KR20060052220A - Radio-sensitive resin composition - Google Patents

Abstract

The present invention is a radiation sensitive resin composition containing a curable alkali-soluble resin (A), a quinonediazide compound (B), and a solvent (C), wherein the solvent (C) is a solvent containing butyl lactate. It is an object to provide a resin composition.

Description

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

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows the process of forming a transparent cured resin pattern using the radiation sensitive resin composition of this invention.

<Explanation of symbols for main parts of drawing>

1: radiation sensitive resin composition layer

11: unexplored area

12: irradiation area

2: substrate

3: mask

4: radiation

5: resin pattern

6: transparent cured resin pattern

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 abbreviated as TFT) type liquid crystal display device, an organic EL insulating film used for an organic EL display device, a diffuse reflecting plate used for a reflective TFT substrate, and solid-state imaging. It is useful as a material for forming a transparent cured resin pattern including a protective film of an element (hereinafter sometimes abbreviated as CCD) (see Japanese Patent Application Laid-Open No. 9-152625).

However, in the development process at the time of forming a transparent cured resin pattern using a radiation sensitive resin composition, peeling of a pattern may generate | occur | produce, and of the radiation sensitive resin composition which gives the pattern which peeling does not occur easily. Development was required.

The inventors of the present invention have found that the radiation-sensitive resin composition containing a solvent containing butyl lactate gives a pattern in which peeling does not easily occur.

An object of the present invention is to provide a radiation-sensitive resin composition in which peeling of a pattern does not easily occur when developing a transparent cured resin pattern.

That is, this invention provides the following [1]-[9].

[1] A radiation-sensitive resin composition containing an alkali-soluble resin (A), a quinonediazide compound (B), and a solvent (C) having curability, wherein the solvent (C) is a solvent containing butyl lactate; Resin composition.

[2] The structural unit (a1) in which the curable alkali-soluble resin (A) is derived from an unsaturated carboxylic acid, and the 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 described in [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), a structural unit derived from an aromatic compound having a polymerizable carbon-carbon unsaturated bond (a32 ), Further comprising 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 [1] The composition as described in any one of [3].

[5] the solvent (C) in the group consisting of diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate and γ-butyrolactone The composition as described in any one of [1]-[4] which is a solvent containing at least 1 sort (s) of organic solvent chosen and butyl lactate.

[6] The composition according to any one of [1] to [5], wherein the content of butyl lactate is 1 to 30% by mass based on the mass fraction of the solvent (C).

[7] A transparent cured resin pattern formed by using the composition according to any one of [1] to [6].

[8] After applying the composition according to any one of [1] to [6] on a substrate, removing the solvent, irradiating with a radiation through a mask, and then developing with an aqueous alkali solution to form a predetermined pattern. Then, the manufacturing method of the transparent cured resin pattern which irradiates a pattern on a board | substrate with radiation.

[9] The production method according to [8], wherein the pattern on the substrate is further irradiated with radiation.

(Form to carry out invention)

The radiation sensitive resin composition of this invention contains curable alkali-soluble resin (A), quinonediazide compound (B), and a solvent (C), and a solvent (C) contains butyl lactate.

As the alkali-soluble resin (A) having curability used in the present invention, a copolymer containing a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having a curable group is preferably used. (However, there is no case where the unsaturated compound derived from the structural unit (a2) is an unsaturated carboxylic acid).

As unsaturated carboxylic acid which guide | induces the said structural unit (a1), unsaturated carboxylic acid etc. which have one or several carboxyl groups in a molecule | numerator, such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid, are mentioned, for example.

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.

As an unsaturated compound which has a curable group which induces the said structural unit (a2), For example, glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta) -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 Epoxy group-containing unsaturated compounds such as 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.

As an unsaturated compound which has a curable group which induces a structural unit (a2), the said oxetanyl group containing unsaturated compound is used preferably, and 3-ethyl-3-methacryloxymethyl oxetane is especially used preferably.

When the radiation sensitive resin composition is prepared using alkali-soluble resin containing an oxetanyl group-containing unsaturated compound as a structural unit (a2), since the storage stability of this composition tends to become favorable, it is preferable.

