JP4403805B2 - 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.

  Radiation sensitive resin compositions include, for example, TFT insulating films used in thin film transistor (hereinafter referred to as TFT) type liquid crystal display devices and organic EL display devices, and diffuse reflectors used in reflective TFT substrates. It is useful as a material for forming a transparent cured resin pattern including an organic EL insulating film, a protective film of a solid-state imaging device (hereinafter, sometimes referred to as CCD), and the like (see Patent Document 1). Further, 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 base step such as a TFT element formed on the substrate (for example, paragraph of Patent Document 1). No. 0009, paragraph No. 0004 of Patent Document 2). Furthermore, in order to obtain a brighter display image, a high transmittance with respect to visible light is required (see, for example, paragraph number 0010 of Patent Document 1).

JP-A-9-152625 (see paragraph numbers 0001, 0009 and 0010) Japanese Patent Laid-Open No. 9-244409 (see paragraph 0004)

However, the radiation-sensitive resin composition and the like also require high sensitivity to radiation used for pattern formation from the viewpoint of the productivity of the TFT substrate.
An object of the present invention is to provide a radiation-sensitive resin composition having high flattening performance, high sensitivity, and the like for use in a transparent cured resin pattern and having a high productivity of the transparent cured resin pattern.

As a result of intensive studies to solve the above problems, the present inventors have completed 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), wherein the solvent (C) contains γ-butyrolactone as a total solvent. A radiation-sensitive resin composition containing 5 to 60% by weight, a transparent cured resin pattern formed from the composition, and the composition is applied, and after removing the solvent, a mask is formed. And then developing with an alkaline aqueous solution to form a predetermined pattern, and then irradiating the entire pattern on the substrate with radiation.
Hereinafter, the present invention will be described in detail.

  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 transparent film formed using the radiation sensitive resin composition has a high transmittance. Therefore, a transparent film with a high yield can be formed with high productivity by using the radiation-sensitive resin composition of the present invention.

  The curable alkali-soluble resin (A) in the present invention includes a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having a curable group. A polymer is preferably used [provided that the unsaturated compound leading to the structural unit (a2) is not an unsaturated carboxylic acid).

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

Examples of the structural unit (a2) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and 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, 3-vinylcyclohexene oxide or 4-vinylcyclohexene oxide. Any epoxy group-containing unsaturated compound; 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-phenyl- 3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meta ) Acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2-pentafluoroethyl-3- (meth) acryloxyethyloxy Such as oxetanyl group-containing unsaturated compound such as Tan and the like.
As the structural unit (a2), the oxetanyl group-containing unsaturated compound is preferable. Preferred oxetanyl group-containing unsaturated compounds include, for example, 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) acryl Roxyethyl oxetane or 2-pentafluoroethyl-3- (meta Such acryloxyethyl oxetane and the like. A particularly preferred oxetanyl group-containing unsaturated compound is 3-ethyl-3-methacryloxymethyloxetane.
When the radiation sensitive resin composition is prepared using an alkali-soluble resin containing an unsaturated compound containing an oxetanyl group as the structural unit (a2), the storage stability of the composition tends to be good. ,preferable.

  In the present invention, the curable alkali-soluble resin (A) further comprises a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond as a copolymer component, and polymerizable carbon-carbon unsaturation. Structural unit (a32) derived from aromatic compound having bond, structural unit (a33) derived from vinyl cyanide compound and N-substituted maleimidation

It can contain at least one structural unit (a3) selected from the group consisting of the structural unit (a34) derived from the compound.
Examples of the carboxylic acid ester having an olefinic double bond include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid esters such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate; ) Unsaturated carboxylic acid aminoalkyl esters such as acrylates; structural units derived from carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate.
Examples of the aromatic compound having a polymerizable carbon-carbon unsaturated bond include structural units derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, and the like.
Examples of the vinyl cyanide compound include structural units derived from vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, or 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.

