JP4687902B2 - Photosensitive resin composition, display panel spacer and display panel - Google Patents

Description

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

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

By the way, in the manufacture of a liquid crystal display panel, the substrate size has been increased from the viewpoint of improving productivity and adapting to a large screen. Substrate sizes are 300mm x 400mm first generation, 370mm x 470mm second generation, 620mm x 750mm third generation, 960mm x 1100mm fourth generation, then 1,100mm x 1,300mm fifth generation Currently mainstream. Further, the sixth generation of 1,500 mm × 1,850 mm, the seventh generation of 1,850 mm × 2,100 mm, and the substrate size will be further increased in the future.
When the substrate size is small, for example, 370 mm × 470 mm or less, the photosensitive resin composition is dropped onto the center of the substrate and applied by a spin coating method. This method has a drawback that a large amount of the photosensitive resin composition solution is required for coating, and it cannot be applied to a large substrate.
When the substrate size is 960 mm × 1,100 mm or less, the coating is performed by the slit & spin method for the purpose of saving the photosensitive resin composition solution. In this method, a photosensitive resin composition solution is applied to a substrate surface from a slit nozzle, and then the substrate is rotated to form a uniform coating film. This method is effective for saving liquid, but it is difficult to cope with the substrate size from the fifth generation onward.

From such a background, as the substrate size increases, coating by a slit die coater has been performed. However, in the case of a slit die coater, selection of the solvent type is important in order to obtain a good coating film. If a solvent having poor resin solubility is used, the storage stability deteriorates. Moreover, when a high boiling point solvent is used, a required time becomes long in the reduced-pressure drying step after the coating step. An increase in the vacuum drying process time is undesirable from the viewpoint of improving productivity. On the other hand, when only a low boiling point solvent is used, the tip of the slit nozzle tends to dry, and vertical stripes are likely to occur during application. Further, the entire surface of the coated film surface by using a slit die coater, a cloud-like unevenness (hereinafter, referred to as "Moyamura".) Is sometimes observed. When such haze is generated, the yield of the liquid crystal panel is lowered, which is a problem. For these reasons, in the slit die coater method, there has been a strong demand for a photosensitive resin composition solution that has good resin storage stability, a short drying time for reduced pressure, and a good coating surface.

Accordingly, an object of the present invention is to provide a photosensitive resin composition solution suitable for the slit die coater method, in which the storage stability of the resin is good, the vacuum drying process time is short, the slit nozzle is difficult to dry, and the coating film surface is good. It is to provide.
Another object of the present invention is to provide a display panel spacer formed from the photosensitive resin composition solution and a display panel including the same.
Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the objects and advantages are as follows:
A photosensitive resin composition comprising an alkali-soluble copolymer [A], a polymerizable compound having an ethylenically unsaturated bond [B], a radiation-sensitive polymerization initiator [C], and a solvent [D],
The solvent [D] is
Following formula (1)

^(Wherein, R 1 to R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents an integer from 1 to 6.)
2 to 20% by weight of a compound represented by
30 to 75% by weight of at least one of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether, and
Boiling point is applied to a substrate by mixing a solvent and a slit die coater containing 20-55 wt% solvent 100 ° C. to 150 DEG ° C., is accomplished by the photosensitive resin composition characterized by.
According to the present invention, the objects and advantages are secondly:
This is achieved by a display panel spacer formed from the photosensitive resin composition of the present invention.
According to the present invention, the object and advantages are thirdly:
This is achieved by a display panel having the display panel spacer of the present invention.

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

The photosensitive resin composition used in the present invention, A alkali-soluble copolymer (A), a polymerizable compound having an ethylenically unsaturated bond (B), the radiation-sensitive polymerization initiator (C) and the above equation (1 compound 2 20 wt% expressed in)
30 to 75% by weight of at least one of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether, and
It consists of a mixed solvent [D] containing 20 to 55% by weight of a solvent having a boiling point of 100 to 150 ° C.

