KR100796123B1 - Photosensitive Resin Composition, Spacer for Display Panel and Display Panel - Google Patents

Abstract

The present invention

[A] a copolymer of (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) another ethylenically unsaturated compound,

[B] a polymerizable compound having an ethylenically unsaturated bond, and

(C) O-acyl oxime type photoinitiator It is related with the photosensitive resin composition characterized by the above-mentioned.

The present invention is highly sensitive and faithfully reproduces the design size of the mask pattern, has excellent adhesion with the substrate, makes it possible to obtain a sufficient spacer shape and film thickness at an exposure amount of 1,500 J / m 2 or less, and also has strength, heat resistance, and the like. It is excellent in the shape of the spacer in the low exposure area and the controllability of the film thickness, it is difficult to generate foreign substances during use during the storage period, it is possible to form a spacer for a display panel excellent in process stability and elapsed time stability It provides a photosensitive resin composition.

Photosensitive resin composition, spacer for display panels, display panel

Description

Photosensitive resin composition, spacer for display panel, and display panel {Photosensitive Resin Composition, Spacer for Display Panel and Display Panel}

1 is a diagram illustrating a cross-sectional shape of a pattern.

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

In the liquid crystal display panel, spacer particles such as glass beads and plastic beads having a predetermined particle size have been conventionally used in order to maintain a constant gap (cell spacing) between two substrates. Since these spacer particles are irregularly dispersed on a transparent substrate such as a glass substrate, when the spacer particles are present in the pixel formation region, the phenomenon that the spacer particles are imprinted or the incident light is scattered causes the contrast of the liquid crystal panel to decrease. There was a problem.

Thus, in order to solve these problems, a method of forming a spacer by photolithography has been adopted. In this method, the photosensitive resin composition is applied onto a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form a dot or stripe-shaped spacer, and the spacer is formed only at a predetermined place other than the pixel formation region. Since it is possible to solve the above problem, the above problem is basically solved.

By the way, when forming a spacer by photolithography on the board | substrate used for a real spacer formation process, for example, a color filter etc., a proximity exposure machine is often used. In this proximity exposure, it exposes at regular intervals between a mask and the board | substrate which apply | coated the photosensitive resin composition, and it is ideal to expose by the pattern of a mask as it is. However, since the gap is filled with air or nitrogen, and light passing through the opening (transparent portion) of the mask diffuses and spreads in the gap, there is a problem that it is exposed to a wider than the design size of the mask pattern.

Thus, in order to solve this problem, the applicant has already disclosed in Japanese Patent Laid-Open No. 2001-261761 as 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- as a photopolymerization initiator of a photosensitive composition. By using (O-benzoyl oxime), it is made clear that the design size of the mask pattern can be faithfully reproduced even by close exposure, and a display panel spacer excellent in strength, heat resistance and the like can be formed.

In addition, as the size of the liquid crystal display panel increases, it is necessary to control the cell spacing more accurately. However, if the adhesion of the film formed of the photosensitive composition for the spacer is insufficient, the formed spacers are deviated from the substrate. It will be impossible to keep accurate. In the liquid crystal display panel, the aperture ratio of the pixel is increasing, and as a result, the area of the black matrix region in which the spacer can be disposed is gradually decreasing. Therefore, even if the spacer enters the pixel region to some extent, higher transparency is required for the spacer, so as not to damage the color tone of the pixel.

However, in the conventional photosensitive resin composition used for the formation of a spacer, including the one disclosed in Japanese Unexamined Patent Application Publication No. 2001-261761, it is not always sufficient in terms of adhesiveness and transparency with a substrate, and also has photosensitive properties that combine these characteristics. The development of the resin composition was strongly desired.

Moreover, in recent years, enlargement of the mother glass substrate is progressing from the large area of a liquid crystal display device, the improvement of productivity, etc. In the conventional board | substrate size (about 680x880 mm), since a board | substrate size is smaller than a mask size, it was possible to respond by the batch exposure system.

However, in large substrates (e.g., about 1,500 x 1,800 mm), it is almost impossible to manufacture a mask size about the same as this substrate size, and it is difficult to cope with the batch exposure method. Therefore, the step exposure method is proposed as a large format board | substrate-adaptive exposure system. However, in the step exposure system, exposure is performed several times on one substrate, and time required for alignment and step movement occurs each time. In the step exposure method, a reduction in the throughput is feared compared to the batch exposure method. In the batch exposure method, the exposure sensitivity of about 3,000 J / m 2 is allowed, but in the step exposure method, the exposure sensitivity is required to be 1,500 J / m 2 or less. However, with existing materials, it is difficult to obtain a sufficient spacer shape and film thickness with an exposure amount of 1,500 J / m 2 or less.

In addition, the requirements regarding the shape of the spacer and the controllability of the film thickness have become increasingly stringent in recent years, and the shape caused by the variation of the process when forming the spacer, the variation in the film thickness, the shape due to the change of the composition solution over time, the film The problem remained about the stability of the thickness. In particular, in the exposure range of 1,500 J / m <2> or less, the subject remained about the controllability of the shape of a spacer with respect to an exposure amount, and a film thickness.

