JP4586703B2 - Radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, a transparent cured resin pattern formed using the same, and a method for producing the same.

The radiation-sensitive resin composition is, for example, a TFT insulating film used in a thin film transistor (hereinafter referred to as TFT) liquid crystal display device or an organic EL display device, or a diffuse reflection used in a reflective TFT substrate. Form cured resin patterns including plates, columnar spacers used for color filter substrates, projection materials for MVA, organic EL insulating films, protective films for solid-state imaging devices (hereinafter sometimes referred to as CCDs), etc. It is useful as a material for this purpose (see, for example, Patent Document 1). Here, in order to obtain a higher performance TFT substrate, the TFT insulating film or the like is required to have a performance of flattening a step of a base such as a TFT element formed on the substrate (for example, Patent Document 2) reference.).
In addition to these, along with the recent increase in the size of the substrate glass used in the manufacture of TFT substrates, the composition application method has been changed from spin coating to coating from slit-like nozzles that do not spin the substrate. Stainless steel is used as a nozzle substrate in a coating apparatus having a slit-shaped nozzle (Patent Documents 3 to 5). In order to apply with these apparatuses, the radiation-sensitive resin composition is applied to the stainless steel substrate. Good wettability is required.

Japanese Patent No. 2933879, page 1, right column, lines 22-25, page 3, left column, lines 13-14 Japanese Patent Laid-Open No. 9-244209, page 1, left column, lines 1 to 3 JP-A-2001-162204, page 4, left column, lines 34-38 JP, 2003-211053, p. 5, left column, lines 33-41 JP-A-8-173875, page 4, left column, line 31-right column, line 9

  An object of the present invention is to provide a radiation sensitive resin composition having good wettability to a stainless steel substrate.

Therefore, the present inventors have intensively studied to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, the present invention relates to a radiation-sensitive resin composition containing a curable alkali-soluble resin (A), a quinonediazide compound (B), a solvent (C) and a silicone surfactant (D). A radiation-sensitive resin composition in which the activator (D) contains a silicone surfactant (D1) having an HLB value of 1 or more and 9 or less and a silicone surfactant (D2) having an HLB value of more than 9. I will provide a.

  Moreover, this invention provides the display apparatus which comprises the transparent cured resin pattern formed with the said radiation sensitive resin composition, and the said pattern.

  According to the radiation-sensitive resin composition of the present invention, the wettability with respect to the stainless steel base material is good, so that it is possible to expect improved coatability in a coating apparatus having a slit-like nozzle.

  In the present invention, the curable alkali-soluble resin (A) is derived from the structural unit (a1) derived from an unsaturated carboxylic acid and an unsaturated compound having a curable group (excluding the unsaturated carboxylic acid). A copolymer containing the structural unit (a2) is preferably used.

Examples of the unsaturated carboxylic acid that leads to the structural unit (a1) include an unsaturated carboxylic acid having one or more carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid and an unsaturated dicarboxylic acid. Examples of the acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.
Here, in this specification, the notation of (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and the notation of (meth) acrylate represents the group consisting of acrylate and methacrylate. And (meth) acryloyl notation represents at least one selected from the group consisting of acryloyl and methacryloyl, and (meth) acryloxy notation is at least selected from the group consisting of acryloxy and methacryloxy. 1 type is represented.

Examples of unsaturated compounds having a curable group that leads to the structural unit (a2) (excluding unsaturated carboxylic acids) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β -Ethylglycidyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meta ) Acrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 2- Vinylcyclohexene oxide, 3- Epoxy group-containing unsaturated compounds such as vinylcyclohexene oxide and 4-vinylcyclohexene oxide;
3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane,
3-methyl-3- [1- (meth) acryloxy] methyl oxetane, 3-ethyl-3- [1- (meth) acryloxy] methyl oxetane, 3-methyl-3- [1- (meth) acryloxy] ethyl oxetane 3-ethyl-3- [1- (meth) acryloxy] ethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 2- Pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 2-phenyl-3- (meth) ) Acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane Other 2-pentafluoroethyl-3- (meth) acryloxy ethyl oxetane, such as 3-methacryloxypropyltrimethoxysilane Roxio xenon oxetanyl group-containing unsaturated compound such as Tan and the like.
As the unsaturated compound having a curable group that leads to the structural unit (a2), the above oxetanyl group-containing unsaturated compound is preferable. Among these, preferable oxetanyl group-containing unsaturated compounds include 3-ethyl-3-methacryloxymethyl oxetane, 3-methyl-3-methacryloxymethyl oxetane, 3-methyl-3- (1-methacryloxy) ethyl oxetane, and 3-methacrylate. Roxyoxetane is mentioned.
When a radiation-sensitive resin composition is prepared using an alkali-soluble resin containing an oxetanyl group-containing unsaturated compound, the storage stability tends to be good, which is preferable.