-Alkali-soluble copolymer [A]-
The component [A] is, for example, (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound, and (a3) other ethylenically unsaturated compounds. It consists of a copolymer with a compound (hereinafter referred to as “copolymer [A]”).
Among the components constituting the copolymer [A], (a1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid anhydride (hereinafter referred to as “unsaturated carboxylic acid monomer”) Examples of (a1) "include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; maleic acid, fumaric acid And dicarboxylic acids such as citraconic acid, mesaconic acid and itaconic acid; and anhydrides of the dicarboxylic acid.
Among these unsaturated carboxylic acid monomers (a1), acrylic acid, methacrylic acid, maleic anhydride are available from the viewpoints of copolymerization reactivity, solubility of the resulting copolymer in an alkaline aqueous solution and easy availability. Etc. are preferred.
The unsaturated carboxylic acid monomer (a1) can be used alone or in admixture of two or more.
In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15%. ~ 30% by weight. If the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is less than 5% by weight, the solubility in an alkaline aqueous solution tends to decrease, whereas if it exceeds 50% by weight, the alkaline aqueous solution There is a possibility that the solubility in is too large.

  Examples of the (a2) epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as “epoxy group-containing monomer (a2)”) include, for example, glycidyl acrylate, 2-methylglycidyl acrylate, 3, 4-epoxybutyl, acrylic acid 6,7-epoxyheptyl, acrylic acid epoxy alkyl ester such as 3,4-epoxycyclohexyl acrylate; glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, Methacrylic acid epoxyalkyl esters such as 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethylacrylic acid 6, - alpha-alkyl acrylic acid epoxy esters and epoxy heptyl; can be exemplified o- vinylbenzyl glycidyl ether, m- vinylbenzyl glycidyl ether, glycidyl ethers such as p- vinylbenzyl glycidyl ether.

Among these epoxy group-containing monomers (a2), from the viewpoint of copolymerization reactivity and spacer strength, glycidyl methacrylate, 2-methylglycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferable.
The epoxy group-containing monomer (a2) can be used alone or in admixture of two or more.
In the copolymer [A], the content of the repeating unit derived from the epoxy group-containing monomer (a2) is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, and particularly preferably 30 to 50%. % By weight. When the content of the repeating unit derived from the epoxy group-containing monomer (a2) is less than 10% by weight, the strength of the obtained spacer tends to be reduced. The storage stability of the coalesced tends to be reduced.

Furthermore, (a3) other ethylenically unsaturated compounds (hereinafter simply referred to as “other monomers (a3)”) include, for example, acrylic acid alkyl esters such as methyl acrylate and i-propyl acrylate; Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricycloacrylate [5.2 .1.0 ^2,6 ] decan-8-yl, acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl, acrylic acid alicyclic, etc. Esters: cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, trimethyl methacrylate B [5.2.1.0 ^2,6] decan-8-yl methacrylate, 2 (tricyclo [5.2.1.0 ^2,6] decan-8-yloxy) ethyl, such as methacrylic acid isobornyl Methacrylic acid alicyclic ester; aryl ester or aralkyl ester of acrylic acid such as phenyl acrylate and benzyl acrylate; aryl ester or aralkyl ester of methacrylic acid such as phenyl methacrylate and benzyl methacrylate; diethyl maleate and diethyl fumarate Dialkyl esters of dicarboxylic acids such as diethyl itaconate; hydroxyalkyl esters of methacrylic acid such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, methacrylate Unsaturated hetero 5- or 6-membered methacrylic acid ester containing one oxygen atom such as tetrahydrofupyran-2-methyl lurate; styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, etc. In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride And vinyl acetate.

Among these other monomers (a3), from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an alkaline aqueous solution, 2-methylcyclohexyl acrylate, t-butyl methacrylate, tricyclomethacrylate [ 5.2.1.0 ^2,6 ] Decan-8-yl, styrene, p-methoxystyrene, tetrahydrofurfuryl methacrylate, 1,3-butadiene and the like are preferable.
In the copolymer [A], the other monomer (a3) can be used alone or in admixture of two or more.
In the copolymer [A], the content of the repeating unit derived from the other monomer (a3) is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, particularly preferably 30 to 50% by weight. %. When the content of the repeating unit derived from the other monomer (a3) is less than 10% by weight, the storage stability of the resulting copolymer tends to be lowered. There exists a tendency for the solubility with respect to the aqueous alkali solution of the copolymer obtained to fall.