The curable alkali-soluble resin (A) used in the present invention contains a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond as a copolymer component and an aromatic compound having a polymerizable carbon-carbon unsaturated bond. At least one structural unit (a3) selected from the group consisting of a structural unit derived from (a32), a structural unit derived from a vinyl cyanide compound (a33), and a structural unit derived from an N-substituted maleimide compound (a34) It may contain.

As carboxylic acid ester which has an olefinic double bond which induces the 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, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, diethyl maleate, diethyl fumarate Unsaturated carboxylic acid esters such as diethyl itaconate; 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 compound which has a polymerizable carbon-carbon unsaturated bond which guide | induces the 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 induces the said structural unit (a33), an acrylonitrile, methacrylonitrile, the (alpha)-chloro (meth) acrylonitrile, etc. are mentioned, for example.

Examples of the N-substituted maleimide compound for inducing the structural unit (a34) include N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide and 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 caproate , N- (1-anilinonaphthyl-4) -maleimide, N- [4- (2-benzoxazolyl) phenyl] maleimide, N- (9-acridinyl) maleimide, and the like. .

The structural units (a1), (a2), (a31), (a32), (a33) and (a34) may each be used alone or in combination of a plurality of structural units derived from the above-described exemplary compounds.

In a copolymer containing a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having a curable group, the content of the structural unit (a1) is relative to the entire structural unit of the copolymer. As molar ratio, Preferably it is 5-50 mol%, More preferably, it is 15-40 mol%. The content of the structural unit (a2) is preferably 95 to 50 mol%, more preferably 85 to 60 mol%, as a molar ratio with respect to the entire structural unit of the copolymer.

In the composition of this invention, when content of the structural unit (a1) and structural unit (a2) in a copolymer exists in the above-mentioned range, it is preferable from a viewpoint of the suitable dissolution rate with respect to a developing solution, and high curability.

In the composition of the present invention, when the alkali-soluble resin (A) is a copolymer containing the structural unit (a1) and the structural unit (a2), other structural units may be used as optional components in addition to the structural unit (a1) and the structural unit (a2). It may contain. When the copolymer contains other structural units as an optional component, the content of the other structural units with respect to the structural units of the copolymer is preferably 0.1 to 90 mol%, more molar ratio with respect to the entire structural units of the copolymer. Preferably it is 5-80 mol%.

Examples of the copolymer containing the structural units (a1) and (a2) include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer and 3-ethyl-3-methacryloxymethyl Oxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / Methacrylic acid / cyclohexyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / methyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / meth Methacrylic acid / methyl methacrylate / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / Methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / benzyl acrylate Copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / isobornylacrylate copolymer , 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / dicyclopentanyl methacrylate copolymer or 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / t-butylacrylate air Copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / phenylmaleimide copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexylmaleimide copolymer, etc. Can be mentioned.

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

Content of the copolymer containing structural unit (a1) and (a2) in the radiation sensitive resin composition of this invention becomes like this. Preferably it is 50-90 mass% with respect to solid content of a radiation sensitive resin composition, More preferably, 60-90 mass%.

As a quinonediazide 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, 2-naphthoquinone diazide sulfonic acid amide etc. are mentioned.

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-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-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-naphthoquinone diazide-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 esters, 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.

The quinonediazide compound (B) may be used alone, or two or more kinds thereof may be used in combination. Content of the quinonediazide compound (B) in this invention becomes like this. Preferably it is 2-50 mass% with respect to solid content of a radiation sensitive resin composition, More preferably, it is 5-40 mass%. 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 it exists in the tendency which can maintain a developing residual film rate high, it is preferable.

The solvent (C) used by this invention is a solvent containing butyl lactate. When the solvent containing butyl lactate is used, since adhesiveness tends to improve at the time of pattern formation, it is preferable.

As a solvent (C), it is preferable that the organic solvent generally used for a radiation sensitive resin composition is mixed with butyl lactate.