In addition, recently, the photosensitive resin composition used in the manufacture of liquid crystal display panels has a serious problem such as contamination of the device due to foreign matters due to the storage period, crystallization of components in the composition during use, and the like. A composition was desired.

Therefore, the problem of the present invention is that it is highly sensitive and can faithfully reproduce the design size of the mask pattern, has excellent adhesion with the substrate, and makes it possible to obtain a sufficient spacer shape and film thickness with an exposure amount of 1,500 J / m 2 or less, A display panel spacer that is excellent in strength, heat resistance, and the like, and has excellent controllability in the shape and thickness of the spacer in a low exposure area, is unlikely to generate foreign substances during use during storage, and has excellent process stability and elapsed time stability. It is providing the photosensitive resin composition, spacer for display panels, and display panel which can be formed.

According to the present invention, the problem is first

[A] a copolymer of (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) another ethylenically unsaturated compound,

[B] a polymerizable compound having an ethylenically unsaturated bond, and

(C) It is achieved by the photosensitive resin composition (henceforth "photosensitive resin composition (a)") containing the photoinitiator containing the compound represented by following formula (1) or (2).

In formula, R <_1> is a C1-C20 alkyl group, a C3-C8 cycloalkyl group, or a phenyl group, R <_2> and R <_3> is a hydrogen atom, a C1-C20 alkyl group, a C3-C8 cycloalkyl group, substitution Or an unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (excluding a cycloalkyl group having 7 to 8 carbon atoms), and the substituent of the substituted 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, 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, and R ₅ is hydrogen or 1 to 12 carbon atoms; Is an alkyl group 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,

In formula, the definition of R <_1> , R <_2> , R <_3> , R <_4> , R <_5> , m, and n is the same as the above, and l is an integer of 0-6.

According to this invention, the said subject is achieved by the spacer for display panels formed by the photosensitive resin composition (a) for the second time.

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

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Photosensitive Resin Composition (A)

Copolymer [A]-

Component [A] in the photosensitive resin composition (A) is a copolymer of (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) other ethylenically unsaturated compounds (hereinafter, " Copolymer [A] ").

Among the components constituting the copolymer [A], (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride (hereinafter, collectively referred to as "unsaturated carboxylic acid monomer (a1)") )), For example, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of the said dicarboxylic acid, etc. are mentioned.

Among these unsaturated carboxylic acid monomers (a1), acrylic acid, methacrylic acid, maleic anhydride and the like are preferred in view of easy copolymerization reactivity and solubility in an aqueous alkali solution of the resulting copolymer.

In the photosensitive resin composition (A), an unsaturated carboxylic acid monomer (a1) can be used individually or in mixture of 2 or more types.

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, particularly preferably 15 to 30% by weight. %to be. When the content rate of the repeating unit derived from an unsaturated carboxylic acid monomer (a1) is less than 5 weight%, there exists a tendency for the solubility to aqueous alkali solution to fall, and when it exceeds 50 weight%, the solubility to aqueous alkali solution will become large too much. There is concern.

In addition, (a2) as another ethylenically unsaturated compound, an epoxy group containing ethylenically unsaturated compound (henceforth "epoxy group containing monomer"), and another ethylenically unsaturated compound which does not have an epoxy group other than it (henceforth a "other Monomers "are preferably used. These are used alone or in combination. Examples of the epoxy group-containing monomers include epoxy acrylates such as glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, and 3,4-epoxycyclohexyl acrylate. Alkyl esters; Meta such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate Crylic acid epoxy alkyl ester; α-alkylacrylic acid epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl; and glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

Of these epoxy group-containing monomers, in terms of copolymerization reactivity and spacer strength, methacrylic acid glycidyl, methacrylic acid 2-methylglycidyl, methacrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether , m-vinylbenzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferable.

In the photosensitive resin composition (A), an epoxy group containing monomer can be used individually or in mixture of 2 or more types.

In the copolymer [A], the content rate of the repeating unit derived from an epoxy group containing monomer becomes like this. Preferably it is 10 to 70 weight%, More preferably, it is 20 to 60 weight%, Especially preferably, it is 30 to 50 weight%. When the content rate of the repeating unit derived from an epoxy group containing monomer is less than 10 weight%, the intensity | strength of the spacer obtained tends to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of the copolymer obtained to fall.

Moreover, as another monomer which is (a2) ethylenically unsaturated compound, For example, alkyl acrylates, such as methyl acrylate and i-propyl acrylate; Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl acrylate Acrylic alicyclic esters such as isoboroyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate Methacrylic acid alicyclic esters such as decan-8-yloxy) ethyl, isobornyl methacrylate; Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; Aryl esters or aralkyl esters of methacrylic acid, such as phenyl methacrylate and benzyl methacrylate; Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl methacrylic acid and 2-hydroxypropyl methacrylic acid; Unsaturated hetero five-membered and six-membered methacrylic acid esters containing one atom of oxygen such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate; Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene; Conjugated diene compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, acetic acid Vinyl and the like.

