TWI377445B - - Google Patents

Description

1377445 (1) Inventive Description of the Invention The present invention relates to a photosensitive resin composition, a spacer for a display panel, and a display panel. More specifically, it is suitable for use as a liquid crystal display panel. A photosensitive resin composition of a material for a spacer used in a display panel such as a touch panel, a spacer for a display panel formed of the composition, and a display panel including the spacer. [Prior Art] In the liquid crystal display panel, spacer particles such as glass beads or plastic beads having a predetermined particle diameter are used in order to keep the interval between the two substrates (cell gap) constant, but these spacer particles are used. Since it is arbitrarily spread on a transparent substrate such as a glass substrate, when spacer particles are present in the pixel formation region, reflection of spacer particles occurs, or incident light is scattered, and the contrast of the liquid crystal panel is lowered. problem. φ Therefore, in order to solve these problems, there is a method of forming spacers by lithography. In this method, a photosensitive resin composition is applied onto a substrate, and after exposure to ultraviolet light by a designated mask, development is performed to form a dot-like or strip-shaped spacer, since it is only in the pixel formation region. The spacer is formed at a predetermined position other than the above, so that the above-described problems are basically solved. In recent years, from the viewpoint of manufacturing cost, there has been an increase in the use of the same process as the materials used in the past. In such a case, there are many cases in which the conditions suitable for the process conditions of the photosensitive resin composition for the interlayer insulating film or the photosensitive resin composition for the spacer are deviated, in particular, -4- (2) 1377445 When the optimum conditions for deviating from the prebaking temperature are obtained, sufficient resolution cannot be obtained, and there is a problem that pattern peeling occurs. Further, as the substrate is enlarged, the warpage of the substrate becomes more remarkable in the case of the near baking, and the temperature distribution also occurs on the same substrate, and the photosensitive film for the interlayer insulating film having a wider process margin must be used. A photosensitive resin composition for a resin composition and a spacer. In order to solve such a problem, the applicant of the present application has already proposed a process having a sufficient process range corresponding to the change of the process conditions, and can impart the necessary heat resistance as an interlayer insulating film and a spacer, as disclosed in Japanese Laid-Open Patent Publication No. 2001-302712. A photosensitive resin composition of a cured product having properties, chemical resistance, transparency, and hardness. In addition, in recent years, the size of the mother glass substrate has increased from about 680 x 880 mm to about 1,87 〇 X 2 and about 200 mm due to the increase in the area of the liquid crystal display element or the improvement in productivity. In the step of forming the spacer, a photosensitive resin composition for forming a spacer is usually applied onto a transparent substrate, and after heating on a hot plate to remove the solvent, the exposure is developed to form a spacer. However, as the substrate is enlarged, the photopolymerization initiator component in the photosensitive resin composition is sublimated at the time of formation of the spacer, and the problem of contamination of the heating furnace or the photomask occurs, which causes a decrease in production tact and an increase in production cost. After that. Further, the applicant of the present invention has shown that 1-(2-bromo-4-morpholinylphenyl)-2 which is a photopolymerization initiator which is a photosensitive resin composition is disclosed in Japanese Patent Laid-Open Publication No. 2001-2356. -benzyl-2-dimethylaminobutan-1-one or 1·(3-di-4-morpholinylphenyl)-2-pyryl-2-dimethylaminobutan-1-one Desert substitution-5- < S > (4) (4)1377445 [A] (al) Ethylene unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride, (a2) following formula (I) or Π):

[In the formulae (I) and (II), R is a hydrogen atom or a carbon number! ～4 alkyl, R, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; r2, r3, 4 and 1 each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; Or a monomer represented by a perfluoroalkyl group having a carbon number of 4 and an integer of n to 1 to 6 and a copolymerization of (a3) another ethylenically unsaturated compound different from the above compounds (ai) and (a2) , [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator, which contains the following formula (ΠΙ): (5) 1377445

