KR20060052212A - Radiation-sensitive resin composition - Google Patents

Abstract

The present invention provides a radiation-sensitive resin composition containing an alkali-soluble resin (A) having a curability, a quinonediazide compound (B), a solvent (C) and a silicone-based surfactant (D), wherein the silicone-based surfactant (D) is Provided is a radiation-sensitive resin composition which is a silicone-based surfactant containing a silicone-based surfactant (D1) having an HLB value of 1 to 9 or less and a silicone-based surfactant (D2) having an HLB value of 9 or more.

Description

Radiation-sensitive resin composition {RADIATION-SENSITIVE RESIN COMPOSITION}

The present invention relates to a radiation sensitive resin composition.

The radiation-sensitive resin composition is, for example, an insulating film of a thin film transistor (hereinafter sometimes referred to as a TFT) type liquid crystal display device, an insulating film of an organic EL display device, a diffuse reflecting plate used for a reflective TFT substrate, a solid-state imaging device (hereinafter, It is useful as a material for forming a cured resin pattern including a protective film of CCD, etc.) (see Japanese Patent No. 2933879). Here, in order to obtain a higher performance TFT substrate, the TFT insulating film is required for the performance of flattening the step difference of the underlying substrate such as a TFT element formed on the substrate (see Japanese Patent Laid-Open No. 9-244009).

In addition to these, with the increase in the size of the substrate glass used in the recent production of TFT substrates, the method of applying the composition has been changed to a method of coating from a slit nozzle that does not spin the substrate in spin coating. In the coating apparatus having a slit-type nozzle, stainless steel is used as the nozzle base material (see Japanese Patent Laid-Open No. 2001-162204, Japanese Patent Laid-Open No. 2003-211053, and Japanese Patent Laid-Open No. 8-173875). In order to apply | coat with an apparatus, the wettability with respect to the stainless steel base material of a radiation sensitive resin composition is calculated | required.

The present inventors found out that the radiation sensitive resin composition containing two types of silicone surfactants has good wettability with respect to a stainless steel base material.

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

That is, this invention provides the following [1]-[8].

[1] A radiation-sensitive resin composition containing an alkali-soluble resin (A) having a curability, a quinonediazide compound (B), a solvent (C) and a silicone-based surfactant (D), wherein the silicone-based surfactant (D) is A radiation sensitive resin composition which is a silicone type surfactant containing the silicone type surfactant (D1) whose HLB value is 1 or more and 9 or less and the silicone type surfactant (D2) whose HLB value is 9 or more.

[2] Structural alkali-soluble resin (A) is a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having a curable group (but not an unsaturated carboxylic acid) ) The composition as described in [1] which is a copolymer containing.

[3] The composition according to [2], wherein the curable group in the structural unit (a2) is an oxetanyl group.

[4] Structural alkali-soluble resin (A) is a structural unit derived from a carboxylic acid ester having an olefinic double bond (a31) or a structural compound derived from an aromatic compound having a polymerizable carbon-carbon unsaturated bond. (a32), which further contains 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 an N-substituted maleimide compound The composition as described in any one of [1]-[3].

[5] The composition according to any one of [1] to [4], wherein the surfactant (D1) is a polyalkylene glycol-modified silicone.

[6] The composition according to any one of [1] to [5], wherein the surfactant (D2) is a polyalkylene glycol-modified silicone.

[7] The composition according to any one of [1] to [6], wherein the content of the silicone surfactant (D) is 1 to 1000 ppm by mass fraction relative to the radiation sensitive resin composition.

[8] The composition according to any one of [1] to [7], wherein the content of the surfactant (D1) is 50 to 90 mass% in a mass fraction with respect to the total amount of the silicone surfactant (D).

[9] The composition according to any one of [1] to [8], which is applied to a coating device having a slit nozzle.

[10] A transparent cured resin pattern formed of the composition according to any one of [1] to [9].

[11] A display device comprising the transparent cured resin pattern described in [10].

The radiation sensitive resin composition of this invention contains alkali-soluble resin (A) which has curability, a quinonediazide compound (B), a solvent (C), and a silicone type surfactant (D), and also the said silicone type surfactant ( D) contains a silicone surfactant (D1) having an HLB value of 1 or more and 9 or less and a silicone surfactant (D2) having an HLB value of more than 9.

As alkali-soluble resin (A) which has sclerosis | hardenability used for this invention, the structure derived from the structural unit (a1) derived from unsaturated carboxylic acid, and the unsaturated compound which has curable group (except unsaturated carboxylic acid) Copolymers containing the unit (a2) are preferably used.

As said unsaturated carboxylic acid, unsaturated carboxylic acid etc. which have 1 or 2 or more carboxyl groups in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, etc. are mentioned, for example.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

Examples of the unsaturated compound having a curable group (except for unsaturated carboxylic acid) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and 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 Epoxy group-containing unsaturated compounds such as vinylbenzyl glycidyl ether, 2-vinylcyclohexene oxide, 3-vinylcyclohexene oxide, and 4-vinylcyclohexene oxide;

3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 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) acrylic And oxetanyl group-containing unsaturated compounds such as oxyethyl oxetane and 2-pentafluoroethyl-3- (meth) acryloxyethyl oxetane.

Among them, 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 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- ( Oxetanyl group-containing unsaturated compounds such as meth) acryloxyethyl oxetane and 2-pentafluoroethyl-3- (meth) acryloxyethyl oxetane are preferably used, and 3-ethyl-3-methacryloxymethyl jade is used. Cetane is more preferably used.

