KR20040036584A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE: Provided is a radiation sensitive resin composition capable of forming a transparent cured resin pattern having high transmission to visible light and excellent coloring resistance, solvent resistance and shape. CONSTITUTION: The radiation sensitive resin composition comprises: (A) a copolymer including (a1) repeating units derived from an unsaturated carboxylic acid and (a2) repeating units derived from an unsaturated compound having an oxetanyl group excluding unsaturated carboxylic acids; (B) a quinone diazide compound; and (C) a cation polymerization initiator formed of hexafluoroantimonate anion and onium cation. The onium cation is preferably iodonium cation.

Description

Radiation sensitive resin composition

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

The radiation-sensitive resin composition is, for example, a thin film transistor (hereinafter also referred to as TFT) type liquid crystal display device, an insulating film of a TFT used in an organic EL display device, a diffusion reflecting plate used in a reflective TFT substrate, an organic EL insulating film. It is useful as a material for forming a transparent cured resin pattern including a protective film of a solid-state imaging device (hereinafter also referred to as CCD). Here, in the insulating film of TFT, etc., high transmittance | permeability with respect to visible light is calculated | required in order to obtain brighter display image. In addition, high solvent resistance is also desired in terms of productivity of the TFT substrate. In addition, the radiation sensitive resin composition is required to have high sensitivity to radiation used for forming the insulating film in terms of productivity of the TFT substrate.

As a photosensitive resin composition, what contains binder resin, a photosensitive agent, and a photoinitiator is known (for example, refer Unexamined-Japanese-Patent No. 2001-281853 etc.). And as binder resin, the copolymer using the acrylate-type copolymer and oxetane is developed. Oxetanes are known to be subjected to cationic polymerization (see, for example, JP-A-2000-239648, etc.).

As the cationic polymerization initiator, onium salts composed of hexafluorophosphate anions are generally used (see, for example, JP-A-9-304931). However, when the pattern formed using the radiation-sensitive resin composition is cured by heat treatment, the thermal deformation of the pattern is significantly faster than the curing, and the resolution and shape of the transparent cured resin pattern cannot be maintained after thermal curing. There was.

An object of the present invention is to provide a radiation-sensitive resin composition which can form a transparent cured resin pattern having no coloration, high transmittance to visible light, and sufficient solvent resistance, and which can form a transparent cured resin pattern having a good shape. It is.

MEANS TO SOLVE THE PROBLEM The present inventors came to this invention as a result of earnestly examining in order to solve said subject.

That is, a copolymer (A) comprising a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group (except for the unsaturated carboxylic acid),

Quinonediazide compound (B) and

A radiation-sensitive resin composition (hereinafter also referred to as the present resin composition) containing a cationic polymerization initiator (C) consisting of a salt of a hexafluoroantimonate anion and an onium cation, and a transparent cured resin formed by the present resin composition Provided is a method for producing a transparent cured resin pattern comprising applying a pattern and the present resin composition to irradiate radiation through a mask, then developing to form a predetermined pattern, and then irradiating radiation.

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

2 is a schematic diagram showing a vertical section with respect to the substrate of the pattern for explaining θ.

(Explanation of the sign)

1: radiation sensitive resin composition layer

2: substrate

3: positive mask

4: radiation

5: transparent cured resin pattern

(theta): The angle which a ridgeline of a cross section and a board surface make in the cross section perpendicular | vertical with respect to the board | substrate of a pattern.

11: unradiated area

12: irradiation area

Copolymer (A) comprising a structural unit (a1) derived from an unsaturated carboxylic acid in the present invention and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group (except for an unsaturated carboxylic acid) Also referred to as Copolymer (A)] is a high molecular compound having an unsaturated carboxylic acid and an oxetanyl group.

An oxetanyl group means the group which has an oxetane (trimethylene oxide) ring.

Examples of the unsaturated carboxylic acid in the structural unit (a1) derived from the unsaturated carboxylic acid (hereinafter sometimes referred to as unit (a1)) include one or two or more molecules in a molecule such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid. Examples of the unsaturated carboxylic acid having a carboxyl group include acrylic acid, methacrylic acid, clotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. As the unit (a1), a structural unit having no epoxy group is preferable because the storage stability tends to be poor.

Unsaturated compound having an oxetanyl group in the structural unit (a2) (hereinafter also referred to as (a2) unit) derived from an unsaturated compound having an oxetanyl group (except for unsaturated carboxylic acid) Carboxylic acid is excluded), for example, 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyl ox Cetane, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyl Oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2- Trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2-pentafluoroethyl-3- (meth) acryloxyethyl oxetane; and the like can be given.

As the structural unit (a2), a structural unit derived from 3-ethyl-3-methacryloxymethyloxetane is particularly preferable.