Cm) # [In the formula (III), 116 represents a linear, branched or cyclic group having a carbon number of 1 to 12, and R7 and R8 independently represent a hydrogen atom and a linear chain of 1 to 12 carbon atoms. R9, Rlfl, R12 and Rl3 independently of each other represent a hydrogen atom 'halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. Or a linear or branched alkoxy group having a carbon number of 1 to 4, and Rn represents a linear, branched or cyclic alkyl group having a carbon number of 1 to 12, a hydroxyl group and a carbon number of 1 a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms substituted with a substituent selected from a group consisting of a linear or branched alkoxy group of ～4, carbon number 1~ a linear or branched alkoxy group of 4, or a carbon number of 2 to 4 substituted by a substituent selected from a group consisting of a hydroxyl group and a linear or branched alkoxy group having 1 to 4 carbon atoms; A compound represented by '* linear or branched alkoxy group>. According to the present invention, the second object of the above object is achieved by the spacer formed of the photosensitive resin composition. According to the present invention, the third aspect of the above object is achieved by a method of forming a spacer. The method is characterized by comprising at least the following steps (a) to (d): -8 - (6) 1377445 (a) a step of forming a film of the radiation sensitive resin composition of the present invention on a substrate, (b) a step of exposing at least a portion of the film, (c) a step of developing the film after exposure, and _ (d) a step of heating the film after development. Finally, in accordance with the present invention, the fourth object of the above object is achieved by a liquid crystal display panel comprising the above-described spacer. [Embodiment] The photosensitive resin composition for forming a spacer of the present invention is the same as the photosensitive resin composition for forming a spacer of the present invention (hereinafter referred to as "photosensitive resin composition (a)"). Detailed. —Copolymer [A] - φ The [A] component of the copolymer used in the photosensitive resin composition (a) of the present invention can be obtained by using the compound (al), the compound (a2) and the compound (a3). The solvent is obtained by radical polymerization in the presence of a polymerization initiator. In the respective components constituting the copolymer [A], (al) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride (hereinafter collectively referred to as "unsaturated carboxylic acid monomer (al)"), For example, it may be acrylic acid, methacrylic acid, crotonic acid, 2-methylpropenyloxyethyl succinic acid, 2-methacryloxyethyl hexahydrophthalic acid monocarboxylic acid; maleic acid, rich Horse acid, -9-(7) (7) 丄 377445 barraconic acid, mesaconic acid, itaconic acid-like dicarboxylic acid; anhydride of the above dicarboxylic acid, and the like. Among these unsaturated carboxylic acid monomers (al), the copolymer obtained from the copolymerization reaction ft' is preferably acrylic acid or methacrylic acid in terms of solubility in an aqueous alkali solution and ease of availability. Maleic anhydride, 2-methylpropanoloxyethyl hexahydrophthalic acid, and the like. In the photosensitive resin composition (a), the unsaturated carboxylic acid monomer Cal) may be used singly or in combination of two or more kinds. In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (al) is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 1 5 to 5 30% by weight. When the content of the repeating unit derived from the unsaturated carboxylic acid monomer (al) is less than 5% by weight, the solubility in the aqueous alkali solution tends to decrease. On the other hand, if it exceeds 50% by weight, the base is used. The solubility in the aqueous solution has become too large. The compound (a2) represented by the above formula (I) may, for example, be 3-(methacryloxymethyl)oxetane or 3-(methacryloxymethyl)-3- Ethyloxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyl Oxetane, 3-(methacryloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloxymethyl)-2-phenyloxalate Cyclobutane, 3-(methacryloxymethyl)-2,2-difluorooxetane, 3-(methacryloxymethyl)-2,2,4-trifluoro Oxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloxyethyl)oxyheterocycle Butane, 3_(methacrylofluorene < 5 > -10- (8) (8) 1377444 base ethyl)-3-ethyloxetane, 2-ethyl-3-(methyl Propylene methoxyethyl)oxetane, 3-(methacryloxyethyl)-2-trifluoromethyloxetane, 3-(methacryloxyethyl) -2-pentafluoroethyl oxetane, 3-(methacryloxyloxy B -2-phenyloxetane, 2,2-difluoro-3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)- 2,2,4-trifluorooxetane, 3-(methacryloxyethyl)-2,2,4,4-tetrafluorooxetane-like methacrylate; -(propylene methoxymethyl) oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-yl Oxycyclobutane, 3-(propylene methoxymethyl)-2-trifluoromethyl oxetane, 3-(propylene methoxymethyl)-2-pentafluoroethyl oxane Butane, 3-(acryloxymethyl)-2-phenyloxetane, 3-(acryloxymethyl)-2,2-difluorooxetane, 3-( Propylene methoxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl)-2,2,4,4-tetrafluorooxetane, 3 -(propylene oxiranyloxy) oxetane, 3-(acryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(acryloxyethyl) Oxetane, 3-(acryloxyethyl)-2-trifluoromethyloxetane, 3-(acryloxyloxy) 2-pentafluoroethyl oxetane, 3-(acryloxyethyl)-2-phenyl oxetane, 2,2-difluoro-3-(acryloxy) Ethyl)oxetane, 3-(acryloxyethyl)-2,2,4-trifluorooxetane, 3-(acryloxyethyl)-2,2,4 , 4-tetrafluorooxetane-like acrylate. The compound (a2) represented by the above formula (II) may, for example, be 2-(methacryloxymethyl)oxetane or 2-methyl-2-(methyl-11 - (9) (9)1377445 Acryloxymethyl)oxetane, 3-methyl-2-(methacryloxymethyl)oxetane, 4-methyl-2-(-) Acetyloxymethyl) oxetane, 2-(methacryloxymethyl)difluoromethyloxetane' 2-(methylpropenyloxymethyl)- 3_Difluoromethyloxetane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, 2-(methacryloxymethyl) 2_pentafluoroethyl oxetane, 2_(methacryloxymethyl)_3_pentafluoroethyl oxetane, 2_(methacryloxymethyl)-4-five Fluoroethyl oxetane, 2_(methylpropionyloxymethyl)·2_phenyloxetan, 2-(methylpropenyloxymethyl)-3-phenyl Oxetane, 2-(methacryloxymethyl) 4-phenyloxetane, 2,3-difluoro-2-(methacryloxymethyl) oxalate Cyclobutane, 2,4-difluoro-2-(methacryl oxime) Methyl)oxetane, 3,3-difluoro-2-(methacryloxymethyl)oxetane, 3,4-difluoro-2-(methacrylofluorene) Methyl)oxetane, 4,4-difluoro-2-(methacryloxymethyl)oxetane, 2·(methacryloxymethyl)-3, 3,4-trifluorooxetane, 2-(methacryloxymethyl)-3,4,4-trifluorooxetane, 2-(methacryloxymethyl) -3,3,4,4·tetrafluorooxetane, 2-(methacryloxyethyl)oxetane, 2-(2-(2-methyloxetane) Base)) Ethyl methacrylate, 2-(2-(3-methyloxetanyl))ethyl methacrylate, 2-(methacryloxyethyl)-2-methyl Oxycyclobutane, 2-(methacryloxyethyl)-4-methyloxetane, 2-(methacryloxyethyl)-2-trifluoromethyloxy Heterocyclobutane, 2-(methacryloxyethyl)-3-trifluoromethyloxetane, 2-(methacryloxy-12- 1377445 do) alkane, butane cyclobutane Heteroepoxyheteromethylfluoro-4-HH - V) I-based-2J 2-2 Ζ ) ) ) ) Basyl B Base oxypropyl fluorofluorofluoropentaphenoxyethylcyclohexane 1*·triazaoxyethoxyethylethanecyclohethane oxyethylallyl methethane ethoxide oxiranyl propyl ethane Oxyxylyl allylformamidine (ν I 2 -ethyloxypropenyl propyl tolyl oxetane, 2-(methacryloxyethyl)-4-phenyl oxetane , 2,3-difluoro-2-(methacryloxyethyl)oxetane, 2,4-difluoro-2-(methacryloxyethyl)oxetane , 3, 3-difluoro-2-(methacryloxyethyl)oxetane, 3,4-difluoro-2-(methacryloxyethyl)oxetane, 4,4-difluoro-2-(methacryloxyethyl)oxetane, 2-(methylpropionateoxyethyl)-3,3,4-trifluorooxetane Alkane, 2-(methacryloxyethyl)-3,4,4-trifluorooxetane, 2-(methacryloxyethyl)-3,3,4,4- Tetrafluorooxetane-like methacrylate; 2-(acryloxymethyl)oxetane, 2-methyl-2-(acryloxymethyl)oxetane 3-A -2-(acryloxymethyl)oxetane, 4-methyl-2-(acryloxymethyl)oxetane, 2-(acryloxymethyl)-2 -trifluoromethyloxetane, 2-(acryloxymethyl)-3-trifluoromethyloxetane, 2-(acryloxymethyl)-4-trifluoromethyl Oxycyclobutane, 2-(propylene methoxymethyl)-2-pentafluoroethyl oxetane, 2-(propylene methoxymethyl)-3-pentafluoroethyl oxocycle Butane, 2-(acryloxymethyl)pentafluoroethyloxetane, 2-(acryloxymethyl)_2-phenyloxetane, 2-(acryloxyloxy) Methyl)-3-phenyloxetane, 2-(acryloxymethyl)-4-phenyloxacyclo-13-(11) (11)1377445 butane, 2,3-di Fluor-2-(propenyloxymethyl)oxetane, 2,4-difluoro-2-(acryloxymethyl)oxetane, 3,3-difluoro-2-( Propylene methoxymethyl)oxetane, 3,4-difluoro-2-(acryloxymethyl)oxetane, 4,4-difluoro-2-(propyleneoxyl) Methyl)oxetane, 2-(acryloxymethyl)-3,3,4-trifluorooxetane , 2-(acryloxymethyl)-3,4,4-trifluorooxetane, 2-(acrylo-oxymethyl)-3,3,4,4-tetrafluorooxocyclo Butane, 2-(acryloxyethyl)oxetane, 2-(acryloxyethyl)-2-methyloxetanium, 2-(acryloxyethyl) -4 - Methyl oxetane, 2 · (Acetylaoxyethyl)-2-trifluoromethyl oxetane, 2-(acryloxyethyl)-3-trifluoro Methyl oxetane, 2-(acryloxyethyl)-4-trifluoromethyl oxetane, 2-(propenyloxyethyl)_2-pentafluoroethyl oxetane Alkane, 2-(acryloxyethyl)-3.pentafluoroethyloxetane, 2-(acryloxyethyl)-4-pentafluoroethyloxetane, 2- (Allyloxyethyl)-2-phenyloxetane, 2-(acryloxyethyl)-3-phenyloxetan, 2-(propionyloxyethyl) - 4_phenyloxetane, difluoro-2(propenyloxyethyl) oxetane, 2,4-difluoro-2-(propyleneoxyethyl) oxalate Cyclobutane, 3,3-difluoro-2-(acryloxyethyl)oxetane, 3,4·difluoro_2 ·(Propyleneoxyethyl)oxetane, 4,4·difluoro-2-((acryloxy)ethyloxetane, 2_(propyleneoxyethyl)-3,3 , 4-trifluorooxetine, 2-(propyl oxyethyl)_3,4,4-difluorooxetane, 2-(acryloxyethyl)·3,3 , 4,4·tetrafluorooxetane-like acrylate. -14- 1377445 Fan Jiaji oxymethylbenzene is a weaker oxygen than methyl hydrazide. See the 3-propanyl substrate, butylene methacrylate group, butyl C oxyalicyclic ring 3- Eucalyptus, C-like oxyalkylene 3-propene-resistant butyl, ketone-based naphthyl-methyl methacrylate C to the spacer oxygen ring 2-deoxy-hybrid From the oxime to the -3- butyl ketone, the propyl group of the fluorene is high in the methyl group, and the oxo is added to the thiol group. -2 Å olefinyl} is surrounded by propylcyclobutane, 2-(methacryloxymethyl)-4-trifluoromethyloxetane, etc. These may be used singly or in combination The copolymer [A] used in the present invention preferably contains 3 to 70% by weight of a repeating unit derived from the compound (a2), more preferably 15 to 50% by weight. The content of the repeating unit is low. When the amount is 3% by weight, the heat resistance of the copolymer [A] tends to be lowered. On the other hand, when it exceeds 70% by weight, the copolymer [A] is hardly dissolved in the aqueous alkali solution. Further, as (a3) Other ethylenically unsaturated compounds (hereinafter referred to as "others" The monomer ") may be, for example, methyl acrylate or isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, Alkyl methacrylate such as tributyl acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5. 2. 1. 〇2'6] fluorene-8-ester, acrylic acid 2-(Tricyclo[5. 2. 1. 02'6]癸-8-yloxy)ethyl ester, isophorone acrylate-like acrylate cyclic ester: cyclohexyl methacrylate, methyl 2-methylcyclohexyl acrylate, tricyclo[meth] methacrylate [5. 2. 1. 02,6] 癸-8-yl, 2-(tricyclo[5. 2. 1 02]癸-8-yloxy)ethyl ester, isophorone methacrylate-like methacrylate cyclic ester; phenyl-15-(13) (13)1377445 base, benzyl acrylate-like acrylic acid An aryl or arylalkyl ester; an aryl or arylalkyl methacrylate like benzyl methacrylate or benzyl methacrylate; diethyl maleate, diethyl fumarate, diethyl ikonate Ester-like dialkyl dicarboxylate; methyl propyl 2-hydroxyethyl acid, 2-hydroxypropyl methacrylate hydroxyalkyl methacrylate; tetrahydrofurfuryl methacrylate, tetrahydrofuran methacrylate, tetrahydropyranyl-2-methacrylate Ester-like oxygen-containing atomic unsaturated penta- or six-membered ring methacrylate; glycidyl acrylate, 2-methyl glycidyl acrylate, 3,4-epoxybutyl acrylate, acrylic acid 6,7 - epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate-like alkyl acrylate; glycidyl methacrylate, 2-methyl glycidyl methacrylate, methacrylic acid 3, 4-epoxybutyl acrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate-based epoxy methacrylate; α-ethyl acrylate Glycidyl ester, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-alkyl acrylate, α-alkyl acrylate, α-alkyl acrylate ; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether-like glycidyl ether Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene-like vinyl aromatic compound; phenyl maleimide, cyclohexylmalayiya Amine, benzyl maleimide, anthracene-succinimide-3-maleimide benzoate, anthracene-succinimide-4-merineimine butyrate, hydrazine - Amber quinone imine-6-maleimide caproate, Ν-amber quinone imido- 3-maleimide propionate, Ν-(9-acridinyl)malaya Amine-like dicarbonyl ruthenium compound; 1,3-butadiene, isoprene, 2,3-dimethyl--16- (14) (14)1377445 ^3-butadiene A conjugated diene compound, and acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, and the like. Among these other monomers (a3), 2-methylcyclohexyl acrylate and hydroxy methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility of the obtained copolymer in an aqueous alkali solution. Ethyl ester, tricyclo[10 2. 1. 〇2'6] 癸-8-ester, styrene, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, 1,3-butadiene Wait. In the copolymer [A], the other monomer (a3) may be used singly or in combination of two or more. The copolymer [A] used in the present invention preferably contains 10 to 92% by weight of the repeating unit derived from the compound (a3), more preferably 20 to 70% by weight, particularly preferably 30 to 50% by weight. When the content of the repeating unit is less than 10% by weight, the storage stability of the copolymer [A] tends to be lowered. On the other hand, if it exceeds 92% by weight, the copolymer [A] becomes insoluble in an aqueous alkali solution. . The copolymer [A]' used in the above-mentioned invention has a carboxyl group and/or a carboxylic anhydride group and an oxetanyl group which has an appropriate solubility in an aqueous alkali solution, and can be used even if a special hardener is not used in combination. It is easily hardened by heating. The photosensitive resin composition containing the above copolymer [A] exhibits good alkali solubility at the time of development, and a spacer of a predetermined pattern can be easily formed. The solvent used in the production of the copolymer [A] may, for example, be an alcohol, an ether 'diol ether, an ethylene glycol alkyl ether acetate, diethylene glycol, or dipropylene 2 -17-(15) 1377445 alcohol. , propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl acid propionate, aromatic hydrocarbon, ketone, ester, and the like. Specific examples of these may be, for example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol or the like as the alcohol; for example, tetrahydrofuran or the like as the ether; The glycol ether' may be, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or the like;