When a radiation sensitive resin composition is manufactured using alkali-soluble resin containing an oxetanyl group containing unsaturated compound, since storage stability tends to become favorable, it is preferable.

The copolymer described above also includes a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond, a structural unit (a32) derived from an aromatic vinyl compound having a polymerizable carbon-carbon unsaturated bond, and vinyl cyanide. At least one structural unit (a3) selected from the group consisting of a structural unit (a33) derived from the compound and a structural unit (a34) derived by cleaving the unsaturated bond of the N-substituted maleimide compound is contained. You may be.

As carboxylic acid ester which has an olefinic double bond which induces said structural unit (a31), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl ( Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, diethyl maleate, fumaric acid Unsaturated carboxylic acid esters such as diethyl and diethyl itaconic acid;

Unsaturated carboxylic acid aminoalkyl esters such as aminoethyl (meth) acrylate;

Carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate, etc. are mentioned.

As an aromatic vinyl compound which has a polymerizable carbon-carbon unsaturated bond which induces said structural unit (a32), an aromatic vinyl compound etc. are mentioned, for example. As this aromatic vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, etc. are mentioned, for example.

As a vinyl cyanide compound which guide | induces said structural unit (a33), vinyl cyanide compounds, such as an acrylonitrile, methacrylonitrile, (alpha)-chloro (meth) acrylonitrile, etc. are mentioned, for example.

As an N-substituted maleimide compound which induces the above-mentioned structural unit (a34), for example, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenylmaleimide, N- (4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide capro Eight, N- (1-anilinonaphthyl-4) -maleimide, N- [4- (2-benzoxazolyl) phenyl] maleimide, N- (9-acridinyl) maleimide, etc. are mentioned. have.

These structural units may be used individually, or may be used in combination of 2 or more type.

In the copolymer containing the structural unit (a1) derived from an unsaturated carboxylic acid and the structural unit (a2) derived from an unsaturated compound having a curing group (except for the unsaturated carboxylic acid), the structural unit (a1) The ratio of is preferably 5 to 50 mol%, more preferably 15 to 40 mol% with respect to the total number of moles of the structural units of the copolymer, and the proportion of the structural units (a2) is the total of the structural units of the copolymer. The molar number is preferably 95 to 50 mol%, more preferably 85 to 60 mol%.

In said copolymer, when the ratio of a structural unit (a1) and a structural unit (a2) exists in the said range, it shows the tendency which shows an appropriate dissolution rate with respect to a developing solution at the time of pattern formation, and the obtained pattern also shows high curability. This is preferable because there is.

The copolymer containing a structural unit (a1) and a structural unit (a2) may contain other structural units as arbitrary components other than a structural unit (a1) and a structural unit (a2). In the case where the copolymer contains other structural units as an optional component, the proportion of the structural unit (a1) is preferably 5 to 50 mol%, more preferably 15 to 40 mol% with respect to the entire structural unit of the copolymer. The ratio of the structural unit (a2) is preferably 95 to 5 mol%, more preferably 85 to 15 mol% with respect to the structural unit of the copolymer, and the ratio of the other structural units is preferably 0.1 to 90 mol. %, More preferably, it is 5-80 mol%.

As a copolymer containing a structural unit (a1) and a structural unit (a2), for example, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3- Methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxy Methyl oxetane / methacrylic acid / cyclohexyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / methyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl Oxetane / methacrylic acid / methyl methacrylate / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methacryl Oxymethyl oxetane / methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / benzyl acryl Copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl acrylate Copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / dicyclopentanyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / t-butylacrylic Latex copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / phenylmaleimide copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexylmaleimide copolymer Etc. can be mentioned.

The weight average molecular weight determined by gel permeation chromatography on the basis of polystyrene in the copolymer containing the structural unit (a1) and the structural unit (a2) is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, More preferably, it is 3,000-20,000. When the weight average molecular weight is in the above-described range, it is preferable because a high development speed tends to be obtained while maintaining the residual film ratio during development.

The content of the copolymer containing the structural unit (a1) and the structural unit (a2) in the radiation-sensitive resin composition of the present invention is preferably 50 to 90% by mass fraction with respect to the solid content of the radiation-sensitive resin composition, More preferably, it is 60 to 90%.

As a quinone diazide compound (B) used for this invention, a 1, 2- benzoquinone diazide sulfonic acid ester, a 1, 2- naphthoquinone diazide sulfonic acid ester, a 1, 2- benzoquinone diazide sulfonic acid amide, 1 And 2-naphthoquinone diazide sulfonic acid amide.

Specific examples of the quinone diazide compound (B) include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1 , 2-naphthoquinone diazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6-trihydroxy 1,2-naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenones, such as benzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2 Naphthoquinone diazide-5-sulfonic acid ester, 2,2 ', 4,3'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2', 4, 3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4 Sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxybenzophenone-1 , 2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4, 4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone -1,2-naphthoquinonedia DE-5-sulfonic acid tetrahydroxy benzophenones 1,2-naphthoquinonediazide sulfonic acid ester of the ester and the like;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxy benzophenones, such as -1, 2- naphthoquinone diazide-5- sulfonic acid ester;

2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6,3 ', 4', 5 ' Hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinone Hexahydroxy benzophene, such as a diazide-4- sulfonic acid ester and a 3,4,5,3 ', 4', 5'-hexahydroxy benzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester Non- 1,2-naphthoquinone diazide 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-naphthoquinone diazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide -5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-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-naphthoquinone diazide-4-sulfonic acid ester, 2,2'-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide-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-hydroxy Phenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Methane-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-naphtho Quinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1 , 2-naphthoquinone diazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinone diazide- (Polyhydroxyphenyl) alkanes such as 4-sulfonic acid ester and 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester 1,2-naphthoquinone diazide sulfonic-acid ester etc. of these are mentioned.