Examples of the organic solvent 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 or diethylene glycol dibutyl ether, diethylene glycol methylethyl ether, diethylene glycol methyl isopropyl ether ; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and etecellosolve acetate; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monopropyl ether acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; 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 lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, butyl acetate, amyl acetate, isoamyl acetate and methyl pyruvate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Preferred solvents used in combination with butyl lactate include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, 3-ethoxypropionate ethyl, lactate ethyl, butyl acetate and T-butyrolactone. Can be mentioned.

The content of butyl lactate is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, still more preferably 1 to 30% by mass with respect to the solvent (C). When content of butyl lactate exists in the said range, since adhesiveness tends to improve at the time of forming a pattern, it is preferable.

The content of the solvent (C) is preferably 50 to 95 mass%, more preferably 65 to 90 mass%, based on the mass fraction with respect to the radiation-sensitive resin composition. When content of a solvent (C) exists in the said range, since it exists in the tendency which can form the film | membrane with favorable flatness, it is preferable.

The radiation-sensitive resin composition of the present invention contains a polymerization initiator (D), a polyhydric phenol compound (E), a crosslinking agent (F), and a polymerizable monomer in addition to the alkali-soluble resin (A), the quinonediazide compound (B), and the solvent (C). (G) etc. may be contained.

As said polymerization initiator (D), the onium salt etc. which are cationic polymerization initiators are mentioned, for example. This onium salt consists of an onium cation and an anion derived from Lewis acid.

As a specific example of the said onium cation, diphenyl iodonium, bis (p-tolyl) iodonium, bis (pt-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium , Bis (p-octyloxyphenyl) iodium, bis (p-octadecyloxyphenyl) iodium, phenyl (p-octadecyloxyphenyl) iodium, (p-tolyl) (p-isopropylphenyl) iodium , 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 (cyclohexyl Oxy) 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) sulfonium, etc. Can be mentioned.

Preferred onium cations include bis (p-tolyl) iodium, (p-tolyl) (p-isopropylphenyl) iodium, bis (pt-butylphenyl) iodium, triphenylsulfonium, tris (pt-butylphenyl) Sulfonium and the like.

Specific examples of the anion derived from the Lewis acid include hexafluorophosphate, hexafluoroarcinate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, and the like. Preferred anions derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.

Said onium cation and anion derived from a Lewis acid can be used in arbitrary combination.

As a specific example of a photocationic polymerization initiator (D), diphenyl iodonium hexafluoro phosphate, bis (p-tolyl) iodonium hexafluoro phosphate, bis (pt-butylphenyl) iodonium hexafluoro phosphate, bis (p- Octylphenyl) iodonium hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodine Nium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate , Ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hex 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 hexafluorophosphate, 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 Pentyloxy) 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 hexafluoro Phosphate, diphenyliodonium hexafluoroarcinate, bis (p-tolyl) iodonium hexafluoroarcinate, bis (pt-butylphenyl) iodonium hexafluoroarcinate, b (p-octylphenyl) iodonium hexafluoroarcinate, bis (p-octadecylphenyl) iodonium hexafluoroarcinate, bis (p-octyloxyphenyl) iodinium hexafluoroarcinate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarcinate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarcinate, (p-tolyl) (p-isopropylphenyl) iodonium hexa Fluoroarcinate, methylnaphthyl iodonium hexafluoroarcinate, ethylnaphthyl iodonium hexafluoroarcinate, triphenylsulfonium hexafluoroarcinate, tris (p-tolyl) sulfonium hexa Fluoroarcinate, tris (p-isopropylphenyl) sulfonium hexafluoroarcinate, tris (2,6-dimethylphenyl) sulfonium hexafluoroarcinate, tris (pt-butylphenyl) sulfonium Hexafluoroarcinate, tris (p-cyanophenyl) sulfonium Hexafluoroarcinate, tris (p-chlorophenyl) sulfoniumhexafluoroarcinate, 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) sulphate Nium 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, 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 Phonohexahexafluoromonate, dimethylnaphthylsulfonium hex Fluoroantimonate, 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 Bromorph Foxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-tri Fluoromethyloctadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Antimonate, diphenyl iodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (pentafluoro Lophenyl) borate, bis (p-octylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octyloxy Phenyl) iodonium tetrakis (pen) Fluorophenyl) borate, bis (p-octadecyloxyphenyl) iodiumtetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodiumtetrakis (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 (pen) Tafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaphthylsulfonium tetrakis (pentafluoro Rophenyl) 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 ( 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 (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) Borei And the like can be mentioned.

