KR100984905B1 - Radiation-sensitive resin composition for forming protrusions or spacers for vertical alignment liquid crystal display elements - Google Patents

Abstract

The present invention provides a vertically-aligned liquid crystal display device which is capable of forming protrusions and spacers having excellent resolution and residual film ratio, excellent pattern shape, heat resistance, solvent resistance, transparency, and the like as photoresist, and excellent in orientation, voltage retention, and the like. It provides the radiation sensitive resin composition which can be manufactured. This resin composition contains (a) alkali-soluble resin and (b) 1,2-quinone diazide compound.

Vertically oriented liquid crystal display element, protrusion, spacer, radiation sensitive resin composition, photoresist

Description

Radiation Sensitive Resin Composition for Formation of Protrusion or Spacer for Vertically Aligned Liquid Crystal Display Device

1 is an example of the schematic diagram of the cross-sectional shape of a processus | protrusion and a spacer.

FIG. 2 is an example of the schematic diagram which illustrates the cross-sectional shape of the vertically-aligned liquid crystal display element which has a processus | protrusion and a spacer.

<Explanation of symbols for the main parts of the drawings>

1: spacer 2: protrusion

3: liquid crystal 4: liquid crystal alignment film

5: color filter 6: glass substrate

The present invention relates to a radiation-sensitive resin composition for forming projections and / or spacers for vertically aligned liquid crystal display elements, and vertically provided with projections and spacers, projections and / or spacers for vertically aligned liquid crystal display elements formed therefrom. An orientation type liquid crystal display element and the formation method of a processus | protrusion and / or a spacer are related.                         

Liquid crystal display devices are the most widely used among flat panel displays, and recently, with the spread of OA devices such as personal computers, word processors, liquid crystal televisions, etc., the display quality of TFT-LCD liquid crystal displays (TFT-LCD) The performance requirements are becoming more stringent.

TN (Twisted Nematic) type LCD is the most widely used type of TFT-LCD at present, and this type has 90 kinds of orientation directions on both outer sides of a substrate having two transparent electrodes (hereinafter referred to as a "transparent electrode substrate"). Another polarizing film is arrange | positioned, the alignment film is arrange | positioned inside two transparent electrode substrates, and a nematic type liquid crystal is arrange | positioned between both alignment films, and the orientation direction of a liquid crystal is 90 from one electrode side to the other electrode side. It is also to be twisted. When unpolarized light enters in this state, since the linearly polarized light which permeate | transmitted one polarizing plate permeate | transmits the polarization direction between liquid crystals, it can permeate | transmit the other polarizing plate and will be in a bright state. Next, when the liquid crystal molecules are made upright by applying a voltage to both electrodes, since the linearly polarized light reaching the liquid crystal is transmitted as it is, the other polarizing plate cannot be transmitted, resulting in a dark state. After that, if the voltage is not applied again, the state returns to the bright state.

In recent years, such TN-type LCDs have improved contrast, color reproducibility, and the like at the front of the CRTs. However, the TN type LCD has a big problem that the viewing angle is narrow.

In order to solve this problem, a multi-domain vertically aligned (MVA) type LCD (vertical alignment liquid crystal display) has been developed.                         

This MVA type LCD has a beneficiation mode of a TN type LCD, as described in "Liquid Crystal" Vol. 3, No. 2, p. 117 (1999) and Japanese Patent Laid-Open No. 11-258605. Rather, the birefringence mode is a combination of a negative liquid crystal having negative dielectric anisotropy and an alignment film in the vertical direction, and since the alignment direction of the liquid crystal in a position close to the alignment film remains almost vertical even without a voltage applied thereto. It is excellent also in the aspect of a manufacturing process, such as being excellent in contrast, viewing angle, etc., and being good even if it does not carry out the grinding | polishing process for orienting a liquid crystal.

In an MVA type LCD, as a domain regulating means for allowing a liquid crystal to take a plurality of alignment directions in one pixel region, the electrode on the display side has a slit in one pixel region and at the same time an incident side electrode substrate of light. In the same pixel region of the image, projections having a slope at a position different from the slit of the electrode, for example, a triangular awl, a semiconvex lens shape, and the like are formed.

In general, in the conventional liquid crystal display, in order to maintain a constant cell gap between two transparent electrode substrates, spherical or rod-shaped spacers such as resin and ceramics are used. When the spacers are bonded to each other by two transparent electrode substrates, the spacers are scattered on either substrate to define the cell gap by the diameter of the spacers.

In addition, in order to avoid defects, such as nonuniformity of the cell gap resulting from the change of the diameter of a spacer, the method of forming protrusions and a spacer using a photoresist is proposed by Unexamined-Japanese-Patent No. 2001-201750. This method has the advantage of being capable of micromachining and easily controlling the shape. However, Japanese Unexamined Patent Application Publication No. 2001-201750 does not specifically describe the composition of the photoresist, and the performance of the formed protrusions and spacers is also not clear.

As the performance required for the photoresist used for the formation of the projections and the spacers for the vertical alignment liquid crystal display element, the cross-sectional shape thereof is appropriate, and the resistance to the solvent used in the subsequent alignment film forming step is applied in the alignment film forming step. It is mentioned that there is high performance in heat resistance, transparency, resolution, residual film ratio and the like. Moreover, what is excellent in the orientation, voltage retention, etc. is calculated | required by the obtained vertical alignment type liquid crystal display element.

Applicant has already described a copolymer of [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, and (a3) unsaturated compounds other than these, [B] unsaturated A radiation sensitive resin composition for simultaneously forming a projection and a spacer containing a polymerizable compound and a [C] radiation sensitive polymerization initiator, a projection and a spacer formed therefrom, and a liquid crystal display device comprising the projection and the spacer (See Japanese Patent Laid-Open No. 2003-29405).

However, the development of the radiation-sensitive resin composition useful for the projection of the vertically aligned liquid crystal display element and the formation of the spacer has an initial stage, and the projection having excellent performance in response to the rapid spread of the TFT-LCD and the increasingly stringent demanded performance. And the development of the new radiation sensitive resin composition which can form a spacer is an important technical subject.

An object of the present invention is to provide a radiation-sensitive resin composition for forming projections and / or spacers for vertically aligned liquid crystal display elements.

Another object of the present invention is a vertically-aligned liquid crystal that is capable of forming protrusions and spacers having excellent resolution and residual film ratio, excellent pattern shape, heat resistance, solvent resistance, transparency, etc., and excellent alignment, voltage retention, etc. as photoresists. It is providing the radiation sensitive resin composition which can manufacture a display element.

