JP2005181353A - Radiation sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition having high planarization performance, high sensitivity and high solvent resistance and ensuring high productivity. <P>SOLUTION: In the radiation sensitive resin composition comprising an alkali-soluble resin (A) having curability, a quinonediazido compound (B) and a solvent (C), ≥40% by mass of the solvent (C) is ethyl lactate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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. It is useful as a material for forming a transparent cured resin pattern including a plate, an organic EL insulating film, a protective film of a solid-state imaging device (hereinafter, sometimes referred to as CCD), and the like (for example, Patent Document 1) reference.). 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, in order to obtain a brighter display image, high solvent resistance is also required in terms of high transmittance for visible light and productivity of the TFT substrate (for example, see Patent Document 3). Furthermore, the radiation sensitive resin composition is required to have high sensitivity to radiation used for pattern formation in terms of productivity.

JP-A-9-152625, page 2, left column, lines 22-25 Japanese Patent Laid-Open No. 9-244409, page 1, left column, lines 1 to 3 Japanese Patent Laid-Open No. 9-152625, page 4, right column, lines 30-41

  An object of the present invention is to provide a radiation-sensitive resin composition having high flattening performance, high sensitivity and high solvent resistance and high productivity.

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 provides a radiation-sensitive resin composition containing a curable alkali-soluble resin (A), a quinonediazide compound (B), and a solvent (C). The above is a radiation-sensitive resin composition that is ethyl lactate, a transparent cured resin pattern formed from the radiation-sensitive resin composition, and the radiation-sensitive resin composition are applied and irradiated through a mask. Then, development is performed to form a predetermined pattern, and then the whole surface is irradiated with radiation, and a method for producing a transparent cured resin pattern is provided.

The radiation-sensitive resin composition of the present invention has high performance for flattening the level difference of the base, and has higher sensitivity during pattern formation. Moreover, the residual film rate and solvent resistance of the coating film formed using the radiation sensitive resin composition of this invention are favorable.
Therefore, by using the radiation sensitive resin composition of the present invention, a transparent cured resin pattern having a high yield can be formed with high productivity.

  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 structural unit (a1) derived from the unsaturated carboxylic acid include unsaturated monomers having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid. Examples thereof include carboxylic acid, and specific examples include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid.

Examples of the structural unit (a2) derived from the unsaturated compound having a curable group (excluding unsaturated carboxylic acid) 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 ( (Meth) 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 Epoxy group-containing unsaturated compounds such as 3-vinylcyclohexene oxide and 4-vinylcyclohexene oxide;
3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl Oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3- Methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane, 2-pentafluoroethyl-3- Unsaturation containing oxetanyl group such as (meth) acryloxyethyl oxetane And preferably include 3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 2- Phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (Meth) acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl Oxetane, 2-pentafluoroethyl-3- (meth) acryloxyethyl oxe It includes oxetanyl group-containing unsaturated compounds such emissions, and more preferably, 3-ethyl-3-methacryloxy methyl oxetane and the like. When a radiation-sensitive resin composition is prepared using an alkali-soluble resin containing an oxetanyl group-containing unsaturated compound, it is preferable that storage stability is expected to be improved.

The copolymer in the radiation-sensitive resin composition of the present invention 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 vinyl compound, and cyanide. It may contain at least one structural unit (a3) selected from the group consisting of a structural unit (a33) derived from a vinyl compound and a structural unit (a34) derived from an N-substituted maleimide compound.
Examples of the structural unit (a31) derived from the carboxylic acid ester having an olefinic double bond include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl. (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Unsaturated carboxylic esters such as phenyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate;
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 structural unit (a32) derived from the aromatic vinyl compound include structural units derived from a polymerizable carbon-carbon unsaturated bond. Specific examples include styrene and α-methylstyrene. And aromatic vinyl compounds such as vinyltoluene.
Examples of the structural unit (a33) derived from the vinyl cyanide compound include vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloro (meth) acrylonitrile.
Examples of the N-substituted maleimide compound 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) male Such as soil and the like.
These structural units can be used alone or in combination of two or more.