Among them, bis (p-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (pt-butylphenyl) iodonium hexafluorophosphate, triphenyl Sulfonium 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) sulfonium hexafluoroarcinate, Bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl) iodonium hexafluoroantimo Nate, Triphenylsulfonium Hexafluoroantimonate , Tris (pt-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodnium Tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) sulfoniumtetrakis (pentafluorophenyl Borate is preferably used, and bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl Iodide hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluoro Lophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodiumtetraki (Pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate is more preferably used.

When using a polymerization initiator (D), 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 (D) exists in the said range, since the fall of the resolution 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 (E), the compound which has a 2 or more phenolic hydroxyl group in a molecule | numerator, the polymer obtained by making at least hydroxy styrene as a raw material monomer, a novolak resin, etc. are mentioned.

Examples of the compound having two or more phenolic hydroxyl groups in the molecule include trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, and hexahydroxybenzophenones as exemplified in the description of the quinone diazide compound. And (polyhydroxyphenyl) alkanes.

Moreover, as a specific example of the polymer obtained using at least hydroxy styrene as a raw material monomer, a polyhydroxy styrene, a hydroxy styrene / methyl methacrylate copolymer, a hydroxy styrene / cyclohexyl methacrylate copolymer, a hydroxy styrene / styrene air Resin which superposed | polymerized hydroxy styrene, such as a copolymer and a hydroxy styrene / alkoxy styrene copolymer, is mentioned.

In addition, examples of the novolak resins include resins obtained by condensation polymerization of at least one compound selected from the group consisting of phenols, cresols and catechols with at least one compound selected from the group consisting of aldehydes and ketones. have.

When using said polyhydric phenol compound (E), 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 (E) exists in the said range, since the resolution improves and a visible light transmittance tends not to fall, it is preferable.

A methylol compound etc. are mentioned as said crosslinking agent (F).

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 an alkoxy methylation melamine resin, a methoxymethylation melamine resin, an ethoxymethylation melamine resin, a propoxymethylation melamine resin, butoxymethylation melamine resin etc. are mentioned, for example. Examples of the alkoxy methylated urea resins include methoxymethylated urea resins, ethoxymethylated urea resins, propoxymethylated urea resins, butoxymethylated urea resins, and the like. Said crosslinking agents may be used independently, respectively and may be used in combination of 2 or more type.

When using a crosslinking agent (F), its content is 0.1-15 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 transparent cured resin pattern improves, it is preferable.

Examples of the polymerizable monomer (G) include a polymerizable monomer capable of radical polymerization by heating, a polymerizable monomer capable of cationic polymerization, and the like. Preferred polymerizable monomers (G) include polymerizable monomers capable of cationic polymerization.

As said polymerizable monomer which can be radically polymerized, the compound which has a polymerizable carbon-carbon unsaturated bond is mentioned, for example. The compound having a polymerizable carbon-carbon unsaturated bond may be a monofunctional polymerizable monomer, may be a bifunctional polymerizable monomer, or may be a polyfunctional (trifunctional or higher) polymerizable monomer.

Examples of the monofunctional polymerizable monomer are nonylphenylcarbitol acrylate, nonylphenylcarbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, etc. are mentioned.

As the bifunctional polymerizable monomer, for example, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neo Pentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentanediol di Methacrylate, and the like.

Examples of the polyfunctional polymerizable monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and pentaerythritol tetramethacrylate. Erythritol pentaacrylate, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned.

Among the compounds having the above-described polymerizable carbon-carbon unsaturated bonds, difunctional or polyfunctional polymerizable 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 polyfunctional polymerizable monomer and the monofunctional polymerizable monomer.

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

As a monomer containing the said 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.

4- (1-propenyloxymethyl) -1,3-dioxolan-2-one etc. are mentioned as a monomer containing the said propenyl ether group.