Among these other monomers, 2-methylcyclohexyl acrylate, t-butyl methacrylate and tricyclo [5.2.1.0 ^2,6 ] decane- in terms of copolymerization reactivity and solubility in an aqueous alkali solution of the resulting copolymer. 8-yl, styrene, p-methoxystyrene, tetrahydrofurfuryl methacrylate, 1,3-butadiene and the like are preferred.

In the photosensitive resin composition (A), another monomer can be used individually or in mixture of 2 or more types.

In copolymer [A], the content rate of the repeating unit derived from another monomer becomes like this. Preferably it is 10-70 weight%, More preferably, it is 20-50 weight%, Especially preferably, it is 30-50 weight%. When the content rate of the repeating unit derived from another monomer is less than 10 weight%, there exists a tendency for the storage stability of the copolymer obtained to fall, and when it exceeds 70 weight%, the solubility with respect to the aqueous alkali solution of the copolymer obtained will fall. There is this.

The copolymer [A] has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, has suitable solubility in aqueous alkali solution, and can be easily cured by heating without using a special curing agent in combination. The photosensitive resin composition (a) containing the said copolymer does not produce | generate the residue and film | membrane at the time of image development, and can form a spacer of a predetermined pattern easily.

Copolymer [A] can be produced by, for example, polymerizing an unsaturated carboxylic acid monomer (a1), an epoxy group-containing monomer and / or another monomer (a2) in the presence of a radical polymerization initiator in a suitable solvent.

Examples of the solvent used in the preparation of the copolymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, Propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones, esters and the like.

As these specific examples, As alcohol, For example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl- 1-propanol etc .;

As the ether, for example, tetrahydrofuran and the like;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As dipropylene glycol, For example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

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 .;

As an aromatic hydrocarbon, For example, toluene, xylene, etc .;

As a ketone, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc .;

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and hydroxyacetic acid. Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl oxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, butoxyacetate Ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 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, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy butyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Butyl, can be given a 3-butoxy-propionic acid propyl, 3-butoxy-propionic acid butyl ester, etc., respectively.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether and propylene glycol alkyl ether acetate are preferred, and among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and dipropylene. Glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate are particularly preferred.

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

Moreover, as a radical polymerization initiator used for the said superposition | polymerization, it does not specifically limit, 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), dimethyl2,2'-azo Azo compounds such as bis (2-methylpropionate) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1-bis (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like. In addition, when using a peroxide as a radical polymerization initiator, you may use it and a reducing agent together as a redox type initiator.

These radical polymerization initiators can be used individually or in mixture of 2 or more types.

The copolymer [A] thus obtained may be used as it is for the production of the photosensitive resin composition or may be separated from the solution and used for the production of the photosensitive resin composition.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by the gel permeation chromatography (GPC) of the copolymer [A] is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. If Mw is less than 2,000, developability, residual film ratio, etc. of the resulting film may be reduced, or pattern shape, heat resistance, etc. may be impaired. On the other hand, if Mw is more than 10,000, resolution may be reduced or pattern shape may be damaged. There is.

Polymerizable Compound [B]-

[B] component in the photosensitive resin composition (a) contains the polymeric compound (henceforth "polymerizable compound [B]") which has an ethylenically unsaturated bond.

Although it does not specifically limit as a polymeric compound [B], The monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester is preferable at the point which has good polymerizability and improves the intensity | strength of the spacer obtained.

As monofunctional (meth) acrylic acid ester, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, iso Boronyl acrylate, Isoboroyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2-methacryl Royloxyethyl-2-hydroxypropyl phthalate etc. are mentioned, As a commercial item, For example, Aronix M-101, Copper M-111, Copper M-114 (made by Toagosei Co., Ltd.); KAYARAD TC-110S and TC-120S (manufactured by Nippon Kayaku Co., Ltd.); Biscot 158, East 2311 (The Osaka Yuki Kagaku Kogyo KK) etc. are mentioned.

Moreover, as bifunctional (meth) acrylic acid ester, For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, Tetraethyleneglycol Dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, 1,9-nonanedioldimethacrylate And bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene dimethacrylate, and the like. Examples of commercially available products include Aronix M-210, Copper M-240, and Copper M-6200. (Product made in Toa Kosei Co., Ltd.), Kayarad HDDA, east HX-220, east R-604 (made in Nippon Kayaku Co., Ltd.), biscot 260, east 312, east 335HP (Osaka Yuuki Kagaku high school) Ltd.) etc. are mentioned.

Moreover, as (meth) acrylic acid ester more than trifunctional, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Acrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acrylic) Royloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, and the like.

In particular, the 9- or more functional (meth) acrylate has an alkylene linear chain and an alicyclic structure, and is a trifunctional, tetrafunctional and 5-functional (meth) compound containing two or more isocyanate groups and one or more hydroxyl groups in the molecule. The urethane acrylate compound obtained by making an 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, TO-1450 (Doago) Ossei Co., Ltd.), Kayarard TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (made by Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (Osaka Yuuki Kagaku Kogyo Co., Ltd.) etc. are mentioned. Commercially available products of polyfunctional urethane acrylates having 9 or more functionalities include, for example, New Frontier R-1150 (above, Daiichi Kogyo Seiyaku Co., Ltd.), Kayarard DPHA-40H (above, Nippon Kayaku Co., Ltd.) Etc. can be mentioned.