The ethylene glycol alkyl ether acetate may, for example, be methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, or the like; As diethylene glycol, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol B Methyl ether or the like: as a propanol - for example, dipropylene glycol monomethyl ether dipropylene glycol monoethyl ether, monopropyl alcohol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl Ether, etc.; as a propanol single-chamber acid', for example, may be propylene glycol monomethyl ether, propanol monoethyl ether, propanol monopropyl ether, propylene glycol monobutyl ether, etc.; as a propanol alkyl group The ether acetate 'for example, may be propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate or the like: as the propanol alkyl ether propionate, for example It can be propylene glycol methyl ether propionate 'propanol ethyl ether propionate, propylene glycol propyl acid propionate, propylene glycol butyl ether Esters and the like;

<S -18-(16) (16)1377445 The aromatic hydrocarbon may be, for example, toluene or xylene; and the ketone' may be, for example, methyl ethyl ketone, cyclohexanone or 4-hydroxy-4-methyl. As the ester, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate , 2-diabase-2-methylpropionic acid ethyl ester, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropyl Methyl ester, ethyl 3-hydroxypropionate, propyl propyl propyl propionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, methoxy Ethyl acetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid propyl vinegar, butyl ethoxy acetate, propoxy Methyl acetate, ethyl acetoacetate, propyl propyl acetate, butyl propyl acetate, methyl acetoacetate, ethyl butyrate, propyl butoxyacetate, butoxyacetic acid Butyl ester, acetic acid 3-A Butyl ketone, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl methoxypropionate, butyl 2-methoxypropionate, 2-ethoxy propyl Methyl ester, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropane Ethyl acetate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropane Acid propyl ester, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid propyl vinegar, 3-ethoxy propyl Butyrate, methyl 3-propoxypropionate 3-ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butoxypropane An ester of methyl ester, ethyl 3-butoxypropionate, 3-butoxy-19. (17) 1377445 propyl propionate, butyl 3-butoxypropionate or the like. Among them, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and the like are preferably diethylene glycol dimethyl. Ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate . • The above solvents may be used singly or in combination of two or more. φ and 'as a radical polymerization initiator to be used in the above polymerization, and are not particularly limited', for example, 2,2,-azobisisobutyronitrile, 2,2,-azobis-(2,4- Dimethylvaleronitrile), 2,2,-azobis-(4.methoxy-2,4-dimethylvaleronitrile), 4,4,-azobis(4-cyanovaleric acid) , dimethyl-2,2,-azobis(2-methylpropionate), 2,2,-azobis(4-methoxy-2,4-dimethylvaleronitrile) Azo compound; benzhydryl peroxide, lauryl peroxide, tert-butyl peroxytrimethyl acetate, hydrazine, hydrazine-bis(t-butylperoxy)cyclohexane Organic peroxide; hydrogen peroxide, etc. Further, # When using a peroxide as a radical polymerization initiator, it can be used as a redox type initiator with a reducing agent. These radical polymerization initiators can be used singly or in combination of two or more kinds. The copolymer [A] thus obtained is prepared by preparing a photosensitive resin composition as it is, and can also be separated from a solution to prepare a photosensitive resin composition. The polystyrene-isolated weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] as measured by gel permeation chromatography (GPC) is preferably -20-(18) (18)1377445 2,000. ~1〇〇, 〇00, more preferably 5, 〇〇〇~50,000. When the Mw is less than 2,000 Å, the development properties of the film obtained, the residual film ratio, and the like are lowered, and the pattern shape and heat resistance are deteriorated. On the other hand, if it exceeds 100,000, the resolution is lowered and the pattern shape is lowered. There is damage. —The polymerizable compound [B] The component [B] in the photosensitive resin composition (a) is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as "polymerizable compound [B]"). The polymerizable compound [B] is not particularly limited, but is preferably a monofunctional, bifunctional or trifunctional or higher (meth)acrylic acid from the viewpoint of improving polymerizability and improving the strength of the obtained spacer. ester. As the above monofunctional (meth) acrylate, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether A Acrylate, isophorone acrylate, isophorone methacrylate, 3·methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-propenyloxyethyl phthalate -2-hydroxypropyl ester, 2-methylpropenyloxyethyl-2-hydroxypropyl phthalate, etc., and as a commercial product, for example, Aronix M-101, M-111, and M-114 (East Asia Synthetic Co., Ltd.); KAYARAD TC-1 10S, the same TC-120S (Nippon Chemical Co., Ltd.); Bis coat 158, the same 2311 (Osaka Organic Chemical Industry Co., Ltd.). Further, the bifunctional (meth) acrylate may, for example, be ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dipropylene-21 - (19) 1377445 enoate, or Ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate 1,9-nonanediol diacrylate, iota, 9-. decanediol dimethacrylate, diphenoxyethanol oxime diacrylate, bisphenoxyethanol oxime dimethacrylate, and the like. Further, as a commercial item, for example, Aronix M-210, M-240, M-6200 (East Asia Synthetic-Share), KAYARAD HDDA, HX-220, and R-604 (Japanese) Pharmaceutical (share) system, Biscoat 260, same as 3 12, same as 3 3 5 HP (Osaka Organic Chemical Industry Co., Ltd.). Further, examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. , pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-φ propylene decyloxy) Ethyl) phosphate, tris(2-methylpropenyloxyethyl) phosphate, and the like. In particular, the hexa-functional or higher (meth) acrylate is a compound having a linear alkyl group and an alicyclic structure and having two or more isocyanato groups and one or more hydroxyl groups in the molecule. A urethane acrylate compound obtained by reacting a functional, tetrafunctional or 5-functional* (meth) acrylate compound. As the above-mentioned commercial products, for example, Aronix M-309, the same M-400, the same M-405, the same M-450, the same M-7100, the same M-8 03 0, the same -22-(20) (20 ) 1377445 Μ-8060, Tongyi-1450 (East Asia Synthetic (stock) system), KAYARAD TMPTA, same DPHA, same DPCA-20, same DPCA-30, same DPCA-60, same DPCA-120 (Nippon Chemicals Co., Ltd. )), Biscoat 295, 300, 3, 60, GPT, 3PA, and 400 (Osaka Organic Chemical Industry Co., Ltd.). Examples of commercial products of a polyfunctional urethane acrylate having a nin or more functional group are Newfrontier R-1150 (the above is manufactured by Daiichi Kogyo Co., Ltd.) and KAYARAD DPHA-40H (the above is manufactured by Nippon Kayaku Co., Ltd.). )Wait. Among these monofunctional, bifunctional or trifunctional or higher (meth) acrylates, more preferably a trifunctional or higher (meth) acrylate, particularly preferably trimethylolpropane triacrylate or pentaerythritol triacrylate Ester, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. The above-mentioned monofunctional 'bifunctional or trifunctional or higher (meth) propyl acrylate may be used singly or in combination of two or more. In the photosensitive resin composition (a), 'polymerizable compound [B] The amount used is preferably from 50 to 200 parts by weight, more preferably from 60 to 150 parts by weight, per part by weight of the copolymer [A]. When the amount of the polymerizable compound [B] used is less than 50 parts by weight, the developer residue may be generated during development, and if it exceeds 200 parts by weight, the adhesion of the obtained spacer may be The tendency to decrease. —Photopolymerization Initiator [C] The component [c] in the photosensitive resin composition (a) of the present invention contains -23-(21) (21)1377445 compound represented by the above formula (III) (hereinafter referred to as "Compound (1)") is an essential component. In the above formula (III), a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R6, R7, R8, R9, R10, R11, Ri2 and R13 may be, for example, a methyl group. , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl-n-decyl, positive Mercapto, n-quinone-based, n-dodecyl, cyclopentyl, cyclohexyl and the like. Further, the halogen atom of R9, R1 (>, Rn, R12 and R13 may be, for example, a fluorine atom, a chlorine atom or a bromine atom. Further, the carbon number of R9, R1(), Rh, R12 and R13 is 1 a linear or branched alkoxy group of ～4, which may be, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group. a group having a carbon number of 1 to 12 substituted with a substituent selected from the group consisting of a hydroxyl group of Rii and a linear or branched alkoxy group having 1 to 4 carbon atoms; In the linear, branched or cyclic alkyl group, the linear or branched alkoxy group having 1 to 4 carbon atoms may be, for example, a straight carbon number of 1 to 4 with respect to R12 and R13. The group exemplified in the chain or branched alkoxy group is the same as the substituent of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms substituted for Rn. Preferably, it is a hydroxyl group or a methoxy group. The linear, branched or cyclic group having 1 to 12 carbon atoms substituted as Ru may be, for example, the above R9, Rio, R11, R!2 and Ri3. -24- (22) 1377445 carbon number 1~I1 2 3 a group similar to the group exemplified in the linear or branched alkyl group. The substituent may be substituted with a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms substituted by Rm. One or more or more are present. In the above formula (III), R6 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, or third. Butyl, n-pentyl, n-hexyl, etc. Further, R·7 and R8 are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and third. Butyl, n-pentyl, n-hexyl, n-butyl, n-octyl, etc. Further, R9, Rw, R丨2 