JP4678271B2 - Photosensitive resin composition, protective film for liquid crystal display panel and spacer, and liquid crystal display panel comprising them - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a protective film for a liquid crystal display panel and a spacer, and a liquid crystal display panel comprising the same, and more specifically, a protective film used for a liquid crystal display panel such as a liquid crystal display panel or a touch panel. The present invention relates to a photosensitive resin composition suitable as a material for forming a spacer, a protective film for a liquid crystal display panel formed from the composition, a spacer, and a liquid crystal display panel comprising the protective film and the spacer.

Radiation devices such as LCD and CCD are subjected to immersion treatment of display elements with a solvent, acid or alkali solution during the manufacturing process, and when forming a wiring electrode layer by sputtering, the element surface is localized. Exposed to high temperatures. Therefore, in order to prevent the element from being deteriorated or damaged by such treatment, a protective film made of a thin film having resistance to these treatments is provided on the surface of the element.
Such a protective film has high adhesion to the substrate or lower layer on which the protective film is to be formed, and further to the layer formed on the protective film, the film itself is smooth and tough, transparent It has excellent heat resistance and light resistance, does not cause deterioration such as coloring, yellowing, and whitening over a long period of time, and has excellent water resistance, solvent resistance, acid resistance, and alkali resistance. Performance is required. As a material for forming a protective film satisfying these various properties, for example, a photosensitive resin composition containing a polymer having a glycidyl group is known (see Patent Document 1).
When such a protective film is used as a protective film for a color liquid crystal display device or a color filter of a charge coupled device, a high transparency of the protective film is generally required.
Japanese Patent No. 3101986

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

  In these protective film and spacer formation processes, from the viewpoint of production cost, there is an increasing demand for photosensitive resin compositions that can be used under the same process conditions as a single product. In this case, there is a demand for a photosensitive resin composition having sufficient adhesion, transparency and heat resistance required for the protective film material, and sufficient resolution and compression characteristics required for the spacer material.

Further, in recent years, the size of the mother glass substrate has been increased from the conventional about 680 × 880 mm to about 1,870 × 2,200 mm due to the increase in the area of the liquid crystal display element and the improvement in productivity. In the process of forming a protective film or spacer, a protective film or a photosensitive resin composition for spacer formation is usually applied to a transparent substrate, baked on a hot plate to remove the solvent, then exposed to light, developed, and then the protective film And spacers are formed. However, as the substrate becomes larger, the photopolymerization initiator component in the photosensitive resin composition sublimates during the formation of the protective film and the spacer, and the problem of contaminating the baking furnace and the photomask is caused by a decrease in production tact and production cost. Concern from causing the rise.
Further, the present applicant has disclosed in Patent Document 2 1- (2-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one as a photopolymerization initiator of a photosensitive resin composition. Alternatively, by using a bromine-substituted acetophenone photopolymerization initiator such as 1- (3-bromo-4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, a photosensitive polymerization initiator component This indicates that contamination of the baking furnace and exhaust duct due to sublimation of the filter, clogging of a filter provided in the development line when the developer is repeatedly used, and the like can be reduced.
JP 2001-235617 A

  However, in this case, it is about the photosensitive resin composition used for forming the spacer, and the protective film using the photosensitive polymerization initiator component described in Patent Document 2 is insufficient from the viewpoint of transparency. . Therefore, using a photosensitive polymerization initiator component that does not sublimate, the adhesiveness, transparency, heat resistance required for the protective film material, and the resolution, compression characteristics required for the spacer material are sufficient. The photosensitive resin composition which has it together is calculated | required.

  It is an object of the present invention to have a sufficient process margin, suppress contamination of a baking furnace or a photomask due to sublimation of a photopolymerization initiator component, and provide adhesion, transparency, and heat resistance required for a protective film material. And a photosensitive resin composition having sufficient resolution and compression characteristics required for the spacer material, a protective film and a spacer formed therefrom, and a method for forming the same, and a liquid crystal display panel having the protective film and the spacer It is to provide.

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

[In the formula (1), n is an integer of 2 to 12, and R ₁ is hydrogen, a hydroxyl group, or any group of structures represented by the following (I), (II), or (III): R ₂ in (III) represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms). And may be substituted with at least one alkoxy group). ]

Secondly, the present invention relates to a photosensitive resin composition used for forming a protective film for a liquid crystal display panel and a spacer, comprising the photosensitive resin composition described above.
Thirdly, the present invention relates to a protective film or spacer for a liquid crystal display panel formed from the photosensitive resin composition described above.
Fourthly, the present invention relates to a method for forming a protective film for a liquid crystal display panel or a spacer comprising at least the following steps (a) to (d).
(B) A step of forming a film of the photosensitive resin composition on a substrate (b) A step of exposing at least a part of the film (c) A step of developing the film after exposure (d) The post-development step Step of heating the coating The fifth aspect of the present invention relates to a liquid crystal display panel comprising the protective film or spacer for a liquid crystal display panel of the present invention.

