spacer material may remain in unnecessary regions due to poor patterning or residues. In particular, when the spacer material remains in the display region, the color tone of the display is changed. Therefore, it is preferable that the spacer material has no wavelength dependence of the transmittance in the visible light wavelength region. In order not to impair the wavelength dependence of the transmittance of the spacer material, the metal oxide ultrafine particles preferably have a particle size of 5 to 100 nm,
50 nm is more preferable.

The metal oxide ultrafine particles can be added to the resin solution as it is when preparing the resin composition for the spacer. From the viewpoint of chemical conversion, it is preferable to add the metal oxide ultrafine particles to the resin solution as a metal oxide ultrafine particle sol dispersed in a solvent.

As a dispersion solvent for the metal oxide ultrafine particles,
Alcohols such as water, ethanol, methanol, isobutanol and 3-methyl-3-methoxybutanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol Diethyl ether, ethers such as diethylene glycol diethyl ether, ethyl acetate, n-butyl acetate,
Esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; and pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone.

Among these solvents, ester-based high-boiling solvents are preferred from the viewpoint of fine dispersibility of metal oxide ultrafine particles and storage stability. It is preferable that these solvents be used alone or in combination of two or more. it can. Particularly, solvents such as propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether acetate are preferable from the viewpoint of high boiling point and storage stability. Further, in view of the storage stability of the spacer resin composition, it is preferable that the dispersion solvent of the metal oxide fine particles be the same as the other solvent used in the spacer resin composition.

Further, (b) the metal alkoxide includes:
Si (OCH ₂ CH ₃ ) ₄ , Ti (OCH (C
_{H 3) 2) 4, Hf} (OCH 2 CH 2 CH 2 CH 3) 4, Ta
(OC ₂ H ₅ ) ₅ , Zr (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , B
a (OC ₂ H ₅ ) ₂ , Pb (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₂ ,
Al (OC ₂ H ₅ ) ₃ , Zn (OC ₂ H ₅ ) ₂ , Ga (OCH
₃ ) ₃ , Ge (OC ₂ H ₅ ) ₄ , W (OC ₂ H ₅ ) ₆ , Nb (O
_{C 2 H 5) 5, Mo} (OC 2 H 5) 6, Y (OCH 3) 3, La
(OC ₂ H ₅ ) ₃ , Te (OC ₂ H ₅ ) _{4 and the} like, and one or more of these can be used in combination.

It is known that the metal alkoxides mentioned above as specific examples generate a hydrolyzate in the presence of water or an alcohol and an acidic catalyst, and are polymerized by a condensation reaction. Therefore, when the above-mentioned metal alkoxide is contained, the storage stability of the spacer resin composition may be poor in a system in which water or an acidic catalyst is present. However, the metal complex formed by the reaction of the β-diketone or β-keto acid ester with the metal alkoxide can suppress the hydrolysis and the condensation reaction, so that the storage stability can be improved. Therefore, when adding a metal alkoxide, the metal alkoxide may be directly added to the resin or solvent to be used, or may be added after converting the metal alkoxide into a metal complex.

Among the metal alkoxides, Si (OCH ₂ CH ₃ ) ₄ and Ti (OCH (C
_{H 3) 2) 4, Hf} (OCH 2 CH 2 CH 2 CH 3) 4, Ta
(OC ₂ H _{5) 5,} it is preferable to use _{Zr (OCH 2 CH 2 CH 2} CH 3) 4. Among them, in particular, Si (OC
H ₂ CH ₃ ) ₄ , Ti (OCH (CH ₃ ) ₂ ) ₄ , Zr (O
Silica such as CH ₂ CH ₂ CH ₂ CH ₃ ) ₄ or an alkoxide of titanium or zirconium is more preferable in terms of stability of metal complex formation and simplicity.

Specific examples of the above-mentioned β-diketones and β-keto acid esters which form a metal complex with a metal alkoxide include acetylacetone, benzoylacetone, dibenzoylmethane, methylacetoacetate, and the like.
Ethyl acetoacetate, benzoylacetoacetate, ethyl benzoyl acetate, methyl benzoyl acetate and the like can be mentioned.

In the present invention, a metal complex may be synthesized from a metal, a metal halide, a metal salt other than a metal halide, a metal oxide or a hydroxide, in addition to the metal alkoxide. Synthesis, synthesis from an organometallic compound, and the like are mentioned. From the viewpoint of availability and toxicity, synthesis from a metal alkoxide is preferable.

Since the above-described method of adding a metal alkoxide to the resin composition for a spacer involves a solution state, it can be uniformly mixed with the resin at a molecular level. Further, by patterning the spacer resin composition on the substrate and then heating the metal alkoxide, the metal alkoxide is chemically bonded to the resin and dispersed at the molecular level in the spacer.

The resin constituting the resin composition for a spacer of the present invention is not particularly limited, but a polyimide resin,
A photosensitive or non-photosensitive material including an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, and a polyolefin resin is preferably exemplified.

As the photosensitive resin, there are types such as a photolytic resin, a photocrosslinkable resin, and a photopolymerizable resin.
A photosensitive composition, a photosensitive polyamic acid composition and the like containing a monomer, an oligomer or a polymer having an ethylenically unsaturated bond and an initiator generating a radical by ultraviolet rays are preferably used.

As the non-photosensitive resin, of the above-mentioned various polymers, those which can be developed are preferably used, but can withstand the heat applied in the process of forming the conductive layer and the process of manufacturing the liquid crystal display device. A resin having such heat resistance is preferable, a resin having resistance to an organic solvent used in a manufacturing process of a liquid crystal display device is preferable, and a polyimide resin is particularly preferable.

Here, the polyimide resin is not particularly limited, but usually a polyimide precursor having a structural unit represented by the following general formula as a main component is imidized by heating or an appropriate catalyst. Those that have been used are preferably used.

[0027]

Embedded image In the above general formula, n is 0 or a number from 1 to 4.
R ₁ is an acid component residue, and R ₁ is a trivalent or tetravalent organic group having at least two carbon atoms. From the viewpoint of heat resistance, R ₁ is preferably a trivalent or tetravalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Examples of R ₁ include phenyl, biphenyl, terphenyl, naphthalene, perylene, diphenylether, diphenylsulfone, diphenylpropane, benzophenone, biphenyltrifluoropropane, cyclobutyl, and cyclopentyl. However, the present invention is not limited thereto.

