TWI377440B - Radiation sensitive resin composition - Google Patents

Description

1377440 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a radiation sensitive resin composition. [Prior Art] The radiation-sensitive resin composition can be used, for example, in an organic germanium display device in order to form an insulating film of a liquid crystal display device of a thin film transistor (hereinafter sometimes referred to as a TFT (thin_f)) type. The organic EL insulating film to be used, the diffuse reflection plate used in the reflective TFT substrate, and the solid-state image sensor (hereinafter referred to as a CCD (charge_coupled device) protective film) are the materials of the cured resin pattern (refer to Japan). Patent No. 2933879). In the TFT insulating film, in order to obtain a TFT substrate of higher performance, it is required to have a high-low drop flatness of a bottom layer such as a TFT π formed on a substrate (refer to Japanese Patent Laid-Open No. Hei 9-244009 ). In addition, in recent years, the coating method for large-sized substrates of the substrate glass size used in the manufacture of TFT substrates has been changed from a spin coating method to a slit nozzle using a nozzle that does not rotate the substrate. The coating method of the cloth device. In the coating device with a slit nozzle, the material of the nozzle is made of non-recorded steel (refer to Japanese Patent Laid-Open (I)) (10), and the Japanese Patent Laid-Open No. Hei 20- 3-21 1053, JP-A-8-173875 ) 'But in order to use the job coating, the radiation sensitive resin composition is required to have good wettability to the stainless steel substrate. The inventors of the present invention have found that the radiation-sensitive tree-yellow composition containing a certain surfactant has good wettability to a non-recorded steel substrate. 317489 5 1377440 SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive resin composition which has good wettability to a stainless steel substrate. That is, the present invention provides the following [1] to [10]. [1] A radiation-sensitive resin composition containing a test for sclerosing [2]

[3] [4]