and preferably a hydrogen atom, a methyl group, an ethyl group, etc. Further, Ru is preferably a Base, ethyl, n-propyl, isopropyl, n-butyl isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl-n-decyl, positive Indenyl, n-undecyl, n-dodecylhydroxymethyl, 1-hydroxyethyl, methoxymethoxy, 2-methoxyethoxy, etc. Cooma: as a compound in the present invention (1) Preferred specific examples of, for example, 2 base) (4-methylbenzyl)·2 -(dimethylamino)-^-1-one, (4-morpholinylphenyl) (4-morpholinylbenzene-25- 2- 1 '(4-ethylbenzyl)-2•(two Methylamino) 丨_( 4 morpholinyl phenyl 2 ketone 3 _ isopropyl benzyl)-2-(dimethylamino) (23) (23) 1377444 base)-but-1-one, 2-( 4-n-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one, 2-(4-isobutylbenzyl)-2- (dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one, 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-( 4-morpholinylphenyl)-butan-1-one, 2-(3,4-dimethylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)- Butan-1-one, 2-(4-methoxybenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one, 2-(4- Ethoxybenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one, 2-(4-hydroxymethylbenzyl)-2-(di) Methylamino)-1-(4-morpholinylphenyl)-butan-1-one, 2-(4-[2-methoxyethoxy]-benzyl)-2-(dimethylamino) )-1-(4-morpholinylphenyl)-butan-1-one, 2-(4-[2-hydroxyethoxy]-benzyl)-2-(dimethylamino)-1-( 4-morpholinylphenyl)-but-1- , 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-oct-1-one, 2-(4-isopropylbenzyl 2-(dimethylamino)-1-(4-morpholinylphenyl)-pentan-one, 2-(4-isopropylbenzyl)-2-(butylmethylamino)- 1-(4-morpholine-26-(24)(24)1377445 phenyl)-butan-1-one, 2-(4-isobutylbenzyl)-2-(butylmethylamino)-1 - (4-morpholinylphenyl)-pentan-1-one, 2-(4-methylbenzyl)-2-(dioctylamino)-1-(4-morpholinylphenyl)-hexyl · 1 · ketone, 2-(4-butoxybenzyl)-2-(butylmethylamino)-1-(4-morpholinylphenyl)-pentan-1 -one, 2-(4-positive Butylbenzyl)-2-(butylmethylamino)-1-(4-morpholinylphenyl)-butan-1-indole. Among these compounds (1), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one is particularly preferred. 2-(4·ethylbenzyl)·2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-one, 2-(4-isopropylbenzyl)-2- (Dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one and the like. The compound (1) is excellent in solubility in a solvent, and does not cause foreign matter such as undissolved matter or precipitation, and does not cause contamination of the calcining furnace, the reticle or the like due to sublimation, and can form an excellent interval without falling off or missing. The active ingredient of the substance. In the present invention, the compound (1) may be used singly or in a mixture of two or more kinds. Further, in the photosensitive resin composition of the present invention, the amount of the compound (1) to be used is preferably from 0.05 to 50 parts by weight based on 100 parts by weight of the [A] copolymer. When the amount of the compound (1) used is less than 5 parts by weight, the residual film ratio tends to decrease. On the other hand, if it exceeds 50% by weight, -27-(26)(26)1377445 alkane-2-indole-acetic acid ester , 1-[9-ethyl-6-benzhydryl- 9.oxa,-oxazol-3-yl]-octane-1-one oxime-indole-acetate, 1-[9-ethyl- 6-(2-Methylbenzylidene)-9.Η.-carbazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1-[9-ethyl-6 - (2-Methylbenzylidene)-9.Η·-咔.哩-3-yl]-ethane-1-one oxime-indole-acetate, 1-[9-ethyl-6-( 1,3,5-trimethylbenzylidene)-9.11.-carbazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1-[9-butyl-6 - (2-ethylbenzylidene)-9.Η.-carbazol-3-yl]-ethane-1-one oxime-indole-benzoic acid _, 1,2-octanedione-1-[ 4-(phenylthio)phenyl]-2-(0-benzylidenehydrazine), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(0- Benzopyridinium), 1,2-butanedione-l-[4-(phenylthio)phenyl]-2-(0-ethenyl), 1,2-octanedione-1- [4-(Methylthio)phenyl]-2-(0-benzylidenehydrazide), 1,2-octanedione-l-[4-(phenylthio)phenyl]-2-(0 - (4-methylbenzhydrylhydrazine) Wait. Among these 0-fluorenyl hydrazinos, 1-[9-ethyl-6-(2-methylbenzhydryl)-9.H.-oxazol-3-yl]-ethane is particularly preferred. -1-ketooxime-0-acetate, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-benzylidenehydrazine). -29 - (28) (28)1377445 2,2'-bis(2-chlorophenyl)-4,4,5,5,-tetrakis(4-ethoxycarbonylphenyl)-1,2'- Bismuth, 2,2'-bis(2-bromophenyl)-4,4,5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-double miso, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4-dichlorophenyl) _4,4,,5,5,_ tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichlorophenyl)·4,4,,5,5, _ tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4,5,5,-tetraphenyl-1,2,-bisimidazole, 2 , 2'-bis(2,4-dibromophenyl)_4,4,5,5,_ tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6- Tribromophenyl)-4,4,5,5,-tetraphenyl-1,2'-biimidazole and the like. Among the above biimidazole compounds, 2,2,-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2,-bisimidazole, 2,2 is preferred. ,-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2,-bis (2,4,6-three Chlorophenyl)-4,4',5,5,-tetraphenyl-1,2,-bisimidazole, etc., particularly preferably 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-Tetraphenyl-1,2'-bisimidazole. The above diimidazole compounds may be used singly or in combination of two or more. By using these diimidazole compounds, sensitivity, resolution, and adhesion can be made better. Further, when a diimidazole compound is used as another polymerization initiator, it is sensitized to -31 - (29) 1377445, and an aromatic compound having a dialkylamine group (hereinafter referred to as "dialkylamine" can be used. The base contains a sensitizer"). The sensitizer containing a dialkylamine group can be, for example, 4,4'-bis(di-methylamino)benzophenone, 4,4,-bis(diethylamino)benzophenone, or Ethyl dimethylaminobenzoate, ethyl p-diethylaminobenzoate, isoamyl p-dimethylaminobenzoate, isoamyl p-diethylaminobenzoate, and the like. - Among these sensitizing agents containing a dialkylamine group, '4,4'-bis φ (diethylamino) benzophenone is preferred. The above dialkylamine group-containing sensitizers may be used singly or in combination of two or more kinds. The amount of the dialkylamine group-containing sensitizer to be used is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the copolymer [A]. When the amount of the dialkylamine group-containing sensitizer used is less than 0.1 part by weight, the resulting spacer is thinned and the pattern shape is damaged. On the other hand, if it exceeds 50 parts by weight, the interval is The pattern shape of the object has a flaw. Further, when a diimidazole compound as a polymerization initiator and a sensitizer containing a dialkylamine group are used, a thiol compound may be added as a hydrogenation compound. The diimidazole compound is sensitized and cleaved by a sensitizing agent containing a dialkylamine group to generate an imidazole radical, but at this time, it is not necessarily capable of exhibiting a high polymerization initiating ability, and the obtained spacer is not suitable for an inverted cone shape. There are many shapes. This problem can be alleviated by adding a thiol compound in a system in which a diimidazole compound and a sensitizer containing a dialkylamine group are present. Ρρ, by supplying a hydrogen radical derived from a thiol compound to the imidazole-free-32-(30) 1377445 group, the imidazole radical can be made into a neutral imidazole, and a sulfur radical component having a high polymerization initiating ability is produced. As a result, the shape of the spacer becomes a better tapered shape. - as the above thiol compound, for example, 2-mercaptobenzothiazole, 2-*. mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-indenyl-5-methoxybenzothiazole Aromatic thiol such as 2-mercapto-5-methoxybenzimidazole, 3-mercapto*propionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 3-methylmercaptopropanoate An aliphatic monothiol such as φ ester. The difunctional or higher aliphatic thiol may be, for example, 3,6-diin-1,8-octanedithiol, pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate). Wait. These thiol compounds can be used singly or in combination 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, per 100 parts by weight of the copolymer [A]. When the amount of the thiol compound used is less than 0.1 part by weight, the film of the obtained φ spacer tends to be thin or the pattern shape is poor. On the other hand, if it exceeds 50 parts by weight, the pattern shape of the spacer There is damage. Further, as the radiation-sensitive cationic polymerization initiator, for example, a key salt and a metallocene compound are preferably used. The key salt may be, for example, phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoro arsenate, phenyldiazonium trifluoromethanesulfonate, benzene. Base weight nitrogen trifluoroacetate, phenyldiazonium p-toluenesulfonate, 4-methoxyphenyldiazepine tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate-33- (31) 1377445 salt, 4·methoxyphenyldiazide Trifluoroacetate, 4-methoxyphenyldiazonium p-toluenesulfonate, 4-tert-butylphenyldiazide tetrafluoroborate, 4-tert-butylphenyldiazonium hexafluoride Phosphate, 4-tert-butylphenyldiazonium hexafluoroarsenate, 4-tert-butylphenyldiazide trifluoromethanesulfonate, 4-tert-butylphenyldiazo a diazo key salt such as a key trifluoroacetate or a 4-tert-butylphenyldiazide p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium Fluorinium arsenate, triphenylsulfonium trifluoromethanesulfonate, φ triphenylsulfonium trifluoroacetate, triphenylsulfonium Benzene sulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate Arsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium Tosylate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphate, 4-phenylthiophenyldiphenylhexafluoroarsenate , 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiobenzene φ phenyl diphenyl p-toluene sulfonate, etc. Clam salt. Further, the metallocene compound may, for example, be (l-6-η-isopropylbenzene) (η-cyclopentadienyl) iron (1 + ) hexafluorophosphoric acid (1-) or the like. ._ As a commercial product of these radiation-sensitive cationic polymerization initiators,