Said quinonediazide compound (B) may be used individually, or may be used in combination of 2 or more type.

The content of the quinonediazide compound (B) is preferably 2 to 50%, more preferably 5 to 40% by mass fraction with respect to the solid content of the radiation-sensitive resin composition. When content of a quinone diazide compound exists in the said range, since the difference of the dissolution rate of an unexposed part and an exposure part becomes high, since there exists a tendency which can maintain high image development residual film ratio, it is preferable.

Examples of the solvent (C) used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, and ethylene glycol mono ethylene glycol monoalkyl such as sec-butyl ether, ethylene glycol mono tert-butyl ether, ethylene glycol mono n-pentyl ether, ethylene glycol mono n-hexyl ether, ethylene glycol mono n-heptyl ether, and ethylene glycol mono n-octyl ether Ethers;

Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol din-propyl ether, diethylene glycol diisopropyl ether, diethylene glycol di n-butyl ether, diethylene glycol disec-butyl ether, diethylene Glycol ditert-butyl ether, diethylene glycol di-pentyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl n-butyl ether, di Ethylene glycol methyl sec-butyl ether, diethylene glycol methyl tert-butyl ether, diethylene glycol methyl n-pentyl ether, diethylene glycol ethyl n-propyl ether, diethylene glycol ethyl isopropyl ether, diethylene glycol ethyl n- Butyl ether, diethylene glycol ethyl sec-butyl ether, diethylene glycol ethyl tert-butyl ether, diethylene glycol ethyl n-pentyl ether, diethylene glycol Col n-propyl isopropyl ether, diethylene glycol n-propyl n-butyl ether, diethylene glycol n-propyl sec-butyl ether, diethylene glycol n-propyl tert-butyl ether, diethylene glycol n-propyl n-pentyl Ether, diethylene glycol isopropyl n-butyl ether, diethylene glycol isopropyl sec-butyl ether, diethylene glycol isopropyl tert-butyl ether, diethylene glycol isopropyl n-pentyl ether, diethylene glycol n-butyl sec- Diethylene such as butyl ether, diethylene glycol n-butyl tert-butyl ether, diethylene glycol n-butyl n-pentyl ether, diethylene glycol sec-butyl tert-butyl ether, diethylene glycol sec-butyl n-pentyl ether Glycol dialkyl ethers;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl lactate, butyl lactate, butyl acetate, amyl acetate, methyl pyruvate and 1,3-butanediol diacetate Can be mentioned.

Said solvent (C) may be used independently, or may be used in combination of 2 or more type.

Among them, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate, ethyl lactate, butyl lactate and butyl acetate are preferably used, and a solvent (C) is combined. It is preferable to use these solvents even if it does.

As a preferable solvent combination, for example, diethylene glycol dimethyl ether and ethyl 3-ethoxy propionate, diethylene glycol dimethyl ether and ethyl lactate, diethylene glycol dimethyl ether and butyl lactate, diethylene glycol dimethyl ether, butyl acetate and diethylene glycol Diethyl ether, ethyl 3-ethoxypropionate, diethylene glycol diethyl ether, ethyl lactate, diethylene glycol diethyl ether, butyl lactate, diethylene glycol diethyl ether, butyl acetate, diethylene glycol methyl ethyl ether, 3- Ethyl ethoxypropionate, diethylene glycol methylethyl ether and ethyl lactate, diethylene glycol methylethyl ether and butyl lactate, diethylene glycol methylethyl ether and butyl acetate, 3-ethoxypropionate ethyl and lactate ethyl, 3-ethoxypropionic acid Ethyl and butyl lactate, ethyl 3-ethoxypropionate and butyl acetate;

Diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate and butyl lactate, diethylene glycol methyl ethyl ether, 3-ethoxy propionate and butyl acetate;

Diethylene glycol methyl ethyl ether, ethyl 3-ethoxy propionate, butyl lactate, and butyl acetate are mentioned.

Diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate and butyl lactate, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate and butyl acetate are more preferably used. Ethyl oxypropionate, butyl lactate and butyl acetate are particularly preferably used.

Content of a solvent (C) is 50-95 mass% with respect to a radiation sensitive resin composition, Preferably it is 50-95 mass%, More preferably, it is 70-90 mass%.

When adapting to the coating device only for the process of apply | coating from a slit-type nozzle, it is preferable that content of a solvent (C) is 75-90 mass% on the same basis as the above. Moreover, in addition to the process of apply | coating from a slit-type nozzle, when applying a composition to the application | coating apparatus which has a process of rotating the coated board | substrate, content of a solvent (C) is 65-80 mass% on the same basis as the above. It is preferable.

When content of a solvent (C) exists in the said range, since there exists a tendency which can form the coating film with little generation | occurrence | production of a stain, it is preferable.

The silicone-based surfactant (D) used in the present invention contains a silicone-based surfactant (D1) having an HLB value of 1 to 9 or less and a silicone-based surfactant (D2) having an HLB value of 9 or more.

Here, the HLB value is specifically measured by the following method.

Dissolve 0.5 g of surfactant / in ethanol / 5 ml. 2% aqueous phenol solution is added dropwise, and the addition amount (ml) when the liquid becomes turbid is recorded as fresh water A. The HLB value is calculated by HLB = 0.89 × (fresh water A) +1.11 (see Nishiichiro: Surfactant Handbook / Sangyo Shosho Co., Ltd.).