[5] Soluble resin (A), hydrazine diazo compound (B), solvent (C), anthrone-based surfactant (D), and fluorine-based surfactant (E): The composition of the above [1], wherein the 'hardening alkali-soluble resin (A) contains a constituent unit (al) derived from an unsaturated carboxylic acid, and an unsaturated compound having a curable group [however, a copolymer of the constituent unit (a2) derived from unsaturated unsaturated acid. In the composition of the above [2], in the structural unit (a2), the curable group is oxetanyl (〇Xetany 1 ). The composition of any one of the above-mentioned [1] to [3], wherein the hardenable alkali-soluble resin (A) further contains: a constituent unit U31 derived from a carboxylic acid ester having an olefinic double bond, a constituent unit (a32) derived from an aromatic compound having a polymerizable carbon-carbon unsaturated bond, a constituent unit derived from a vinyl cyanide compound (a33), and an N-substituted maleimide compound At least one constituent unit (a3) selected from the group consisting of the derived constituent units (a34). The composition according to any one of the above [1] to [4] wherein the fluorine-based surfactant (8) is a fluorine-based surfactant containing an epoxy group. The composition of any one of [1] to [5] wherein the fluorine-based surfactant (E) has a molecular weight of 1 Å or more and 1 Torr or less. [7] The compound of any one of the above [i] to [6] wherein the alkaloid surfactant (D) is a polyalkylene glycol modified fluorenone. [8] The composition according to any one of the above [1] to [7] which is applied to a coating device having a slit nozzle. [9] A transparent hardened resin pattern formed of the composition of any one of the above [丨] to [8]. [10] A display device comprising the transparent cured resin pattern according to the above [9]. [Embodiment] The radiation-sensitive resin composition of the present invention contains a curable resin (A), a diazonium compound (β), a solvent ([), and a zealand J surfactant (D). And fluorine-based surfactants. The hardenable soluble resin (A) used in the present invention is preferably composed of a constituent unit (al) derived from an unsaturated carboxylic acid and an unsaturated compound having a curable group [however, in addition to the unsaturated acid buffer) a copolymer of the constituent unit φ (a2) derived therefrom. The above-mentioned unsaturated carboxylic acid' may, for example, be an unsaturated carboxylic acid having one or two or more carboxyl groups in a molecule such as an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid, and specifically, for example, Dilute acid, mercapto acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, transgenic; co-acid, mesaconic acid, etc. The unsaturated compound having a hardening group as described in the month IJ (except for the unsaturated acid) may, for example, be a glycidyl (meth)acrylate, a (meth)acrylic acid, a methyl glycidyl ester, or a (methyl group). Acetyl methacrylate, 3-methyl-3, 4-epoxybutyl (meth)acrylate, 3-ethyl 317489 7 1377440 .-3, 4_epoxy Ester, 4-methyl-4, 5-epoxypentyl (meth)acrylate 2, 3-epoxycyclohexylmethyl (meth)acrylate, 3, 4-epoxy ring Hexyl decyl ester, Zou vinyl strepto methyl glycidyl ether, m-vinyl benzoyl glycidyl ether, p-vinylphenyl fluorenyl ether, 2 - vinyl ring hexene oxide, 3-vinyl ring An unsaturated compound containing a cyclodecyl group such as a hexene oxide or a 4-vinylcyclohexene oxide; 3-(meth)acryloxymethyloxybutane, 3-methyl_3_ (曱)鲁 ) 醯 醯 曱 曱 曱 氧 氧 氧 、 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 ) ) ) Methoxyoxymethyloxide Heterocyclic butyl, 2-difluoromethyl-3-(indenyl)propenyloxymethyloxetane, 2-pentafluoroethyl_3_(methyl)propenyloxymethyloxalate Cyclobutane, 3-methyl-3-(indenyl)propenyloxyethyloxetane, 3-ethyl-3-(indenyl)propanyloxyethyloxetane, 2 _Phenyl_3_(methyl)propenyloxyethyloxetane, 2-trifluoromethyl_3_(methyl)propene oxime ethoxylate#Niobane, 2-pentafluoroethyl Alkyl-3-(indenyl) propylene oxime oxirane oxime ♦ An unsaturated compound such as an oxetanyl group such as butyl or the like. Among them, 3-(meth) propylene methoxymethyl oxetane, 3-methyl-3-(methyl) propylene fluorenyl oxetane, 3-ethyl group is preferably used. ^ (fluorenyl) propylene methoxymethyl oxetane, 2 - stupyl _3 - (meth) propylene hydrazine, mercapto oxetane, 2-trifluoromethyl _3_ (a Acetyloxymethyl, oxalatine, 2-pentafluoroethyl_3_(methyl)propene, oxymethyloxy 2 cyclobutane, 3-fyl-3-(fluorenyl) Ethyl ethoxyethyl oxetane, ethyl 3-(methyl) propylene oxiranoxy oxetane, phenyl thiol ethyl oxirane Alkane, 2_trifluoromethyl) 3] 7489 8 1377440 The vinyl cyanide compound derived from the above-mentioned constituent unit (a33) may, for example, be acrylonitrile, methacrylonitrile or α-chloro(indenyl)propene. Nitrile and the like. • A hydrazine-substituted maleimide compound derived from the above-mentioned constituent unit (a34), which may be, for example, N-mercaptomaleimine, N-ethylmaleimide, N-butylmaine Yttrium, N_cyclohexylmaleimide, N-benzylated maleimine, N-phenylmaleimide, n-(4-ethylmercaptophenyl)malaya Amine, N-(2,6-diethylphenyl)maleimide, n-(4-didecylaminolu-3,5-dinitrophenyl)maleimide, N _Amber 醯imino-3_maleimide benzoic acid condensate (1^1-311〇^11^11^(171-3-maleimidobenzoate), N-amber quinone imine-3-malay醯iminopropionic acid condensate, N-brodecylimine-4-maleimine butyric acid condensate, N_amber succinimide-6-maleimide hexanoic acid condensate, N_( Bupropionylnaphthyl-4)-maleimide, N_[4_(2-benzoxazolyl)phenyl]maleimide, N-(9-acridinyl)maleimide, etc. The constituent units may be used singly or in combination of two or more. Including a constituent unit (al) derived from an unsaturated carboxylic acid, and being unsaturated with a hardened group In the copolymer of the constituent unit (a2) derived from the compound (except for the unsaturated carboxylic acid), the ratio of the constituent unit (al) is usually 5 to the total number of moles of the constituent unit of the copolymer. 50 mol%, preferably 15 to 40 mol%. The ratio of the constituent unit (a2) is usually 95 to 5 mol%, preferably 60 mol, relative to the total number of moles of the constituent units of the copolymer. %. ^ In the above copolymer, the ratio of the constituent unit (al) and the constituent unit (a2) is 317489 10 1377440. When it is within the above range, it is suitable for the developing solution due to the formation of the solution. The rate of life is solved, and the obtained map is better. >, there is a tendency for the king to be hardened, and thus r other constituents: =):;=:= ratio of the two units (al), relative The composition of the polymer: 'r is 5 to 5 ° mol%, preferably 15 to 40 mol%, early, 2), relative to the constituent unit of the copolymer, usually = to 5 mol%, preferably 85 to 15 mol%, the ratio of other constituent units is from 〇" to 90 mol%, and preferably from 5 to 8 mol%. The copolymer containing the constituent unit (8) and the constituent unit (a2) may, for example, be 3-ethyl-3-one. Alkyl propylene oxymethyl oxetane / methyl acrylate benzyl acetate / methyl propyl ketone copolymer, 3-ethyl _ 3 methyl propyl oxymethyl oxetane Hyun/methyl acrylate benzyl acetate / methyl acrylate / styrene copolymer, 3-ethyl-3-mercapto propylene methoxy methyl oxetane / methacrylic acid / benzene Ethylene copolymer, 3-ethyl_3_mercaptopropenyloxymethyloxetane/methacrylic acid/cyclohexyl methacrylate copolymer, = ethyl-3-mercaptopropenyloxy Mercapto oxetane / methacrylic acid / decyl methacrylate copolymer, 3-ethyl-3-mercapto propylene oxime oxirane oxetane / methacrylic acid / decyl methacrylate /Stupid ethylene copolymer, 3-ethyl-3-methylpropenyloxydecyloxybutane/methylacrylic acid/mercaptopropene tert-butyl ester copolymer, 3-ethyl- 3-fluorenyl dilute oxymethyloxetane/mercaptoacrylic acid/isobutyl methacrylate g 317489 11 1377440 • Polymer, 3-ethyl-3-methylpropenyloxy Oxycyclobutane/methylpropenoic acid/coumyl acrylate copolymer, 3-ethyl-3_A Acryloxymethoxymethyl oxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl-3-mercapto propylene methoxymethyl oxetane / fluorenyl Acrylic acid/isobornyl acrylate copolymer, 3-ethyl-3-methylpropenyloxymethyloxetane/mercaptoacrylic acid/dicyclopentanyl acrylate copolymer, 3-ethyl-3 -Methyl propylene oxime. Methyl oxetane / methacrylic acid / propenic acid second butyl ester, 3-ethyl-3-methylpropenyloxymethyl oxetane / Methylpropionic acid/local-based maleimide copolymer, ethylmercaptopropenyloxydecyloxybutane/methacrylic acid/cyclohexylmaleimide copolymer, and the like. The copolymer containing the constituent unit (al) and the constituent unit (a2) is subjected to gel permeation chromatography to determine the weight average molecular weight based on polystyrene, usually 2,000 to 1 Torr, 〇〇〇, Good for 2, 〇〇〇 to 5〇, 〇〇〇, better for 3' 000 to 20, 〇〇〇. When the weight average molecular weight is from 2, 〇〇〇 to 1,000,000, it is preferable because the residual film ratio at the time of development can be maintained to obtain a high development speed. In the radiation-sensitive resin composition of the present invention, the content of the copolymer of the constituent unit (al) and the constituent unit (a2) is usually 5 Å based on the mass fraction of the solid content of the radiation-sensitive resin composition. Up to 90% is preferably from 60 to 90%. Examples of the hydrazine diazo compound (B) used in the present invention include, for example, α,2 benzoquinonediazonium sulfonate, 1,2-naphthoquinonediazide sulfonate, and [,2-benzoindole Diazonite yellow amine, 1,2-naphthoquinone diazosulfonamide, and the like. 317489 12 1377440 1,2-naphthoquinonediazidesulfonate of hexahydroxydibenzophenone such as 1,2-naphthoquinonediazo-5-sulfonate; • bis(2,4-dihydroxyl) Phenyl)methane-1,2-naphthoquinonediazo-4-sulfonic acid, bis(2,4-dihydroxyphenyl)decane-1,2-naphthoquinonediazo-5-sulfonic acid Vinegar, bis(p-hydroxyphenyl)decane-1,2-naphthoquinonediazo-4-sulfonate, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazo-5-sulfonate Acid ester, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazo-4-sulfonate, 1,1,b-I (p-hydroxyphenyl)ethane -1,2-naphthoquinonediazo-5-sulfonate, bis(2,3,4-di-perphenyl) oxime-1,2-cai|kundiazo-4-acid 、, bis(2,3,4-di-phenyl) oxime-1,2-Cai Ikundiazide-5-continuation acid, 2, 2'-bis (2,3,4 - Di-phenylphenyl)propane-1,2-caiwu Kun Diazo-4-platinic acid vinegar, 2,2'-bis(2,3,4-trihydroxyphenyl)propane-1,2 -naphthoquinonediazo-5-sulfonic acid oxime, 1,1,3-parade (2,5-dimethyl-4-transphenyl)-3-phenylpropan-1,2-naphthalene醌Diazo-4-sulfonate, 1,1,3-parameter 2,5-Dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazo-5-sulfonate, 4,4,-_ [1-[4-[ 1-[4-hydroxyphenyl]-1-indolylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazo-5-sulfonate, bis(2, 5-di) Methyl-4-hydroxyphenyl)-2-hydroxyphenyl decane-l,2-naphthoquinonediazo-4-sulfonate, bis(2,5-didecyl-4-hydroxyphenyl) 2-hydroxyphenyl nonane-1,2-naphthoquinonediazo-5-sulfonate, 3,3,3,,3,-tetradecyl-1,1,-spirobi-5, 6, 7, 5, 6, 6, 7, hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3, 3, 3,, 3'-tetradecyl-1, fluorene- Spirobiindole-5, 6, 7, 5',6',7'-hexanol-1,2-naphthoquinonediazo-5-sulfonate, 2,2,4-trimethyl-7, 2,4,-trihydroxyflavan-1,2-naphthoquinonediazo-4-sulfonate, 2,2,4-trimethyl-7,2,,4,-trihydroxyflavan- 1,2- 14 317489 1377440 Naphthalene vinegar diazo H acid g is equivalent to (poly(tetra)phenyl) flammable nitrogen sulfonate. • The above-mentioned awakening diazonium compound (8) can be used singly or in combination of two or more. The content of the awake heavy nitrogen compound (8) in the present invention, and the solid content mass fraction of the phase ray sensitive resin composition are usually in the range of preferably 5 to 4% by weight. The content of the quinonediazide compound is larger in the above-described range, and the difference between the dissolution rate of the unexposed portion and the exposed portion is increased, and it is preferable because the high residual film ratio can be maintained. The present invention cuts (4) (4) (6), for example, such as ethylene glycol monoethyl, ethylene glycol monoethyl, ethylene glycol mono-n-propyl ether, ethylene glycol monodiol single heart, bismuth Alcohol monobutyl ketone, B, early: butyl hydrazine, ethylene glycol mono-n-pentyl test, ethylene glycol mono-n-butyl--, ethyl alcohol mono-n-heptyl, ethanol mono-ethyl ether; Ethylene glycol monoalkane such as early n-octyl ether = ethylene glycol dimethyl _, diethylene glycol diethyl propylene, diethylene glycol di propyl ether, diethylene glycol diisopropyl ether, Diethylene glycol di-n-diethylene glycol di-second butadiene, diethylene glycol ",, diethylene glycol methyl ethyl acephate, diethylene glycol methyl propyl ether, diethylene glycol Ethyl isobutyl ketone - ethyl ketone methyl ether n- propyl ether methyl ether second butyl (tetra), diethylene di(tetra) ether glycol MM n-pentyl, diethylene glycol ethyl shunt diethylene glycol Ethyl ether isopropyl scale, diethylene glycol ethyl sulfonate; diethylene glycol ethyl ether second butyl test, diethylene glycol ethyl stern third test, - B: alcohol ethyl _ n-pentyl hydrazine, diethylene glycol n-propyl shouting 317489 15 ethylene glycol positive Squama n-butyl, diethylene glycol n-propyl group::::, diethylene glycol n-propyl test third butyl (four) 'diethylene glycol di-n-n-n-pentyl hydrazine, diethylene glycol isopropyl ether Butyl ether, diethylene glycol isopropyl ether, second butyl ether, bis-yiyi isopropyl ether, tert-butyl ether, di-% isopropyl-n-pentyl, diethylene glycol n-butyl趟Second butyl: US: ethylene glycol n-butyl ternary butyl (tetra), diethylene glycol n-butyl butyl butyl butyl phthalate, etc. Ethyl ether ether acetic acid such as ethyl ether acetate, ethylene glycol ethyl ether acetate; benzene, toluene, xylene methyl ethyl! same, propyl hexanone, etc.; ethanol, C Alcohol, butanol alcohol; diol mono-acetic acid vinegar, propylene glycol monoethyl acetate acetate, propyl, monopropyl hydrazine acetic acid g, dipropylene glycol mono thiophene (IV), dipropylene glycol early ethyl ether acetate vinegar, etc. Propylene glycol alkyl ether acetate vinegar; aromatic hydrocarbons such as mesitylene; decyl amyl ketone, methyl isobutyl ketone, cyclohexanol, cyclohexanol, ethylene glycol, glycerin, etc. 3~·ethoxyl Ethyl propionate, 3-methyl Ethyl propyl propionate, 2-hydroxyisobutyl I oxime, ethyl lactic acid, butyl lactic acid, butyl acetate, valeric acetate, acetone acetaminophen, 1,3-butanediol diacetate And other esters; L; the granules may be used singly or in combination of two or more. It is preferred to use diethylene glycol dimethyl ether, diethylene glycol diethyl ether, decyl ether, 3-ethyl Ethyl oxypropionate, ethyl lactate, lactic acid butyl 317489 16 1377440 vinegar, butyl acetate vinegar 'when using a solvent combination' is also preferred to use a combination of such solvents. A preferred combination of solvents can be exemplified by: Alcohol dimethyl scales and ethyl 3-ethoxypropionate, diethylene glycol dimercapto and ethyl lactate, diethylene glycol dimethyl ether and butyl lactic acid, diethylene glycol dimethyl ether Butyl acetate