In addition, the copolymer (A) is a structural unit derived from a carboxylic acid ester having an olefinic double bond, a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structure derived from an N-substituted maleimide compound. It may include one or more structural units (a3) (hereinafter also referred to as (a3) units) selected from the group consisting of units.

As said structural unit (a3), the structural unit derived from a polymerizable carbon-carbon unsaturated bond is mentioned, for example, Specifically, For example, aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, and vinyltoluene ,

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl meta Acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, propyl acrylate, propyl methacrylate, pentyl acrylate, pentyl methacrylate, 2-hydroxybutyl acrylate Unsaturated carboxylic acid esters such as 2-hydroxybutyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, phenyl acrylate, phenyl methacrylate, diethyl maleate, diethyl difumarate and diethyl itaconate ,

Unsaturated carboxylic aminoalkyl esters of aminoethyl acrylate,

Carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate,

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloronitrile; and

N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethyl amino-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-anilininonaphthyl-4) -maleimide, N-substituted imide compounds, such as N- [4- (2-benzoxazolyl) phenyl] maleimide and N- (9-acridinyl) maleimide, etc. are mentioned.

As the unit (a3), dicyclopentanyl methacrylate, dicyclopentanyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, N-cyclohexyl maleimide and N-phenyl maleimide are derived. Structural units are particularly preferred.

These structural units can be used individually or in combination of 2 or more types, respectively.

The content of the unit (a1) in the copolymer (A) is usually 5 to 50 mol%, preferably 15 to 40 mol% with respect to the entire structural unit of the copolymer (A), and the content of the (a2) unit is It is 5 to 95 mol% normally with respect to the whole structural unit of copolymer (A), Preferably it is 15 to 85 mol%.

When the copolymer (A) consists essentially of only (a1) units and (a2) units, the (a1) unit / (a2) unit (molar ratio) is usually 5/95 to 50/50, preferably 15/85 To 40/60. When the composition ratio of the unit (a1) and the unit (a2) is in the above range, the transparent cured resin layer obtained by using the present resin composition tends to exhibit high curability while having an appropriate dissolution rate with respect to the developer. Do.

When the copolymer (A) contains other structural units such as the (a3) unit, the content of the (a1) unit is usually 5 to 50 mol%, preferably 15 to 15, based on the total constitutional units of the copolymer (A). 40 mol%, and the content of the unit (a2) is usually 94 to 5 mol%, preferably 80 to 15 mol% with respect to the total constitutional units of the copolymer (A), and the structural unit of the other copolymer such as (a3) units. Is usually 1 to 90 mol%, preferably 5 to 80 mol%.

As a specific example of the copolymer (A) in this invention, 3-ethyl-3-methacryloxymethyl oxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryl Oxymethyloxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl jade Cetane / methacrylic acid / cyclohexyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / methyl methacrylate / styrene copolymer, 3-ethyl-3-methacryloxymethyl Oxetane / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-methacryloxymethyloxetane / methacrylic acid / isobonyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl jade Cetane / methacrylic acid / benzyl acrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cycle Hexyl acrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / isobonyl acrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / t-butyl Acrylate copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / phenylmaleimide copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexylmaleimide aerial Coalescence, etc. are mentioned.

Copolymer (A) has a weight average molecular weight, as determined by gel permeation chromatography, based on polystyrene, usually in the range of 2, OO to 100,000, preferably 2,000 to 50,000, and more preferably 3,000 to 30,000. When the weight average molecular weight is 2,000 to 100,000, the pattern development of the transparent cured resin layer obtained using the present resin composition is preferred because a high developing speed tends to be obtained while maintaining the remaining film ratio during development. In the present resin composition, the content of the copolymer (A) is usually 50 to 94.99%, preferably 60 to 90% by mass fraction with respect to the solid content of the resin composition.

In addition, solid content of this resin composition in this specification means the sum total of the components except a solvent in this resin composition.

As a quinone diazide compound (B) in this invention, a 1, 2- benzoquinone diazide sulfonic acid ester, a 1, 2- naphthoquinone diazide sulfonic acid ester, a 1, 2- benzoquinone diazide, for example Sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, and the like.

Specifically, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone- 1,2-naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenones, such as a 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-naphthoquinone Diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,2'-tetra Hydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydrate Roxy-3'-methoxybenzofe L, 2-naphthoquinonediazide-5-sulfonic acid tetrahydro-hydroxy-benzophenone 1,2-naphthoquinonediazide sulfonic acid ester of nonryu esters and the like; 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzo 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxy benzophenones, such as phenone-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-naph Hexa such as toquinone diazide-4-sulfonic acid ester and 3,4,5,3 ', 4', 5'-hexahydroxy benzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester 1,2-naphthoquinone diazide sulfonic acid ester of hydroxy benzophenones; Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonedia Zide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphtho Quinonediazide-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-tri Hydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2'-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonedia G -5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1 , 1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [ 4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4 -Hydroxyphenyl) -2-hydroxyphenyl methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl methane -1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ' , 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7 , 5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-t Hydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-2-naphthoquinonediazide 1,2-naphthoquinone diazide sulfonic acid ester of (polyhydroxyphenyl) alkane, such as -5-sulfonic acid ester, etc. are mentioned.