Since various HLB can be set with the polyether introduction amount or the ethylene oxide / propylene oxide ratio in a polyether, polyether modified silicone oil is used suitably as silicone type surfactant (D) of this invention.

As silicone type surfactant (D1) whose HLB value is 1 or more and 9 or less, FS1265, SH710, SH203, BY16-880, SH3775, SH3748, SH3749, SF8410, SF8421, SH8400, SH28PA (made by Toray Dow Corning Silicone Co., Ltd.) etc. are mentioned, for example. Can be mentioned.

As silicone type surfactant (D2) whose HLB value exceeds 9, for example, SH3771M, SH3746 (made by Toray Dow Corning Silicon Co., Ltd.), PS558 (made by United Chemicals, Inc.), Q2-5211 (made by Dow Co., Ltd.) ), SILWET 408, L-7210, L-7200 (above, all are manufactured by Oshi Specialty Co., Ltd.), and the like.

The content of the silicone-based surfactant (D) is preferably 1 to 1000 ppm, more preferably 10 to 500 ppm, still more preferably 50 to 300 ppm in terms of mass fraction with respect to the radiation sensitive resin composition. When content of a silicone type surfactant exists in the said range, since it exists in the tendency which can form the coating film with little generation | occurrence | production of a stain, it is preferable.

Moreover, it is preferable that content of the silicone type surfactant (D1) of 1 <= HLB <= 9 is 50-90 mass% in mass fraction with respect to the total effective amount of a silicone type surfactant (D).

The radiation-sensitive resin composition of the present invention may contain a polymerization initiator (F), a polyhydric phenol compound (G), a crosslinking agent (H), a polymerizable monomer (I), a silane coupling agent (J), or the like as other components. .

As said polymerization initiator (F), the onium salt which is a photocationic polymerization initiator is mentioned, for example. The onium salt is composed of an onium cation and an anion derived from Lewis acid.

Specifically as said onium cation, diphenyl iodonium, bis (p-tolyl) iodonium, bis (pt-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl Iodide, bis (p-octyloxyphenyl) iodium, bis (p-octadecyloxyphenyl) iodium, phenyl (p-octadecyloxyphenyl) iodium, (p-tolyl) (p-isopropylphenyl Iodide, triphenylsulfonium, tris (p-tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (pt-butylphenyl) sulfonium , Tris (p-cyanophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy ) Sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecaneoxy) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (t-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (Sicle Lohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, Dimethyl (8-nitrooctyloxy) sulfonium, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, dimethyl (tris (trichloromethyl) methyl) sulphate Phosphium, etc., Preferably bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (pt-butylphenyl) iodonium, triphenylsulfonium, tris (pt-butylphenyl) sulfonium etc. are mentioned.

Specific examples of the anion derived from Lewis acid include hexafluorophosphate, hexafluoroarcinate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, and the like. Monate and tetrakis (pentafluorophenyl) borate are preferably used.

Said onium cation and anion derived from a Lewis acid can be combined arbitrarily.

As a specific example of a photocationic polymerization initiator, diphenyl iodonium hexafluoro phosphate, bis (p-tolyl) iodonium hexafluoro phosphate, bis (pt-butylphenyl) iodonium hexafluoro phosphate, bis (p-octylphenyl Iodide hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexa Fluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate, ethyl Naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexa Fluorophosphate, tris (2,6-dimethylphenyl) sulfonium hexafluorophosphate, tris (pt-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluoro phosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulphate Phosphorous hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecaneoxy) sulfonium Hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (t-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclo Yloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluoro Phosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl ( 18-trifluoromethyloctadecaneoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluorophosphate , Diphenyliodonium hexafluoroarcinate, bis (p-tolyl) iodonium hexafluoroarcinate, bis (pt-butylphenyl) iodonium hexafluoroarcinate, bis (p -Octylphenyl) iodonium hexafluoroarcinate, bis (p-octadecylphenyl) iodonium hexafluoroarcinate, bis (p-octyloxyphenyl) iodonium hexafluoroarcinate, bis (p Octadecyloxyphenyl) iodonium hexafluoroarcinate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarcinate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoro Arcinate, methylnaphthyl iodonium hexafluoroarcinate, ethylnaphthyl iodonium hexafluoroarcinate, triphenylsulfonium hexafluoro arcinate, tris (p-tolyl) sulfonium hexafluoro Arcinate, tris (p-isopropylphenyl) sulfonium hexafluoroarcinate, tris (2,6-dimethylphenyl) sulfonium hexafluoroarcinate, tris (pt-butylphenyl) sulfonium hexafluor Roarcinate, tris (p-cyanophenyl) sulfonium Safluoroarcinate, tris (p-chlorophenyl) sulfonium hexafluoroarcinate, dimethylnaphthylsulfonium hexafluoroarcinate, diethylnaphthylsulfonium hexafluoroarcinate, dimethyl (methoxy Sulphonium hexafluoroarcinate, dimethyl (ethoxy) sulfonium hexafluoroarcinate, dimethyl (propoxy) sulfonium hexafluoroarcinate, dimethyl (butoxy) sulfonium hexafluoroarcy Nate, dimethyl (octyloxy) sulfonium hexafluoroarcinate, dimethyl (octadecaneoxy) sulfonium hexafluoroarcinate, dimethyl (isopropoxy) sulfonium hexafluoroarcinate, dimethyl (t- Butoxy) sulfonium hexafluoroarcinate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarcinate, dimethyl (cyclohexyloxy) sulfonium hexafluoroarcinate, dimethyl (fluoromethoxy) sulfo Hexafluoroarcinate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarcinate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarcinate, dimethyl (4-cyanobutoxy) Sulfonium hexafluoroarcinate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarcinate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroarcinate, dimethyl (2 Hydroxyisopropoxy) sulfonium hexafluoroarcinate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarcinate, diphenyliodiumhexafluoroantimonate, bis (p- Tolyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p-octadecyl Phenyl) iodium hexafluoroantimonate, non S (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodiumhexafluoroantimony Monate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenyl Sulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris (2,6-dimethylphenyl) Sulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulphate Phosphorous hexafluoroantimonate, dimethylnaphthylsulfonium hexa Luoroantimonate, diethylnaphthylsulfonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy ) Sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroanti Monate, 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 Bromopro Sulphonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18- Trifluoromethyloctadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfoniumhexafluoro Roantimonate, diphenyl iodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (penta) Fluorophenyl) borate, bis (p-octylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octyl Oxyphenyl) Iodonium Tetrakis (Penta) Fluorophenyl) borate, bis (p-octadecyloxyphenyl) iodium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodium tetrakis (pentafluorophenyl) borate, (p -Tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyl iodonium tetrakis (pentafluorophenyl) Borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluoro Phenyl) borate, tris (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-cyano Phenyl) sulfonium tetrakis (penta) Fluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaphthylsulfonium tetrakis (pentafluoro Phenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (penta) Fluorophenyl) borate, dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecaneoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (t-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl ( Clopentyloxy) 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 (4-cyanobu Methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) Borate Etc., Preferably, bis (p-tolyl) iodonium hexafluoro phosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoro phosphate, bis (pt-butylphenyl) iodonium Hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (pt-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarcinate, (p-tolyl) (p Isopropylphenyl) iodonium hexafluoroarcinate, bis (pt-butylphenyl) iodonium hexafluoroarcinate, triphenylsulfonium hexafluoroarcinate, tris (pt-butylphenyl) sulphate Phosphorous hexafluoroarcinate, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl Iodide hexafluoroantimonate, triphenylsulfonium hexaple Uroroantimonate, tris (pt-butylphenyl) sulfoniumhexafluoroantimonate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropyl Phenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) sulfonium tetrakis ( Pentafluorophenyl) borate, and the like.

