JP2001125113A - Method of forming spacer and liquid crystal device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of forming a spacer which has excellent functions as a spacer such as uniformity and strength and which is hardly damaged by rubbing or the like, and to provide a liquid crystal device having no display defects caused by defects of the spacer. SOLUTION: The method includes (1) a process of subjecting a photosensitive resin layer having 0.3 to 10 μm thickness to pattern exposure at 20 to 500 μm proximity in a deoxidized atmosphere, (2) a process of subjecting a photosensitive resin layer having 0.3 to 10 μm thickness and 0.3 to 0.8 optical density at the exposure wavelength to pattern exposure, (3) a process of subjecting a positive photosensitive resin layer to pattern exposure at 20 to 500 μm proximity, or (4) a process subjecting a photosensitive resin layer to pattern exposure and successively to development, then a process of post exposure with 10 mJ/cm2 to 2000 mJ/cm2 energy, and further a process of post baking at 150 to 250 deg.C for 5 to 120 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a spacer which is a member used for a liquid crystal element applied to a flat display or the like, and a liquid crystal display element obtained by applying the method.

[0002]

2. Description of the Related Art Liquid crystal devices which can be used for flat displays such as personal digital assistants, personal computers, word processors, amusement equipment, television sets, etc., display boards utilizing a shutter effect, windows, doors, walls, etc. In the "spacer", that is,
The "structural member housed in the liquid crystal cell sandwiched between the two substrates and in contact with the liquid crystal" maintains the space between the two substrates and maintains the uniformity of the liquid crystal display portion sandwiched between the substrates. Serve important functions. Conventionally, this spacer has generally been formed by scattering glass beads or the like between substrates.

Since the spacer is used in contact with the liquid crystal inside the liquid crystal cell, a rubbing treatment is performed with a cloth roller after an alignment film is formed on the surface (Polymer 48, September issue, issued by The Polymer Society of Japan). See page 707). During this rubbing treatment, the spacer is partially broken or chipped by friction with the cloth roller, the spacer is peeled off and falls off, the spacer is easily damaged, and the display quality is lowered, A spacer having high rubbing resistance is desired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above problems, and an object of the present invention is to provide a spacer having excellent functions as a spacer such as uniformity and strength.
An object of the present invention is to provide a method for forming a spacer which is hardly damaged by rubbing or the like and a liquid crystal element free from display defects caused by a defect of the spacer.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventor has revealed that a resin layer composed of a photosensitive composition is exposed to light under specific conditions,
It has been found that by performing development, a spacer having excellent properties and hardly damaged by the rubbing treatment can be formed, and the present invention has been completed. That is, in the method of forming a spacer according to the present invention, the photosensitive resin layer having a thickness of 0.3 to 10 μm is placed in a deoxygenated atmosphere at a proximity of 20 to 500 μm.
A pattern exposure step. In the method for forming a spacer according to the present invention according to claim 2, the method for forming the spacer has a thickness of 0.1 mm.
3 to 10 μm, and the optical density at the exposure wavelength is 0.
It is characterized by including a step of pattern-exposing the photosensitive resin layer of 3 to 0.8.

[0006] According to a third aspect of the present invention, there is provided a method of forming a spacer.
The positive type photosensitive resin layer is provided with a proximity of 20 μm to 5 μm.
It is characterized by including a step of pattern exposure at 00 μm. Further, the method for forming a spacer according to claim 4 is as follows.
The photosensitive resin layer to pattern exposure, a step of subsequently developing, then, and performing post-exposure of ^{10mJ / cm 2 ~2000mJ / cm 2} , further temperature 0.99 ° C. to 25
Performing a post-bake treatment at 0 ° C. for 5 minutes to 120 minutes. According to a fifth aspect of the present invention, there is provided a liquid crystal element including a spacer obtained on the substrate by the above method for forming a spacer.

In the method of the present invention, since the spacer itself is formed of a photosensitive resin and the photosensitive resin layer is formed in close contact with the substrate, the spacer itself has excellent strength and adhesion to the substrate. It is possible to adjust the cross-sectional inclination angle and the like by controlling the exposure to the photosensitive resin layer and the post-treatment conditions as described above, in which the friction and the like during the rubbing treatment hardly cause damage or peeling. , Spacers of any shape can be formed,
The alignment of the liquid crystal is stabilized due to the reduction of the cell gap variation and other reasons, and the display quality of the finally obtained liquid crystal display element is improved.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The spacer is formed by first forming a photosensitive resin layer on the substrate on which the spacer is to be formed, exposing it to solubilize or harden the light-irradiated portion, removing unnecessary portions by development, and removing the spacer. Is formed. In the present invention, the photosensitive resin layer is a layer having a function of causing a chemical change such as photopolymerization or photoacid generation in a portion irradiated with light. Usually, it contains a compound that undergoes a chemical change by light and a binder resin for forming a layer, but a compound having a function of polymerizing and curing the binder resin itself by light is also used.

The photosensitive resin layer of the present invention includes, for example, a photosensitive resin layer comprising a negative type diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition comprising an azide compound and a binder, And cinnamic acid type photosensitive resin compositions. Among them, particularly preferred is a layer composed of a photosensitive resin containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. Known materials for the photosensitive resin layer of the present invention are disclosed in, for example, JP-A-3-28.
All photosensitive resins described in JP-A-2404 can be used.

As the photosensitive resin, those which can be developed with an aqueous alkali solution and those which can be developed with an organic solvent are known, but those which can be developed with an aqueous alkali solution from the viewpoint of preventing pollution and ensuring labor safety. preferable. As the photosensitive resin layer of the present invention, "polymerizable compound B", "polymerization initiator C", etc. described in JP-A-11-133600 can also be used. Further, various additives can be used in combination in the photosensitive resin layer, and the “surfactant” described in the above-mentioned publication is used.
"Adhesion aids" and other additives can be applied. Further, dyes, pigments, ultraviolet absorbers and the like used for the purpose of adjusting the optical density of the photosensitive resin layer described in detail in the second embodiment can also be added.

In the method of forming a spacer according to the present invention,
If the thickness of the photosensitive resin layer is too large, the rubbing resistance is reduced. If the thickness is too small, the spacer effect, the orientation control effect, and the like are reduced. For this reason, the thickness of the photosensitive resin layer is preferably 0.3 to 10 μm, more preferably 0.7 to 7 μm,
Most preferably, it is 0.8 to 6 μm.

In the method of forming a spacer according to the first aspect of the present invention, when exposing the photosensitive resin layer, it is necessary to perform the exposure in a deoxygenated atmosphere. In the present invention, the term "under a deoxygenated atmosphere" refers to a state in which the supply of oxygen gas to the photosensitive resin layer is restricted, and the means for realizing the method include a method of removing oxygen from the atmosphere and a method of removing oxygen from the atmosphere to the photosensitive resin layer. There are ways to limit diffusion. The method of removing oxygen from the atmosphere is realized by putting a substrate to be exposed into an inert gas (nitrogen, argon, helium, carbon dioxide) or a vacuum and performing exposure under the atmosphere. You. The oxygen concentration is preferably 1/5 to 1/100000 of the standard atmosphere,
It is more preferably 1/10 to 1 / 10,000, and most preferably 1/100 to 1/5000.

Further, a method of limiting diffusion of oxygen from the atmosphere to the photosensitive resin layer is realized by forming an oxygen blocking film adjacent to the photosensitive resin layer. In this case, the atmosphere for exposure may be a standard atmosphere. The acid blocking membrane is usually
The photosensitive resin layer is formed on the side opposite to the substrate, that is, on the side exposed to the atmosphere. Another functional layer may be provided between the oxygen barrier film and the photosensitive resin layer. Further, the oxygen barrier film may be located on the substrate side with respect to the photosensitive resin layer.
As a method of performing exposure under a deoxygenated atmosphere, an oxygen blocking film is used because a uniform shape can be obtained, and the atmosphere during exposure can be arbitrarily selected and a closed region is not required. The method is preferred. The oxygen barrier film may be formed of a material having low oxygen permeability. Among them, a method using an oxygen barrier film containing PVA (polyvinyl alcohol) is preferable from the viewpoint that oxygen permeability is extremely low. The method of laminating a film on which a photosensitive resin layer and a photosensitive resin layer are integrated with a substrate is most preferable.

The oxygen barrier film of the present invention preferably has a low oxygen permeability and is preferably dispersed or dissolved in water or an aqueous alkaline 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, and carboxyalkyl starch described in JP-A-46-2121 and JP-B-56-40824. Water-soluble salts, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and their analogs consisting of starch Salts, styrene / maleic acid copolymers, and maleate resins.

Of these, a combination of polyvinyl alcohol and polyvinylpyrrolidone 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 oxygen barrier film. If the amount is less than 1% by weight, sufficient adhesion with the photosensitive resin layer cannot be obtained. If the amount exceeds 75% by weight, the oxygen barrier film is dissolved when the photosensitive resin layer coating solution is applied thereon. The oxygen barrier film cannot be formed. The thickness of the oxygen barrier film is very thin, about 0.1-5 μm, especially 0.5-2 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 for development or removal of the oxygen barrier film.