The copolymer further includes a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond, a structural unit (a32) derived from an aromatic compound having a polymerizable carbon-carbon unsaturated bond, A structural unit (a3) derived from a vinyl cyanide compound and at least one structural unit (a3) selected from the group consisting of a structural unit (a34) derived from cleavage of an unsaturated bond of an N-substituted maleimide compound be able to.
Examples of the carboxylic acid ester having an olefinic double bond that leads to the structural unit (a31) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , Unsaturated carboxylic acids such as benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate Acid esters;
Unsaturated alkyl carboxylic acid aminoalkyl esters such as aminoethyl (meth) acrylate;
Examples thereof include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate.
Examples of the aromatic compound having a polymerizable carbon-carbon unsaturated bond that leads to the structural unit (a32) include aromatic vinyl compounds. Specific examples include styrene, α-methylstyrene, vinyltoluene, and the like. Can be mentioned.
Examples of the vinyl cyanide compound that leads to the structural unit (a33) include acrylonitrile, methacrylonitrile, α-chloro (meth) acrylonitrile, and the like.
Examples of the N-substituted maleimide compound that leads to the structural unit (a34) include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N -(4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl -3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N- (1-anilinonaphthyl-4) -maleimide, N- [4- (2 -Benzoxazolyl) phenyl] maleimide N-(9-acridinyl) maleimide and the like.
Such structural units can be used alone or in combination of two or more.

In the copolymer containing the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having a curing group (excluding the unsaturated carboxylic acid) in the present invention, The constituent ratio of a1) is preferably 5 to 50 mole%, more preferably 15 to 40 mole%, based on the total number of moles of the constituent units of the copolymer, and the constituent ratio of (a2) is the copolymer. Preferably it is 95-50 mol% with respect to the total number of moles of the structural unit of, More preferably, it is 85-60 mol%.
In the copolymer, when the ratio of the structural unit (a1) and the structural unit (a2) is in the above range, an appropriate dissolution rate is obtained with respect to the developer during pattern formation, and the obtained pattern is It tends to show high curability and is preferable.

The copolymer containing the structural unit (a1) and the structural unit (a2) in the present invention may contain other structural units as optional components in addition to the structural unit (a1) and the structural unit (a2). When the copolymer includes other structural units as optional components, the proportion of the structural unit (a1) is preferably 5 to 50 mol%, more preferably 15 to the total moles of the structural units of the copolymer. The proportion of the structural unit (a2) is preferably 95 to 5 mol%, more preferably 85 to 15 mol%, and the proportion of the other structural units is preferably Is 0.1 to 90 mol%, more preferably 5 to 80 mol%.
Examples of the copolymer containing the structural unit (a1) and the structural unit (a2) in the present invention include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacrylic acid, and the like. Roxymethyl oxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / cyclohexyl methacrylate Copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate / styrene copolymer, 3- Ethyl-3- Tacryloxymethyl oxetane / methacrylic acid / tert-butyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacryl Acid / benzyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / dicyclopentanyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / tert-butyl acrylate Coalescence, 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / phenylmaleimide copolymer, 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / cyclohexyl maleimide copolymer.

The copolymer containing the structural unit (a1) and the structural unit (a2) in the present invention has a weight average molecular weight determined by gel permeation chromatography based on polystyrene, preferably 2,000 to 100,000, More preferably, it is used in the range of 2,000 to 50,000, particularly preferably 3,000 to 20,000. When the weight average molecular weight is in the above range, a high development speed tends to be obtained while maintaining the remaining film ratio during development, which is preferable.
The content of the copolymer containing the structural unit (a1) and the structural unit (a2) in the radiation-sensitive resin composition of the present invention is a mass fraction with respect to the solid content of the radiation-sensitive resin composition, preferably 50 to 90%, more preferably 60 to 90%.

  Examples of the quinone diazide compound (B) in the present invention include 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfone. And acid amides.

Specifically, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 1,2-naphthoquinonediazide sulfonic acid esters of benzophenones;
2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxy -3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as;
2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphtho 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones such as quinone diazide-5-sulfonic acid ester;
2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 3,4, 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as 5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester;
Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri ( p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( 2,3,4-Trihydroxyphenyl) methane-1,2-naphthoquinonediazide 4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) Propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1 , 3-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4 -Hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [4- [1- 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphtho Quinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3 ′ -Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol 1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′- Hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, or 2, 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as 2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester Is mentioned.