  The photosensitive resin composition of the present invention has a sufficient process margin, can suppress contamination of a baking furnace, a photomask, etc. due to sublimation of the photopolymerization initiator component, and has adhesion and transparency required for a protective film material. It is a photosensitive resin composition that has sufficient properties, heat resistance, and resolution and compression characteristics required for spacer materials.

Hereinafter, each component of the protective film and the photosensitive resin composition for forming a spacer (hereinafter simply referred to as “photosensitive resin composition”) of the present invention will be described in detail.
-Copolymer [A]-
[A] component in the photosensitive resin composition of this invention can be manufactured by radically polymerizing a compound (a1) and a compound (a2) in presence of a polymerization initiator in a solvent.

  Among the components constituting the copolymer [A], (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid anhydride (hereinafter collectively 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 above dicarboxylic acids.

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. 2-methacryloyloxyethyl hexahydrophthalic acid is preferred.
In the copolymer [A], the unsaturated carboxylic acid monomer (a1) can be used alone or in admixture of two or more.

  In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15%. ~ 30% by weight. In this case, when 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 when it exceeds 40% by weight. There is a possibility that the solubility in an aqueous alkali solution becomes too large.

Further, (a2) other ethylenically unsaturated compounds (hereinafter simply referred to as “other monomers”) include, for example, alkyl acrylates such as methyl acrylate and i-propyl acrylate; methyl methacrylate Alkyl methacrylates such as ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 2- (tricyclo [
5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl, alicyclic esters of acrylic acid such as isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid 2- (tricyclo [
5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; Aryl or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate; Diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Dicarboxylic acid dialkyl esters of
Methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; non-oxygen containing one oxygen atom such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydrofupyran-2-methyl methacrylate Saturated hetero 5- and 6-membered methacrylic acid esters; glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, etc. Acrylic acid epoxy alkyl esters of
Methacrylic acid epoxy alkyl esters such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate; α-ethylacrylic Α-alkylacrylic acid epoxyalkyl esters such as glycidyl acid, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl;
glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyl) Oxetane alkyl esters of methacrylic acid such as oxymethyl) -4-trifluoromethyloxetane;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
Phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, Dicarbonylimide derivatives such as N- (9-acridinyl) maleimide;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, etc. be able to.

Among these other monomers, 2-methylcyclohexyl acrylate, hydroxyethyl methacrylate, tricyclomethacrylate [5.2. From the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an alkaline aqueous solution. 1.0 ^2,6 ] decan-8-yl, styrene, glycidyl methacrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane, tetrahydrofurfuryl methacrylate, 1,3-butadiene, phenylmaleimide, cyclohexylmaleimide, etc. Is preferred.
In the copolymer [A], other monomers can be used alone or in admixture of two or more.

  The copolymer [A] used in the present invention contains a repeating unit derived from the compound (a2), preferably 50 to 95% by weight, more preferably 60 to 90% by weight, particularly preferably 70 to 85% by weight. Contains. In this case, when the repeating unit is less than 10% by weight, the storage stability of the copolymer [A] tends to be lowered, whereas when it exceeds 70% by weight, the copolymer [A] is dissolved in the alkaline aqueous solution. It becomes difficult to do.

As described above, the copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic acid anhydride group and another ethylenically unsaturated compound, and is appropriately dissolved in an alkaline aqueous solution. And can be easily cured by heating without using a special curing agent.
The photosensitive resin composition containing the copolymer [A] described above exhibits good alkali solubility during development and can easily form a spacer having a predetermined pattern.

  Examples of the solvent used for the production of the copolymer [A] include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and propylene glycol. Examples include alkyl ether propionates, aromatic hydrocarbons, ketones and esters.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.
Examples of dipropylene glycol include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
As propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like;
As propylene glycol alkyl ether acetate, 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 ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, 3-methoxybutyl 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, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Lopyl, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate and the like.

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, propylene glycol methyl ether acetate, and 3-methoxybutyl acetate.
The said solvent can be used individually or in mixture of 2 or more types.
The amount of the solvent used is usually 50 to 90 parts by weight, preferably 55 to 85 parts by weight with respect to 100 parts by weight of the total amount of (a1) and (a2).

The radical polymerization initiator used for the polymerization is not particularly limited. 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) Organic peroxides such as peroxy) cyclohexane; hydrogen peroxide and the like. Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator combining it and a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.
The amount of the radical polymerization initiator used is usually 0.1 to 10.0 parts by weight, preferably 1.0 to 8.0 parts by weight with respect to 100 parts by weight of the total amount of the above (a1) and (a2). is there.
In the radical polymerization, the polymerization temperature is usually 60 to 100 ° C., preferably 70 to 90 ° C., and the polymerization time is usually 2 to 6 hours, preferably 3 to 5 hours.
The copolymer [A] thus obtained may be used in the preparation of the photosensitive resin composition as a solution, or may be separated from the solution and used in the preparation of the photosensitive resin composition.