Among them, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl) iodonium hexafluoro Rhoantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis ( Pentafluorophenyl) borate and tris (pt-butylphenyl) sulfoniumtetrakis (pentafluorophenyl) borate are preferably used.

When using a polymerization initiator (F), the content is 0.01-10 mass% 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 mass%. When content of a polymerization initiator (F) exists in the said range, since the resolution fall at the time of thermosetting is suppressed and the solvent resistance of a cured film tends to improve by increasing the hardening rate at the time of thermosetting, it is preferable.

As said polyhydric phenol compound (G), the compound etc. which have 2 or more phenolic hydroxyl group in a molecule | numerator are mentioned, for example.

Examples of the polyhydric phenol compound (G) include trihydroxy benzophenones, tetrahydroxy benzophenones, pentahydroxy benzophenones, hexahydroxy benzophenones, and the like as described in the quinone diazide compound. And polyhydric phenols such as oxyphenyl) alkanes.

Moreover, as a polyhydric phenol compound (G), the polymer which uses hydroxystyrene as a raw material monomer at least is also mentioned, for example.

Specific examples of the polyhydric phenol compound (G) include polyhydroxy styrene, hydroxy styrene / methyl methacrylate copolymer, hydroxy styrene / cyclohexyl methacrylate copolymer, hydroxy styrene / styrene copolymer, hydroxy styrene / Resins polymerized with hydroxy styrene such as alkoxy styrene copolymers; and at least one compound selected from the group consisting of phenols, cresols and catechols, and aldehydes and ketones. And novolak resins obtained by condensation polymerization of one or more compounds.

When using said polyhydric phenol compound (G), the content is 0.01-40 mass%, More preferably, it is 0.1-25 mass% in mass fraction with respect to solid content of a radiation sensitive resin composition. When content of a polyhydric phenol compound (G) exists in the said range, since the resolution improves and there exists a tendency for visible light transmittance to fall, it is preferable.

As said crosslinking agent (H), a methylol compound etc. are mentioned, for example.

As said methylol compound, the alkoxy methylation amino resin, such as an alkoxy methylation melamine resin and an alkoxy methylation urea resin, etc. are mentioned, for example. Here, as the alkoxy methylated melamine resin, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, and the like, and as alkoxymethylated urea resin, methoxymethylated urea resin, ethoxymethylated urea resin, Propoxymethylated urea resins, butoxymethylated urea resins, and the like. Said crosslinking agent (H) may be used individually, respectively, and may be used in combination of 2 or more type.

When using a crosslinking agent (H), the content is preferably 0.01-15 mass% in mass fraction with respect to solid content of a radiation sensitive resin composition. When content of a crosslinking agent exists in the said range, since the visible light transmittance of the film | membrane obtained increases and the performance as a cured resin pattern improves, it is preferable.

As said polymerizable monomer (I), the polymerizable monomer which can be radically polymerized by heating, the polymerizable monomer which can be cationicly polymerized, etc. are mentioned, for example. Among these, polymerizable monomers capable of cationic polymerization are preferably used.

As said radically polymerizable polymerizable monomer, the compound which has a polymerizable carbon-carbon unsaturated bond is mentioned, for example, A monofunctional polymerizable monomer may be sufficient, A bifunctional polymerizable monomer or a trifunctional or more than trifunctional polymerizable monomer Etc., a polyfunctional polymerizable monomer may be sufficient.