R ₂ represents a divalent organic group having at least two carbon atoms. From the viewpoint of heat resistance, R ₂ is preferably a divalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Examples of R ₂ include phenyl, biphenyl, terphenyl, naphthalene, perylene, diphenylether, diphenylsulfone, diphenylpropane, benzophenone, biphenyltrifluoropropane, diphenylmethane, cyclohexylmethane, and the like. Derived groups include, but are not limited to.
The polymer having a structural unit represented by the above general formula as a main component may be a copolymer in which R ₁ and R ₂ are each composed of one or two or more. There may be.

Also, a spacer containing an acrylic resin is preferably used. The acrylic resin used at this time is acrylic acid, methacrylic acid, methyl acrylate,
Alkyl acrylates or alkyl methacrylates such as methyl methacrylate, cyclic acrylates or methacrylates, hydroxyethyl acrylates or methacrylates are used, and a resin polymerized to a molecular weight of about 5,000 to 200,000 using about 3 to 5 types of monomers. preferable. When an acrylic resin is contained, the resin composition for the spacer is not limited to photosensitive or non-photosensitive, but a photosensitive material is preferably used from the viewpoint of ease of fine processing of the spacer. In the case of a photosensitive resin, a composition comprising an acrylic resin, a photopolymerizable monomer, and a photopolymerization initiator is preferably used.

As photopolymerizable monomers, there are bifunctional, trifunctional and polyfunctional monomers.
-Hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol acrylate, etc., and trifunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, etc. And polyfunctional monomers such as ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate. As the photopolymerization initiator, benzophenone, thioxanthone, imidazole, triazine and the like are used alone or in combination.

Epoxy resins can also be preferably used. Specifically, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cycloaliphatic epoxy resin, fatty acid Those obtained by curing an aromatic polyglycidyl ether or the like with a curing agent can be used.

If necessary, an additive may be separately added to the spacer resin composition. As additives,
There are coloring agents such as organic pigments, inorganic pigments, and dyes used for color pixels, black matrices, and overcoat films, and various additives such as ultraviolet absorbers, dispersants, and leveling agents. When the light shielding property is required for the spacer,
In addition to light-blocking agents such as metal oxide powders such as carbon black, titanium oxide and iron tetroxide, metal sulfide powders and metal powders, mixtures of pigments such as red, blue and green can be used. When a spacer is formed with a colored layer, it is preferable to use a resin in which a coloring agent such as a pigment such as red, blue, or green is dispersed or dissolved in a resin. There is no particular limitation on the amount of the colorant and the light-shielding agent to be added, but it is preferable that the weight ratio of the colorant and the light-shielding agent component to the resin component is 10: 0 to 1: 9 from the viewpoint of forming the spacer.

When the substrate is a color filter and a spacer composed of a plurality of layers is formed by laminating a color pixel, a black matrix, an overcoat film and the like, at least one of the layers constituting the spacer is provided with a resin for the spacer. It may be formed using a composition. For example, using a resin composition in which a red pigment is dispersed in a resin composition for a spacer, it is conceivable to form a red pixel and to form one layer of a spacer composed of a plurality of layers. A method of forming a spacer by stacking color pixels will be described later.

Solvents used in the spacer resin composition include water, alcohols such as ethanol, methanol, isobutanol and 3-methyl-3-methoxybutanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and diethyl. Ethers such as ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethyl acetate, n-butyl acetate, 3-methoxy-3-methylbutyl acetate, ethylene glycol monomethyl ether acetate; Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Esters such as methyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; And pyrrolidones such as -pyrrolidone and N-methylpyrrolidone. Among these,
Ester-based high-boiling solvents are preferred from the viewpoint of coatability of the spacer material coating liquid, and they can be used alone or as a mixture of two or more. Particularly, solvents such as propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether acetate are preferable from the viewpoint of high boiling point and storage stability.

In the present invention, (a) ultrafine metal oxide particles and / or (b) in the resin composition for a spacer are used.
The content of the metal alkoxide is 1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the resin.
More preferably, it is 1 to 50 parts by weight. If the addition amount of the components (a) and / or (b) is less than this, it is not preferable from the viewpoint of the effect of preventing the spacer from being crushed, and if it is more than this, it is not preferable from the viewpoint of coating properties of the spacer resin composition. The amount is more preferably from 10 to 50 parts by weight from the viewpoints of coatability of the resin composition for a spacer and prevention of collapse.

The difference in dispersion between (a) and (b) is that (a) physically disperses ultrafine particles in resin, while (b)
Is to chemically disperse the metal oxide. However, there is no significant difference in the crush prevention effect using either (a) or (b).

For the purpose of improving the coatability of the spacer resin composition and the uniformity of the spacer height, a surfactant can be added to the spacer resin composition.
The addition amount of the surfactant is based on 100 parts by weight of the resin.
0.01 to 10 parts by weight is preferable, and 0.03 to 1 part by weight is more preferable. If the addition amount is too small, there is no effect of improving the coating properties, the smoothness of the film surface, or the dispersibility of the fine particles, while if it is too large, the coating properties become poor or the toughness of the coating film decreases. And the fine particles tend to agglomerate.

Specific examples of the surfactant include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, alkyl, fluorine-modified silicone oil, polyether, alcohol-modified silicone oil, amino-modified silicone oil, and epoxy-modified silicone oil. Modified silicone oils such as phenol, carboxy, mercapto-modified silicone oils, anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as lauryl trimethyl ammonium chloride, lauryl dimethyl Amphoteric surfactants such as amine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauri Ether, polyoxyethylene stearyl ether, but such nonionic surfactants such as sorbitan monostearate and the like, without limitation. The above surfactants can be used alone or in combination of two or more. The surfactant can be added at any time before and after the addition of the metal oxide ultrafine particles or the metal alkoxide. However, depending on the timing of addition, the dispersibility of the metal oxide ultrafine particles may change, so it is necessary to appropriately set the addition procedure.