  The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer [A] by gel permeation chromatography (GPC) is usually 2,000 to 100,000, preferably 5,000 to 50,000. is there. In this case, if the Mw is less than 2,000, the developability and the remaining film ratio of the resulting film may decrease, and the pattern shape, heat resistance, etc. may be impaired. , There is a possibility that the resolution is lowered or the pattern shape is damaged.

-Polymerizable compound [B]-
[B] component in the photosensitive resin composition of this invention is a polymeric compound (henceforth "polymerizable compound [B]") which has an ethylenically unsaturated bond.
Although it does not specifically limit as polymeric compound [B], Monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester has favorable polymerizability, and the intensity | strength of the spacer obtained is good. It is preferable from the viewpoint of improvement.

  Examples of the monofunctional (meth) acrylic acid esters include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3 -Methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate and the like can be mentioned. -101, M-111, M-114 (manufactured by Toa Gosei Co., Ltd.); KAYARAD TC-110S, TC-120S (Nippon Kayaku Co., Ltd.) ); Viscoat 158, and the like the 2311 (Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the bifunctional (meth) acrylic acid esters 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 commercially available products, for example, Aronix M-210, M-240, M-6200 (Toa Gosei Co., Ltd.) ), KAYARAD HDDA, the HX-220, manufactured by the same R-604 (Nippon Kayaku Co.), Viscoat 260, the 312, manufactured by the same 335HP (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.

Further, the trifunctional or higher functional (meth) acrylic acid esters include, 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. Can do.
In particular, the (meth) acrylate having 9 or more functional groups has an alkylene straight chain and an alicyclic structure, a compound containing 2 or more isocyanate groups, and a trifunctional, 4 functional and 1 or more hydroxyl group in the molecule. The urethane acrylate compound obtained by making a pentafunctional (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.). Commercially available products of 9 or more polyfunctional urethane acrylates include, for example, New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), etc. 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 esters can be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the amount of the polymerizable compound [B] used is preferably 50 to 200 parts by weight, more preferably 60 to 150 parts by weight with respect to 100 parts by weight of the copolymer [A]. It is. In this case, if the amount of the polymerizable compound [B] used is less than 50 parts by weight, there may be a residual image during development. On the other hand, if it exceeds 200 parts by weight, the adhesion of the resulting spacer tends to decrease. .

-Photopolymerization initiator [C]-
The [C] component in the photosensitive resin composition of the present invention comprises a compound represented by the above general formula (1) (hereinafter referred to as “compound 1”) as an essential component.

In the formula (1), n is an integer of 2 to 12, and R ₁ is hydrogen, a hydroxyl group, or any group having the structure represented by the above (I), (II), or (III). R ₂ in (III) is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms) And may be substituted with at least one group).
Here, examples of the alkyl group having 1 to 12 carbon atoms and the cycloalkyl group having 3 to 8 carbon atoms of R ₂ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, Examples thereof include an n-dodecyl group, a cyclopentyl group, and a cyclohexyl group.

  Moreover, as a C1-C6 alkyl group substituted by a phenyl group, a C1-C6 alkoxy group, as a C1-C6 alkyl group, a methyl group, an ethyl group, n-propyl group, As an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, and an alkoxy group having 1 to 6 carbon atoms, for example, Examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a t-butoxy group.

Specific examples of preferred compound (1) in the present invention include
2-methyl-1- [4- (ethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-propylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (i-propylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-butylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (i-butylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (t-butylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-pentylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-hexylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-heptylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-octylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (n-dodecylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-hydroxyethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (3-hydroxypropylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (4-hydroxybutylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (5-hydroxyheptylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (5-hydroxyhexylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-acryloyloxyethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-methacryloyloxyethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (3-acryloyloxypropylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (3-methacryloyloxypropylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (4-acryloyloxybutylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (4-methacryloyloxybutylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-acetylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-acetylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-propionylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-butyrylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-valerylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-hexanoylethylthio) phenyl] -2-morpholinopropan-1-one,
2-methyl-1- [4- (2-benzoylethylthio) phenyl] -2-morpholinopropan-1-one,
And 2-methyl-1- [4- (4-acetylbutylthio) phenyl] -2-morpholinopropan-1-one.

Of these compounds (1), in particular, 2-methyl-1- [4- (ethylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (n-propylthio) phenyl] 2-morpholinopropan-1-one, 2-methyl-1- [4- (n-butylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (2-hydroxyethyl) Thio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (3-hydroxybutylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4 -(2-acryloyloxyethylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-1- [4- (2-methacryloyloxyethylthio) phenyl] -2-morpho Nopuropan-1-one, 2-methyl-1- [4- (4-acetyl-butyl) phenyl] -2-morpholino-1-one are preferred.
Compound (1) is excellent in solubility in a solvent, does not cause foreign matters such as undissolved substances and precipitation, does not cause contamination of a baking furnace or a photomask due to sublimation, and impairs the transparency of the protective film. It is a component that can form an excellent spacer without pattern loss and defect.
In this invention, a compound (1) can be used individually or in mixture of 2 or more types.