Still another object of the present invention is to provide a method for forming a projection and / or a spacer for a vertical alignment liquid crystal display device using the radiation-sensitive resin composition of the present invention.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention firstly comprise (a) an alkali-soluble resin and (b) a 1,2-quinone diazide compound, and a projection for vertically oriented liquid crystal display device and / or It is achieved by the radiation sensitive resin composition characterized by the formation of a spacer.

According to the present invention, the above objects and advantages of the present invention are secondly achieved by projections for the vertically aligned liquid crystal display element formed from the radiation-sensitive resin composition of the present invention.

According to this invention, the said objective and advantage of this invention are 3rd achieved by the spacer for the vertically-aligned liquid crystal display element formed from the radiation sensitive resin composition of this invention.

Moreover, the said objective and advantage of this invention are achieved by the vertically-aligned liquid crystal display element provided 4th with the said processus | protrusion and / or spacer of this invention according to this invention.

Finally, according to the present invention, the above object and advantage of the present invention, the fifth step of forming a film of the radiation-sensitive resin composition of the present invention on a substrate, the step of exposing the radiation to the film through a photomask, exposure A process of forming a pattern by developing a subsequent film with an alkaline developer and exposing radiation to the pattern is achieved by a method for forming a projection and / or a spacer for a vertical alignment liquid crystal display element. .

Preferred Embodiments of the Invention

Hereinafter, each component of the radiation sensitive resin composition in this invention is demonstrated in detail.

(a) alkali-soluble resin

The term "alkali solubility" used for the alkali-soluble resin used in the present invention means that a film of the radiation-sensitive resin composition according to the present invention is formed on a substrate by the method of forming a protrusion and / or a spacer described later, and then exposed. When developing the said film after exposure with the alkali developing solution, it means the property which can substantially dissolve and remove all the exposure part of the said film after exposure.                     

As alkali-soluble resin in this invention, it will not specifically limit, as long as it has the said characteristic. For example, a homopolymer of a radical polymerizable monomer having a phenolic hydroxyl group and / or a carboxyl group (hereinafter referred to as an "acidic radical polymerizable monomer"), a copolymer of acidic radical polymerizable monomers or an acidic radical polymerizable monomer and Copolymers with other radically polymerizable monomers (hereinafter referred to as "other radically polymerizable monomers") (hereinafter, these homopolymers and copolymers are collectively referred to as "alkali-soluble resins (a1)") are preferable.

As the acidic radical polymerizable monomer, for example

o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, and these The benzene ring in the compound of is a carboxyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms, a linear or branched halogenated alkyl group having 1 to 4 carbon atoms, halogen Substituted hydroxystyrene substituted with one or more selected from the group consisting of an atom, a nitro group, a cyano group, a straight or branched amide group having 1 to 4 carbon atoms, and a straight or branched ester group having 2 to 8 carbon atoms ;

Vinyl group-containing polyphenols such as vinylhydroquinone, 5-vinyl pyrogallol, 6-vinyl pyrogallol, and 1-vinylfluoroglycinol;

O-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and the benzene ring in these compounds are a C1-C4 linear or branched alkyl group, C1-C4 linear or branched alkoxyl group, carbon number A straight or branched halogenated alkyl group of 1 to 4, a halogen atom, a nitro group, a cyano group, a straight or branched amide group having 1 to 4 carbon atoms, and a straight or branched ester group having 2 to 8 carbon atoms Substituted vinyl benzoic acid substituted by one or more selected from the group;

The α position of acrylic acid, methacrylic acid and acrylic acid is composed of a linear or branched alkoxyl group having 1 to 4 carbon atoms, a linear or branched halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group and a cyano group. Substituted α-substituted unsaturated monocarboxylic acids selected from the group;

Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexene dicarboxylic acid, and one of these unsaturated dicarboxylic acids Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, phenyl, o-tolyl, m-tolyl or p-tolyl groups Unsaturated dicarboxylic acid derivatives such as esterified half esters, and half amides in which one of these unsaturated dicarboxylic acids has been converted to a linear or branched amide group having 1 to 4 carbon atoms.

 Etc. can be mentioned.

Among these acidic radically polymerizable monomers, m-hydroxystyrene, p-hydroxystyrene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and the like are preferable.

The said acidic radically polymerizable monomer can be used individually or in mixture of 2 or more types.

Moreover, as another radically polymerizable monomer, for example                     

Styrene, α-methylstyrene, and the benzene ring in these compounds are linear or branched alkyl groups having 1 to 4 carbon atoms, linear or branched alkoxyl groups having 1 to 4 carbon atoms, linear or branched carbon atoms 1 to 4 At least one selected from the group consisting of tertiary halogenated alkyl groups, halogen atoms, nitro groups, cyano groups, linear or branched amide groups having 1 to 4 carbon atoms, and linear or branched ester groups having 2 to 8 carbon atoms; Substituted substituted styrenes;

Conjugated diolefins such as 1,3-butadiene, isoprene and chloroprene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, i-pentyl (meth) acrylate, lauryl (meth) acrylic Latex, cyclohexyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthra Quinonyl (meth) acrylate, piperonyl (meth) acrylate, salicylic (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, triphenyl Methyl (meth) acrylate, cumyl (meth) acrylate, Adamantyl (meth) acrylate, tricyclo [5.2.1.O ^2,6] decan-8-yl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, 3-hydroxypropyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, heptafluoro-n-propyl (meth) Acrylate, heptafluoro-i-propyl (meth) acrylate, glycidyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 3- (N, N-dimethyl (Meth) acrylic acid esters such as amino) propyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate;

(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-di- (meth) acrylamides such as i-propyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-anthranyl (meth) acrylamide;

Unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, N-phenylmaleimide, N- (p-hydroxyphenyl) maleimide, N-cyclo Hexyl maleimide, N- (meth) acryloyl phthalimide, N-acryloyl phthalimide, p-vinylbenzyl glycidyl ether, etc. are mentioned.

Among these other radically polymerizable monomers, styrene, 1,3-butadiene, phenyl (meth) acrylate, lauryl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylic Preference is given to latex, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, N-cyclohexyl maleimide, p-vinylbenzyl glycidyl ether and the like.

The said other radically polymerizable monomer can be used individually or in mixture of 2 or more types.

In the alkali-soluble resin (a1), the copolymerization ratio of the other radically polymerizable monomer is preferably 60 to 95 parts by weight, more preferably 65 to 90 parts by weight based on 100 parts by weight of the total monomers. In this case, when the copolymerization ratio of the other radically polymerizable monomer is less than 60 parts by weight, the solubility of the resulting resin in the alkali developer is too high, so that the film after alkali development may be difficult to maintain an appropriate film thickness. If it exceeds, there exists a possibility that the solubility of the resin obtained in alkaline developing solution may become inadequate.