Next, a method of laminating and using an integrated film in which an oxygen barrier film and a photosensitive resin layer are integrated will be described. In order to obtain such an integrated laminate film, a thermoplastic resin layer and a photosensitive resin layer for forming an oxygen barrier film are sequentially formed on a temporary support, and then the temporary support is peeled off. Can be used. The temporary support of the integrated film according to the present invention should be chemically and thermally stable and should be composed of a flexible material, specifically, polyethylene terephthalate,
A thin sheet of polycarbonate, polyethylene, polypropylene or the like or a laminate thereof is preferred. The thickness of the temporary support is suitably 5 to 300 μm, preferably 2 to 300 μm.
0 to 150 μm.

For the purpose of improving the adhesion to the thermoplastic resin layer, these sheets are subjected to glow discharge treatment, corona treatment,
Surface treatment such as ultraviolet irradiation treatment, undercoat treatment of polyvinylidene chloride resin, styrene butadiene rubber, gelatin, etc., addition of phenolic substances such as cresol novolak resin and resorcin in the thermoplastic resin layer, and furthermore, these treatments Combined processing can be performed. When the thermoplastic resin layer is alkali-soluble, among these, a polyethylene terephthalate film coated with gelatin is preferred because of excellent adhesion, and a polyethylene terephthalate film coated with gelatin after corona treatment is more excellent. It is more preferable because it gives close contact. In this case, the preferred thickness of the gelatin layer is 0.01 μm to 2 μm.

Next, a thermoplastic resin layer is formed. As the organic polymer substance used as the thermoplastic resin layer, the Vicat method (specifically, American Material Testing Method: A
It is preferable that the softening point is selected from organic polymer substances having a softening point of about 80 ° C. or lower by STM D1235. The reason for this is that by using a polymer with a low softening point, when transferring an integrated film onto an uneven substrate with heat and pressure, the unevenness of the base is completely absorbed and the film is transferred without any residual air bubbles. This is because it becomes possible. When a polymer having a high softening point is used, it is necessary to transfer at a high temperature, which is disadvantageous in actual work. From such a point, the organic polymer substance used in the thermoplastic resin layer has a softening point by Vicat method of about 80 ° C. or lower, preferably about 60 ° C. or lower, particularly preferably about 50 ° C. or lower. Polyolefins having a softening point of about 80 ° C. or less include polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylate esters or saponified products thereof, polyvinyl chloride, and chlorides. Vinyl chloride copolymer such as vinyl and vinyl acetate and its saponified product, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylate or its saponified product, polyvinyl Toluene, vinyltoluene copolymers such as vinyltoluene and (meth) acrylates or saponified products thereof, poly (meth) acrylates, and (meth) acrylates such as butyl (meth) acrylate and vinyl acetate Polymer,
It is preferable to select at least one from organic polymers such as vinyl acetate copolymer nylon, copolymerized nylon, polyamide resin such as N-alkoxymethylated nylon and N-dimethylaminoated nylon. (Edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, 1968)
An organic polymer having a softening point of about 80 ° C. or lower (October 25, 2005) can be used.

It is also possible to add various plasticizers compatible with the high-molecular substance to these organic high-molecular substances to lower the substantial softening point. By adding various plasticizers compatible with the polymer material to the organic polymer material, the substantial softening point can be reduced to 80 ° C. or less.

The solubility characteristics of these organic polymer substances may be made to sufficiently match the solubility characteristics of the photosensitive resin layer, or may have a solubility characteristic soluble in a solvent in which the photosensitive resin layer is not completely dissolved. . In addition, in order to control the adhesive force with the temporary support in these organic polymer substances, various polymers, supercooled substances, adhesion improvers or surfactants are used as long as the substantial softening point does not exceed 80 ° C. It is possible to add a release agent.

The thickness of the thermoplastic resin layer is preferably at least 6 μm. The reason for this is that the thickness of the thermoplastic resin layer is 5 μm.
This is because if it is less than m, it is impossible to completely absorb irregularities of the underlayer of 1 μm or more. The upper limit is preferably 100 μm or less, more preferably about 50 μm or less.

As the alkali-soluble thermoplastic resin to be laminated, one soluble in an alkaline aqueous solution is appropriately selected from those having a softening point of about 80 ° C. or less. The alkaline aqueous solution in this case may be the same as or different from the alkaline developer of the integrated film of the present invention. Here, the alkaline aqueous solution mainly refers to an aqueous solution of an alkaline substance, but also includes a solution to which a small amount of an organic solvent miscible with water is added. Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate,
Potassium carbonate), alkali metal bicarbonates (sodium hydrogen carbonate, potassium hydrogen carbonate), alkali metal silicates (sodium silicate, potassium silicate), alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanol Amines, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is from 0.01% by weight to 30% by weight.
% By weight, and the pH is preferably from 8 to 14. Suitable water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. The concentration of the water-miscible organic solvent is 0.1% to 30% by weight. Further, a known surfactant can be added. The concentration of the surfactant is preferably 0.01% by weight to 10% by weight.

Examples of the resin soluble in the aqueous alkali solution include known polymer binders used for the alkali-soluble photopolymerizable resin. Copolymers of (meth) acrylic acid and alkyl (meth) acrylate (alkyl groups such as methyl group, ethyl group, butyl group, etc.), poly (meth) acrylic acid, styrene and maleic anhydride, etc. Examples include copolymers with saturated dibasic acid anhydrides, reactants of the polymers with alcohols, and reactants of cellulose with polybasic acid anhydrides. Among the above-mentioned polymers, those preferably used in the present invention include styrene / maleic anhydride copolymer, and methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / methacrylic described in JP-A-60-258439. Benzyl terpolymer, styrene / maleic acid mono-n-butyl ester copolymer described in JP-B-55-38961,
Quaternary copolymer of styrene / methyl methacrylate / ethyl acrylate / methacrylic acid described in JP-B-54-25957; benzyl methacrylate / methacrylic acid copolymer described in JP-A-52-99810; Tokunosho 5
8-123577 terpolymer of acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid and terpolymer of methyl methacrylate / ethyl acrylate / acrylic acid described in JP-B-55-6210. And styrene / maleic anhydride copolymer partially esterified with a polymer and isopropanol.

[0024] The alkali-soluble thermoplastic resin needs to exhibit releasability from the oxygen-blocking film. For this reason, it is preferable to add a release agent to the alkali-soluble thermoplastic resin. Silicone compounds and fluorinated alkyl group-containing compounds are known as release agents, and any of them can be advantageously used. Particularly preferred specific examples include silicone compounds such as Evecryl 1360 and 35 manufactured by Daicel UCB Co., Ltd.
0, Toshiba Silicone Co., Ltd. dimethyl silicone oil TSF400, methyl phenyl silicone oil TS
F4300, silicone polyether copolymer TSF4
445, TSF4446, TSF4460, TSF44
52. Examples of the fluorinated alkyl group-containing compound include a fluorine-based surfactant and a fluorine-based graft polymer. Specific examples of the fluorine-based surfactant include Dainippon Ink and Chemicals, Inc.
Perfluoroalkyl group / hydrophilic group-containing oligomer F-171, perfluoroalkyl group / lipophilic group-containing oligomer F-173, perfluoroalkyl group / hydrophilic group / lipophilic group-containing oligomer F-177, perfluoro Urethanes containing alkyl group / lipophilic group F-183, F-1
84, and examples of the fluorine-based graft polymer include Aaron GF-300 and GF-150 manufactured by Toa Gosei Chemical Co., Ltd.

In the integrated film according to the present invention, a thermoplastic resin layer solution is provided on a temporary support and dried to form a thermoplastic resin layer, and thereafter, the thermoplastic resin layer is not dissolved on the thermoplastic resin layer. A solution of a material for an oxygen barrier film composed of a solvent is applied and dried, and then the photosensitive resin layer is applied and dried using a solvent that does not dissolve the oxygen barrier film. Alternatively, a photosensitive resin layer is provided on another cover sheet, and both sheets of the thermoplastic resin layer and the sheet having the oxygen barrier film on the temporary support are so contacted that the oxygen barrier film and the photosensitive resin layer are in contact with each other. Attached to each other, or as a separate covering sheet, prepare a temporary support having a thermoplastic resin layer, this thermoplastic resin layer, the photosensitive resin layer on the covering sheet and the sheet comprising the oxygen barrier film It is advantageously manufactured by bonding with an oxygen barrier film.

