JP4148098B2 - Radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, 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 TFT insulating film used in a thin film transistor (hereinafter referred to as TFT) liquid crystal display device or an organic EL display device, or a diffuse reflection used in a reflective TFT substrate. It is useful as a material for forming a transparent cured resin pattern including a plate, an organic EL insulating film, a protective film of a solid-state imaging device (hereinafter, sometimes referred to as CCD), and the like. Here, in order to obtain a brighter display image, the TFT insulating film or the like is required to have a high visible light transmittance. In addition, high solvent resistance is also required in terms of the productivity of the TFT substrate. Furthermore, the radiation-sensitive resin composition is required to have high sensitivity to radiation used for forming the insulating film in terms of the 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 patent document 1 etc.). As binder resins, acrylate copolymers and copolymers using oxetanes have been developed. Oxetanes are known to undergo cationic polymerization (see, for example, Patent Document 2).
Moreover, as a cationic polymerization initiator, the onium salt which consists of a hexafluorophosphate anion is generally used (for example, refer patent document 3 etc.). However, when a pattern formed using a 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. was there.

Japanese Patent Laid-Open No. 2001-281853, page 2, left column, lines 2-25 JP 2000-239648, page 5, right column, line 38-page 6, left column, line 1; page 7, left column, line 3-right column, line 34 JP-A-9-304931, page 2, left column, lines 2-30

  An object of the present invention is to provide a radiation-sensitive resin that is capable of forming a transparent cured resin pattern that is not colored, has a high visible light transmittance, has sufficient solvent resistance, and has a good shape. It is to provide a composition.

（式中、Ｑ ^４ は、式（４−１）で示される置換基を示す。）

Therefore, the present inventors have intensively studied to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, in the present invention, as the binder resin, the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid) are used. Radiation-sensitive resin composition containing a salt comprising a hexafluoroantimonate anion and an onium cation as a copolymer (A), a quinonediazide compound (B) represented by the general formula (4), and a cationic polymerization initiator (C) A transparent cured resin pattern formed from the above-mentioned radiation-sensitive resin composition, and the radiation-sensitive resin composition is applied, irradiated with radiation through a mask, and then developed to form a predetermined pattern And providing a method for producing a transparent cured resin pattern, which is then irradiated with radiation.

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

  Since the radiation-sensitive resin composition of the present invention is not colored, it can form a transparent cured resin pattern having high transmittance for visible light, sufficient solvent resistance, and good profile controllability. The radiation sensitive resin composition of the present invention can form, for example, a TFT substrate with high productivity.

In the radiation-sensitive resin composition of the present invention, the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid) are used. The copolymer (A) to be contained is a polymer compound having an unsaturated carboxylic acid and an oxetanyl group.
The oxetanyl group means a group having an oxetane (trimethylene oxide) ring.

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

As the structural unit (a2) derived from the unsaturated compound having the oxetanyl group (excluding the unsaturated carboxylic acid), for example, 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) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3 -(Meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) act Etc. b carboxyethyl oxetane or 2-pentafluoroethyl-3- (meth) acryloxy ethyl oxetane and the like.
As the structural unit (a2), 3-ethyl-3-methacryloxymethyloxetane is particularly preferable.

The copolymer (A) in the radiation-sensitive resin composition of the present invention further includes a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond and a structural unit (a32) derived from an aromatic vinyl compound. And 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.
Further, the structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond, a structural unit (a32) derived from an aromatic vinyl compound, and a structural unit (a33) derived from a vinyl cyanide compound. It is preferable to include at least one selected structural unit (a3).
Examples of the structural unit (a3) include structural units derived from a polymerizable carbon-carbon unsaturated bond.
As the structural unit derived from the carboxylic acid ester having an olefinic double bond (a31), a structural unit derived from an unsaturated carboxylic acid ester can also be used. For example, methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, propyl acrylate, propyl methacrylate, pentyl Acrylate, pentyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate Acrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, phenyl acrylate, phenyl methacrylate, unsaturated carboxylic acid ester of diethyl maleate, diethyl fumarate, itaconic acid diethyl;
Unsaturated alkyl carboxylic acid aminoalkyl esters such as aminoethyl acrylate;
Examples thereof include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate.
Examples of the structural unit (a32) derived from the aromatic vinyl compound include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene.
Examples of the structural unit (a33) derived from the vinyl cyanide compound include vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloronitrile.
Examples of the structural unit (a34) derived from the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (4-acetylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N- Succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N- (1-anilinonaphthyl-4) -maleimide, N- [4- ( 2-Benzoxazolyl) phenyl] male Bromide, etc. N-(9-acridinyl) N- substituted maleimide compounds such as maleimide.
Among them, as the at least one structural unit (a3) selected from the group consisting of (a31), (a32), (a33) and (a34), dicyclopentanyl methacrylate, dicyclopentanyl acrylate, cyclohexyl methacrylate, cyclohexyl Particularly preferred are acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.
Such structural units can be used alone or in combination of two or more.