The shape of the spacer, that is, the cross-sectional shape when the spacer is cut along a plane parallel to the substrate is not particularly limited, but may be a circle, an ellipse, a polygon with rounded corners, a cross,
A T or L shape is preferred. In the case where the spacer is formed by lamination, the shape of the spacer in each layer is not particularly limited, but is preferably a circle, an ellipse, a polygon having rounded corners, a cross, a T-shape or an L-shape, and these may be arbitrarily selected. They may be laminated to form a spacer.

The height of the spacer is preferably 1 to 9 μm, more preferably 2 to 8 μm. If the height of the spacer is lower than 1 μm, it is difficult to secure a sufficient cell gap. On the other hand, if the thickness exceeds 9 μm, the cell gap of the liquid crystal display device becomes too large, and the voltage required for driving becomes undesirably high. In addition, the height of the spacer refers to a single spacer, and means the distance between the opening coloring layer of the color filter and the uppermost surface of the spacer. When there is unevenness in the height of the display portion flat portion on the substrate, it indicates the largest one of the distances between the uppermost surface of the spacer and each display portion flat portion.

From the viewpoint of increasing the uniformity of the distance between the two substrates for the liquid crystal display device held by the spacer in the screen,
The spacer is preferably formed in the non-display area inside and outside the screen, but may be formed in either the non-display area inside the screen or outside the screen.

The area and arrangement location of each spacer are greatly affected by the structure of the liquid crystal display device. Constraints of the area of the non-display region 1 in the pixel in a color filter having a fixed spacer, the spacer area per one screen is preferably 10μm ² ~1000μm ^2. More preferably, 10 μm ^{2 to} 25
0 μm ² . The spacer area here is the top of the spacer formed on the color filter,
It refers to the area of a portion that comes into contact with a counter substrate or the area of a portion that comes into contact with a spacer formed on a counter substrate when a liquid crystal display device is manufactured. When the area of each spacer is smaller than 10 μm ² , it is difficult to form a precise pattern and to form a laminate. If the area of each spacer is larger than 1000 μm ² , the formation and lamination of the spacer pattern are facilitated, but the spacers in the screen appear in the display area and cause display failure. On the other hand, when a spacer outside the screen is provided, the spacer outside the screen does not appear in the display area.
It is preferable to make the area equal to or larger than the area of each spacer in the screen from the viewpoint of facilitating the formation of the spacer.

Further, in the present invention, it is desirable that the spacer is designed so that the area of the contact portion with the glass substrate facing the glass substrate is smaller than the area of the bottom of the spacer when the patterns are laminated.

The spacer of the present invention is preferably formed by a method such as a photolithography method, a transfer method, a printing method, an electrodeposition method, and an ink-jet method. Among them, the spacer is preferably formed by a photolithography method since the spacer can be easily formed at a designed position. The photolithography method is a method in which a resin composition for a spacer is applied on a substrate, dried, exposed through a mask having a spacer pattern, developed, and patterned. As a method of applying the resin composition for a spacer,
A dip method, a roll coater method, a spinner method, a die coating method, a wire bar coating method, or the like is suitably used. Thereafter, if necessary, heat drying (semi-curing) is performed using an oven or a hot plate. Semi-curing conditions vary depending on the presence or absence of a metal alkoxide, the resin used, the solvent, and the amount of resin applied.
Preferably, heating is performed for 60 minutes. In the case where the resin is a non-photosensitive resin, after forming a photoresist film thereon,
When the resin is a photosensitive resin, exposure and development are performed as it is or after forming an oxygen blocking film.
If necessary, the photoresist film or the oxygen barrier film is removed, and the film is dried by heating (this cure). By the above process, a spacer is formed on the transparent substrate. When it is difficult to obtain a sufficient height by one patterning, it is also possible to perform a step of forming a spacer a plurality of times and laminate resin layers to obtain a sufficient height.

In the transfer method, a transfer substrate in which a photosensitive resin layer is formed on a base material in advance is prepared, and the transfer substrate is overlaid on the substrate while applying heat and pressure as necessary, and exposed and developed. Then, the base material is peeled off and the spacer is formed on the substrate, or the spacer is formed on the transfer substrate in advance by photolithography or the like, and then the heat and pressure are applied to the substrate to transfer the spacer. Is the way.

Next, a liquid crystal display substrate and a liquid crystal display device using the spacer of the present invention will be described.

The substrate for the liquid crystal display device may be of a liquid crystal type, and may have electrodes, thin film transistors and color pixels on the substrate as necessary. Specifically, a color filter having color pixels or a monochrome filter may be used, or a thin film transistor (T
A substrate having a plurality of transistors, such as a substrate with FT), may be used.

The substrate for a liquid crystal display device and the liquid crystal display device of the present invention will be further described with reference to the drawings.

FIG. 1 is a schematic view of an example of the substrate for a liquid crystal display of the present invention. Black matrix 4 and blue pixel 1,
After the red pixel 2 and the green pixel 3 are formed, an electrode layer 6
a is a glass substrate 5a on which a patterned resin composition 12 for a spacer is formed on an electrode layer 6a.

FIG. 2 is a schematic view of an example of a liquid crystal display device using the liquid crystal display device substrate of FIG. 1, and a substrate in which an alignment film 7 is further formed on the liquid crystal display device substrate shown in FIG.
After the alignment film 7 is formed on the glass substrate 5b on which the electrode layer 6b and the thin film transistor 9 are formed, the alignment film 7 is adhered to the glass substrate 5b, and the liquid crystal is injected. Is maintained by the patterned spacer 12.

An overcoat film may be formed on the liquid crystal display device substrate before and / or after the spacer is formed. The application of such an overcoat film is disadvantageous in that the structure of the substrate for a liquid crystal display device is complicated and the production cost is high, but the control of the spacer height and
This is advantageous for preventing impurities from being stained from the surface of the substrate for the liquid crystal display device and the spacer and for flattening the surface. It is sufficient to judge whether or not to employ the material in view of the overall required characteristics. By forming the overcoat film in the spacer portion, a part of the spacer is constituted by the overcoat film. The material is not particularly limited, and an inorganic glass film, a resin film, or the like is used. Specifically, as an inorganic glass film, a condensate of tetramethoxysilane or a condensate of tetraethoxysilane, and as a resin film, an epoxy resin,
Examples include, but are not limited to, acrylic resins, siloxane resins, and polyimide resins.