Among these monofunctional, bifunctional or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher (meth) acrylic acid esters are more preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylic acid are particularly preferred. Preference, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferred.

The said monofunctional, bifunctional, or trifunctional or more than (meth) acrylic acid ester can be used individually or in combination of 2 or more types.

In the photosensitive resin composition (A), the usage-amount of a polymeric compound [B] becomes like this. Preferably it is 50-140 weight part, More preferably, it is 60-120 weight part with respect to 100 weight part of copolymers [A]. When the usage-amount of polymeric compound [B] is less than 50 weight part, there exists a possibility that image development residue may arise at the time of image development, and when it exceeds 140 weight part, there exists a tendency for the hardness of the spacer obtained to fall.

-Photoinitiator [C]-

[C] component in the photosensitive resin composition (A) contains an O-acyl oxime type photoinitiator, Especially the compound represented by the said General formula (1) or 2 (henceforth "photoinitiator [C]") This is preferred.

The photoinitiator as used in this invention means the component which generate | occur | produces the active species which can start superposition | polymerization of a polymeric compound [B] by exposure by visible light, an ultraviolet-ray, an ultraviolet-ray, a charged particle beam, X-rays, etc. .

In "photoinitiator [C]" represented by the said Formula (1) or (2), R <_1> is a C1-C20 alkyl group, a C3-C8 cycloalkyl group, or a phenyl group. R ₂ and R ₃ each represent 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 (with the exception of a cycloalkyl group having 7 to 8 carbon atoms). Is). The substituent of the substituted phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom. These substituents may 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 1-5, m is an integer of 0-5, n + m <= 5, and l is an integer of 0-6.

In Formula 1 or 2, the alkyl group having 1 to 20 carbon atoms of R ₁ may be a linear or branched alkyl group, and specific examples thereof include 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 is mentioned. As a C3-C8 cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example.

Further, the alkyl group having 1 to 20 carbon atoms of R ₂ and R ₃ may be linear or branched, and specific examples thereof include 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 Can be mentioned. As a C3-C8 cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example.

The alkyl group having 1 to 6 carbon atoms as a substituent of the substituted phenyl group of R ₂ and R ₃ may be linear, branched or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n- A butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

In addition, the alkoxy group having 1 to 6 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, t- Butoxy group etc. are mentioned. As a halogen atom, a fluorine atom, a chlorine atom, etc. are mentioned, for example.

Examples of the alicyclic group having 7 to 20 carbon atoms (excluding cycloalkyl groups having 7 to 8 carbon atoms) include bicycloalkyl group, tricycloalkyl group, spiroalkyl group, tert-cycloalkyl group, terpene skeleton-containing group, and adamantyl skeleton. And the like can be mentioned.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms for R ₄ , the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms include, for example, a thioranyl group, an azepinyl group and a dihydroazinyl group. , Dioxolanyl group, triazinyl group, oxathinyl group, thiazolyl group, oxadiazinyl group, dioxadinyl group, dicianaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, iso Oxazolyl, thiazolyl, isothiazolyl, pyrazolyl, prazanyl, pyranyl, pyridinyl, pyridazinyl, pyrimidyl, pyrazinyl, pyrrolinyl, morphonyl, piperadi Nilyl group, quinuclidinyl group, indolyl group, isoindolyl group, benzofuranyl group, benzothiophenyl group, indolinyl group, chromenyl group, quinolinyl group, isoquinolinyl group, purinyl group, quinazolinyl group, cinnoline Neyl group, phthalazinyl group, putridinyl group, carbazolyl group, acridi Group, and the like phenanthridine D group, thioxanthone te group, a phenacyl possess group, a group possess phenothiazine, page noksa T group, page noksa di group, Tian tray group, a tetrahydrofuranyl group, a tetrahydropyranyl group. Among these, tetrahydrofuranyl group, tetrahydropyranyl group, etc. are especially preferable.

The alkyl group of 1 to 12 carbon atoms of R ₅ may be linear, branched or cyclic, and specific examples thereof include 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, cyclophene Tyl group, cyclohexyl group, etc. are mentioned.

In addition, alkoxy groups 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, t- Butoxy, n-pentyloxy group, etc. are mentioned.

As R <_5> , among these, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, a methoxy group, and an ethoxy group are preferable especially.

It is preferable that n is 1. It is preferable that m is any one of 0, 1, 2, It is especially preferable that it is 1, It is preferable that l is any of 0, 1, 2, It is especially preferable that it is 1.

As a specific example of such a compound [C],

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-benzoylacetyloxime) ;

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-dioxoranyl) methoxybenzoyl] -9.H.-carbazol-3-yl ]-, 1- (O-acetyloxime), etc. are mentioned.