  The quinonediazide compound (B) in the above is used individually or in combination of 2 or more types, respectively. Content of the quinonediazide compound (B) in this invention is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 2-50%, More preferably, it is 5-40%. When the content of the quinonediazide compound is within the above range, the difference in dissolution rate between the unexposed area and the exposed area tends to be high, and thus there is a tendency that the developed residual film ratio tends to be kept high.

The radiation sensitive resin composition of this invention contains a solvent (C). Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono sec-butyl ether, ethylene glycol mono ethylene glycol monoalkyl ethers such as tert-butyl ether, ethylene glycol mono n-pentyl ether, ethylene glycol mono n-hexyl ether, tylene glycol mono n-heptyl ether, tylene glycol mono n-octyl ether;
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di n-propyl ether, diethylene glycol diisopropyl ether, diethylene glycol di n-butyl ether, diethylene glycol di sec-butyl ether, diethylene glycol di tert-butyl ether, diethylene glycol di n-pentyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl n-butyl ether, diethylene glycol methyl sec-butyl ether, diethylene glycol methyl tert-butyl ether, diethylene glycol methyl n-pent Ether, diethylene glycol ethyl n-propyl ether, diethylene glycol ethyl isopropyl ether, diethylene glycol ethyl n-butyl ether, diethylene glycol ethyl sec-butyl ether, diethylene glycol ethyl tert-butyl ether, diethylene glycol ethyl n-pentyl ether, diethylene glycol n-propyl isopropyl ether, diethylene glycol n-propyl n-butyl ether, diethylene glycol n-propyl sec-butyl ether, diethylene glycol n-propyl tert-butyl ether, diethylene glycol n-propyl n-pentyl ether, diethylene glycol isopropyl n-butyl ether, diethylene glycol isopropyl se -Butyl ether, diethylene glycol isopropyl tert-butyl ether, diethylene glycol isopropyl n-pentyl ether, diethylene glycol n-butyl sec-butyl ether, diethylene glycol n-butyl tert-butyl ether, diethylene glycol n-butyl n-pentyl ether, diethylene glycol sec-butyl tert-butyl ether, diethylene glycol diethylene glycol dialkyl ethers such as sec-butyl n-pentyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate;
Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 2-hydroxyisobutanoate, ethyl lactate, butyl lactate, butyl acetate, amyl acetate, methyl pyruvate, 1,3-butanediol diacetate, etc. Is mentioned. The above solvents may be used alone or in combination.
Preferred solvents include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate, ethyl lactate, butyl lactate, butyl acetate, and these solvents should be used in combination. Is preferred.
Preferred solvent combinations include diethylene glycol dimethyl ether and ethyl 3-ethoxypropionate, diethylene glycol dimethyl ether and ethyl lactate, diethylene glycol dimethyl ether and butyl lactate, diethylene glycol dimethyl ether and butyl acetate, diethylene glycol diethyl ether and ethyl 3-ethoxypropionate, diethylene glycol diethyl ether and lactic acid. Ethyl, diethylene glycol diethyl ether and butyl lactate, diethylene glycol diethyl ether and butyl acetate, diethylene glycol methyl ethyl ether and ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether and ethyl lactate, diethylene glycol methyl ethyl ether and butyl lactate, diethylene glycol Rumethyl ethyl ether and butyl acetate, ethyl 3-ethoxypropionate and ethyl lactate, ethyl 3-ethoxypropionate and butyl lactate, ethyl 3-ethoxypropionate and butyl acetate, diethylene glycol methyl ethyl ether and ethyl 3-ethoxypropionate Butyl lactate, diethylene glycol methyl ethyl ether and ethyl 3-ethoxypropionate and butyl acetate, diethylene glycol methyl ethyl ether and ethyl lactate and butyl acetate, diethylene glycol methyl ethyl ether and butyl lactate and butyl acetate, diethylene glycol methyl ethyl ether and 3-ethoxypropionic acid And ethyl, butyl lactate, and butyl acetate, and more preferably diethylene glycol methyl ethyl ether and 3-ethoxypropionic acid. Le and butyl lactate, include diethylene glycol methyl ethyl ether and ethyl 3-ethoxypropionate and butyl acetate, diethylene glycol methyl ethyl ether and ethyl 3-ethoxypropionate and butyl lactate and butyl acetate are particularly preferred.