The quinonediazide compound (B) is used individually or in combination of 2 or more types, respectively. The content of the quinone diazide compound (B) in the present invention is usually 2 to 50%, preferably 5 to 40% by mass fraction with respect to the solid content of the radiation-sensitive resin composition. When the content of the quinone diazide compound is 2 to 50%, the dissolution rate difference between the unexposed portion and the exposed portion is increased, so that the developing residual film ratio can be maintained high, which is preferable.

As a structure of the onium cation in the cation polymerization initiator (C) (henceforth a polymerization initiator (C) hereafter) which consists of a salt of the hexafluoro antimonate anion and onium cation in this invention, Or an onium cation of the formula (2).

In Formula 1 and Formula 2 above,

R ¹ to R ³ are each independently one or more hydrogen atoms on the benzene ring is an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group A phenyl group which may be substituted with a group selected from the group consisting of:

At least one hydrogen atom on the naphthalene ring can be substituted with a group selected from the group consisting of an alkoxyl group having 1 to 12 carbon atoms, a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group,

A linear alkyl group having 1 to 18 carbon atoms in which at least one hydrogen atom on the alkyl group may be substituted with a group selected from the group consisting of a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group,

Branched alkyl groups of 3 to 18 carbon atoms in which at least one of the hydrogen atoms on the alkyl group may be substituted with a group selected from the group consisting of halogen atoms, carboxyl groups, mercapto groups, cyano groups and nitro groups, or

At least one hydrogen atom on the alkyl group is a cyclic alkyl group having 3 to 18 carbon atoms which may be substituted with a group selected from the group consisting of a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group.

Specific examples of the onium cations of formula (1) include diphenyl iodonium, bis (p-tolyl) iodonium, bis (pt-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p Octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p- Tolyl) (p-isopropylphenyl) iodonium, etc. are mentioned.

Specific examples of the onium cation of formula (2) include triphenylsulfonium, tris (p-tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-sia) Nophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl ( Octyloxy) sulfonium, dimethyl (octadecyloxy) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (t-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy ) Sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8 -Nitrooctyloxy) sulfonium, dimethyl (18,18,18-trifluorooctadecyloxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, dimethyl (tri S (trichloromethyl) methyl) sulfonium and the like. As iodonium salt, Preferably, bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (pt-butylphenyl) iodonium, etc. are mentioned, Especially preferably, (p-tolyl) (p-isopropylphenyl) iodonium etc. are mentioned.

The content of the polymerization initiator (C) in the present invention is usually 0.01 to 10%, preferably 0.1 to 5% by mass fraction with respect to the solid content of the resin composition. When the content of the polymerization initiator (C) is 0.01 to 10%, it is preferable to promote the curing in the exposure after the development at the time of forming the transparent cured resin pattern using the present resin composition, thereby suppressing the resolution reduction during thermal curing. .

In this resin composition, in addition to a copolymer (A), a quinonediazide compound (B), and a polymerization initiator (C), a naphthol compound (D), a polyhydric phenol compound (E), a crosslinking agent (F), a polymerizable monomer as needed. (G), a solvent (H), etc. can be contained.

As the naphthol compound (D), for example, 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-di Hydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2 , 7-dihydroxynaphthalene, 4-methoxy-1-naphthol, and the like. In particular, 1-naphthol, 2-naphthol, 4-methoxy-1-naphthol is preferable.

Its content in the case of containing a naphthol compound (D) is 0.01 to 10% by mass fraction with respect to solid content of this resin composition, Preferably it is 0.1 to 5%. When 0.1 to 10% of a naphthol compound (D) is contained as said reference | standard, it acts as a sensitizer of a polymerization initiator (C) in the exposure after image development at the time of transparent cured resin pattern formation using this resin composition, and photocures at the time of exposure. This is preferable because it prevents the resolution decrease during thermosetting.

It is preferable that a polyhydric phenol compound (E) is a compound which has a 2 or more phenolic hydroxyl group in a molecule | numerator. As a polyhydric phenol compound (E), For example, trihydroxy benzophenone, tetrahydroxy benzophenone, pentahydroxy benzophenone, hexahydroxy benzophenone, (polyhydroxyphenyl) alkane, etc. And polyhydric phenols. Specific examples include compounds in which the 1,2-naphthoquinonediazide-4 or 5-sulfonyl moiety of the specific compound described in the quinonediazide compound (B) is substituted with a hydrogen atom. Can be.