Diethylene glycol diethyl ether and ethyl 3-ethoxypropionate, diethylene glycol diethyl ether and ethyl lactate, diethylene glycol diethyl ether and butyl lactate, / diethylene glycol Diethyl ether and butyl acetate, diethylene glycol methyl ether ethyl ether and ethyl 3-ethoxypropionate, diethylene glycol methyl ether ethyl ether and ethyl lactate, diethylene glycol Based on ethyl _ lactic acid η, diethylene glycol methyl (tetra) acetyl acetate and butyl acetate, 3-ethoxypropionic acid ethyl vinegar and lactic acid ethyl acetate, 3 - ethoxy propionate ethyl vinegar and lactic acid butyl vinegar, Ethyl 3-ethoxypropionate with butyl acetate, diethylene glycol methyl ether ethyl ether and ethyl 3-ethoxypropane acetate and butyl lactic acid, diethylene glycol methyl hydrazine ethyl hydrazine Ethyl 3-ethoxypropionate and butyl vinegar, diethylene glycol, ethyl sulphate and 3-ethoxypropionic acid, glycerol, butyl acrylate (10) and acetic acid butyl acetate, etc. For example, diethylene glycol methyl hydrazine ethyl hydrazine and ethyl 3-ethoxypropionate and butyl lactate, diethylene glycol methyl ethyl ester and 3-ethoxypropionate Butyl acetate, etc., especially good ones are diethylene glycol methyl ethyl sulphate and 3 ethoxy propionate vinegar With lactic acid butyl vinegar and acetic acid butyl vinegar. The content of the solvent (C) is preferably from 5 〇 to 95% by mass, more preferably from 70 to 9 〇, in terms of the shelling fraction of the radiation-sensitive resin composition. The content of the coating device chelating agent (C) in the slit nozzle coating step is preferably 75 to 90 317489 1377440% by mass based on the same basis as described above. Further, in addition to the slit-shaped nozzle coating step, it is also suitable for the case where the solvent (C) is contained in the coating device in which the composition is applied to the substrate to rotate the step, and is the same as described above. Under the benchmark, it is best at 65 to 80% by mass. When the content of the solvent (C) is in the above range, it tends to cause a small amount of coating film to form spots, which is preferable. Examples of the anthrone-based surfactant used in the present invention include, for example, trade names DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, Lu SH30PA, ST80PA, SH83PA, SH86PA, SH550, SH710C Toray Road * Corning ketone (share) system, KP32, KP322, KP323, KP324, KP326, KP340 or KP34U, the company is a ketone-based leveling agent; trade names BY16-004, BY16-036, BY16-880, FS1265 , SH8400, SF8410, SH842, SH8427, SF8428, SH203, SH710, SH3746, SH3748, SH3749, SH3771M, SH3772M, SH3773M, SH3775M, SH3775, SH8400, SH8700, SH28PA (Dongli Dao Kangning φ ketone) KF-35, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-60U, KF-6015C Shin-Ethanone (share)); TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4453, TSF4460 (GE Toshiba Ketone Co., Ltd.), PS558 (manufactured by United Chemical Technologies, Inc.), Q2-5211 (manufactured by Dow Corning Corp), SILWET 408, L-7210, L-7200C or higher, either one is OSi Speci Alties company and other polyether modified ketone oil. The anthrone-based surfactant (D) is preferably a polyether-modified anthrone oil. 18 317489 1377440 • The content of the anthrone-based surfactant (D) relative to the mass fraction of the radiation-sensitive resin composition, to! It is preferably 1 to ppm, preferably 1 to 500 ppm, more preferably 50 to 300 ppm. When the content of the anthrone-based surfactant (d) is within the above range, it tends to cause a small amount of coating film to form spots. The fluorine-based surfactant (E) used in the present invention is preferably a fluorine-based surfactant having an epoxy group. Examples of the epoxy group-containing surfactants of the epoxy group can be exemplified by the compounds represented by the formulae (E1) to (E4). Chemical formula (E1) to (E4)

PfcF2|cH2^CH-CH2 (E1) f3c, f3c/CfvCF2}xCH2-c\h7ch2 (E2)