Further, a conductive layer may be formed on the substrate for a liquid crystal display device of the present invention before or after the spacer is formed, if necessary. Note that it is preferable that at least one of the two substrates for a liquid crystal display device constituting the liquid crystal display device has a conductive layer. A voltage can be applied to the liquid crystal through the conductive layer to drive the liquid crystal display. When the conductive layer formed on the spacer or on the spacer side wall adversely affects the display characteristics of the liquid crystal display device, it is preferable to form the electrode layer before forming the spacer. When the spacer is desired to have conductivity, it is preferable to provide an electrode layer after the spacer is formed. As the electrode layer, a transparent conductive thin film such as indium tin oxide (ITO) is employed.
In the case of a color liquid crystal display device, a color filter, which is a substrate for a liquid crystal display device including color pixels, is preferable as a substrate for a liquid crystal display device having a fixed spacer from the viewpoint of easy formation of the spacer.

Hereinafter, the present invention will be described in more detail by taking, as an example, the case where the substrate for a liquid crystal display device is a color filter including color pixels.

The color filter of the present invention is preferably one in which a black matrix is provided on a substrate as required, and a plurality of color pixels consisting of at least three primary colors are arranged thereon. The black matrix referred to herein indicates a light-shielding region arranged between pixels, is provided to improve display contrast of a liquid crystal display device, and to prevent light from being incident on an active element such as a TFT and causing a malfunction.

The substrate used for the color filter is not particularly limited, and inorganic glass such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with silica, and organic plastic film Alternatively, a transparent substrate such as a sheet is preferably used.

The black matrix may be formed by overcoating a metal such as chromium or nickel, an oxide thereof, or a colored film. However, forming a resin black matrix composed of a resin and a light-shielding agent requires a low production cost. It is preferable from the viewpoint of waste disposal cost. In this case, the resin used for the black matrix is not particularly limited, but is a photosensitive or non-photosensitive material such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, and a polyolefin resin. Is preferably used. The resin for the resin black matrix is preferably a resin having higher heat resistance than the resin used for the pixels and the protective film, and since a resin having resistance to the organic solvent used in the step after the formation of the black matrix is preferable, A polyimide resin is particularly preferably used. In addition, as a preferable polyimide-based resin, a resin suitable for forming the above-described spacer can be used.

Examples of the light-shielding agent for the black matrix include metal oxide powders such as carbon black, titanium oxide and iron tetroxide, metal oxide ultrafine particles, metal sulfide powder and metal powder, as well as red, blue and green. And the like. Among them, carbon black is particularly preferable because of its excellent light-shielding properties. Since carbon black having a good dispersion and a small particle size mainly exhibits a brownish color tone, it is preferable to mix a pigment of a complementary color to carbon black to obtain an achromatic color.

One layer of the spacer composed of a plurality of layers may be formed by using a resin black matrix in which a light-shielding agent is added to a spacer resin composition containing metal oxide fine particles and / or metal alkoxide.

When the resin for the black matrix is a polyimide resin, the black paste solvent is usually N
Amide polar solvents such as -methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and lactone polar solvents such as γ-butyrolactone are preferably used.

As a method for dispersing a light-shielding agent such as a pigment of a complementary color to carbon black or carbon black, for example, a method of mixing a light-shielding agent and the following additives as necessary into a polyimide precursor solution is used. , A three-roll, a sand grinder, a method of dispersing in a disperser such as a ball mill, and the like, but the method is not particularly limited. Additives are mainly added for improving the dispersibility of carbon black, or for improving applicability and leveling property.

As a method for producing a resin black matrix, a black paste is applied on a transparent substrate, dried, and then
Perform patterning. As a method for applying the black paste, a dip method, a roll coater method, a spinner method, a die coating method, a wire bar coating method, or the like is suitably used. After that, heat drying (semi-curing) using an oven or a hot plate is performed. Do. The semi-curing conditions vary depending on the resin, solvent and paste applied amount, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.

The black paste film obtained in this manner is formed after forming a photoresist film on the non-photosensitive resin when the resin is a non-photosensitive resin, or after forming a photoresist film on the non-photosensitive resin. Exposure and development are performed as it is or after forming an oxygen barrier film. If necessary, the positive photoresist film or the oxygen barrier film is removed, and the film is dried by heating (this cure). These curing conditions are slightly different depending on the amount of the polyimide resin to be obtained from the precursor, but may be usually heated at 200 to 300 ° C. for 1 to 60 minutes. In the case of acrylic resin, the curing conditions are as follows:
Usually, heating may be performed at 150 to 300 ° C. for 1 to 60 minutes. Through the above process, a black matrix is formed on the substrate.

The resin black matrix may be formed by a transfer method. A black matrix may be formed by stacking colored layers described later.

The thickness of the resin black matrix is preferably 0.5 to 2.0 μm, more preferably 0.8 to 1.
5 μm. When the film thickness is smaller than 0.5 μm,
When a spacer is produced by further laminating a resin layer on the resin black matrix, it is difficult to form a spacer having a sufficient height, and the light-shielding property is insufficient, which is not preferable. On the other hand, when the film thickness is greater than 2.0 μm, although the light-shielding property can be ensured, the flatness of the color filter is easily sacrificed, and a step is easily generated.

The light shielding property of the resin black matrix is O
It is represented by a D value (common logarithm of the reciprocal of transmittance), and is preferably 1.6 or more, more preferably 2.0 or more, in order to improve the display quality of the liquid crystal display device.
More preferably, it is 3.0 or more. In addition, although the preferred range of the thickness of the resin black matrix is specified, the OD
The upper limit of the value should be set in this connection.

Usually, (2)
An opening of 0 to 200) μm × (20 to 300) μm is provided.
A plurality of primary color pixels are arranged. That is,
One opening is covered with any one color pixel of the three primary colors, and a plurality of pixels of each color are arranged.

In the case of a color filter, a color pixel includes at least three layers of three primary colors, red (R), green (G), blue (B), or cyan (C), magenta (M), and yellow (Y). Each color pixel is provided with one colored layer of any of these three colors.

