KR101314033B1 - Photosensitive resin composition, method for forming spacer for display panel - Google Patents

Abstract

The present invention relates to a photosensitive resin composition applied to a substrate by a slit die coater using a mixed solvent containing 2 to 20% by weight of the compound represented by the following formula (1) as a solvent.

≪ Formula 1 >

In formula, R <^1> -R <^5> is respectively independently a hydrogen atom or a C1-C6 alkyl group, n is an integer of 1-6.

Moreover, this invention provides the photosensitive resin composition solution suitable for the slit die coater method which is favorable in the storage stability of resin, short in a reduced-pressure drying process time, a slit nozzle is hard to dry, and a coating film surface is favorable.

Photosensitive resin composition, spacer for display panels, mixed solvent, slit die coater, board | substrate

Description

Method for forming photosensitive resin composition and spacer for display panel {PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR FORMING SPACER FOR DISPLAY PANEL}

The present invention relates to a photosensitive resin composition, a spacer for a display panel, and a display panel. In addition, 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 preferable 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 diameter are conventionally used to maintain a constant gap (cell spacing) between two substrates, but these spacer particles are transparent such as glass substrates. Since the particles are irregularly scattered on the substrate, when the spacer particles are present in the pixel formation region, there is a problem that the spacer particles are imprinted or the incident light is scattered and the contrast of the liquid crystal panel is lowered.

Therefore, in order to solve these problems, the method of forming a spacer by photolithography has been employ | adopted. In this method, the photosensitive resin composition is coated on a substrate, and exposed to ultraviolet rays through a predetermined mask, followed by development to form a dot or stripe-shaped spacer, and the spacer is placed only at a predetermined place other than the pixel formation region. Since it can form, the problem as mentioned above is basically solved.

By the way, in manufacture of a liquid crystal display panel, board | substrate size enlargement is advanced from a viewpoint of productivity improvement and correspondence to a large screen. Substrate size is 1,100 mm × 1,300 mm through the first generation of 300 mm × 400 mm, the second generation of 370 mm × 470 mm, the third generation of 620 mm × 750 mm, and the fourth generation of 960 mm × 1100 mm The fifth generation of people is now mainstream. In addition, the sixth generation of 1,500 mm × 1,850 mm, the seventh generation of 1,850 mm × 2,100 mm, and the substrate size become larger in the future.

When the substrate size is small, for example, 370 mm x 470 mm or less, the photosensitive resin composition is dropped in the center on the substrate and applied by spin coating. In this method, a large amount of photosensitive resin composition solution is required at the time of coating, and there is a drawback that it cannot cope with a large substrate.

When the board | substrate size is 960 mm x 1,100 mm or less, application | coating is performed by the slit-and-spin method for the purpose of saving the photosensitive resin composition solution. This method forms a uniform coating film by apply | coating the photosensitive resin composition solution to a board | substrate surface from a slit nozzle, and then rotating a board | substrate. This method is effective in saving the solution, but it is difficult to cope with the substrate size after the fifth generation.

From this background, the application by the slit die coater is performed with the increase of the substrate size. However, in the case of a slit die coater, selection of a solvent type becomes important in order to obtain a favorable coating film. When the solvent with low resin solubility is used, storage stability will worsen. Moreover, when a high boiling point solvent is used, a required time will become long in the pressure reduction drying process after an application | coating process. It is unpreferable from the viewpoint of productivity improvement that increasing pressure reduction drying process time increases. On the contrary, when only a low boiling point solvent is used, the front-end | tip of a slit nozzle will become dry easily and a vertical stripe will arise easily at the time of application | coating. In addition, fog-like stains (hereinafter, referred to as "cloudy stains") may be observed on the entire surface of the coating film surface coated using the slit die coater. When such cloudy spots arise, the yield of a liquid crystal panel is reduced and it becomes a problem. For this reason, in the slit die coater method, the photosensitive resin composition solution which the storage stability of resin is favorable, the pressure reduction drying process time is short, and the coating film surface is favorable has been strongly desired.

Accordingly, an object of the present invention is to provide a photosensitive resin composition solution suitable for a slit die coater method having a good storage stability of resin, a short drying time under reduced pressure, a slit nozzle being difficult to dry, and a good coating film surface.

Another object of the present invention is to provide a spacer for a display panel formed of the photosensitive resin composition solution and a display panel having the same.