F-(cf24-〇 V

•?F—CH2—CH-CH2 cf3 V (E3) h{cf2^-ch2^o-ch2^ch-ch2 (E4) where w, x, y, and z are independent 丨 to 2〇 The integer. For example, the compound of the formula (E1) is, for example, 2, 3, 3, 4, 4, 4-heptafluorobutyl) Ethylene bromide, (2, 2, 3, 3, 4, 4, 5, 5, 5 —9-fluoropentyl) Ethylene Ethylene, 2' 3' 3' 4' 4' 5' 5' 6' 6' 7' 7' 7-Tetrafluoroheptyl) Epoxy Ethylene, 2' 2' 3, 3, 4' 4' 5, 5' 6, 6, 7, 7, 8, 8, 9, 9, 9-heptadecafluoromethyl) Ethylene bromide, (2, 2, 3, 3, 4, 4, 5, 5, 6, 6' 7, 7' 8' 8' 9' 9' 10' 1〇, U, u, 11 Twenty-one fluorine eleven) Ethylene oxide and the like. For example, a compound represented by the formula (10): [2, 3, 3, 3-tetrafluoro-2-(trifluoromethylpropyl)oxirane, [2, 2, 3, 3, 4, 5, 5, 5_八^4_(Trifluoromethyl) fluorenyl] Epoxy Ethylene, [2,2,3,3,4,4,5,5,6,7,7,7_12 to _ 317489 1377440 (trimethylmethyl)heptyl]epoxy Ethylene, [2,2,3,3,4,4,5 5 6 6 7 7 9 9, 9-hexaH(trifluoromethyl)indenyl] Ethylene oxide, hydrazine methyl) eleven base] ethylene oxide and the like. The compound represented by the formula (10) is, for example, [2,3,33_tetraqi_2-((yl)propyl)epoxyethylene, [2,3,3,3-tetraheptanepropoxyl). Propyl] ethylene oxide and the like. The compound represented by the formula (E4) is, for example, glycidyl 2, 2, & 3 tetrafluoropropane (tetra), glycidyl 2'2'3, 3, 4, 4, 5, 5 - 18 gas fluorenyl , glycidyl 2'2, 3, 3, 4, 4, 5, 5, 6, 6 7, 7 - 12-fluoroheptane, glycidyl 2, 2' 3, 3, 4' 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9-hexadecafluorodecyl ether and the like. Commercial products of the organic fluorine-based surfactants represented by the formulae (E1) and (E2) include, for example, E-1430, E-1630, E-1830, E-2030, E-3430, and E-3630. E-3830, E-5244, E-5444, E-5644, E-5844 (all of the above are all made by Taijin Chemicals Sales Co., Ltd.). The molecular weight of the gas-based surfactant (E) is preferably 1 Torr or more and 1 Torr or less. The content of the fluorine-based surfactant (E) is preferably from 1 to 1000 ppm, more preferably from 10 to 50,000 ppm, more preferably from 5 to 3 Å, based on the mass fraction of the radiation-sensitive resin composition. 〇ppm. When the content of the fluorine-based surfactant (E) is within the above range, it tends to be less likely to form a coating due to the formation of spots. 1 The content of the fluorine-based surfactant (E), relative to the anthraquinone interface activity 20 317489 ^ / / 440 _ 刟 (D) and the fluorine-based surfactant (E) total effective mass fraction, to 1 It is better to be 50% by mass. The composition of the rose-ray sensitive resin of the present invention may further comprise a polymerization starting (F) compound (G), a crosslinking agent (η), a polymerizable monomer (an oxime, a decane coupling agent (J), etc. Other components: The above-mentioned polymerization initiator may, for example, be an iron salt as a cationic polymerization initiator. The phosphonium salt is composed of a complex cation and an anion derived from Lewis acid. - Specific examples of the above-mentioned defective cation For example, diphenyl hydrazine, bis (p-tolyl) cleavage, bis(p-butylphenyl) fluorene, bis(p-octylphenyl) fluorene, bis(p-octadecanyl) Phenyl)anthracene, bis(p-octyloxyphenyl)anthracene, bis(p-octadecyloxyphenyl)anthracene, phenyl(p-octadecyloxyphenyl)anthracene, (p-decyl) P-isopropylphenyl) steel, triphenyl sulfonium, cis (p-tolyl) sulphide, cis (p-isopropylphenyl) fluorene, ginseng (2, 6-dimethylphenyl ubiquinone, ginseng (pair Tertiary butyl group) hydrazine, ginseng (p-cyanophenyl) fluorene, ginseng (p-chlorophenyl) fluorene, dimethyl Φ (methoxy) hydrazine, dimethyl (ethoxy) hydrazine, dimethyl (propoxy) mirror, Di-(butoxy)anthracene, diindolyl (octyloxy) vegetable, dimethyl (octadecyloxy) hydrazine, methyl (isopropoxy) mirror, dimethyl (third butoxide) Sulfhydryl, diindenyl (cyclopentyloxy) hydrazine, dimethyl (cyclohexyloxy) fluorene, dimethyl (fluoromethoxy) hydrazine, di-f-based (2-chloroethoxy), Dimethyl (3 - bromopropoxy) vegetable, dimethyl (4-cyanobutoxy) sparing, di-yl (8-stone Schottyl octyloxy, di-decyl (18-trifluoromethyl-10- Human oxy) vegetable, dimethyl (2-pyridylisopropoxy), dimethyl (paraxyl (methyl)methyl) hydrazine, etc., * double (p-tolyl) lock (pair Phenylphenyl)(p-isopropylphenyl)-locked, bis(10)decyltributylphenyl) 317489 21 1377440

