JP2007065607A - Photosensitive resin composition, spacer for display panel and the display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of faithfully reproducing the design size of a mask pattern with high sensitivity, superior in adhesion to a substrate, capable of giving satisfactory spacer shape and film thickness with an exposure energy of ≤1,500 J/m<SP>2</SP>, superior also in strength and heat resistance, excellent in controllability of spacer shape and film thickness in a low exposure energy region, less liable to generate foreign substances during the storage period and during use, and capable of forming spacers for a display panel that is superior in process stability and temporal stability, and to provide spacers for a display panel and a display panel. <P>SOLUTION: The photosensitive resin composition contains [A] a copolymer of (a1) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic acid anhydride and (a2) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] an o-acyloxime type photopolymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a display panel spacer, and a display panel. More specifically, a photosensitive resin composition suitable as a material for forming a spacer used in a display panel such as a liquid crystal display panel or a touch panel, a display panel spacer formed from the composition, and the spacer. It relates to a display panel.

Conventionally, spacer particles such as glass beads and plastic beads having a predetermined particle diameter have been used for liquid crystal display panels in order to keep a distance (cell gap) between two substrates constant. Since these spacer particles are randomly distributed on a transparent substrate such as a glass substrate, if the spacer particles are present in the pixel formation region, the spacer particles may be reflected or incident light may be scattered, There was a problem that the contrast was lowered.
In order to solve these problems, a method of forming a spacer by photolithography has been adopted. In this method, a photosensitive resin composition is applied onto a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form dot-like or stripe-like spacers. Since the spacer can be formed only at a predetermined place, the above-described problem is basically solved.

By the way, when a spacer is formed by photolithography on a substrate used in an actual spacer forming process, for example, a color filter, a proximity exposure machine is often used. In the case of this proximity exposure, exposure is performed by providing a certain gap between the mask and the substrate coated with the photosensitive resin composition, and it is ideal that the exposure is performed in a pattern according to the mask. However, the gap is filled with air or nitrogen, and light that has passed through the opening (transparent portion) of the mask diffuses and spreads in the gap, so that the exposure is performed wider than the design size of the mask pattern. was there.
Therefore, in order to solve such a problem, the present applicant has already disclosed in Patent Document 1 1,2-octanedione-1- [4- (phenylthio) phenyl]-as a photopolymerization initiator of a photosensitive composition. By using 2- (O-benzoyloxime), it has been clarified that the design size of the mask pattern can be faithfully reproduced by proximity exposure, and a display panel spacer having excellent strength and heat resistance can be formed. ing.

Furthermore, as the liquid crystal display panel becomes larger, it is necessary to control the cell gap more accurately, but it is formed when the adhesion of the coating formed from the photosensitive composition for the spacer to the substrate is insufficient. As a result, it becomes impossible to maintain the cell gap accurately. In the liquid crystal display panel, the aperture ratio of the pixels is increasing, and as a result, the area of the black matrix region where the spacer can be arranged is gradually decreasing. Therefore, the spacer is required to have higher transparency so that the color tone of the pixel is not impaired even if the spacer enters the pixel region to some extent.
However, conventional photosensitive resin compositions used for the formation of spacers, including those described in Patent Document 1, are still not sufficient in terms of adhesion to the substrate and transparency, and these characteristics are also provided. Development of a photosensitive resin composition has been strongly desired.

In recent years, the mother glass substrate has been increased in size due to an increase in the area of liquid crystal display devices and an improvement in productivity. With the conventional substrate size (about 680 × 880 mm), since the substrate size is smaller than the mask size, it was possible to cope with the batch exposure method.
However, with a large substrate (for example, about 1,500 × 1,800 mm), it is almost impossible to create a mask size comparable to this substrate size, and it is difficult to cope with the batch exposure method. Therefore, a step exposure method has been proposed as an exposure method for large substrates. However, in the step exposure method, exposure is performed several times on one substrate, and time required for alignment and step movement is generated each time. In the step exposure method, there is a concern about a reduction in throughput as compared with the batch exposure method. Bulk The exposure method has been acceptable in the exposure sensitivity of about 3,000 J / m ^2, in step exposure method are required to the exposure sensitivity below 1,500J / m ^2. However, with existing materials, it is difficult to obtain a sufficient spacer shape and film thickness with an exposure dose of 1,500 J / m ² or less.

