JP2006039269A - Radiation sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition having good wettability to a stainless steel base and used for forming a transparent cured resin pattern such as an insulating film of TFT. <P>SOLUTION: The radiation sensitive resin composition contains a curable alkali-soluble resin (A), a quinonediazido compound (B) and a solvent (C), wherein the solvent (C) contains a compound represented by the formula (1): R<SP>1</SP>-O-[CH(CH<SB>3</SB>)CH<SB>2</SB>O]<SB>n</SB>-R<SP>2</SP>and an alkyl lactate (where the alkyl is a 1-4C alkyl). In the formula (1), R<SP>1</SP>and R<SP>2</SP>each independently represent a 1-4C alkyl; and n represents an integer of 1-4. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

The radiation-sensitive resin composition is, for example, a TFT insulating film used in a thin film transistor (hereinafter referred to as TFT) liquid crystal display device or an organic EL display device, or a diffuse reflection used in a reflective TFT substrate. It is useful as a material for forming a cured resin pattern including a plate, an organic EL insulating film, a protective film of a solid-state imaging device (hereinafter, sometimes referred to as CCD), and the like (for example, Patent Documents 1 and 2). Etc.)
With the recent increase in the size of the substrate glass used for TFT substrate production, the composition application method has been changed from spin coating to slit coating that does not spin the substrate. Stainless steel is used as the nozzle base material in the slit coating applicator (Patent Documents 3 to 5), but the wettability of the radiation-sensitive resin composition to the stainless steel base material is good for application by slit coating. It is required to be.

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

  The objective of this invention is providing the radiation sensitive resin composition used in order to form transparent cured resin patterns, such as an insulating film of TFT, with good wettability with respect to a stainless steel base material.

Therefore, the present inventors have intensively studied to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, the present invention provides a radiation-sensitive resin composition containing a curable alkali-soluble resin (A), a quinonediazide compound (B), and a solvent (C), and is represented by the formula (1) in the solvent (C). A radiation-sensitive resin composition comprising the above compound and an alkyl lactate (the alkyl group represents an alkyl group having 1 to 4 carbon atoms).

R ¹ —O— [CH (CH ₃ ) CH ₂ O] _n —R ² (1)

[In Formula (1), R < ¹ > and R < ² > represents a C1-C4 alkyl group each independently.
n represents an integer of 1 to 4. ]

  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.

  According to the radiation-sensitive resin composition of the present invention, the wettability with respect to the stainless steel substrate is good, and the coating property by the slit coater can be improved.

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

  Examples of the structural unit (a1) derived from the unsaturated carboxylic acid include unsaturated monomers having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid. Specific examples include carboxylic acid, and specific examples 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) derived from the unsaturated compound having a curable group (excluding unsaturated carboxylic acid) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl ( (Meth) acrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 2 -Vinylcyclohexene oxide Epoxy group-containing unsaturated compounds such as 3-vinylcyclohexene oxide and 4-vinylcyclohexene oxide;
3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl Oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxyethyloxetane, 3- Methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane, 2-pentafluoroethyl-3- Unsaturation containing oxetanyl group such as (meth) acryloxyethyl oxetane And preferably include 3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 2- Phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3- (Meth) acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl Oxetane, 2-pentafluoroethyl-3- (meth) acryloxyethyl oxe It includes oxetanyl group-containing unsaturated compounds such emissions, and more preferably, 3-ethyl-3-methacryloxy methyl oxetane and the like. When a radiation-sensitive resin composition is prepared using an alkali-soluble resin containing an oxetanyl group-containing unsaturated compound, the storage stability tends to be good, which is preferable.