Examples of the compound containing an epoxy group include bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cyclic aliphatic epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and heterocyclic compounds. Epoxy resin etc. are mentioned.

Examples of the compound containing the oxetanyl group include bis {3- (3-ethyloxetanyl) methyl} ether, 1,4-bis {3- (3-ethyloxetanyl) methoxy} benzene, 1,4 -Bis {3- (3-ethyloxetanyl) methoxy} methylbenzene, 1,4-bis {3- (3-ethyloxetanyl) methoxy} cyclohexane, 1,4-bis {3- ( 3-ethyloxetanyl) methoxy} methylcyclohexane, 3- (3-ethyloxetanyl) methylated novolak resin, etc. are mentioned.

Said polymerizable monomer (G) may be used independently and may be used in combination of 2 or more type.

When it contains a polymerizable monomer (G), the content is 0.1-20 mass% in mass fraction with respect to solid content of a radiation sensitive resin composition.

The radiation sensitive resin composition of the present invention further contains other additives such as surfactants, antioxidants, dissolution inhibitors, sensitizers, ultraviolet absorbers, light stabilizers, adhesion modifiers, electron donors and the like, as necessary. You may be.

The radiation sensitive resin composition of this invention can be prepared by mixing the solution which melt | dissolved the said alkali-soluble resin (A) in the solvent (C), and the solution which melt | dissolved the quinone diazide compound (B) in the solvent (C), for example. Moreover, after mixing, you may add a solvent (C) further. Moreover, after mixing a solution, it is preferable to remove solids by filtration. The filtration is preferably filtered using a filter having a pore diameter of 3 µm or less (preferably about 0.1 µm to 2 µm). The solvent (c) used with respect to the said alkali-soluble resin (A) and the quinonediazide compound (B) may be mutually same or different. In addition, as long as they are mutually compatible, you may use a some solvent (C).

When forming a transparent cured resin pattern using the radiation sensitive resin composition of this invention, the layer 1 which consists of said radiation sensitive resin composition is formed on the board | substrate 2, for example (refer FIG. 1 (a)), and a mask What is necessary is just to irradiate and expose the said layer 1 to the above-mentioned layer 1 through (3) (refer FIG. 1 (b)), and develop it (refer FIG. 1 (c)).

As the board | substrate 2, a transparent glass plate etc. are mentioned, for example. Circuits, such as TFT and CCD, a color filter, etc. may be formed on the said board | substrate.

The layer 1 made of the radiation-sensitive resin composition can be formed by, for example, a method of applying the radiation-sensitive resin composition onto the substrate 2. The coating is performed by, for example, spin coating, cast coating, roll coating, slit and spin coating, slit coating, or the like. After coating, the radiation-sensitive resin composition layer 1 is formed by heating after drying by heating (prebaking) or drying under reduced pressure to volatilize a volatile component such as a solvent. Here, the temperature of heating is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The formed radiation sensitive resin composition layer 1 contains almost no volatile component. Moreover, the thickness of the said radiation sensitive resin composition layer 1 is about 1.5-5 micrometers.

After that, the radiation 4 is irradiated to the radiation sensitive resin composition layer 1 through the mask 3. The pattern of the mask 3 is suitably selected according to the pattern shape made into the objective of a resin pattern. As the radiation, light rays such as g-rays or i-rays are used. The radiation is preferably irradiated using, for example, a mask aligner, a stepper (not shown), or the like so as to be irradiated in parallel over the entire surface or a part of the radiation sensitive resin composition layer. By irradiating radiation in this way, the mask 3 and the radiation sensitive resin composition layer 1 can be aligned correctly.

It develops after the said exposure. The development can be performed by the paddle method, the immersion method, the shower method, or the like, for example, the radiation-sensitive resin composition layer 1 after exposure. As a developing solution, alkaline aqueous solution is used normally. As the aqueous alkali solution, an aqueous solution of an alkaline compound is used, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

As inorganic alkaline compounds, for example, 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, sodium carbonate Potassium hydrogen, sodium borate, potassium borate, ammonia and the like.