As the colorant used for the color pixel, organic pigments, inorganic pigments, dyes and the like can be preferably used. Further, various additives such as an ultraviolet absorber, a dispersant and a leveling agent are added. You may. As the pigment, Pigment Red 9, 97, 122, 123, 149, as red (R),
168, 177, 180, 192, 215, etc., such as Pigment Green 7, 36 as green (G) and Pigment Blue 15, 22, 60, 64, etc. as blue (B) are generally used. A wide range of dispersants such as surfactants, pigment intermediates, dye intermediates, and polymer dispersants are used.

The resin used for the color pixel is not particularly limited, but may be an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin,
A photosensitive or non-photosensitive material such as a polyolefin resin can be employed. From the viewpoint of dispersing the colorant, it is preferable to use an acrylic resin or a polyimide resin as the resin constituting the color pixel, and more preferably use a polyimide resin.

As a method of forming a color pixel, a color paste containing a colorant is applied to a substrate on which a black matrix is formed, dried, and then patterned. As a method of obtaining a colored paste by dispersing or dissolving the colorant, after mixing the resin and the colorant in a solvent, three-roll, sand grinder, there is a method of dispersing in a dispersing machine such as a ball mill, The method is not particularly limited.

As a method for applying the colored paste, a dipping method, a roll coater method, a spinner method, a die coating method, a wire bar coating method, etc. are preferably used, as in the case of the black paste, and thereafter, an oven or hot Heat drying (semi-cure) is performed using a plate. The semi-curing conditions vary depending on the resin used, the solvent, and the amount of the paste applied, but it is usually preferable to heat at 60 to 200 ° C for 1 to 60 minutes.

When the resin is a non-photosensitive resin, the colored paste film thus obtained is formed after forming a photoresist film thereon, and when the resin is a photosensitive resin, Exposure and development are performed as it is or after forming an oxygen barrier film. If necessary, the photoresist film or the oxygen barrier film is removed, and the film is dried by heating (this cure).

The curing conditions are slightly different depending on the amount of coating when a polyimide resin is obtained from the precursor, but it is usually sufficient to heat at 200 to 300 ° C. for 1 to 60 minutes. In the case of an acrylic resin, the curing conditions are usually 150 to 3
What is necessary is just to heat at 00 degreeC for 1 to 60 minutes. Through the above process, a patterned colored layer is formed on the substrate on which the black matrix is formed. Further, a colored layer may be formed on the black matrix by a so-called transfer method.

After the first color layer is formed over the entire surface of the substrate on which the black matrix is formed as described above, unnecessary portions are removed by photolithography, and the desired first color layer is removed. Is formed. The same operation is repeated to form a color pixel pattern of the second color layer and a color pixel pattern of the third color layer.

When forming a spacer on a color filter, a process of forming a spacer is not required separately, or in order to realize a spacer having a sufficient height, a color pixel of a color filter is simultaneously processed with a color pixel. It is preferable to form a spacer formed by lamination. When a spacer is constituted by the color pixels of the color filter, a color resin containing either (a) or (b) or a resin containing both (a) and (b) is used. Is also good.

A part or all of the spacers can be formed by laminating colored layers of color pixels. For example, when a desired color pixel pattern of the first color is formed with the color layer of the first color pixel on the substrate on which the black matrix is formed, a portion that covers the opening of the black matrix, The coloring layer is left in the portion where the spacer is formed by lamination. The same operation is repeated for the second color and the third color, so that one colored layer is formed on the opening of the black matrix, and part or all of the spacer is formed. In order to secure a sufficient cell gap as a spacer, it is preferable that two to three colored layers of color pixels are stacked at the spacer forming position.

After the colored layers of the color pixels are laminated, the above-mentioned resin composition for a spacer may be further applied, and the spacer may be formed by patterning as necessary.

When a part or all of the spacer is formed by lamination of a colored layer or the like, any one of the layers constituting the spacer may include a layer using the spacer resin composition of the present invention. .

Further, together with the formation of the spacer, a laminate having a height that does not function as a spacer, in other words, a height lower than the spacer may be formed. For example, when the spacer is formed by four layers, three layers, two layers, or one layer
In the case where the laminate composed of layers and the spacer are formed of three layers, a laminate composed of two layers or one layer may be formed. These do not normally come into contact with the opposing substrate, but when the liquid crystal display device is pressurized, it comes into contact with the opposing substrate to secure a cell gap and improve the reliability of the display quality of the liquid crystal display device. Can be enhanced.

The coloring layer on the opening and the coloring layer forming the spacer may be continuous or separated.

When manufacturing a liquid crystal display device using the substrate for a liquid crystal display device of the present invention, it is preferable to perform an appropriate liquid crystal alignment treatment. Examples of the liquid crystal alignment treatment include a method of applying an alignment film, a method of performing a rubbing treatment, and a method of performing a light alignment treatment by irradiation with ultraviolet light or the like. In the present invention, for example, after subjecting a liquid crystal display device substrate to an appropriate liquid crystal alignment treatment, two liquid crystal display device substrates are bonded to each other facing each other using an epoxy adhesive or the like as a sealing agent, and Liquid crystal is injected from the provided injection port. After the liquid crystal is injected, the injection port is sealed, and a polarizing plate is attached to the outside of the substrate, whereby a liquid crystal display device can be manufactured.

The liquid crystal used in the liquid crystal display device of the present invention is not particularly limited, but a nematic liquid crystal, a ferroelectric liquid crystal, an antiferroelectric liquid crystal, a thresholdless antiferroelectric liquid crystal and the like are preferably used.

The substrate for a liquid crystal display device and the liquid crystal display device of the present invention are used for display screens of personal computers, word processors, engineering workstations, navigation systems, liquid crystal televisions and the like, and are also suitably used for liquid crystal projection and the like. . Further, in the field of optical communication and optical information processing, it is suitably used as a spatial modulation element using a liquid crystal. A spatial modulation element modulates the intensity, phase, polarization direction, etc. of light incident on the element according to an input signal to the element, and is used for real-time holography, a spatial filter, incoherent / coherent conversion, and the like. It is.

[0084]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In the present invention, the OD value, the film thickness, and the surface resistance are values measured by the following methods.

(1) OD value The optical density (OD) value, which is an index of the light-shielding property, was measured at a wavelength of 4 using a microspectroscope (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).
In the visible light region of 30 to 640 nm, it was obtained from the following relational expression. OD value = log10 (I0 / I) where I0 is the incident light intensity and I is the transmitted light intensity.