As preferable alkali-soluble resin (a1) in this invention, poly (p-hydroxy styrene), p-hydroxy styrene / p-hydroxy- (alpha)-methylstyrene copolymer, p-hydroxy styrene /, for example. Styrene copolymer, (meth) acrylic acid / styrene / glycidyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylic Rate / glycidyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / glycidyl (meth) acrylate / N-cyclohexyl maleimide copolymer, (meth) acrylic acid / styrene / glycidyl (meth ) Acrylate / N-cyclohexyl maleimide / p-vinylbenzyl glycidyl ether copolymer, (meth) acrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate / Glycidyl (meth) acrylate / 1,3-butadiene copolymer, (meth) acrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decane -8-yl (meth) acrylate / glycidyl (meth) acrylate / p-vinylbenzyl glycidyl ether copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / tricyclo [5.2 .1.O ^2,6 ] decane-8-yl (meth) acrylate / glycidyl (meth) acrylate / p-vinylbenzyl glycidyl ether copolymer, (meth) acrylic acid / lauryl (meth) acrylic Rate / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate / glycidyl (meth) acrylate / p-vinylbenzyl glycidyl ether copolymer, (meth) acrylic acid / Styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate / glycidyl (meth) acrylate / N-cyclohexyl maleimide / 1,3-butadiene copolymer and the like. have.

Alkali-soluble resin (a1) can be manufactured by superposing | polymerizing an acidic radically polymerizable monomer with a radical polymerization initiator in a suitable solvent with other radically polymerizable monomers as the case may be, for example.

As a solvent used for superposition | polymerization, For example, Alcohol, such as methanol, ethanol, diacetone alcohol; Ethers such as tetrahydrofuran, tetrahydropyran, dioxane; Ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Diethylene glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;

Propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate; Propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n-propylether propionate, propylene glycol n-butylether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, hydroxyacetic acid ethyl, hydroxyacetic acid n-butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid n-propyl, Methoxyacetic acid n-butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid n-propyl, ethoxyacetic acid n-butyl, n-propoxyacetic acid methyl, n-propoxyacetic acid ethyl, n-propoxyacetic acid n-propyl, n-propoxyacetic acid n-butyl, n-butoxyacetic acid methyl, n-butoxyacetic acid ethyl, n-butoxyacetic acid n-propyl, n-butoxyacetic acid n-butyl, methyl lactate, ethyl lactate , N-propyl lactate, n-butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionic acid, n-butyl 3-hydroxypropionate, 2-hydroxy-2- Methylpropy Methyl acid, 2-hydroxy-2-methylpropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionic acid, n-butyl 2-methoxypropionic acid, 2-e Methyl oxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, 2-n N-propyl propoxypropionate, n-butyl 2-propoxypropionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, 2- n-butoxypropionate n-butyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-methoxypropionic acid n-propyl, 3-methoxypropionic acid n-butyl, 3-ethoxypropionate methyl, 3- Ethyl ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n-propoxypropion Methyl, 3-n-propoxypropionate, 3-n-propoxypropionic acid n-propyl, 3-n-propoxypropionic acid n-butyl, 3-n-butoxypropionic acid methyl, 3-n-butoxypropionic acid And other esters such as n-propyl 3-n-butoxypropionic acid, n-butyl 3-n-butoxypropionic acid, and methyl 2-hydroxy-3-methylbutanoate.

These solvent can be used individually or in mixture of 2 or more types.

The amount of the solvent used during the polymerization is preferably 20 to 1,000 parts by weight per 100 parts by weight of the total radical polymerizable monomer.

As a radical polymerization initiator used for superposition | polymerization, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis, for example Azo compounds such as-(4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide; Examples thereof include redox initiators composed of these peroxides and reducing agents.

Moreover, as another manufacturing method of alkali-soluble resin (a1), after (co) polymerizing the monomer which protected the phenolic hydroxyl group and / or carboxyl group of the said acidic radically polymerizable monomer with protecting groups, such as an alkyl group, an acetyl group, and a penacyl group, And a method of leaving the protecting group by hydrolysis or the like.

In addition, in this invention, when alkali-soluble resin has a carbon-carbon unsaturated bond, hydrogenation can be used, and transparency and a softening point can be adjusted by this.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the alkali-soluble resin is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 5,000 to 30,000. By using alkali-soluble resin which has Mw of this range, the radiation sensitive resin composition excellent in the resolution, developability, and sensitivity can be obtained, and the processus | protrusion and spacer which are excellent in shape and heat resistance can be formed.

Moreover, as alkali-soluble resin in this invention, as a brand name, for example, Maruka linker M, copper PHM-C (above, Maruzen Sekiyu Chemical Co., Ltd. make), VP-15000 (Nihon Soda Co., Ltd.) Commercial products, such as a hydroxy styrene (co) polymer or its partial hydrogenated substance, etc. can also be used.

Alkali-soluble resin in this invention can be used individually or in mixture of 2 or more types.

(b) 1,2-quinone diazide compounds

As a 1, 2- quinone diazide compound used by this invention, the compound which produces | generates a carboxylic acid by exposure of radiation, for example, 1, 2- benzoquinone diazide- 4-sulfonic acid ester, 1, 2- benzo Quinone diazide-5-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 1,2-benzoquinone diazide-4- Sulfonic acid amide, 1,2-benzoquinone diazide-5-sulfonic acid amide, 1,2-naphthoquinone diazide-4-sulfonic acid amide, 1,2-naphthoquinone diazide-5-sulfonic acid amide, and the like, More preferably 1,2-naphthoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-5-sulfonic acid ester.

As specific examples of 1,2-naphthoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-5-sulfonic acid ester,

2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5 Sulfonic acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone 1,2-naphthoquinone diazide sulfonic acid ester of trihydroxybenzophenone, such as diazide-5-sulfonic acid ester;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2 Naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,3 ' Tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methyl Benzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinone diazide-5- Sulfonic acid esters, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid esters, 2,3,4,4'-tetrahydrate Roxy-3'-methoxybene 1,2-naphthoquinone diazide sulfonic acid ester of tetrahydroxybenzophenone, such as jophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxybenzophenone, such as -1,2-naphthoquinone diazide-5-sulfonic acid ester;

2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6,3 ', 4', 5 ' Hexahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone Hexahydroxybenzophene, such as diazide-4-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester Discussion 1,2-naphthoquinone diazide sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide -5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide -5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinone dia Zide-5-sulfonic acid ester, 2,2,2-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2,2-tri (p-hydroxy Phenyl) ethane-1,2-naphthoquinone diazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,2-bis (2,3,4- Trihydroxyphenyl) propane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide -5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,1 , 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazide-5-sulfonic acid ester, 4,4 '-[1- {4- ( 1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinone diazide-4-sulfonic acid ester, 4,4 '-[1- {4- (1 -[4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinone diazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) (2-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) (2-hydroxyphenyl) methane-1,2 Naphthoquinone diazide-5-sul Acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinone Diazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1, 2-naphthoquinone diazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphtho quinone diazide-5-sulfonic acid ester, 2-methyl-2- (2,4-dihydrate Hydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2-methyl-2- (2,4-dihydroxy Phenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman-1,2-naphthoquinone diazide-5-sulfonic acid ester,

