JP2006048017A - Radiation sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition which can form a curing resin pattern having a high transmission factor at a wavelength of 400 nm. <P>SOLUTION: A radiation sensitive resin composition includes (A) an alkali soluble resin having a constitution unit introduced from an unsaturated carboxylic acid and a constitution unit introduced from an oxetanil group as a curing property, (B) a quinone diazide compound; (C) a lower fatty acid ester solvent, and (D) a silane coupling agent having an epoxy group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation-sensitive resin composition, a cured resin pattern formed using the same, and a display device including the cured resin pattern.

  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 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 (see, for example, Patent Document 1) .) The cured resin pattern is required to have a high transmittance for visible light in order to obtain a brighter display image (for example, see Patent Document 1).

Japanese Patent No. 2933879, page 1, right column, lines 22-25, page 3, left column, lines 13-14

  The objective of this invention is providing the radiation sensitive resin composition which can form the cured resin pattern which has a high transmittance | permeability in wavelength 400nm.

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), a solvent (C), and a silane coupling agent (D).

  Moreover, this invention provides the liquid crystal display device containing the cured resin pattern formed with the said radiation sensitive resin composition, and the said cured resin pattern.

  When a cured resin pattern is formed using the radiation sensitive resin composition of the present invention, a pattern with improved transmittance at a wavelength of 400 nm can be formed.

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

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

Examples of unsaturated compounds having a curable group that leads to the structural unit (a2) (excluding unsaturated carboxylic acids) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β -Ethylglycidyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meta ) Acrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 2- Vinylcyclohexene oxide, 3- Epoxy group-containing unsaturated compounds such as vinylcyclohexene oxide and 4-vinylcyclohexene oxide;
3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 2-phenyl-3- (meth) Acryloyloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloyloxymethyl oxetane, 2-pentafluoroethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryl Leuoxyethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 2-phenyl-3- (meth) acryloyloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloyloxyethyl Oxetane, 2-pentafluoroethyl-3- (meth) acryloyloxye Examples thereof include oxetanyl group-containing unsaturated compounds such as luoxetane, preferably 3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- ( (Meth) acryloyloxymethyl oxetane, 2-phenyl-3- (meth) acryloyloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloyloxymethyl oxetane, 2-pentafluoroethyl-3- (meta ) Acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 2-phenyl-3- (meth) acryloyloxyethyl Oxetane, 2-trifluoromethyl-3- (meth) acryloiro Examples include oxetanyl group-containing unsaturated compounds such as cyethyl oxetane and 2-pentafluoroethyl-3- (meth) acryloyloxyethyl oxetane, and more preferably 3-ethyl-3-methacryloyloxymethyl oxetane. . When a radiation-sensitive resin composition is prepared using an alkali-soluble resin containing a structural unit derived from an oxetanyl group-containing unsaturated compound, it is preferable because storage stability tends to be good.

The copolymer further includes a structural unit (a31) derived from a carboxylic acid ester, a structural unit (a32) derived from an aromatic vinyl compound, a structural unit (a33) derived from a vinyl cyanide compound, and an N-substituted maleimide. It may contain at least one structural unit (a3) selected from the group consisting of the structural unit (a34) derived by cleavage of the unsaturated bond of the compound.
Examples of the carboxylic acid ester having an olefinic double bond that leads to (a31) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and benzyl. Unsaturated carboxylic acid esters such as (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or dicyclopentanyl (meth) acrylate, 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 aromatic compound having a polymerizable carbon-carbon unsaturated bond leading to (a32) include an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like.
Examples of the vinyl cyanide compound that leads to (a33) include vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloro (meth) acrylonitrile.
Examples of the N-substituted maleimide compound that leads to (a34) include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- ( 4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3 -Maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N- (1-anilinonaphthyl-4) -maleimide, N- [4- (2-benz Oxazolyl) phenyl] maleimide, N- ( - acridinyl) maleimide and the like.
Such structural units can be used alone or in combination of two or more.