For example, it may be a heavy nitrogen salt salt of Adkultraset(R)-33 ((ED) ADEKA), an OPTOMER SP-150 of strontium salt, the same -1 70 (manufactured by AD ΕΚ A), and an Irgacure of a metallocene compound. 261 (made by Ciba Specialty Chemicals Co., Ltd.). The above radiation-sensitive polymerization initiator may be used singly or in a mixture of 2 e »· **ι· v a > -34- (32) 1377445 or more. In the photosensitive resin composition (a), the use ratio of the other photopolymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, based on 100 parts by weight of all the photopolymerization initiators. It is preferably 60 _ parts by weight or less. When the ratio of use of the other photopolymerization initiator exceeds 100 parts by weight, the effects expected by the present invention are impaired. Φ - Additive - In the photosensitive resin composition (a), an additive other than the above components may be blended as needed within a range not impairing the effects expected by the present invention. For example, in order to improve coatability, a surfactant may be blended. As the surfactant, a fluorine-based surfactant and a polyfluorene-based surfactant can be used. As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkyl group at at least one position of φ at the terminal, main chain and side chain can be used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether and 1,1,2,2-tetrafluorooctylhexyl. Ether, octaethylene glycol di(i,i,2,2-tetrafluoro..butyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, eight Propylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexapropanediol di(i,i,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl sulfate 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluoroindole, fluorine-based benzenesulfonic acid Sodium, sodium fluoride sodium phosphate, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), -35- (33) 1377445 fluoroalkylammonium iodide, Fluoroalkylbetaine, fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol, perfluoroalkyl alkoxide, fluoroalkyl ester, and the like. Moreover, as such a commercial item, for example, BM-1000, BM-1100 (above, BM CHEMIE company), Megfac F142D, the same F1 72 'F173, the same F183, the same F178, the same F191, the same F471, Same as F476 (above is the Dainippon Ink Chemical Industry Co., Ltd.),

Fluorad FC170C, FC-171, FC-430, FC-431 (above Sumitomo 3M (share) system), Sarfron S-112, same S-113, same S-131, same S-141, same S-145, Same as S-382, same SC-101, same SC-102, same SC-103, same SC-104, same SC-105, same SC-106C and above are Asahi Glass Co., Ltd., FtopEF301, same 303, same 352 (The above is the new Akita Chemicals Co., Ltd.), Ftergent FT-100, the same FT-110, the same FT-140A, the same FT-150, the same FT-250, the same FT-251, the same FTX-251, the same FTX- 218, with FT-300, with FT-310, with FT-400S (above (NE) system). Further, the polyfluorene-based surfactant may be, for example, Toray Polyoxyn DC3PA, the same DC7PA, the same SH11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH-190, and the same SH-193 ' Same as SZ-6032, with SF-8428, with DC-57, with DC-190 (above is Toray Dow Corning. Polyoxyl (manufacturing)), TSF-4 44 0, TSF-4300, TSF-4445, Commercially available under the trade names of TSF-4446, TSF-4460, and TSF-4452 (the above are manufactured by GE Toshiba Polymers Co., Ltd.). Further, as the surfactant other than the above, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether-36-(34) 1377445-like polyoxyethylene alkyl hydrazine may be used. Polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-decyl phenyl ether-like polyoxyethylene aryl ether; polyethylene oxide dilaurate, polyethylene oxide distearate-like polyethylene oxide A nonionic surfactant such as a dialkyl ester or a commercially available product, for example, KP 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Poly flow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) Wait. - These surfactants can be used singly or in combination of two or more. The amount of the surfactant to be added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 1 part by weight of the copolymer [A]. When the amount of the surfactant to be added exceeds 5 parts by weight, the film tends to be easily formed during coating. Further, in order to further improve the adhesion to the substrate, an adhesion aid can be blended. As the above-mentioned adhesion promoter, for example, a functional decane coupling agent is preferable, and φ is an example of a decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl fluorenyl group, an isocyanate group or an epoxy group. More specifically, for example, it may be trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanide. Acid propyl triethoxy decane, γ-glycidoxy propyl trimethoxy oxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and the like. These adhesion aids can be used singly or in combination of two or more. The amount of the adhesion aid is relative to 100 parts by weight of the copolymer [A] -37- (35) (35)