2- [bis (5-i-propyl-4-hydroxy-2-methylphenyl) methyl] phenol-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2- [bis (5-i-propyl- 4-hydroxy-2-methylphenyl) methyl] phenol-1,2-naphthoquinone diazide-5-sulfonic acid ester, 1- [1- {3- (1- [4-hydroxyphenyl] -1-methyl Ethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydrate Hydroxyphenyl} -1-methylethyl] benzene-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl } -1-methylethyl] benzene-1,2-naphthoquinone diazide-5-sulfonic acid ester, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3- Dihydroxybenzene-1,2-naphthoquinone diazide-4-sulfonic acid ester, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybene L, 2 and the like naphthoquinonediazide-5-sulfonic acid ester, such as poly (hydroxyphenyl) alkane, 1,2-naphthoquinonediazide sulfonic acid ester.

In addition to these compounds, J. Kosar, Light-Sensitive Systems (John Wiley & Sons, 1965) p.339] and [W. 1,2-naphthoquinone diazide-4-sulfonic acid ester or 1,2-naphthoquinone diazide described in S. De Fores, Photoresist (McGraw-Hill, 1975). -5-sulfonic acid ester can be used.

Of these 1,2-naphthoquinone diazide-4-sulfonic acid esters and 1,2-naphthoquinone diazide-5-sulfonic acid esters, 1,2-naphthoquinone diazide-5-sulfonic acid esters are preferred, in particular 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone dia Zide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazide-5-sulfonic acid ester, 4, 4'-4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinone diazide-5-sulfonic acid Ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,2,2-tri (p-hydride Hydroxyphenyl) ethane-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxy Roxychroman-1, 2-naphthoquinone diazide-5-sulfonic acid ester etc. are preferable from a viewpoint of the dissolution inhibiting effect to (a) alkali developing solution of alkali-soluble resin.

The said 1,2-quinone diazide compound can be used individually or in mixture of 2 or more types.

The amount of the 1,2-quinone diazide compound used is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin. In this case, when the usage-amount of a 1, 2- quinone diazide compound is less than 5 weight part, the amount of carboxylic acid produced | generated by exposure will become small, and pattern formation will become difficult, and when it exceeds 50 weight part, exposure of a short time will be carried out. In the above, it is difficult to decompose all of the added 1,2-quinone diazide compounds, and there is a fear that development with an alkaline developer becomes difficult.

additive

In the radiation-sensitive resin composition according to the present invention, (c) an alkali having two or more epoxy groups in the molecule (hereinafter referred to as "compound (c)") and / or (d) a compound represented by the following formula (1) It is preferable to add an insoluble or alkali poorly soluble compound (hereinafter referred to as "compound (d)").

In the formula, R ¹ to R ⁶ independently represent a hydrogen atom or a —CH ₂ OR group, and R represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

Compound (c)

As the compound (c), for example, hexamethylol melamine, hexabutylol melamine, partially methylolated melamine, and hydrogen atoms of at least one hydroxyl group in these compounds are linear or branched carbon atoms of 1 to 6 carbon atoms. The compound substituted by the alkyl group etc. are mentioned.

In addition, as a commercial item of the compound (c), for example, Cymel 202, 238, 266, 267, 272, 300, 301, 303, 325, 327, 370, 701, East 1141, East 1156, East 1158 (above, Mitsui Cyanamid Co., Ltd.), Nikarak Mx-31, East 40, East 45, East 032, East 706, East 708, East 750, Nikarak Ms-11 , Copper 001, Nikarak Mw-22, copper 30 (above, Sanwa Chemical Co., Ltd.), etc. are mentioned.

The said compound (c) can be used individually or in mixture of 2 or more types.

The addition amount at the time of using a compound (c) is 1-50 weight part with respect to 100 weight part of (a) alkali-soluble resin, More preferably, it is 5-40 weight part. By adding a compound (c) in the quantity of the said range, the protrusion and spacer of a favorable shape can be formed and the radiation sensitive resin composition which shows moderate solubility with respect to an alkaline developing solution can be obtained.

Compound (d)

Examples of the compound (d) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cyclic aliphatic polyglycidyl ethers, aliphatic polyglycidyl ethers, The glycidyl ether of bisphenol A, the glycidyl ether of bisphenol F, etc. are mentioned.

Among these compounds (d), bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic polyglycidyl ethers have alkali developability of radiation-sensitive resin compositions. And it is preferable from a viewpoint of shape control of the processus | protrusion and spacer obtained.

Moreover, as a commercial item of the compound (d), for example, a bisphenol-A epoxy resin is epicoat 828, copper 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010 (above, yuka cell epoxy ( Note) manufacture), etc .; Epicoat 807 (manufactured by Yucatel Epoxy Co., Ltd.) as a bisphenol F type epoxy resin; Epicoat 152, copper 154 (above, manufactured by Yucatel Epoxy Co., Ltd.), EPPN201, copper 202 (above, manufactured by Nippon Kayaku Co., Ltd.), and the like as a phenol novolak type epoxy resin; EOCN-102, copper 103S, copper 104S, copper 1020, copper 1025, copper 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), epicoat 180S75 (manufactured by Yuka Cell Epoxy Co., Ltd.), etc. ; As cyclic aliphatic polyglycidyl ether, CY-175, copper 177, copper 179 (above, manufactured by Ciba-Geigy Co., Ltd.), ERL-4206, copper 4221, copper 4234, copper 4299 (above, manufactured by UCC Corporation), Shodine 509 (Showa Denko Co., Ltd.), Aldarite CY-182, Copper 184, Copper 192 (above, manufactured by Shiba-Kaiyi Co., Ltd.), Epichron 200, Copper 400 (above, manufactured by Dainippon Ink, Inc.), Epi Coat 871, copper 872 (above, manufactured by Yucatel Epoxy Co., Ltd.), ED-5661, copper 5662 (above, manufactured by Seranise Coating Co., Ltd.), and the like; Examples of the aliphatic polyglycidyl ethers include epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by Nippon Oil and Fats Co., Ltd.), and the like.

The said compound (d) can be used individually or in mixture of 2 or more types.