(2) Film thickness measurement Kosaka Laboratory Co., Ltd. (product) “Surfc”
Using order “SE-3300”, the film thickness was determined by measuring the level difference depending on the presence or absence of the transparent conductive film.

(3) Surface resistance "Lorest", a surface resistance measurement device manufactured by Mitsubishi Yuka Co., Ltd.
Using "a" or "Hiresta", the surface resistance (sheet resistance) was measured by a four-point probe method, and the specific resistance was determined by multiplying the film thickness.

Example 1 (Preparation of color filter) [Preparation of black matrix] γ-butyrolactone and N
In a mixed solvent of -methyl-2-pyrrolidone, pyromellitic dianhydride (0.5 molar equivalent), benzophenonetetracarboxylic dianhydride (0.49 molar equivalent), 4,4 '
-Diaminodiphenyl ether (0.95 molar equivalent),
Bis-3- (aminopropyl) tetramethylsiloxane (0.05 molar equivalent) was reacted to obtain a polyimide precursor solution (polymer concentration: 20% by weight).

200 g of this polyimide precursor solution was taken out, and 186 g of γ-butyrolactone and 64 g of butyl cellosolve were added to obtain a polyamic acid solution having a polymer concentration of 10% by weight.

4 g of carbon black, N-methyl-2-
Using a homogenizer, 40 g of pyrrolidone and 6 g of butyl cellosolve together with 100 g of glass beads were used for 7000 r.
After a dispersion treatment at pm for 30 minutes, the glass beads were removed by filtration to obtain a pigment dispersion having a pigment concentration of 8% by weight.

To 30 g of the pigment dispersion, 28 g of the polyimide precursor solution having a polymer concentration of 10% by weight was added and mixed to prepare a black paste. After applying this paste on a non-alkali glass substrate, pre-bake at 125 ° C,
A polyimide precursor black colored film was formed. After cooling, a positive photoresist was applied and dried by heating at 90 ° C. to form a photoresist film. This was exposed through a photomask using an ultraviolet exposure machine. After the exposure, the film was immersed in an alkaline developer, and the development of the photoresist and the etching of the polyimide precursor black colored film were simultaneously performed to form openings. After the etching, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. The etched polyimide precursor black colored film was heated to 290 ° C. and thermally cured to be converted to polyimide to form a resin black matrix.

[Preparation of Pixel] Next, dianthraquinone pigments represented by Pigment Red 177, phthalocyanine green pigments represented by Pigment Green 36, and Pigment Blue 15-4 as red, green, and blue pigments, respectively. A phthalocyanine blue pigment was prepared. The polyimide precursor solution and the pigment were mixed and dispersed at a weight ratio of 6: 4 (polyimide precursor: pigment) to obtain three types of colored pastes of red, green, and blue. Using this colored paste, red pixels, green pixels, and blue pixels were formed.

Further, a polyimide siloxane precursor solution was applied on the substrate to form an overcoat film made of polyimide siloxane, thereby producing a color filter.

[Preparation of Spacer Resin Composition and Spacer] Celloxide 20 manufactured by Daicel Chemical Industries, Ltd.
10 g of 21P (alicyclic epoxy compound), 0.2 g of Adeka Optoma SP-150 (photopolymerization initiator) by Asahi Denka Kogyo Co., Ltd., and 5 g of an SiO ₂ methanol sol solution having a solid concentration of 30% were added to 3-methoxy. It was dissolved in -3-methylbutyl acetate and adjusted to have a total solid content concentration of 30%. After the obtained solution was filtered through a membrane filter having a pore size of 0.2 μm, the solution was applied on a color filter using a spin coater, and heated at 100 ° C. for 10 minutes.

After cooling, this was exposed through a photomask using an ultraviolet exposure machine. After the exposure, the film was immersed in a developing solution, and the resin composition for a spacer was etched to form a spacer portion. The etched resin composition for a spacer was heated to 230 ° C. and thermally cured to cure the coating film. Spacers were formed on the black matrix in the screen, on the frame, on the seal around the frame, and outside the seal. The spacer on the in-screen black matrix is a three-layer laminate of a black matrix layer, an overcoat film, and a layer composed of a spacer resin composition. The height of the spacers on the black matrix in the screen was 4 μm, and the area of each spacer was 100 μm ² . The spacer outside the seal portion was 3 μm, and the area of each spacer was 200 μm ² .

(Production and Evaluation of Color Liquid Crystal Display Device) A polyimide-based alignment film was provided on this color filter and rubbed. Similarly, a liquid crystal display device substrate having a thin film transistor opposed thereto was also provided with a polyimide-based alignment film and subjected to a rubbing treatment. This 2
After bonding the two substrates together using an epoxy adhesive as a sealant, a nematic liquid crystal was injected from an injection port provided in the seal portion. After injecting the liquid crystal, seal the injection port,
Further, a polarizing plate was attached to the outside of the substrate to produce a liquid crystal display device. The liquid crystal display device according to the first embodiment is a display device driven by a lateral electric field liquid crystal.

Based on such a method, 100 liquid crystal display devices were manufactured through certain known manufacturing steps. As a result, a liquid crystal display device having no particular problem could be obtained. The display quality of these liquid crystal display devices was evaluated. The display quality was good. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

Comparative Example 1 A spacer was obtained in the same manner as in Example 1 except that the SiO ₂ methanol sol solution was not added, and 100 liquid crystal display devices were manufactured through the same manufacturing steps as in Example 1. In 15 liquid crystal display devices, the display quality was deteriorated. Analysis of the cause revealed that the spacer was crushed.

Example 2 (Preparation of color filter) [Preparation of black matrix] On a non-alkali glass substrate, a light-shielding film made of chromium and its oxide was formed by vacuum evaporation. A photoresist was applied thereto and dried by heating to form a photoresist film. This was exposed through a photomask using an ultraviolet exposure machine.
After the exposure, the photoresist was immersed in an alkaline developer to develop the photoresist. Thereafter, the light-shielding film was etched with an acid developer, and after the etching, the unnecessary photoresist layer was peeled off to form a black matrix.