Examples of the monofunctional polymerizable monomer include nonylphenylcarbitol acrylate, nonylphenylcarbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl methacrylate. , 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-vinylpyrrolidone and the like.

Examples of the bifunctional polymerizable monomer include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, Neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentanediol Dimethacrylate etc. are mentioned.

Moreover, as a trifunctional or more than trifunctional polymerizable monomer, a trimethylol propane triacrylate, a trimethylol propane trimethacrylate, a pentaerythritol triacrylate, a pentaerythritol trimethacrylate, a pentaerythritol tetramethacrylate, a pentaerythritol tetramethacryl, for example. The rate, pentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned.

Among the polymerizable monomers described above, bifunctional or trifunctional or higher functional monomers are preferably used. Specifically, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like are preferably used, and dipentaerythritol hexaacrylate is more preferably used. Moreover, you may use combining the bifunctional or trifunctional or more than trifunctional polymerizable monomer and the monofunctional polymerizable monomer.

As a polymerizable monomer which can carry out cation polymerization, the polymerizable monomer which has cationically polymerizable functional groups, such as a vinyl ether group, a propenyl ether group, an epoxy group, and an oxetanyl group, is mentioned, for example.

As a compound containing a vinyl ether group, triethylene glycol divinyl ether, 1, 4- cyclohexane dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, etc. are mentioned, for example, a propenyl ether group Examples of the compound to be contained include 4- (1-propenyloxymethyl) -1,3-dioxolan-2-one and the like, and examples of the compound containing an epoxy group include bisphenol A type epoxy resins and phenol novolacs. Epoxy resins, cresol novolac epoxy resins, cyclic aliphatic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, heterocyclic epoxy resins, and the like. Examples of the compound containing an oxetanyl group For example, 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 above-mentioned polymerizable monomer (I), polymerizable monomer (I) may be used individually, respectively, or may be used in combination of 2 or more type. Content of a polymerizable monomer (I) is 0.1-20 mass% normally in mass fraction with respect to solid content of a radiation sensitive resin composition.

As said silane coupling agent (J), for example, methyl trimethoxysilane, methyl triethoxysilane, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, and vinyl tris (2) -Methoxyethoxy) silane, 3-chloropropyl-trimethoxysilane, 3-chloropropylmethyl-dichlorosilane, 3-chloropropylmethyl-dimethoxysilane, 3-chloropropylmethyl-diethoxysilane, 3-gly Cydoxypropyl-trimethoxysilane, 3-glycidoxypropyl-triethoxysilane, 3-glycidoxypropylmethyl-dimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-methacryloyl Oxypropyl-trimethoxysilane, 3-methacryloyloxypropylmethyl-dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, N-2- (N-vinylbenzylamino Ethyl) -3-aminopropyl-trimethoxysilane 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-ureapropyl-trimethoxy Silane, 3-ureapropyl-triethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxysilane, N-aminoethyl-3-aminopropylmethyl-dimethoxysilane, N-methyl-3-amino Propyl-trimethoxysilane, N-phenyl-3-aminopropyl-trimethoxysilane, and the like.

In these, the silane coupling agent which has an epoxy group in the structure is used preferably.

Examples of the silane coupling agent having an epoxy group in the above structure include 3-glycidoxypropyl-trimethoxysilane, 3-glycidoxypropyl-triethoxysilane, 3-glycidoxypropylmethyl-dimethoxysilane, And 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, and silane coupling agents having an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane It is preferably used.

The content of the silane coupling agent (J) is preferably 0.01 to 10% by mass, more preferably 0.1 to 2% by mass, still more preferably 0.2 to 1% by mass with respect to the radiation-sensitive resin composition. . When content of a silane coupling agent exists in the said range, when the cured resin pattern is formed using the radiation sensitive resin composition of this invention, since the visible light transmittance of the cured resin pattern improves, transparency tends to improve. In addition, since adhesiveness with the cured resin pattern and a base material improves, it is preferable.

If necessary, the radiation-sensitive resin composition of the present invention may further contain other additives such as antioxidants, dissolution inhibitors, sensitizers, ultraviolet absorbers, light stabilizers, adhesion improving agents, electron donors and the like. good.

The radiation sensitive resin composition of this invention is a solution which melt | dissolved the alkali-soluble resin (A) which has curability in the solvent (C), the solution which melt | dissolved the quinone diazide compound (B) in the solvent (C), and a silicone type surfactant (D), for example. ) Can be prepared by mixing. Moreover, you may add a solvent (C) and a fluorine-type surfactant (E) further as needed after mixing. In addition, it is preferable to filter and remove a solid after mixing a solution, For example, it is preferable to filter using a filter of 3 micrometers or less of pore diameters, Preferably it is 0.1 micrometer or more and about 2 micrometers or less. The solvent used with respect to each component mentioned above may be the same, and may differ if it is compatible.

In order to form a transparent cured resin pattern using the radiation sensitive resin composition of the present invention, for example, a layer made of the radiation sensitive resin composition of the present invention is formed on a substrate, and the radiation is irradiated to the above layer through a mask to expose the layer. After development, it is good.

As a board | substrate, a transparent glass plate etc. are mentioned, for example. A circuit such as a TFT or a CCD, a color filter, or the like may be formed on the substrate.

It is preferable that the layer which consists of a radiation sensitive resin composition is apply | coated using the coating apparatus which has a slit-type nozzle. As a coating device which has a slit-type nozzle, a slit coater, a die coater, a curtain flow coater, etc. are mentioned, for example.