It is preferred that ruthenium, ruthenium ruthenium, ginseng (p-butylphenyl) ruthenium, and the like Specific examples of the above-mentioned anion derived from the hexamic acid include, for example, a 2-acid salt, a hexa-gas sulphate, a hexa-halo citrate, a lanthanum (penta-phenylene) ruthenium-ruthenium, preferably a hexafluorocarbon. Citrate, bismuth (pentafluorophenyl) borate. The above-mentioned mis-cations are also derived from combinations. The anion of Lewis acid is optional, and specific examples of the photocationic polymerization initiator (F) include, for example, two stupid #鐄 hexafluorophosphate, bis(p-phenyl) hexafluorophosphate, and double ( Pentium hexafluorophosphate, bis(p-octyl) hexafluorophosphate: bis(p-octadecylphenyl)-locked hexafluorophosphate, bis(p-octyloxy)錤: fluorophosphate, bis(p-octadecyloxyphenyl)phosphonium hexafluorophosphate, & s-(p-octadecyloxyphenyl)phosphonium hexafluorophosphate, (p-tolyl) ( P-isopropylphenyl) pin hexafluorophosphate, methylnaphthylphosphonium hexafluorophosphate, ethylnaphthyl dihexafluorophosphate, trisuccinyl hexafluorophosphate, ginseng (p-tolyl) fluorene Fluorophosphate, ginseng (p-isopropylphenyl) sulfonium hexafluorophosphate, ginseng (2,6-dimethylphenylhydrazino) hexafluorophosphate, ginseng (p-tert-butylphenyl) fluorene Fluorophosphate t cis (p-cyanophenyl) sulfonium hexafluorophosphate, ginseng (p-phenyl) hexafluorophosphate, dimethylnaphthyl quinone hexafluorophosphate, diethyl naphthyl fluorene hexafluorophosphate Phosphate, .dimethyl (A) Hexafluorophosphate, dimethyl(ethoxy)phosphonium hexafluorophosphate, dimethyl(propoxy)phosphonium hexafluoroantimonate, dimethyl(butoxy) mirror hexafluoro-acid Salt, dimethyl(octyloxy)phosphonium hexafluoroate, dimethyl(octadecyloxy)phosphonium hexafluorophosphate, dimethyl(isopropoxy)phosphonium hexafluorophosphate, dimethyl (third T oxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) ruthenium hexafluorophosphate, dimethyl (cyclohexyloxy) sulphur hexafluorophosphate, dimethyl (fluorine 22 317489 1377440 —Methoxy)phosphonium hexafluorophosphate, dimethyl(2-chloroethoxy)phosphonium hexafluorophosphate, dimethyl(3-bromopropoxy)phosphonium hexafluorophosphate, diterpenes (4-cyanobutyryloxy) hexafluorophosphate, dimethyl(8-nitrooctyloxy)phosphonium hexafluorophosphate, dimercapto (18-trifluoromethyloctadecyloxy)锍 hexafluorophosphate 'dimethyl (2-isopropoxy) sulfonium hexafluorophosphate, dimercapto (paraxyl (trimethyl) methyl) hexafluorophosphate, diphenyl sulfonium Fluor arsenate, bis(p-tolyl) ruthenium hexafluoroarsenate, double Tert-butylphenyl)phosphonium hexafluoroarsenate, bis(p-octylphenyl)phosphonium hexafluoroarsenate, bis(p-octadecylphenyl)phosphonium hexafluoroarsenate, double (pair) Octyloxy arsenate, bis(p-octadecyloxyphenyl)phosphonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl)phosphonium hexafluoroarsenate, (p-tolyl)(p-isopropylphenyl)phosphonium hexafluoroarsenate, methylnaphthylphosphonium hexafluoroarsenate, ethylnaphthylphosphonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate Salt, ginseng (p-phenyl) hexafluoroarsenate, ginseng (p-isopropylphenyl) hexafluoroundonate, ginseng (2,6-dimethylphenyl)phosphonium hexafluoroarsenate , ginseng (p-butylphenyl) hexafluoroarsenate, ginseng (p-cyanophenyl) sulfonium hexafluoroarsenate, ginseng (p-chlorophenyl) hexafluoroarsenate, dimethyl Naphthyl hydrazine hexafluoroarsenate, diethyl naphthyl hydrazine hexafluoroarsenate, dinonyl (decyloxy) ruthenium hexafluoroarsenate, dimercapto (ethoxy) ruthenium hexafluoroarsenate Salt, dimercapto (propoxy) fluorene-hexa-sodium arsenate, dimethyl(butoxy)phosphonium hexafluoroarsenic Salt, dimercapto (octyloxy)phosphonium hexafluoroarsenate, dimethyl(octadecyloxy)phosphonium hexafluoroarsenate, dimethyl(isopropoxy)phosphonium hexafluoroarsenate, Dimercapto-tert-butoxy hexafluoro-octaate, di-n-cyclopentyloxy hexafluoroarsenate, di-decyl (cyclohexyloxy) sulphide arsenate, di- fluorenyl (fluoride)曱oxy)phosphonium hexafluoroarsenate, dimercapto (2-glycoloxy)phosphonium hexafluoroarsenate, dimercapto (3-bromopropoxy)phosphonium hexafluoride 23 317489 1377440 arsenate, two Mercapto(4-cyanobutoxy)phosphonium hexafluoroarsenate, dimercapto (8-'nitrooctyloxy)phosphonium hexafluoroarsenate, dimethyl (18-trifluorodecyl) Alkoxy-yl)phosphonium hexafluoroarsenate, dinonyl (2-hydroxyisopropoxy)phosphonium hexafluoroarsenate, dimercapto (xhenyltrimethyl)methyl)phosphonium hexafluoroarsenate Salt, diphenylphosphonium hexafluoroantimonate, bis(p-tolyl)phosphonium hexafluoroantimonate, bis(p-tert-butylphenyl)phosphonium hexafluoroantimonate, bis(p-octylphenyl) Hexafluoroantimonate, bis(p-octadecylphenyl)phosphonium hexafluoroantimonate, bis(p-octyloxyphenyl) Hexafluoroantimonate, bis(p-octadecyloxyphenyl)phosphonium hexafluoroantimonate, phenyl (p-octadecano-oxyphenyl)phosphonium hexafluoroantimonate, (p-phenylene) (p-isopropylphenyl) decyl citrate, methylnaphthyl hydrazine hexafluoroantimonate, ethyl naphthyl fluorene hexafluoroantimonate, triphenyl sulfonium hexafluoroantimonate, ginseng Phenylphenyl)phosphonium hexafluoroantimonate, ginseng (p-isopropylphenyl)phosphonium hexafluoroantimonate, ginseng (2,6-dimercaptophenyl)phosphonium hexafluoroantimonate, ginseng Tributyl phenyl) hexafluoroantimonate, ginseng (p-cyanophenyl) hexafluoroantimonate, ginseng (p-phenyl) hexafluoroantimonate, dimethylnaphthyl fluorene hexafluorophosphate Citrate, diethylnaphthylfluorene hexafluoroantimonate, dimethyl (methoxy) hexafluoroantimonate, dimercapto (ethoxy) hexafluoroantimonate, dimethyl (propoxy)phosphonium hexafluoroantimonate, dimercapto(butoxy)phosphonium hexafluoroantimonate, dinonyl (octyloxy)phosphonium hexafluoroantimonate, dimethyl (octadecyloxy) Hexafluoroantimonate, dinonyl (isopropoxy) hexafluoroantimonate, dimercapto (third Oxy)phosphonium hexafluoroantimonate, dimethyl(cyclopentyloxy)phosphonium hexafluoroantimonate, dinonyl (cyclohexyloxy)phosphonium hexafluoroantimonate, dimercapto (fluoromethoxy)锍 hexafluoroantimonate, dimercapto (2- ethoxy) hexafluoroantimonate, dimethyl (3-bromopropoxy) hexafluoroantimonate, dimercapto (4- Cyanobutoxy)phosphonium hexafluoroantimonate, dimercapto (8-nitrooctyloxy)phosphonium hexafluoroantimonate, dimethyl (18-35 317489 1377440, fluorodecyl octadecyloxy)锍 锍 hexafluoroantimonate, dimercapto (2-hydroxyisopropoxy) hydrazine 1 fluoro citrate, dimercapto ( ginseng (trichloromethyl) methyl) hexafluoroantimonic acid salt, Diphenylphosphonium (pentafluorophenyl)borate, bis(p-tolyl)phosphonium (pentafluorophenyl)borate, bis(p-tert-butylphenyl)phosphonium (pentafluorophenyl)borate Salt, bis(p-octylphenyl)phosphonium (pentafluorophenyl)borate, bis(p-octadecylphenyl)-locked quinone (pentafluorophenyl)borate, bis(p-octyloxyphenyl) ) quinone (pentafluorophenyl) borate, bis (p-octadecyloxy) hydrazine (five Phenyl) borate, phenyl (p-octadecyloxyphenyl) ruthenium (pentafluorophenyl) borate, (p-methylphenyl) (p-isopropylphenyl) ruthenium (pentafluorobenzene) Borate, methylnaphthyl quinone (pentafluorophenyl) borate, ethylnaphthyl hydrazine (pentafluorophenyl) rotate, dibenyl quinone (pentafluorophenyl) borate, Paraxyl (p-tolyl) ruthenium (pentafluorophenyl) borate, ginseng (p-isopropylphenyl) ruthenium (pentafluorophenyl) borate, ginseng (2, 6-dimethylphenyl) hydrazine肆(pentafluorophenyl)borate, ginseng (p-butylphenyl) ruthenium (pentafluorophenyl) borate, ginseng (p-cyanophenyl) ruthenium (pentafluorophenyl) borate, Para-(p-chlorophenyl)phosphonium (pentafluorophenyl)borate, dimethylnaphthyl quinone (pentafluorophenyl) borate, diethylnaphthyl quinone (pentafluorophenyl) boric acid Salt, dimethyl (methoxy) hydrazine (pentafluorophenyl) borate, dimethyl (ethoxy) hydrazine (pentafluorophenyl) side acid salt, dimethyl (propoxy) hydrazine Bis(pentafluorophenyl)borate, dinonyl (butoxy)毓肆(pentafluorophenyl)borate, dimethyl(octyloxy)phosphonium (pentafluorophenyl)borate, dimethyl(octadecyloxy) phytonate (pentafluorophenyl)boronic acid Salt, dimethyl(isopropoxy)phosphonium (pentafluorophenyl)borate, dimethyl (t-butoxy) quinone (pentafluorophenyl) borate, dimercapto (cyclopentyloxy) Ethyl (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) ruthenium (pentafluorophenyl) borate, dimethyl (fluorine 317489 25 1377440 decyloxy) ruthenium (pentafluoro Phenyl) shed acid salt, dimethyl (2-chloroethoxy) ruthenium (pentafluorophenyl) boron sulfonium salt, dimercapto (3-bromopropoxy) ruthenium (pentafluorophenyl) • Borate, dimercapto (4-cyanobutoxy) ruthenium (pentafluorophenyl) borate, dimercapto (8-nitrooctyloxy) ruthenium (pentafluorophenyl) borate, two Mercapto (18-trifluorodecyl octadecyloxy) ruthenium (pentafluorophenyl) borate, dimethyl (2-perisopropoxy) vegetable (pentafluorophenyl) succinate Diterpenoid (parade (trimethane) fluorenyl) quinone (pentafluorophenyl) boric acid Salt and so on. Among them, bis(p-tolyl)phosphonium hexafluorophosphate, (p-phenylene)*(p-isopropylphenyl)phosphonium hexafluorophosphate, bis(p-tert-butylphenyl)phosphonium hexafluorophosphate Phosphate, trisyl sulfonium hexafluorophosphate, ginseng (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis(p-phenylphenyl)phosphonium hexafluoroarsenate, (p-phenylene) (pair) Isopropyl phenyl) hexafluoroarsenate, bis(p-butylphenyl)phosphonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, ginseng (p-tert-butylphenyl) Hexafluoroarsenate, bis(p-phenylene)phosphonium hexafluoroantimonate, (p-phenylene) (p-isopropylphenyl)phosphonium hexafluoroantimonate, bis (p-tert-butylbenzene)錤 錤 hexafluoroantimonate _ salt, triphenyl sulfonium hexafluoroantimonate, ginseng (p-tert-butylphenyl) hexafluoroantimonate, bis(p-phenylene) hydrazine (pentafluorobenzene) Borate, (p-phenylene) (p-isopropylphenyl) ruthenium (pentafluorophenyl) borate, bis(p-tert-butylphenyl) ruthenium (pentafluorophenyl) succinic acid Salt, triphenylsulfonium (pentafluorophenyl) borate, ginseng (for the third Butyl phenyl) quinone (pentafluorophenyl) borate is preferably used to use bis(p-phenylphenyl)phosphonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) fluorene hexafluorophosphate Citrate, bis(p-butylphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, bis(p-butylphenyl)phosphonium hexafluoroantimonate, double P-phenylphenyl)phosphonium (pentafluorophenyl)borate, (p-phenylene) (p-isopropyl 26 317489 1377440. phenyl) quinone (pentafluorophenyl) borate, double (for third Butyl phenyl) quinone (pentafluorophenyl) borate, triphenyl sulfonium (pentafluorophenyl) borate, ginseng (p-butyl phenyl) vegetable quinone (pentafluorophenyl) borate Better. When the polymerization initiator (F) is used, the content thereof is preferably 〇1 to 1% by mass, and 0.1 to 5% by mass, based on the mass fraction of the solid content of the radiation-sensitive resin composition. More preferably, when the content i of the polymerization initiator (F) is in the above range, the curing rate at the time of thermal curing is high, so that the resolution of the cured film can be suppressed and the solvent resistance of the cured film can be improved. Sexual tendencies are therefore preferred. The above polyvalent fluorene compound (G) may, for example, be a compound having two or more phenolic hydroxyl groups in the molecule. Examples of the polyhydric phenol compound (G) include trihydroxy dibenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, and hexahydroxydiphenyl which are the same as those described for the diazonium compound. A variety of compounds such as ketones and (basic bases). Further, the multi-aged compound (G)' is, for example, a polymer having at least a base styrene-based monomer. Specific examples thereof include: polypyridylbenzene, transphenylene/methyl methacrylate copolymer, hydroxystyrene/cyclohexyl methacrylate copolymer, hydroxystyrene/styrene copolymer, and hydroxyl group. A resin of a polymerized hydroxystyrene such as a stupid ethylene/alkoxy stupid ethylene copolymer. Further, examples of the above polyhydric phenol compound (G) include, for example, a compound selected from the group consisting of phenols, cresols, and coodiols, and consisting of acids and ketones. A novolak resin obtained by polycondensation of one or more kinds of compounds is selected from the group. 317489 27 1^//440 * Use the above polyhydric phenol compound ((〇, its content, relative to the mass fraction of the solid content of the destructive resin composition, preferably 〇〇i to denim, and 〇l$〇 c; temporary denier 0 / 、, 里 / When the (4) compound (8) is contained in the above-mentioned ruthenium, the resolution of the visible light increases, and the visible light transmittance tends to decrease, so it is preferable to lower the above-mentioned crosslinking agent. Examples of the (H) include, for example, a methyl compound, etc. Examples of the above-mentioned nail-based compound include, for example, a silk-based methylamine-amine resin, and a silk-based methylated urea resin oxymethyl pure (10) - Therefore, as the alkoxylated T-based melamine resin, there may be mentioned, for example, an oxygen=chemical triazide resin, an ethoxymethylated trimeric amine: an oxomethylated melamine resin , a butoxymethylated trimeric amine resin, etc., as an alkoxymethylated urea resin, for example, methoxymethylated urea resin, ethoxymethylated urea resin, propoxy甲甲美·=: Use a butoxymethylated urea resin, etc. The above-mentioned _ _ knife may be used alone or in combination of two or more. When the crosslinking agent (8) is used, the content thereof is relative to the mass fraction of the radiation-sensitive resin composition, preferably from 1 to 15% by mass, and when the crosslinking agent is contained within the above range. Since the visible light transmittance of the obtained film is increased and the performance of the cured resin pattern is improved, it is preferable. Examples of the polymerizable monomer (1) include a polymerizable monomer and a cation obtained by heating a radical. The polymerizable monomer obtained by polymerization is preferably used, but it is preferred to use a polymerizable monomer obtained by cationic polymerization. The above-mentioned radically polymerizable monomer can be exemplified by polymerization: 317489 28 1377440 • Carbon-carbon The compound having an unsaturated bond may be a monofunctional polymerizable monomer, a 2-functional polymerizable monomer or a polymerizable monomer having 3 or more functions, or a multifunctional polymerizable monomer. Examples of the monofunctional polymerizable monomer include mercaptophenyl carbitol acrylate, mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and mercapto group. 2-hydroxy-3-phenylphenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-ethylhexylcarbitol methacrylate, S-S, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-vinyl D is a pyrrolidone or the like. Examples of the polymerizable monomer having a bifunctional group include, for example, 16-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, and ethylene. Alcohol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimercapto acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bisphenol A bis (propylene醯 methoxyethyl)ether, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, etc. Further, a trifunctional group-containing polymerizable monomer can be exemplified by: Hydroxymethylpropane diacrylate, trimethylolpropane trimethacrylate, pentaerythritol-acrylic sulphuric acid, pentaerythritol trimethyl acrylate, pentaerythritol tetrapropylene S 夂 g day, pentaerythritol tetramethacrylic acid Ester, pentaerythritol pentaacrylate 'pentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipenta Hexa methyl acrylic ester and the like. In the above polymerizable monomer, it is preferred to use a bifunctional group having a bifunctional group or a trifunctional group, and it is preferred to use pentaerythritol tetraacrylate vinegar or dipentaerythritol hexaacrylate for use. Dipentaerythritol six 29 317489 1377440 Acrylate is preferred. Further, it is also possible to use a polymerizable monomer having a bifunctional group or a trifunctional group, and a single-orthracene or a person. The group of polymerizable monomers having an early s-energy group can be exemplified by a cationic polymerization of a cationic monomer, such as: a base group, an acryl group, an epoxy group, an oxetan group, and a functional group. Polymerizable monomer.                                                      Butyl propyl propyl ether-containing servant private ^ / t gas base: base): 1: wm - propylene 3 with a jade emulsion based on the compound can be listed with the heart · Germany, grease, novolac type Epoxy 榭 # ^ 牛· phenol A type epoxy resin aliphatic epoxy tree _ varnish type epoxy resin, cyclic epoxy resin, heterocyclic epoxy resin, etc.. Tree glutathionamine type 'oxygen Examples of the compound of the group include, for example, bis[3-(3'ethyl p-oxy-V 4 , U, [3-(3-ethyloxetanyl) benzene, i 4 - fluorene ['3 ( 3[3-(3-ethyloxetanyl)methoxy]methyl 1 4 cone "also (ethyl oxetanyl) methoxy) cyclohexane, '4 bis [3-(3 - Ethyloxycyclohexane, tymidine, methyl hexane, ethyl acetonide butyl) methylated novolac resin, etc. When the body (1) is used alone, the polymerizable monomer (1) can be separately The amount, the radiation sensitivity 317489 30 1377440 is usually 0.1 to 20% by mass. The decane coupling agent (J) may, for example, be a methyl trisium, a methyltriethylamine, a vinyl trigas, an ethylene tris methoxy sulphur, a vinyl triethoxy sulphur , Ethyl-based triethyl ethoxylate XI Xi, Ethyl ginseng (2-methoxyethoxy) 垸 垸, 3- chloropropyl _ trimethoxy oxalate, 3- propyl propyl group - Dioxane, 3-propylmethyl-dimethoxyoxime, 3-chloropropylmethyl-diethoxyxanthine, 3-glycidoxypropyl-trioxetane , 3-glycidoxypropyl-triethoxydecane, 3-glycidyloxypropylmethyl-di-f-oxydecane, 3-mercaptopropyl-trimethoxydecane, 3-methyl Acryloxypropyl-trimethoxydecane, 3-mercaptopropenyloxypropyl-dimethoxydecane, 2-(3 4_epoxycyclohexyl)ethyl-trimethoxydecane , N-2-(N-vinylbenzylaminoethyl)_3_aminopropyl-trimethoxydecane hydrochloride, hexamethyldioxanylamine, diaminodecane, diaminopropyl -trimethoxy decane, 3-aminopropyl-trimethoxy decane, 3-aminopropyl-triethoxy decane 3_Aminopropyl fluorenyl-diethoxy φ decane, 3-aminopropyl-parade (2-methoxyethoxyethoxy)decane, 3-(2-aminoethyl)- 3-aminopropyl-trimethoxydecane, 3-(2-aminoethyl)-3-aminopropyl-decyl-dimethoxydecane, 3-ureidopropyl-trimethoxy-decane, 3-_Urylic propyl-triethoxy decane, N-aminoethyl-3-aminopropyl-trimethoxy decane, N-aminoethyl-3-aminopropylmethyl _ Methoxydecane, N-mercapto-3-aminopropyl-trimethoxyoxydecane, N-phenyl-3-monopropylpropyl-trimethoxydecane, and the like. Among them, an oxime coupling agent containing an epoxy group in this structure is preferably used. The decane coupling agent containing an epoxy group in the above structure can be listed as 317489 1377440. For example, .3-3⁄4 oxypropoxypropyl-trimethoxydecane, 3-glycidoxypropyl-two Ethoxy decane, 3-glycidoxypropylmethyl-dimethoxy oxime, 2-(3,4-epoxycyclohexyl)ethyl-trimethoxydecane, etc., preferably 2 ( An alicyclic epoxy-containing breaker coupling agent such as 3,4-epoxycyclohexyl)ethyl-trimethoxy decane. The content of the decane coupling agent (J) is preferably 0.01 to 10% by mass based on the mass fraction of the solid content of the radiation-sensitive resin composition, preferably Oi, 2 to K, and 0.2 to 1 by mass. % is better. When the heat-sensitive resin pattern is formed by using the radiation-sensitive resin composition of the present invention, the visible light transmittance of the cured resin pattern is improved, so that the transparency tends to be improved. Further, it is preferable because the adhesion between the cured resin pattern and the substrate is improved. The radiation sensitive resin composition of the present invention may contain other components such as an antioxidant, a dissolution inhibitor, a sensitizer, an ultraviolet absorber, a light stabilizer, an adhesion improver, an electron donor, etc., depending on the demand. Additions of each type. The radiation-sensitive resin composition of the present invention' is, for example, a solution of the solvent (C), 醌