The copolymer further includes a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond, and a structural unit (a32) derived from an aromatic vinyl compound having a polymerizable carbon-carbon unsaturated bond. At least one structural unit (a3) selected from the group consisting of a structural unit (a33) derived from a vinyl cyanide compound and a structural unit (a34) derived from cleavage of an unsaturated bond of an N-substituted maleimide compound Can be included.
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 structural ratio of (a1) is usually 5 to 50 mol%, preferably 15 to 40 mol%, based on the entire structural units of the copolymer. And the constituent ratio of (a2) is usually 95 to 5 mol%, preferably 85 to 15 mol%, with respect to the constituent units of the copolymer, and the constituent ratio of the other constituent units is preferably 0. .1 to 90 mol%, more preferably 5 to 80 mol%.
Examples of the copolymer containing (a1) and (a2) in the present invention include, for example, 3-ethyl-3-methacryloxymethyl oxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl oxetane / Benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / cyclohexyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate / styrene copolymer, 3-ethyl-3- Methacryloxyme Luoxetane / 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, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / t-butyl acrylate copolymer, 3-ethyl-3-meta Lilo carboxymethyl oxetane / methacrylic acid / phenylmaleimide copolymer, and 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / cyclohexyl maleimide copolymer.

In the present invention, the copolymer containing (a1) and (a2) has a weight average molecular weight determined by gel permeation chromatography based on polystyrene, usually from 2,000 to 100,000, preferably 2,000. 50,000 to 50,000, 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.
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 usually 50 to 90%. , Preferably 60 to 90%.

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

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

  The quinonediazide compound (B) 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% normally, Preferably it is 5-40%. When the content of the quinonediazide compound is within the above range, the difference in dissolution rate between the unexposed area and the exposed area tends to be high, and thus there is a tendency that the developed residual film ratio tends to be kept high.

  The solvent (C) contained in the radiation sensitive resin composition of the present invention contains a compound represented by the formula (1) and an alkyl lactate (the alkyl group represents an alkyl group having 1 to 4 carbon atoms). .

R ¹ —O— [CH (CH ₃ ) CH ₂ O] _n —R ² (1)

[In Formula (1), R < ¹ > and R < ² > represents a C1-C4 alkyl group each independently.
n represents an integer of 1 to 4. ]

  Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. , A methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group.

Specific examples of the compound represented by the formula (1) include propylene glycol dimethyl ether, propylene glycol ethyl methyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol diethyl ether, tripropylene glycol Examples include propylene glycol dimethyl ether, tripropylene glycol ethyl methyl ether, tripropylene glycol diethyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol ethyl methyl ether, tetrapropylene glycol diethyl ether, and the like, preferably dipropylene glycol dimethyl ether, dipropylene glycol ethyl Methyl ether, dipro Examples include lenglycol diethyl ether, tripropylene glycol dimethyl ether, tripropylene glycol ethyl methyl ether, and tripropylene glycol diethyl ether, preferably dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether. , Tripropylene glycol ethyl methyl ether, and tripropylene glycol diethyl ether, and more preferably dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, and dipropylene glycol diethyl ether.
The compounds represented by formula (1) are used singly or in combination of two or more.

  Specific examples of the alkyl lactate include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, s-butyl lactate, t-butyl lactate, preferably ethyl lactate, Examples thereof include n-propyl lactate, isopropyl lactate, and n-butyl lactate, and more preferably ethyl lactate, n-propyl lactate, and n-butyl lactate. The alkyl lactates are used alone or in combination of two or more.

Moreover, you may mix the compound and alkyl lactate represented by said Formula (1), and another solvent.
Examples of the other 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;
Examples include esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 2-hydroxyisobutanoate, butyl acetate, amyl acetate, and methyl pyruvate.