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

According to the present invention, the above objects and advantages are firstly,

2 to 20% by weight of the compound represented by Formula 1,
At least one of diethylene glycol dimethyl ether and diethylene glycol methylethyl ether,
Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, methyl isobutyl ketone, cyclohexanone, acetic anhydride, toluene, chlorobenzene and propyl A solvent having a boiling point of 100 ° C. to 150 ° C. selected from acetate, and
Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octane A boiling point of 180 ° C. to 250 ° C. selected from all, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenylcellosolve acetate solvent
It is achieved by the photosensitive resin composition which makes a mixed solvent containing the solvent into a solvent, and is apply | coated to a board | substrate by a slit die coater.

In formula, R <^1> -R <^5> is respectively independently a hydrogen atom or a C1-C6 alkyl group, n is an integer of 1-6.

According to the present invention, the above objects and advantages are second,

It is achieved by the spacer for display panels formed from the photosensitive resin composition of this invention.

According to the present invention, the above object and advantages are third,

It is achieved by the display panel provided with the spacer for display panel of this invention.

The photosensitive resin composition used in the present invention is preferably an alkali-soluble copolymer [A], a polymerizable compound [B] having an ethylenically unsaturated bond, a radiation sensitive polymerization initiator [C] and a compound represented by the above formula (1). Mixed solvent [D] containing 2 to 20% by weight.

Alkali-soluble copolymer [A]-

The said [A] component is (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride, (a2) epoxy group containing ethylenically unsaturated compound, and (a3) other ethylenically unsaturated compound, Copolymer (hereinafter referred to as "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; And anhydrides of the above dicarboxylic acids.

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 copolymer obtained.

An unsaturated carboxylic acid type 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. 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 be excessive. There is a risk of growing.

As the (a2) epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as "epoxy group-containing monomer (a2)"), for example, glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxy butyl acrylate. Acrylic acid epoxy alkyl esters such as acrylic acid 6,7-epoxyheptyl and acrylic acid 3,4-epoxycyclohexyl; Meta, such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, and 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 and 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.

Among these epoxy group-containing monomers (a2), in terms of copolymerization reactivity and the strength of the spacers, methacrylate glycidyl, methacrylic acid 2-methylglycidyl, methacrylic acid 6,7-epoxyheptyl, o-vinylbenzyl Glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are preferable.

An epoxy group containing monomer (a2) can be used individually or in mixture of 2 or more types.

In copolymer [A], the content rate of the repeating unit derived from an epoxy group containing monomer (a2) becomes like this. Preferably it is 10-70 weight%, More preferably, it is 20-60 weight%, Especially preferably, it is 30-50 weight% to be. When the content rate of the repeating unit derived from an epoxy group containing monomer (a2) is less than 10 weight%, there exists a tendency for the intensity | strength of the spacer obtained to fall, and when it exceeds 70 weight%, the storage stability of the copolymer obtained will fall. have.

Moreover, as (a3) another ethylenically unsaturated compound (henceforth "other monomer (a3)"), For example, alkyl acrylates, such as methyl acrylate and i-propyl acrylate; Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decan- , Acrylic acid alicyclic ester such as isobornyl acrylate; 2-methylcyclohexyl methacrylate, tricyclohexyl methacrylate [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxy) ethyl methacrylate, isobornyl methacrylate and the like; 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 5- or 6-membered ring methacrylic acid esters containing 1 atom of oxygen such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate and the like; Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene; In addition to conjugated diene-based compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, Vinyl acetate etc. are mentioned.

Among these other monomers (a3), 2-methylcyclohexyl acrylate, t-butyl methacrylate and tricyclo methacrylate [5.2.1.0 ^2,6] from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution of the resulting copolymer. ] Decane-8-yl, styrene, p-methoxystyrene, tetrahydrofurfuryl methacrylate, 1,3-butadiene and the like are preferred.

In copolymer [A], another monomer (a3) 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 (a3) becomes like this. Preferably it is 10 to 70 weight%, More preferably, it is 20 to 50 weight%, Especially preferably, it is 30 to 50 weight%. . When the content rate of the repeating unit derived from another monomer (a3) is less than 10 weight%, the storage stability of the copolymer obtained tends to fall, and when it exceeds 70 weight%, the solubility with respect to the aqueous alkali solution of the copolymer obtained is There is a tendency to decrease.