The copolymer comprising 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 copolymer (A1) is usually used in the range of 5 to 50 mol%, preferably 15 to 40 mol%, based on the entire constituent units of the copolymer, and (a2) is used in the entire constituent units of the copolymer. On the other hand, it is usually used in the range of 5 to 95 mol%, preferably 15 to 85 mol%.
In the above-mentioned copolymer, it is preferable that the constituent ratios of (a1) and (a2) are in the above-mentioned range because it tends to exhibit high curability while having an appropriate dissolution rate in the developer.

When the copolymer (A) in the present invention contains the structural unit (a3), the content is usually 0.01 to 90 moles, with the total mole ratio of all the structural components of (A) being 100 mole%. %, Preferably 0.01 to 70 mol%.
Examples of the copolymer (A) in the present invention include 3-ethyl-3-methacryloxymethyl oxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl 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-methacryloxymethyl oxetane / Meta Rylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / benzyl acrylate Polymer, 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 / t-butyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxy Tan / methacrylic acid / phenylmaleimide copolymer, and 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / cyclohexyl maleimide copolymer.

The copolymer (A) in the radiation-sensitive resin composition of the present invention has a weight average molecular weight determined by gel permeation chromatography based on polystyrene, usually from 2,000 to 100,000, preferably 2, It is used in the range of 000 to 50,000, more preferably 3,000 to 20,000. When the weight average molecular weight of the copolymer (A) is in the range of 2,000 to 100,000, a high development speed tends to be obtained while maintaining the remaining film ratio during development, which is preferable.
The content of the copolymer (A) containing (a1) and (a2) in the radiation-sensitive resin composition of the present invention is usually 50 to 50% by mass with respect to the solid content of the radiation-sensitive resin composition. 98%, preferably 60-95%.

  Examples of the quinonediazide compound (B) in the radiation-sensitive resin composition of the present invention include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, Examples include 1,2-naphthoquinonediazide sulfonic 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, 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, 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, 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-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 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-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane- 1,2-naphthoquinonediazide-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-naphth Toquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl- And 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as 7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester.

  The quinonediazide compound (B) is used alone or in combination of two or more. The content of the quinonediazide compound (B) in the present invention is usually 2 to 50%, preferably 5 to 40% by mass fraction with respect to the solid content of the radiation-sensitive resin composition. When the content of the quinonediazide compound is 2 to 50%, the difference in the dissolution rate between the unexposed area and the exposed area tends to be high, so that the development residual film ratio tends to be kept high, which is preferable.

  The solvent (C) contained in the radiation-sensitive resin composition of the present invention is a mass fraction with respect to the total amount of solvent, and 40% or more is ethyl lactate. If it is less than 40%, the solubility in the developing solution of the portion to be removed by development tends to be lowered, so that the sensitivity tends to be lowered, and the effect of improving the flattening performance tends to be reduced, which is not preferable.

  In addition, when the solvent (C) contains a solvent having a boiling point of 180 ° C. or higher and 240 ° C. or lower in a mass fraction of 0.1% or more and 20% or less, the planarization performance tends to be further improved.

Examples of the solvent having a boiling point of 180 ° C. or higher and 240 ° C. or lower include butyl lactate, γ-butyrolactone, dimethyl sulfoxide, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, isophorone, 3-methyl-3-methoxybutyl acetate, and N-methylpyrrolidone. 1,3-dimethyl-2-imidazolidinone and the like.
Moreover, as a solvent which may be mixed with ethyl lactate, a compound known so far as an organic solvent for the radiation-sensitive resin composition can be used.
Examples of the solvent that may be mixed include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl 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;
Aromatic hydrocarbons such as benzene, toluene, xylene;
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;
Examples include esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 2-hydroxyisobutanoate, butyl acetate, amyl acetate, and methyl pyruvate.
As for the usage-amount of the said solvent (C), the ratio of a solvent (C) is a mass fraction with respect to the radiation sensitive resin composition whole quantity, and 50-95% is preferable normally, More preferably, it is 70-90%. . When the amount of the solvent (C) used is 50 to 95%, a film with good flatness tends to be formed, which is preferable.