Content of a solvent (C) is a mass fraction with respect to a radiation sensitive resin composition, Preferably it is 50-95 mass%, More preferably, it is 70-90 mass%.
Especially, when applying to the coating device only of the process apply | coated from a slit-shaped nozzle, it is especially preferable that content of a solvent (C) is 75-90 mass% on the same basis as the above. Moreover, when applying to the coating device which has the process of rotating the board | substrate which apply | coated the composition in addition to the process of apply | coating from a slit-shaped nozzle, content of a solvent (C) is the same reference | standard as the above. 65 to 80% by mass is particularly preferable.
When the content of the solvent (C) is in the above range, a coating film with less unevenness tends to be formed, which is preferable.

As the silicone surfactant (D) in the present invention, a silicone surfactant (D1) having an HLB value of 1 or more and 9 or less and a silicone surfactant (D2) having an HLB value of more than 9 are contained. To do.
Here, the HLB value of the surfactant is specifically measured by the following method.
Surfactant / 0.5 g is dissolved in ethanol / 5 ml. A 2% aqueous phenol solution is added dropwise, and the addition amount (ml) when the solution becomes cloudy is recorded as the cloudiness number A. The HLB value is calculated by HLB = 0.89 × (cloud number A) +1.11. (See Ichiro Nishi: Surfactant Handbook / Sangyo Tosho Co., Ltd.)
Since various HLBs can be set depending on the amount of polyether introduced and the ethylene oxide / propylene oxide ratio in the polyether, a polyether-modified silicone oil is preferred as the silicone surfactant (D) of the present invention.

  Examples of the silicone surfactant (D1) having an HLB value of 1 or more and 9 or less are FS1265, SH710, SH203, BY16-880, SH3775, SH3748, SH3749, SF8410, SF8421, SH8400, SH28PA (Toray Dow Corning Silicone ( Co., Ltd.), TSF4445, TSF4446 (manufactured by GE Toshiba Silicone Co., Ltd.), and the like.

  Examples of the silicone surfactant (D2) having an HLB value exceeding 9 include SH3771M, SH3746, SF8427, BY16-201 (manufactured by Toray Dow Corning Silicone Co., Ltd.), PS558 (manufactured by United Chemical Technologies, Inc.), Q2 -5211 (manufactured by Dow Corning Corp), SILWET 408, L-7210, L-7200 (all of which are manufactured by OSi Specialties), TSF4440, TSF4452 (manufactured by GE Toshiba Silicones Co., Ltd.), and the like. In the silicone surfactant (D2) having an HLB value exceeding 9, the HLB value is preferably more than 9 and 25 or less, more preferably 10-20.

Content of silicone type surfactant (D) is a mass fraction with respect to a composition, Preferably it is 1-1000 ppm, More preferably, it is 10-500 ppm, Especially preferably, it is 50-300 ppm. When the content of the silicone-based surfactant is in the above range, a coating film with less unevenness tends to be formed, which is preferable.
The content of the silicone surfactant (D1) having an HLB value of 1 or more and 9 or less is 50 to 90% by mass in terms of mass fraction with respect to the total effective amount of the silicone surfactant (D). Is preferred.

  The radiation sensitive resin composition of the present invention includes, as other components, a polymerization initiator (F), a polyhydric phenol compound (G), a crosslinking agent (H), a polymerizable monomer (I), a silane coupling agent (J ) Can be contained.

Examples of the polymerization initiator (F) include onium salts that are cationic polymerization initiators. The onium salt is composed of an onium cation and an anion derived from a Lewis acid.
Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, Bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p -Tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p- Ananophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromo Propoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitro) Octyloxy) sulfonium, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, dimethyl (tris (trichloromethyl) methyl) sulfonium, and the like, preferably bis (p-tolyl) Examples include iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium, and tris (p-tert-butylphenyl) sulfonium.
Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, and preferably hexafluoroantimonate, tetrakis (penta). Fluorophenyl) borate.
The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Specifically, as the photocationic polymerization initiator (F), diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octyl) Phenyl) iodonium hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyl) Oxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafur Lophosphate, methylnaphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2 , 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthyl Sulfonium hexafluorophosphate, diethyla Tylsulfonium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluoro Phosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfur Honium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluoro Phosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluorophosphate;
Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate, dimethyl (octyloxy) sulfonium hexafluoroarsenate , Dimethyl (octadecanoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-butoxy) sulfonium hexafluoroarsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) ) Sulfonium hexafluoroarsenate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluoroarsenate;
Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Rufonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyl) Oxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro Antimonate, dimethyl (cyclohexyl) Ruoxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyano Butoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate , Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Nchimoneto;
Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis Pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenyl Sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium teto Kiss (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, Diethyl naphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (pentafluorophenyl) borate, Dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) bo Dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate , Dimethyl (2-chloroethoxy) sulfonium tetra (Pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) Methyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, preferably bis (p-tolyl) Donium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert- Butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarcete , Triphenylsulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsene Bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium Hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (penta Fluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris ( -Tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate Bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluoro) Phenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert) Butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenyl sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