After application | coating, it heats after drying by heat drying (before baking) or drying under reduced pressure, and removes some or all of volatile components, such as a solvent, and the radiation sensitive resin composition layer in which content of a solvent was reduced is formed. In addition, the thickness of this radiation sensitive resin composition layer is about 1.5 micrometers-5 micrometers, for example.

Subsequently, radiation is irradiated to a radiation sensitive resin composition layer through a mask. The pattern of a mask is suitably selected according to the pattern made into the objective of a cured resin pattern. As the radiation, for example, light rays such as g-rays and i-rays are used. The radiation is preferably irradiated using, for example, a mask aligner, a stepper, or the like so that the radiation can be irradiated in parallel across the entire surface of the radiation sensitive resin composition layer.

It develops after exposing like this. The development can be performed by a method of bringing the radiation-sensitive resin composition layer after exposure into contact with the developer, for example. As a developing solution, aqueous alkali solution is used normally. As aqueous alkali solution, the aqueous solution of an alkaline compound is used normally, and an alkaline compound may be an inorganic alkaline compound, or an organic alkaline compound may be sufficient as it.

Examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, Potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, and monoisopropylamine. , Diisopropylamine, ethanolamine and the like.

Said alkaline compounds may be used individually, respectively, or may be used in combination of 2 or more type.

The developing solution 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 developing solution.

The developing solution may contain surfactant. As surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, etc. are mentioned, for example.

As nonionic surfactant, For example, polyoxyethylene derivatives, such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, an oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene Sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and the like.

As cationic surfactant, amine salts, such as stearylamine hydrochloride, quaternary ammonium salts, such as lauryl trimethylammonium chloride, etc. are mentioned, for example.

Examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate and dodecyl. Alkyl aryl sulfonates, such as sodium naphthalene sulfonate, etc. are mentioned.

These surfactants may be used alone, or two or more kinds may be used in combination.

In addition, the developing solution may contain the organic solvent. As said organic solvent, water-soluble organic solvents, such as methanol and ethanol, etc. are mentioned, for example.

What is necessary is just to immerse the board | substrate with which the radiation sensitive resin composition layer was formed, for example in order to make a radiation sensitive resin composition layer contact a developing solution. By the development, the radiation-irradiated area | region to which radiation was irradiated in the previous exposure in a radiation sensitive resin composition layer melt | dissolves in a developing solution, and the unirradiated area | region which was not irradiated with radiation remains insoluble in a developing solution, and forms a pattern. do.

Since the radiation sensitive resin composition of this invention contains a quinonediazide compound (B), even if the time for contacting a radiation sensitive resin composition layer with a developing solution is short, a radiation area will melt | dissolve easily and remove. Moreover, since it contains a quinone diazide compound (B), even if the time for contacting a radiation sensitive resin composition layer with a developing solution becomes long, a non-irradiated area | region does not melt | dissolve and disappear in a developing solution.

After image development, it is usually washed with water and dried. After drying, the entire surface or part of the additionally obtained pattern is irradiated with radiation. It is preferable that the radiation irradiated here is ultraviolet rays or deep ultraviolet rays, and it is preferable that the irradiation amount per unit area is larger than the irradiation amount in the previous exposure.

It is preferable to heat-process (after baking) the pattern formed in this way from a viewpoint that the heat resistance, solvent resistance, etc. of a cured resin pattern improve. Heating is performed by the method of heating the board | substrate after irradiating a radiation over the whole surface with heating apparatuses, such as a hotplate and a clean oven. Heating temperature is 150 degreeC-250 degreeC normally, Preferably it is 180 degreeC-240 degreeC. Heating time is 5 minutes-120 minutes normally, Preferably they are 15 minutes-90 minutes. The pattern is cured by heating, and a cured resin pattern is formed.

According to this invention, it becomes possible to provide the radiation sensitive resin composition with favorable wettability with respect to a stainless steel base material. Therefore, the radiation sensitive resin composition of this invention can improve the applicability | paintability by the coating apparatus which has a slit-shaped nozzle.

The cured resin pattern formed using the radiation-sensitive resin composition of the present invention may be, for example, an insulating film of a TFT substrate or an organic EL element, a photo spacer, a diffuse reflecting plate used for a reflective TFT substrate, a liquid crystal alignment projection, a protective film of a CCD, or the like. It is used suitably as cured resin pattern which comprises these.

Example

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited by the Examples.

Preparation Example 1 Resin A1

In a 300 ml four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 36 g of ethyl lactate and 146 g of ethyl 3-ethoxypropionate as a solvent, 2.2 g of azobisisobutyronitrile as a polymerization initiator and the following monomers It put in, and it stirred for 3 hours, maintaining internal temperature at 100-110 degreeC under nitrogen stream, and obtained the solution containing resin A1. The polystyrene reduced weight average molecular weight of this resin A1 was 7,900.

10.8 g of methacrylic acid

36.9 g of 3-ethyl-3-methacryloxymethyloxetane

31.4 g of N-cyclohexylmaleimide

[Measurement of Polystyrene Equivalent Weight Average Molecular Weight (Mw)]

It carried out on condition of the following using GPC method.

Device; HLC-8120GPC (manufactured by Tosoh Corporation)

column; TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 ml / min

Injection amount; 50 μl

Detectors; RI

Measurement sample concentration; 0.6 mass% (solvent; THF)

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

[Example of Measurement of HLB Value of Surfactant]

0.5 g of surfactant / dissolved in 5 ml of ethanol. The 2% aqueous phenol solution was dripped, and the addition amount (ml) when liquid became turbid was made into fresh water A. The HLB value was calculated by HLB = 0.89 × (fresh water A) +1.11. (See Nishiichiro: Surfactant Handbook / Sangyo Shosho Co., Ltd.)