In the copolymer containing the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having a curing group (excluding the unsaturated carboxylic acid) in the present invention, The constituent ratio of a1) is usually 5 to 50 mol%, preferably 15 to 40 mol%, based on the total number of moles of constituent units of the copolymer, and the constituent ratio of (a2) is that of the copolymer. The amount is usually 95 to 50 mol%, preferably 85 to 60 mol%, based on the total number of moles of the structural units.
In the above copolymer, when the constituent ratio of (a1) and (a2) is in the above range, an appropriate dissolution rate with respect to a developing solution is exhibited during pattern formation, and the resulting pattern has high curability. This is also preferable.

The copolymer containing (a1) and (a2) in the present invention may contain other structural units as optional components in addition to (a1) and (a2). When the copolymer includes other structural units as optional components, the ratio of (a1) is usually 5 to 50 mol%, preferably 15 to 40, based on the total number of moles of the structural units of the copolymer. It is used in the range of mol%, and the ratio of (a2) is usually 95 to 5 mol%, preferably 85 to 15 mol% on the same basis. Furthermore, when a copolymer contains another structural unit, the ratio is used on the same basis as the above, Preferably it is 0.1-90 mol%, More preferably, it is used at 5-80 mol%.
Examples of the copolymer containing (a1) and (a2) in the present invention include, for example, 3-ethyl-3-methacryloyloxymethyl oxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloyloxymethyl Oxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / cyclohexyl methacrylate Copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / methyl methacrylate copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / methyl methacrylate / styrene copolymer, 3-Echi -3-Methacryloyloxymethyl oxetane / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacrylate Leuoxymethyl oxetane / methacrylic acid / benzyl acrylate copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / Isobornyl acrylate copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / dicyclopentanyl methacrylate copolymer, 3-ethyl-3-methacryloyloxymethyl oxetane / methacrylic acid / -Butyl acrylate copolymer, 3-ethyl-3-methacryloyloxymethyloxetane / methacrylic acid / phenylmaleimide copolymer, 3-ethyl-3-methacryloyloxymethyloxetane / methacrylic acid / cyclohexylmaleimide copolymer, etc. Can be mentioned.

The weight average molecular weight in terms of polystyrene determined by the GPC method of the copolymer containing (a1) and (a2) in the present invention is usually from 2,000 to 100,000, preferably from 2,000 to 50,000. Preferably it is 3,000-20,000. When the weight average molecular weight in terms of polystyrene is in the above range, a high development speed tends to be obtained while maintaining the remaining film ratio during development, which is preferable.
Content of the copolymer containing (a1) and (a2) in the radiation sensitive resin composition of this invention is a mass fraction with respect to solid content of a radiation sensitive resin composition, and is normally 50-90 mass. %, Preferably 60 to 90% by mass. Here, solid content means what remove | excluded the solvent component of the radiation sensitive resin composition.

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

Specifically, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 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-5-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-4-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphtho Quinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3 ′ -Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol 1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′- Hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2, 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as 2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester Is mentioned.

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

  The radiation sensitive resin composition of this invention contains a solvent (C). The solvent (C) preferably contains a compound represented by the formula (1) and ethyl lactate.

R ¹ —COO—R ² (1)

[In formula (1), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms.
R ² represents an alkyl group having 3 to 10 carbon atoms. ]

Specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, Preferably, a C1-C3 linear alkyl group is mentioned, Specifically, a methyl group, an ethyl group, and n-propyl group are mentioned, More preferably, it is a C1-C2 linear chain | strand. And an alkyl group, specifically, a methyl group and an ethyl group.
R ² is preferably a linear alkyl group having 4 to 8 carbon atoms or a branched alkyl group having 4 to 8 carbon atoms, and specifically includes an n-butyl group, an n-hexyl group, and an n-heptyl group. , N-octyl group, isobutyl group, sec-pentyl group, and isopentyl group.