  In the photosensitive resin composition of this invention, the usage-amount of a compound (1) becomes like this. Preferably it is 5-50 weight part with respect to 100 weight part of [A] copolymers, More preferably, it is 5-30 weight part. is there. In this case, when the amount of the compound (1) used is less than 5 parts by weight, the residual film ratio tends to decrease, whereas when it exceeds 50 parts by weight, the solubility of the unexposed part in the alkaline developer tends to decrease. is there.

Moreover, in the photosensitive resin composition of this invention, at least 1 sort (s) of other photoinitiators can be used together with a compound (1).
Examples of the other photopolymerization initiators include, for example, O-acyloxime type compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, and onium as a radiation-sensitive cationic polymerization initiator. Examples thereof include salts and metallocene compounds. Among these, acetophenone compounds, biimidazole compounds, and radiation-sensitive cationic polymerization initiators are preferable.

The O-acyloxime type compound is a component having an effect of further improving sensitivity.
Specific examples of the O-acyloxime type compound include
1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate,
1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate,
1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate,
1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -octane-1-one oxime-O-acetate,
1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate,
1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate,
1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate,
1- [9-butyl-6- (2-ethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate,
1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime),
1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime),
1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime),
1,2-octadione-1- [4- (methylthio) phenyl] -2- (O-benzoyloxime),
And 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyloxime)).

Of these O-acyloxime types, in particular 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1 , 2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is preferred.
In the present invention, the O-acyloxime type compounds can be used alone or in admixture of two or more.

  In the photosensitive resin composition of the present invention, the total amount of the O-acyloxime type compound is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the polymerizable compound [B]. Part. In this case, if the amount of the O-acyloxime compound used is less than 1 part by weight, the remaining film ratio tends to decrease during development. There is a tendency for solubility to decrease.

Examples of the acetophenone compounds include α-hydroxy ketone compounds, α-amino ketone compounds, and other compounds.
These acetophenone compounds can be used alone or in admixture of two or more.
In the present invention, by using an acetophenone compound as the other polymerization initiator, it is possible to further improve the sensitivity, the shape of the obtained spacer, the compressive strength, and the like.

Specific examples of the biimidazole compound include, for example,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

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

In addition, when a biimidazole compound is used as another polymerization initiator, an aromatic compound having a dialkylamino group (hereinafter referred to as “dialkylamino group-containing sensitizer”) is used in combination to sensitize it. be able to.
Examples of the dialkylamino group-containing sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, Examples include i-amyl p-dimethylaminobenzoate and i-amyl p-diethylaminobenzoate.
Of these dialkylamino group-containing sensitizers, 4,4′-bis (diethylamino) benzophenone is preferred.
The above-mentioned dialkylamino group-containing sensitizers can be used alone or in admixture of two or more.
The amount of the dialkylamino group-containing sensitizer used is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the copolymer [A]. In this case, if the amount of the dialkylamino group-containing sensitizer used is less than 0.1 parts by weight, the resulting spacer film may be reduced or the pattern shape may be impaired. On the other hand, 50 parts by weight If it exceeds, the pattern shape of the spacer may be impaired.

  Furthermore, when a biimidazole compound and a dialkylamino group-containing sensitizer are used in combination as other polymerization initiators, a thiol compound can be added as a hydrogen donor compound. Biimidazole compounds are sensitized and cleaved by a dialkylamino group-containing sensitizer to generate imidazole radicals, but at this time, high polymerization initiation ability is not necessarily expressed, and the resulting spacer has a reverse taper shape. In many cases, such an unfavorable shape is obtained. This problem can be alleviated by adding a thiol compound to a system in which a biimidazole compound and a dialkylamino group-containing sensitizer coexist. That is, hydrogen radicals are donated to the imidazole radical from the thiol compound, so that the imidazole radical becomes a neutral imidazole and a component having a sulfur radical having a high polymerization initiating ability is generated. It becomes a shape.

Examples of the thiol compound include aromatics such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole. Aliphatic monothiols such as thiols, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate. Examples of the bifunctional or higher aliphatic thiol include 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetra (mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), and the like.
These thiol compounds can be used alone or in admixture of two or more.

  The use ratio of the thiol compound is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the copolymer [A]. In this case, if the amount of the thiol compound used is less than 0.1 parts by weight, the resulting spacer tends to be reduced in film thickness or pattern shape, whereas if it exceeds 50 parts by weight, the spacer pattern shape is impaired. There is a fear.