Copolymer [A] has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, has moderate solubility with respect to aqueous alkali solution, and can be easily hardened by heating, without using a special hardening | curing agent. The photosensitive resin composition containing the copolymer can easily form a spacer of a predetermined pattern without developing residue and film reduction during development.

Copolymer [A] can be manufactured by, for example, polymerizing an unsaturated carboxylic acid monomer (a1), an epoxy group-containing monomer (a2) and another monomer (a3) in a suitable solvent in the presence of a radical polymerization initiator.

As a solvent used for manufacture of copolymer [A], for example, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, 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 ethers, For example, tetrahydrofuran etc .;

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 aromatic hydrocarbons, for example, toluene, xylene and the like;

As the ketone, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of esters include esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Propyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, Butyl methacrylate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid propyl, Propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, 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 preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and dipropylene glycol are preferred. Dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate are particularly preferred.

These solvents may be used alone or in combination of two or more.

Moreover, it does not specifically limit as a radical polymerization initiator used for the said superposition | polymerization, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile ), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl 2,2'-azobis Azo compounds such as (2-methylpropionate) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, and 1,1-bis (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like. Moreover, when using a peroxide as a radical polymerization initiator, it can also be used as a redox type initiator in combination with a reducing agent.

These radical polymerization initiators may be used alone or in combination of two or more.

Thus obtained copolymer [A] can be used for manufacture of a radiation sensitive resin composition as it is, or can also be used for manufacture of a radiation sensitive resin composition separately from a solution.

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 100,000, resolution may be reduced or pattern shape may be damaged. have.

-Polymeric compound [B] having an ethylenically unsaturated bond-

[B] component in the photosensitive resin composition is a 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 the intensity | strength of the spacer obtained improves.

As said monofunctional (meth) acrylic acid ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, Isoboroyl acrylate, Isoboroyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2-metha Cryloyl oxyethyl-2-hydroxypropyl phthalate etc. are mentioned, Furthermore, as a commercial item, For example, Aronix M-101, Copper M-111, Copper M-114 (made by Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku Co., Ltd.); Biscoat 158, copper 2311 (manufactured by Osaka Yuki Chemical Co., Ltd.), and the like.

Moreover, as said bifunctional (meth) acrylic acid ester, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate , Tetraethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, 1,9-nonanedioldimethacryl Bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene dimethacrylate, etc. are mentioned, As a commercial item, it is Aronix M-210, copper M-240, copper M, for example. -6200 (manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, East HX-220, East R-604 (manufactured by Nippon Kayaku Co., Ltd.), Biscot 260, East 312, East 335HP (Osaka Yuki Kagaku High School) ) Production).

Moreover, as said (meth) acrylic acid ester more than trifunctional, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2- Acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, etc. are mentioned.

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 (Toa Kosei) KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360 , Copper GPT, copper 3PA, copper 400 (manufactured by Osaka Yuki Chemical Co., Ltd.), and the like. 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.), KAYARAD DPHA-40H (above, Nippon Kayaku Co., Ltd.) 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, the amount of the polymerizable compound [B] 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]. 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.

-Radiation sensitive polymerization initiator [C]-

A radiation sensitive polymerization initiator is a component which produces | generates the active species which can start superposition | polymerization of the polymeric compound which has [B] ethylenically unsaturated bond in response to radiation.

As such a radiation sensitive polymerization initiator, a radiation sensitive radical polymerization initiator is preferable, for example.

As said radiation sensitive radical polymerization initiator, For example, alpha-diketones, such as benzyl and diacetyl; Acyl phosphorus such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzo Benzophenones such as phenone; Acetophenone, p-dimethylaminoacetophenone, 4- (α, α'-dimethoxyacetoxy) benzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl Aceto, such as 2-morpholino-1- (4-methylthiophenyl) -1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Phenones; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide, bis (2,4,6-trimethylbenzoyl) phenylforce Acyl phosphine oxides, such as pin oxide; Peroxides, such as di-t- butyl peroxide, etc. are mentioned.