  When the polymerization initiator (F) is contained, the content thereof is a mass fraction with respect to the solid content of the radiation-sensitive resin composition, preferably 0.01 to 10% by mass, more preferably 0.1 to 0.1% by mass. 5% by mass. When the content of the polymerization initiator (F) is in the above range, by increasing the curing rate at the time of thermosetting, a decrease in resolution at the time of thermosetting is suppressed, and the solvent resistance of the cured film is further improved. Is preferable.

  As said polyhydric phenol compound (G), the compound which has a 2 or more phenolic hydroxyl group in a molecule | numerator is mentioned. Examples of the polyhydric phenol compound include polyhydroxy phenols such as trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, and (polyhydroxyphenyl) alkanes similar to those described in the quinonediazide compound. And the like.

  Moreover, as said polyhydric phenol compound (G), the polymer which uses at least hydroxystyrene as a raw material monomer is mentioned. Specific examples of the polyhydric phenol compound (G) include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer, and hydroxystyrene / alkoxystyrene copolymer. Examples thereof include a resin obtained by polymerizing hydroxystyrene such as a polymer. Furthermore, a novolak resin obtained by condensation polymerization of at least one compound selected from the group consisting of phenols, cresols and catechols and one or more compounds selected from the group consisting of aldehydes and ketones, etc. Can be mentioned.

  When the polyhydric phenol compound (G) is contained, the content thereof is a mass fraction with respect to the solid content of the radiation-sensitive resin composition, preferably 0.01 to 40% by mass, more preferably 0. .1 to 25% by mass. When the content of the polyhydric phenol compound (G) is in the above range, the resolution is improved and the visible light transmittance tends not to decrease, which is preferable.

  Examples of the crosslinking agent (H) include methylol compounds.

  Examples of the methylol compound include alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins. Here, as the alkoxymethylated melamine resin, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, etc., as alkoxymethylated urea resin, methoxymethylated urea resin Ethoxymethylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin, and the like. The above crosslinking agents can be used alone or in combination of two or more.

  When it contains a crosslinking agent (H), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 0.01-15 mass%. When the content of the crosslinking agent is within the above range, the visible light transmittance of the obtained film is increased, and the performance as a cured resin pattern is improved, which is preferable.

  Examples of the polymerizable monomer (I) include a polymerizable monomer that can be radically polymerized by heating, a polymerizable monomer that can be cationically polymerized, and a polymerizable monomer that can preferably be cationically polymerized. .

  Examples of the polymerizable monomer capable of radical polymerization include compounds having a polymerizable carbon-carbon unsaturated bond, which may be a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, or 3 It may be a polyfunctional polymerizable monomer such as a polymerizable monomer having higher functionality.

  Examples of the monofunctional polymerizable monomer include nonylphenyl carbitol acrylate, nonylphenyl carbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-ethylhexyl carbitol acrylate, Examples include 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and N-vinyl pyrrolidone.

  Examples of the bifunctional polymerizable monomer include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, and neopentyl glycol dimethacrylate. , Triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, and the like.

  Examples of the tri- or higher functional polymerizable monomer include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate. Pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Among the above polymerizable monomers, bifunctional or trifunctional or higher polymerizable monomers are preferably used. Specifically, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like are preferable, and dipentaerythritol hexaacrylate is more preferable. Further, a bifunctional or trifunctional or higher functional polymerizable monomer and a monofunctional polymerizable monomer may be used in combination.

  Examples of the polymerizable monomer capable of cationic polymerization include polymerizable monomers having a cationic polymerizable functional group such as a vinyl ether group, a propenyl ether group, an epoxy group, and an oxetanyl group. Specifically, as a compound containing a vinyl ether group Examples thereof include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether and the like. As a compound containing a propenyl ether group, 4- (1-propenyloxymethyl)- 1,3-dioxolan-2-one and the like, and as a compound containing an epoxy group, a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy Si resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, oxetanyl group-containing compounds such as bis {3- (3-ethyloxetanyl) methyl} ether, 1,4-bis {3- (3-ethyloxetanyl) methoxy} benzene, 1,4-bis {3- (3-ethyloxetanyl) methoxy} methylbenzene, 1,4-bis {3- (3-ethyloxetanyl) methoxy} cyclohexane, 1,4 -Bis {3- (3-ethyloxetanyl) methoxy} methylcyclohexane, 3- (3-ethyloxetanyl) methylated novolak resin, and the like. These may be used alone or in combination of two or more.