Content of a solvent (C) is a mass fraction with respect to a radiation sensitive resin composition, and is 75-88 mass%, Preferably it is 80-88 mass%, More preferably, it is 82-88 mass%. When the content of the solvent (C) is in the above range, a low-viscosity composition tends to be obtained, which is preferable.
Content of the compound represented by Formula (1) is a mass fraction with respect to the total amount of a solvent (C), Preferably it is 50-99 mass%, More preferably, it is 55-99 mass%, Most preferably, it is 60. It is -99 mass%. When the content of the compound represented by the formula (1) is in the above range, a low-viscosity composition is obtained, and the wettability of the substrate tends to be improved, which is preferable.
Content of alkyl lactate is a mass fraction with respect to the total amount of a solvent (C), Preferably it is 1-50 mass%, More preferably, it is 1-45 mass%, Most preferably, it is 1-40 mass%. When the alkyl lactate content is within the above range, a low-viscosity composition is obtained, the substrate wettability tends to be improved, and the solubility of the composition components tends to be high, which is preferable.

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

As said polymerization initiator (D), the onium salt which is a cationic polymerization initiator is mentioned. 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 (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, tris (pt-butylphenyl) sulfonium tetrakis Pentafluorophenyl) borate.

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

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

  Examples of the polyhydric phenol compound (E) include a polymer having at least hydroxystyrene as a raw material monomer. Specific examples of the polyhydric phenol compound (E) include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer, hydroxystyrene / alkoxystyrene copolymer. Examples thereof include a resin obtained by polymerizing hydroxystyrene such as a polymer. 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 (E), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 0.01-40 mass%, More preferably, it is 0.00. 1 to 25% by mass. When the content of the polyhydric phenol compound (E) 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 (F) 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 (F), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 0.01-15 mass%. When the content of the crosslinking agent is within the above range, the visible light transmittance of the obtained film is increased, and the performance as a cured resin pattern is improved, which is preferable.

  Examples of the polymerizable monomer (G) include a polymerizable monomer capable of radical polymerization upon heating, a polymerizable monomer capable of cationic polymerization, and the like, and preferably 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, 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 (G), this is used individually or in combination of 2 or more types, respectively. Content of a polymerizable monomer (G) is a mass fraction with respect to solid content of a radiation sensitive resin composition, and is 0.1-20 mass% normally.

As the silane coupling agent (H), as the silane coupling agent (D), methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane Vinyltris (2-methoxyethoxy) silane, 3-chloropropyl-trimethoxysilane, 3-chloropropylmethyl-dichlorosilane, 3-chloropropylmethyl-dimethoxysilane, 3-chloropropylmethyl-diethoxysilane, 3-glycol Sidoxypropyl-trimethoxysilane, 3-glycidoxypropyl-triethoxysilane, 3-glycidoxypropylmethyl-dimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-methacryloyloxypropyl- Limethoxysilane, 3-methacryloyloxypropylmethyl-dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, N-2- (N-vinylbenzylaminoethyl) -3-aminopropyl-tri Methoxysilane hydrochloride, hexamethyldisilazane, diaminosilane, triaminopropyl-trimethoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropylmethyl-diethoxysilane, 3 -Aminopropyl-tris (2-methoxyethoxyethoxy) silane, 3- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -3-aminopropylmethyl-dimethoxysilane, 3-ureidopropyl-trime Xysilane, 3-ureidopropyl-triethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxysilane, N-aminoethyl-3-aminopropylmethyl-dimethoxysilane, N-methyl-3-aminopropyl-trimethoxy Examples thereof include silane and N-phenyl-3-aminopropyl-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.

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 name E5844 (manufactured by Daikin Fine Chemical Laboratory);
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 comprises, for example, mixing a solution obtained by dissolving a curable alkali-soluble resin (A) in a solvent (C) and a solution obtained by dissolving a quinonediazide compound (B) in a solvent (C). Can be prepared. Moreover, you may add a solvent (C) after mixing. Furthermore, after mixing the solution, it is preferable to remove solid matter by filtration, and for example, it is preferable to filter using a filter having a pore diameter of 3 μm or less, preferably 0.1 μm or more and 2 μm or less. The solvent used for each component may be the same or different as long as it is compatible.