The addition amount at the time of using a compound (d) is 1-50 weight part with respect to 100 weight part of (a) alkali-soluble resin, More preferably, it is 5-30 weight part. By adding compound (d) in an amount in the above range, protrusions and spacers excellent in heat resistance and polishing resistance can be formed. In addition, when the addition amount of the compound (d) is less than 1 part by weight, (b) the reaction with the carboxylic acid produced by the exposure to the 1,2-quinone diazide compound is difficult to proceed sufficiently, and the formation of the formed protrusions and spacers There exists a possibility that heat resistance and solvent resistance may become inadequate, On the other hand, when it exceeds 50 weight part, the softening point of the processus | protrusion and spacer formed will fall, and it may become difficult to maintain a shape during the heat processing in these formation processes.

Other additives

The following other additive can be added to the radiation sensitive resin composition in this invention as needed.

-Sensitizer-

A sensitizer is a component which has an effect which further improves the sensitivity of a radiation sensitive resin composition.

As such a sensitizer, for example, 2H-pyride- (3,2-b) -1,4-oxazine-3 (4H)-warm, 10H-pyride- (3,2-b)-(1 (4) -benzothiazines, urazoles, hydantoins, barbiturates, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides, flavones, dibenzalacetones, dibenzalcyclohexane , Chalcones, xanthines, thioxanthines, porphyrins, phthalocyanines, acridines, anthracenes, benzophenones, acetophenones, coumarins having substituents in the 3-position and / or 7-positions Etc. can be mentioned.

These sensitizers can be used individually or in mixture of 2 or more types.

The addition amount of the sensitizer is preferably 30 parts by weight or less, more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.

-Trihalomethyl group containing -s-triazine-

Trihalomethyl group containing -s-triazine consists of a compound represented by following formula (2).                     

In the formula, X represents a halogen atom, A represents a group represented by -CX ₃ or the following formulas i to vi, B, D and E independently of each other a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carboxyl group, Hydroxyl group, straight or branched alkyl group of 1 to 10 carbon atoms, aryl group of 6 to 12 carbon atoms, straight or branched alkoxyl group of 1 to 10 carbon atoms, straight or branched alkyl tea of 1 to 10 carbon atoms Or a secondary amino group having an aryloxy group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched keto having 1 to 10 carbon atoms An alkyl group, a C6-C12 ketoaryl group, a C2-C20 linear or branched alkoxycarbonyl group, or a C2-C20 linear or branched alkylcarbonyloxy group is represented, m is 1- Is an integer of 5.

Examples of the trihalomethyl group-containing s-triazine include 2,4,6-tris (trichloromethyl) -s-triazine and 2-phenyl-4,6-bis (trichloromethyl) -s- Triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (2-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (3-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (2-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3-methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxy-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxy-β-styryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3- Methylthio-β-styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -4,6-bis (trichloro Romethyl) -s-triazine, 2- (2-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and the like.

Among these compounds, 2- (3-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine and the like are preferable.

The said trihalomethyl group containing -s-triazine can be used individually or in mixture of 2 or more types.

The addition amount of the trihalomethyl group-containing s-triazine is preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the (a) alkali-soluble resin.

Low molecular weight compounds containing other phenolic hydroxyl groups

As another phenolic hydroxyl group containing low molecular weight compound, for example, 1, 1-bis (2, 5- dimethyl- 4-hydroxyphenyl) acetone, 1, 1-bis (2, 4- dihydroxyphenyl) acetone, 1 , 1-bis (2,6-dimethyl-4-hydroxyphenyl) acetone, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxy-2-methylbenzene, etc. are mentioned.

These other phenolic hydroxyl group containing low molecular weight compounds can be used individually or in mixture of 2 or more types.

The addition amount of another phenolic hydroxyl group containing low molecular weight compound becomes like this. Preferably it is 50 weight part or less, More preferably, it is 45 weight part or less with respect to 100 weight part of (a) alkali-soluble resin.

Onium salt compound

An onium salt compound consists of a compound represented by following formula (3).

(A) _n Z ⁺ Y ^-

Wherein, A is the same meaning as A in the formula 2, n is 2 or 3, Z ⁺ denotes the S ⁺ or I ^+, Y ^- is _{^{BF 4 - PF 6 -, SbF}} 6 -, AsF ₆ ^-, p- toluenesulfonic represents a sulfonic acid anion, acetate anion of methane sulfonic acid anion or trifluoroacetate trifluoroacetic.

As an onium salt compound, for example

Diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodo Trifluoroacetate, diphenyliodonium p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-medium Methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoroacetate, 4-methoxyphenylphenylio Donium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophosphonate, bis (4-t- Butylphenyl) iodonium hexafluoroarsenate, Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium p- Diaryl iodonium salts, such as toluene sulfonate;

Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate , Triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium Hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium p-toluenesulfo Nitrate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroacene , Triaryl such as 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, and 4-phenylthiophenyldiphenylsulfonium p-toluenesulfonate Sulfonium salts

Etc. can be mentioned.

Among these compounds, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, and 4-methoxyphenylphenyl iodo Trifluoroacetate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsul Phenium trifluoroacetate, 4-phenylthiophenyl diphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyl diphenylsulfonium trifluoroacetate, etc. are preferable.

The onium salt compounds may be used alone or in combination of two or more thereof.

The addition amount of the onium salt compound is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less based on 100 parts by weight of the alkali-soluble resin.

-Surfactants-

Surfactant is a component which has an effect | action which improves applicability | paintability, for example, striation, or improves the alkali developability of the exposed part after film formation.

As such surfactant, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nontope surfactants, such as polyethyleneglycol dialkylate, such as polyethyleneglycol dilaurate and polyethyleneglycol distearate, and the following brand names: FTOP EF301, copper 303, copper 352 ), Megapack F171, Copper 172, Copper 173 (above, manufactured by Dainippon Ink Co., Ltd.), Flowride FC430, Copper 431 (above, manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Supron S-382, Fluorine-based surfactants such as Surflon SC-101, Copper 102, Copper 103, Copper 104, Copper 105, and 106 (above, manufactured by Asahi Glass Co., Ltd.); KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); Polyflow No. 57, Copper 95 (above, Kyosha Chemical Co., Ltd.), etc. are mentioned.

The said surfactant can be used individually or in mixture of 2 or more types.

The amount of the surfactant added is preferably 0.5 parts by weight or less, and more preferably 0.2 parts by weight or less based on the total solid of the radiation-sensitive resin composition.

Composition solution

It is preferable to make the radiation sensitive resin composition in this invention into the solution (henceforth "a composition solution") melt | dissolved in the suitable solvent, and to use.

As a solvent used for a composition solution, it is preferable to melt | dissolve each component of a radiation sensitive resin composition, and to have a suitable vapor pressure, without reacting with each said component.