Further, as the radiation-sensitive cationic polymerization initiator, onium salts such as phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphonate, phenyldiazonium hexafluoroarsenate, phenyldiazonium trifluoromethanesulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium- p-toluenesulfonate, 4-methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphonate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazoniumtri Fluoroacetate, 4-methoxypheny Diazonium-p-toluenesulfonate, 4-ter-butylphenyldiazonium tetrafluoroborate, 4-ter-butylphenyldiazonium hexafluorophosphonate, 4-ter-butylphenyldiazonium hexafluoroarsenate, 4-ter-butylphenyldiazonium trifluoro Diazonium salts such as romethanesulfonate, 4-ter-butylphenyldiazonium trifluoroacetate, 4-ter-butylphenyldiazonium-p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium Hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, Phenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxy Phenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate 4-phenylthiophenyl dipheny Hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, sulfonium salts such as 4-phenylthiophenyldiphenylsulfonium -p- toluenesulfonate.
Examples of the metallocene compounds include (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-).
Commercially available products of these radiation-sensitive cationic polymerization initiators include, for example, Adeka Ultra Set PP-33 (made by Asahi Denka Kogyo Co., Ltd.) which is a diazonium salt, OPTOMER SP-150 and 170 (both Asahi Denka) which are sulfonium salts. Kogyo Co., Ltd.) and Irgacure 261 (Ciba Specialty Chemicals Co., Ltd.), which is a metallocene compound.
Said photoinitiator can be used individually or in mixture of 2 or more types.

  In the photosensitive resin composition of the present invention, the use ratio of the other photopolymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, particularly preferably 100 parts by weight of the total photopolymerization initiator. Is 60 parts by weight or less. In this case, if the use ratio of the other photopolymerization initiator exceeds 100 parts by weight, the intended effect of the present invention may be impaired.

-Additives-
In the photosensitive resin composition of the present invention, additives other than the above components may be blended as necessary within a 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, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,1 , 10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, diglycerin Examples thereof include tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and fluorine-based alkyl ester. .

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 FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S ) Made by Neos).
Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF -8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (The above-mentioned, GE Toshiba Silicone Co., Ltd. product) etc. can be mentioned what is marketed.

  Examples of surfactants other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxy Polyoxyethylene aryl ethers such as ethylene 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 Industry Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.).

These surfactants can be used alone or in admixture of two or more.
The blending amount of the surfactant is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. In this case, when the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film roughening is likely to occur during coating.

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

Other additives can be added to the photosensitive resin composition of the present invention for the purpose of improving storage stability. Specific examples include sulfur, quinones, hydroquinones, polyoxy compounds, amines, and nitronitroso compounds. Examples thereof include 4-methoxyphenol and N-nitroso-N-phenylhydroxylamine aluminum. These are preferably used in an amount of 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the copolymer [A]. When the amount exceeds 3.0 parts by weight, sufficient sensitivity cannot be obtained, and the pattern shape deteriorates.
In addition, the photosensitive resin composition of the present invention has an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, and a bifunctional or higher functional epoxy group in one molecule for improving heat resistance. Compounds can be added.
Specific examples of the N- (alkoxymethyl) glycoluril compound include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) glycol Examples include uril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like. Of these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.
Specific examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa ( Ethoxymethyl) melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) melamine, N, N , N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like. Of these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable. Examples of these commercially available products include Nicalac N-2702 and MW-30M (manufactured by Sanwa Chemical Co., Ltd.).
Furthermore, as a compound having a bifunctional or higher functional epoxy group in one molecule, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Examples include diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol A diglycidyl ether. . Specific examples of these commercially available products include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 3002 (and more) Chemical Co., Ltd.). These can be used alone or in combination of two or more.

Composition Solution When the photosensitive resin composition of the present invention is used, it usually dissolves a constituent solvent such as a copolymer [A], a polymerizable compound [B], a photopolymerization initiator [C] in an appropriate solvent. Then, it is prepared as a composition solution.
As a solvent used for the preparation of the composition solution, a solvent that uniformly dissolves each component constituting the photosensitive resin composition and does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

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

Furthermore, in order to improve the in-plane uniformity of the film thickness together with the above solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.
The composition solution prepared in this way can be used for use after filtration through a Millipore filter having a pore size of, for example, about 0.2 to 0.5 μm, if necessary.

  The photosensitive resin composition of the present invention is particularly suitable as a material for forming a protective film for liquid crystal display panels such as liquid crystal panels and touch panels and spacers.

Method for Forming Protective Film for Display Panel and Spacer for Display Panel The method for forming the protective film for liquid crystal display panel or the spacer in the present invention comprises at least the following steps in the order described below.
(B) Step of forming a film of the photosensitive resin composition of the present invention on a substrate (b) Step of exposing at least part of the film (c) Step of developing the film after exposure (d) After development Heating the coating

(I) Process A transparent conductive film is formed on one surface of a transparent substrate, a photosensitive resin composition is applied onto the transparent conductive film, and then the coated surface is heated (prebaked) to form a coating film.
Examples of the transparent substrate used for forming the spacer include a glass substrate and a resin substrate. More specifically, glass substrates such as soda lime glass and non-alkali glass; polyethylene terephthalate, polybutylene terephthalate, Examples thereof include a resin substrate made of a plastic such as polyethersulfone, polycarbonate, and polyimide.
As a transparent conductive film provided on one surface of a transparent substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., it is normally about 1 to 15 minutes at 70-120 degreeC.