[Preparation of Pixel] Next, as red, green and blue pigments, dianthraquinone pigments represented by Pigment Red 177, phthalocyanine green pigments represented by Pigment Green 36, and Pigment Blue 15-4, respectively. A phthalocyanine blue pigment was prepared. The polyimide precursor solution described in Example 1 and the above-mentioned pigment were mixed and dispersed at a weight ratio of 6: 4 (polyimide precursor: pigment), and red,
Green and blue colored pastes were obtained. Using this colored paste, red pixels, green pixels, and blue pixels were formed. Thereafter, a transparent electrode was formed by a sputtering method. The thickness of the transparent electrode was 150 nm, and the surface resistance was 20 Ω / □.

[Preparation of Spacer] Using the spacer resin composition used in Example 1, a spacer was formed on a color filter in the same manner as in Example 1. The formation location is on the display screen black matrix and on the frame,
A spacer was formed on the seal around the frame.
The spacer on the black matrix is a two-layer laminate of a black matrix layer and a layer composed of a resin composition for a spacer. The height of the spacer was 4.5 μm, and the area of the spacer per display screen was 80 μm ² .

(Production and Evaluation of Color Liquid Crystal Display Device) A polyimide-based alignment film was provided on this color filter and rubbed. Similarly, a liquid crystal display device substrate having a thin film transistor opposed thereto was also provided with a polyimide-based alignment film and subjected to a rubbing treatment. This 2
After bonding the two substrates together using an epoxy adhesive as a sealant, a nematic liquid crystal was injected from an injection port provided in the seal portion. After injecting the liquid crystal, seal the injection port,
Further, a polarizing plate was attached to the outside of the substrate to produce a liquid crystal display device.

The liquid crystal display device of the second embodiment is of a display type in which the liquid crystal display device is driven between electrodes formed on two substrates for a liquid crystal display device. When 100 liquid crystal display devices were manufactured through a certain known manufacturing process based on such a method, a liquid crystal display device having no particular problem could be obtained. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

Comparative Example 2 A spacer was obtained in the same manner as in Example 2 except that the methanol sol solution of SiO ₂ was not added, and 100 liquid crystal display devices were manufactured through the same manufacturing steps as in Example 2. In 13 liquid crystal display devices, display quality was deteriorated. Analysis of the cause revealed that the spacer was crushed.

Example 3 As in Example 1, a black matrix, pixels, and an overcoat film were formed. Thereafter, a transparent electrode was formed by a sputtering method. The thickness of the transparent electrode was 130 nm, and the surface resistance was 22 Ω / □.

Next, a spacer material was obtained in the same manner as in Example 1 except that an Sb ₂ O ₅ methanol sol solution was used instead of the SiO ₂ methanol sol solution. A spacer was formed in the same manner as in Example 1 using a spacer material. The height of the spacer was 3.8 μm, and the area of the spacer per one display screen was 30 μm ² .

Through the same manufacturing steps as in Example 2, 100
When the liquid crystal display devices were manufactured, a liquid crystal display device having no particular problem could be obtained. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

Comparative Example 3 A spacer was obtained in the same manner as in Example 3 except that the SiO ₂ methanol sol solution was not added, and 100 liquid crystal display devices were manufactured through the same manufacturing steps as in Example 3. In 18 liquid crystal display devices, a decrease in display quality was observed. Analysis of the cause revealed that the spacer was crushed.

Example 4 (Production of color filter) A black matrix was produced in the same manner as in Example 1. However, at the same time as the black matrix pattern, a plurality of 20 μm square spacer patterns were formed around the screen by etching.

The polyimide precursor solution shown in Example 1 was added and mixed at a weight ratio of 1: 1 of a SiO ₂ methanol sol solution having a solid content of 30%. Next, a dianthraquinone pigment represented by Pigment Red 177, a phthalocyanine green pigment represented by Pigment Green 36, and a phthalocyanine blue pigment represented by Pigment Blue 15-4 were prepared as red, green, and blue pigments. The pigments were mixed and dispersed at a weight ratio of 6: 2 (polyimide precursor: pigment) to obtain three kinds of colored pastes of red, green and blue. Using this colored paste, a red pixel, a green pixel and a blue pixel are formed, and at the same time, a spacer is formed by laminating an image material on a 20 μm square spacer pattern on the screen black matrix and on the picture frame and around the screen. Was.

This resin black matrix and red pixel
A transparent conductive film was formed by a sputtering method on a substrate having a green pixel, a blue pixel, and a spacer to obtain a color filter. 1.2μm thickness of resin black matrix
Met. The height of the spacer was 4.3 μm, and the area of the spacer per display screen was 70 μm ² .
The spacer is a four-layer laminate including a black matrix layer, red pixels, green pixels, and blue pixels.

Through the same manufacturing steps as in Example 2, 100
When the liquid crystal display devices were manufactured, a liquid crystal display device having no particular problem could be obtained. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

Example 7 A black matrix, pixels and an overcoat film were formed in the same manner as in Example 1. Thereafter, a transparent electrode was formed by a sputtering method. The thickness of the transparent electrode was 130 nm, and the surface resistance was 22 Ω / □.

The N 2 -methyl-2-pyrrolidone solution of polyamic acid used for preparing the resin black matrix of Example 1 was added to 200 g of an N 2 -methyl-2-pyrrolidone solution having a solid concentration of 30% SiO ₂
200 g of a methanol sol solution was added to obtain a resin composition for a spacer. A spacer was formed using the spacer resin composition. The height of the spacer was 4.0 μm, and the area of the spacer per display screen portion was 35 μm ² .

Through the same manufacturing steps as in Example 2, 100
When the liquid crystal display devices were manufactured, a liquid crystal display device having no particular problem could be obtained. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

Example 8 In the same manner as in Example 1, a black matrix, pixels, and an overcoat film were formed. Thereafter, a transparent electrode was formed by a sputtering method. The thickness of the transparent electrode was 130 nm, and the surface resistance was 22 Ω / □.

4.5 g of acetylacetone was added to 5 g of Ti (OCH (CH ₃ ) ₂ ) ₄ to form titanium acetylacetonate, and then 0.5 g of pure water was added. this,
It was added to the NMP solution of the polyamic acid used to prepare the resin black matrix of Example 1 to obtain a resin composition for a spacer. Using the resin composition for a spacer, a spacer was formed in the same manner as in Example 7. However, the heating temperature after coating was set to 50 ° C. The height of the spacer was 4.5 μm, and the area of the spacer per display screen was 20 μm ² .