Instead of the temporary support provided with the thermoplastic resin layer by coating, a two-layer or multilayer sheet in which a thermoplastic resin sheet and a temporary support sheet are adhered may be used. As the thermoplastic resin sheet, the above-mentioned materials for the thermoplastic resin layer can be used, and among them, polyethylene film and polypropylene film are particularly preferable. As a method of providing a polyethylene film or a polypropylene film on the temporary support, an adhesive layer is applied by applying a solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane, natural rubber, synthetic rubber, etc. on the temporary support. A method of laminating a polyethylene film or a polypropylene film thereon under pressure and heat, an ethylene / vinyl acetate copolymer, an ethylene / acrylate copolymer, a polyamide resin, a petroleum resin, a rosin,
A method of laminating a polyethylene film or a polypropylene film immediately after applying an adhesive made of a mixture of waxes on a temporary support by heating and melting the same, making the polyethylene or polypropylene a molten state, and extruding the film by an extruder, A method of laminating the temporary support by pressing it in a molten state may be used.

Here, if the temporary support is to be peeled off after the photosensitive resin layer of the integrated film is brought into close contact with the permanent support, the film and the human body may be charged and an unpleasant electric shock may occur. In addition, due to the charging, dust may be attracted from the surroundings and an unexposed portion may be formed in a subsequent exposure process, which may cause a pinhole. In the integrated film of the present invention, in order to prevent electrification, a conductive layer is provided on at least one surface of the temporary support to reduce the surface electric resistance by one.
0 ¹³ Omega follows the one, or it is preferable to use a material obtained by the surface electrical resistance less than 10 ¹³ Omega temporary support itself to impart conductivity.

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 metal oxides, zinc oxide, titanium oxide,
At least one crystalline metal oxide selected from tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide;
And / or fine particles of the composite oxide thereof. Examples of the antistatic agent include alkyl phosphates as anionic surfactants (for example, Electrostripper A of Kao Soap Co., Ltd., Eleanon No. 19 of Daiichi Kogyo Seiyaku Co., Ltd.) and betaine as an amphoteric surfactant. For example, Amogen K of Daiichi Kogyo Seiyaku Co., Ltd.) and polyoxyethylene fatty acid ester (for example, Nitsusan Nonion L of Nippon Oil & Fats Co., Ltd.) and polyoxyethylene alkyl as nonionic surfactants Ether type (for example, Emulgen 106, 120, 147, 420 of Kao Soap Co., Ltd.)
220, 905, 910, Nitsan Nonion E of Nippon Yushi Co., Ltd., etc.) 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, and in particular, ZnO, TiO.
₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO,
A method of containing at least one type of crystalline metal oxide selected from BaO and MoO ₃ and / or fine particles of a composite oxide thereof is preferable because it exhibits conductivity that is not affected by humidity. The fine particles of the crystalline metal oxide or the composite oxide thereof preferably have a volume resistance of 10 ⁷ Ω · cm or less, particularly preferably 10 ⁵ Ω · cm or less. In addition, the particle size is 0.01-0.7μ
m, 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 described in JP-A-56-14.
No. 3430, which is briefly described below. First, a method in which metal oxide fine particles are produced by firing and heat treatment is performed in the presence of a heteroatom for improving conductivity, and secondly, firing is performed. A method of coexisting heterogeneous atoms for improving conductivity when producing metal oxide fine particles, and thirdly, reducing oxygen concentration in the atmosphere when producing metal oxide fine particles by firing to reduce oxygen defects. It is a method to introduce. As an example including a hetero atom, A
l, In, etc. For TiO ₂ , Nb, Ta, etc., SnO ₂
, Sb, Nb, halogen elements and the like. 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 is 0.05g / m ² ~20g / m ^{2 selfishness, 0.1g / m 2 ~10g / m} 2 is particularly preferred.

In the conductive layer according to the present invention, as a binder, cellulose ester such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinylidene chloride, chloride, etc. Homopolymers or copolymers containing vinyl, styrene, acrylonitrile, vinyl acetate, alkyl (alkyl group having 1 to 4 carbon atoms) acrylate, vinylpyrrolidone, or the like, copolymers, soluble polyesters, polycarbonates, soluble polyamides, and the like can be used. When the conductive particles are dispersed in these binders, a dispersion such as a titanium-based dispersant or a silane-based dispersant may be added. Even if a binder crosslinking agent or the like is added, there is no problem. Examples of the titanium-based dispersant include titanate-based coupling agents described in U.S. Pat. Nos. 4,069,192 and 4,080,353, and Prenact (trade name: manufactured by Ajinomoto Co., Inc.). Can do things. Examples of the silane-based dispersant include vinyl trichlorosilane, vinyl triethoxy silane, vinyl tris (β
-Methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like are known, and are commercially available from Shin-Etsu Chemical Co., Ltd. as “silane coupling agents”. As the binder crosslinking agent, for example, an epoxy-based crosslinking agent,
Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, and an epoxy-based crosslinking agent. The preferred conductive layer in the present invention may be provided by dispersing conductive fine particles in a binder and providing the support on a support, or applying a subbing treatment to the support, and applying the conductive fine particles thereon. it can.

In the present invention, when the conductive layer is provided on the surface of the support opposite to the photosensitive resin layer, a hydrophobic layer is further formed on the conductive layer in order to improve the scratch resistance. It is preferable to provide a polymer layer. In this case, the hydrophobic polymer layer may be applied in the form of a solution dissolved in an organic solvent or an aqueous latex, and the coating amount is 0.0
5g / m ² ~1g / m ² about is good. Examples of the hydrophobic polymer include cellulose esters (eg, nitrocellulose, cellulose acetate), vinyl chloride, vinylidene chloride,
Examples include vinyl-based polymers containing vinyl acrylate and the like, and polymers such as polyamides and polyesters soluble in organic solvents. In this layer, a slipping agent for imparting a sliding property, for example, an organic carboxylic acid amide as described in JP-A-55-79435 may be used, or a matting agent may be added. No problem at all. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer of the present invention is not substantially affected. When an undercoat layer is provided, JP-A-51-135526, U.S. Pat.
143,421, 3,586,508, 2,6
98,235, 3,567,452, etc .; vinylidene chloride-based copolymers;
No. 114120, diolefin copolymers such as butadiene as described in U.S. Pat. No. 3,615,556, and glycidyl acrylate or glycidyl methacrylate as described in JP-A-51-58469. It is possible to use a copolymer, a polyamide / epichlorohydrin resin described in JP-A-48-24923, a maleic anhydride-containing copolymer described in JP-A-50-39536, or the like. it can.
In the present invention, JP-A No. 56-82504,
JP-A-56-143443, JP-A-57-10493
No. 1, JP-A-57-118242, JP-A-58-62
647 and JP-A-60-258541 can be used as appropriate.

When the conductive layer is contained in the same or different plastic raw material as the temporary support film and is simultaneously co-extruded when the temporary support film is extruded, the conductive layer has excellent adhesion and scratch resistance. Since the layer can be easily obtained, in this case, it is not necessary to provide the hydrophobic polymer layer or the undercoat layer, which is a particularly preferred embodiment of the conductive layer in the present invention. When applying the conductive layer, a usual method such as a roller coat, an air knife coat, a gravure coat, a bar coat, a curtain coat and the like can be adopted.

In order to prevent electrostatic shock due to charging by using the image forming material of the present invention, the conductive layer or the support provided with conductivity should have a surface electric resistance of 10 ¹³ Ω or less. It is necessary, and it is more preferable to set the resistance to 10 ¹² Ω or less. In order to improve the slipperiness or to prevent the photosensitive resin layer from inadvertently adhering to the backside of the temporary support, the backside of the temporary support contains a known fine particle-containing slippery composition or a silicone compound. It is also useful to apply a release agent composition or the like.

When a conductive layer is provided on the side of the temporary support on which the thermoplastic resin layer is not provided, the temporary support may be provided with a glow, for example, to increase the adhesive strength between the thermoplastic resin layer and the support. Performs surface treatment such as discharge treatment, corona treatment, and ultraviolet irradiation treatment, adds phenolic substances such as cresol novolak resin and resorcin to the thermoplastic resin layer, and adds polyvinylidene chloride resin and styrene butadiene rubber to the temporary support. And undercoating of gelatin or the like, or a combination of these treatments. In the case where the thermoplastic resin is alkali-soluble, among these, a polyethylene terephthalate film subbed with gelatin after corona treatment is particularly preferred because it gives particularly excellent adhesion. In this case, the preferred thickness of the gelatin layer is 0.01 μm to 2 μm.

In the method of the present invention, the photosensitive resin layer is subjected to pattern exposure to form a spacer. Here, the pattern exposure means irradiating the photosensitive resin layer with patterned light through a shadow mask in which an image pattern is formed in advance in consideration of the shape, interval, surface area, etc. of a spacer to be formed. In the case of this embodiment, the photosensitive resin layer at the irradiated portion is cured to form a spacer portion. The distance between the image pattern portion of the shadow mask and the photosensitive resin layer is called proximity. In the present invention, by adjusting the proximity, the cross-sectional shape of the obtained spacer can be controlled as specifically described in the examples described later. If the proximity is too small, the rubbing resistance decreases. If the proximity is too large, a long developing time is required to form an image around the pixel into a sufficient shape, and in that case, the rubbing resistance also decreases. Proximity is preferably 20-500μ, more preferably 50-300μ, most preferably 100-250μ. The rubbing resistance of the spacer of the present invention depends on the exposure amount of the pattern exposure.