In addition, the required values for the controllability of the spacer shape and film thickness have become increasingly strict in recent years. The shape due to process variations when forming the spacer, the film thickness fluctuation, and the shape that accompanies changes over time in the composition solution. The problem regarding the stability of the film thickness remained. In particular, in the exposure amount region of 1,500 J / m ² or less, problems remain with respect to the controllability of the spacer shape and film thickness with respect to the exposure amount.
Furthermore, the photosensitive resin compositions used in recent liquid crystal display panel production have become serious problems such as contamination during the storage period and the occurrence of foreign substances due to crystallization of components in the composition during use. Thus, a photosensitive resin composition with reduced such problems has been desired.
JP 2001-261761 A

An object of the present invention can faithfully reproduce the design size of the mask pattern with high sensitivity, and excellent adhesion to the substrate, a sufficient spacer shape and thickness in 1,500J / m ² or less of exposure Excellent in strength, heat resistance, etc. In addition, it has excellent spacer shape and film thickness controllability in the low-exposure area, and is less likely to generate foreign matter during storage and use. Process stability Another object of the present invention is to provide a photosensitive resin composition, a display panel spacer, and a display panel that can form a display panel spacer excellent in elapsed time stability.

According to the present invention, the problem is firstly
[A] (a1) a copolymer of an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid anhydride and (a2) another ethylenically unsaturated compound,
[B] A photopolymerization initiator comprising a polymerizable compound having an ethylenically unsaturated bond and [C] a compound represented by the following formula (1) or (2)

Wherein, _{R 1} is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a phenyl group having 3 to 8 carbon atoms, _{R 2} and _{R 3} are each a hydrogen atom, an alkyl having 1 to 20 carbon atoms A cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (excluding a cycloalkyl group having 7 to 8 carbon atoms), The substituent of the phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, and R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, the number of carbon atoms A nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms; n is an integer of 1-5, m is 0-5. A number, a n + m ≦ 5,

Where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m and n are as defined above, and l is an integer from 0 to 6,
A photosensitive resin composition (hereinafter referred to as “photosensitive resin composition (a)”),
Achieved by:

  According to the present invention, secondly, the above object is achieved by a display panel spacer formed from the photosensitive resin composition (a).

  According to the present invention, thirdly, the object is achieved by a display panel comprising the display panel spacer.

The photosensitive resin composition (a) of the present invention has high sensitivity, can faithfully reproduce the design size of the mask pattern, has excellent adhesion to the substrate, and is a sufficient spacer with an exposure amount of 1,500 J / m ² or less. It is possible to obtain a shape and film thickness, and is excellent in strength, heat resistance, etc., excellent in the control of the spacer shape and film thickness in the low-exposure area, and hardly generates foreign matter during storage and use. .

  Hereinafter, the present invention will be described in detail.

Photosensitive resin composition (I)
-Copolymer [A]-
The component [A] in the photosensitive resin composition (a) is a copolymer of (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid anhydride and (a2) another ethylenically unsaturated compound. It consists of a coalescence (hereinafter referred to as “copolymer [A]”).
Among the components constituting the copolymer [A], (a1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid anhydride (hereinafter referred to as “unsaturated carboxylic acid monomer”) Examples of (a1) ”include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; maleic acid, fumaric acid Examples thereof include dicarboxylic acids such as acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of the dicarboxylic acid.

Among these unsaturated carboxylic acid monomers (a1), acrylic acid, methacrylic acid, maleic anhydride are available from the viewpoints of copolymerization reactivity, solubility of the resulting copolymer in an alkaline aqueous solution and easy availability. Etc. are preferred.
In the photosensitive resin composition (a), the unsaturated carboxylic acid monomer (a1) can be used alone or in admixture of two or more.

  In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15%. ~ 30% by weight. If the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is less than 5% by weight, the solubility in an alkaline aqueous solution tends to decrease, whereas if it exceeds 50% by weight, the alkaline aqueous solution There is a possibility that the solubility in is too large.

  Further, (a2) other ethylenically unsaturated compounds include epoxy group-containing ethylenically unsaturated compounds (hereinafter referred to as “epoxy group-containing monomers”) and other ethylenic groups having no other epoxy groups. Unsaturated compounds (hereinafter simply referred to as “other monomers”) are preferably used. These may be used alone or in combination. Examples of the epoxy group-containing monomer include glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, and 3,4-epoxycyclohexyl acrylate. Epoxy alkyl esters of acrylic acid; glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, etc. Α-alkylacrylic acid epoxy alkyl esters such as glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl; Examples thereof include glycidyl ethers such as vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether.