  The structural units (a1), (a2), (a31), (a32), (a33), and (a34) can be used as a single unit or a combination of units derived from the exemplified compounds.

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 the curable group, the unit (a1) is a copolymer. The amount is usually in the range of 5 to 50 mol%, preferably 15 to 40 mol% with respect to the entire structural unit. The unit (a2) is usually 95 to 5 mol%, preferably 95 to 15 mol%, more preferably 95 to 50 mol%, particularly preferably 85 to 60 mol%, based on the entire structural unit of the copolymer. Range.
In the composition of the present invention, it is preferable that the constituent ratio of the units (a1) and (a2) in the copolymer is in the above-mentioned range from the viewpoint of an appropriate dissolution rate in the developer and high curability.

In the composition of the present invention, when the alkali-soluble resin (A) is a copolymer containing units (a1) and (a2), in addition to units (a1) and (a2), other structural units as optional components May be included. When the copolymer contains (a3), the content thereof is usually 0.01 to 90 mol%, preferably 0.01 to 70, with the total molar ratio of all components (A) being 100 mol%. Used in mol%.
Examples of the copolymer containing the units (a1) and (a2) include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzyl. Methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / 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-methacrylic Roxymethyl Oki Tan / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic 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, or 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / t-butyl acrylate copolymer, 3-ethyl-3-methacrylate B carboxymethyl oxetane / methacrylic acid / phenylmaleimide copolymer, and 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / cyclohexyl maleimide copolymer.

The copolymer containing the units (a1) and (a2) has a weight average molecular weight of 2,000 to 100,000, preferably 2,000 to 50, as determined by gel permeation chromatography based on polystyrene. 1,000, more preferably 3,000 to 20,000. When the weight average molecular weight is from 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 containing units (a1) and (a2) in the radiation-sensitive resin composition of the present invention is usually in the range of 50 to 98% by weight with respect to the total solid content of the radiation-sensitive resin composition. It is preferably 50 to 90% by weight, more preferably 60 to 90% by weight.

  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, 1,2-naphthoquinonediazide sulfonic acid amide and the like.

  Specific examples of the quinonediazide compound (B) include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 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-sulfone 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones such as acid esters; 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid esters, 2,2 ′ , 4,4'-Tetrahydroxybenzofe Non-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-naphthoquinonediazide-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′- 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as methoxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester; 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1, 1,2- of pentahydroxybenzophenones such as 2-naphthoquinonediazide-4-sulfonic acid ester or 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester Naphthoquinone diazide sulfonate; 2, , 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 or 3,4,5,3 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as ', 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-dihydride) Roxyphenyl) 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-sulfone 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- -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-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyl Laban-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester ( Polyhydroxyphenyl) alkanes such as 1,2-naphthoquinonediazide sulfonic acid ester.

  The quinonediazide compound (B) is used alone or in combination of two or more. Content of the quinonediazide compound (B) in this invention is the range of 2-50 weight% normally with respect to the total solid of a radiation sensitive resin composition, Preferably it is the range of 5-40 weight%. When the content of the quinonediazide compound is in the range of 2 to 50% by weight, the difference in the dissolution rate between the unexposed area and the exposed area tends to be high, which tends to maintain a high development residual film ratio, which is preferable.