Specific examples of the compound represented by the formula (1) include n-pentyl acetate, sec-pentyl acetate, isopentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, n-butyl propionate, isobutyl propionate, and propionic acid. n-pentyl, sec-pentyl propionate, isopentyl propionate, hexyl propionate, heptyl propionate, octyl propionate, n-butyl butyrate, isobutyl butyrate, n-pentyl butyrate, sec-pentyl butyrate, isopentyl butyrate, hexyl butyrate, Examples include heptyl butyrate, isooctyl butyrate, n-butyl butyrate, isobutyl isobutyrate, n-pentyl isobutyrate, sec-pentyl isobutyrate, isopentyl isobutyrate, hexyl isobutyrate, heptyl isobutyrate, octyl isobutyrate, preferably acetic acid n Pentyl, sec-pentyl acetate, isopentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, n-butyl propionate, isobutyl propionate, n-pentyl propionate, sec-pentyl propionate, isopentyl propionate, hexyl propionate, propionate Examples include heptyl acid and octyl propionate, more preferably n-pentyl acetate, sec-pentyl acetate, isopentyl acetate, n-butyl propionate, isobutyl propionate, n-pentyl propionate, sec-pentyl propionate, and propionic acid. Isopentyl is mentioned.
The compounds represented by the formula (1) are used alone or in combination of two or more.

Moreover, you may mix the compound represented with said Formula (1), ethyl lactate, and another solvent.
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;
Cyclic esters such as ethylene carbonate, propylene carbonate, butyrolactone;
And ether esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

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

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

Examples of the polymerization initiator (E) 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 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 (cyclopentyl)

Ruoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (penta Fluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluoro) Phenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfoni Mutetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like, preferably bis (P-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (pt-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p -T-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsinate, p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsinate, bis (pt-butylphenyl) iodonium hexafluoroarsinate, triphenylsulfonium hexafluoroalcinate, tris (pt-butylphenyl) sulfonium hexa Fluoroarsinate, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl) iodonium hexafluoroantimonate, triphenyl Sulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (penta Fluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p -T-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate Bis (pt-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfur Nium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) Examples thereof include iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, and tris (pt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

  When using a polymerization initiator (E), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, and is 0.01-10 mass% normally, Preferably it is 0.1-8 mass. %. When the content of the polymerization initiator (E) is in the above range, by increasing the curing rate at the time of thermosetting, a decrease in resolution at the time of thermosetting is suppressed, and the solvent resistance of the cured film is further improved. Is preferable.

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

  When using the said polyhydric phenol compound (F), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, and is 0.01-40 mass% normally, Preferably it is 0.1. -25% by mass. When the content of the polyhydric phenol compound (F) is in the above range, the resolution is improved and the visible light transmittance tends not to decrease, which is preferable.

  Examples of the crosslinking agent (G) 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.

  When using a crosslinking agent (G), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, and is 0.01-15 mass% normally, Preferably it is 1-10 mass%. . When the content of the crosslinking agent is within the above range, the visible light transmittance of the obtained film is increased, and the performance as a cured resin pattern is improved, which is preferable.

  Examples of the polymerizable monomer (H) 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, 2-ethylhexyl carbitol acrylate, Examples include 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and N-vinyl pyrrolidone.

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

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

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

  When using the said polymerizable monomer (H), this is used individually or in combination of 2 or more types, respectively. Content of a polymerizable monomer (H) is a mass fraction with respect to solid content of a radiation sensitive resin composition, and is 0.1-20 mass% normally.