As such a solvent, For example, Ethylene glycol ether, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methylethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol-n-propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, 2-heptanone, methyl isobutyl ketone and cyclohexanone; Ethyl acetate, n-butyl acetate, 3-methyl-3-methoxybutylacetate, ethyl hydroxyacetate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate, methyl lactate, ethyl lactate, 2- Ethyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-butyl 3-methoxypropionate, 2-hydroxy-3- And other esters such as methyl methyl butyrate and 3-methyl-3-methoxybutyl butyrate.

These solvents can be used individually or in mixture of 2 or more types.

If necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, acetoniyl acetone, isophorone, and caproic acid may be used as necessary. , Caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate It is also possible to add a high boiling point solvent such as carbitol acetate.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

Solid content concentration is adjusted to 20-40 weight%, for example, and the composition solution in this invention can also be used, for example, filtering by the filter of about 0.2 micrometer of pore diameters as needed.

Method of forming protrusions and / or spacers

Next, using the radiation-sensitive resin composition in the present invention, a projection for a vertical alignment liquid crystal display element and / or a spacer for a vertical alignment liquid crystal display element, preferably for a vertical alignment liquid crystal display element, on a substrate. Only the protrusions or the method of forming the protrusions and the spacer for the vertical alignment liquid crystal display element will be described.

First, after apply | coating a composition solution to a board | substrate, a solvent is removed by prebaking and a film is formed.

As said board | substrate, what consists of glass, quartz, silicone, a transparent resin, etc. can be used, for example.

As a coating method of a composition solution, various methods, such as the spraying method, the roll coating method, the rotation coating method, can be used, for example.

In addition, although the conditions of prebaking differ also with the kind of each component, a compounding ratio, etc., the conditions for about 1 to 15 minutes are suitable at 70-90 degreeC.

Subsequently, after irradiating a film with radiation, such as an ultraviolet-ray, it develops with alkaline developing solution, and removes an unnecessary part and forms a predetermined pattern.

As a pattern mask and an exposure operation to be used for exposure, (A) a method of exposing once using one kind of photomask having both patterns of the projection portion and the spacer portion, and (B) the photomask and spacer having only the projection portion. Any method of exposing twice using two types of photomask which has only a part may be sufficient. Moreover, as a pattern mask used for the method of (a), it is also possible to use what has a different transmittance | permeability in a projection part and a spacer part.

In the case where only one of the projections and the spacer is formed on the substrate, a method of exposing once using either a photomask having only the projection portion and a photomask having only the spacer portion is employed. In this case, the remaining projections or spacers required for the vertically aligned liquid crystal display element are formed by a conventionally known method.

As radiation used for exposure, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used, but ultraviolet rays are preferred.

Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; Primary amines such as ethylamine, n-propylamine: secondary amines such as diethylamine, di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; Alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Cyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine, quinoline; Aqueous solutions, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added to the alkaline developer.

As the developing method, any of paddle method, dipping method, shower method and the like may be used. The developing time is preferably 30 to 180 seconds.

After alkali development, a pattern is formed by elongating in flowing water for 30 to 90 second, for example, by drying with compressed air or compressed nitrogen, for example.

Subsequently, after exposing the radiation to the pattern after alkali development again, the heating plate is preferably a predetermined time, for example, a heating plate at a predetermined temperature, for example, 150 to 250 ° C., for example, in a heating apparatus such as a heating plate or an oven. Precursors and / or spacers can be formed by postbaking on the substrate for 5 to 30 minutes and in the open for 30 to 90 minutes. A photomask may or may not be used for exposure in this process.

The height of the projections formed in this way is preferably 0.1 to 3.0 µm, more preferably 0.5 to 2.0 µm, particularly preferably 1.0 to 1.5 µm. In addition, the height of the spacer is preferably 1 to 10 µm, more preferably 2 to 8 µm, particularly preferably 3 to 5 µm.

According to the method for forming the projections and / or spacers for the vertically aligned liquid crystal display device according to the present invention, microfabrication is possible, and the shape and size, for example, the height and bottom dimension can be easily controlled, and the pattern shape and heat resistance The fine projections and spacers excellent in solvent resistance, transparency, and the like can be formed with stable and good productivity, and a vertically aligned liquid crystal display device excellent in orientation, voltage retention and the like can be manufactured.                     

<Examples>

Hereinafter, although an Example of this invention is described concretely by an Example, this invention is not restrict | limited at all by these Examples.

Synthesis Example 1

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were placed in a flask equipped with a cooling tube and a stirrer, 22 parts by weight of methacrylic acid, and styrene 5 28 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 45 parts by weight of glycidyl methacrylate, and 5 parts by weight of α-methylstyrene dimer were added and nitrogen-substituted. Thereafter, the temperature of the reaction solution was raised to 70 ° C while gradually stirring, and the solution was maintained (solid content concentration 29.8 wt%) by carrying out polymerization for 4 hours while maintaining this temperature.

Mw of obtained alkali-soluble resin was 8,000. This alkali-soluble resin is called "resin (a-1)."

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were added, 15 parts by weight of methacrylic acid, and styrene 12 28 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 45 parts by weight of glycidyl methacrylate, and 5 parts by weight of α-methylstyrene dimer were added and nitrogen-substituted. Thereafter, the temperature of the reaction solution was raised to 70 ° C. while gradually stirring, and the solution was maintained (solid content concentration 29.0% by weight) by maintaining the temperature and carrying out polymerization for 4 hours.

Mw of obtained alkali-soluble resin was 7,800. This alkali-soluble resin is called "resin (a-2)."

&Lt; Synthesis Example 3 &

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of diethylene glycol ethylmethyl ether, 18 parts by weight of methacrylic acid, and styrene 6 Parts by weight, 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 33 parts by weight of glycidyl methacrylate, 33 parts by weight of p-vinylbenzyl glycidylether and α-methyl After adding 3 parts by weight of styrene dimer and replacing with nitrogen, the temperature of the reaction solution was raised to 70 ° C. while gradually stirring, and then maintained at this temperature to carry out polymerization for 5 hours (solid content concentration of 31.5% by weight). Got.

Mw of obtained alkali-soluble resin was 11,000. This alkali-soluble resin is called "resin (a-3)."

&Lt; Synthesis Example 4 &

In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added, 12 parts by weight of methacrylic acid and 2- 25 parts by weight of hydroxyethyl methacrylate, 6 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 27 parts by weight of glycidyl methacrylate, p-vinylbenzyl glycidyl ether 30 weight part and 3 weight part of (alpha) -methylstyrene dimers were further added, and after nitrogen-substituting, the temperature of reaction solution was raised to 70 degreeC, stirring gradually, maintaining this temperature, and superposing | polymerizing for 4.5 hours, A solution (solid content concentration 32.7 wt%) was obtained.