The solvent (C) in the radiation sensitive resin composition of the present invention contains γ-butyrolactone in the range of 5 to 60% by weight. When the content of γ-butyrolactone in the solvent (C) is in the above range, the flattening performance of the transparent cured resin pattern obtained from the radiation-sensitive resin composition tends to be good.
Moreover, as a solvent other than (gamma) -butyrolactone in a solvent (C), the organic solvent generally used for a radiation sensitive resin composition can be used.
Examples of such organic solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, or ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Diethylene glycol dialkyl ethers such as ether or diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate or ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or propylene Propylene glycol alkyl ether acetates such as ethylene glycol monopropyl ether acetate; aromatic hydrocarbons such as benzene, toluene or xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone; ethanol, propanol, Alcohols such as butanol, hexanol, cyclohexanol, ethylene glycol or glycerin; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 2-hydroxyisobutanoate, ethyl lactate, butyl lactate, butyl acetate, amyl acetate or pyruvin And esters such as methyl acid.
In the radiation sensitive resin composition of the present invention, the solvent (C) is preferably a composition containing ethyl lactate and / or methyl 2-hydroxyisobutanoate in a range of 40 to 95% by weight in the total solvent.
The amount of the solvent (C) used is preferably in the range of 50 to 95% by weight and more preferably in the range of 70 to 90% by weight with respect to the total amount of the radiation sensitive resin composition. When the amount of the solvent (C) used is in the range of 50 to 95% by weight with respect to the total amount of the radiation sensitive resin composition, a film having good flatness tends to be formed, which is preferable.

  In addition to the alkali-soluble resin (A), the quinonediazide compound (B) and the solvent (C), the radiation-sensitive resin composition of the present invention comprises a polymerization initiator (D), a polyhydric phenol compound (E), and a crosslinking agent (F ) Or a polymerizable monomer (G).

Examples of the polymerization initiator (D) 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-cyanophenyl) 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) sulfur Chloride, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium and the like.
Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (pt-butylphenyl) iodonium, triphenylsulfonium or tris (pt-butylphenyl). ) Sulfonium and the like.
Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroalcinate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acids include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.
The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Specific examples of the cationic photopolymerization initiator (D) include 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 hexafluoroalcinate, 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, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium 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 hexafluoroarsinate, (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, or tris (pt-butylphenyl) sulfonium teto Such as tetrakis (pentafluorophenyl) borate.

  Content of the said polymerization initiator (D) is the range of 0.01 to 10 weight% normally with respect to the total solid of a radiation sensitive resin composition, Preferably it is the range of 0.1 to 5 weight% It is. When the content of the polymerization initiator (D) is in the range of 0.01 to 10% by weight, a decrease in resolution at the time of thermosetting is suppressed by increasing the curing rate at the time of thermosetting, and further the resistance of the cured film is improved. This is preferable because the solvent property tends to be improved.

Examples of the polyhydric phenol compound (E) include compounds having two or more phenolic hydroxyl groups in the molecule, polymers obtained using at least hydroxystyrene as a raw material monomer, or novolak resins.
Examples of the compound having two or more phenolic hydroxyl groups in the molecule include trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones or (polyhydroxy) exemplified in the description of the quinonediazide compound. And the same polyhydric phenols as phenyl) alkanes.

Specific examples of the polymer obtained using at least hydroxystyrene as a raw material monomer include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer or hydroxy Examples thereof include resins obtained by polymerizing hydroxystyrene such as styrene / alkoxystyrene copolymers.
Further, the novolak resin may be, for example, one or more compounds selected from the group consisting of phenols, cresols and catechols and one or more compounds selected from the group consisting of aldehydes and ketones. Examples thereof include resins obtained by polymerization.

  The amount of the polyhydric phenol compound (E) added is usually 40% by weight or less, preferably 25% by weight or less, based on the total solid content of the radiation-sensitive resin composition. When the amount of the polyhydric phenol compound (E) is 40% by weight or less, the resolution is improved and the visible light transmittance tends not to decrease, which is preferable.

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

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

  In the radiation sensitive resin composition of the present invention, the addition amount when the crosslinking agent (F) is used is preferably 15% by weight or less based on the total solid content of the 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 improved, which is preferable.

  Examples of the polymerizable monomer (G) include a polymerizable monomer that can be radically polymerized by heating or a polymerizable monomer that can be cationically polymerized. A preferable polymerizable monomer (G) includes a polymerizable monomer capable of cationic polymerization.

  Examples of the polymerizable monomer capable of radical polymerization include compounds having a polymerizable carbon-carbon unsaturated bond. The compound having a polymerizable carbon-carbon unsaturated bond may be a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, or a polyfunctional (trifunctional or higher functional) polymerizable monomer. There may be.