In the case of 1377445, it is preferably 20 parts by weight or less, and more preferably 10 parts by weight of the auxiliary agent exceeds 20 parts by weight, and development tends to occur. In the photosensitive resin composition of the present invention, an agent is used. The additives specifically exemplified below are added to improve storage. Specifically, for example, sulfur, hydrazines, hydroquinones, amines, nitronitroso compounds. Examples thereof are 4-methoxy-N-phenylhydroxylamine aluminum and the like. These are preferably used in an amount of 3.0 parts by weight or less, more preferably 5% by weight, based on 1 Å [A]. If it exceeds 3.0 parts by weight, the degree of patterning is deteriorated. In order to improve heat resistance, a compound of an N-(alkylurea compound, an N-(alkoxymethyl)melamine compound, or a bifunctional or higher epoxy group may be added. Specific examples of the above N-(house urea compound are as follows) N,N,N',N'-tetra(methylurea, N,N,N',N'-tetrakis(ethoxymethyl)glycoluril, (n-propoxymethyl)glycolil, N,N , N', N'-tetra (isoglycoluril, N, N, N', N'-tetrakis (n-butoxymethyl) glycoluril tetrakis(t-butoxymethyl) glycoluril, etc. N, N, N', N'-tetrakis(methoxymethyl) glycoluril. Specific examples of the above-mentioned base melamine compounds are n, n, n', n', n: methyl group) honey Amine, N, N, N', N', N", N"-hexa(B! Amine, N, N, N', N', N", N"-hexa(n-propoxymethyl N, N , N', N', N", N"-hexa (isopropoxymethyl group: less than the following. Adhesion: slag has become easy to add other added bismuth, etc. for the purpose of polyoxyl, phenol, N-nitrous The weight fraction of the copolymer I used 0.001~ to obtain a sufficient sensitized oxymethyl group) has an oxymethyl)glyoxymethyl group in the molecule Among N,N,N',N'-tetrapropoxymethyl);, N,N,N',N'-, especially preferably N-(alkoxymethyl), N"-hexa Methoxyoxymethyl)melyl)melamine, :) melamine, -38- (36) 1377445 N,N,N',N',N",N"·hexa(n-butoxymethyl) Melamine, N, N, N', N', N", N"-hexa(t-butoxymethyl) melamine, and the like. Among them, N, N, N', N', N", N"-hexa(methoxymethyl) melamine is particularly preferred as a commercially available product such as Nikalac N-2702. MW-30M (above is Sanwa Chemical Co., Ltd.).

The compound having a bifunctional or higher epoxy group in one molecule may, for example, be ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether or propylene glycol diglycidyl ether. Tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether Hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like. Specific examples of these commercial products are Epolite 40E 'Epolite 100E, Epolite 200E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 1 500NP,

Epolite 1 6 0 0, Epolite 8 0MF ' Epolite 1 00MF, Epolite φ 4000, Epolite 3 002 (above is Kyoritsu Chemical Co., Ltd.). These may be used singly or in combination of two or more. In the composition of the photosensitive resin composition (a), it is preferred to dissolve the constituent components such as the copolymer [A], the polymerizable compound [B], and the photopolymerization initiator [C] in an appropriate solvent. Become a composition solution. The solvent used in the preparation of the above composition solution is such that the components constituting the photosensitive resin composition (a) are uniformly dissolved and are not reacted with each component. As such a solvent, for example, the same solvent as that exemplified as the usable solvent in the production of the above copolymer [A] can be used. Among such solvents, from the viewpoints of solubility of each component, reactivity with each component, easiness of formation of a coating film, and the like, for example, an alcohol, a glycol ether, or an ethylene glycol alkyl acid is preferably used. Acetate, ester and diethylene glycol. Among these, for example, it is particularly preferable to use benzyl alcohol, 2-phenylethanol, 3-phenyl-1-φ 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, methoxypropionic acid Methyl ester, ethyl ethoxy propionate. Further, in order to improve the in-plane uniformity of the solvent and the film thickness, a high boiling point solvent may be used as a suitable high boiling point solvent which can be used, for example, N-methylformamide 'N, N - dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidine φ ketone, dimethyl hydrazine, benzyl Ethyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, citric acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Malay Diethyl acid, γ-butyrolactone, ethyl carbonate, propyl carbonate, phenyl cellosolve acetate, and the like. Among them, particularly preferred are Ν-methylpyrrolidone, γ-butyrolactone, hydrazine, hydrazine-dimethylacetamide. * The composition solution thus prepared can be used by filtration through a micropore filter having a pore diameter of, for example, about 0.2 to 0.5 μm, if necessary. The photosensitive resin composition (a) is particularly suitably used as a material for forming a spacer for a display panel such as a liquid crystal panel or a touch panel. -40- (38) (38)1377445 When the spacer for a display panel is formed using the photosensitive resin composition (a), the composition solution is applied to the surface of the substrate, and then pre-baked. Bake to remove the solvent to form a film. The method of forming the film of the photosensitive resin composition of the present invention can be carried out, for example, by (1) coating method or (2) dry film method. (1) When the coating method is applied, the photosensitive resin composition of the present invention is preferably applied as a composition solution on a substrate, and then the coated surface is heated (prebaked) to form a film. As a coating method of the composition solution, for example, a suitable method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a rod coating method, or an inkjet coating method can be employed. Particularly preferred is a spin coating method or a slit die coating method. The prebaking conditions vary depending on the type of the components, the blending ratio, and the like, but it is preferably about 1 to 15 minutes at 70 to 120 °C. Further, in the case of forming the film of the photosensitive resin composition of the present invention, when the (2) dry film method is employed, the dry film is formed on the base film, preferably on the flexible base film, and laminated. A photosensitive layer formed of a photosensitive resin composition (hereinafter referred to as "photosensitive dry film"). The photosensitive dry film can be coated with the photosensitive resin composition of the present invention on a base film. (preferably, the liquid composition), the solvent is removed, and a photosensitive layer is laminated to form. As the base film of the photosensitive dry film, for example, a film of a synthetic resin such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate-41-(39) 1377445 ester, or polyvinyl chloride can be used. The thickness of the base film is suitably in the range of 15 to 125 μm. The thickness of the photosensitive layer obtained is preferably about 1 to 30 μm. The removal of the solvent is preferably carried out by heating at 80 to 150 ° C for about 1 to 10 minutes. Further, when the photosensitive dry film is not used, a cover film may be laminated on the photosensitive layer and stored. The cover film is not peeled off when it is not used, and can be easily peeled off during use, and must have appropriate peelability. As the cover film which satisfies such a condition as φ, for example, a polyfluorene-based release agent can be applied or baked on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film or a polyvinyl chloride film. film. The thickness of the cover film is usually preferably about 5 to 30 μm. The cover film can also be used as a cover film in which two or three layers are laminated as needed. When the radiation sensitive resin composition of the present invention is used as a solution, the solid content concentration (the ratio of the weight after subtracting the solvent from the composition to the total composition weight) is preferably from 15 to 80% by weight. . More preferably • The solid content concentration varies depending on the method of forming the film. In the case where the coating method is used in the formation of the film, the solid content concentration is preferably 15 to 30% by weight. The dry film method is used in the formation of the film, and the solid content concentration is preferably 50 to 70% by weight. Then, the formed film was exposed to light through a mask of a predetermined pattern to be imaged by the developing liquid after the polymerization, and the unnecessary portion was removed to form a pattern. As the radiation used for the exposure, visible light, ultraviolet light, far ultraviolet light, charged particle light, X-ray, or the like can be appropriately selected. Radiation lines having a wavelength in the range of t - 42 - (40) 1377445 1 90 to 45 Onm are preferred. The exposure amount is preferably 100 to 3,000 J/m 2 '. However, the photosensitive resin composition of the present invention can exhibit desired effects even when the exposure amount is 1,5 Å or less, for example, the exposure amount can be made. Become 1 〇〇~1,500J/m2. As the development method, for example, any of the liquid pool method, the dipping method, and the shower method may be used, and the development time is preferably 30 to 180 seconds. - the above-mentioned developing solution may, for example, be sodium hydroxide, potassium hydroxide, sodium carbon citrate, sodium citrate, sodium metasilicate, or an inorganic base such as ammonia; ethylamine or n-propylamine-like primary amine; Ethylamine, di-n-propylamine-like amine; trimethylamine, methyldiethylamine, ethyldimethylamine, triethylamine-like tertiary amine; dimethylethanolamine, methyldiethanolamine, triethanolamine General 3-stage alkanolamine; pyrrole, piperene, N-methyl piperene, N-methylpyrrolidine, 1,8-diazabicyclo[5. 4·0]-7-undecene, 1 , 5-diazabicyclo[4.3.0]-5-decane-like alicyclic tertiary amine; pyridine, azidine, lutidine, quinoline-like aromatic tertiary amine; An aqueous solution of a φ basic compound such as tetramethylammonium or tetraethylammonium hydroxide-like quaternary ammonium salt. Further, a water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the aqueous solution of the basic compound in an appropriate amount. After the development, for example, by washing with running water or the like, for example, washing for 30 to 90 seconds to remove unnecessary portions, drying is performed by blowing compressed air or compressed nitrogen to form a predetermined pattern. Then, by means of a heating device such as a heating plate, an oven, etc., at a specified temperature, for example, at 150 to 250 ° C, at a specified time on a hot plate, for example 5 to 30 minutes, in an oven, For example, in the case of 30 to 90 minutes, the heat treatment of Fig. 43-(41) 1377445 is carried out to obtain a spacer for the purpose. As described above, the photosensitive resin composition (a) of the present invention has a sufficient process range, and can suppress the sublimation of the photopolymerization initiator component. • For the contamination of the calciner or the mask, foreign matter does not occur in the liquid. Further, it is a photosensitive resin group which is a spacer which can easily form a separator having excellent cross-sectional shape, compressive strength, abrasion resistance, and adhesion to a transparent substrate. EXAMPLES The present invention will be more specifically illustrated by the following examples and comparative examples, but the present invention is not limited by these examples. Synthesis Example 1 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. . Next, 20 parts by weight of styrene, 16 parts by weight of methacrylic acid, 18 parts by weight of tricyclo[5. 2. 1. 〇2'6] fluorene-8-ester, and 40 parts by weight of 3 were charged. -(Methethyloxymethyl)-3-.ethyloxetane and after nitrogen substitution, stirring was slowly started. The temperature of the solution was raised to 7 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-1]. The solid content concentration of the obtained polymer solution was 33.0% by weight, and the weight average molecular weight of the polymer was 24,000 重量. The average molecular weight was GPC (gel permeation chromatography) HLC-8020 (manufactured by Tosoh Corporation). The measured polystyrene-converted molecular weight (in the case of -44-1377445 42 as in the following Synthesis Example 2 in a flask equipped with a cooling tube and a stirrer), 7 parts by weight of 2,2'-azobis (2,4-di) was charged. Methyl valeronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate. Next, 20 parts by weight of styrene, 16 parts by weight of methacrylic acid, and 18 parts by weight of trimethyl methacrylate [5. 2_1] were charged. After the 〇2'6]癸-8-ester and 40 parts by weight of 3-(methacryloxymethyl)-2-trifluoromethyloxetane were replaced with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2]. The solid content concentration of the obtained polymer solution was 33.0% by weight, and the weight of the polymer. The average molecular weight is 23,200 〇. Synthesis Example 3 is placed in a flask equipped with a cooling tube and a stirrer. 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 'input of 20 parts by weight of styrene, 16 parts by weight Methacrylic acid, 18 parts by weight of tricyclo[5. 2. 1. 〇2,6] fluorene-8-ester, 40 parts by weight of 3-(methacryloxymethyl)-2- After the phenyloxetane was replaced with nitrogen, stirring was started slowly, and the temperature of the solution was raised to 7 ° C. The temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-3]. The solid content concentration of the obtained polymer solution was 32.7 wt% 'The weight average molecular weight of the polymer was 24,600. -45- (43) 1377445 Synthesis Example 4 In a flask equipped with a cooling tube and a stirrer, 7 weights were added • 2, 2 '-Azobis(2,4-dimethylvaleronitrile), 200 parts by weight of oxybutyl acetate, followed by 18 parts by weight of methacrylic acid, 18 parts of trimethyl methacrylate [5. 2. 1. 02'6] 癸-8-ester, 5 parts by weight of * ene, 5 parts by weight of butadiene, 17 parts by weight of 3-(methacryl 醯 φ methyl)-3-ethyl oxacyclohexane Butane, 17 parts by weight The furan-2 methacrylate was replaced with nitrogen, and the solution was allowed to rise to 80 ° C while stirring, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer. The solid content was 32.5 wt%, and the weight average molecular weight of the polymer was 18,000. Synthesis Example 5 In a flask equipped with a cooling tube and a stirrer, 5 parts of φ 2,2'-azobis(2,4-dimethyl group) was charged. Valeronitrile), 200 parts by weight of diethylethyl ethyl ether, followed by 18 parts by weight of methacrylic acid, 40 parts of glycidyl methacrylate, 5 parts by weight of styrene, 32 parts of methacrylic acid Ring [5. 2· 1. 02'6] 癸-8-ester, after nitrogen, 5 parts by weight of 1,3-butadiene was added, and the temperature of the liquid was raised to 70 ° C while stirring slowly. The solution was maintained while maintaining the temperature for 5 hours, while the copolymer [A-5]. The obtained polymer solution has a solid content of 33.3% by weight, a weight average molecular weight of the polymer of 20, and a 3-part phenoxytetrahydro temperature [A-4] degree of the aliquot. Diol weight substitution by weight to obtain a concentrated concentration -46-(44) (44)1377445 Preparation of the composition solution of Example 1 100 parts by weight (solid content) was obtained as Synthesis Example 1 of the copolymer [A] a solution of the copolymer [A-1], 80 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound [B], and 5 parts by weight of 2- as a photopolymerization initiator [C] 4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one (Irgacure 3 79, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a solid component The solution was dissolved in propylene glycol monomethyl ether acetate in a concentration of 30% by weight, and then filtered with a micropore filter having a pore size of 0.2 μm to prepare a composition solution (S-1). (I) Evaluation of sensitivity On the alkali-free glass substrate, the above composition solution was applied using a spin coater, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a film thickness of 4. 〇μηι membrane. The coating film obtained as described above was subjected to a mask having a residual pattern of 1 μm, and the exposure gap was 150 μm, and the exposure intensity at a wavelength of 3 65 nm was 300 W/m 2 , and the exposure time was used as a variable. exposure. Subsequently, it was developed by a potassium hydroxide 〇.〇5 wt% aqueous solution at 25 ° C for 60 seconds, and then rinsed with pure water for 1 minute. Further, it was heated in an oven at 150 ° C for 120 minutes to form a spacer. At this time, the minimum exposure amount when the residual film ratio after development was 90% or more was evaluated as the sensitivity. When the 値 is l, 5 〇〇 J/m2 or less, the sensitivity is good. -47- (45) 1377445 (II) Evaluation of resolution In the above (I), the exposure amount was taken as (I). 値, at the prebaking temperature at 80, 90, 100 ° C, the time was obtained. In the pattern, the hollow pattern can be used as X when the solution is solved. Formation of φ ( III) spacer