The exposure characteristics of the photosensitive resin layer vary depending on the composition of the photopolymerization initiation system, the optical density of the photosensitive resin layer, the reflectance of the photosensitive resin layer and the substrate, and the development process conditions. Is described as a relative value (magnification) of the 厚 thickness exposure amount as follows. In the present invention, “１ ／ thick exposure amount” is defined as “exposure amount in which the thickness after development is half the thickness before development under the development condition of 1.5 times the shortest development time”.
The magnification of the pattern exposure to the １ ／ thickness exposure is
Preferably 3 to 100 times, more preferably 6 to 50 times,
Most preferably, it is 8 to 30 times. The rubbing resistance of the spacer is also affected by the optical density of the photosensitive resin layer. That is, if the optical density is too high, the inclination angle becomes too large, and 9
In some cases, the rubbing resistance may be lower than 0 degree, and if the optical density is too low, a long developing time is required. In this case, the rubbing resistance also tends to be lowered. The optical density of the photosensitive resin layer at the exposure wavelength is preferably 0.02 to 0.4, more preferably 0.1 to 0.4.
05-0.30, most preferably 0.06-0.2.
0.

Next, unnecessary portions which are not cured by the exposure of the photosensitive resin layer through the exposure process under the above-described conditions are removed by a development process to complete the spacer. The rubbing resistance of the spacer obtained by the method of the present invention also depends on the development process conditions described below. In the present invention, the "shortest development time" is "the shortest development time capable of removing all the unexposed photosensitive resin layer in the development of the photosensitive resin layer", and the "development ratio" is "the development time with respect to the shortest development time". Magnification ”. If the development magnification is too low, development is not sufficiently performed. Increasing the developing magnification tends to increase the tilt angle. If the developing magnification is too high, the damage to the pixels will increase, and the rubbing resistance will decrease. The development magnification is preferably 1.2 to 6 times,
More preferably 1.3 times to 5 times, most preferably 1.4 times.
2 to 3 times.

When a brush is used in combination with the development, the development time can be shortened and the damage caused by the development can be reduced. In the present invention, it is preferable to use a brush at the time of development. As described above, following the step of pattern exposure of the photosensitive resin layer having a thickness of 0.3 to 10 μm in a deoxygenated atmosphere at a proximity of 20 to 500 μm, a development step of performing development to remove unnecessary portions Are sequentially performed, the remaining cured photosensitive resin layer forms a spacer having a sufficiently controlled shape and size and excellent rubbing resistance.

A method for forming a spacer in the case where the oxygen barrier film and the photosensitive resin layer are formed of an integrated film will be described. First, if necessary, the cover sheet of the integral film is removed, and the photosensitive resin layer is bonded to the substrate under pressure and heat. Conventionally known laminators and vacuum laminators can be used for lamination, and an auto-cut laminator can be used to further increase productivity. Thereafter, after the temporary support and the thermoplastic resin layer are peeled off, exposure is performed through a predetermined mask and an oxygen blocking film, and then development is performed. The development is performed by immersing in a solvent or an aqueous developer, particularly an alkaline aqueous solution, or spraying the developer from a spray, and further rubbing with a brush or irradiating ultrasonic waves in a known manner as described above. This is done by processing.

Since the substrate forming the spacer is often used as it is as the substrate of the liquid crystal element, if a plate having good smoothness is used, the surface of the transferred integrated film is reduced. Since it adheres to the substrate, the substrate side surface of the finally formed pattern has the same smoothness as the substrate. If this pattern is further transferred to a final support, a pattern having excellent surface smoothness can be obtained.

Next, a second embodiment in which such a spacer can be formed will be described. Second forming spacer
Is characterized by including a step of pattern-exposing a photosensitive resin layer having a thickness of 0.3 to 10 μm and an optical density of 0.3 to 0.8 at an exposure wavelength. As described above, the rubbing resistance of the spacer depends to some extent on the optical density of the photosensitive resin layer.However, the present inventors have specified the thickness of the photosensitive resin layer and this optical density to be within a predetermined range. Have been found to achieve the object of the present invention. That is, if the optical density is too high, the tilt angle becomes too high, sometimes exceeding 90 degrees, and the rubbing resistance is reduced. If the optical density is too low, it is necessary to lengthen the development time for forming an image around the pixel into a sufficient shape, so that the rubbing resistance also decreases in this case. According to the study of the present inventors, in the second aspect of the present invention, the optical density of the photosensitive resin layer needs to be 0.3 to 0.8, and preferably is 0.1 to 0.8.
It is 4 to 0.7, most preferably 0.5 to 0.6. The optical density here is a value obtained by forming a photosensitive resin layer on a glass substrate and measuring the glass substrate as a control with a spectrophotometer. The optical density is measured by a photosensitive light wavelength (exposure light wavelength) used for exposing the photosensitive resin layer. In a general photopolymerization initiator system, a wavelength of 365 n
m. In the photosensitive resin layer of the present invention, an appropriate optical density can be obtained by adding a dye, a pigment, and an ultraviolet absorber described below, in addition to obtaining an optical density by light absorption of a photopolymerization initiator. In particular, in this second aspect of the invention,
It is necessary to increase the optical density of the photosensitive resin layer at the exposure wavelength to be higher than the optical density of the photopolymerization initiator. For this purpose, an appropriate optical density can be obtained by adding a dye, a pigment and an ultraviolet absorber described below. When the spacer of the present invention is used inside a pixel of a liquid crystal cell, one having no light absorption in a visible light region is desired, and an ultraviolet absorber is preferable. Among the ultraviolet absorbents, those having a vapor pressure (20 ° C.) of 10 ⁻⁶ pa or less are more preferable, and a vapor pressure (20 ° C.) of 10 ⁻⁹ pa
The following ultraviolet absorbers (eg, 2- [2-hydroxy-3,
5-bis (α, α-dimethylbenzyl) phenyl] -2
H-benzotriazole) is most preferred.

Also in this embodiment, in consideration of the rubbing resistance, the thickness of the photosensitive resin layer is preferably 0.3 to 10 μm, more preferably 0.1 μm, as in the first embodiment.
It is 7 to 7 μm, most preferably 0.8 to 6 μm. Similarly, proximity when performing pattern exposure is also preferably 20 to 500 μm, more preferably 50 to 500 μm.
300μ, most preferably 100-250μ. Further, regarding the pattern exposure amount, similarly, the pattern exposure amount is preferably 5 times to 200 times the half thickness exposure amount.
Times, more preferably 8 to 100 times the 1/2 thick exposure amount, and most preferably 10 to 50 times the 1/2 thick exposure amount. After such an exposing step, a developing step is performed to form a spacer. Even for the main body, the developing magnification is preferably 1.2 to 6 times, more preferably 1.5 to 5 times, and most preferably 1.5 to 5 times. Preferably it is 2 to 4 times. In the development step, it is preferable to use a brush because the development time can be shortened and damage due to development can be reduced.

The third method according to the method of forming a spacer of the present invention.
In the embodiment, the positive photosensitive resin layer is
This includes a step of performing pattern exposure at 0 μm to 500 μm. Unlike the above two embodiments, the present embodiment is characterized in that a positive photosensitive material is used for the photosensitive resin layer. In the positive photosensitive resin layer, the part irradiated with light undergoes a chemical change such as a change in solubility in a developing solution or a decrease in development resistance. It is a layer having the property of being removed. Examples of the positive photosensitive resin layer that can be used in the present invention include those using a novolak resin. Examples of novolak resins include naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenol-novolak resin (Sumitomo Bakelite, Sumiregin PR50235) (molecular weight approx.
1300). In the case of this example, ethanol is used for the development processing. Further, an alkali-soluble novolak resin system described in JP-A-7-43899 can be used. In this case, development processing with an alkali developing solution is possible. Also, a positive photosensitive resin layer described in JP-A-6-148888, that is, an alkali-soluble resin described in the publication, 1,2-naphthoquinonediazidesulfonic acid ester as a photosensitive agent and a thermosetting agent described in the publication. A photosensitive resin layer containing a mixture can be applied. further,
The composition described in JP-A-5-262850 is also applicable.

In this embodiment, pattern exposure is performed in the exposure step as in the first embodiment, but the proximity needs to be 20 to 500 μm, more preferably 50 to 300 μm, most preferably. 100-250μ
It is. Even in the case of a photosensitive resin layer using a positive type material, its thickness is preferably 0.3 to 10 μm, more preferably 0.7 to 7 μm, and most preferably 0.8 to 6 μm.
m. Even when a positive photosensitive resin layer is used, development processing is performed after the exposure processing step. In this case, the exposed portion is solubilized and removed by the development process. In the case of the present embodiment, the developing process conditions are examined in consideration of the rubbing resistance of the spacer. In the processing step, it is preferable to use a brush. Method of forming spacers according to the fourth aspect of the present invention, the photosensitive resin layer to pattern exposure, a step of subsequently developing, then, and performing post-exposure of ^{10mJ / cm 2 ~2000mJ / cm 2} , further Performing a post-baking treatment at a temperature of 150 ° C. to 250 ° C. for 5 minutes to 120 minutes.