Mw of obtained alkali-soluble resin was 13,000. This alkali-soluble resin is called "resin (a-4)."

&Lt; Synthesis Example 5 &

In a flask equipped with a cooling tube and a stirrer, 8.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 220 parts by weight of diethylene glycol ethylmethyl ether, 15 parts by weight of methacrylic acid, and lauryl 10 parts by weight of methacrylate, 30 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 35 parts by weight of glycidyl methacrylate, 10 parts by weight of p-vinylbenzyl glycidyl ether And 3 weight part of (alpha) -methylstyrene dimers were added, and after nitrogen-substituting, the temperature of the reaction solution was raised to 70 degreeC, stirring gradually, maintaining this temperature, and superposing | polymerizing for 4.5 hours, the solution of alkali-soluble resin (solid content Concentration 31.5% by weight).

Mw of obtained alkali-soluble resin was 8,000. This alkali-soluble resin is called "resin (a-5)."

&Lt; Example 1 >

100 parts by weight of the resin (a-1) as the component (a), and 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethyl as the component (b) 4,4 '-[1- {4- (1- [4-hydroxyphenyl]-consisting of a condensation product of 1.0 mole of lidene] bisphenol and 2.0 moles of 1,2-naphthoquinone diazide-5-sulfonic acid chloride 30 parts by weight of 1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinone diazide-5-sulfonic acid ester, and 0.01 parts by weight of Megapack F172 as a surfactant, and the total solid concentration was 25% by weight. After diluting and dissolving with diethylene glycol ethyl methyl ether so as to be, the mixture was filtered through a membrane filter having a pore diameter of 0.2 µm to prepare a composition solution (S-1).

Subsequently, protrusions and spacers were formed in the following order, and various evaluations were performed. The evaluation results are shown in Tables 2 and 3 below.

(1-1) Formation of protrusions and spacers

After apply | coating composition solution (S-1) on a glass substrate using the spinner, it prebaked for 2 minutes on the 90 degreeC heating plate, and formed the film of 4.0 micrometers in film thicknesses. Thereafter, through a photomask having a remaining pattern having a width of 5 µm corresponding to the protruding portion and a remaining pattern of 30 µm dots corresponding to the spacer portion, ultraviolet rays having an intensity of 100 W / m ² at a wavelength of 365 nm were applied for 10 seconds. It exposed. Then, after developing at 25 degreeC for 60 second with 0.4 weight% tetramethylammonium hydroxide aqueous solution, it wash | cleaned for 1 minute with pure water. Thereafter, ultraviolet light having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 30 seconds, and then postbaked at 220 ° C. for 60 minutes in an oven to form protrusions and spacers.

(1-2) Formation of Projections and Spacers

After apply | coating composition solution (S-1) on a glass substrate using the spinner, it prebaked for 2 minutes on the 90 degreeC heating plate, and formed the film of 4.0 micrometers in film thicknesses. Thereafter, an ultraviolet ray having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds through a photomask having a remaining pattern having a width of 5 μm corresponding to the protruding portion. Thereafter, an ultraviolet ray having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds through a photomask having a remaining pattern of 30 μm dots corresponding to the spacer portion. Then, after developing at 25 degreeC for 60 second with 0.4 weight% tetramethylammonium hydroxide aqueous solution, it wash | cleaned for 1 minute with pure water. Thereafter, ultraviolet light having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 30 seconds, and then postbaked at 220 ° C. for 60 minutes in an oven to form protrusions and spacers.

(2) evaluation of resolution

When the pattern was formed in the order of the above (1-1) and (1-2), the case where the pattern was resolved was "good" and the case where it was not resolved was "bad".

(3) Evaluation of residual film rate

When forming projections and spacers using the radiation-sensitive resin composition, as disclosed in Japanese Patent Laid-Open No. 2001-201750, when the exposure energy amount (exposure time) is changed, It is preferable that the change is mild and has a high residual ratio. Therefore, the residual film rate when the ultraviolet ray having an intensity of 100 W / m ² at the wavelength of 365 nm was exposed for 4 seconds, 5 seconds, or 6 seconds was measured, respectively. The case where it exists in 90 to 110% of range with respect to the residual film rate at the time of exposing for 5 second was made into "good | favorableness."

(4-1) Evaluation of cross-sectional shape of protrusion

When the cross-sectional shape A, B or C of the protrusion is defined as follows, the cross-sectional shape of the formed protrusion is observed by a scanning electron microscope, and the case of A or B is "good" and the case of C is "bad". It was. The schematic diagram of cross-sectional shape A, B, and C of a processus | protrusion is as showing in FIG.

A: When the dimension of the bottom part exceeds 5 micrometers and is 7 micrometers or less,

B: when the dimension of the bottom part exceeds 7 micrometers,

C: Trapezoidal shape regardless of the bottom dimension.

(4-2) Evaluation of Cross-sectional Shape of Spacer

When the cross-sectional shapes A, B and C of the spacer were defined as follows, the cross-sectional shapes of the formed spacers were observed by a scanning electron microscope, and the case of A or C was "good" and the case of B was "bad". It was. The schematic diagram of the cross-sectional shape A, B, and C of a spacer is as showing in FIG.

A: When the dimension of a bottom part exceeds 30 micrometers and is 36 micrometers or less,

B: when the dimension of the bottom part exceeds 36 micrometers,

C: Trapezoidal shape regardless of the bottom dimension.                     

(5) Evaluation of heat resistance

After apply | coating composition solution (S-1) using a spinner on a silicon board | substrate, it prebaked on a 90 degreeC heating plate for 2 minutes, and formed the film of 4.0 micrometers in thickness, and Canon Co., Ltd. product is produced to the obtained film. Using a PLA-501F exposure machine (ultra high pressure mercury lamp), ultraviolet rays having an intensity of 100 W / m ² at a wavelength of 365 nm were exposed for 10 seconds. Then, the board | substrate was post-baked at 220 degreeC for 1 hour in the clean oven, the cured film was formed, and the film thickness T1 was measured. Furthermore, after performing the post-baking of the board | substrate which formed the said cured film in a clean oven at 240 degreeC for 1 hour, the film thickness (T2) of a cured film was measured and the film thickness change rate (| T2-T1 | / by further baking) T1) × 100 (%) was calculated and evaluated. When the value is 5% or less, it can be said that heat resistance is favorable.

(6) Evaluation of solvent resistance

In the same manner as in the above (5), the film thickness (T2) of the cured film was measured. Thereafter, the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide held at 70 ° C. for 20 minutes, and then the film thickness t2 of the cured film was measured, and the film thickness change rate by immersion (| t2-T2 | / T2 ) X 100 (%) was calculated and evaluated. When the value is 5% or less, it can be said that solvent resistance is favorable.