  The radiation sensitive resin composition of this invention can contain a polymerization initiator (D), a polyhydric phenol compound (E), a crosslinking agent (F), and a polymerizable monomer (G) as other components.

Examples of the polymerization initiator (D) that can be used in the present invention 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 (pt-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 (pt-butylphenyl) sulfonium, tris (p-cyanopheny ) 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 (t-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) ) Sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitrooctyloxy) s Examples thereof include phonium, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, dimethyl (tris (trichloromethyl) methyl) sulfonium, and preferably bis (p-tolyl) iodonium, (P-Tolyl) (p-isopropylphenyl) iodonium, bis (pt-butylphenyl) iodonium, triphenylsulfonium, tris (pt-butylphenyl) sulfonium and the like can be mentioned.
Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroalcinate, 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 (B), diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (pt-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 hexafluorophosphate Fate, methyl naphthyl 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 (pt-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethyl naphthyl sulfo Um hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate , Dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (t-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexaful Orophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium Hexafluorophosphate, diphenyliodonium hexafluo Arsinate, bis (p-tolyl) iodonium hexafluoroarsinate, bis (pt-butylphenyl) iodonium hexafluoroarsinate, bis (p-octylphenyl) iodonium hexafluoroalcinate, bis (p-octadecylphenyl) iodonium Hexafluoroarsinate, bis (p-octyloxyphenyl) iodonium hexafluoroarsinate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsinate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroalcinate, (p- Tolyl) (p-isopropylphenyl) iodonium hexafluoroarsinate, methyl naphthyl iodonium hexafluoroarsinate, ethyl naphthy Iodonium hexafluoroarsinate, triphenylsulfonium hexafluoroarsinate, tris (p-tolyl) sulfonium hexafluoroarsinate, tris (p-isopropylphenyl) sulfonium hexafluoroalcinate, tris (2,6-dimethylphenyl) sulfonium hexa Fluoroalcinate, tris (pt-butylphenyl) sulfonium hexafluoroalcinate, tris (p-cyanophenyl) sulfonium hexafluoroalcinate, tris (p-chlorophenyl) sulfonium hexafluoroalcinate, dimethyl naphthylsulfonium hexafluoroarsi , Diethyl naphthylsulfonium hexafluoroarsinate, dimethyl (methoxy) sulfonium hexafluoro Alcinate, dimethyl (ethoxy) sulfonium hexafluoroarsinate, dimethyl (propoxy) sulfonium hexafluoroarsinate, dimethyl (butoxy) sulfonium hexafluoroarsinate, dimethyl (octyloxy) sulfonium hexafluoroarsinate, dimethyl (octadecanoxy) sulfonium hexa Fluoroalcinate, dimethyl (isopropoxy) sulfonium hexafluoroalcinate, dimethyl (t-butoxy) sulfonium hexafluoroalcinate, dimethyl (cyclopentyloxy) sulfonium hexafluoroalcinate, dimethyl (cyclohexyloxy) sulfonium hexafluoroalcinate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarushi Dimethyl (2-chloroethoxy) sulfonium hexafluoroarsinate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsinate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsinate, dimethyl (8-nitrooctyloxy) Sulfonium hexafluoroarsinate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsinate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroalcinate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroalcinate Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, S (pt-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, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, Methyl naphthyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenyl sulfate Honium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris (2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p -T-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate, diethylnaphthylsulfonium hexafluoro Antimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) Honium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (Isopropoxy) sulfonium hexafluoroantimonate, dimethyl (t-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium Hexafluoroantimonate, dimethyl 2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate Dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate, diphenyliodonium tetrakis ( Pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (penta Fluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (penta) Fluorophenyl) 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 (pentafluoropheny ) Borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethyl naphthyl iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium 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 (pt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) ) Borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, Lis (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaphthylsulfonium 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) borate, dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) ) Borate, dimethyl (octadecanoxy) sulfo Nium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (t-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 tetrakis (pentafluorophenyl) borate, dimethyl (3- Bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl Ru (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) Examples include borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) borate, and preferably bis (p-tolyl) iodonium. Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (pt Butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (pt-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropyl) Phenyl) iodonium hexafluoroarsinate, bis (pt-butylphenyl) iodonium hexafluoroarsinate, triphenylsulfonium hexafluoroalcinate, tris (pt-butylphenyl) sulfonium hexafluoroalcinate, bis (p- Tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p -T-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (P-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) ) Sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p- Ril) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimony Bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (penta Fluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) sulfonium tetrakis Pentafluorophenyl) borate.