The copolymer [A] has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, has an appropriate solubility in an alkaline aqueous solution, and does not require the use of a special curing agent. It can be easily cured by heating. The photosensitive resin composition containing the copolymer can easily form a spacer having a predetermined pattern without developing residue and film loss during development.
For example, the copolymer [A] is obtained by starting radical polymerization of an unsaturated carboxylic acid monomer (a1), an epoxy group-containing monomer (a2), and another monomer (a3) in an appropriate solvent. It can manufacture by superposing | polymerizing in presence of an agent.
Examples of the solvent used for the production of the copolymer [A] include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol. Examples include alkyl ether propionates, aromatic hydrocarbons, ketones and esters.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
Examples of dipropylene glycol include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;

Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate;
As propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc .;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropion Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

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

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

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

-Polymerizable compound [B] having an ethylenically unsaturated bond-
[B] component in the photosensitive resin composition is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as “polymerizable compound [B]”).
Although it does not specifically limit as polymeric compound [B], Monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester has good polymerizability, and the strength of the spacer obtained is improved. This is preferable.
Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3- Examples thereof include methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, and 2-methacryloyloxyethyl-2-hydroxypropyl phthalate. Commercial products include, for example, Aronix M- 101, M-111, M-114 (manufactured by Toa Gosei Co., Ltd.); KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku Co., Ltd.); Viscoat 158, 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like can be mentioned.

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

Furthermore, as the tri- or higher functional (meth) acrylic acid ester, for example, trimethylolpropane triacrylate, trimethylolpropane 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. it can.
In particular, a (meth) acrylate having 9 or more functional groups has an alkylene straight chain and an alicyclic structure, a compound containing two or more isocyanate groups, and a trifunctional, tetrafunctional and 5 functional group containing one or more hydroxyl groups in the molecule. The urethane acrylate compound obtained by making a functional (meth) acrylate compound react is mentioned.

As said commercial item, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, M-8060, TO-1450 (Toa Gosei ( KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (produced by Osaka Organic Chemical Industry Co., Ltd.) and the like. Commercially available products of polyfunctional urethane acrylates having 9 or more functional groups include, for example, New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) Is mentioned.
Among these monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher functional (meth) acrylic acid esters are more preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol. Tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferred.
The monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester can be used alone or in combination of two or more.
In the photosensitive resin composition, the amount of the polymerizable compound [B] used is preferably 50 to 140 parts by weight, and more preferably 60 to 120 parts by weight with respect to 100 parts by weight of the copolymer [A]. If the amount of the polymerizable compound [B] used is less than 50 parts by weight, there may be a residual image during development, while if it exceeds 140 parts by weight, the hardness of the resulting spacer tends to decrease.

-Radiation-sensitive polymerization initiator [C]-
The radiation-sensitive polymerization initiator is a component that generates an active species capable of initiating polymerization of a polymerizable compound having an ethylenically unsaturated bond [B] in response to radiation.
As such a radiation sensitive polymerization initiator, for example, a radiation sensitive radical polymerization initiator is preferable.
Examples of the radiation-sensitive radical polymerization initiator include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, Benzophenones such as 4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, 4 -(Α, α'-dimethoxyacetoxy) benzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiopheny Acetophenones such as 1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl Halogen compounds such as chloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-triazine; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Examples include acylphosphine oxides such as trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; peroxides such as di-t-butyl peroxide.

Moreover, as a commercial item of a radiation sensitive radical polymerization initiator, IRGACURE-124, the same -149, the same -184, the same -369, the same -500, the same -651, the same -819, the same -907, the same- 1000, -1700, -1800, -1850, -1959, Darocur-1116, -1173, -1664, -2959, -4093 (above, manufactured by Ciba Specialty Chemicals), KAYACURE -DETX, the same -MBP, the same -DMBI, the same -EPA, the same -OA (above, manufactured by Nippon Kayaku Co., Ltd.), the LUCIRIN TPO (made by BASF), the VICURE-10, the same -55 (above, STAUFFER) ), TRIGONALP1 (manufactured by AKZO), SANDORAY 1000 (manufactured by SANDOZ), DEAP (AP OHN Co., Ltd.), QUANTACURE-PDO, the -ITX, same -EPD (or more, can be mentioned WARD BLEKINSOP Co., Ltd.), and the like.
These radiation-sensitive radical polymerization initiators can be used alone or in admixture of two or more.
In addition, by using one or more radiation sensitizers together with the radiation-sensitive radical polymerization initiator, it is possible to obtain a highly sensitive radiation-sensitive resin composition that is less deactivated by oxygen in the air. is there.