  When it contains said polymerizable monomer (I), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 0.1-20 mass%.

Examples of the silane coupling agent (J) include methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, 3-chloropropyl-trimethoxysilane, 3-chloropropylmethyl-dichlorosilane, 3-chloropropylmethyl-dimethoxysilane, 3-chloropropylmethyl-diethoxysilane, 3-glycidoxypropyl-trimethoxysilane, 3- Glycidoxypropyl-triethoxysilane, 3-glycidoxypropylmethyl-dimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-methacryloyloxypropyl-trimethoxysilane, 3-methacryloyl Xylpropylmethyl-dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, N-2- (N-vinylbenzylaminoethyl) -3-aminopropyl-trimethoxysilane hydrochloride, hexamethyldi Silazane, diaminosilane, triaminopropyl-trimethoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropylmethyl-diethoxysilane, 3-aminopropyl-tris (2- Methoxyethoxyethoxy) silane, 3- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -3-aminopropylmethyl-dimethoxysilane, 3-ureidopropyl-trimethoxysilane 3-ureidopropyl Liethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxysilane, N-aminoethyl-3-aminopropylmethyl-dimethoxysilane, N-methyl-3-aminopropyl-trimethoxysilane, N-phenyl-3 -Aminopropyl-trimethoxysilane and the like. Among these, a silane coupling agent having an epoxy group in its structure is preferable. Examples of the silane coupling agent having an epoxy group in the structure include 3-glycidoxypropyl-trimethoxysilane, 3-glycidoxypropyl-triethoxysilane, and 3-glycidoxypropylmethyl-dimethoxy. Silane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, and more preferably, a silane cup having an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane A ring agent is mentioned.
When the silane coupling agent (J) is contained, the content thereof is a mass fraction with respect to the radiation-sensitive resin composition, preferably 0.01 to 10% by mass, more preferably 0.1 to 0.1% by mass. It is 2 mass%, Most preferably, it is 0.2-1 mass%. When the content of the silane coupling agent is in the above range, when the cured resin pattern is formed using the radiation-sensitive resin composition of the present invention, the visible light transmittance of the cured resin pattern is improved, so that it is transparent. In addition to the tendency to improve the adhesion, the adhesion between the cured resin pattern and the substrate is improved, which is preferable.

  The radiation-sensitive resin composition of the present invention may further comprise other components as necessary, for example, an antioxidant, a dissolution inhibitor, a sensitizer, an ultraviolet absorber, a light stabilizer, an adhesion improver, an electron donor. Various additives can also be contained.

  The radiation-sensitive resin composition of the present invention includes, for example, a solution obtained by dissolving a curable alkali-soluble resin (A) in a solvent (C), a solution obtained by dissolving a quinonediazide compound (B) in a solvent (C), silicone It can be prepared by mixing the system surfactant (D). Further, after mixing, a solvent (C) and, if necessary, a fluorine-based surfactant (E) may be added. Further, after mixing the solution, it is preferable to remove insoluble matter by filtration, and for example, it is preferable to filter using a filter having a pore size of 3 μm or less, preferably about 0.1 to 2 μm. The solvent used for each component may be the same or different as long as it is compatible.

  In order to form a transparent cured resin pattern using the radiation-sensitive resin composition of the present invention, for example, a layer made of the radiation-sensitive resin composition of the present invention is formed on a substrate, and the above-described layer is formed through a mask. The layer may be exposed after being exposed to radiation and then developed.

  Examples of the substrate include a transparent glass plate. A circuit such as a TFT or a CCD, a color filter, or the like may be formed on the substrate.

It is preferable to apply | coat the layer which consists of a radiation sensitive resin composition using the coating device which has a slit-shaped nozzle. Examples of the coating apparatus having a slit nozzle include a slit coater, a die coater, and a curtain flow coater.
After application, heating or drying after drying (prebaking) or drying under reduced pressure removes part or all of the volatile components such as the solvent, thereby forming a radiation-sensitive resin composition layer having a reduced solvent content. . Moreover, the thickness of this radiation sensitive resin composition layer is about 1.5 micrometers-about 5 micrometers, for example.

  Next, the radiation-sensitive resin composition layer is irradiated with radiation through a mask. The mask pattern is appropriately selected according to the target pattern of the cured resin pattern. As the radiation, for example, light rays such as g-line and i-line are used. The radiation is preferably irradiated using, for example, a mask aligner or a stepper so that it can be irradiated in parallel over the entire surface of the radiation-sensitive resin composition layer.