The material of the photosensitive resin layer, the conditions for pattern exposure and the various conditions in the developing step in the fourth embodiment of the present invention are the same as those in the above embodiments. The photosensitive resin layer used in the fourth embodiment may be a positive type or a negative type. In the case of this embodiment, after the exposure step and the development step, 10 mJ / cm ^{2 to} 2000 m
A post-exposure step is performed under the condition of mJ / cm ² ,
Further, a post-baking process is performed at a temperature of 150 ° C. to 250 ° C. for 5 minutes to 120 minutes.

After pattern exposure and development of the photosensitive resin layer, the step of further irradiating light is called post exposure. Post exposure is performed after pattern exposure and development and before heat treatment. The rubbing resistance of the spacer of the present invention depends on the amount of post exposure. The effect is particularly great when the exposure amount is low. If the post-exposure amount is too large or too small, the rubbing resistance decreases. The post exposure amount is preferably 10 to
2000 mJ / cm ² , more preferably 30 to 500 mJ
/ Cm ² , most preferably 50 to 200 mJ / cm ² . After the post-exposure step, post-bake processing is performed.
The processing temperature is 150 ° C. to 250 ° C., and the processing time is 10 minutes to 200 minutes. The treatment atmosphere in the post-bake treatment step may be performed in air, but may be performed in a state filled with a gas such as nitrogen, argon, or carbon dioxide gas, or in a vacuum atmosphere.

Next, the details of the constitution of the photosensitive resin layer and the developing conditions common to these embodiments will be described. A dye, a pigment, and an ultraviolet absorber can be further added to the photosensitive resin layer. All pigments must be uniformly dispersed in the photosensitive resin layer and have a particle size of preferably 5 μm or less, particularly preferably 1 μm or less. Preferred UV absorbers include salicylates, benzophenones, benzotriazoles, cyanoacrylates, nickel chelates, hindered amines and the like. Phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate, 2,4- Di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-5 '
-Methylphenyl) benzotriazole, 2- (2'-
(Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenylacrylate, 2,2'-
Hydroxy-4-methoxybenzophenone, nickel dibutyl dithiocarbamate, bis (2,2,6,6-tetramethol-4-pyridine) -sebacate, 4-t-butylphenyl salicylate, phenyl salicylate, 4-
Hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl) -ester, 2- [2-hydroxy-3,5- Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazin-2-yl] amino} -3-phenylcoumarin.

Examples of preferred dyes and pigments are as follows. Victoria Pure Blue BO (CI.42
595), Auramine (CI.41000), Fat Black HB (CI. 26150), Monolight Yellow GT (CI. Pigment Yellow 12), Permanent Yellow GR (CI. Pigment. Yellow 1
7), permanent yellow HR (CI pigment yellow 83), permanent carmine FBB (C.I.
I. Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19),
Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fast Blue (CI Pigment Blue 15), Monolight
First Black B (CI Pigment Black 1) and carbon. Further, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I.
I. Pigment Red 149, C.I. I. Pigment
Red 168, C.I. I. Pigment Red 177,
C. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 21
5, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 1
5: 1, C.I. I. Pigment Blue 15: 4, C.I.
I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I.
I. Pigment Blue 64.

It is preferable to provide a thin covering sheet on the photosensitive resin layer in order to protect it from contamination and damage during storage. The cover sheet may be made of the same or similar material as the temporary support, but must be easily separated from the photosensitive resin layer. Suitable coating sheet materials are, for example, silicone paper, polyolefin or polytetrafluoroethylene sheets. The thickness of the covering sheet is about 5
Preferably it is あ る 100 μm. Particularly preferably 10
It is a polyethylene or polypropylene film having a thickness of ３０30 μm.

The alkali developing solution used for developing the photosensitive resin layer is mainly an aqueous solution of an alkaline substance, and includes an aqueous solution containing a small amount of an organic solvent miscible with water. Suitable alkaline materials include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate,
Potassium metal bicarbonate), alkali metal silicates (sodium silicate, potassium silicate), alkali metal metasilicates (sodium metasilicate, potassium metasilicate),
Triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01% by weight to 30% by weight, and the pH is preferably 8 to 14. Preferred organic solvents having miscibility with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol,
Acetone, methyl ethyl ketone, cyclohexanone, ε
-Caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone. The concentration of the water-miscible organic solvent is 0.1% to 30% by weight. Further, known surfactants can be added. The concentration of the surfactant is preferably 0.01% by weight to 10% by weight.

The developing solution can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photopolymerizable resin layer, a method such as rubbing with a rotating brush or a wet sponge in a developer can be combined. The temperature of the developer is usually preferably around room temperature to 40 ° C. It is also possible to insert a washing step after the development processing.

The spacer formed by the method of the present invention can be used in the MVA described in JP-A-7-159787.
It is also used for a display device that needs to have a specific distribution in the alignment of liquid crystal, such as a liquid crystal display device of a (Multi domain Vertical Alignment) mode.

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. All of the sample preparation processes described in this example were performed in the following environment. Cleanliness: room 1000 class, equipment part class 100 temperature and humidity: 23 ± 2 ° C. 50 ± 5% RH illumination: yellow light [Example 1] First Embodiment] Temporary support of 75 μm thick polyethylene terephthalate film (conductive fine particles on the side opposite to the coated surface (conductive material (9) described in paragraph [0046] of JP-A-5-173320)) 0.18μ
m having a conductivity of 50 m.
While conveying at a speed of m / min, the following formulation H was placed on the temporary support.
1 is applied with an extrusion-type greaser, and sequentially passed through a drying zone at a temperature of 50 ° C. to 120 ° C. to be dried. Then, a coating solution having the following formulation B1 is applied with an extrusion-type greaser. , Temperature 5
It is dried by sequentially passing through a drying zone at 0 ° C. to 120 ° C., and a photosensitive solution A which is a coating solution for a photosensitive resin layer described below.
Apply 1 to A8 with an extrusion type greaser,
Drying is performed by sequentially passing through a drying zone at a temperature of 50 ° C. to 120 ° C. A thermoplastic resin layer having a dry film thickness of 14.6 μm and an oxygen barrier film having a dry film thickness of 1.6 μm are formed on the temporary support. A photosensitive resin layer having a thickness of 1.1 μm was provided, and a covering sheet (trade name: Alphan E-501, Oji Paper, thickness 12
μm polypropylene film) was pressed with a nip roller, and then wound up. In this manner, a film in which the temporary support, the thermoplastic resin layer, the oxygen barrier film, and the photosensitive resin layer were integrated was prepared, and the respective sample names were integrated using the symbols A1 to A8 of the used photosensitive solution. Film A1
A8.

Thermoplastic resin layer formulation H1: 290.0 parts by weight of vinyl chloride / vinyl acetate copolymer (weight ratio: PVC / vinyl acetate = 75/25, degree of polymerization: about 400, MPR manufactured by Nissin Chemical Co., Ltd.) -TSL) 76.0 parts by weight of vinyl chloride-vinyl acetate-maleic acid copolymer (weight ratio: vinyl chloride / vinyl acetate / maleic acid = 86/13/1, degree of polymerization: about 400, manufactured by Nissin Chemical Co., Ltd.) MPR-TM) 88.5 parts by weight of dibutyl phthalate Fluorinated surfactant (F-177P manufactured by Dainippon Ink and Chemicals, Inc.) 5.4 parts by weight MEK 975.0 parts by weight

Oxygen barrier film formulation B1: 173.2 parts by weight of polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 8 parts by weight of fluorinated surfactant 2800 parts by weight of distilled water

Preparation of Photosensitive Solution A1 (Raw Material 1) Cyclohexanone 205 parts by weight (Raw Material 2) Polymer Solution 95 parts by weight Styrene / maleic acid copolymer benzylamine modified product / methacryloyloxyethyldiphenyl phosphate = 40/32 / MEK solution containing 28 (molar ratio) 36% by weight (Raw material 3) 34 parts by weight of dipentaerythritol hexaacrylate (Raw material 4) 0.009 parts by weight of phenidone (Raw material 5) 360 parts by weight of methyl ethyl ketone (Raw material 7) Surfactant 0.33 parts by weight poly- (N-propylperfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) copolymerization ratio 40:60 (molar ratio) (raw material 8) 2,4-diethylthioxanthone ( CAS82799-44-8) 0.3 parts by weight Material 9) a photopolymerization initiator IRG907 (CAS7-868-10-5) 1.2 parts by weight