Combination: a hardening alkali-soluble resin (4) dissolved in a solvent (c) a heavy gas compound (B) (a solution of a solvent in the solvent (c), and a fluorine-based surfactant (E) Further, after mixing, the solvent (C). After the solution is mixed, it is filtered to remove the solid 317489 32 1377440. When the cured resin pattern is formed using the radiation-sensitive resin composition of the present invention, for example, the present invention is formed on the substrate. The layer formed of the radiation-sensitive resin composition is irradiated with radiation to the above layer via a mask. After exposure, it is sufficient to develop the image. As the substrate, a transparent glass plate or the like can be cited. A circuit such as a TFT or a CCD, a color filter, or the like may be formed on the substrate. The layer formed of the radiation sensitive resin composition is preferably coated with a coating device having a slit-like nozzle. The nozzle coating device is disposed, for example, as a slit coater, a die coater, a curtain flow coater, etc. After coating, heating and drying (prebaking), or drying under reduced pressure, By removing some or all of the solvent The volatile component is formed into a radiation sensitive resin composition layer having a reduced solvent content. Further, the thickness of the radiation sensitive resin composition layer is, for example, about 至5 to 5 #m. Next, the radiation sensitive resin composition layer The radiation is irradiated through the mask. The pattern of the mask is appropriately selected in accordance with the pattern for the pattern of the cured resin. For the radiation 'for example, light such as a g-line or a twisted wire can be used. The radiation is used to completely cross the radiation-sensitive resin. The composition layer is irradiated in parallel. For example, a mask aligner or a stepper may be used. Thus, after exposure, the image is formed by exposing the radiation-sensitive resin after exposure. The layer can be carried out, for example, by a method of contacting a developing solution, and the developing solution is usually an aqueous solution of an aqueous solution. The alkaline aqueous solution is an aqueous solution of an organic compound, and the basic compound can be an inorganic basic compound or an organic compound. Basic compound π 317489 33 1377440 Inorganic basic compound ' can be exemplified by sodium hydroxide, hydrazine hydroxide, disodium hydrogen phosphate, dihydrogen phosphate , diammonium hydrogen phosphate, dihydrogen phosphate 'potassium dihydrogen potassium, sodium citrate, potassium citrate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, boric acid clock, ammonia, etc. The compound may, for example, be tetramethylammonium hydroxide, 2-hydroxyethyltrimonylammonium hydroxide, monodecylamine, dimethylamine or trimethylamine.