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

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

The layer made of the radiation sensitive resin composition is performed by a slit coating method that does not spin the substrate. Examples of the coating apparatus used in the slit coating method include a slit coater, a die coater, and a curtain flow coater.
After application, heat-drying (pre-baking) or vacuum-drying after heating to remove part or all of the volatile components such as the solvent, a radiation-sensitive resin composition layer having a reduced solvent content is formed. . Moreover, the thickness of this radiation sensitive resin composition layer is about 1.5 micrometers-about 5 micrometers, for example.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The cured resin pattern thus formed is obtained by curing the radiation-sensitive resin composition of the present invention. For example, the cured resin pattern is cured to constitute a TFT substrate, an insulating film for an organic EL element, a protective film for a CCD, or the like. Useful as a resin pattern.

  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: Resin A1
A 300 mL four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 116 g of ethyl lactate as a solvent, 2.2 g of azobisisobutyronitrile as a polymerization initiator, and the following monomers, The reaction was carried out with stirring for 3 hours while maintaining the internal temperature at 100 to 110 ° C. to obtain a solution containing the resin A1. The polystyrene equivalent weight average molecular weight of this resin A1 was 8,300.

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

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

Example 1
The following components were mixed at 23 ° C. and then pressure filtered through a cartridge filter made of polytetrafluoroethylene having a pore size of 1.0 μm to obtain a radiation sensitive resin composition as a filtrate. Content of the solvent (C) in the obtained radiation sensitive resin composition was 84.9%.

Solution containing resin A1 250 parts by mass (solid content conversion: 100 parts by mass)
Compound represented by formula (2) 20 parts by mass Adekaoptomer SP-172 (photocation polymerization catalyst; manufactured by Asahi Denka Kogyo Co., Ltd.) 2 parts by mass Sun-Aid SI-100L (thermal cation polymerization catalyst; Sanshin Chemical Industry ( 2 parts by mass KBM-303 (silane coupling agent; β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass dipropylene glycol dimethyl ether (formula (1) 554 parts by mass of a compound represented by

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

  Table 1 shows the composition.

Comparative Example 1
A radiation sensitive resin composition was obtained in the same manner as in Example 1 except that ethyl lactate was used instead of dipropylene glycol dimethyl ether. Content of the solvent (C) in the obtained radiation sensitive resin composition was 84.9%. Table 1 shows the composition.

Synthesis example 2
The reaction was conducted in the same manner as in Synthesis Example 1 except that 36 g of ethyl lactate and 146 g of ethyl 3-ethoxypropionate were used as the solvent to be used, and a solution containing the resin A2 was obtained. The polystyrene equivalent weight average molecular weight of this resin A2 was 7,900 as measured by the same GPC method as described above.

Example 2
The following components were mixed at 23 ° C. and then pressure filtered through a cartridge filter made of polytetrafluoroethylene having a pore size of 1.0 μm to obtain a radiation sensitive resin composition as a filtrate. Content of the solvent (C) in the obtained radiation sensitive resin composition was 84.9%.

333 parts by mass of solution containing resin A2 (in terms of solid content; 100 parts by mass)
Compound represented by formula (2) 20 parts by mass Adekaoptomer SP-172 (photocation polymerization catalyst; manufactured by Asahi Denka Kogyo Co., Ltd.) 2 parts by mass Sun-Aid SI-100L (thermal cation polymerization catalyst; Sanshin Chemical Industry ( 2 parts by mass KBM-303 (silane coupling agent; β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass dipropylene glycol dimethyl ether (formula (1) 468 parts by mass of a compound represented by

  Table 2 shows the composition.

Comparative Example 2
A radiation-sensitive resin composition was obtained in the same manner as in Example 2 except that ethyl lactate was used instead of dipropylene glycol dimethyl ether. Content of the solvent (C) in the obtained radiation sensitive resin composition was 84.9%. Table 2 shows the composition.