Preparation of Photosensitive Solution A2 (Raw Material 1) Cyclohexanone 205 parts by weight (Raw Material 2) Polymer Solution 95 parts by weight Styrene / maleic acid copolymer benzylamine modified product / methacryloyloxyethyldiphenyl phosphate = 40/44/28 (Mole ratio) MEK solution containing 36% by weight (Raw material 3) 51 parts by weight of dipentaerythritol hexaacrylate (Raw material 4) 0.012 parts by weight of phenidone (Raw material 5) 360 parts by weight of methyl ethyl ketone (Raw material 7) Activator 0. 33 parts by weight Poly- (N-propylperfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) Copolymerization ratio 40:60 (Molar ratio) (Raw material 8) Photopolymerization initiator IRG819 (CAS162881-26) -7) 1.2 parts by weight

Preparation of Photosensitive Solution A3 (Raw Material 1) Cyclohexanone 205 parts by weight (Raw Material 2) Polymer solution 95 parts by weight Styrene / maleic acid copolymer benzylamine modified product = 68/32 (molar ratio) 30% by weight MEK solution (raw material 3) 51 parts by weight of dipentaerythritol hexaacrylate (raw material 4) 0.012 parts by weight of phenidone (raw material 5) 360 parts by weight of methyl ethyl ketone (raw material 7) 0.33 parts by weight of surfactant poly- (N- Propyl perfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) Copolymerization ratio 40:60 (molar ratio) (Raw material 8) Photopolymerization initiator IRG651 (CAS24650-42-8) 2.1 parts by weight

Preparation of Photosensitive Solution A4 (Raw material 1) Malachite green 9 parts by weight (Raw material 2) Methanol 950 parts by weight (Raw material 3) Methyl ethyl ketone 685 parts by weight (Raw material 4) Polymer solution 585 parts by weight Styrene / maleic acid copolymer Benzylamine-modified = 68/32 (molar ratio) 43% by weight of cyclohexanone solution (raw material 5) 195 parts by weight of dipentaerythritol hexaacrylate (raw material 6) 730 parts by weight of cyclohexanone (raw material 7) 0.11 weight of surfactant Part poly- (N-propylperfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) copolymerization ratio 40:60 (molar ratio) (raw material 8) photopolymerization initiator IRG184 (CAS947-19-3) ) 9.0 parts by weight

Preparation of Photosensitive Solution A5 (Raw Material 1) 2,2-Dimethoxy-1,2-diphenylethan-1-one 2.15 parts by weight (Raw Material 2) Phenidone 0.0056 parts by weight (Raw Material 3) Cyclohexanone 67 0.4 parts by weight (Raw material 4) 50 parts by weight of methyl ethyl ketone (MEK) (Raw material 5) 9.03 parts by weight of dipentaerythritol hexaacrylate (Raw material 6) 6.77 parts by weight of R-712 4,4'-methylenebis (acryloyloxy) (Ethyl polyoxy ethylene phenyl ether) (Raw material 7) M-315 6.77 parts by weight Tris (acryloxyethyl) isocyanurate (Raw material 8) Polymer solution 50 parts by weight Styrene / maleic acid copolymer benzylamine modified product / methacryloyl Oxyethyldiphenyl phosphate = 40/32/28 (mol MEK solution) containing 36 wt%

Preparation of Photosensitive Solution A6 (Raw Material 1) 268 parts by weight of 1-methoxy-2-propyl acetate (Raw Material 2) 126 parts by weight of polymer solution Poly- (benzyl methacrylate) -co- (methacrylic acid) Copolymerization ratio 72 1-Methoxy-2-propyl acetate solution containing 27% by weight to 28 parts (molar ratio) (raw material 3) Monomer solution 45 parts by weight 1-methoxy-2-propyl acetate solution containing 76% by weight of dipentaerythritol hexaacrylate (Raw material 4) Methyl ethyl ketone 503 parts by weight (Raw material 5) Surfactant 0.33 parts by weight Poly- (N-propylperfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) Copolymerization ratio 40:60 (Mole ratio) (Raw material 6) Light Initiator 1.1 parts by weight 2,4-bis (trichloromethyl) -6- [4- (N, N'- di-ethoxycarbonylmethyl) -3-bromophenyl] -5-triazine

Raw material 1 was placed in a tank whose temperature was adjusted to 25 ± 1 ° C.
Raw materials 3 were charged in this order and stirred for 5 minutes. Then, Raw materials 4 to 6 were sequentially charged and further stirred for 30 minutes to obtain a photosensitive resin layer coating liquid.

Preparation of Photosensitive Solution A7 (Raw Material 1) 1-methoxy-2-propyl acetate 268 parts by weight (Raw Material 2) Polymer solution 126 parts by weight Poly- (benzyl methacrylate) -co- (methacrylic acid) Copolymerization ratio 72 1-methoxy-2-propyl acetate solution containing 27% by weight to 28 parts (molar ratio) (raw material 3) Monomer solution 7 45 parts by weight A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (average number of functional groups: 5 .1) -methoxy-2-propyl acetate solution containing 76% by weight (raw material 4) 185 parts by weight of cyclohexanone (raw material 5) 348 parts by weight of methyl ethyl ketone (raw material 6) 24 parts by weight of a dye solution 5 parts by weight of Victoria Pure Blue Containing methanol solution (raw material 7) surface activity 0.33 parts by weight Poly- (N-propylperfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) Copolymerization ratio 40:60 (molar ratio) (Raw material 8) Phenothiazine 0.053 parts by weight (Raw material 9) Photopolymerization initiator 1.1 parts by weight 2,4-bis (trichloromethyl) -6- [4- (N, N'-diethoxycarbonylmethyl) -3-bromophenyl] -5-triazine

Preparation of Photosensitive Solution A8 (Raw Material 1) Polymer 97 parts by weight Poly- (benzyl methacrylate) -co- (methacrylic acid) (Raw Material 2) 98 parts by weight of dipentaerythritol hexaacrylate (Raw Material 3) Phenothiazine 0.05 Parts by weight (raw material 4) photopolymerization initiator 5 parts by weight 2,4-bis (trichloromethyl) -6- [4- (N, N'-diethoxycarbonylmethyl) -3-bromophenyl] -5-triazine ( Raw material 5) 1-methoxy-2-propyl acetate 320 parts by weight Copolymerization ratio 73:27 (molar ratio) (Raw material 6) Silica dispersion 200 parts by weight (2 parts by weight of solid silica based on the total solid content of the photosensitive resin layer) %) (Raw material 7) 480 parts by weight of methyl ethyl ketone

The temperature of the tank with a stirring wing having a double structure is adjusted to 30 ± 2 ° C. so that the temperature-regulated water can circulate in the side wall and the bottom wall. Raw materials 1 to 3 are charged in this order and stirred for 5 minutes. Thereafter, the raw materials 4 to 9 were sequentially charged, and then stirred for 30 minutes to obtain a photosensitive resin layer coating liquid.

[Formation of Spacer] <Cleaning of Substrate> 320 mm long 400 mm thick 1.1 mm thick
The glass substrate was rinsed with a glass cleaning agent at room temperature for 30 seconds with a brush, washed with glass at 40 ° C. for 1 minute with ultrasonic waves, rinsed with pure water at room temperature for 1 minute, drained with an air blow, and dried.

<Formation of Color Filter>
JP-A-97665 and JP-A-11-64621 disclose the cover film of a multilayer film for color filter (trade name: Transer) R, and then exfoliate at a temperature of 130 ° C and a linear pressure of 100.
Lamination was performed at an N / cm transfer speed of 1.0 m / min. After pattern exposure of 40 mJ / cm ^{2 with} an ultra-high pressure mercury lamp, shower development was performed at 38 ° C. for 35 seconds with a PD solution for a transer to remove the thermoplastic resin layer and the oxygen barrier film.
After developing each photosensitive resin layer at 3 ° C. for 26 seconds, the photosensitive resin layer was developed, and then developed once with an SD solution at 33 ° C. for 30 seconds to remove residues. After that, 500 mJ / cm ² post exposure from both sides, followed by post baking at 220 ° C. for 25 minutes,
A red (R) pixel was obtained. Similarly, pixels of the color filter G were formed. The exposure was 45 mJ / cm ² and the brush was applied three times. Similarly, a color filter B was formed. However, exposure was performed at 35 mJ / cm ² , brushing was performed three times, and post-baking was performed at 240 ° C. for 30 minutes. Similarly, a black matrix B was formed. However, exposure is 100 mJ / cm ² from the back side, and development is 40 ° C. 50
2 seconds shower development, no CD solution development, SD solution 40 ° C 60
A second shower (no brush), no post-exposure, and post-bake were performed at 220 ° C. for 130 minutes.

<Formation of overcoat> JP-A-6-82
The multilayer film for overcoat described in Example of Japanese Patent Application Publication No. 620 was laminated in the same manner as for forming a color filter.
After exposing this to 2000 mJ / cm ² with an ultra-high pressure mercury lamp,
Shower development was performed at 38 ° C. for 35 seconds with the D solution, at 33 ° C. for 20 seconds with the CD solution, and at 33 ° C. for 30 seconds with the SD solution. 230 ° C 70
Minutes post-baked. An ITO was formed thereon by sputtering, and a pattern was formed using an ITO resist.