Amine, monoethylamine, diethyl/amine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. The above-mentioned basic compounds may be used alone or in combination of two or more. The developing solution usually contains 1 to 1 part by mass of the basic compound per 100 parts by mass of the developing liquid, and preferably 〇.丨 to 5 parts by mass. The developing solution may also contain a surfactant. Examples of the surfactant include a nonionic surfactant, a cationic surfactant, and an anionic surfactant. ... nonionic surfactants can be exemplified by: polyethylene oxide alkyl ether, ♦ polyethylene oxide wire It, polyepoxy aryl aryl polyepoxide, bio-epoxy / Ethylene propylene compound aged copolymer, sorbitol liver fat 聚, poly lactic acid ethoxylated sorbitol wild fatty acid vinegar, polyepoxy sorbitan fatty acid 酉, glycerin fatty acid vinegar, poly Ethylene bromide fatty acid vinegar, polyethylene oxide alkylamine, and the like. Examples of the cation-positive surfactant include a quaternary ammonium salt such as an amine such as stearylamine hydrochloride or a quaternary ammonium salt such as a dimethicone vapor. ☆ Anionic surfactants include, for example, sodium lauryl sulfate, / higher alcohol sulfates such as sodium citrate; sodium lauryl sulfate, lauryl 317489 34 1377440, ammonium sulfate, etc. Base sulfate; alkyl aryl sulfonate such as sodium dodecyl sulfonate, sodium dodecyl naphthalene sulfonate, and the like. These surfactants may be used alone or in combination of two or more. σ Further, the developing solution may contain an organic solvent, and examples of the organic solvent include a water-soluble organic solvent such as decyl alcohol or ethanol.