In the radiation-sensitive resin composition of the present invention, the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid) are used. In the copolymer (A) to be contained, the structural unit (a1) derived from the unsaturated carboxylic acid is usually 5 to 50 mol%, preferably 15 to 40 mol%, based on the entire structural unit of the copolymer (A). The structural unit (a2) derived from an unsaturated compound having an oxetanyl group (excluding unsaturated carboxylic acid) is usually 5 to 5 relative to the entire structural unit of the copolymer (A). It is used in the range of 95 mol%, preferably 15 to 85 mol%.
In the copolymer (A), the structural unit (a2) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid). When the composition ratio is within the above range, it is preferable because it has a tendency to exhibit high curability while having an appropriate dissolution rate with respect to the developer.

  The content of the structural unit (a3) in the copolymer (A) in the present invention is usually 0 to 90 mol%, preferably 0 to 70 mol%.

  The structural unit (a1) derived from the unsaturated carboxylic acid in the radiation-sensitive resin composition of the present invention and the structural unit (a2) derived from an unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid) are included. Examples of the copolymer (A) include 3-ethyl-3-methacryloxymethyl oxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl oxetane / benzyl methacrylate / methacrylic acid / styrene copolymer. Polymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexyl methacrylate copolymer, 3-ethyl-3-methacryloxy Methyl oxetane / methacrylic acid / metac Co-methyl methyl / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / t-butyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl methacrylate Polymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / benzyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / cyclohexyl acrylate, 3-ethyl-3-methacryloxymethyl oxetane / Methacrylic acid / isobornyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / t-butyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / pheny Maleimide copolymer, and 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / cyclohexyl maleimide copolymer.

In the radiation-sensitive resin composition of the present invention, the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid) are used. The copolymer (A) to be contained has a weight average molecular weight determined by gel permeation chromatography based on polystyrene, which is usually 2,000 to 100,000, preferably 2,000 to 50,000, more preferably. It is used in the range of 3,000 to 30,000. When the weight average molecular weight is from 2,000 to 100,000, a high development speed tends to be obtained while maintaining the remaining film ratio during development, which is preferable.
In the radiation-sensitive resin composition of the present invention, the structural unit (a1) derived from the unsaturated carboxylic acid and the structural unit (a2) derived from the unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid) are used. The content of the copolymer (A) to be contained is usually 50 to 94.99%, preferably 60 to 90% by mass fraction with respect to the solid content of the radiation-sensitive resin composition.

  Examples of the quinonediazide compound (B) in the radiation-sensitive resin composition of the present invention include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, Examples include 1,2-naphthoquinonediazide sulfonic acid amides.

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

  The quinonediazide compound (B) is used alone or in combination of two or more. The content of the quinonediazide 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 quinonediazide compound is 2 to 50%, the difference in the dissolution rate between the unexposed area and the exposed area tends to be high, so that the development residual film ratio tends to be kept high, which is preferable.

  The structure of the onium cation of the cationic polymerization initiator (C) which is an onium salt composed of a hexafluoroantimonate anion and an onium cation in the radiation sensitive resin composition of the present invention is selected from the general formulas (1) to (2) Onium cations.