Moreover, as a commercial item of a radiation sensitive radical polymerization initiator, for example, IRGACURE-124, copper-149, copper-184, copper-369, copper-500, copper-651, copper-819, copper-907, copper-1000 , East-1700, East-1800, East-1850, East-2959, Darocur-1116, East-1173, East-1664, East-2959, East-4043 (above, Ciba specialty chemicals company make), KAYACURE- DETX, copper-MBP, copper-DMBI, copper-EPA, copper-OA (above, manufactured by Nippon Kayaku Co., Ltd.), LUCIRIN TPO (manufactured by BASF), VICURE-10, copper-55 (above, manufactured by STAUFFER company ), TRIGONALP1 (manufactured by AKZO), SANDORAY 1000 (manufactured by SANDOZ), DEAP (manufactured by APJOHN), QUANTACURE-PDO, copper-ITX, copper-EPD (above, manufactured by WARD BLEKINSOP), and the like.

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

Moreover, by using together a radiation sensitive sensitizer with 1 or more types together with the said radiation sensitive radical polymerization initiator, the deactivation by oxygen in air is little and it is also possible to obtain a highly sensitive radiation sensitive resin composition.

The amount of each component used in the photosensitive resin composition of the present invention is preferably 10 to 150 parts by weight of the polymerizable compound having [B] ethylenically unsaturated bond, based on 100 parts by weight of the alkali-soluble copolymer [A]. Preferably it is 20-120 weight part, and [C] radiation sensitive polymerization initiator is 1-40 weight part with respect to 100 weight part of alkali-soluble copolymers [A], Preferably it is 3-35 weight part to be.

When the usage-amount of a polymeric compound is less than 10 weight part, it will become difficult to form a coating film with a uniform film thickness, and when it exceeds 150 weight part, adhesiveness with a board | substrate will fall. Moreover, when the usage-amount of a [C] radiation sensitive polymerization initiator is less than 1 weight part, there exists a tendency for heat resistance, surface hardness, and chemical resistance to fall, and when it exceeds 40 weight part, there exists a tendency for transparency to fall.

Solvent [D]-

It is preferable that the photosensitive resin composition is manufactured as a composition solution which melt | dissolves structural components, such as a copolymer [A], a polymeric compound [B], a photosensitive polymerization initiator [C], in a suitable solvent at the time of its use.

As a solvent [D] used for manufacture of the said composition solution, the thing which melt | dissolves each component which comprises the photosensitive resin composition 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 said copolymer [A] is mentioned.

Among these solvents, in order to apply the photosensitive resin composition using a slit die coater, a mixed solvent containing a compound represented by the following formula (1) is used in that it is effective for suppressing cloudy spots on the coating film surface. The content of the compound represented by the following formula (1) in 100 parts by weight of the total mixed solvent is 2 to 20% by weight. If it is less than 2 weight%, it will have no effect with respect to a cloudy stain, and when it exceeds 20 weight%, reduced pressure drying time will become long and productivity of a panel will worsen.

&Lt; Formula 1 >

In formula, R <^1> -R <^5> is respectively independently a hydrogen atom or an alkyl group of 1-6 carbon atoms, n is an integer of 1-6.

Examples of the compound represented by the formula (1) include benzyl alcohol, 2-methylbenzyl alcohol, 3-phenyl-1-propanol, 2-methylphenethyl alcohol, 2,4-dimethylbenzyl alcohol, 4-ethylbenzyl alcohol , 4-phenyl-1-butanol, 5-phenyl-1-pentanol, 4-butylbenzyl alcohol, 6-phenyl-1-hexanol, 2,3,4,5,6-pentamethylbenzyl alcohol have. Among them, benzyl alcohol is particularly preferable in view of boiling point and solubility of other compositions.

The mixed solvent preferably contains a diethylene glycol alkyl ether solvent such as diethylene glycol dimethyl ether and diethylene glycol methylethyl ether in order to obtain storage stability of the resin solution. The content of the diethylene glycol alkyl ether solvent in 100 parts by weight of the total mixed solvent is preferably 30 to 75% by weight. If it is less than 30 weight%, the storage stability of a resin liquid will deteriorate, and when it exceeds 75 weight%, a reduced pressure drying time will become long.