Examples of a method for forming a protective film for a liquid crystal display panel and a spacer on a substrate such as a transparent substrate or a resin substrate using the photosensitive resin composition of the present invention include (1) coating method and (2) dry film method. be able to.
As a coating method of the composition solution, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method can be employed. In particular, a spin coating method and a slit die coating method are preferable.

  Further, when the film of the photosensitive resin composition of the present invention is formed, (2) when the dry film method is adopted, the dry film is formed on the base film, preferably a flexible base film. And a photosensitive layer made of the photosensitive resin composition (hereinafter referred to as “photosensitive dry film”).

  The photosensitive dry film can be formed by laminating a photosensitive layer on the base film by applying the photosensitive resin composition of the present invention, preferably as a liquid composition, and then drying. As a base film of the photosensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride, or the like can be used. The thickness of the base film is suitably in the range of 15 to 125 μm. The thickness of the obtained photosensitive layer is preferably about 1 to 30 μm.

  Moreover, the photosensitive dry film can also be preserve | saved by laminating | stacking a cover film on the photosensitive layer at the time of unused. This cover film needs to have an appropriate releasability so that it does not peel off when not in use and can be easily peeled off when in use. As a cover film satisfying such conditions, for example, a film based on a silicone-based release agent or a baking film can be used on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, or a polyvinyl chloride film. . A thickness of about 25 μm is usually sufficient for the cover film.

  It is preferable to pre-bake after forming the film of the photosensitive resin composition of the present invention on the substrate. The prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are usually about 70 to 90 ° C. for about 1 to 15 minutes.

(B) Step Next, the pre-baked coating film (film) is polymerized by exposure through at least a part of the coating film, for example, a mask having a predetermined pattern.
Visible light, ultraviolet rays, far ultraviolet rays, charged particle beams, X-rays, and the like can be appropriately selected as radiation used for exposure, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
The exposure dose is usually 100 to 10,000 J / m ² , preferably 1, as the value of the intensity of the exposed radiation at a wavelength of 365 nm measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). 500 to 4,000 J / m ² .

Step (c) Next, the exposed film is developed with a developer, and unnecessary portions are removed to form a pattern.
As the developing method, for example, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is usually 30 to 180 seconds.
Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine, triethylamine; tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperidine , N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene 3 Secondary amines; pyridine, It can be used tetramethylammonium hydroxide, the aqueous solution of an alkaline compound such as quaternary ammonium salts such as tetraethylammonium hydroxide; lysine, lutidine, aromatic tertiary amines such as quinoline.
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.

(D) Process After development, this pattern (coating film) is subjected to a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time on a hot plate, for example, 5 to 30 minutes on the hot plate by a heating device such as a hot plate or oven. For example, the target protective film or spacer can be obtained by heat treatment for 30 to 90 minutes.

Liquid crystal display panel The liquid crystal display panel of the present invention is produced by the following method. First, two substrates on which the protective film having the liquid crystal alignment ability of the present invention is formed are prepared, and the two substrates are separated by a gap (cell gap) so that the liquid crystal alignment directions in the respective protective films are orthogonal or antiparallel. ), The peripheral portions of the two substrates are bonded together via the spacer of the present invention, the surface of the substrate and the cell gap defined by the spacer are filled with liquid crystal, and the filling hole is sealed A liquid crystal cell is constructed. Then, on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, a polarizing plate is aligned or orthogonal to the liquid crystal alignment direction of the protective film formed on one surface of the substrate. Thus, the liquid crystal display panel of the present invention is obtained.

  Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane. Type liquid crystal, cubane type liquid crystal, etc. are used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

  In addition, the polarizing plate used outside the liquid crystal cell is composed of a polarizing plate in which a polarizing film called an H film that has absorbed iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.

  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 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, styrene 5 parts by weight, methacrylic acid 20 parts by weight, methacrylic acid tricyclo [
5.2.1.0 ^2,6 ] decan-8-yl 25 parts by weight, 3- (methacryloyloxymethyl) -3-ethyloxetane 25 parts by weight, tetrahydrofurfuryl methacrylate 20 parts by weight, 1,3-butadiene After 5 parts by weight were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-1]. The resulting polymer solution had a solid content concentration of 30.0% by weight, and the polymer had a weight average molecular weight of 18,000 (weight average molecular weight was GPC (gel permeation chromatography) HLC-8020. (Molecular weight in terms of polystyrene measured using Tosoh Corporation).