  The content of the polymerization initiator (D) that can be used in the radiation-sensitive resin composition of the present invention is usually 0.01 to 10% by mass fraction with respect to the solid content of the radiation-sensitive resin composition. Preferably, it is 0.1 to 5%. When the content of the polymerization initiator (D) is in the above range, the curing speed at the time of thermosetting is increased, thereby suppressing a decrease in resolution at the time of thermosetting, and further improving the solvent resistance of the transparent cured resin pattern. This is preferable.

  Examples of the polyhydric phenol compound (E) that can be used in the present invention include compounds having two or more phenolic hydroxyl groups in the molecule. 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.

  Examples of the polyhydric phenol compound (E) include a polymer having at least hydroxystyrene as a raw material monomer. Specific examples of the polyhydric phenol compound (E) include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer, hydroxystyrene / alkoxystyrene copolymer. Examples thereof include a resin obtained by polymerizing hydroxystyrene such as a polymer. Further, 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 Can be mentioned.

  The addition amount of the polyhydric phenol compound (E) is usually 40% or less, preferably 25% or less by mass fraction with respect to the solid content of the radiation-sensitive resin composition. When the amount of the polyhydric phenol compound (E) is 40% or less, the resolution is improved and the visible light transmittance tends to reduce the decrease, which is preferable.

  Examples of the crosslinking agent (F) that can be used in the present invention 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.

  In the radiation sensitive resin composition of this invention, when using a crosslinking agent (F), it is preferable that the addition amount is 15% or less by mass fraction with respect to solid content of a radiation sensitive resin composition. . When the content of the crosslinking agent is 15% or less, the visible light transmittance of the obtained film is increased, and the performance as a transparent cured resin pattern is preferably improved.

  Examples of the polymerizable monomer (G) that can be used in the present invention include a polymerizable monomer that can be radically polymerized by heating, a polymerizable monomer that can be cationically polymerized, and a polymer that can preferably be cationically polymerized. Ionic monomer.

  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, and 2-ethylhexyl carbitol. Examples include acrylate, 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and N-vinylpyrrolidone.

  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. Examples include dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, and 3-methylpentanediol dimethacrylate.

  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. Examples include pentaacrylate, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. 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 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, and specifically include a vinyl ether group. Examples of the compound include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, and the like. As the 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, bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cyclic fat Epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins, compounds containing oxetanyl groups include 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.

  When using the said polymerizable monomer (G), this is used individually or in combination of 2 or more types, respectively, The addition amount of the said polymerizable monomer in the radiation sensitive resin composition of this invention is radiation sensitive. The mass fraction is preferably 20% or less with respect to the solid content of the resin composition.