Moreover, as a polyhydric phenol compound (E), the polymer which uses hydroxystyrene at least as a raw material monomer is mentioned. Specifically, hydroxy such as polyhydroxy styrene, hydroxy styrene / methyl methacrylate copolymer, hydroxy styrene / cyclohexyl methacrylate copolymer, hydroxy styrene / styrene copolymer, hydroxy styrene / alkoxy styrene copolymer The resin which superposed | polymerized the oxy styrene is mentioned. In addition, a novolak resin 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 may be mentioned.

In the case of containing the polyhydric phenol compound (E), the content thereof is preferably 0.1 to 40%, more preferably 1 to 25% by mass fraction with respect to the solid content of the resin composition. When the content of the polyhydric phenol compound is 0.1 to 40%, the visible light transmittance of the transparent cured resin pattern obtained using the present resin composition is increased, and the performance is preferable.

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

As a methylol compound, the alkoxy methylation amino resin, such as an alkoxy methylation melamine resin and an alkoxy methylation urea resin, etc. are mentioned. Here, as the alkoxy methylated melamine resin, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, etc. may be mentioned. Urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, butoxy methylated urea resin and the like. Crosslinking agent (F) is used individually or in combination of 2 or more types, respectively.

It is preferable that it is 0.1 to 15% by mass fraction with respect to solid content of this resin composition in the case where a crosslinking agent (F) is included. When content of a crosslinking agent (F) is 0.1 to 15%, since reliability, such as chemical-resistance of the transparent cured resin pattern obtained using this resin composition improves and performance 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, and preferably a polymerizable monomer capable of cationic polymerization. have.

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

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

As a bifunctional polymerizable monomer, for example, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacryl Latex, neopentylglycol dimethacrylate, triethylglycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methyl Pentanediol dimethacrylate etc. are mentioned.

Moreover, as a trifunctional or more than trifunctional polymerizable monomer, For example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Among the above polymerizable monomers, bifunctional or trifunctional or higher functional monomers are preferably used. Specifically, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like are preferable, and dipentaerythritol hexaacrylate is more preferable. Moreover, the bifunctional or trifunctional or more than trifunctional polymerizable monomer and monofunctional polymerizable monomer can be used in combination.

As a polymerizable monomer which can be cationicly polymerized in a polymerizable monomer (G), the polymerizable monomer which has cationically polymerizable functional groups, such as a vinyl ether group, a propenyl ether group, an oxetanyl group, is mentioned, for example. Specific examples of the compound containing a vinyl ether group include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether, and the like. And 4- (1-propenyloxymethyl) -1,3-dioxolan-2-one etc. as a compound containing a propenyl ether group, As a compound containing an oxetanyl group, bis {3- (3-ethyloxetanyl) methyl} ether, 1,4-bis {3- (3-ethyloxetanyl) methoxy} benzene, 1,4-bis {3- (3-ethyloxetanyl) meth Methoxy} methylbenzene, 1,4-bis {3- (3-ethyloxetanyl) methoxy} cyclohexane, 1,4-bis {3- (3-ethyloxetanyl) methoxy } Methyl cyclohexane, and the like.

A polymerizable monomer (G) can be used individually or in combination of 2 or more types, The content in the case of using a polymerizable monomer (G) is 0.1-20% in mass fraction with respect to solid content of this resin composition. Is preferably.

The present resin composition is usually provided in a diluted state in the presence of a solvent (H). As the solvent (H), for example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl 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, glycerin; Esters such as methyl 2-hydroxyisobutyrate, ethyl lactate, ethyl 3-ethoxypropionate, and ethyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone. Preferred solvents include methyl 2-hydroxyisobutyrate, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and the like. Among these, 2-hydroxyisobutyrate is preferable.

Solvent (H) is used individually or in combination of 2 or more types, respectively, and its content is 50-95% in mass fraction with respect to the total amount of this resin composition, Preferably it is 60-90%.

The present resin composition may further contain various additives such as other components, such as surfactants, antioxidants, dissolution inhibitors, ultraviolet absorbers, adhesive modifiers, and electron donors, if necessary.

This resin composition is, for example, a solution in which a copolymer (A) is dissolved in a solvent (H), a solution in which a quinone diazide compound (B) is dissolved in a solvent (H), and a polymerization initiator (C) in a solvent (H). It can manufacture by the method of mixing a solution. When a naphthol compound, a polyhydric phenol compound, a crosslinking agent, a polymerizable monomer, an additive, etc. are used, these can be added further. In addition, after mixing, the solvent (H) can be further added. After mixing, it is preferable to filter and remove solids, for example, it is preferable to filter using a filter of 3 micrometers or less of pore diameters, Preferably it is about 0.1-2 micrometers. The solvent used with respect to each said component may be the same, and if it is compatible, it may be different.

In forming the transparent cured resin pattern using the present resin composition, for example, the present resin composition layer 1 is formed on the substrate 2 [FIG. 1 (a)], and the positive mask 3 is used to form the transparent cured resin pattern. The layer 1 can be developed after irradiating the radiation 4 with exposure (Fig. 1 (b)) (Fig. 1 (c)).