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, styrene 5 parts by weight, methacrylic acid 20 parts by weight, methacrylic acid tricyclo [
5.2.1.0 ^2,6 ] decane-8-yl 25 parts by weight, glycidyl methacrylate 25 parts by weight, tetrahydrofurfuryl methacrylate 20 parts by weight, 1,3-butadiene 5 parts by weight were charged with nitrogen. After that, gentle stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2]. The obtained polymer solution had a solid content concentration of 31.0% by weight, and the polymer had a weight average molecular weight of 20,000 (weight average molecular weight was GPC (gel permeation chromatography) HLC-8020. (Molecular weight in terms of polystyrene measured using Tosoh Corporation).

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 30 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by weight of benzyl methacrylate, tetrahydrofurfuryl methacrylate 20 After adding a weight part and substituting with nitrogen, stirring was started gently. The temperature of the solution was raised to 90 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The solid content concentration of the obtained polymer solution was 31.0% by weight, and the weight average molecular weight of the polymer was 21,000 (weight average molecular weight was GPC (gel permeation chromatography) HLC-8020. (Molecular weight in terms of polystyrene measured using Tosoh Corporation).

Example 1
Preparation of Composition Solution 100 parts by weight (solid content) of the copolymer [A-1] obtained in Synthesis Example 1 as a copolymer [A], and KAYARAD DPHA (Nippon Kayaku) as a polymerizable compound [B] 80 parts by weight, photopolymerization initiator [C] 2-methyl-1- [4- (n-butylthio) phenyl] -2-morpholinopropan-1-one 20 parts by weight, 1,2-octadione -1- [4- (Phenylthio) phenyl] -2- (O-benzoyloxime) (CGI-124 manufactured by Ciba Specialty Chemicals) 3 parts by weight of propylene so that the solid content concentration becomes 30% by weight After dissolving in glycol monomethyl ether acetate, the solution was filtered through a Millipore filter having a pore size of 0.2 μm to prepare a composition solution (S-1).

(I) Formation of Protective Film After applying the above composition solution on a non-alkali glass substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film having a thickness of 1.5 μm. .
The coating film obtained above was exposed to ultraviolet rays having an exposure gap of 150 μm and an exposure intensity of 200 W / m ^{2 at} a wavelength of 365 nm without using a mask. Subsequently, after developing for 60 seconds at 25 ° C. with a 0.05 wt% aqueous solution of potassium hydroxide, it was rinsed with pure water for 1 minute. Furthermore, it heated at 220 degreeC for 60 minute (s) in oven, and formed the protective film.

(II) Formation of Spacer The above composition solution was applied on a non-alkali glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film having a thickness of 4.0 μm.
The coating film obtained above was exposed to ultraviolet rays having an exposure gap at a wavelength of 365 nm of 300 W / m ² with an exposure gap of 150 μm through a mask having a 10 μm square pattern. Subsequently, after developing for 60 seconds at 25 ° C. with a 0.05% by weight aqueous solution of potassium hydroxide, it was rinsed with pure water for 1 minute. Furthermore, it heated at 220 degreeC for 60 minute (s) in oven, and formed the spacer.

(III) Evaluation of transparency Using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)), the transmittance of the protective film was measured at 400 to 800 nm, with a minimum transmittance of 97. The case where it exceeded% was marked with ○, the case where it was 90-97% was marked with Δ, and the case where it was less than 90% was marked with ×.

(IV) Evaluation of resolution Except that the exposure amount was changed, it was solved in the same way as the formation of the spacer in (II) above, when the spacer was formed, the exposure amount at which the residual film ratio after development was 90% or more. Evaluation was based on the minimum pattern size to be imaged.

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

(VI) Evaluation of adhesiveness It carried out similarly to said (I), the cured film for adhesiveness evaluation was formed, and the adhesiveness test was done. The test method followed the cross-cut tape method of 8.5.2 in the adhesion test of JIS K-5400 (1900) 8.5.

(VII) Evaluation of heat resistance In the above (I), the protective film formed at a pre-baking temperature of 90 ° C was heated in an oven at 250 ° C for 60 minutes. The change rate of the film thickness at this time was measured. When the rate of change is within 5% before and after heating, the heat-resistant stability is good, and when it exceeds 5%, the heat-resistant dimensional stability is poor.