Moreover, the curable resin composition of the present invention contains at least one surfactant selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. It is preferable.
Examples of the silicone-based surfactants include trade names such as Torresilicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, and SH30PA (produced by Torresilicone); trade name polyether-modified silicone oil SH8400 (Trade name KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (manufactured by Shin-Etsu Silicone)); trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446 , TSF4452 and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

Examples of the fluorosurfactant include Fluorard FC430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.); MegaFac (trade name) F142D, F171, F172, F173, F177, F183, and R183 (trade name). Dainippon Ink & Chemicals, Inc.); Ftop (trade name) EF301, EF303, EF351 and EF352 (made by Shin-Akita Kasei Co., Ltd.);
Surflon (trade name) S381, S382, SC101 and SC105 (Asahi Glass Co., Ltd.);
Product names E1830, E5844 (Daikin Fine Chemical Laboratory Co., Ltd.);
Product names BM-1000, BM-1100 (manufactured by BM Chemie) and the like can be mentioned.
Examples of the silicone surfactant having a fluorine atom include Megafac (trade name) R08, BL20, F475, F477 and F443 (Dainippon Ink Chemical Co., Ltd.).
These surfactants can be used alone or in combination of two or more.

Furthermore, you may use together other surfactants, such as an acrylic polymer type surfactant and a vinyl polymer type surfactant, in the curable resin composition of this invention.
Examples of the acrylic polymer surfactant include Disparon (trade name) OX-880, OX-881, OX-883, OX-70, OX-77, OX-77HF, OX-60, and OX-60. OX-710, OX-720, OX-740, OX-750, OX-8040, 1970, 230, L-1980-50, L-1982-50, L-1983-50 L-1984-50, L-1985-50, LAP-10, LAP-20, LAP-30 and LHP-95 (manufactured by Enomoto Kasei Co., Ltd.); trade names BYK-352, BYK -354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361 and BYK-390 (manufactured by BYK Chemie Japan); Efcar (trade name) LP3 78 (Efka Chemicals Co., Ltd.), and the like.

  Examples of the vinyl polymer surfactant include Disparon (trade name) 1922, 1927, 1950, 1951, P-410, P-410HF, P-420, P-425, and PD-7. And LHP-90 (manufactured by Enomoto Kasei Co., Ltd.).

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

  The radiation sensitive resin composition of the present invention includes, for example, a solution obtained by dissolving a curable alkali-soluble resin (A) in a solvent (C), a solution obtained by dissolving a quinonediazide compound (B) in a solvent (C), and a silane cup. It can prepare by mixing the solution which melt | dissolved the ring agent (D) in the solvent (C). 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.

  When forming a cured resin pattern using a radiation-sensitive resin composition, for example, a layer made of a radiation-sensitive resin composition is formed on a substrate, and the layer is irradiated with radiation through a mask. After exposure, development is performed to obtain a resin pattern, and heat treatment is performed to obtain a cured resin pattern.

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

  The layer composed of the radiation sensitive resin composition can be formed by, for example, a method of applying the radiation sensitive resin composition on the substrate. The coating is performed by, for example, a spin coating method, a casting coating method, a roll coating method, a slit and spin coating method, a slit coating method, a die coating method, or a curtain flow coating method. After application, the radiation-sensitive resin composition layer is formed by volatilizing volatile components such as a solvent by heat drying (pre-baking), vacuum drying, or a combination of both. The thickness of the radiation sensitive resin composition layer is usually 1 to 5 μm.

  Next, the radiation-sensitive resin composition layer is irradiated with radiation through a mask. The mask pattern is appropriately selected according to the target pattern of the cured resin pattern. As the radiation, for example, light rays such as g-line and i-line are used. The irradiation with radiation is preferably performed using, for example, a mask aligner or a stepper.

After radiation irradiation, the radiation sensitive resin composition layer is developed. Development can be performed on the radiation-sensitive resin composition layer 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 include potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

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

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

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

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

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

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

Of the radiation-sensitive resin composition layer, the radiation-irradiated area irradiated with radiation in the previous exposure is dissolved in the developer by the development, and the radiation-unirradiated area not irradiated with radiation is dissolved in the developer. The resin pattern is formed without any remaining.
After alkali development, it is usually washed with water and dried. After drying, the whole or part of the obtained resin pattern is further irradiated with radiation. As the light source of the radiation, a light source containing radiation having a wavelength of 330 to 380 nm is preferably used.