  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, or 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 polyfunctional polymerizable monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate, pentaerythritol. Examples include pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.
Among the compounds having a polymerizable carbon-carbon unsaturated bond, a bifunctional or polyfunctional polymerizable monomer is preferably used. Specifically, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate is preferable, and dipentaerythritol hexaacrylate is more preferable. Further, a bifunctional or polyfunctional polymerizable monomer and a monofunctional polymerizable monomer may be used in combination.

Examples of the polymerizable monomer capable of cationic polymerization include monomers having a cationic polymerizable functional group such as vinyl ether group, propenyl ether group, epoxy group or oxetanyl group.
Examples of the monomer containing a vinyl ether group include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, and dodecyl vinyl ether.
Examples of the monomer containing the propenyl ether group include 4- (1-propenyloxymethyl) -1,3-dioxolan-2-one.
Examples of the compound containing an epoxy group include a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and a heterocyclic type. An epoxy resin etc. are mentioned.
Examples of the compound containing the oxetanyl group 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 or And 3- (3-ethyloxetanyl) methylated novolak resin.

The said polymerizable monomer (G) is used individually or in combination of 2 or more types.
The addition amount of the polymerizable monomer (G) in the radiation sensitive resin composition of the present invention is preferably 20% by weight or less based on the total solid content of the radiation sensitive 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. Or various additives, such as an electron donor, can also be contained.

  The radiation sensitive resin composition of the present invention is prepared by, for example, mixing a solution in which the alkali-soluble resin (A) is dissolved in the solvent (C) and a solution in which the quinonediazide compound (B) is dissolved in the solvent (C). Can be prepared. Moreover, you may add and mix a solvent (C) to the liquid after preparation. Furthermore, it is preferable to remove solids by filtration after mixing the solutions. The filtration is preferably performed using a filter having a pore size of 3 μm or less (preferably about 0.1 to 2 μm). The solvent (C) used for the alkali-soluble resin (A) and the quinonediazide compound (B) may be the same as each other. A plurality of solvents (C) may be used as long as they are compatible with each other.

  When forming a transparent cured resin pattern using the radiation sensitive resin composition of the present invention, for example, a layer (1) composed of the radiation sensitive resin composition is formed on a substrate (2) [FIG. (See (a)], the layer (1) is exposed to radiation (4) through a positive mask (3) and exposed (see FIG. 1 (b)), and then developed (FIG. 1 (c)). reference].

  Examples of the substrate (2) include a transparent glass plate. Circuits such as TFTs and CCDs, color filters, and the like may be formed on the substrate.

  The layer (1) comprising the radiation sensitive resin composition can be formed by, for example, a method of applying the radiation sensitive resin composition on the substrate (2). The coating is performed, for example, by spin coating, casting coating, roll coating, slit and spin coating, or slit coating. After application, the radiation-sensitive resin composition layer (1) is formed by heat-drying (pre-baking) or vacuum-drying after heating to volatilize volatile components such as a solvent. The physical layer (1) contains almost no volatile components. Moreover, the thickness of the said radiation sensitive resin composition layer is about 1.5-5 micrometers.

  Thereafter, 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, light rays such as g-line or i-line are used. The radiation is preferably irradiated using, for example, a mask aligner or a stepper (not shown) so as to be irradiated in parallel over the entire surface of the radiation-sensitive resin composition layer.

  After the exposure, development is performed. Development can be performed on the radiation-sensitive resin composition layer (1) after exposure by, for example, a paddle method, a dipping method, or a shower method. As the developer, an alkaline aqueous solution is usually used. As the alkaline aqueous solution, an aqueous solution of an alkaline compound is used, 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 thereof include potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate or 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 may be used alone or in combination of two or more. The developer usually contains an alkaline compound in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight 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 the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; sodium dodecylbenzenesulfonate or dodecylnaphthalenesulfone. Examples thereof include alkyl aryl sulfonates such as sodium acid. These surfactants may be 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.