  Development is performed after the exposure. Development can be performed by, for example, a method in which the radiation-sensitive resin composition layer after exposure is brought into contact with a developer. As the developer, an alkaline aqueous solution is used as usual. As an alkaline aqueous solution, an aqueous solution of an alkaline compound is used as usual, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

  Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, Examples include potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

  Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. It is done. The above alkaline compounds are used alone or in combination of two or more. The developer usually contains 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass of the alkaline compound per 100 parts by mass of the developer.

  The developer may contain a surfactant. Examples of the surfactant include nonionic surfactants, cationic surfactants, and anionic surfactants.

  Nonionic surfactants include, for example, polyoxyethylene derivatives such as polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene derivatives, and the like. Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

  Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and quaternary ammonium salts such as lauryltrimethylammonium chloride.

  Examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, kill sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and dodecylnaphthalene. Examples thereof include alkyl aryl sulfonates such as sodium sulfonate. These surfactants are used alone or in combination of two or more.

  Further, the developer may contain an organic solvent. Examples of the organic solvent include water-soluble organic solvents such as methanol and ethanol.

  In order to bring the radiation-sensitive resin composition layer into contact with the developer, for example, the substrate on which the radiation-sensitive resin composition layer is formed may be immersed in the developer. Of the radiation-sensitive resin composition layer, the radiation-irradiated area irradiated with radiation in the previous exposure is dissolved in the developer by the development, and the radiation-unirradiated area not irradiated with radiation is dissolved in the developer. Leave behind and form a pattern.

  Since the radiation sensitive resin composition of the present invention contains the quinonediazide compound (B), even if the time for contacting the radiation sensitive resin composition layer with the developer is short, the radiation irradiation region is easily dissolved, Removed. Moreover, since it contains a quinonediazide compound (B), even if the time during which the radiation-sensitive resin composition layer is brought into contact with the developer is increased, the radiation non-irradiated region does not dissolve and disappear in the developer.

  After development, it is usually washed with water and dried. After drying, the whole or part of the obtained pattern is irradiated with radiation. The radiation irradiated here is preferably ultraviolet rays or deep ultraviolet rays, and the irradiation amount per unit area is preferably larger than the irradiation amount in the previous exposure.

  It is preferable that the pattern thus formed is further subjected to heat treatment (post-baking) from the viewpoint of improving the heat resistance and solvent resistance of the cured resin pattern. Heating is performed by a method in which the substrate after irradiation with radiation over the entire surface is heated by a heating device such as a hot plate or a clean oven. The heating temperature is usually 150 ° C to 250 ° C, preferably 180 ° C to 240 ° C. The heating time is usually 5 minutes to 120 minutes, preferably 15 minutes to 90 minutes. By heating, the pattern is cured and a cured resin pattern is formed.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the radiation sensitive resin composition with favorable wettability with respect to a stainless steel base material. Therefore, the radiation sensitive resin composition of this invention can improve the applicability | paintability by the coating device which has a slit-shaped nozzle.
The cured resin pattern thus formed is obtained by curing the radiation-sensitive resin composition of the present invention. For example, the cured resin pattern is cured to constitute a TFT substrate, an insulating film for an organic EL element, a protective film for a CCD, or the like. Useful as a resin pattern.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Synthesis 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 as a solvent, 146 g of ethyl 3-ethoxypropionate, 2.2 g of azobisisobutyronitrile as a polymerization initiator, and the following The monomer was charged, and the reaction was carried out by stirring for 3 hours while maintaining the internal temperature at 100 to 110 ° C. under a nitrogen stream to obtain a solution containing the resin A1. This resin A1 had a weight average molecular weight in terms of polystyrene of 7,900.

Methacrylic acid 10.8g
3-ethyl-3-methacryloxymethyloxetane 36.9 g
N-cyclohexylmaleimide 31.4g

Here, the polystyrene equivalent weight average molecular weight (Mw) was measured using the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6 mass% (solvent: THF)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Example of measuring HLB value of surfactant Surfactant / 0.5 g was dissolved in ethanol / 5 ml. A 2% aqueous phenol solution was added dropwise, and the amount of addition (ml) when the solution became cloudy was designated as the cloud number A. The HLB value was calculated by HLB = 0.89 × (clouding number A) +1.11. (See Ichiro Nishi: Surfactant Handbook / Sangyo Tosho Co., Ltd.)