In the above (I), the exposure amount is (I) 値, and the other is the same as (I), and the cross-sectional shape of the inter-R (IV) pattern is formed by observation by a scanning electron microscope. As a result of the cross-sectional shape, it is shown that the shape of the shape is A to C. The pattern edge 焉 φ of A is good in shape, and the edge of the pattern such as B is substantially good in the shape of the vertical shape. In the rubbing step of the inverted taper (the inverted triangle shape which is longer than the side on the substrate side), the possibility of pattern peeling becomes non-shape defective. (V) Evaluation of rubbing resistance On the substrate obtained in the above (III), when the evaluation was performed under the same conditions, the sensitivity was not evaluated. III) The obtained pattern is shown in Fig. 1 In the case of a tapered shape, when it is formed, the shape of the surface of the film in the shape of the image is often high at a later time. Therefore, such a liquid crystal alignment film is coated with -48 - (46) 1377445 by a printing machine. Liquid crystal alignment agent AL3 046 (manufactured by JSR), dried at 180 ° C for 1 small To form a dry coating thickness of 0.0 5μιη agent to the ligand. • The coating film was subjected to a rubbing treatment by a friction machine having a roll coated with an Nellon cloth at a rotation speed of 500 rPm and a moving speed of the stage of 1 cm/sec. Table 2 shows whether the spacer pattern at this time is cut or peeled off. (VI) Evaluation of Adhesiveness A cured film for adhesion evaluation was formed in the same manner as in the above (III) except that the pattern mask was not used, and the adhesion test was performed. The test method is in accordance with the checkerboard method of 8_5·2 in the adhesion test of Jis K-5400 (1 900) 8.5. In this case, the number of remaining checkerboards is shown in Table 2. Evaluation of preservation stability of φ (VII) The radiation sensitive resin composition was placed in a constant temperature layer at 40 ° C for 1 week, and the rate of change of viscosity was measured. If the increase rate of viscosity is less than 5%, _ means that the preservation stability is good, and if it is 5% or more, it means that the preservation stability is poor. (VIII) Evaluation of heat-resistant dimensional stability In the above (II), a film pattern formed at a prebaking temperature of 80 ° C was heated in an oven at 250 ° C for 60 minutes. The dimensional change rate of the film thickness -49-(47) 1377445 at this time is shown in Table 2. When the dimensional change rate is within 5% before and after heating, the heat stability is good, and when it exceeds 5%, the heat resistance dimensional stability is poor. - (IX) Evaluation of sublimation property The above composition solution was applied onto a substrate and then dried to form a film having a film thickness of 6.0 μm. Then, for the film, n-octane was used as the standard material (specific gravity = 0.7 〇 1, injection amount: 0.02 μl), and the rinsing bar Φ was ioot/io minutes for headspace phase chromatography/mass analysis. (headspace sampler: JHS-100A, gas chromatography/mass spectrometer; JEOL JMS-AX5 05W mass spectrometer manufactured by Nippon Analytical Industries Co., Ltd.), obtained from radiation-sensitive polymerization initiators The peak area A is calculated by the following calculation formula to calculate the amount of volatilization in terms of n-octane. The larger the amount of volatilization, the greater the sublimation. Calculation formula of volatilization amount converted from n-octane φ Volatile amount (Mg) = Ax (amount of n-octane) (pg) / (peak area of n-octane) (X) Evaluation of foreign matter in liquid The above composition The solution was stored at -15 ° C for 7 days, and the presence or absence of recrystallization of the radiation-sensitive polymerization initiator component was visually observed. In addition, when the liquid temperature of the composition solution after the storage was increased from -15 ° C to 23 ° C, a light scattering type liquid particle detector (KS-28B, manufactured by RION Co., Ltd.) was used to measure 1 μl. The number of solids (residual foreign matter) having a size of 〇·5 μm or more remaining in the composition solution without re-dissolving. -50- (48) 1377445 Example 2 to 1 Ο, Comparative Examples 1 to 3 In addition to the types and amounts described in Table 1, as the [Α] component to the [C] component in Example 1, In the same manner as in Example 1, a composition solution was prepared to form a spacer, and the evaluation was carried out. The amount of [Β] to [C] is the weight - part with respect to 1 part by weight of the copolymer [Α]. Example 1 1 The same procedure as in Examples 1 to 10 was carried out except that the liquid composition (S-11) of the radiation-sensitive resin composition was formed into a film by a dry film method without using a spin coater. The film was formed to form a pattern-like film and evaluated. Table 1 shows the components of the liquid composition (S-11). Further, the peeling removal of the base film was carried out before the exposure step. The evaluation results are shown in Table 2. Further, Table 2 also shows the evaluation results of the transferability described below. The production and transfer of the φ dry film are carried out as follows. On a polyethylene terephthalate (PET) base film having a thickness of 38 μm, a coating machine was used to apply a liquid composition (S-11) of a radiation-sensitive resin composition, and the coating film was at 100°. C was heated for 5 minutes to prepare a radiation-sensitive dry film (J-1) having a thickness of 4 μm. Next, on the surface of the glass substrate, the surface of the radiation-sensitive transfer layer is spliced, and the radiation-sensitive transfer dry film is laminated, and the radiation-sensitive dry film is laminated by thermal compression bonding. (J-1) Transfer onto a glass substrate. At this time, the dry film system can be uniformly transferred onto the glass substrate. -51 - (49) 1377445 Example 1 2 In addition to the liquid composition (S-11) of the radiation sensitive resin composition in Example 11, the liquid composition of the radiation sensitive resin was used. In the same manner as in Example 11, except that the composition (S-12), a radiation-sensitive dry film (J-2) was produced, and a patterned film was formed, which was evaluated. Table 1 shows the components of the liquid composition (S-12). Table 2 shows the evaluation results in φ. The dry film system can be uniformly transferred onto the glass substrate. In Table 1, the abbreviations of the components represent the following compounds. (B-1) : KAYARAD DPHA (Nippon Chemical Co., Ltd.) (B-2) : KAYARAD D Ρ Η A · 4 Ο Η (Nippon Chemical Co., Ltd.) (Cl) : 2-(4- Methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one (Irgacure 379 by Ciba Specialty Chemicals Co., Ltd.), • (〇-2) :1-[9-Ethyl-6-(2-methylbenzyl-yl)-9.>1.-carbazol-3-yl]-ethane-1-one oxime-indole-acetate ( CGI-242 by Ciba Specialty Chemicals Co., Ltd. (C-3) : 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-benzhydrylhydrazine) (CGI-124, Ciba Specialty Chemicals Co., Ltd.) (C-4): 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1- 1-(Vapor) Irgacure 907) (C-5): 2,2'-bis(2-chlorophenyl)-4,4',5,5,-tetraphenyl-1,2 bisimidazole-52 - (50) (50)1377445 (C-6) : 4,4'-bis(diethylamino)benzophenone (C-7) : 2-mercaptobenzothiazole (C-8) · 2 - Mercapto-2-(-methylamino)-1-(4-norlinylphenyl)-butan-1-one (Irgacure 3 69 by Ciba Specialty Chemicals Co., Ltd.) In Table 1, the symbol "" means no Add this ingredient. The evaluation results are shown in Table 2.