When the radiation sensitive resin composition layer is brought into contact with the development liquid, for example, the substrate on which the radiation sensitive resin composition layer is formed may be immersed in the developing liquid. In the radiation-sensitive resin composition layer, the radiation-irradiated area irradiated by the radiation in the first exposure is dissolved in the developing liquid, and the radiation-exposed area which is not irradiated with the radiation is not dissolved in the image. The liquid remains and forms a pattern. The radiation-sensitive resin composition of the present invention contains yttrium-difluoride α (Β). Therefore, the time during which the radiation-sensitive resin composition layer is in contact with the developing solution is short, and the radiation-irradiated region is easily dissolved and removed. . Further, since 3 has a I diazonium compound (Β), the radiation sensitive resin composition layer becomes long in contact with the developing solution, and the radiation non-irradiated region does not dissolve in the developing solution and disappears. After eight imaging, it is usually washed and dried. After drying, the resulting full or partial pattern is irradiated with radiation. The radiation to be irradiated is preferably ultraviolet or deep ultraviolet rays, and the amount of irradiation per unit area is preferably more than the exposure amount of the previous exposure. The pattern thus formed is preferably subjected to heat treatment (post-baking) from the viewpoint of improving the heat resistance and the resistance of the cured resin pattern. The heating system 317489 35 丄377440 is used to heat the substrate after the irradiation of the entire radiation by a heating method such as a heating plate or a cleaning furnace. The heating temperature is usually 15 Torr to 25 Torr, preferably 1801 to 2401, and the heating time is usually 5 minutes to 12 minutes, preferably 15 minutes to 90 minutes. The pattern is hardened by heating to form a hardened resin pattern. According to the present invention, a radiation-sensitive resin composition having good wettability to a stainless steel substrate can be provided. Since the composition of the radiation-sensitive resin of the present invention is excellent in wettability to a stainless steel substrate, the coating property of a coating apparatus having a slit nozzle can be improved. The hardened resin pattern formed by using the radiation-sensitive resin composition of the present invention can be applied, for example, to an insulating film of a thin film organic EL element constituting a TFT-type liquid crystal display device, and a light spacer (ph〇t〇Spacer) A cured resin pattern of a diffuser, a diffuse reflector used for a reflective TFT substrate, a liquid crystal alignment protrusion, a CCD protective film, or the like. EXAMPLES The following is a detailed description of the present invention based on the following examples, but the scope of the present invention is of course not limited to such embodiments. Production Example 1: Resin A1 In a 300 mL four-necked flask equipped with a stirrer, a condenser, and a thermometer, 36 g of ethyl lactate and 146 g of ethyl 3-ethoxypropionate were placed as a solvent. The initiator azobisisobutyronitrile 2.2g, and the following monomer was placed under the nitrogen gas stream, the internal temperature was maintained at 100 to 110 ° C, and the mixture was mixed for 3 hours and reacted to obtain a resin A1. The solution A, the polystyrene-equivalent weight average molecular weight of the resin A1 was 7,9 。. 36 317489 1377440 Methyl acetoacetate ' 10.8 g 3-ethyl-3-mercapto propylene fluorenyloxy oxetane 36 9 boge • N-cyclohexylmaleimide 31. 4 g The measurement of the weight average molecular weight (Mw) converted to polystyrene was carried out under the following conditions using a GPC method. Device·· HLC-8120 GPC (Tosoh Co., Ltd.)

Column: TSK-GELG4_HXL+TSK-GELG2〇〇〇HXL; in-line connection) Lu column temperature: 40°C Solvent: THF Flow rate: 1. 〇mL/min Injection volume: 5 0 v L Detector: RI determination sample Concentration: 〇. 6 mass% (solvent: THF) Standard material for calibration: TSK standard polystyrene F-40, F-4, F-1, A-2500, A-500 (made by Tosoh Co., Ltd.) _ Example 1 After mixing the following components at 23° C., an additional 8400 (polyether/modified oxime oil) as an anthrone-based surfactant (d) component corresponding to 2 〇〇ppm of the entire composition was added; E-1830 ((2, 2, 3, 3, 4, 4, 5'5) as a fluorine-based surfactant (E) equivalent to 1 〇〇ppm of the total composition of the composition. '6, 6, 7, 7, 8, 8, 9, 9, 9-heptadecafluorodecyl) ethylene oxide; Taijin finished product sales (stock) system. The filtrate of the radiation-sensitive resin composition 1 was obtained by passing through a tubular filter of polytetrafluoroethylene having a pore diameter of 1. 〇 β m and pressurizing it through 遽'. The obtained solvent 317489 37 1377440 The solvent (c) content in the radiation sensitive resin composition is 72.5%, the solvent composition ratio is ethyl lactate: 3-ethoxypropionate ethyl ester: butyl acetate: C1 Drunk monoterpene ether = 16: 60: 20: 4. 333 parts by mass of the solution containing the resin A1 (in terms of solid content: 1 part by mass), the compound represented by the formula (1), 20 parts by mass

Adeka optomer-SP-172 (photocationic polymerization catalyst; Asahi Chemical Industry 2 parts by mass)

Sun Aid SI-100L (thermal cationic polymerization catalyst; manufactured by Sanshin Chemical Industry Co., Ltd.) 2 parts by mass of decane: Shin-Etsu Chemical Co., Ltd.) Ethyl lactate 3-ethoxypropionate ethyl butyl acetate propylene glycol Monomethyl ether KBM-303 (Shi Xi siu coupling agent; y? - (3, 4-epoxycyclohexyl) ethyl trimethoxy 3 parts by mass of 8. 1 part by mass of 16. 2 parts by mass of 67 parts by mass 13.4 mass Parts Φ OQ4

(1) (wherein Q4 represents a substituent represented by (1-1) 〇

II (Μ) 317489 38 1377440 Example 2 In addition to E-1830, E-5844 (glycidyl 2, 2, 3, 3, 4, 4, 5, 5, 6) was added to add loo ppm equivalent to the entire composition. , the same operation as in Example 1 except for the use of the same as in Example 1, to obtain a radiation-sensitive resin composition, except for the hexagram of the hexagram product; 2. Comparative Example 1 A radiation sensitive resin composition 3 was obtained in the same manner as in Example 1 except that the fluorine-based surfactant was not used. Comparative Example 2 A radiation-sensitive resin composition 4 was obtained in the same manner as in Example 除了 except that the SH 8400 was changed to 300 ppm' and the fluorine-based surfactant was not used. <Measurement Example of Fluidity> The radiation-sensitive resin composition obtained in the above Examples and Comparative Examples was placed on a horizontally placed SUS 630 plate (size: 1 〇〇 mm x 2 〇〇 with x 10 mm, surface) Thickness: One direction is adjusted to correspond to JIS B 〇659 12. 5-S hair-line finish), by Papillon dropper (5 - 3 / 4"; made by Fischer ), 10# L was dropped, and the SUS SUS630 plate was erected vertically in the vertical direction. At this time, the hairline of the plate became vertical with respect to the dropping direction of the liquid droplets. The radiation of the composition until the flow stopped was measured. The flow distance of the sensitive resin composition is regarded as the flow distance. The measurement results are shown in Table 1. In addition, when the liquid flows, the liquid stays on the hairline for more than a second, and the flow is temporarily stopped. x, liquid did not stop and 317489 39 1377440 smooth flow of the flow is 流动, the fluidity is good, the wettability of the stainless steel substrate is good. The judgment results are shown in Table 1. Table 1

Example 1 Example 2 Comparative Example 1 Comparative Example 2 (D) component SH 8400 200 200 200 300 (E) Component E-1830 100 E-5844 100 Determination Flow distance 80 82 75 74 Fluidity 〇 〇 X X

40 317489

Claims (1)

1377440 '· Patent No. 94,335,321 Patent < I 〇1 July 丨6曰Revision and Replacement Page 10, Patent Application Range: · A radiation-sensitive resin composition containing a hardening base • Soluble resin (A), a hydrazine compound (B), a solvent (an anthraquinone-based surfactant (D), and a fluorine-containing surfactant (E) containing an epoxy group. a composition in which the hardenable alkali-soluble resin (A) contains: a composition of a single carboxylic acid derived from an unsaturated carboxylic acid, and an unsaturated compound having a hardening group [but not unsaturated A copolymer of the constituting unit (a2) derived from the carboxylic acid. 3. The composition of the second aspect of the invention, wherein the 'hardening group' in the constituent unit (a2) is an oxetanyl group. The composition of any one of the above-mentioned claims, wherein the hardening alkali-soluble resin (A) further comprises: a constituent unit derived from a carboxylic acid ester having an olefinic double bond (a31) ) derived from an aromatic compound having a polymeric carbon-stone unsaturation bond At least one constituent unit selected from the group consisting of the constituent unit (a32), the constituent unit derived from the vinyl cyanide compound (a33), and the constituent unit derived from the N_substituted maleimine compound (a34) (a3) 5. The composition of any one of the claims of claim 4, wherein the molecular weight of the fluorine-based surfactant (E) is 1 〇〇 or more and 1 〇〇〇 or less. The composition of any one of the above-mentioned items, wherein the 矽-type surfactant (D) is a polyalkylene glycol-modified fluorenone. 7. If the scope of the patent application is from the third to the third A composition which is suitable for a coating device having a slit nozzle. 8. A transparent hardening resin pattern, which is amended by the patent application No. 1 to γ 317489, Patent No. 1,377, 540, No. 94,135, 321, The composition of any one of the replacement page items is modified on the 16th of the month. 9. A display device having a transparent hardened resin pattern as in claim 8 of the patent application.