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

Said alkaline compounds may be used independently, respectively and may be used in combination of 2 or more type. The content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass in terms of mass fraction with respect to the developer.

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

Examples of nonionic surfactants include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, and polyoxyethylene alkyl aryl ether, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbents. Non-fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

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

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; Alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate, etc. are mentioned.

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

Moreover, 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.

In the radiation-sensitive resin composition layer 1 by the development, the radiation irradiated region 12 irradiated with radiation in the previous exposure is dissolved in the developer, and the unradiated region 11 without irradiated radiation is applied to the developer. The resin pattern 5 is formed without remaining dissolved.

Since the radiation sensitive resin composition of this invention contains a quinonediazide compound (B), even if the time for making the radiation sensitive resin composition layer 1 contact with a developing solution is short, the irradiation area 12 will melt | dissolve easily. Removed. Moreover, since it contains a quinonediazide compound (B), even if the time for contacting the radiation sensitive resin composition layer 1 to a developing solution becomes long, the unilluminated area | region 11 will not melt | dissolve in a developing solution and will not disappear. .

After alkali development, it is washed with water and dried normally. After drying, the entire surface or part of the obtained resin pattern 5 is irradiated with radiation. It is preferable that the radiation irradiated here is an ultraviolet-ray or far ultraviolet ray, 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 (post-baking) from the viewpoint of improving the heat resistance, solvent resistance, etc. of the transparent cured resin pattern 6 finally obtained thus formed pattern. 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. The heating temperature is usually 150 ° C to 250 ° C, preferably about 180 ° C to 240 ° C, and the heating time is usually 5 minutes to 120 minutes, preferably 15 minutes to 90 minutes. By heating, the pattern is cured and the transparent cured resin pattern 6 is formed.

Thus, the formed transparent cured resin pattern has high adhesiveness to a base. Therefore, when the radiation sensitive resin composition of this invention is used, the transparent cured resin pattern with high yield can be formed efficiently.

The transparent cured resin pattern obtained using the radiation sensitive resin composition of this invention can be used suitably, for example, the insulating film of a TFT substrate, an organic electroluminescent element, the protective film of CCD.

(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

Into a 200 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, the following raw materials were placed in, and the four-necked flask was immersed in an oil bath under nitrogen flow, and stirred for 3 hours while maintaining the flask internal temperature at 85 to 95 ° C. Was performed to obtain a solution containing Resin A1. The polystyrene reduced weight average molecular weight of this resin A1 was 8,000.

6.8 g of methacrylic acid

14.2 g of N-cyclohexylmaleimide

17.8 g of 3-ethyl-3-methacryloxymethyloxetane

90.7 g of ethyl lactate

1.1 g of azobisisobutyronitrile

Here, the polystyrene reduced weight average molecular weight of this resin A1 was measured on condition of the following.

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

column ; TSK-GELG2000HXL, TSK-GELG4000HXL Serial

Column temperature; 40 ℃

Mobile phase solvent; Tetrahydrofuran

Flow rate; 1.0 ml / min

Injection volume; 50 μl

Detector; RI

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

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

Example 1

Resin A1 (100 parts by mass), a compound represented by the following general formula (1) (22 parts by mass), (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate (Rhodorsil Photoinitiator2074; rhodiasa (2 parts by mass), ethyl 3-ethoxypropionate (285 parts by mass), butyl acetate (34 parts by mass) and butyl lactate (17 parts by mass) were mixed at 23 ° C., followed by polytetra with a pore diameter of 1.0 μm. It filtered under pressure through the fluoroethylene cartridge filter and obtained the radiation sensitive resin composition (1).

Spin-coating the radiation sensitive resin composition (1) obtained above on the transparent glass substrate (# 1737 (made by Corning Corporation)), and heating (prebaking) for 3 minutes at 100 degreeC using a clean oven, and radiation-sensitive radiation of 3 micrometers thickness The resin composition layer 1 was formed (see Fig. 1 (a)). The film thickness was measured by a film thickness meter (DEKTAK3; manufactured by ULVAC, Inc.).