The amount of each component used in the photosensitive resin composition of the present invention is preferably such that [B] the polymerizable compound having an ethylenically unsaturated bond is 100 parts by weight of the alkali-soluble copolymer [A]. 150 parts by weight, more preferably 20 to 120 parts by weight, and [C] the radiation-sensitive polymerization initiator is preferably 1 to 40 parts by weight, more preferably 100 parts by weight of the alkali-soluble copolymer [A]. Is 3 to 35 parts by weight.
[B] If the amount of the polymerizable compound used is less than 10 parts by weight, it tends to be difficult to form a coating film having a uniform film thickness. On the other hand, if it exceeds 150 parts by weight, the adhesion to the substrate decreases. Tend to. In addition, when the amount of the [C] radiation sensitive polymerization initiator used is less than 1 part by weight, the heat resistance, surface hardness and chemical resistance tend to decrease, whereas when it exceeds 40 parts by weight, the transparency tends to decrease. There is.

-Solvent [D]-
The photosensitive resin composition is a composition solution obtained by dissolving constituent components such as a copolymer [A], a polymerizable compound [B], and a radiation-sensitive polymerization initiator [C] in an appropriate solvent. It is preferable to be prepared as
As the solvent [D] used for the preparation of the composition solution, a solvent that uniformly dissolves each component constituting the photosensitive resin composition 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 the copolymer [A] mentioned above can be mentioned.
Among these solvents, since the photosensitive resin composition is applied using a slit die coater, the following formula (1)

^(Wherein, R 1 to R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents an integer from 1 to 6.)
A mixed solvent containing a compound represented by the formula: The content of the compound represented by the above formula (1) in 100 parts by weight of the total mixed solvent is 2 to 20% by weight. If the amount is less than 2% by weight, there is no effect on moyamur, and if it exceeds 20% by weight, the drying time under reduced pressure becomes long, and the productivity of the panel deteriorates.
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. it can. Of these, benzyl alcohol is particularly desirable from the viewpoint of boiling point and other composition solubility.

Solvent mixture to obtain the storage stability of the resin solution, containing di ethylene glycol alkyl ether solvent i.e. diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether. The content of the diethylene glycol alkyl ether solvent in 100 parts by weight of the total mixed solvent is 30 to 75% by weight. When it is less than 30% by weight, the storage stability of the resin liquid is deteriorated, and when it exceeds 75% by weight, the drying time under reduced pressure becomes long.
In addition, it is preferable that the drying time under reduced pressure is short from the viewpoint of panel productivity. From the viewpoint of shortening the vacuum drying time, solvent mixture, in addition to the boiling point of the compound represented by the above formula (1) (boiling point at 1 atm, the same below.) Are you containing 100 ° C. to 150 DEG ° C. of the solvent. When the boiling point is less than 100 ° C., solvent odor may be a problem. When the boiling point exceeds 150 ° C., the drying time under reduced pressure is not effective. The content of the solvent having a boiling point of 100 ° C. to 150 ° C. in 100 parts by weight of the total mixed solvent is 20 to 55% by weight. When the amount is less than 20% by weight, the drying time under reduced pressure is not effective. When the amount exceeds 55% by weight, the storage stability may be deteriorated. Examples of the solvent having a boiling point of 100 ° C. to 150 ° C. that can be used in combination include 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, Examples include chlorobenzene and propyl acetate.