As the board | substrate 2, resin substrates, such as a polycarbonate board | substrate, a polyester board | substrate, an aromatic polyamide board | substrate, a polyamideimide board | substrate, a polyimide board | substrate, etc. besides a transparent glass plate, a silicon wafer, etc. are mentioned, for example. A circuit of a CCD or TFT, a color filter, a transparent electrode, or the like may be formed in advance on the substrate.

The present resin composition layer 1 can be formed by a common method, for example, by applying the present resin composition onto the substrate 2. Coating is a well-known coating method, such as the method of apply | coating using liquid saving coating machines, such as the spin coating method (spin coat method), the flexible coating method, the roll coating method, the slit and spin coating method, and the slit coat method, for example. After apply | coating on a board | substrate etc., this resin composition layer 1 is formed by volatilizing a solvent by heating-drying (it may be called prebaking hereafter) or pressure-reducing, for example, a solvent, but volatilizing a solvent, This resin composition layer 1 after making it consists of solid content of this resin composition, and contains little volatile component. In addition, the thickness of the said resin composition layer is about 1.5-5 micrometers, for example.

Next, the radiation 4 is irradiated to the present resin composition layer 1 through the positive mask 3. The pattern of the positive mask 3 is suitably selected according to the pattern made into the objective of a transparent cured resin pattern. As radiation, light rays, such as g line | wire and i line | wire, are used, for example. The radiation is preferably irradiated using, for example, a mask aligner or a stepper (not shown).

It develops after exposing like this. After exposing this resin composition layer 1, it can develop by the method of making it contact with a developing solution, 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, An alkaline compound should just be an inorganic alkaline compound, and an organic alkaline compound is also favorable.

Examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium cinnamic acid, potassium cinnamic acid, sodium carbonate, and carbonic acid. Potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

As an organic alkaline compound, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, monoiso Propyl amine, diisopropyl amine, ethanolamine and the like. Said alkaline compounds are used individually or in combination of 2 or more types, respectively. 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 developer may contain a 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, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, poly Oxyethylene 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, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned. These surfactant can be used individually or in combination of 2 or more types, respectively.

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

After exposing this resin composition layer 1, in order to make it contact a developing solution, for example, after exposing the board | substrate 2 in which the present resin composition layer 1 was formed, it is good to immerse in a developing solution. By the development, the radiation-irradiated area 12 irradiated with radiation at the above exposure in the present resin composition layer 1 is dissolved in the developer, and the unradiated non-radiated area 11 in which the radiation is not irradiated is not dissolved in the developer. It remains without forming the pattern 5.

Since the radiation sensitive resin composition of this invention contains a quinonediazide compound (B), even if the time which makes this resin composition layer 1 contact with a developing solution is short, the radiation area 11 is easily melt | dissolved and removed. do. Moreover, since it contains a quinonediazide compound (B), even if the time which makes this resin composition layer 1 contact a developing solution becomes long, the unirradiated area | region 12 of a radiation will melt | dissolve in a developing solution and will not lose.

After development, it is usually washed with water and dried. After drying, radiation is further irradiated over the obtained pattern 5. Irradiation of radiation is usually carried out directly or without a mask on the pattern formed on the substrate, but radiation is preferably applied over the entire surface of the pattern. In addition, irradiation of a radiation can be performed from the back surface of a board | substrate. It is preferable that the radiation irradiated here is an ultraviolet-ray or deep ultraviolet-ray containing radiation of 250-330 nm wavelength, and the irradiation amount per unit area is usually larger than the irradiation amount in exposure through said mask.

By heat-processing (post-baking) the pattern 5 formed in this way, since heat resistance, solvent resistance, etc. of a transparent cured resin pattern improve, it is preferable to perform the said process. After development, the substrate after irradiation with radiation is heated by a method using a heating apparatus such as a hot plate or a clean oven. The heating temperature is usually 150 to 250 ° C, preferably about 180 to 240 ° C, and the heating time is usually 5 to 120 minutes, preferably about 15 to 90 minutes. By heating, the pattern is further cured and a more rigid transparent cured resin pattern is formed.

The thus formed transparent cured resin pattern is obtained by curing the radiation-sensitive resin composition of the present invention, and is useful as a transparent cured resin pattern such as an insulating film of a TFT substrate, an insulating film of an organic EL element, a CCD protective film, or the like.

As mentioned above, although embodiment of this invention was described, embodiment of this invention described above is an illustration to the last, and the scope of the present invention is not limited to these embodiment. The scope of the invention is indicated by the claims, and includes all modifications within the meaning and range equivalent to the description of the claims. Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

Synthesis Example 1

The following raw materials were injected into a 200 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, and the four-necked flask was immersed in an oil bath under nitrogen flow, and the flask internal temperature was maintained at 85 to 95 ° C. The reaction is carried out by stirring for a time to obtain Resin A1. The polystyrene reduced weight average molecular weight of this resin A1 is 15,000.