<Formation of Spacer> The integrated films A1 to A7 according to the present invention obtained as described above were laminated thereon in the same manner as in the formation of the color filter. A1 = 20 mJ / cm ² A2 = 45 mJ / c with ultra high pressure mercury lamp
m ² A3 = 300 mJ / cm ² A4 = 50 mJ / cm ²
A5 = 110 mJ / cm ² A6 = 40 mJ / cm ²
A7 = 50 mJ / exposure of ^{cm 2 A8 = 40mJ / cm 2} (25 times both 1/2 thickness exposure), a stripe-shaped mask pattern exposure (width 80 [mu] m in proximity 200 [mu] m, 40 × 80 [mu] m dot-shaped mask, 10 × 10
μm dot mask, 10μmφ circular mask used)
Thereafter, the thermoplastic resin layer and the oxygen barrier film are removed by shower development with a PD solution at 38 ° C. for 35 seconds, and then the photosensitive resin layer is shower-developed with a CD solution at 28 ° C. for 24 seconds (1.5 times the minimum development time). Was developed once with an SD solution at 33 ° C. for 30 seconds with a shower and a brush to obtain pixels for spacers. Then 15 from both sides
After 0 mJ / cm ² post-exposure, post-baking was performed at 230 ° C. for 25 minutes to form a spacer. Using the symbols of the integrated film used, the spacers A1 to A1 of the present invention are used.
A7 was formed.

[Comparative Example 1] Instead of using an integral film to form a spacer in Example 1, a photosensitive solution C1 having the following formulation was applied by a spinner and prebaked at 90 ° C for 2 minutes to obtain a thickness of 1.1 µm. Was formed. Prebake 90 ° C
After pattern exposure with an exposure amount of 800 mJ / cm ² (25 times the 1/2 thickness exposure amount) and proximity of 200 μm for 2 minutes, shower development was performed with a CD solution at 33 ° C. for 30 seconds to obtain spacer pixels. Next, after 150 mJ / cm ² post-exposure from both surfaces, post-baking was subsequently performed at 230 ° C. for 25 minutes to form a spacer, which was used as a spacer of Comparative Example 1. Preparation of photosensitive solution C1 (Raw material 1) 1-methoxy-2-propyl acetate 100 parts by weight (Raw material 2) Polymer solution 141 parts by weight Polymer solution: poly- (benzyl methacrylate) -co- (methacrylic acid) Copolymerization ratio 72 1-methoxy-2-propyl acetate solution containing 27% by weight to 28 (molar ratio) (raw material 3) 40 parts by weight of monomer solution 1-methoxy-2-propyl acetate containing 76% by weight of dipentaerythritol hexaacrylate Solution (raw material 4) Surfactant 0.01 part by weight Poly- (N-propylperfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) Copolymerization ratio 40:60 (molar ratio) (raw material 5) 2,4-diethylthioxanthone (CAS82799-44-8) 0.5 Parts by weight (material 6) a photopolymerization initiator IRG907 (CAS7-868-10-5) 2.1 parts by weight

Comparative Example 2 A coating liquid A7 was used in place of the coating liquid C1 of Comparative Example 1, and the same procedure as in Comparative Example 1 was carried out. At this time, even if the exposure amount is increased to 5000 mJ / cm ² , a sufficient residual film ratio after development (90% of the thickness before development) is obtained.
The above image was not obtained. This sample was used as a spacer of Comparative Example 2.

[Evaluation] After cooling the substrate on which these spacers were formed with liquid nitrogen, the spacer portions were cut at right angles to the spacer pixels to form cross sections. This cross-sectional sample was observed by SEM, and the cross-sectional shape and the inclination angle (angle with respect to the substrate) of the side wall of the spacer were measured. Next, the rubbing resistance was measured. A rubbing machine having a roll wound with a nylon cloth was used, and the rotation speed of the roll was set to 2000 RPM and the moving speed of the stage was set to 0.1 cm / sec in order to make the conditions strict. 200 spacers at each level were observed and counted as NG counts of chipping, cracks, scratches, and falling off, and the rubbing resistance was determined. The numbers in the “rubbing resistance” column in the table below are the NG numbers, and the smaller the NG number, the better the evaluation.

Types of spacers Cross-sectional shape of side wall Inclination angle Rubbing-resistant spacer A1 (present invention) Substantially linear 18 degrees 5 Spacer A2 (present invention) Substantially linear 12 degrees 3 Spacer A3 (present invention) Substantially linear 16 degrees 4 Spacer A4 (the present invention) Substantially linear 20 degrees 4 Spacer A5 (the present invention) Substantially linear 14 degrees 3 Spacer A6 (the present invention) Substantially linear 17 degrees 3 Spacer A7 (the present invention) Substantially linear 15 degrees 2 Spacer A8 (Invention) Substantially linear 15 degrees 0 No measurement could be performed without the convex downward curved linear portion of the spacer of Comparative Example 1 37 No measurement was possible without the convex downward curved linear portion of the spacer of Comparative Example 2 76

[Example 2] With respect to the integrated film A8 used in Example 1, only the thickness of the photosensitive resin layer was changed to form an integrated film, and the integrated film was used in the same manner as in Example 1 to form a spacer. Was formed. Evaluation was performed in the same manner as in Example 1. The inclination angle and the rubbing resistance are as follows. From the table, it can be seen that the spacer according to the method of the present invention in which an oxygen blocking film is provided adjacent to the photosensitive resin layer and the exposure step is performed under a deoxygenated atmosphere, good results can be obtained in both the tilt angle and the rubbing resistance. .

5. Thickness of photosensitive resin layer Tilt angle Rubbing resistance (μm) 0.2 Less than 10 degrees 21 0.3 10 degrees 11 0.7 12 degrees 6 0.8 15 degrees 0 2.0 20 degrees 0 6. 0 25 degrees 3 7.0 35 degrees 9 10 50 degrees 18 20 110 degrees 68

In the above evaluation, the thickness of the photosensitive resin layer was determined by forming the photosensitive resin layer on the temporary support in the same manner as when forming the integrated film, and removing the photosensitive resin layer partially. The difference between the removed portion and the portion having the photosensitive resin layer was measured with a stylus-type thickness gauge. From the table, the thickness of the photosensitive resin layer is 0.3 to 10 μm.
It can be seen that in the range of m, good results are obtained for both the inclination angle and the rubbing resistance.

Example 3 In the same manner as in the case of the spacer A7 in Example 1, a spacer was formed by changing only the amount of proximity during exposure. The inclination angle and the rubbing resistance are as follows.

Proximity (μm) Inclination angle (degrees) Rubbing resistance 0 80 31 20 50 15 50 33 7 100 20 1200 200 150 250 150 14 0 300 12 6 500 10 12 1000 Less than 10 degrees 26 5000 Less than 10 degrees 48 From the proximity of 20 to 500 μm,
It can be seen that good results are obtained for both the inclination angle and the rubbing resistance.

Example 4 (Study on Exposure Amount) In the same manner as in the case of the spacer A7 of Example 1, a spacer was formed by changing the proximity to 100 μm and changing only the exposure amount. The magnification and the inclination angle with respect to the 厚 thickness exposure amount are as follows. From the following results, a rubbing resistance of a practically acceptable level is obtained in a range of 3 to 100 times the preferred range of the magnification with respect to the 厚 thickness exposure amount, and a more preferred range of 6 to 100 times.
At 50 times, the most preferable range of 8 to 30 times,
It was found that better rubbing resistance was obtained.

Exposure magnification with respect to 厚 thick exposure dose Inclination angle Rubbing resistance 3 50 20 6 35 9 8 25 5 25 18 18 30 30 15 1 50 12 6 100 10 11

Example 5, Comparative Example 3: Second Embodiment Instead of using an integrated film for forming the spacer in Example 1, the following photosensitive resin layer coating solution: photosensitive solution A8 (ultraviolet absorbent) (A8-1 to A8-8) were prepared by applying different amounts of, and applied by a spinner and prebaked at 90 ° C for 2 minutes to form a 2.8 µm thick photosensitive resin layer. After pre-baking at 90 ° C. for 2 minutes, exposure at 800 mJ / cm ² (25 times of 1/2 thick exposure) and pattern exposure at 200 μm proximity, shower-developed with CD solution at 33 ° C. for 30 seconds to obtain spacer pixels. Was. Next, after 150 mJ / cm ² post-exposure from both sides, post-baking was performed at 230 ° C. for 25 minutes to form a spacer.