Moreover, it is preferable that the vacuum drying time is short from a viewpoint of productivity of a panel. From the viewpoint of shortening the vacuum drying time, it is preferable that the mixed solvent contains a solvent having a boiling point (boiling point at 1 atmosphere, the same below) in addition to the compound represented by the formula (1). When boiling point is less than 100 degreeC, the malodor of a solvent may become a problem, and when it exceeds 150 degreeC, it is ineffective for shortening a reduced pressure drying time. The boiling point of 100 parts by weight of the total mixed solvent is preferably 20 to 55% by weight of the solvent at 100 ° C to 150 ° C. When it is less than 20 weight%, it is ineffective in shortening a reduced pressure drying time, and when it exceeds 55 weight%, storage stability may worsen. As a solvent which can use together, the boiling point of 100 degreeC-150 degreeC is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, for example. And methyl isobutyl ketone, cyclohexanone, acetic anhydride, toluene, chlorobenzene, propyl acetate and the like.

Moreover, when apply | coating a photosensitive resin composition using a slit die coater, a nozzle tip may dry and a vertical streak may arise in a coating film, or it may be a cause of a foreign material. By using a high boiling point solvent together as a structural component of a mixed solvent, drying of the front-end | tip of a nozzle can be suppressed. As a solvent which is effective in suppressing the drying of the tip of a nozzle, the solvent whose boiling point is 180 degreeC-250 degreeC (except the compound of General formula (1)) is preferable. If the boiling point is less than 180 ° C., it is ineffective for preventing the drying of the nozzle. If the boiling point is higher than 250 ° C., it will affect the reduced pressure drying time, and a high boiling point solvent may remain in the coating film, which is not preferable. As for content of the solvent whose boiling point which occupies 100 weight part of total mixed solvents is 180 degreeC-250 degreeC, 3-15 weight% is preferable. When it is less than 3 weight%, it is ineffective in suppressing drying of a nozzle tip, and when it exceeds 15 weight%, it affects a reduced pressure drying time and there exists a possibility that a high boiling point solvent remains in a coating film. As a high boiling point solvent which can be used together, for example, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, N-methylformamide, N , N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetoniyl acetone Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcello Solvate acetate etc. are mentioned. Among these, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether and N-methylpyrrolidone are preferable.

-additive-

Additives other than the said component can also be mix | blended with the photosensitive resin composition 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, a fluorine-based surfactant and a silicone-based surfactant can be preferably used.

As the fluorine-based surfactant, a compound having a fluoroalkyl or a fluoroalkylene group at any one or more of the terminal, main chain and side chain can be preferably used. Specific examples thereof include 1,1,2,2-tetra Fluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluoro Butyl) 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-deca Fluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkyl carboxylate, fluoroalkylpolyoxyethylene ether , Digly Lintetrakis (fluoroalkylpolyoxyethyleneether), fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylpolyoxyethyleneether, perfluoroalkylpolyoxyethanol, perfluoroalkylalkoxylate, Fluorine-type alkyl ester etc. are mentioned.

Moreover, as these commercial items, for example, BM-1000, BM-1100 (above, BM CHEMIE company make), Megapack F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471, copper F476 (Above, Dai Nippon Ink Chemical Co., Ltd.), Florade FC 170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Suplon S-112, copper S-113, S-131, S-141, S-145, S-382, SSC-101, SSC-102, SSC-103, SSC-104, SSC-105, S SC-106 (above, Asahi Glass Co., Ltd.), f-top EF301, east 303, east 352 (above, Shinagawa Kasei Co., Ltd.), pgentant FT-100, east FT-110, east FT-140A , FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (above, manufactured by Neos) Can be 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, 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; Nonionic surfactants, such as polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, and KP341 (made by Shin-Etsu Chemical Co., Ltd.) and polyflow No. 57 as a commercial item. And 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

These surfactants may be used alone or in combination of two or more.

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]. When the compounding quantity of surfactant exceeds 5 weight part, there exists a tendency for a film | membrane to become rough easily at the time of application | coating.

Moreover, in order to further improve adhesiveness with a base, 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, More specifically, Oxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane etc. are mentioned.

These adhesion promoters may be used alone or in combination of two or more.

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 cannot be obtained and a pattern shape will deteriorate.

Moreover, in order to improve heat resistance, the compound which has an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, and a bifunctional or more than 2 functional epoxy group in 1 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) 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 (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 can be given. Among these, 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, trimethylene 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 Kyoeisha Chemical Co., Ltd. product) etc. are mentioned. These may be used alone or in combination of two or more.