(7) evaluation of transparency

A cured film was formed on a glass substrate in the same manner as in the above (5) except that a glass substrate "Corning 7059" (manufactured by Corning Corporation) was used instead of the silicon substrate. Then, the light transmittance of the wavelength range of 400-800 nm was measured and measured with respect to the said board | substrate using the spectrophotometer "150-20 type double beam" (made by Hitachi, Ltd.). When the value is 95% or more, it can be said that transparency is favorable.

(8) Evaluation of orientation and voltage retention

Using the composition solution (S-1), protrusions and spacers were formed in the same manner as in the above (1-1) on the electrode surface of the glass substrate having the ITO (indium oxide doped tin) film as an electrode. Then, after apply | coating AL1H659 (brand name, JSR Corporation make) to the glass substrate which formed the processus | protrusion and a spacer with the liquid crystal aligning film coating machine as a liquid crystal aligning agent, it dries at 180 degreeC for 1 hour, and is 0.05 micrometer in film thickness. A film was formed.

Moreover, AL1H659 was apply | coated to the electrode surface of the other glass substrate which has an ITO film | membrane by the printing machine for liquid crystal aligning film application, as a liquid crystal aligning agent, and it dried at 180 degreeC for 1 hour, and formed the film of 0.05 micrometer in film thickness.

Subsequently, an epoxy resin adhesive containing a glass fiber having a diameter of 5 µm was applied to the liquid crystal alignment film outer surfaces of each of the obtained substrates by screen printing, and both substrates were pressed to face each other so that the liquid crystal alignment film surfaces faced, and then the adhesive was cured. I was. Thereafter, the liquid crystal injection liquid crystal MLC-6608 (trade name) manufactured by Merck Co., Ltd. was filled between the two substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy adhesive. To produce a vertically aligned liquid crystal display device. The longitudinal cross-sectional view of the obtained vertical alignment liquid crystal display element is typically shown in FIG. In Fig. 2, 1 is a spacer, 2 is a projection, 3 is a liquid crystal, 4 is a liquid crystal alignment film, 5 is a color filter, and 6 is a glass substrate.

Then, the orientation and voltage retention of the obtained vertically-aligned liquid crystal display element were evaluated as follows.

In evaluation of orientation, it observed with a polarizing microscope whether abnormal domains generate | occur | produce in a liquid crystal cell when a voltage was turned on / off, and made the case where the abnormal domain was not confirmed.

In the evaluation of the voltage retention, after applying a voltage of 5 V to the liquid crystal display element, the circuit is opened, and then the holding voltage after 16.7 milliseconds is measured, and the ratio to the applied voltage (5 V) is calculated. And the case where the value is 98% or more was "good" and the case below 98% was called "defect".

<Examples 2 to 14>

Using each component shown in Table 1, except having changed the density | concentration of the tetramethylammonium hydroxide aqueous solution which is a developing solution as shown in Table 1, it carried out similarly to Example 1, the composition solution was prepared, protrusion and spacer were formed, Various evaluations were performed. The evaluation results are shown in Tables 2 and 3.                     

(B)-(d) component in Table 1 is as follows.

b-1: 1.0 mol of 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol, and 1,2-naphthoquinone diazide- Condensate with 2.0 moles of 5-sulfonic acid chloride

b-2: Condensate of 1.0 mol of 2,3,4-trihydroxybenzophenone with 2.6 mol of 1,2-naphthoquinone diazide-5-sulfonic acid chloride

b-3: Condensate of 1.0 mol of 2,3,4,4'-tetrahydroxybenzophenone with 2.5 mol of 1,2-naphthoquinone diazide-5-sulfonic acid chloride

b-4: 1.0 mole of 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and 1.9 mole of 1,2-naphthoquinone diazide-5-sulfonic acid chloride Condensate

b-5: 1.0 mol of 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman and 1,2-naphthoquinone diazide- Condensate with 3.0 moles of 5-sulfonic acid chloride

c-1: cymel 300                     

c-2: cymel 272

c-3: Nikarak Ms-11

d-1: epicoat 828

d-2: epolite 100MF

<Example 15>

Using the composition solution (S-1) prepared in Example 1, the composition solution (S-1) was applied by a spinner on a glass substrate, and then prebaked on a 90 ° C. heating plate for 2 minutes to form a film thickness of 4.0. A micrometer film was formed. Thereafter, an ultraviolet ray having an intensity of 100 W / m ² at a wavelength of 365 nm was exposed for 10 seconds through a photomask having a remaining pattern having a width of 5 μm corresponding to the protruding portion. Then, after developing at 25 degreeC for 60 second with 0.4 weight% tetramethylammonium hydroxide aqueous solution, it wash | cleaned for 1 minute with pure water. Then, after exposing the ultraviolet-ray whose intensity | strength is 100 W / m <^2> at wavelength 365nm for 30 second, it post-baked for 60 minutes at 220 degreeC in oven, and formed protrusion.

It was A when the cross-sectional shape was observed and evaluated by the scanning electron microscope in the same way as said (4-1) about the obtained processus | protrusion.

As mentioned above, the radiation sensitive resin composition for forming the processus | protrusion and / or spacer for a vertically-aligned liquid crystal display element of this invention is excellent in resolution and a residual film rate, and has pattern shape, heat resistance, solvent resistance, Protrusion and / or spacer which are excellent in transparency, etc. can be formed, and also the vertically-aligned liquid crystal display element excellent in orientation, voltage retention, etc. can be manufactured.

In addition, the method for forming the projections and / or spacers for the vertically aligned liquid crystal display element of the present invention can be finely processed, and it is also easy to control the shape and size, for example, the height and the bottom dimension, and the pattern shape, Fine projections and spacers excellent in heat resistance, solvent resistance, transparency, and the like can be formed stably and with good productivity, and a vertically aligned liquid crystal display device excellent in orientation, voltage retention and the like can be manufactured.

Claims (8)

Alkali-soluble resin containing the homopolymer or copolymer of the radically polymerizable monomer which has (a) phenolic hydroxyl group or a carboxyl group, or both, (b) 1,2-quinone diazide compound, and (c) following General formula (1) Forming a film of a radiation sensitive resin composition containing a compound represented by A step of exposing radiation to the film once using one kind of photomask having both patterns of protrusions and spacers, Developing a film after exposure with an alkali developer to form a pattern, and Exposing the radiation to the pattern A method of forming a projection and a spacer for a vertical alignment liquid crystal display device, characterized in that it comprises a. <Formula 1>

In the formula, R ¹ to R ⁶ independently represent a hydrogen atom or a —CH ₂ OR group, and R represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. delete delete delete delete delete delete delete

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