  The radiation-sensitive resin composition of the present invention may further comprise other components as necessary, for example, surfactants, antioxidants, dissolution inhibitors, sensitizers, ultraviolet absorbers, light stabilizers, and adhesion improvers. Various additives such as an electron donor can also be contained.

  The radiation-sensitive resin composition of the present invention is prepared by mixing, for example, a solution obtained by dissolving a curable alkali-soluble resin (A) in a solvent (C) and a solution obtained by dissolving a quinonediazide compound (B) in a solvent (C). Can be prepared. Moreover, you may add a solvent (C) after mixing. Furthermore, after mixing the solution, it is preferable to remove solid matter by filtration, and for example, it is preferable to filter using a filter having a pore diameter of 3 μm or less, preferably 0.1 μm or more and 2 μm or less. 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 (1) made of the radiation sensitive resin composition of the present invention is formed on a substrate (2) ( 1 (a)), the layer (1) is exposed to radiation (4) through a positive mask (3), exposed (FIG. 1 (b)), and then developed (FIG. 1 (c)). ).

  Examples of the substrate (2) include resin substrates such as a transparent glass plate and a silicon wafer, as well as a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. A circuit such as a TFT or a CCD, a color filter, or the like may be formed on the substrate.

  The layer (1) comprising the radiation-sensitive resin composition can be formed by a usual method, for example, a method of applying the radiation-sensitive resin composition of the present invention on the substrate (2). The coating is performed by, for example, spin coating, casting coating method, roll coating method, slit & spin coating, slit coating method or the like. After application, heat-drying (pre-baking) or vacuum-drying after heating to volatilize volatile components such as the solvent, the radiation-sensitive resin composition layer (1) having a reduced solvent content is formed. The said radiation sensitive resin composition layer (1) hardly contains a volatile component. 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 (1) is irradiated with radiation (4) through a positive mask (3). The pattern of the positive mask (3) is appropriately selected according to the target pattern of the transparent cured resin pattern. As the radiation, for example, rays such as g-line and i-line are used. The radiation is preferably irradiated using, for example, a mask aligner or a stepper (not shown) 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 of bringing the radiation-sensitive resin composition layer (1) after exposure 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, and silicic acid. Examples include sodium, 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. Is mentioned. The 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.

  Examples of the nonionic surfactant include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, and polyoxyethylene alkyl aryl ether, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters. , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

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

  Examples of the anionic surfactant 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, Examples thereof include alkyl aryl sulfonates such as sodium dodecyl naphthalene 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.

  Examples of the method for bringing the radiation-sensitive resin composition layer (1) into contact with the developer include a paddle method, a dipping method, and a shower method. Of the radiation-sensitive resin composition layer (1), the radiation-irradiated region (12) irradiated with radiation in the previous exposure is dissolved in the developer by the development, and the radiation-unirradiated region (not irradiated with radiation) ( 11) remains without dissolving in the developer to form pattern (5).

  Since the radiation sensitive resin composition of this invention contains a quinonediazide compound (B), even if the time which makes a radiation sensitive resin composition layer (1) contact with a developing solution is short, a radiation irradiation area | region (11) is. Easily dissolves and is removed. Moreover, since it contains a quinonediazide compound (B), even if the time during which the radiation-sensitive resin composition layer (1) is brought into contact with the developer becomes long, the radiation non-irradiated region (12) dissolves in the developer and disappears. There is nothing to do.

  After development, it is usually washed with water and dried. After drying, the obtained pattern (5) is further irradiated with radiation. The radiation to be irradiated here is preferably ultraviolet rays or deep ultraviolet rays, and the irradiation amount per unit area is usually preferably larger than the irradiation amount in the previous exposure.

  The pattern (5) thus formed is preferably further heat-treated (post-baked) from the viewpoint of improving the heat resistance and solvent resistance of the transparent 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., and the heating time is usually 5 minutes to 120 minutes, preferably 15 minutes to 90 minutes. By heating, the pattern is cured and a transparent cured resin pattern is formed.