  The resin pattern thus formed is preferably further heat-treated (post-baked) from the viewpoint of improving the heat resistance and solvent resistance of the resulting cured resin pattern. The heating is performed by a method of heating the substrate after irradiating the entire surface or a part thereof with a heating device such as a hot plate or a clean oven. The heating temperature is usually 150 ° C to 250 ° C, preferably 180 ° C to 240 ° C. The heating time is usually 5 minutes to 120 minutes, preferably 15 minutes to 90 minutes. By heating, the pattern is cured and a cured resin pattern is formed.

  The cured resin pattern thus formed is useful as a cured resin pattern constituting a display device such as an imaging device or a liquid crystal display device such as a TFT substrate, an organic EL element insulating film, and a CCD protective film.

  While 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
A 500 mL four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with the following monomer and 343 g of ethyl lactate and 3.4 g of azobisisobutyronitrile, and the internal temperature was kept at 85 to 95 ° C. under a nitrogen stream. While stirring for 3 hours, the reaction was carried out to obtain a resin A1 solution (solid content concentration of 30% by mass). The obtained resin A1 had a weight average molecular weight in terms of polystyrene of 7,800.

Methacrylic acid 22g
56 g of N-cyclohexylmaleimide
70 g of 3-ethyl-3-methacryloyloxymethyloxetane

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)

Synthesis example 2
The resin A1 solution is sealed in a container, the pressure is reduced to 0.5 to 1 kPa, the temperature is reduced to 60 to 70 ° C., the solvent is distilled off and the solution is concentrated, and the resin solution A2 solution (solid content concentration: 40 mass%) Got. The weight average molecular weight in terms of polystyrene of the obtained resin A2 was not changed from the molecular weight of A1.

Synthesis example 3
The reaction was performed in the same manner as in Synthesis Example 1 except that ethyl lactate / 3-ethoxypropionate 36 g / 146 g was used in place of ethyl lactate 343 g to obtain a resin A3 solution (solid content concentration 30% by mass). The obtained resin A3 had a polystyrene equivalent weight average molecular weight of 7,900.

Example 1
The following components were mixed at 23 ° C. and then filtered under pressure through a cartridge filter made of polytetrafluoroethylene having a pore size of 1.0 μm to obtain a radiation sensitive resin composition 1 as a filtrate. The solid content concentration of the radiation sensitive resin composition 1 was 30%.

Resin A1 solution 333 parts by mass (solid content 100 parts by mass)
Compound represented by formula (2) (quinonediazide compound) 24 parts by mass Adekaoptomer SP-172 (photocationic polymerization catalyst; manufactured by Asahi Denka Kogyo Co., Ltd.) 2 parts by mass Sunaid SI-100L (thermal cationic polymerization catalyst; three 2 parts by weight KBM-403 (silane coupling agent; γ-glycidoxypropyl-trimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight isoamyl acetate (formula (1)) Compound represented) (solvent) 60 parts by mass

(In formula (2), Q ⁴ represents a substituent represented by formula (2-1).)

A radiation-sensitive resin composition obtained by spin-coating the radiation-sensitive resin composition 1 obtained above on a transparent glass substrate [# 1737; manufactured by Corning] and heating (pre-baking) at 100 ° C. for 2 minutes using a hot plate. The material layer 1 was formed, and the whole surface was irradiated with radiation using a DUV lamp [UXM-501MD; manufactured by Ushio Corporation]. 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. Further, the above-mentioned DUV lamp was used to irradiate the entire surface with radiation (intensity of 300 mJ / cm ^{2 based on a} wavelength of 313 nm), and heated in a clean oven at 220 ° C. for 30 minutes to cure the radiation-sensitive resin composition. Layer 1 was obtained. When the film thickness was measured using a film thickness meter [DEKTAK3; manufactured by ULVAC, Inc.], it was 3.6 μm. When the transmittance of the cured photosensitive resin solid layer 1 was measured using a microspectrophotometer [OSP-200; manufactured by Olympus Optical Co., Ltd.], the obtained film of the cured photosensitive resin solid layer 1 was obtained. The average light transmittance at a wavelength of 400 nm per 3 μm thickness was 94.3%, indicating high transparency.