Among these epoxy group-containing monomers, from the viewpoint of copolymerization reactivity and spacer strength, glycidyl methacrylate, 2-methylglycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferable.
In the photosensitive resin composition (A), the epoxy group-containing monomers can be used alone or in admixture of two or more.

  In the copolymer [A], the content of the repeating unit derived from the epoxy group-containing monomer is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, and particularly preferably 30 to 50% by weight. is there. When the content of the repeating unit derived from the epoxy group-containing monomer is less than 10% by weight, the strength of the obtained spacer tends to be reduced. On the other hand, when the content exceeds 70% by weight, the resulting copolymer is stored. There is a tendency for stability to decrease.

Furthermore, (a2) Other monomers that are ethylenically unsaturated compounds include, for example, alkyl acrylates such as methyl acrylate and i-propyl acrylate; methyl methacrylate, ethyl methacrylate, and n methacrylate. Methacrylic acid alkyl esters such as butyl, sec-butyl methacrylate, t-butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricycloacrylate [5.2.1.0 ^2,6 ] decane-8 -Yl, 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl acrylate, acrylic alicyclic esters such as isobornyl acrylate; cyclohexyl methacrylate, 2-methyl methacrylate Cyclohexyl, tricyclomethacrylate [5.2.1.0 ^2,6 ] Decan-8-yl, methacrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl, methacrylic acid alicyclic ester such as isobornyl methacrylate; phenyl acrylate, acrylic Aryl ester or aralkyl ester of acrylic acid such as benzyl acid; aryl ester or aralkyl ester of methacrylic acid such as phenyl methacrylate, benzyl methacrylate; dicarboxylic acid dialkyl ester such as diethyl maleate, diethyl fumarate, diethyl itaconate; Methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acid, 2-hydroxypropyl methacrylate; tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydride methacrylate Unsaturated hetero 5- and 6-membered methacrylic acid esters containing one atom of oxygen such as fupyran-2-methyl; vinyl aromatics such as styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene Compound: Conjugated diene compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, etc. be able to.

Among these other monomers, 2-methylcyclohexyl acrylate, t-butyl methacrylate, tricyclomethacrylate [5.2 from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an aqueous alkali solution. .1.0 ^2,6] decan-8-yl, styrene, p- methoxy styrene, tetrahydrofurfuryl methacrylate, 1,3-butadiene and the like are preferable.
In the photosensitive resin composition (A), the other monomers can be used alone or in admixture of two or more.

In the copolymer [A], the content of repeating units derived from other monomers is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, and particularly preferably 30 to 50% by weight. . If the content of repeating units derived from other monomers is less than 10% by weight, the storage stability of the resulting copolymer tends to be reduced, whereas if it exceeds 70% by weight, the resulting copolymer weight There exists a tendency for the solubility with respect to the alkaline aqueous solution of a coalescence to fall.
The copolymer [A] has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, has an appropriate solubility in an alkaline aqueous solution, and does not require the use of a special curing agent. It can be easily cured by heating, and the photosensitive resin composition (a) containing the copolymer can easily form a spacer with a predetermined pattern without developing residue and film loss during development. Can be formed.

The copolymer [A] is obtained by, for example, subjecting an unsaturated carboxylic acid monomer (a1), an epoxy group-containing monomer and / or another monomer (a2) to a radical polymerization initiator in a suitable solvent. It can manufacture by superposing | polymerizing in presence of this.
Examples of the solvent used for the production of the copolymer [A] include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and propylene glycol. Examples include alkyl ether propionates, aromatic hydrocarbons, ketones and esters.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
Examples of dipropylene glycol include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate;
As propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc .;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

Of these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable. Among them, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl Particularly preferred are methyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
The said solvent can be used individually or in mixture of 2 or more types.

The radical polymerization initiator used for the polymerization is not particularly limited, and for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvalero). Nitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobis (2-methylpro) Azo compounds such as 2,7'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butyl) Organic peroxides such as peroxy) cyclohexane; hydrogen peroxide and the like. Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator combining it and a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

The copolymer [A] thus obtained may be used for the preparation of the radiation-sensitive resin composition in the form of a solution, or may be separated from the solution and used for the preparation of the radiation-sensitive resin composition. .
The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer [A] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50. , 000. If the Mw is less than 2,000, the developability and the remaining film ratio of the resulting film may be reduced, and the pattern shape, heat resistance, etc. may be impaired. There exists a possibility that it may fall or a pattern shape may be impaired.