  The flattening rate of the pattern can be obtained using equation (2) from h1 (step difference of the stepped substrate) and h2 (step difference after application of the radiation-sensitive resin composition) shown in FIG.

  Planarization rate (%) = (1− (h2) / (h1)) × 100 Formula (2)

  In the pattern formed using the radiation sensitive resin composition of the present invention, the flattening ratio obtained by the formula (2) is preferably 36% or more, more preferably 40% or more, and 45%. The above is particularly preferable. When the flattening ratio obtained by the formula (2) is in the above range, it is preferable that a step is hardly generated in the alignment film formed on the pattern, and thereby the disorder of the liquid crystal is expected to be reduced.

  The transparent cured resin pattern thus formed is formed by curing the radiation-sensitive resin composition of the present invention, and constitutes, for example, a TFT substrate, an organic EL element insulating film, a CCD protective film, and the like. It is useful as a transparent cured 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
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A1. This resin A1 had a weight average molecular weight in terms of polystyrene of 15,000.

Methacrylic acid 7.3g
Cyclohexyl methacrylate 12.5g
17.8 g of 3-ethyl-3-methacryloxymethyloxetane
Ethyl lactate 87.6g
Azobisisobutyronitrile 0.9g

Synthesis example 2
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A2. The polystyrene equivalent weight average molecular weight of this resin A2 was 15,000.

Methacrylic acid 7.3g
Cyclohexyl methacrylate 12.5g
17.8 g of 3-ethyl-3-methacryloxymethyloxetane
Propylene glycol methyl ether acetate 87.6g
Azobisisobutyronitrile 0.9g

Synthesis example 3
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A3. This resin A3 had a polystyrene equivalent weight average molecular weight of 15,000.
6.8 g of methacrylic acid
13.7 g of N-phenylmaleimide
17.8 g of 3-ethyl-3-methacryloxymethyloxetane
89.5g of ethyl lactate
Azobisisobutyronitrile 0.9g

Synthesis example 4
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A4. This resin A4 had a polystyrene equivalent weight average molecular weight of 15,000.
6.8 g of methacrylic acid
14.2 g of N-cyclohexylmaleimide
17.8 g of 3-ethyl-3-methacryloxymethyloxetane
Ethyl lactate 90.7g
Azobisisobutyronitrile 0.9g

In addition, the measurement conditions of said polystyrene conversion weight average molecular weight are as follows.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL, TSK-GELG4000HXL in-line column temperature; 40 ° C
Mobile phase solvent; tetrahydrofuran flow rate; 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6% by mass (solvent: tetrahydrofuran)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Example 1
Resin A1 (100 parts by mass),
A compound represented by the formula (1) (22 parts by mass),

（式中、Ｑ⁴は、式（１−１）で示される置換基を示す。）

(In the formula, Q ⁴ represents a substituent represented by the formula (1-1).)

Formula (1-1)

(P-Tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate [Rhodorsil Photoinitiator 2074 (manufactured by Rhodia)] (2 parts by mass) and ethyl lactate (392 parts by mass) at 23 ° C. A radiation sensitive resin composition was obtained as a filtrate by pressure filtration through a 1.0 μm polytetrafluoroethylene cartridge filter.

The radiation-sensitive resin composition obtained above is spin-coated on a 4-inch silicon wafer (2), and heated (prebaked) at 100 ° C. for 2 minutes using a hot plate, the radiation-sensitive resin composition layer (1 ) And the film thickness was measured using a film thickness meter [Lambda Ace (Dainippon Screen Mfg. Co., Ltd.)], and it was 2.6 μm (FIG. 1 (a)).
Thereafter, an i-line stepper [NSR-1755i7A (NA = 0.5) (manufactured by Nikon Corporation)] was used for the obtained radiation-sensitive resin composition layer (1) through a positive mask (3). Radiation (4) was irradiated and exposed (FIG. 1 (b)). As the positive mask (3), a positive mask for forming a contact hole pattern with a line width of 3 μm in a transparent cured resin pattern with an interval of 9 μm was used.