Preparation of Photosensitive Solution A8 (Raw Material 1) 1-Methoxy-2-propyl acetate 100 parts by weight (Raw Material 2) Polymer solution 141 parts by weight Poly- (benzyl methacrylate) -co- (methacrylic acid) Copolymerization ratio 72 1-methoxy-2-propyl acetate solution containing 27% by weight to 28 parts (molar ratio) (raw material 3) Monomer solution 40 parts by weight 1-methoxy-2-propyl acetate solution containing 76% by weight of dipentaerythritol hexaacrylate (Raw material 4) Surfactant 0.01 part by weight Poly- (N-propylperfluorooctanesulfonamidoethyl acrylate) -co- (polypropylene glycol methyl ether acrylate) Copolymerization ratio 40:60 (Molar ratio) (Raw material 5) 2,4-diethylthioxanthone (CAS82799-44-8) 0.53 Parts by weight (Raw material 6) Photopolymerization initiator IRG907 (CAS7-868-10-5) 2.1 parts by weight (Raw material 7) UV absorber X parts by weight 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole Existing chemical substance No. (5) -5459 Vapor pressure (20 ℃) 2.1 × 10 ^-10 pa

In the solution A8, X represents 0
(A8-1), 0.81 (A8-2), 1.1 (A8-
3) 1.6 (A8-4), 1.9 (A8-5), 2.
4 (A8-6), 2.8 (A8-7), 5.7 (A8-
8 types of liquids were prepared instead of 8). Among them, A8-1 and A8-8 having optical densities (OD) of 0.1 and 1.5 are comparative examples. The optical density of the photosensitive resin layer after coating was as follows.

Optical density Cross-sectional shape Inclination angle Rubbing resistance 0.1 Curve convex downwards Unmeasurable without linear portion 23 0.3 Linear curved slightly downward 12 degrees 13 0.4 Substantially linear 13 degrees 90. 5 Substantially linear 16 degrees 2 0.6 Substantially linear 22 degrees 1 0.7 Substantially linear 30 degrees 6 0.8 Straight upwardly curved linear 50 degrees 11 1.5 Outside slightly convex 112 degrees 71

From the above results, the optical density (OD) was 0.3
In the range of from 0.8 to 0.8, both the shape and the rubbing resistance are good, but Comparative Example 3 (A8-
1 and A8-8) are not preferable.

Example 6: Third Embodiment Instead of using the integrated film used for forming the spacer in Example 1, a positive photosensitive resin layer coating solution was used instead of the esterification degree of 45.
% Phenol novolak resin (manufactured by Sumitomo Bakelite,
Naphthoquinone-1,2-diazide of “Sumiresin” PR50235)
-5- 10% by weight of sulfonic acid ester (molecular weight about 1300)
The dioxane solution is applied with a spinner,
After drying for a minimum, a positive photosensitive resin layer having a thickness of 2 μm was provided. Pattern exposure through a shadow mask with an ultra-high pressure mercury lamp exposure machine, remove the exposed part in an ethanol bath,
After washing with water, drying was performed to obtain a spacer. Evaluation was performed in the same manner as in Example 1. The results are shown below.

Proximity Inclination angle Rubbing resistance 0 μm 85 degrees 22 20 50 12 50 35 6 100 25 0 250 15 1 300 12 7 500 10 13 1000 725 From the table, the proximity is in the range of 20 to 500 μm.
It can be seen that good results are obtained for both the inclination angle and the rubbing resistance.

[Embodiment 7: Fourth Embodiment] In Embodiment 1, the integrated film A6 was used, and the proximity 100 was used.
The exposure process was performed in the same manner as in Example 1 except that the exposure amount for pattern exposure was set to 9 mJ / cm ² at μm. Also,
After the development, as shown in the following table, the exposure amount was 0 to 5000 m
Post-exposure was performed by changing to J / cm ² . Thereafter, a post-baking process was further performed at 230 ° C. for 25 minutes.

[0089] From the table, the post exposure amount is in the range of 10 to 2000 μm,
It can be seen that a spacer having good rubbing resistance can be obtained.

Example 8 (Example of Making Oriented Divided Panel for MVA) JP-A-7-209
An orientation division panel for MVA was prepared with reference to JP-A-646. Proximity 25 was applied to the glass substrate to which the film A7 obtained in Example 1 was attached by using a shadow mask in which light transmitting portions of 5 μm square were arranged at intervals of 6 μm.
50 mJ / cm ² exposure was performed at 0 μm. Thereafter, development, post-exposure, and post-baking were performed in the same manner as in Example 1. 11
Rough quadrangular pyramids were formed at μ pitch.

Example 9 (Example of Forming Film for Array Substrate) The method of forming a spacer of the present invention can be applied to formation of a spacer on an array substrate. Since the TFT array may be broken by static electricity, the following two films S1 and S2 having an antistatic function were prepared for application to this array. Film S1: The film S7 was prepared in the same manner as in the film A7 in Example 1, except that the oxygen-barrier film contained 5% by weight of the conductive fine particles. Film S2: Film S2 was prepared in the same manner as film A7 in Example 1, except that aluminum foil (JIS 1N30, thickness 15 μm) was used as the covering sheet. When the cover sheet is peeled off, the film is easily charged with static electricity, but the film S1 is less charged than the film A7,
No charging was observed in the film S2.

(Preparation of Active Matrix Substrate) A gate signal line and an additional capacitance electrode are formed on an active matrix substrate (array substrate), and a gate insulating film is formed thereon. After that, a semiconductor layer and a channel protection layer are formed, and an n + Si layer serving as a source and a drain of the TFT is formed. Subsequently, a drain layer and a source signal line are formed by forming a metal layer and an ITO film by a sputtering method and patterning them. Next, the interlayer insulating film is formed by the DFL method using a dry film.
(Colored organic film) A red film piece, a green film piece, a blue film piece, and a light-shielding film piece are sequentially formed.

First, a 3 μm-thick transparent organic film having a negative sensitivity and having a red pigment dispersed therein, which is a dry film, is adhered by a laminating method, and the support film is peeled off. Only the portion excluding the contact hole and the TFT from the pixel displaying red is exposed, the cushion layer is developed, the red transparent organic film is developed with an alkaline developer, and a red film piece covering the red pixel is developed. And baking at 250 ° C. The taper angle of this contact hole is 45 degrees, and the baking treatment is for the purpose of preventing elution of impurities and improving the adhesion of the underlayer, and does not affect the discoloration of the pigment or a-Si by this treatment. Green, blue and black film pieces were formed in the same manner as this red film piece.
However, in the case of black, exposure to portions (other than the contact holes) where the film pieces of each color are not arranged and the metal film is not arranged below was performed from the back surface of the active matrix substrate. Thereby, the positional accuracy of the black color is increased, and the defective portion can be repaired.

A black film was also placed on a portion where no film piece of each color was placed and where a metal film was placed below. Thereby, the irregularities can be alleviated and the disorder of the alignment of the liquid crystal molecules can be suppressed. The active matrix substrate with a colored organic film thus obtained is inspected, and washed and baked again. Then UV
An asher treatment is performed, an ITO film is formed by a sputtering method, a pixel electrode is formed by patterning the ITO film, and the pixel electrode is connected to a drain signal line via a contact hole.

(Formation of Spacer) Using the film S2 obtained above, an S2 spacer was formed through the same steps as in the case of using the film A7 in Example 1.
The spacer was provided in a non-pixel portion.

(Completion of Liquid Crystal Element) An alignment film was formed on the substrate having the S2 spacers obtained as described above,
The alignment film is subjected to a rubbing treatment. On the other hand, a counter electrode and an alignment film are sequentially stacked on the lower surface of the opposing substrate. The active matrix substrate and the opposing substrate are arranged to face each other, and liquid crystal is injected between them to complete a liquid crystal element. The liquid crystal element obtained by applying the method for forming a spacer of the present invention thus prepared has excellent characteristics without display defects due to partial destruction or loss of the spacer and no influence of electrification when the film is peeled off. Met.

[0097]

According to the spacer forming method of the present invention, it is possible to form a spacer which is excellent in function as a spacer such as uniformity and strength, and which is hardly damaged by rubbing or the like. Further, the liquid crystal element obtained by applying this method for forming a spacer has an excellent effect that there is no display defect caused by the defect of the spacer.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H089 LA09 MA04X NA14 NA24 NA58 PA05 QA14 TA01 TA04 TA09 TA12 5C094 AA31 AA43 BA43 EC01 EC03 GB10 JA07 JA11 5G435 AA01 AA14 BB12 BB15 EE12 LL08

Claims (5)

[Claims] A photosensitive resin layer having a thickness of 0.3 to 10 μm is placed in a deoxygenated atmosphere at a proximity of 20 to 500 μm.
Forming a spacer by pattern exposure. 2. A method for forming a spacer, comprising a step of pattern-exposing a photosensitive resin layer having a thickness of 0.3 to 10 μm and an optical density at an exposure wavelength of 0.3 to 0.8. 3. A method for forming a spacer, comprising a step of pattern-exposing a positive photosensitive resin layer at a proximity of 20 μm to 500 μm. 4. A step of subjecting the photosensitive resin layer to pattern exposure and subsequent development, and thereafter, from 10 mJ / cm ² to 200 mJ / cm ^2.
A method for forming a spacer, comprising: a step of performing post-exposure of 0 mJ / cm ² ; and a step of performing post-baking at a temperature of 150 ° C. to 250 ° C. for 5 minutes to 120 minutes. 5. A liquid crystal device comprising a spacer formed on a substrate by the method for forming a spacer according to any one of claims 1 to 4.