Among these, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyl Oxime); 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-dioxoranyl) methoxybenzoyl] -9.H.-carbazol-3-yl ]-And 1- (O-acetyloxime) are preferred.

These photoinitiators [C] can also be used individually or in combination of 2 or more types.

As a photoinitiator [C], O-acyl oxime type photoinitiators other than the said Formula (1) (henceforth "photoinitiator [C-2]") can also be used together.

Specific examples of these photoinitiators [C-2] include 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and 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-octadione-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyl oxime)) etc. are mentioned. Among them, 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is particularly preferable. It is preferable to use photoinitiator [C-2] in 30 weight% or less of photoinitiator [C].

By using these photoinitiators [C], it is possible to obtain the spacer which has sufficient sensitivity and adhesiveness with the exposure amount of 1,500 J / m <2> or less.

The amount of the photopolymerization initiator [C] 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]. If the amount of the photopolymerization initiator [C] is less than 1 part by weight, the remaining film ratio at the time of development tends to be lowered. On the other hand, if it exceeds 20 parts by weight, the solubility in the alkaline developer at the unexposed portion is decreased. have.

In addition, in photosensitive resin composition (a), 1 or more types of photoinitiators other than O-acyl oxime type photoinitiator can be used together with photoinitiator [C].

As said other photoinitiator, a biimidazole type compound, a benzoin type compound, an acetophenone type compound, a benzophenone type compound, the (alpha)-diketone type compound, a polynuclear quinone type compound, a xanthone type compound, a phosphine type compound, Triazine type compound etc. are mentioned. Among these, acetophenone compounds (hereinafter sometimes referred to as "(D) component") and nonimidazole compound (hereinafter referred to as "(E) component") are preferable.

(D) Component: Acetophenone-Based Compound

Moreover, as an acetophenone type compound, the (alpha)-hydroxy ketone type compound, the (alpha)-amino ketone type compound, compounds other than these are mentioned, for example.

Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methyl Propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned. Specific examples of the α-aminoketone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. are mentioned. Specific examples of the compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

These acetophenone type compounds can be used individually or in mixture of 2 or more types.

By using these acetophenone compounds, it is possible to further improve the sensitivity, the spacer shape and the compressive strength.

(E) Component: Biimidazole Compound

As a specific example of a biimidazole type 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,

2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

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 particularly preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole.

The said biimidazole type compound can be used individually or in mixture of 2 or more types.

By using these biimidazole type compounds, it is possible to further improve sensitivity, resolution, and adhesiveness.

In addition, in order to sensitize the biimidazole compound, an aliphatic or aromatic compound having a dialkylamino group (hereinafter sometimes referred to as "sensitizer [E-2]") can be used.

As a specific example of the sensitizer [E-2], for example, N-methyldiethanolamine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and p-dimethylaminobenzoic acid ethyl, p-dimethylaminobenzoic acid i-amyl, etc. are mentioned. Among these sensitizers, 4,4'-bis (diethylamino) benzophenone is preferable.

These sensitizers [E-2] can be used individually or in combination of 2 or more types.

The amount of the sensitizer [E-2] to be 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 part by weight, there is a tendency that the film of the spacer obtained is reduced or a pattern shape defect occurs. When the amount of the sensitizer [E-2] is exceeded, a pattern shape defect tends to occur similarly.

In the case of using a biimidazole compound, a thiol compound (hereinafter sometimes referred to as "thiol compound [E-3]") can be used as the hydrogen donor compound. A biimidazole type compound is sensitized by the benzophenone type compound which has a dialkylamino group, and a biimidazole type compound cleaves and produces an imidazole radical. In this case, high radical polymerization initiation ability is not expressed, and in many cases, it becomes an undesirable shape like reverse taper shape. This problem is alleviated by adding thiol-based compound [E-3] to the system in which the biimidazole-based compound and the benzophenone-based compound having a dialkylamino group coexist. By donating a hydrogen radical from a thiol type compound to an imidazole radical, a compound having neutral imidazole and a sulfur radical having a high polymerization initiation capacity is generated. Thereby, a more preferable forward taper shape becomes 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 part by weight, the film of the spacer obtained tends to decrease or a pattern shape defect occurs. When the amount of the thiol compound [E-3] exceeds 50 parts by weight, a pattern shape defect tends to occur.

Specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-meth And aliphatic monothiols such as aromatic thiols such as oxybenzoimidazole, 3-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 another photoinitiator becomes like this. Preferably it is 100 weight part or less, More preferably, it is 80 weight part or less, Especially preferably, it is 60 weight part or less with respect to 100 weight part of all photoinitiators. In this case, when the use ratio of another photoinitiator exceeds 100 weight part, the desired effect of this invention may be impaired.

-additive-

You may mix | blend additives other than the said component with the photosensitive resin composition (a) as needed in the range which does not impair the desired effect of this invention.

For example, in order to improve applicability | paintability, surfactant can be mix | blended. As the surfactant, fluorine-based surfactants and silicone-based surfactants can be preferably used.