-Polymerizable compound [B]-
[B] component in the photosensitive resin composition (A) is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as “polymerizable compound [B]”).
Although it does not specifically limit as polymeric compound [B], Monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester has favorable polymerizability, and improves the intensity | strength of the spacer obtained. It is preferable from the point of making it.

  Examples of monofunctional (meth) acrylic acid esters include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3-methoxy. Examples thereof include butyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate and the like, and commercially available products include, for example, Aronix M-101. M-111, M-114 (manufactured by Toa Gosei Co., Ltd.); KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku Co., Ltd.); Court 158, mention may be made of the same 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and 1,6-hexane. Diol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, etc. Examples of commercially available products include Aronix M-210, M-240, and M-6200 (manufactured by Toa Gosei Co., Ltd.), K YARAD HDDA, the HX-220, the R-604 (manufactured by Nippon Kayaku Co.), Viscoat 260, the 312, can be exemplified by the same 335HP (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.

  Further, trifunctional or higher functional (meth) acrylic acid esters include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, diester Examples include pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, and the like. .

In particular, a (meth) acrylate having 9 or more functional groups has an alkylene straight chain and an alicyclic structure, a compound containing two or more isocyanate groups, and a trifunctional, tetrafunctional and 5 functional group containing one or more hydroxyl groups in the molecule. The urethane acrylate compound obtained by making a functional (meth) acrylate compound react is mentioned.
As said commercial item, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, M-8060, TO-1450 (Toa Gosei ( KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (produced by Osaka Organic Chemical Industry Co., Ltd.) and the like. Examples of commercially available products of polyfunctional urethane acrylates having 9 or more functional groups include New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) Is mentioned.

Among these monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher functional (meth) acrylic acid esters are more preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol. Tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferred.
The monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester can be used alone or in combination of two or more.
In the photosensitive resin composition (A), the amount of the polymerizable compound [B] used is preferably 50 to 140 parts by weight, more preferably 60 to 120 parts by weight, based on 100 parts by weight of the copolymer [A]. It is. If the amount of the polymerizable compound [B] used is less than 50 parts by weight, there may be a residual image during development, while if it exceeds 140 parts by weight, the hardness of the resulting spacer tends to decrease.

-Photopolymerization initiator [C]-
[C] component in photosensitive resin composition (I) consists of an O-acyl oxime type photoinitiator, especially the compound (henceforth "photoinitiator" represented by said Formula (1) or (2). [C] ") is preferred.
The photopolymerization initiator as used in the present invention means a component that generates an active species capable of initiating polymerization of the polymerizable compound [B] by exposure with visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like. To do.

In the “photopolymerization initiator [C]” represented by the formula (1) or (2), R ₁ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. It is. R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms ( However, except a C7-C8 cycloalkyl group). Substituents of the substituted phenyl group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, phenyl groups, and halogen atoms. These substituents can be 1-5. R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms. R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. n is an integer of 1 to 5, m is an integer of 0 to 5, n + m ≦ 5, and l is an integer of 0 to 6.

The alkyl group having 1 to 20 carbon atoms of R _{1 in} the formula (1) or (2) can be a linear or branched alkyl group, and specific examples thereof include, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, An n-decyl group, an n-undecyl group, and an n-dodecyl group can be exemplified. Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group.

The alkyl group having 1 to 20 carbon atoms R ₂ and R ₃ may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, n- propyl group, i- Propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An undecyl group and n-dodecyl group can be mentioned. Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group.
The alkyl group having 1 to 6 carbon atoms which is a substituent of the substituted phenyl group of R ₂ and R ₃ can be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, Examples thereof include an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclopentyl group, and a cyclohexyl group.

The alkoxy group having 1 to 6 carbon atoms can be linear, branched or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n- Examples thereof include a butoxy group and a t-butoxy group. Examples of the halogen atom include a fluorine atom and a chlorine atom.
Examples of alicyclic groups having 7 to 20 carbon atoms (excluding cycloalkyl groups having 7 to 8 carbon atoms) include bicycloalkyl groups, tricycloalkyl groups, spiroalkyl groups, ter-cycloalkyl groups, and terpene skeletons Group, adamantyl skeleton-containing group and the like.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms of R ₄ include, for example, thiolanyl group, azepinyl group, dihydro Azepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, dioxaindanyl group, dihianaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, Isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, pyrrolinyl group, morpholyl group, piperazinyl group, quinuclidinyl group, indolyl group, isoindolyl group, benzofuranyl group, benzothiophenyl Group, indolizinyl group, Romenyl group, quinolinyl group, isoquinolinyl group, purinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenanthridinyl group, thioxanthenyl group, phenazinyl group, phenothiazinyl group, phenoxathinyl group Group, phenoxazinyl group, thiantenyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. Of these, a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like are particularly preferable.