Example 1

After mixing the following components at 23 ° C, SH8400 (HLB value = 8.0, polyether-modified silicone oil; manufactured by Shin-Etsu Silicone Co., Ltd.) as a silicone-based surfactant (D1) component having an HLB value of 1 to 9 or less; 200 ppm and 100 ppm of SH3746 (HLB value = 14.0, polyether modified silicone oil; Shin-Etsu Silicone Co., Ltd. product) were added as a silicone type surfactant (D2) component whose HLB value exceeds 9.

It filtered under pressure through the polytetrafluoroethylene cartridge filter of 1.0 micrometer of pore diameters, and obtained the radiation sensitive resin composition 1 as a filtrate. Content of the solvent (C) in the obtained radiation sensitive resin composition was 72.5%, and the solvent composition ratio was ethyl lactate: ethyl 3-ethoxypropionate: butyl acetate: propylene glycol monomethyl ether = 16: 60: 20: 4.

333 mass parts (solid content: 100 mass parts) of the solution containing resin A1.

20 parts by mass of a compound represented by the following formula (1):

2 parts by mass of adekaoptomer SP-172 (photocationic polymerization catalyst; manufactured by Asahi Denka Kogyo Co., Ltd.)

2 parts by mass of acid aid SI-100L (thermal cationic polymerization catalyst; manufactured by Sanshin Chemical Co., Ltd.)

3 parts by mass of KBM-303 (a silane coupling agent; β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.)

8.1 parts by mass of ethyl lactate

16.2 parts by mass of ethyl 3-ethoxypropionate

Butyl acetate 67 parts by mass

13.4 parts propylene glycol monomethyl ether

Formula 1

Wherein Q ⁴ represents a substituent represented by the formula (2)

Formula 1-1

Comparative Example 1

A radiation sensitive resin composition 2 was obtained in the same manner as in Example 1 except that SH3746 was not used.

Comparative Example 2

A radiation sensitive resin composition 3 was obtained in the same manner as in Example 1 except that SH8400 was not used at 300 ppm and SH3746.

<Measuring example of liquidity>

SUS630 plate (size: 100 mm x 200 mm x 10 mm, surface roughness: JIS BO659 12.5-S equivalent one-way hairline finish which installed the radiation sensitive resin composition obtained in the said Example and comparative example horizontally) 10 µl was added dropwise from the passtool pipette (5-3 / 4 "; manufactured by Fisher), and the SUS630 plate was placed in the vertical direction immediately after the dropping. At this time, the hairline of the plate was set in the liquid dropping direction. To be vertical.

The radiation sensitive resin composition measured the flow distance until it stopped the flow, and set it as the flow distance. The measurement results are shown in Table 1 below.

In addition, when liquid flowed, it was determined that fluid stayed on the hairline for 10 seconds or more and liquid flow stopped temporarily, and fluidity (circle) which flowed smoothly without stopping liquid. The good fluidity | liquidity judged that the wettability of the stainless steel base material was also favorable.

Table 1 shows the judgment results.

Example 1 Comparative Example 1 Comparative Example 2 (D1 component) SH8400 (HLB value = 8.0) 200 200 300 (D2 component) SH3746 (HLB value = 14.0) 100 Judgment Flow distance 78 75 74 liquidity ○ × ×

According to this invention, the radiation sensitive resin composition with favorable wettability with respect to a stainless steel base material is provided.

Claims (11)

A radiation sensitive resin composition containing an alkali-soluble resin (A) having a curability, a quinonediazide compound (B), a solvent (C), and a silicone surfactant (D), wherein the silicone surfactant (D) has an HLB value of 1 The radiation sensitive resin composition which is a silicone type surfactant containing the silicone type surfactant (D1) which is more than 9 or less, and the silicone type surfactant (D2) whose HLB value exceeds 9. The structure according to claim 1, wherein the alkali-soluble resin (A) having curability is derived from a structural unit (a1) derived from an unsaturated carboxylic acid and an unsaturated compound having a curable group (but not an unsaturated carboxylic acid). The composition which is a copolymer containing unit (a2). The composition according to claim 2, wherein the curable group in the structural unit (a2) is an oxetanyl group. The structural unit (a31) or polymerizable carbon-carbon unsaturation according to any one of claims 1 to 3, wherein the alkali-soluble resin (A) having curability is derived from a carboxylic acid ester having an olefinic double bond. At least one member selected from the group consisting of a structural unit (a32) derived from an aromatic compound having a bond, a structural unit (a33) derived from a vinyl cyanide compound, and a structural unit (a34) derived from an N-substituted maleimide compound The composition further containing the structural unit (a3). The composition according to any one of claims 1 to 4, wherein the surfactant (D1) is polyalkylene glycol modified silicone. The composition according to any one of claims 1 to 5, wherein the surfactant (D2) is polyalkylene glycol modified silicone. The composition as described in any one of Claims 1-6 whose content of silicone type surfactant (D) is 1-1000 ppm by mass fraction with respect to a radiation sensitive resin composition. The composition as described in any one of Claims 1-7 whose content of surfactant (D1) is 50-90 mass% in mass fraction with respect to the total amount of silicone type surfactant (D). The composition according to any one of claims 1 to 8, which is applied to an application device having a slit nozzle. The transparent cured resin pattern formed with the composition as described in any one of Claims 1-9. The display apparatus provided with the transparent cured resin pattern of Claim 10.