6.4 g methacrylic acid

11.7 g of cyclohexyl methacrylate

17.7 g of 3-ethyl-3-methacryloxymethyloxetane

Methyl 2-hydroxyisobutane 83.3g

0.9 g of azobisisobutyronitrile

Synthesis Example 2

The following raw materials were injected into a 200 mL four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 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. The reaction is carried out to obtain Resin A2. The polystyrene reduced weight average molecular weight of A2 is 15,000.

Methacrylic acid 6.8 g

N-phenylmaleimide 13.7 g

3-ethyl-3-methacryloxymethyloxetane 17.8 g

89.5 g of 2-hydroxyisobutyrate

0.9 g of azobisisobutyronitrile

Synthesis Example 3

The following raw materials were injected into a 200 mL four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 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. The reaction is carried out to obtain Resin A3. The polystyrene reduced weight average molecular weight of this resin A3 is 15,000.

Methacrylic acid 6.8 g

N-cyclohexylmaleimide 14.2 g

3-ethyl-3-methacryloxymethyloxetane 17.8 g

90.7 g of 2-hydroxyisobutyrate

0.9 g of azobisisobutyronitrile

In addition, the measurement conditions of said polystyrene conversion weight average molecular weight are as follows.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Columns: TSK-GELG2000HXL and TSK-GELG4000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration: 0.6%

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosso Corporation)

Example 1

(A) Resin A1 (100 mass parts), (B) Compound (22 mass parts) of Formula (3), (C) After mixing salt (brand name: Sunaid SI-100, Sanshinka Kagyo Kogyo Co., Ltd. product) (2 mass parts), and (G) 2-hydroxyisobutyrate carbonate (429 mass part) at 23 degreeC, Filtration was carried out through a cartridge filter made of polytetrafluoroethylene having a diameter of 1.0 mu m to obtain a radiation sensitive resin composition as a filtrate.

In Formula 3 above,

Q ⁴ is a substituent of Formula 3a.

Spin-coating the radiation-sensitive resin composition obtained above on the 4-inch silicon wafer 2, and heating (prebaking) it for 2 minutes at 100 degreeC using a hotplate, and forming the radiation-sensitive resin composition layer 1 The thickness of the film was measured using a thick film gauge (see: Lambda Ace, manufactured by Dainippon Screen Seiko Co., Ltd.), and found to be 2.6 탆 (Fig. 1 (a)).

Thereafter, the obtained radiation-sensitive resin composition layer 1 was subjected to radiation (4) through a positive mask 3 using an i-line stepper [reference: NSR-1755i7A (NA = 0.5), manufactured by Nikon Corporation]. ) Is irradiated and exposed (Fig. 1 (b)). As the positive mask 3, a positive mask for forming a contact hole pattern with a line width of 3 mu m at a spacing of 9 mu m in the transparent cured resin pattern is used.

After exposure, it is immersed in 23 degreeC tetramethylammonium hydroxide aqueous solution (containing 0.2 mass part of tetramethylammonium hydroxide in 100 mass parts) for 70 second, and after developing, it wash | cleans with ultrapure water and dries. In the pattern after development, when the exposure amount of the mask exposure whose diameter of a contact hole becomes 3 micrometers is made into the effective sensitivity, the effective sensitivity is 79 mJ / cm <2>, and it is 90 degrees when the angle (theta) which a cross section of a pattern and a board | substrate make is measured. After drying, using a DUV lamp (reference: UXM-501MD, manufactured by Ushio Co., Ltd.), radiation (300 mJ / cm 2 intensity at a wavelength of 313 nm standard) was irradiated over the entire surface for 30 minutes at 220 ° C. in a clean oven. It heats and the transparent cured resin pattern 5 is formed (FIG. 1 (c)).

It was 1.8 micrometers when the thickness T1 of the obtained transparent cured resin pattern 5 was measured using the film thickness meter.

The visible light transmittance is a transparent cured resin film formed by the above method, except that the transparent glass substrate [reference: # 1737, manufactured by Corning Co., Ltd.] is not subjected to a stepper exposure step. -200, manufactured by Olympasco Furniture Co., Ltd.]. The thickness of the film is measured by a thickness gauge (see DEKTAK3, manufactured by ULVAC Co., Ltd.). At a wavelength of 400-750 nm per 1 micrometer of the obtained transparent cured resin film, the average light transmittance was 99.3%, indicating high transparency, and no coloring was observed. The angle θ formed between the cross section of the cured resin pattern and the substrate is 54 degrees. Moreover, when the board | substrate with which the transparent cured resin pattern was formed was immersed in methyl ethyl ketone or N-methylpyrrolidone (23 degreeC) for 30 minutes, and the solvent resistance test was performed, the change was not seen before and after immersion.