(VIII) Evaluation of sublimation property The above composition solution was applied on a substrate and then dried to form a film having a thickness of 6.0 μm. Then, for this coating, using n-octane as a standard substance (specific gravity = 0.701, injection amount; 0.02 μl), purging conditions at 100 ° C./10 minutes, headspace gas chromatography / mass Analysis (head space sampler: JHS-100A manufactured by Nippon Analytical Industry Co., Ltd., gas chromatography / mass spectrometer; JEOL JMS-AX505W type mass spectrometer) is performed to determine the peak area A derived from the photopolymerization initiator. The amount of volatilization in terms of n-octane was calculated by the following formula. It can be said that the greater the amount of volatilization, the greater the sublimation property.
Calculation formula of volatilization amount in terms of n-octane Volatilization amount (μg) = A × (amount of n-octane) (μg) / (peak area of n-octane)

(IX) Evaluation of compression characteristics About the obtained spacer, using a micro compression tester (trade name: FISCHER SCOPE H100C, manufactured by Fisher Instruments Co., Ltd.) Both were set to 2.6 mN / sec, a load up to 50 mN was applied and held for 5 seconds, then unloaded, and a load-deformation curve and a load-deformation curve during slow loading were prepared. At this time, as shown in FIG. 2, the difference between the deformation amount at the load of 50 mN and the deformation amount at the load of 5 mN is L1, and the deformation amount at the load of 50 mN and the deformation amount at the load of 5 mN at unloading. The elastic recovery rate was calculated by the following formula, with the difference between L2 and L2.
Elastic recovery rate (%) = L2 × 100 / L1

Examples 2-6, Comparative Examples 1-4
In Example 1, the composition solution [S-2 to S-] was used in the same manner as in Example 1 except that the types and amounts shown in Table 1 were used as the [A] component to [C] component. 6, s-1 to s-4], spacers were formed and evaluated. The addition amount of [B]-[C] is a weight ratio with respect to 100 parts by weight of the copolymer [A].
The evaluation results are shown in Table 2.

In Table 1, the abbreviations of the components indicate the following compounds.
(B-1): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
(C-1): 2-methyl-1- [4- (n-butylthio) phenyl] -2-morpholinopropan-1-one (C-2): 2-methyl-1- [4- (2-hydroxy Ethylthio) phenyl] -2-morpholinopropan-1-one (C-3): 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (Ciba Specialty)・ CGI-124 manufactured by Chemicals
(C-4): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty Chemicals)
(C-5): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (C-6): 4,4′-bis (Diethylamino) benzophenone (C-7): 2-mercaptobenzothiazole

It is a figure which illustrates the cross-sectional shape of a pattern. It is a figure which illustrates the load-deformation amount curve at the time of the load in evaluation of an elastic recovery factor, and a slow load.

Claims (11)

[A] a copolymer of (a1) an ethylenically unsaturated carboxylic acid and (a2) another ethylenically unsaturated compound (excluding an ethylenically unsaturated carboxylic acid anhydride) ,
[B] A photosensitive resin composition comprising a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator comprising a compound represented by the following formula (1).
[In the formula (1), n is an integer of 2 to 12, and R ₁ is hydrogen, a hydroxyl group, or any group of structures represented by the following (I), (II), or (III): R ₂ in (III) represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group (however, an alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms) And may be substituted with at least one alkoxy group. ]
(A1) The ethylenically unsaturated carboxylic acid is acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, mesacone Acid and at least one selected from the group of itaconic acid, and (a2) other ethylenically unsaturated compound is 2-methylcyclohexyl acrylate, hydroxyethyl methacrylate, tricyclomethacrylate [5.2.1 .0 ^2,6 ] Selected from the group of decane-8-yl, styrene, glycidyl methacrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane, tetrahydrofurfuryl methacrylate, 1,3-butadiene, phenylmaleimide, and cyclohexylmaleimide 2. The photosensitive resin composition according to claim 1, which is at least one kind. In the copolymer [A], the content of the repeating unit derived from (a1) is 5 to 50% by weight, and the content of the repeating unit derived from (a2) is 95 to 50% by weight. 3. The photosensitive resin composition according to 1 or 2. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polymerizable compound [B] is a monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester. The photosensitive resin composition according to any one of claims 1 to 4, wherein an amount of the polymerizable compound [B] used is 50 to 200 parts by weight with respect to 100 parts by weight of the copolymer [A]. The photosensitive resin composition according to any one of claims 1 to 5, wherein the amount of the photopolymerization initiator [C] used is 5 to 50 parts by weight with respect to 100 parts by weight of the copolymer [A]. In addition to the photopolymerization initiator [C], selected from O-acyloxime type compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds or α-diketone compounds, or onium salts or metallocene compounds The photosensitivity according to any one of claims 1 to 6, wherein at least one of other photopolymerization initiators comprising a radiation-sensitive cationic polymerization initiator is used in an amount of 60 parts by weight or less based on 100 parts by weight of the total photopolymerization initiator. Resin composition. The photosensitive resin composition according to claim 1, which is used for forming a protective film for a liquid crystal display panel or for forming a spacer. The protective film or spacer for liquid crystal display panels formed from the photosensitive resin composition of Claim 8 . A method for forming a protective film or spacer for a liquid crystal display panel, comprising at least the following steps in the order described below.
(B) A step of forming a film of the photosensitive resin composition according to claim 8 on a substrate (b) A step of exposing at least a part of the film (c) A step of developing the film after exposure ) A step of heating the film after development A liquid crystal display panel comprising the protective film or spacer for a liquid crystal display panel according to claim 9 .