The alkyl group having 1 to 12 carbon atoms of R ₅ can be linear, branched or cyclic, and specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, i-propyl group. N-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group , N-dodecyl group, cyclopentyl group, cyclohexyl group and the like.

In addition, the alkoxy group having 1 to 12 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group. Group, t-butoxy, n-pentyloxy group and the like.
Among these, R ₅ is particularly preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, or an ethoxy group.
n is preferably 1. m is preferably any one of 0, 1, 2 and particularly preferably 1, and l is preferably any one of 0, 1, 2 and particularly preferably 1.

Specific examples of the compound [C] include
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime)
Etc.

Of these, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) is preferred.
These photopolymerization initiators [C] may be used alone or in combination of two or more.

As the photopolymerization initiator [C], an O-acyloxime photopolymerization initiator other than the formula (1) (hereinafter referred to as “photopolymerization initiator [C-2]”) can be used in combination.
Specific examples of these photopolymerization initiators [C-2] include 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [ 4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2-octadione-1 -[4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyloxime)), etc. Can be mentioned. Of these, 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is particularly preferable. The photopolymerization initiator [C-2] is preferably used at 30% by weight or less of the photopolymerization initiator [C].

By using these photopolymerization initiators (C), making it possible to obtain sufficient sensitivity in 1,500J / m ² or less of the exposure amount, the spacer having adhesiveness.
The amount of the photopolymerization initiator [C] used in the photosensitive resin composition (A) is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the polymerizable compound [B]. It is. If the amount of the photopolymerization initiator [C] used is less than 1 part by weight, the residual film ratio tends to decrease during development, whereas if it exceeds 20 parts by weight, the solubility of the unexposed part in an alkaline developer during development is increased. Tends to decrease.

In the photosensitive resin composition (A), at least one photopolymerization initiator other than the O-acyloxime type photopolymerization initiator can be used in combination with the photopolymerization initiator [C].
Examples of the other photopolymerization initiator include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, and triazine compounds. A compound etc. can be mentioned. Of these, acetophenone compounds (hereinafter sometimes referred to as “component (D)”) and biimidazole compounds (hereinafter sometimes referred to as “component (E)”) are preferred.

(D) Component: Acetophenone-based compound Examples of the acetophenone-based compound include an α-hydroxyketone compound, an α-aminoketone compound, and other compounds.
Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -On, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like can be mentioned. Specific examples of α-aminoketone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino And phenyl) -butanone-1,2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. Specific examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

These acetophenone compounds can be used alone or in admixture of two or more.
By using these acetophenone compounds, it is possible to further improve sensitivity, spacer shape and compressive strength.

(E) component: biimidazole compound As a specific example of a biimidazole compound,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

Among the biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, is particularly preferable. 2'-biimidazole.
The biimidazole compounds can be used alone or in admixture of two or more.

By using these biimidazole compounds, sensitivity, resolution, and adhesion can be further improved.
Moreover, in order to sensitize a biimidazole type compound, the aliphatic or aromatic type compound (henceforth "sensitizer [E-2]") which has a dialkylamino group can be used.

Specific examples of the sensitizer [E-2] include, for example, N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, p-dimethylaminobenzoic acid. Examples include ethyl acrylate, i-amyl p-dimethylaminobenzoate, and the like. Of these sensitizers, 4,4′-bis (diethylamino) benzophenone is preferred.
These sensitizers [E-2] may be used alone or in combination of two or more.
The amount of the sensitizer [E-2] used is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of [A].
When the amount of the sensitizer [E-2] is less than 0.1 parts by weight, the resulting spacer tends to cause film slippage or poor pattern shape. When the amount exceeds 50 parts by weight, the pattern shape is similarly increased. Defects tend to occur.

  When a biimidazole compound is used, a thiol compound (hereinafter sometimes referred to as “thiol compound [E-3]”) can be used as the hydrogen donor compound. The biimidazole compound is sensitized by a benzophenone compound having a dialkylamino group, and the biimidazole compound is cleaved to generate an imidazole radical. In this case, a high radical polymerization initiating ability is not expressed, and an unfavorable shape such as a reverse taper shape is often obtained. This problem is alleviated by adding the thiol compound [E-3] to a system in which a biimidazole compound and a benzophenone compound having a dialkylamino group coexist. A hydrogen radical is donated from the thiol compound to the imidazole radical, thereby generating a compound having a neutral imidazole and a sulfur radical having a high polymerization initiating ability. Thereby, it becomes a more preferable forward taper shape from a reverse taper shape.