Example 2

(C) Sunaid SI-100 [Reference: Sanshin Kagaku Kogyo Co., Ltd.] A radiation sensitive resin composition was obtained in the same manner as in Example 1 except that the salt was changed to a salt (trade name: Sun-Aid SI-150, manufactured by Sanshinka Furniture Co., Ltd.).

The same operation as in Example 1 is performed to form a transparent cured resin pattern on the substrate. The 3 micrometer contact hole pattern was resolved with an effective sensitivity of 89 mJ / cm <2>, and the angle ((theta)) of the cross section of the pattern after image development, and a board | substrate is 90 degrees. The light transmittance measured and operated in the same manner as in Example 1 was 99.3%, indicating high transparency, and no coloring appeared. The angle θ formed between the cross section of the cured resin pattern and the substrate after the heat treatment is 52 degrees. In the same solvent resistance test as in Example 1, there was no change in the coating film before and after immersion.

Example 3

(C) Sunaid SI-100 [Reference: Sanshin Kagaku Kogyo Co., Ltd.] The same procedure as in Example 1 was carried out except that the salt was changed to a salt (trade name: Adeka Optomer SP-170, manufactured by Asahi Denka Kogyo Co., Ltd.) to obtain a radiation sensitive acid composition.

The same operation as in Example 1 is performed to form a transparent cured resin pattern on the substrate. The 3 占 퐉 contact hole pattern was resolved at an effective sensitivity of 100 mJ / cm 2, and the angle θ formed between the cross-section of the pattern after development and the substrate was 90 degrees. The light transmittance measured in the same manner as in Example 1 was 99.3%, indicating high transparency, and no coloration was observed. The angle θ formed between the cross section of the cured resin pattern after the heat treatment and the substrate is 57 degrees. In the same solvent resistance test as in Example 1, there was no change in the coating film before and after immersion.

Example 4

(C) Sun-aid SI-100 (Reference: Sanshin Kagaku Kogyo Co., Ltd.) A radiation sensitive resin composition was obtained in the same manner as in Example 1 except that the salt was changed to a salt (trade name: Adeka Optomer SP-172, manufactured by Asahi Denka Kogyo Co., Ltd.).

The front exposure performed after development was the same as in Example 1 except that the ultra-high pressure mercury lamp (see USH-250D manufactured by Ushio Co., Ltd.) was radiated over the entire surface (the intensity at the wavelength of 365 nm was 300 mJ / cm 2). The operation is performed to form a transparent cured resin pattern on the substrate. The 3 占 퐉 contact hole pattern is resolved at an effective sensitivity of 150 mJ / cm 2. It was 2.0 micrometers when the thickness T1 of the obtained transparent cured resin pattern 5 was measured using the film thickness meter.

The angle θ formed between the cross section of the pattern after development and the substrate is 90 degrees. The light transmittance measured in the same manner as in Example 1 was 99.3%, indicating high transparency, and no coloration appeared. The cross section of the cured resin pattern after the heat treatment and the angle formed with the substrate were 56 degrees. In the same solvent resistance test as in Example 1, there was no change in the coating film before and after immersion.

Example 5

(A) Except changing the resin A1 (100 mass parts) to (A) resin A2 (100 mass parts), it operated like Example 4 and obtains a radiation sensitive resin composition.

The same operation as in Example 1 was carried out except that the entire surface exposure performed after the development was carried out under the same conditions as in Example 4 to form a transparent cured resin pattern on the substrate. Effectiveness 120mJ / ㎠ 3 micrometer contact hole pattern is resolved. It was 2.1 micrometers when the thickness T1 of the obtained transparent cured resin pattern 5 was measured using the film thickness meter.

The angle θ formed between the cross section of the pattern after development and the substrate is 90 degrees. The light transmittance measured by operation similar to Example 1 shows high transparency with 99.5%, and coloring does not appear. The angle θ formed between the cross section of the cured resin pattern after the heat treatment and the substrate is 66 degrees. In the same solvent resistance test as in Example 1, there was no change in the coating film before and after immersion.

Example 6

A radiation sensitive resin composition was obtained in the same manner as in Example 4 except that (A) resin A1 (100 parts by mass) was changed to (A) resin A3 (100 parts by mass).

The same operation as in Example 1 was carried out except that the entire surface exposure performed after the development was carried out under the same conditions as in Example 4 to form a transparent cured resin pattern on the substrate. The 3 占 퐉 contact hole pattern is resolved at an effective sensitivity of 100 mJ / cm 2. It was 2.0 micrometers when the thickness T1 of the obtained transparent cured resin pattern 5 was measured using the film thickness meter.

After development, the angle θ formed between the cross section of the pattern and the substrate is 90 degrees. The light transmittance measured and operated in the same manner as in Example 1 showed high transparency at 99.3%, and no coloration appeared. The angle θ formed between the cross section of the cured resin pattern and the substrate after the heat treatment is 72 degrees. In the same solvent resistance test as in Example 1, there was no change in the coating film before and after immersion.