  Moreover, when apply | coating the photosensitive resin composition using a slit die coater, a nozzle tip may dry, a vertical stripe may be produced in a coating film, and it may become a cause of a foreign material. By using a high boiling point solvent in combination as a component of the mixed solvent, it is possible to suppress drying of the nozzle tip. As a solvent effective in suppressing the drying of the nozzle tip, a solvent having a boiling point of 180 ° C. to 250 ° C. (excluding the compound represented by the above formula (1)) is preferable. If the boiling point is less than 180 ° C., there is no effect for preventing the nozzle from drying, and if it exceeds 250 ° C., the drying time under reduced pressure is affected. The content of the solvent having a boiling point of 180 ° C. to 250 ° C. in 100 parts by weight of the total mixed solvent is preferably 3 to 15% by weight. If it is less than 3% by weight, there is no effect in suppressing the drying of the nozzle tip, and if it exceeds 15% by weight, the drying time under reduced pressure is affected, and a high boiling point solvent may remain in the coating film. Examples of the high-boiling solvent that can be used in combination include 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, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl celloso Etc. Bed acetate. Of these, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, and N-methylpyrrolidone are preferred.

-Additives-
In the photosensitive resin composition, additives other than the above-mentioned components can be blended as necessary within the range not impairing the intended effect of the present invention.
For example, in order to improve applicability, a surfactant can be blended. As the surfactant, a fluorine-based surfactant and a silicone-based surfactant can be suitably used.
As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific examples thereof include 1,1,2 , 2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol 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, perfluorododecylsulfonic acid sodium Lilium, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, fluoroalkyl Sodium phosphonate, sodium fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl poly Examples include oxyethanol, perfluoroalkyl alkoxylates, and fluorine-based alkyl esters.

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

Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF -8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (The above-mentioned, GE Toshiba Silicone Co., Ltd. product) etc. can be mentioned what is marketed.
Examples of the surfactant other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and commercially available products such as KP341 (Shin-Etsu Chemical ( Manufactured by Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
These surfactants can be used alone or in admixture of two or more.
The blending amount of the surfactant is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. When the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film roughening tends to occur during coating.
Moreover, in order to further improve the adhesion to the substrate, an adhesion assistant can be blended.

As the adhesion assistant, a functional silane coupling agent is preferable, and examples thereof include a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, More specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.
These adhesion assistants can be used alone or in admixture of two or more.
The compounding amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. When the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue tends to occur.

Other additives can be added. It is added for the purpose of improving storage stability. Specific examples include sulfur, quinones, hydroquinones, polyoxy compounds, amines, and nitronitroso compounds. Examples thereof include 4-methoxyphenol and N-nitroso-N-phenylhydroxylamine aluminum. These are preferably used in an amount of 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, based on 100 parts by weight of the copolymer [A]. When the amount exceeds 3.0 parts by weight, sufficient sensitivity cannot be obtained, and the pattern shape deteriorates.
In order to improve heat resistance, an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, and a compound having a bifunctional or higher functional epoxy group in one molecule can be added. Specific examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ′, N′-tetra (methoxymethyl) glycoluril, N, N, N ′, N′-tetra (ethoxymethyl) glycol. Uril, N, N, N ′, N′-tetra (n-propoxymethyl) glycoluril, N, N, N ′, N′-tetra (i-propoxymethyl) glycoluril, N, N, N ′, N Examples include '-tetra (n-butoxymethyl) glycoluril, N, N, N', N'-tetra (t-butoxymethyl) glycoluril, and the like. Of these, N, N, N ′, N′-tetra (methoxymethyl) glycoluril is particularly preferable. Specific examples of the N- (alkoxymethyl) melamine compound include N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine, N, N, N ′, N ′, N ″. , N ″ -hexa (ethoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N "-Hexa (i-propoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-butoxymethyl) melamine, N, N, N ', N', N", N “-Hexa (t-butoxymethyl) melamine” and the like. Of these, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is particularly preferable. Examples of these commercially available products include Nicalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.

  Examples of compounds having two or more functional epoxy groups in one molecule include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Examples include ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol A diglycidyl ether. Specific examples of these commercially available products include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 3002 (and more) Chemical Co., Ltd.). These can be used alone or in combination of two or more.