  The use ratio of the thiol-based compound [E-3] is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the compound [C]. . When the amount of the thiol-based compound [E-3] is less than 0.1 parts by weight, the resulting spacer tends to cause film slippage or poor pattern shape. Defects tend to occur.

  Specific examples thereof include aromatic thiols such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3 -Aliphatic monothiols such as mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate and octyl 3-mercaptopropionate. Examples of the bifunctional or higher aliphatic thiol include 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetra (mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), and the like.

  The use ratio of the other photopolymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, and particularly preferably 60 parts by weight or less with respect to 100 parts by weight of the total photopolymerization initiator. In this case, if the use ratio of the other photopolymerization initiator exceeds 100 parts by weight, the intended effect of the present invention may be impaired.

-Additives-
In the photosensitive resin composition (A), additives other than the above components can be blended as necessary within the range not impairing the intended effect of the present invention.
For example, in order to improve applicability, a surfactant can be blended. As the surfactant, a fluorine-based surfactant and a silicone-based surfactant can be suitably used.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol diester. (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2- Tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9, 9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, fluoro Sodium alkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl Examples thereof include alkoxylates and fluorine alkyl esters.

  Examples of these commercially available products include BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, F471, and F476. (Above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC 170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( Asahi Glass Co., Ltd.), Ftop EF301, 303, 352 (above, Shin-Akita Kasei Co., Ltd.), Footent FT-100, FT-11 0, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (above, ( (Manufactured by Neos Co., Ltd.).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF -8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (The above-mentioned, GE Toshiba Silicone Co., Ltd. product) etc. can be mentioned what is marketed.

Examples of surfactants other than those described above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and commercially available products such as KP341 (Shin-Etsu Chemical ( Manufactured by Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and the like.
These surfactants can be used alone or in admixture of two or more.

The blending amount of the surfactant is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. In this case, when the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film roughening tends to occur during application.
Moreover, in order to further improve the adhesion to the substrate, an adhesion assistant can be blended.

As the adhesion assistant, a functional silane coupling agent is preferable, and examples thereof include a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. More specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.
These adhesion assistants can be used alone or in admixture of two or more.

The compounding amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. When the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue tends to occur.
Other additives can be added. It is added for the purpose of improving storage stability. Specific examples include sulfur, quinones, hydroquinones, polyoxy compounds, amines, and nitronitroso compounds. Examples thereof include 4-methoxyphenol and N-nitroso-N-phenylhydroxylamine aluminum. These are preferably used in an amount of 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the copolymer [A]. When the amount exceeds 3.0 parts by weight, sufficient sensitivity cannot be obtained, and the pattern shape deteriorates.

In order to improve heat resistance, an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, and a compound having a bifunctional or higher functional epoxy group in one molecule can be added. Specific examples of the N- (alkoxymethyl) glycoluril compound include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) glycol Examples include uril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like. Of these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable. Specific examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxymethyl). ) Melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) melamine, N, N, N , N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like. Of these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable. Examples of these commercially available products include Nicalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.
Examples of compounds having two or more functional epoxy groups in one molecule include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Examples include ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol A diglycidyl ether. Specific examples of these commercially available products include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 3002 (and more) Chemical Co., Ltd.). These can be used alone or in combination of two or more.

Composition solution The photosensitive resin composition (A) is preferably dissolved in a suitable solvent, such as a copolymer [A], a polymerizable compound [B], a photopolymerization initiator [C], in use. Then, it is prepared as a composition solution.
As a solvent used for the preparation of the composition solution, a solvent that uniformly dissolves each component constituting the photosensitive resin composition (A) and does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

  Of these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. It is done. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

The composition solution prepared in this way can be used for use after filtration through a Millipore filter having a pore size of, for example, about 0.2 to 0.5 μm, if necessary.
The photosensitive resin composition (A) is particularly suitable as a material for forming spacers for display panels such as liquid crystal panels and touch panels.