The composition solution thus prepared may be used, if necessary, by filtration with a Millipore filter having a pore size of, for example, about 0.2 to 0.5 µm.

The photosensitive resin composition 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, after apply | coating a composition solution to the surface of a board | substrate, it pre-bakes and removes a solvent and a coating film is formed.

The coating method of the composition solution is a slit die coating method.

In addition, although the conditions of prebaking differ also with kinds, compounding 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 by interposing a mask of a predetermined pattern in the prebaked coating film, and developing with a developing solution, and removing an unnecessary part and forming 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, for example, it may be any of a paddle method, an immersion method, a shower method, etc., and developing time is 30 to 180 second, for example.

As said developing solution, For example, inorganic alkali, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine and 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 and 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 for 30 to 90 seconds to remove unnecessary portions, a predetermined pattern is formed by blowing compressed air or compressed nitrogen and drying.

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.

As described above, the photosensitive resin composition 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.

<Examples>

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

&Lt; Synthesis Example 1 &

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

Solid content concentration of this solution was 33.1 weight%, and Mw of copolymer [A-1] was 11,000.

&Lt; Synthesis Example 2 &

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

Solid content concentration of this solution was 33.0 weight%, and Mw of copolymer [A-2] was 11,000.

&Lt; Synthesis Example 3 &

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 100 parts by weight of diethylene glycol ethylmethyl ether and 100 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 10 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 40 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate were added, followed by nitrogen substitution. Subsequently, 5 parts by weight of 1,3-butadiene was further added, while slowly stirring, the temperature of the solution was raised to 70 ° C., maintained at this temperature for 5 hours, and then polymerized to obtain a solution of the copolymer [A-3]. Got it.

Solid content concentration of this solution was 33.2 weight%, and Mw of the copolymer [A-3] was 10,000.

&Lt; Synthesis Example 4 &

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 100 parts by weight of diethylene glycol dimethyl ether and 100 parts by weight of propylene glycol monomethyl ether were added to a flask equipped with a cooling tube and a stirrer. 10 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 40 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate were added, followed by nitrogen replacement. Further, 5 parts by weight of 1,3-butadiene was added, the temperature of the solution was raised to 70 ° C. while stirring slowly, and the temperature was maintained for 5 hours and then polymerized to obtain a solution of copolymer [A-4].

Solid content concentration of this solution was 33.1 weight%, and Mw of copolymer [A-4] was 10,000.

&Lt; Example 1 >

Preparation of Composition Solution

100 parts by weight of a solution of copolymer [A-1] obtained in Synthesis Example 1 as a copolymer [A] (as a solid), 100 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the polymerizable compound [B], 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone (trade name "Irgacure 369", Ciba specialty as a photoinitiator [C]) 15 parts by weight of Chemicals Co., Ltd. is mixed and the solid content concentration is 25.5% by weight, and the weight ratio of diethylene glycol ethylmethyl ether, propylene glycol monomethyl ether acetate, benzyl alcohol and ethylene glycol monobutyl ether acetate is 55: The mixture was mixed to 30: 10: 5, dissolved, and filtered through a PTFE (polytetrafluoroethylene) filter having a pore diameter of 0.2 µm to prepare a composition solution (S-1).

(I) Evaluation of Resin Liquid Storage Stability

The viscosity in the resin composition solution manufactured in Example 1 was measured using the ELD type viscometer of Tokyo Keiki Co., Ltd. product. Thereafter, the solution viscosity at 25 캜 was measured daily while the composition was kept at 25 캜. The number of days required to thicken 5% based on the viscosity immediately after manufacture was calculated | required, and the days are shown in Table 1 below. When the number of days is 20 days or more, storage stability can be said to be favorable.

(II) Evaluation of vacuum drying time (VCD)

On the 550x650 mm chromium film formation glass, the manufactured composition solution was apply | coated on the conditions which the film thickness after hardening will be 4 micrometers using the slit die coater (TR632105-CL, Toago Kogyo Co., Ltd. product). Thereafter, the time until the reduced pressure reached 0.5 Torr from normal pressure (hereinafter referred to as VCD time) was measured. VCD time is advantageously short.