As the fluorine-based surfactant, a compound having fluoroalkyl or fluoroalkylene in at least one of terminal, main chain and side chain can be preferably used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, and octa. Ethylene glycol di (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 perfluorododecyl sulfonate, 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, Sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodido, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether , Perfluoro Kill poly there may be mentioned oxy ethanol, perfluoroalkyl alkoxylates, fluorinated alkyl esters and the like.

In addition, as these commercial items, for example, BM-1000, BM-1100 (above, BM CHEMIE), Megapack F142D, F172, F173, F183, F178, F191, F191, F471 , F476 (above, Dai Nippon Ink Chemical Co., Ltd.), Florard FC 170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Suplon S- 112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC- 105, east SC-106 (above, made by Asahi Glass Co., Ltd.), F-top EF 301, east 303, east 352 (above, made by Shinsei Kasei Co., Ltd.), butagent FT-100, east FT-110, East FT-140A, East FT-150, East FT-250, East FT-251, East FTX-251, East FTX-218, East FT-300, East FT-310, East FT-400S Neo's) etc. are mentioned.

Moreover, as silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF -8428, copper DC-57, copper DC-190 (above, made by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 What is marketed by brand names, such as GE Toshiba Silicone Co., Ltd., are mentioned above.

Moreover, as surfactant other than the above, 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; As nonionic surfactants, such as polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, and a commercial item, KP341 (made by Shin-Etsu Chemical Co., Ltd.), polyflow No. . 57, 95 (manufactured by Kyoeisha Oil Chemical Industries, Ltd.) and the like.

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

The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the copolymer [A]. In this case, when the compounding quantity of surfactant exceeds 5 weight part, it exists in the tendency for a film | membrane to become easy at the time of application | coating.

  Moreover, in order to further improve adhesiveness with a base | substrate, an adhesion | attachment adjuvant can be mix | blended.

As said adhesion | attachment adjuvant, a functional silane coupling agent is preferable, The silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned as an example. More specifically, trimethoxysilyl benzoic acid, (gamma) -methacryloyloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, (gamma) -isocyanate propyl triethoxysilane, (gamma)-glycidoxy Propyl trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

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

The compounding quantity of an adhesion | attachment adjuvant becomes like this. Preferably it is 20 weight part or less, More preferably, it is 10 weight part or less with respect to 100 weight part of copolymers [A]. When the compounding quantity of an adhesion | attachment adjuvant exceeds 20 weight part, there exists a tendency for image development residue to occur easily.

Other additives can be added. It is added for the purpose of improvement of storage stability, etc. Specifically, sulfur, quinones, hydroquinones, a polyoxy compound, an amine, a nitronitroso compound are mentioned. As the example, 4-methoxy phenol, N-nitroso-N-phenylhydroxylamine aluminum, etc. are mentioned. 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 it exceeds 3.0 weight part, sufficient sensitivity will not be acquired and a pattern shape will deteriorate.

In addition, a compound having an N- (alkoxymethyl) glycol uril compound, an N- (alkoxymethyl) melamine compound, and a bifunctional or higher epoxy group in one molecule can be added for improving heat resistance. 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, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n- Butoxymethyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, etc. are mentioned. Among them, 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 (e) Methoxymethyl) 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. Among them, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable. As these commercial items, Nikarak N-2702, MW-30M (above, Sanwa Chemical Co., Ltd. product), etc. are mentioned. Examples of the compound having a bifunctional or higher functional epoxy group in one molecule include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol di. Glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, Bisphenol A diglycidyl ether, etc. are mentioned. 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 (above, Kyoesha Chemical Co., Ltd. make), etc. are mentioned. These can be used individually or in combination of 2 or more types.

Composition solution

When using the photosensitive resin composition (A), components, such as a copolymer [A], a polymeric compound [B], and a photoinitiator [C], are dissolved in a suitable solvent, and are manufactured as a composition solution.

As a solvent used for manufacture of the said composition solution, the thing which melt | dissolves each component which comprises the photosensitive resin composition (a) uniformly, 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 is mentioned.

Among these solvents, for example, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among them, 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 ethylmethyl Ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate, ethyl ethoxypropionate can be particularly preferably used.

Moreover, in order to raise the in-plane uniformity of a film thickness with the said solvent, you may use together a high boiling point solvent. As a high boiling point solvent which can be used together, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methyl, for example Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

The composition solution thus prepared can be filtered for use by a Millipore filter or the like having a pore size of, for example, about 0.2 to 0.5 µm, and used for use.

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.

For display panels Spacer

When forming the spacer for display panels using the photosensitive resin composition (A), after apply | coating a composition solution to the surface of a board | substrate, it pre-bakes and removes a solvent and forms a coating film.

As a coating method of the composition solution, for example, a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet coating method, or the like can be adopted, and in particular, spin The coating method and the slit die coating method are preferable.

In addition, although the conditions of prebaking differ also with kinds, mixing ratio, etc. of each structural component, it is about 1 to 15 minutes at 70-90 degreeC, for example.