When forming a display panel spacer using the display panel spacer photosensitive resin composition (a), after applying the composition solution to the surface of the substrate, pre-baking to remove the solvent, the coating film Form.
As a coating method of the composition solution, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method can be employed. In particular, a spin coating method and a slit die coating method are preferable.
Moreover, although the conditions of prebaking differ also with the kind of each structural component, a mixture ratio, etc., it is about 1 to 15 minutes at 70-90 degreeC, for example.
Next, the pre-baked coating film is exposed and polymerized through a mask having a predetermined pattern, and then developed with a developing solution, and unnecessary portions are removed to form a pattern.

As radiation used for exposure, visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray and the like can be appropriately selected, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
As the developing method, for example, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is usually 30 to 180 seconds.

  Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-n. Secondary amines such as propylamine; tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine, triethylamine; tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperidine, N-methylpiperidine , Alicyclic tertiary amines such as N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene; Collidine, Le Jin, such aromatic tertiary amine quinoline; tetramethylammonium hydroxide, the aqueous solution of an alkaline compound of a quaternary ammonium salt such as tetraethyl ammonium hydroxide may be used.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.
After development, for example, by washing with running water, for example, for 30 to 90 seconds, unnecessary portions are removed, and then compressed air or compressed nitrogen is blown to dry to form a predetermined pattern.
Thereafter, the pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, for 5 to 30 minutes on the hot plate, or for 30 to 90 minutes in the oven. By doing so, the target spacer can be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 18 parts by weight of methacrylic acid and methacrylic acid. After charging 40 parts by weight of glycidyl, 5 parts by weight of styrene, and 32 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and substituting with nitrogen, 5 weights of 1,3-butadiene is further added. The temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 5 hours for polymerization to obtain a solution of copolymer [A-1].
The solid content concentration of this solution was 33.0% by weight, and the Mw of the copolymer [A-1] was 11,000.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 15 parts by weight of methacrylic acid and methacrylic acid. 20 parts by weight of glycidyl, 25 parts by weight of 2-methylglycidyl methacrylate, 5 parts by weight of styrene, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate 10 First, 5 parts by weight of 1,3-butadiene was added, and the temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 5 hours for polymerization. A solution of copolymer [A-2] was obtained.
The solid content concentration of this solution was 33.4% by weight, and the Mw of the copolymer [A-2] was 7,000.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobis (isobutyronitrile) and 250 parts of diethylene glycol methyl ethyl ether, followed by 10 parts of methacrylic acid and 30 parts of 2-methacryloyloxyethyl succinic acid. Parts, 25 parts of n-butyl methacrylate and 30 parts of benzyl methacrylate, and after purging with nitrogen, further, 5 parts by weight of 1,3-butadiene was added, and the temperature of the solution was raised to 80 ° C. while gently stirring. Then, polymerization was carried out while maintaining this temperature for 5 hours to obtain a solution of copolymer [A-3] having a solid content concentration of 28.0% by weight. Mw of the obtained copolymer [A-3] was 9,000.

Example 1
Preparation of Composition Solution 100 parts by weight (solid content) of the copolymer [A-1] obtained in Synthesis Example 1 as a copolymer [A], and KAYARAD DPHA (Nippon Kayaku) as a polymerizable compound [B] Co., Ltd.) 80 parts by weight, as photopolymerization initiator [C], ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazole-3- Yl]-, 1- (O-acetyloxime) 5 parts by weight was dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 35% by weight, and then filtered through a Millipore filter having a pore size of 0.2 μm. A composition solution (S-1) was prepared.

(I) Formation of Spacer The above composition solution was applied on a non-alkali glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film having a thickness of 6.0 μm.

The coating film obtained above was exposed to ultraviolet rays having an exposure gap at a wavelength of 365 nm of 300 W / m ² with an exposure gap of 150 μm through a mask having a 10 μm square pattern. Next, development was performed with a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, followed by rinsing with pure water for 1 minute. Furthermore, it heated at 150 degreeC for 120 minute (s) in oven, and the spacer was formed.

(II) Evaluation of resolution In the pattern obtained in the above (I), the evaluation was performed with the minimum pattern size in the sensitivity where the remaining film ratio after development (film thickness after development / initial film thickness × 100) is 90% or more. . The smaller the pattern size, the better the resolution. The results are shown in Table 2.

(III) Sensitivity Evaluation In the pattern obtained in (I) above, if the sensitivity at which the residual film ratio after development is 90% or more is 1,500 J / m ² or less, it can be said that the sensitivity is good.