(III) Evaluation of coating property (cloudy stain on coating film surface)

On the 550 x 650 mm chromium film-formed glass, the prepared composition solution was applied using a slit die coater. After drying under reduced pressure to 0.5 Torr, the baking film was prebaked at 100 ° C. for 2 minutes to form a coating film, followed by exposure at an exposure dose of 2000 J / m 2, whereby the film thickness from the upper surface of the chromium film-forming glass was 4 μm. A film was formed.

The film surface was illuminated with a sodium lamp, and the surface of the coating film was visually checked. When the cloudy stain could be confirmed reliably, when it was able to confirm slightly, it was (triangle | delta), and when it was hardly confirmed, it was set as (circle).

(IV) Evaluation of Dryness of Slit Nozzle

On the 550 x 650 mm chromium film-formed glass, the prepared composition solution was applied using a slit die coater. After application | coating, the nozzle tip was left without washing. 10 minutes later, the same application | coating was performed without washing | cleaning a nozzle tip, and the coating film similar to evaluation of (III) applicability | paintability (cloudy stain on the coating film surface) was manufactured.

The film surface was illuminated with a sodium lamp, and the surface of the coating film was visually checked. When the vertical stripe unevenness | corrugation can be confirmed reliably, it was set as (triangle | delta), and when it was hardly confirmed, it was set as (circle).

<Examples 2 to 16, Comparative Examples 1 to 3>

In Example 1, the composition solution was manufactured like Example 1 except having used the kind and quantity as Table 1 as component [A]-[D]. In adjustment of solid content concentration of a composition solution, it carried out so that the mixing ratio of [D] component might become as shown in Table 1. About the obtained composition [S-2]-[S-16] and [s-1]-[s-3], the result of having evaluated the resin liquid storage stability and application | coating evaluation similarly to Example 1 is shown in Table 1 Shown in

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

(B-1): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(B-2): KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.)

(C-1): 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irucure 369 by Ciba Specialty Chemicals)

(C-2): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Irucure 907 by Ciba Specialty Chemicals Co., Ltd.)

(C-3): 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole

(C-4): 4,4'-bis (diethylamino) benzophenone

(C-5): 2-mercaptobenzothiazole

(D-1): diethylene glycol ethyl methyl ether

(D-2): diethylene glycol dimethyl ether

(D-3): Propylene glycol monomethyl ether acetate

(D-4): propylene glycol monomethyl ether

(D-5): benzyl alcohol

(D-6): ethylene glycol monobutyl ether acetate

(D-7): diethylene glycol monoethyl ether acetate

In Table 1,-mark shows that the said component is not added.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition solution suitable for the slit die coater method which the storage stability of resin is favorable, the pressure reduction drying process time is short, a slit nozzle is hard to dry, and a coating film surface is favorable is provided.

Claims (7)

2 to 20% by weight of the compound represented by Formula 1, At least one of diethylene glycol dimethyl ether and diethylene glycol methylethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, methyl isobutyl ketone, cyclohexanone, acetic anhydride, toluene, chlorobenzene and propyl A solvent having a boiling point of 100 ° C. to 150 ° C. selected from acetate, and Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octane A boiling point of 180 ° C. to 250 ° C. selected from all, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenylcellosolve acetate solvent A photosensitive resin composition, which is applied to a substrate by a slit die coater using a mixed solvent containing a solvent as a solvent. &Lt; Formula 1 >

In formula, R <^1> -R <^5> is respectively independently a hydrogen atom or a C1-C6 alkyl group, n is an integer of 1-6. The photosensitive resin composition of Claim 1 in which the mixed solvent contains 30-75 weight% of any one or more of diethylene glycol dimethyl ether and diethylene glycol methylethyl ether. The photosensitive resin composition of Claim 1 in which the mixed solvent contains 20-55 weight% of solvents whose boiling point is 100 degreeC-150 degreeC. The photosensitive resin composition of Claim 1 in which the mixed solvent contains 3-15 weight% of solvents (except the compound of the said Formula 1) whose boiling point is 180 degreeC-250 degreeC. The solvent according to claim 1, wherein the solvent having a boiling point of 100 ° C to 150 ° C is any one of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether, The photosensitive resin composition whose solvent whose boiling point is 180 degreeC-250 degreeC is either ethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate. The photosensitive resin composition of any one of Claims 1-5 is apply | coated to the surface of a board | substrate by the slit die coating method, and a coating film is formed, Then, after exposing the coating film, it develops and heats. A method of forming a spacer for a display panel, characterized in that. delete