After exposure, after developing by immersing in an aqueous solution of tetramethylammonium hydroxide at 23 ° C. (containing 0.4 parts by mass of tetramethylammonium hydroxide in 100 parts by mass), it was washed with ultrapure water, Dried. In the developed pattern, the effective sensitivity was 135 mJ / cm ^{2 when} the exposure amount in the mask exposure in which the diameter of the contact hole was 3 μm was defined as the effective sensitivity. After drying, the whole surface was irradiated with radiation using a DUV lamp [UXM-501MD (manufactured by Ushio Co., Ltd.)] (intensity of 300 mJ / cm ^{2 based on a} wavelength of 313 nm), and 30 ° C. at 220 ° C. in a clean oven. By heating for a minute, a transparent cured resin pattern (5) was formed (FIG. 1 (c)).
It was 2.0 micrometers when the thickness (T1) of the obtained transparent cured resin pattern (5) was measured using the film thickness meter.

The visible light transmittance was determined by forming a transparent cured resin film on the transparent glass substrate [# 1737 (manufactured by Corning)] by the above method except that the exposure step using a stepper was not performed, and the microspectrophotometer [OSP-200 ( Olympus Optical Co., Ltd.)]. The film thickness was measured with a film thickness meter [DEKTAK3 (manufactured by ULVAC)]. The average light transmittance at a wavelength of 400 to 750 nm per 1 μm of the obtained transparent cured resin film was as high as 99.4%, and no coloring was observed. Further, the substrate on which the transparent cured resin pattern was formed was immersed in methyl ethyl ketone or N-methylpyrrolidone (23 ° C.) for 30 minutes and subjected to a solvent resistance test. As a result, no change was observed before and after the immersion.
As for the flattening rate, an evaluation substrate is prepared by spin-coating and pre-baking the composition on a glass substrate on which a step of a 50 μm line and space pattern having a thickness of 1 μm is formed in the same manner as the visible light transmittance evaluation substrate. The level | step difference of the board | substrate was measured with the film thickness meter [DEKTAK3 (made by ULVAC, Inc.)], and the planarization rate was calculated | required by Formula (2). The flattening rate obtained was 49%.

Example 2
The radiation-sensitive resin composition was operated in the same manner as in Example 1 except that ethyl lactate (233 parts by mass) and methyl α-hydroxyisobutanoate (233 parts by mass) (ethyl lactate in all solvents 50%) were used as the solvent. Got.

As a result of performing the same operation as in Example 1, the thickness (T1) of the transparent cured resin pattern (5) obtained with an effective sensitivity of 100 mJ / cm ² was 2.0 μm. The light transmittance was 99.5%, and no change was observed before and after immersion in the solvent resistance test. The flattening rate obtained by the formula (2) was 48%.

Example 3
A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that ethyl lactate (376 parts by mass) and γ-butyrolactone (20 parts by mass) (ethyl lactate in all solvents 95%) were used as the solvent. .

As a result of performing the same operation as in Example 1, the thickness (T1) of the transparent cured resin pattern (5) obtained with an effective sensitivity of 120 mJ / cm ² was 2.0 μm. The light transmittance was 99.5%, and no change was observed before and after immersion in the solvent resistance test. The flattening rate obtained by the formula (2) was 57%.

Example 4
A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that (A) resin A1 (100 parts by mass) was changed to (A) resin A3 (100 parts by mass).
The same operation as in Example 1 was performed to form a transparent cured resin pattern on the substrate. A 3 μm contact hole pattern was resolved with an effective sensitivity of 90 mJ / cm ² . The light transmittance measured by operating in the same manner as in Example 1 was as high as 99.6%, and no coloring was observed. The flattening rate obtained by the formula (2) was 57%.