(IV) Evaluation of pattern cross-sectional shape As a result of observing the cross-sectional shape of the pattern obtained in the above (I) with a scanning electron microscope, it showed which shape of A to C shown in FIG. . When the pattern edge is forward tapered as in A, the pattern shape is good. When the pattern edge is formed in a vertical shape as in B, the pattern shape is slightly good.
In addition, as shown in C, the shape that is inversely tapered (in which the side of the film surface in the cross-sectional shape is longer than the side on the substrate side, the inverted triangle shape) is likely to cause the pattern to peel off during the subsequent rubbing process. Therefore, such a shape was regarded as defective.

(V) Evaluation of compressive strength The compressive strength of the spacer obtained in the above (I) was evaluated using a micro compression tester (MCTM-200, manufactured by Shimadzu Corporation). The amount of deformation when a load of 10 mN was applied was measured with a flat indenter with a diameter of 50 μm (measurement temperature: 23 ° C.). When this value is 0.5 or less, the compressive strength is good. The results are shown in Table 2.

(VI) Evaluation of rubbing resistance AL3046 (manufactured by JSR Co., Ltd.) as a liquid crystal aligning agent was applied to the substrate obtained in the above (I) with a printer for applying a liquid crystal alignment film, and dried at 180 ° C. for 1 hour. A coating film of an orientation agent having a dry film thickness of 0.05 μm was formed.
The coating film was rubbed with a rubbing machine having a roll around which a nylon cloth was wound at a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. Table 2 shows the presence or absence of scraping or peeling of the spacer pattern.

(VII) Evaluation of adhesiveness Except not using a pattern mask, it implemented similarly to said (I), formed the cured film for adhesiveness evaluation, and performed the adhesiveness test. The test method followed the cross-cut tape method of 8.5.2 in the adhesion test of JIS K-5400 (1900) 8.5. Table 2 shows the number of the remaining grids.

(VIII) Evaluation of storage stability After preparing the composition, the composition was stored at -15 ° C, and the change in the required exposure amount with time when the residual film ratio after development was 90% or more was tracked in the same manner as in the (III) sensitivity evaluation. The relative values of the sensitivity after 3 months after storage and the sensitivity immediately after preparation were measured. Moreover, the generation | occurrence | production degree of the 0.5 micrometer or more foreign material in the solution after 3 months was measured with the light-scattering type | mold in-liquid particle | grain detector (KS-28B, the product made by Rion Co., Ltd.). The results are shown in Table 2.

(IX) Evaluation of heat resistance A cured film was formed in the same manner as in the spacer formation except that no mask was used, and then heated in an oven at 240 ° C for 60 minutes, and the film thickness before and after heating was measured. Evaluation was made based on the residual film ratio (film thickness after heating × 100 / initial film thickness). The results are shown in Table 2.

Examples 2-11, Comparative Examples 1-4
In Example 1, a composition solution was prepared and a spacer was formed in the same manner as in Example 1 except that the types and amounts shown in Table 1 were used as the [A] component to the [E] component. And evaluated. The addition amount of [B]-[E] is a weight ratio with respect to 100 weight part of copolymer [A].

In Table 1, the abbreviations of the components indicate the following compounds.
(B-1): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
(B-2): KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.)
(B-3): Diethylene glycol diacrylate (C-1): ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl ]-, 1- (O-acetyloxime)
(C-2): Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime )
(C-3): Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyl) Oxime)
(C-4): Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime )
(C-5): Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime)
(D-1): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals)
(D-2): 2- (4-Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
(Irgacure 369 manufactured by Ciba Specialty Chemicals)
(E-1): 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (E-2): 4,4 ′ -Bis (diethylamino) benzophenone (E-3): 2-mercaptobenzothiazole In Table 1,-mark shows that this component is not added.

  The evaluation results are shown in Table 2.

It is a figure which illustrates the cross-sectional shape of a pattern.

Claims (3)

[A] (a1) a copolymer of an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid anhydride and (a2) another ethylenically unsaturated compound,
[B] A photopolymerization initiator comprising a polymerizable compound having an ethylenically unsaturated bond and [C] a compound represented by the following formula (1) or (2)

Here, R ₁ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ₂ and R ₃ are each a hydrogen atom or an alkyl having 1 to 20 carbon atoms. A cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (excluding a cycloalkyl group having 7 to 8 carbon atoms), The substituent of the phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, and R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, the number of carbon atoms A nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms; n is an integer of 1-5, m is 0-5. A number, a n + m ≦ 5,

Where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m and n are as defined above, and l is an integer from 0 to 6,
A photosensitive resin composition comprising:   A display panel spacer formed from the photosensitive resin composition according to claim 1. A display panel comprising the display panel spacer according to claim 2.

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