Through the same manufacturing steps as in Example 2, 100
When the liquid crystal display devices were manufactured, a liquid crystal display device having no particular problem could be obtained. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

Example 9 A black matrix, pixels, and an overcoat film were formed in the same manner as in Example 8. Thereafter, a transparent electrode was formed by a sputtering method. The thickness of the transparent electrode was 130 nm, and the surface resistance was 22 Ω / □.

Ti (OCH (CH ₃ ) ₂ ) ₄ and Ti
After coating with a spacer coating liquid in which O ₂ was dispersed, exposure and development were carried out. The height of the spacer was 4 μm, and the area per display screen was 50 μm ² . Through the same manufacturing process as in Example 2, 100 liquid crystal display devices were manufactured.
A liquid crystal display device having no particular problem was obtained. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

Example 10 A black matrix, pixels, and an overcoat film were formed in the same manner as in Example 1. Thereafter, a transparent electrode was formed by a sputtering method. The thickness of the transparent electrode was 130 nm, and the surface resistance was 22 Ω / □.

On this substrate, a photosensitive acrylic resin containing Ti
After coating with a spacer coating liquid in which O ₂ was dispersed, exposure and development were carried out. The height of the spacer was 4 μm, and the area per display screen was 50 μm ² . Through the same manufacturing process as in Example 2, 100 liquid crystal display devices were manufactured.
A liquid crystal display device having no particular problem was obtained. After confirming the display quality, the liquid crystal display device was disassembled and the spacer was observed under an optical microscope or the like, but no collapse of the spacer was confirmed.

[0123]

The spacer of the present invention is a spacer formed on a substrate for a liquid crystal display device. The spacer is formed by using a resin composition for a spacer containing ultrafine metal oxide particles and / or metal alkoxide. Therefore, the liquid crystal display device using the substrate for a liquid crystal display device having the spacer of the present invention realizes a sufficient cell gap, maintains a uniform cell gap in the screen, and applies an external force or When an impact is applied, the deterioration of display quality due to the collapse of the patterned spacer is less likely to occur than before. Further, the productivity of the liquid crystal display device can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic view of an example of a substrate for a liquid crystal display device using a patterned spacer of the present invention.

FIG. 2 is a schematic view of an example of a liquid crystal display device using a patterned spacer of the present invention.

FIG. 3 is a schematic diagram of a liquid crystal display device using a conventional bead-shaped spacer.

[Explanation of symbols]

 1, 1 ': blue pixel 2, 2': red pixel 3, 3 ': green pixel 4, 4': black matrix 5a, 5b, 5'a, 5'b: glass substrate 6a, 6b, 6'a, 6'b: Electrode layer 7, 7 ': Alignment film 8, 8': Sealant 9, 9 ': Thin film transistor 10, 10': Liquid crystal 11: Bead-shaped spacer 12: Patterned resin composition for spacer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G02F 1/1335 505 G02F 1/1335 505 F-term (Reference) 2H048 BA45 BA48 BB00 BB02 BB14 BB37 BB44 2H089 LA07 LA19 LA20 MA04X MA13X NA05 NA24 TA09 TA12 TA13 2H091 FA02Y FA35Y FB02 FB04 FC12 GA08 GA16 HA12 LA03 LA15 4J002 BB001 BG031 CD001 CD011 CD021 CD051 CD061 CF001 CK021 CM041 DE096 DE126 DE136 DE146 DE156 DJ016 EC076 EX036 EZ036 FD310 GP00 G00

Claims (18)

[Claims] 1. A resin composition for a spacer formed on a substrate for a liquid crystal display device, comprising a metal oxide ultrafine particle and / or a metal alkoxide. 2. The resin composition for a spacer according to claim 1, wherein the resin contains an acrylic resin. 3. The resin composition for a spacer according to claim 1, wherein the resin contains a polyimide resin. 4. The resin composition for a spacer according to claim 1, wherein the resin contains an epoxy resin. 5. The spacer resin composition according to claim 1, further comprising a coloring agent. 6. A substrate for a liquid crystal display device having a spacer formed using the resin composition for a spacer according to claim 1. 7. The substrate for a liquid crystal display device according to claim 6, wherein the spacer is formed inside and / or outside the screen. 8. The substrate for a liquid crystal display device according to claim 6, wherein the height of the spacer is 1 to 9 μm. 9. The substrate for a liquid crystal display device according to claim 6, wherein the spacer comprises a single resin layer. 10. The substrate for a liquid crystal display device according to claim 6, wherein the spacer is a laminate of resin layers. 11. The substrate for a liquid crystal display device according to claim 7, wherein an area of the spacer in the screen in contact with the opposing substrate is 10 to 1000 μm ² per unit. 12. The substrate for a liquid crystal display device according to claim 7, further comprising a color filter having patterned color pixels of at least three primary colors. 13. A color pixel, a black matrix and at least one of an overcoat film formed of a resin composition for a spacer containing ultrafine metal oxide particles and / or metal alkoxide, wherein the spacer has a color 13. The substrate for a liquid crystal display device according to claim 12, wherein the substrate is a laminate including at least one layer containing a resin composition for a spacer among pixels, a black matrix, and an overcoat. 14. A metal oxide ultrafine particle and / or a metal alkoxide is formed on a single layer or a laminate of two or more of the color pixels, the black matrix, and the overcoat film. 13. The substrate for a liquid crystal display device according to claim 12, which is formed using a resin composition for a spacer contained therein. 15. The substrate for a liquid crystal display device according to claim 7, wherein the black matrix is made of a resin in which a black pigment is dispersed. 16. The liquid crystal display substrate according to claim 7, wherein at least one of the resin components of the black matrix, the color pixels, and the overcoat contains a polyimide resin. 17. A liquid crystal display device in which a liquid crystal layer is sandwiched between two liquid crystal display device substrates, wherein at least one of the liquid crystal display device substrates has a resin composition for a spacer containing ultrafine metal oxide particles and / or metal alkoxides. A liquid crystal display device comprising a substrate for a liquid crystal display device having a spacer formed using an object. 18. The liquid crystal display device according to claim 17, wherein the liquid crystal is driven by a thin film transistor.