Example 5
A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that (A) resin A1 (100 parts by mass) was changed to (A) resin A4 (100 parts by mass).
The same operation as in Example 1 was performed to form a transparent cured resin pattern on the substrate. A 3 μm contact hole pattern was resolved with an effective sensitivity of 75 mJ / cm ² . The light transmittance measured by operating in the same manner as in Example 1 was as high as 99.5%, and no coloring was observed. The flattening rate obtained by the formula (2) was 56%.

Comparative Example 1
A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that resin A2 was used and propylene glycol methyl ether acetate (392 parts by mass) was used as the solvent.
As a result of performing the same operation as in Example 1, the thickness (T1) of the transparent cured resin pattern (5) obtained with an effective sensitivity of 180 mJ / cm ² was 1.9 μm. The flattening rate obtained by the equation (2) was 35%.

  The radiation-sensitive resin composition of the present invention is used to protect TFT insulating films used in liquid crystal display devices and organic EL display devices, diffuse reflectors used in reflective TFT substrates, organic EL insulating films, and solid-state imaging devices. It is useful as a material for forming a transparent cured resin pattern including a film.

It is a schematic diagram which shows the process of forming a transparent cured resin pattern using the radiation sensitive resin composition of this invention. In Formula (2), it is a figure which shows the measurement place for calculating | requiring the planarization rate.

Explanation of symbols

1: Radiation sensitive resin composition layer 11: Unirradiated region
12: Irradiation area 2: Substrate 3: Positive mask 4: Radiation 5: Transparent cured resin pattern h1: Step difference on stepped substrate h2: Step difference after application of radiation-sensitive resin composition

Claims (10)

  In the radiation-sensitive resin composition containing the curable alkali-soluble resin (A), the quinonediazide compound (B), and the solvent (C), 40% or more of ethyl lactate is contained in the solvent (C) by mass fraction. Radiation sensitive resin composition.   The radiation-sensitive resin composition according to claim 1, wherein the amount of the solvent (C) in the radiation-sensitive resin composition is 50 to 95% by mass in mass fraction.   Radiation sensitive according to claim 1 or 2, wherein the solvent (C) contains a solvent having a boiling point of 180 ° C or higher and 240 ° C or lower in a mass fraction of 0.1% to 20% with respect to the total amount of the radiation sensitive resin composition. Resin composition.   The curable alkali-soluble resin (A) is derived from the structural unit (a1) derived from the unsaturated carboxylic acid and the unsaturated compound having a curable group (excluding the unsaturated carboxylic acid). It is a copolymer containing (a2), The radiation sensitive resin composition in any one of Claims 1-3.   The radiation-sensitive resin composition according to claim 4, wherein in the structural unit (a2) derived from an unsaturated compound having a curable group (excluding unsaturated carboxylic acid), the curable group is oxetane. .   The curable alkali-soluble resin (A) further comprises a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond, a structural unit (a32) derived from an aromatic vinyl compound, and a vinyl cyanide compound. The structural unit (a33) derived and at least one structural unit (a3) selected from the group consisting of the structural unit (a34) derived from an N-substituted maleimide compound, Composition.   The curable alkali-soluble resin (A) further comprises a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond, a structural unit (a32) derived from an aromatic vinyl compound, and a vinyl cyanide compound. The radiation-sensitive resin composition according to any one of claims 1 to 6, which is a copolymer comprising at least one structural unit (a3) selected from the group consisting of derived structural units (a33).   The transparent cured resin pattern formed with the radiation sensitive resin composition in any one of Claims 1-7.   Applying the radiation-sensitive resin composition according to any one of claims 1 to 7 on a substrate, irradiating with radiation through a mask, developing to form a predetermined pattern, and then irradiating with radiation A method for producing a transparent cured resin pattern characterized by the following. The manufacturing method of the transparent cured resin pattern of Claim 9 which heats after irradiating a radiation.

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