Example 1
After mixing the following components at 23 ° C., SH8400 (HLB value = 8.0, polyether-modified silicone oil; Shin-Etsu Silicone Co., Ltd.) as a silicone surfactant (D1) component having an HLB value of 1 to 9 SH3746 (HLB value = 14.0, polyether-modified silicone oil; manufactured by Shin-Etsu Silicone Co., Ltd.) as a silicone surfactant (D2) component having an HLB value of more than 9 and 200 ppm of the total composition. 100 ppm of the whole product was added.
The mixture was filtered under pressure through a cartridge filter made of polytetrafluoroethylene having a pore diameter of 1.0 μm to obtain a radiation sensitive resin composition 1 as a filtrate. The content of the solvent (C) in the obtained radiation-sensitive resin composition is 72.5%, and the solvent composition ratio is ethyl lactate: ethyl 3-ethoxypropionate: butyl acetate: propylene glycol monomethyl ether = 16: 60: 20: 4.

333 parts by mass of solution containing resin A1 (solid content conversion: 100 parts by mass)
Compound represented by formula (2) 20 parts by mass Adekaoptomer SP-172 (photocation polymerization catalyst; manufactured by Asahi Denka Kogyo Co., Ltd.) 2 parts by mass Sun-Aid SI-100L (thermal cation polymerization catalyst; Sanshin Chemical Industry ( 2 parts by weight KBM-303 (silane coupling agent; β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by weight ethyl lactate 8.1 parts by weight 3- Ethyl ethoxypropionate 16.2 parts by mass Butyl acetate 67 parts by mass Propylene glycol monomethyl ether 13.4 parts

(Wherein, ^{Q 4} represents a substituent represented by the formula (1-1).)

Comparative Example 1
A radiation sensitive resin composition 2 was obtained in the same manner as in Example 1 except that SH3746 was not used.
Comparative Example 2
The radiation-sensitive resin composition 3 was obtained in the same manner as in Example 1 except that the SH8400 content was 300 ppm with respect to the radiation-sensitive resin composition, and SH3746 was not used.

<Example of flowability measurement>
Each of the radiation-sensitive resin compositions obtained in the above Examples and Comparative Examples is a horizontally installed SUS630 plate (size: 100 mm × 200 mm × 10 mm, surface roughness: equivalent to JIS B0659 12.5-S). 10 μl was dropped from a Pasteur pipette (5-3 / 4 ″; manufactured by Fischer) onto the unidirectional hairline finish), and immediately after the dropping, the SUS630 plate was set up in the vertical direction. It was made to become perpendicular | vertical with respect to the dripping direction of a liquid.
The distance that the radiation-sensitive resin composition flowed until the composition stopped flowing was measured and taken as the flow distance. The measurement results are shown in Table 1.
Moreover, when the liquid flowed, the liquid stayed on the hairline for 10 seconds or more and the flow of the liquid stopped temporarily was determined to be flowability x, and the liquid smoothly flowed without stopping was determined to be flowability ○. At the same time, the one having good flowability can be said to have good wettability of the stainless steel substrate, which is a problem to be solved.
The determination results are shown in Table 1.

The radiation-sensitive resin composition of the present invention comprises a TFT insulating film and a photo spacer used in a TFT type liquid crystal display device and an organic EL display device, a diffuse reflector used in a reflective TFT substrate, a liquid crystal alignment protrusion, It can be used to form a transparent cured resin pattern such as an organic EL insulating film and a CCD protective film.

Claims (8)

  A radiation-sensitive resin composition containing a curable alkali-soluble resin (A), a quinonediazide compound (B), a solvent (C), and a silicone surfactant (D), wherein the silicone surfactant (D) is A radiation-sensitive resin composition containing a silicone surfactant (D1) having an HLB value of 1 or more and 9 or less and a silicone surfactant (D2) having an HLB value of more than 9.   The radiation sensitive resin composition according to claim 1, wherein the surfactant (D1) is a polyalkylene glycol-modified silicone.   The radiation sensitive resin composition according to claim 1 or 2, wherein the surfactant (D2) is a polyalkylene glycol-modified silicone.   The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the content of the silicone-based surfactant (D) is 1 to 1000 ppm by mass with respect to the radiation-sensitive resin composition.   The radiation sensitive composition according to any one of claims 1 to 4, wherein the content of the surfactant (D1) is 50 to 90% by mass with respect to the total amount of the silicone surfactant (D). Resin composition.   The radiation-sensitive resin composition according to claim 1, which is applied to a coating apparatus having a slit-like nozzle.   The transparent cured resin pattern formed with the radiation sensitive resin composition in any one of Claims 1-6. A display device comprising the transparent cured resin pattern according to claim 7.