Subsequently, it exposes and superpose | polymerizes through the prebaked coating film through the mask of a predetermined pattern, and develops with a developing solution, and removes an unnecessary part and forms a pattern.

As radiation used for exposure, visible rays, ultraviolet rays, far ultraviolet rays, charged particle beams, X rays, and the like can be appropriately selected, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

As a developing method, any of a paddle method, an immersion method, a shower method, etc. may be used, for example, and developing time is 30 to 180 second normally.

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, n-propylamine; Secondary amines such as diethylamine, di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine, triethylamine; Tertiary 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] Alicyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine, quinoline; Aqueous solutions of alkaline compounds, 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 aqueous solution of the alkaline compound.

After the development, for example, by washing with running water or the like, for example, washing is performed for 30 to 90 seconds to remove unnecessary portions, and then a predetermined pattern is formed by blowing by blowing compressed air or compressed nitrogen.

Then, this 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 and on the hot plate, for example, for 5 to 30 minutes, in the oven, for example, for 30 to The target spacer can be obtained by heat-processing for 90 minutes.

The photosensitive resin composition (a) of the present invention is highly sensitive and can faithfully reproduce the design size of the mask pattern, has excellent adhesion with the substrate, and obtain sufficient spacer shape and film thickness at an exposure amount of 1,500 J / m 2 or less. It is made possible, and also excellent in strength, heat resistance, etc., excellent in controllability of the shape and thickness of the spacer in the low exposure amount region, and foreign matter hardly occurs during use during the storage period.

<Example>

Although an Example and a comparative example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to these Examples.

Synthesis Example 1

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 18 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 32 parts by weight of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl were substituted with nitrogen, followed by further 1,3-butadiene. 5 parts by weight was added and the temperature of the solution was raised to 70 ° C. while stirring slowly, and the polymerization was carried out while maintaining the temperature for 5 hours to obtain a solution of copolymer [A-1].

Solid content concentration of this solution was 33.0 weight%, and Mw of copolymer [A-1] was 11,000.

Synthesis Example 2

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 methylethyl ether were added, and then 15 parts by weight of methacrylic acid, 20 parts by weight of glycidyl methacrylate, 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 ] decane-8-yl, 10 parts by weight of tetrahydrofurfuryl methacrylate was added, followed by nitrogen substitution, and then 5 parts by weight of 1,3-butadiene was added, and the temperature of the solution was raised to 70 ° C. while stirring slowly, and the temperature was maintained for 5 hours. It superposed | polymerized and obtained the solution of copolymer [A-2].

Solid content concentration of this solution was 33.4 weight%, and Mw of the copolymer [A-2] was 7,000.

Synthesis Example 3

5 parts of 2,2'- azobis (isobutyronitrile) and 250 parts of diethylene glycol methylethyl ether were put into a flask equipped with a cooling tube and a stirrer, and then 10 parts of methacrylic acid and 2-methacryloyloxy 30 parts of ethyl succinic acid, 25 parts of n-butyl methacrylate and 30 parts of benzyl methacrylate were added thereto, and after nitrogen replacement, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was gradually decreased to 80 ° C. The solution was copolymerized while maintaining the temperature for 5 hours to obtain a solution of a copolymer [A-3] having a solid content concentration of 28.0 wt%. Mw of the obtained copolymer [A-3] was 9,000.

<Example 1>

Preparation of Composition Solution

100 parts by weight (solid content) of the solution of the copolymer [A-1] obtained in Synthesis Example 1 as the copolymer [A], 80 parts by weight of Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the polymerizable compound [B], As photoinitiator [C] ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- 5 parts by weight of (O-acetyl oxime) was dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 35% by weight, followed by filtration with a Millipore filter having a pore diameter of 0.2 µm to prepare a composition solution (S-1).

(I) formation of spacer

After applying the composition solution using a spinner on an alkali free glass substrate, the composition was prebaked at 90 ° C. for 3 minutes on a hot plate to form a coating film having a thickness of 6.0 μm.

The exposure film | membrane was made into 150 micrometers through the mask of the remaining pattern of 10 micrometer side to the coating film obtained above, and exposure by the ultraviolet-ray whose exposure intensity in wavelength 365nm is 300 W / m <2> was performed. Subsequently, it developed for 25 second at 60 degreeC in 0.05weight% of potassium hydroxide aqueous solution, and rinsed with pure water for 1 minute. Furthermore, it heated in 150 degreeC for 120 minutes in oven, and formed the spacer.

(II) evaluation of resolution

In the pattern obtained in the above (I), the residual film ratio after development (film thickness after initial development / initial film thickness × 100) was evaluated by the minimum pattern size at a sensitivity of 90% or more. The smaller the pattern size, the better the resolution. The results are shown in Table 2 below.

(III) sensitivity evaluation

In the pattern obtained by said (I), if the sensitivity which becomes 90% or more of residual film ratio after image development is 1,500 J / m <2> or less, it can be said that a sensitivity is favorable.

(IV) Evaluation of pattern cross-sectional shape

The cross-sectional shape of the pattern obtained in said (I) was observed with the scanning electron microscope, and it showed which shape among A to C shown in FIG. When the pattern edge is a forward taper as in A, the pattern shape can be said to be good. When the pattern edge is formed vertically like B, it can be said that a pattern shape is slightly favorable.