Example 2
Radiation sensitivity in the same manner as in Example 1 except that 5 parts by mass of KBM-303 (β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of KBM-403. Resin composition 2 was obtained. Using the obtained radiation sensitive resin composition 2, an experiment was conducted in the same manner as in Example 1 to obtain a cured radiation sensitive resin composition layer 2 having a thickness of 3.4 μm. The obtained cured radiation sensitive resin composition layer 2 had a transmittance of 95.4% per 3 μm thickness at a wavelength of 400 nm, indicating high transparency.

Comparative Example 1
A radiation sensitive resin composition 3 was obtained in the same manner as in Example 1 except that KBM-403 was not used. Using the obtained radiation sensitive resin composition 3, an experiment was conducted in the same manner as in Example 1 to obtain a cured radiation sensitive resin composition layer 3 having a thickness of 3.5 μm. The transmittance of the obtained cured radiation-sensitive resin composition layer 3 per 3 μm at a wavelength of 400 nm was 93.8%.

The radiation sensitive resin composition of the present invention is useful as a cured resin pattern constituting an imaging device such as a TFT substrate, a cured resin pattern constituting an organic EL element insulating film or a liquid crystal display, and a CCD protective film. It is.

Claims (12)

  A radiation-sensitive resin composition comprising a curable alkali-soluble resin (A), a quinonediazide compound (B), a solvent (C), and a silane coupling agent (D).   The radiation-sensitive resin composition according to claim 1, wherein the silane coupling agent (D) is a silane coupling agent having an epoxy group in its structure. The radiation sensitive resin composition of Claim 1 or 2 containing at least 1 sort (s) chosen from the group which consists of a compound represented by Formula (1), and ethyl lactate as a solvent (C).
R ¹ —COO—R ² (1)
[In formula (1), ^{R 1} represents an alkyl group having 1 to 4 carbon atoms.
R ² represents an alkyl group having 3 to 10 carbon atoms. ] The R ¹ represents a linear alkyl group having 1 or 2 carbon atoms, and R ² represents a linear alkyl group having 4 to 8 carbon atoms or a branched alkyl group having 4 to 8 carbon atoms. Radiation sensitive resin composition.   The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the content of the solvent (C) is 50 to 80% by mass with respect to the radiation sensitive resin composition.   The radiation sensitive resin composition according to any one of claims 3 to 5, wherein the content of the compound represented by formula (1) is 10 to 90% by mass with respect to the total amount of the solvent. .   The radiation sensitive resin composition according to any one of claims 3 to 6, wherein the content of ethyl lactate is 5 to 50% by mass with respect to the total amount of the solvent.   The curable alkali-soluble resin (A) has a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an 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 1-7.   The radiation-sensitive resin composition according to claim 8, wherein in the structural unit (a2) derived from an unsaturated compound having a curable group (excluding unsaturated carboxylic acid), the curable group is an oxetanyl group. object.   The curable alkali-soluble resin (A) further includes a structural unit (a31) derived from a carboxylic acid ester, a structural unit (a32) derived from an aromatic vinyl compound, and a structural unit (a33) derived from a vinyl cyanide compound. And a copolymer comprising at least one structural unit (a3) selected from the group consisting of structural units (a34) derived from cleavage of unsaturated bonds of N-substituted maleimide compounds. Radiation sensitive resin composition.   The cured resin pattern formed with the radiation sensitive resin composition in any one of Claims 1-10. A display device comprising the cured resin pattern according to claim 11.