<Measurement example of viscosity>
The viscosity at 23 ° C. of the radiation-sensitive resin compositions obtained in the above Examples and Comparative Examples was measured using a viscometer (TV-30L viscometer (No. 1 rotor); manufactured by Toki Sangyo Co., Ltd.). And measured. The measurement results are shown in Tables 1 and 2.

<Example of flowability measurement>
A SUS630 plate (size: 100 mm × 200 mm × 10 mm, surface roughness: unidirectional equivalent to JIS B0659 12.5-S) obtained from the radiation-sensitive resin compositions obtained in the above examples and comparative examples. 10 μl was dropped from a Pasteur pipette (5-3 / 4 ″; manufactured by Fischer) onto the hairline finish), and immediately after the dropping, the SUS630 plate was set up in the vertical direction. It was set to be perpendicular to the dropping direction.
The distance that the radiation-sensitive resin composition flowed until the composition stopped flowing was measured and taken as the flow distance. The measurement results are shown in Tables 1 and 2.
In addition, when the liquid flowed, the flowability was determined as x when the trajectory was bent by 5% or more of the flow distance in the hairline direction, and ○ when the trajectory was bent within 5% of the flow distance. The determination results are shown in Tables 1 and 2.

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

Example; The locus | trajectory of a radiation sensitive resin composition when flowability is determined using the radiation sensitive resin composition of an Example is shown. Comparative Example: The trajectory of the radiation sensitive resin composition when the flowability is determined using the radiation sensitive resin composition of the comparative example is shown.

Claims (11)

A radiation-sensitive resin composition containing a curable alkali-soluble resin (A), a quinonediazide compound (B), and a solvent (C), the compound represented by the formula (1) and lactic acid in the solvent (C) A radiation-sensitive resin composition containing alkyl (the alkyl group represents an alkyl group having 1 to 4 carbon atoms).
R ¹ —O— [CH (CH ₃ ) CH ₂ O] _n —R ² (1)
[In Formula (1), R < ¹ > and R < ² > represents a C1-C4 alkyl group each independently.
n represents an integer of 1 to 4. ] The radiation sensitive resin composition according to claim 1, wherein R ¹ and R ² each independently represent a methyl group or an ethyl group.   The radiation sensitive resin composition according to claim 1 or 2, wherein n represents an integer of 2 or 3.   The radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the content of the solvent (C) is 75 to 88% by mass with respect to the radiation-sensitive resin composition.   The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the content of the compound represented by the formula (1) is 50 to 99% by mass with respect to the total amount of the solvent. .   The content of alkyl lactate (the alkyl group represents an alkyl group having 1 to 4 carbon atoms) is 1 to 50% by mass in terms of mass fraction with respect to the total amount of the solvent. The radiation sensitive resin composition in any one.   The curable alkali-soluble resin (A) is derived from the structural unit (a1) derived from the unsaturated carboxylic acid and the unsaturated compound having a curable group (excluding the unsaturated carboxylic acid). It is a copolymer containing (a2), The radiation sensitive resin composition in any one of Claims 1-6.   The radiation-sensitive resin composition according to claim 7, wherein the curable group is an oxetanyl group in the structural unit (a2) derived from an unsaturated compound having a curable group (excluding an unsaturated carboxylic acid). object.   The curable alkali-soluble resin (A) is further derived from a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond and an aromatic vinyl compound having a polymerizable carbon-carbon unsaturated bond. At least one component selected from the group consisting of the structural unit (a32), the structural unit (a33) derived from the vinyl cyanide compound, and the structural unit (a34) derived from cleavage of the unsaturated bond of the N-substituted maleimide compound. It is a copolymer containing a unit (a3), The radiation sensitive resin composition in any one of Claims 1-8.   The cured resin pattern formed with the radiation sensitive resin composition in any one of Claims 1-9. A liquid crystal display device comprising the cured resin pattern according to claim 10.

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