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

In forming a spacer for a display panel using the display panel spacer for the photosensitive resin composition is, after applying the composition solution to a surface of the substrate, by removing the solvent by prebaking to form a coating film .
The coating method of the composition solution is a slit die coating method.
Moreover, although the conditions of prebaking differ also with the kind of each structural component, a mixture ratio, etc., it is about 1 to 15 minutes at 70-90 degreeC, for example.
Next, the pre-baked coating film is exposed and polymerized through a mask having a predetermined pattern, and then developed with a developing solution, and unnecessary portions are removed to form a pattern.
As radiation used for exposure, visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray and the like can be appropriately selected, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

As the developing method, for example, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is, for example, 30 to 180 seconds.
Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-n. Secondary amines such as propylamine; tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine and triethylamine; tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; pyrrole, piperidine and N-methylpiperidine Alicyclic tertiary amines such as N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene; Collidine, lutidine, kino Aromatic tertiary amines such as emissions; tetramethylammonium hydroxide, the aqueous solution of an alkaline compound such as quaternary ammonium salts such as tetraethyl ammonium hydroxide may be used.
In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.
After development, for example, by washing with running water, for example, for 30 to 90 seconds, unnecessary portions are removed, and then compressed air or compressed nitrogen is blown to dry to form a predetermined pattern.

  Thereafter, the pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, for 5 to 30 minutes on the hot plate, or for 30 to 90 minutes in the oven. By doing so, the target spacer can be obtained.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether, followed by 18 parts by weight of methacrylic acid and methacrylic acid. After charging 40 parts by weight of glycidyl, 5 parts by weight of styrene, and 32 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and substituting with nitrogen, 5 weights of 1,3-butadiene is further added. The temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 5 hours for polymerization to obtain a solution of copolymer [A-1].
The solid content concentration of this solution was 33.1% by weight, and the Mw of the copolymer [A-1] was 11,000.
Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol dimethyl ether, followed by 18 parts by weight of methacrylic acid, 40 of glycidyl methacrylate. Parts by weight, 5 parts by weight of styrene, 32 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and after purging with nitrogen, 5 parts by weight of 1,3-butadiene was further added. While stirring and gently stirring, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a solution of copolymer [A-2].
The solid content concentration of this solution was 33.0% by weight, and Mw of the copolymer [A-2] was 11,000.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile), 100 parts by weight of diethylene glycol ethyl methyl ether and 100 parts by weight of propylene glycol monomethyl ether acetate, and subsequently. 10 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, 40 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, Further, 5 parts by weight of 1,3-butadiene was added, the temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 5 hours to polymerize to obtain a copolymer [A-3]. A solution was obtained.
The solid content concentration of this solution was 33.2% by weight, and the Mw of the copolymer [A-3] was 10,000.
Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 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, followed by methacrylic acid. 10 parts by weight, 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 ] decan-8-yl methacrylate were charged and replaced with nitrogen. , 3-Butadiene is charged in 5 parts by weight, the temperature of the solution is raised to 70 ° C. while gently stirring, and polymerization is carried out while maintaining this temperature for 5 hours to obtain a solution of the copolymer [A-4]. It was.
The solid content concentration of this solution was 33.1% by weight, and the Mw of the copolymer [A-4] was 10,000.

Example 1
Preparation of composition solution As copolymer [A], 100 parts by weight (as solids) of the solution of copolymer [A-1] obtained in Synthesis Example 1, and KAYARAD DPHA (Nippon Kayaku) as polymerizable compound [B] 100 parts by weight manufactured by (Co., Ltd.), 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone (trade name “IRGACURE 369”) as a photopolymerization initiator [C], Ciba Specialty Chemicals Co., Ltd.) is mixed with 15 parts by weight to give a solid concentration of 25.5% by weight, and diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, benzyl alcohol and ethylene glycol monobutyl ether acetate as solvents. After mixing and dissolving to a weight ratio of 55: 30: 10: 5, the pores And filtered through a 0.2μm PTFE (polytetrafluoroethylene) filter to prepare a composition solution (S-1).