Then, the intensity | strength in the radiation 4 (wavelength 365nm reference | standard) through the mask 3 using the contact aligner (M-2Li; manufactured by Mikasa Co., Ltd.) to the obtained radiation sensitive resin composition layer 1 250 mJ / cm 2) was irradiated and exposed (see FIG. 1 (b)).

After exposure, the solution was immersed in an aqueous solution of 0.4% by mass of tetramethylammonium hydroxide at 23 ° C. for 70 seconds to develop, then washed with ultrapure water and dried. Peeling was not seen after image development, and adhesiveness was favorable.

In the resin pattern 5 after image development, after drying, radiation (300 mJ / cm 2 at the wavelength of 365 nm standard) was applied over the entire surface using a contact aligner (M-2Li; manufactured by Mikasa Co., Ltd.). It irradiated and heated for 30 minutes in the clean oven of 220 degreeC, and formed the transparent cured resin pattern 6 (refer FIG. 1 (c)).

It was 2.5 micrometers when the thickness T1 of the obtained transparent cured resin pattern 6 was measured using the film thickness meter.

The visible light transmittance was measured using a microscopic spectrophotometer (OSP-200; manufactured by Olympusco Co., Ltd.). The light transmittance in wavelength 400-750 nm per 1 micrometer of obtained cured resin films showed high transparency with 99.6%, and coloring was not seen.

Example 2

Operation was carried out in the same manner as in Example 1 except for using 3-ethoxypropionate ethyl (151 parts by mass), diethylene glycol methylethyl ether (151 parts by mass), butyl acetate (17 parts by mass) and butyl lactate (17 parts by mass). And the radiation sensitive resin composition was obtained as a filtrate after pressure filtration.

As a result of performing the same operation as in Example 1, the adhesion after development was good and peeling was not observed, and the thickness T1 obtained a 2.5 µm transparent cured resin pattern 6. In addition, the light transmittance was 99.6%.

Comparative Example 1

A radiation sensitive resin composition was obtained in the same manner as in Example 1 except that diethylene glycol methyl ethyl ether (287 parts by mass) and butyl acetate (32 parts by mass) were used as the filtrate after pressure filtration.

As a result of performing the same operation as in Example 1, the adhesion was poor, and the coating film was peeled off after development, and the resin pattern 5 could not be obtained.

The radiation sensitive resin composition of this invention does not produce peeling of a pattern easily when developing a transparent cured resin pattern.

Claims (9)

A radiation sensitive resin composition containing an alkali-soluble resin (A) having a curability, a quinonediazide compound (B), and a solvent (C), wherein the solvent (C) is a solvent containing butyl lactate. The structural unit (a1) according to claim 1, wherein the alkali-soluble resin (A) having curability is a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated compound having a curable group (but not an unsaturated carboxylic acid) ( A radiation sensitive resin composition which is a copolymer containing a2). The radiation sensitive resin composition of Claim 2 whose curable group is an oxetanyl group in a structural unit (a2). The structural unit (a31) or polymerizable carbon-carbon unsaturated bond 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 compound, a structural unit (a33) derived from a vinyl cyanide compound, and a structural unit (a34) derived from an N-substituted maleimide compound The radiation sensitive resin composition which further contains a unit (a3). The solvent (C) according to any one of claims 1 to 4, wherein the solvent (C) is diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl lactate, acetic acid. A radiation-sensitive resin composition, which is a solvent containing at least one organic solvent selected from the group consisting of butyl and γ-butyrolactone and butyl lactate. The radiation sensitive resin composition of any one of Claims 1-5 whose content of butyl lactate is 1-30 mass% in mass fraction with respect to a solvent (C). The transparent cured resin pattern formed using the composition as described in any one of Claims 1-6. After apply | coating the composition of any one of Claims 1-6 on a board | substrate, removing a solvent, irradiating a radiation through a mask, and then developing in aqueous alkali solution, and forming a predetermined pattern, The manufacturing method of the transparent cured resin pattern which irradiates a pattern on a board | substrate. The manufacturing method of the transparent cured resin pattern of Claim 8 which heats further after irradiating a pattern on a board | substrate with a radiation.

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