  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 being dissolved in the developer to form a positive 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 (12) 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 (11) dissolves in the developer and disappears. There is nothing to do.

  After alkali development, it is usually washed with water and dried. After drying, radiation is irradiated over the entire surface of the obtained transparent film pattern (5). The radiation irradiated here is preferably ultraviolet rays or deep ultraviolet rays, and the irradiation amount per unit area is usually larger than the irradiation amount in the previous exposure.

  The pattern (5) thus formed is preferably further subjected to heat treatment (post-baking) from the viewpoint of improving the heat resistance and solvent resistance of the transparent cured resin pattern. The heating is performed by a method of heating the substrate after irradiation with radiation over the entire surface with a heating device such as a hot plate or a clean oven. The heating temperature is usually about 150 ° C to 250 ° C, preferably about 180 ° C to 240 ° C, and the heating time is usually about 5 minutes to 120 minutes, preferably about 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 by using the following 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.
Flattening rate (%) = (1− (h2) / (h1)) × 100 (2)
It is preferable that the planarization rate calculated | required by Formula (2) is 45% or more.

  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.

  As mentioned above, although embodiment of this invention was described, embodiment of the said disclosed invention is an illustration to the last, Comprising: The scope of the present invention is not limited to these embodiment. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  EXAMPLES Hereinafter, although an Example etc. demonstrate 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

Here, the polystyrene equivalent weight average molecular weight of this resin was measured under the following conditions.
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)

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
Methyl 2-hydroxyisobutanoate 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.

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

Example 1
100 parts by weight of resin A1, the following formula (1)

（式中、Ｑ⁴は、下式（１−１）で示される置換基を示す。）

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

22 parts by weight of the compound represented by formula (2), 2 parts by weight of (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate [Rhodorsil Photoinitiator 2074 (manufactured by Rhodia)], 88 parts by weight of γ-butyrolactone, After mixing 352 parts by weight of ethyl lactate (the content of γ-butyrolactone in all solvents is 20% by weight) at 23 ° C., the mixture was filtered under pressure through a cartridge filter made of polytetrafluoroethylene having a pore size of 1.0 μm, and a radiation sensitive resin. A composition was obtained.

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 The film thickness was measured using a film thickness meter [Lambda Ace (Dainippon Screen Mfg. Co., Ltd.)] and found to be 2.6 μm [see FIG. 1 (a)].
Thereafter, radiation was applied to the obtained radiation-sensitive resin composition layer (1) through a positive mask (3) using an i-line stepper [NSR-1755i7A (NA = 0.5) manufactured by Nikon Corporation]. (4) was irradiated and exposed [see 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 the exposure, the film was developed by dipping in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 70 seconds, washed with ultrapure water, and dried. In the pattern after development, the effective sensitivity was 180 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 a DUV lamp (UXM-501MD manufactured by Ushio Corp.) and irradiated with radiation (intensity of 300 mJ / cm ^{2 based on a} wavelength of 313 nm) in a clean oven at 220 ° C. Heated for minutes to form a transparent cured resin pattern (5) [see FIG. 1 (c)].
It was 2.1 micrometers when the thickness (T1) of the obtained transparent cured resin pattern (5) was measured using the film thickness meter.

Visible light transmittance was determined by forming a transparent cured resin film on a transparent glass substrate [# 1737 (manufactured by Corning)] by the above method except that the exposure step using a stepper was not performed. OSP-200 manufactured by Co., Ltd.]. The film thickness was measured with a film thickness meter [DEKTAK3 manufactured by ULVAC, Inc.]. 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 by Corporation | KK ULVAC], and the planarization rate was calculated | required by Formula (2). The flattening rate obtained was 57%.

Example 2
The filtrate after pressure filtration was operated in the same manner as in Example 1 except that a mixed solvent of 198 parts by weight of γ-butyrolactone and 242 parts by weight of ethyl lactate (the content of γ-butyrolactone in the total solvent was 45%) was used. As a result, a radiation sensitive resin composition was obtained.