Comparative Example 1

(C) Sun-aid SI-110 (reference: Sanshin Kagaku Kogyo Co., Ltd.) A radiation sensitive resin composition was obtained in the same manner as in Example 1 except that the salt was changed to a salt (trade name: Sun-Aid SI-110, manufactured by Sanshin Kagaku Kogyo Co., Ltd.).

The same operation as in Example 1 is performed to form a transparent cured resin pattern on the substrate. Although the 3 micrometer contact hole pattern was resolved with the effective sensitivity of 75 mJ / cm <2>, the angle ((theta)) of the cross section of the pattern after image development, and a board | substrate is 90 degree | times, but the pattern melt | dissolved in heat processing and the transparent resin pattern could not be formed. The light transmittance measured by operation in the same manner as in Example 1 was 99.3%, and no coloration appeared. In the same solvent resistance test as in Example 1, an increase in film thickness of 5% appears in the coated film after immersion.

Since the radiation sensitive resin composition of this invention does not have coloring, it is possible to form a transparent cured resin pattern having high transmittance to visible light and good profile controllability having sufficient solvent resistance. By the radiation sensitive resin composition of the present invention, for example, the productivity of the TFT substrate can be increased.

Claims (10)

A copolymer (A) comprising a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group (except for the unsaturated carboxylic acid), Quinonediazide compound (B) and A radiation sensitive resin composition containing a cationic polymerization initiator (C) consisting of a salt of a hexafluoroantimonate anion and an onium cation. The radiation sensitive resin composition according to claim 1, wherein the onium cation of the cationic polymerization initiator (C) is an onium cation of the formula (1) or (2). Formula 1 Formula 2 In Formula 1 and Formula 2 above, R ¹ to R ³ are each independently one or more of the hydrogen atoms on the benzene ring is an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group A phenyl group which may be substituted with a group selected from the group, At least one hydrogen atom on the naphthalene ring is a naphthyl group which may be substituted with a group selected from the group consisting of an alkoxyl group having 1 to 12 carbon atoms, a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group, A linear alkyl group having 1 to 18 carbon atoms, in which at least one of the hydrogen atoms on the alkyl group may be substituted with a group selected from the group consisting of a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group, Branched alkyl groups of 3 to 18 carbon atoms, in which at least one of the hydrogen atoms on the alkyl group may be substituted with a group selected from the group consisting of a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group, or At least one of the hydrogen atoms on the alkyl group is a cyclic alkyl group having 3 to 18 carbon atoms which may be substituted with a group selected from the group consisting of a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group. The radiation sensitive resin composition of Claim 1 or 2 whose onium cation of a cationic polymerization initiator (C) is an iodonium cation. The structural unit (a2) according to any one of claims 1 to 3, wherein the structural unit (a1) derived from an unsaturated carboxylic acid and the structural unit (a2) derived from an unsaturated compound having an oxetanyl group (except for the unsaturated carboxylic acid) are used. The content of the copolymer (A) to be contained is 50 to 94.99% by mass fraction with respect to the solid content of the radiation-sensitive resin composition, and the content of the quinone diazide compound (B) is relative to the solid content of the radiation-sensitive resin composition. , The mass fraction is 5 to 40%, and the content of the cationic polymerization initiator (C) consisting of a salt of hexafluoroantimonate and an onium cation is O.01 in mass fraction with respect to the solid content of the radiation-sensitive resin composition. To 10% of a radiation-sensitive resin composition. The composition according to any one of claims 1 to 4, wherein the copolymer (A) is a structural unit derived from a carboxylic acid ester having an olefinic double bond, a structural unit derived from an aromatic vinyl compound, and a structure derived from a vinyl cyanide compound. A radiation sensitive resin composition further comprising at least one structural unit (a3) selected from the group consisting of units. The composition according to any one of claims 1 to 4, wherein the copolymer (A) is a structural unit derived from a carboxylic acid ester having an olefinic double bond, a structural unit derived from an aromatic vinyl compound, or a composition derived from a vinyl cyanide compound. A radiation sensitive resin composition further comprising at least one structural unit (a3) selected from the group consisting of units and structural units derived from N-substituted maleimide compounds. The transparent cured resin pattern formed by the radiation sensitive resin composition of any one of Claims 1-6. The radiation-sensitive resin composition according to any one of claims 1 to 6 is applied onto a substrate, irradiated with radiation through a mask, then developed to form a predetermined pattern, and then irradiated with radiation. The manufacturing method of the transparent cured resin pattern containing the thing. The method according to claim 8, wherein irradiation with radiation after development is performed with radiation having a wavelength of 250 to 330 nm. The method according to claim 8 or 9, wherein the development is followed by irradiation with radiation and then further heating.