In addition, as shown in C, the shape of the reverse taper (the side of the film surface in the cross-sectional shape longer than the side of the substrate side, the inverted triangle shape) has a high possibility that the pattern is peeled off during the subsequent rubbing process. The shape was called defective.

(V) evaluation of compressive strength

The compressive strength of the spacer obtained in said (I) was evaluated using the microcompression tester (MCTM-200, the Shimadzu Corporation make). The amount of deformation when a load of 10 mN was applied by a plane indenter having a diameter of 50 µm was measured (measured 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 Corporation) was applied as a liquid crystal aligning agent to a substrate obtained in the above (I) by a printing machine for applying a liquid crystal aligning film, dried at 180 ° C. for 1 hour, and a coating film of an aligning agent having a dry film thickness of 0.05 μm. Formed.

The rubbing process was performed at the rotation speed of a roll of 500 rpm and the moving speed of 1 cm / sec by the rubbing machine which has the roll wound the cloth made of nylon to this coating film. Table 2 shows the presence or absence of chipping or peeling of the spacer pattern at this time.

(VII) Evaluation of adhesion

Except not using a pattern mask, it carried out similarly to said (I), the cured film for adhesive evaluation was formed, and the adhesive test was done. The test method followed the lattice tape method of 8.5.2 among the adhesion tests of JISK-5400 (1900) 8.5. At that time, the number of remaining gratings is shown in Table 2.

(VIII) Evaluation of Preservation Stability

After the composition was prepared, it was stored at -15 ° C, and the change over time of the necessary exposure amount such that the residual film ratio after development was 90% or more in the same manner as in the above (III) sensitivity evaluation was traced, and the sensitivity after 3 months after storage and immediately after production Relative values for sensitivity were measured. In addition, the generation | occurrence | production state of the foreign material 0.5 micrometer or more in the solution after 3 months was measured with the light-scattering liquid particle detector (KS-28B, the product made by Leon Co., Ltd.). The results are shown in Table 2.

(IX) Evaluation of heat resistance

Except not using a mask, a cured film was formed in the same manner as the formation of the spacer, and then heated in an oven at 240 ° C. for 60 minutes, and the film thickness before and after heating was measured to determine the remaining film ratio (film thickness after heating × 100 / initial stage). Film thickness). The results are shown in Table 2.

<Examples 2 to 11, Comparative Examples 1 to 4>

In Example 1, the composition solution was produced like Example 1 except having used the kind and quantity as Table 1 below as component [A]-[E], and the spacer was formed and evaluated. The addition amount of [B]-[E] is a weight ratio with respect to 100 weight part of copolymers [A].

In Table 1, the abbreviated-name of a component shows the following compound.

(B-1): Kayarard DPHA (made by Nippon Kayaku Co., Ltd.)

(B-2): Kayarard DPHA-40H (made 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-acetyl oxime)

(C-2): ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- ( O-acetyl oxime)

(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-acetyl oxime)

(C-5): ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxoranyl) methoxybenzoyl] -9.H.- Carbazol-3-yl]-, 1- (O-acetyloxime)

(D-1): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Irgacure 907 made by Ciba specialty chemicals company)

(D-2): 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irucure 369 by Ciba specialty chemicals company)

(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 the said component is not added.

The evaluation results are shown in Table 2.

According to the present invention, it is possible to faithfully reproduce the design size of the mask pattern with high sensitivity, to be excellent in adhesion to the substrate, to make it possible to obtain a sufficient spacer shape and film thickness at an exposure amount of 1,500 J / m 2 or less, It is excellent in heat resistance and the like, and has excellent controllability of the shape and thickness of the spacer in the low exposure region, and is unlikely to generate foreign substances during use during the storage period, and can form a spacer for a display panel having excellent process stability and elapsed time stability. Provided are a photosensitive resin composition, a spacer for a display panel, and a display panel.

Claims (3)

[A] a copolymer of (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] A photosensitive resin composition containing a photoinitiator containing a compound represented by the following formula (1) or (2). <Formula 1>

In formula, R <_1> is a C1-C20 alkyl group, a C3-C8 cycloalkyl group, or a phenyl group, R <_2> and R <_3> is a hydrogen atom, a C1-C20 alkyl group, a C3-C8 cycloalkyl group, substitution Or an unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (excluding a cycloalkyl group having 7 to 8 carbon atoms), and the substituent of the substituted 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, 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, and R ₅ is hydrogen or 1 to 12 carbon atoms; Is an alkyl group or a C1-C12 alkoxyl group, n is an integer of 1-5, m is an integer of 0-5, and n + m <= 5. <Formula 2>

In formula, the definition of R <_1> , R <_2> , R <_3> , R <_4> , R <_5> , m, and n is the same as the above, and l is an integer of 0-6. The display panel spacer formed from the photosensitive resin composition of Claim 1. The display panel provided with the display panel spacer of Claim 2.

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