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 65%.

Example 3
The filtrate after pressure filtration was operated in the same manner as in Example 1 except that a mixed solvent of 376 parts by weight of ethyl lactate and 20 parts by weight of γ-butyrolactone (content of γ-butyrolactone in the total solvent was 5%) was used. As a result, a radiation sensitive resin composition was obtained.

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
Example 1 except that Resin A2 (100 parts by mass) was used and the solvent was methyl 2-hydroxyisobutanoate (250 parts by mass) and γ-butyrolactone (167 parts by mass) (γ-butyrolactone 40% in all solvents). The same operation was performed to obtain a radiation sensitive resin composition.

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 2.1 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 62%.

Example 5
The same operation as in Example 1 was carried out except that Resin A4 (100 parts by mass) was used and the solvent was ethyl lactate (250 parts by mass) and γ-butyrolactone (167 parts by mass) (γ-butyrolactone 40% in all solvents). Thus, a radiation sensitive resin composition was obtained.

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 2.1 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 equation (2) was 63%.

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 methyl 2-hydroxyisobutanoate (437 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 135 mJ / cm ² was 2.0 μm. The flattening rate obtained by the equation (2) was 37%.

Comparative Example 2
A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that resin A3 was used and propylene glycol methyl ether acetate (393 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 comprises a thin film transistor (hereinafter sometimes referred to as TFT) type liquid crystal display device and a TFT insulating film used in an organic EL display device, and 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 for a solid-state imaging device (hereinafter, sometimes referred to as CCD), and the like.

It is a schematic diagram which shows the process of forming a transparent film using the radiation sensitive resin composition of this invention. It is a figure which shows the measurement place at the time of calculating | requiring a planarization rate by Formula (2).

Explanation of symbols

1. Radiation sensitive resin composition layer,
11. ・ Radiation-unirradiated area,
12. ・ Radiation irradiation area,
2 ... Board,
3. Positive mask,
4. Radiation,
5. Transparent cured resin pattern,
h1 .. Level difference of step board,
h2 ·· Step after application of radiation-sensitive resin composition

Claims (7)

In the radiation-sensitive resin composition containing the curable alkali-soluble resin (A), the quinonediazide compound (B), and the solvent (C), the solvent (C) contains γ-butyrolactone in an amount of 5 to 60 wt. only contains a percentage range,
The alkali-soluble resin (A) having curability is a copolymer containing a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group. Characteristic radiation-sensitive resin composition [however, structural unit (a
The unsaturated compound leading to 2) is never an unsaturated carboxylic acid] . The radiation-sensitive resin composition according to claim 1, wherein the solvent (C) contains ethyl lactate and / or methyl 2-hydroxyisobutanoate in a range of 40 to 95% by weight in the total solvent . 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 composition according to claim 1 or 2 , comprising at least one structural unit (a3) selected from the group consisting of the structural unit (a33) derived and the structural unit (a34) derived from an N-substituted maleimide compound. The alkali-soluble resin (A) having curability is further derived from a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond and an aromatic compound having a polymerizable carbon-carbon unsaturated bond. at least one copolymer structure including a unit (a3) of selected from the group consisting of structural units (a32) and the structural unit derived from a vinyl cyanide compound (a33) according to any one of claims 1 to 3 Radiation sensitive resin composition. The transparent cured resin pattern formed with the radiation sensitive resin composition in any one of Claims 1-4 . A radiation-sensitive resin composition according to any one of claims 1 to 4 is applied onto a substrate, the solvent is removed, radiation is applied through a mask, and then development is performed with an alkaline aqueous solution to form a predetermined pattern. Then, the manufacturing method of the transparent cured resin pattern characterized by irradiating the whole pattern surface on a board | substrate with radiation. The manufacturing method of the transparent cured resin pattern of Claim 6 which heats after irradiating a radiation to the whole pattern surface on a board | substrate.

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