(I) Evaluation of storage stability of resin solution The viscosity of the resin composition solution prepared in Example 1 was measured using an ELD viscometer manufactured by Tokyo Keiki Co., Ltd. Thereafter, the solution viscosity at 25 ° C. was measured every day while the composition was allowed to stand at 25 ° C. The number of days required to increase the viscosity by 5% based on the viscosity immediately after the preparation was determined, and the number of days is shown in Table 1. When this number of days is 20 days or more, it can be said that the storage stability is good.
(II) Evaluation of vacuum drying (VCD) time On the 550 × 650 mm chromium film-forming glass, the prepared composition solution was cured using a slit die coater (TR632105-CL, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The film thickness was 4 μm. Thereafter, the time until the degree of reduced pressure reached 0.5 Torr from normal pressure (hereinafter referred to as VCD time) was measured. A shorter VCD time is advantageous.
(III) Evaluation of applicability (moisture unevenness of coating film surface) The prepared composition solution was applied on a 550 × 650 mm chromium-deposited glass using a slit die coater. After drying under reduced pressure to 0.5 Torr, pre-baking in a baking oven at 100 ° C. for 2 minutes to form a coating film, and further exposing at an exposure amount of 2000 J / m ² , the chromium film from the top surface A film having a thickness of 4 μm was formed.
The surface of the film was illuminated with a sodium lamp, and the coated film surface was visually confirmed. The mark was X when the mist was clearly confirmed, △ when the mist was slightly confirmed, and ◯ when the mist was hardly confirmed.
(IV) Dryability Evaluation of Slit Nozzle The prepared composition solution was applied on a 550 × 650 mm chromium-deposited glass using a slit die coater. After coating, the nozzle tip was not washed and left as it was. After 10 minutes, the same coating was performed without cleaning the nozzle tip, and a coating film similar to (III) evaluation of coating property (moisture unevenness on the coating film surface) was produced.
The surface of the film was illuminated with a sodium lamp, and the coated film surface was visually confirmed. When the vertical stripe unevenness was clearly confirmed, it was evaluated as x, when it was slightly confirmed, Δ, when it was hardly confirmed, it was evaluated as ◯.

Examples 2-16, Comparative Examples 1-3
In Example 1, a composition solution was prepared in the same manner as in Example 1, except that the types and amounts shown in Table 1 were used as the components [A] to [D]. Adjustment of the solid content concentration of the composition solution was performed so that the mixing ratio of the component [D] was as shown in Table 1. With respect to the obtained compositions [S-2] to [S-16] and [s-1] to [s-3], evaluation of resin solution storage stability and coating evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
Examples 15 and 16 are reference examples.

In Table 1, the abbreviations of the components indicate the following compounds.
(B-1): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
(B-2): KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.)
(C-1): 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals)
(C-2): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals)
(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,-indicates that the component is not added Indicates.

Claims (7)

A photosensitive resin composition comprising an alkali-soluble copolymer [A], a polymerizable compound having an ethylenically unsaturated bond [B], a radiation-sensitive polymerization initiator [C], and a solvent [D],
The solvent [D] is
Following formula (1)

^(Wherein, R 1 to R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents an integer from 1 to 6.)
2 to 20% by weight of a compound represented by
30 to 75% by weight of at least one of diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether, and
Boiling point is applied to a substrate by mixing a solvent and a slit die coater containing 20-55 wt% solvent 100 ° C. to 150 DEG ° C., the photosensitive resin composition characterized by.   The alkali-soluble copolymer [A] comprises (a1) an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound, and (a3) another ethylene. The photosensitive resin composition of Claim 1 which is a copolymer with a photosensitive unsaturated compound.   The photosensitive resin composition of Claim 1 or 2 whose polymeric compound [B] which has the said ethylenically unsaturated bond is (meth) acrylic acid ester more than trifunctional.   The photosensitive resin according to any one of claims 1 to 3, wherein the mixed solvent contains 3 to 15% by weight of a solvent having a boiling point of 180 ° C to 250 ° C (excluding the compound represented by the formula (1)). Composition.   The spacer for display panels formed from the photosensitive resin composition in any one of Claims 1-4.   A display panel comprising the display panel spacer according to claim 5. Use according photosensitive resin composition according to any one of claim 1 to 4, and the photosensitive resin composition applied to a substrate by a slit die coater.