-53- 1377445

-54- 1377445

3谳Rear resistance test with or without peeling m 壊壊壊壊璀m 蓥壊蕻壊 鹿 鹿 cross-section shape <<<<<<<<<<< CQ 0Q PQ << Mm 1500 1300 1300 1500 1300 1500 1300 1500 1300 1300 650 600 3500 3500 2000 1500 Resolution pre-baking · · 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 XX pre-baking: 90 〇 C 〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇Prebaking: 80°C 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇Composition type (S-1) (S-2) (S -3) (S-4) (S-5) (S-6) (S-7) (S-8) (S-9) (S-10) (S-11) (S-12), (s-3) (s-4) Photosensitive film 1 1 1 1 1 1 1 1 1 1 (N η-s Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Implementation Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 -55- (53)1377445 Table 2 (Continued)

Adhesion (/100) Evaluation of stability and heat resistance dimensional stability Evaluation of foreign matter in the ascending liquid (μβ) Recrystallization of foreign matter Residual foreign matter number Example 1 100 4% 1% ίκ yiw Μ 0 Example 2 100 1% 1% Τπτ. ΙιΓΓ ^ΙΙΓ ittr /» 0 Example 3 100 2% 1% Ε 姐 y»\> 0 Example 4 100 4% 1% /fnr MM" /»,, te y»\> 0 Example 5 100 1% 1% te J t \N AilF. Itlf 0 Example 6 100 4% 1% ittr yt, J\\\ 0 Example 7 100 1% 1% ΛΤΤΤ. tilt yi,, mt* y» \\ 0 Example 8 100 4% 1% ^TTT. /»,, sister y»,, 0 Example 9 100 1% 1% sister>fnr- 1ΪΓΓ /»\N 0 Example 10 100 2% 1 % itTTT 移 0 Example 11 100 — 1% — — — Example 12 100 — 1% — — — Comparative Example 1 100 2% 3% 1.2 Arrr II11: 0 Comparative Example 2 100 2% 3% 1.2 int. TIM: 0 Comparative Example 3 100 9% 10% iTTT AttT ΤΓΤΓ 0 Comparative Example 4 100 9% 10% M / 1, with 400

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the cross-sectional shape of a pattern. -56-

Claims (1)

1377445 Ο) X. A patented range of photosensitive resin compositions characterized by comprising: [A] (al) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride, (a2) having the following formula (〇) Or (π): H2C—C—c—〇-II 〇 H2C=c—C—0II 〇 CH -CH N T1 2-f-C c r3 η r4 9 —o r5 A 丨2 -c—r3 〇— c R4 Rs In the formulae (I) and (II), the R-based hydrogen atom or the alkyl group having 1 to 4 carbon atoms is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2, R3, R4 and R5 are each independently a monomer represented by a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6] and (a3) a copolymer of another ethylenically unsaturated compound different from the above (al) and (a2) compounds, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator, which contains the following formula (ΠΙ): -57- 1377445 (2) CR9R10 ΠΙ [In the formula (III), 116 represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and R7 and R8 independently represent a hydrogen atom and a linear chain of 1 to 12 carbon atoms. a branched or cyclic alkyl group or a benzyl group, and R9, R1(), R12 and R13 each independently represent a hydrogen atom, a halogen atom, and a linear, branched or cyclic alkane having 1 to 12 carbon atoms; a linear or branched alkoxy group having 1 to 4 carbon atoms, and Rn represents a linear, branched or cyclic alkyl group having a carbon number of 1 to 12, a hydroxyl group and a carbon number. a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms substituted by a substituent selected from a group consisting of a linear or branched alkoxy group of 1 to 4, and having a carbon number of 1 to a linear or branched alkoxy group of 4, or a carbon number of 2 to 4 substituted by a substituent selected from a group consisting of a hydroxyl group and a linear or branched alkoxy group having 1 to 4 carbon atoms; A compound represented by a linear or branched alkoxy group]. 2. The photosensitive resin composition of claim 1 which is used for the formation of a spacer for a liquid crystal display panel. A liquid crystal display panel spacer which is formed of a photosensitive resin composition as in the second aspect of the patent application. 4. A method for forming a spacer for a liquid crystal display panel, characterized in that -58-(3) (3)1377445 comprises at least the following steps in the following order: (a) forming on the substrate as in claim 1 a step of coating a photosensitive resin composition, (b) a step of exposing at least a portion of the film, (c) a step of developing the film after exposure, and (d) a step of developing the film The film is heated for the step. A liquid crystal display panel having a spacer as in the third aspect of the patent application. < S -59-