(Wherein R ^{1 to} R ³ are at least selected from the group consisting of 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 optionally substituted by one substituent,
A naphthyl group which may be substituted with at least one substituent 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 which may be substituted with at least one substituent selected from the group consisting of a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group;
A branched alkyl group having 3 to 18 carbon atoms which may be substituted with at least one substituent selected from the group consisting of a halogen atom, a carboxyl group, a mercapto group, a cyano group and a nitro group;
It represents any of a C3-C18 cyclic alkyl group which may be substituted with at least one substituent 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 cation represented by the general formula (1) include diphenyliodonium, bis (p-tolyl) iodonium, bis (pt-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, Bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) Examples include iodonium.
Specific examples of the onium cation represented by the general formula (2) include triphenylsulfonium, tris (p-tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (t-butylphenyl) sulfonium, tris ( 2,6-dimethylphenyl) 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 (octadecyloxy) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (t-butoxy) sulfonium, dimethyl (cyclopentyl) Xy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitro) Octyloxy) sulfonium, dimethyl (18,18,18-trifluorooctadecyloxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, dimethyl (tris (trichloromethyl) methyl) sulfonium, dimethyl (2-oxopropyl) sulfonium, Dimethyl (2-oxobutyl) sulfonium, dimethyl (2-oxopentyl) sulfonium, dimethyl (2-oxohexyl) sulfonium, dimethyl (2 Oxoheptyl) sulfonium, dimethyl (2-oxooctyl) sulfonium, dimethyl (3-methyl-2-oxobutyl) sulfonium, 3,3-dimethyl-2-oxobutyldimethylsulfonium, 2-cyclohexyl-2-oxoethyldimethylsulfonium, 2-cyclopentyl-2-oxoethyldimethylsulfonium, 2-oxo-2-phenylethyldimethylsulfonium, 2-naphthyl-2-oxoethyldimethylsulfonium, 3,3-dimethyl-2-oxobutylthiacyclopentanium, 2- Phenyl-2-oxoethylthiacyclopentanium, 2-naphthyl-2-oxoethylthiacyclopentanium, dimethyl (4-hydroxyphenyl) sulfonium, benzyl (4-hydroxyphenyl) methylsulfonium , (4-hydroxyphenyl) (1-naphthylmethyl) methylsulfonium, (4-hydroxyphenyl) (4-methylbenzyl) methylsulfonium, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium, dimethyl (4- Acetophenyl) sulfonium, benzyl (4-acetophenyl) methylsulfonium, dimethyl (4-methoxycarbonylphenyl) sulfonium, benzyl (4-methoxycarbonylphenyl) methylsulfonium, dimethyl (4-benzyloxycarbonylphenyl) sulfonium, benzyl (4 -Benzyloxycarbonylphenyl) methylsulfonium, diphenyl (4-phenylthiophenyl) sulfonium, diphenyl (4-phenyloxyphenyl) sulfonium, bis (diphenyl) Sulfonio) phenyl sulfide, and bis (diphenylsulfonio) phenyl ether.
Preferably, diphenyliodonium, bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (pt-butylphenyl) iodonium, bis (pt-butylphenyl) iodonium, tri Examples thereof include phenylsulfonium and tris (t-butylphenyl) sulfonium. The content of the cationic polymerization initiator (C) in the radiation-sensitive resin composition of the present invention is usually 0.01 to 10% by mass fraction with respect to the solid content of the radiation-sensitive resin composition, preferably Is 0.1 to 5%. When the content of the cationic polymerization initiator (C) is in the above range, the curing rate at the time of heat curing tends to be increased and the resolution reduction at the time of heat curing tends to be suppressed, which is preferable.

  As other components, in the radiation-sensitive resin composition of the present invention, in addition to the copolymer (A) containing (a1) and (a2), the quinonediazide compound (B), and the cationic polymerization initiator (C) If necessary, a sensitizer (D), a polyhydric phenol compound (E), a crosslinking agent (F), a polymerizable monomer (G), and a solvent (H) can be contained.

Examples of the sensitizer (D) include 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, , 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4-methoxy-1-naphthol, etc. Examples include naphthols. In particular, 1-naphthol, 2-naphthol, and 4-methoxy-1-naphthol are preferable.
In the radiation sensitive resin composition of this invention, when it contains the said sensitizer (D), the content is 0.01 mass by mass with respect to solid content of a radiation sensitive resin composition normally. -10%, preferably 0.1-5%. When the content of the sensitizer (D) is in the above range, the resolution of the thermal curing is reduced by promoting the decomposition of the cationic polymerization initiator during the exposure after the development and increasing the curing speed during the thermal curing. Further, the visible light transmittance of the obtained coating film is preferable because it does not decrease to a certain extent in practical use.

  The polyhydric phenol compound (E) in the radiation-sensitive resin composition of the present invention is preferably a compound having two or more phenolic hydroxyl groups in the molecule. Examples of the polyhydric phenol compound include polyhydric phenols such as trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, and (polyhydroxyphenyl) alkanes similar to those described in the quinonediazide compound. And the like.

  Examples of the polyhydric phenol compound (E) include a polymer having at least hydroxystyrene as a raw material monomer. Specific examples of the polyphenol compound (E) include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer, and hydroxystyrene / alkoxystyrene copolymer. Examples thereof include resins obtained by polymerizing hydroxystyrene such as coalescence. Furthermore, a novolak resin obtained by polycondensation of at least one compound selected from the group consisting of phenols, cresols and catechols and one or more compounds selected from the group consisting of aldehydes and ketones is also included. It is done.

  In the radiation sensitive resin composition of this invention, when it contains the said polyhydric phenol compound (E), the content is 0-mass normally with respect to solid content of a radiation sensitive resin composition. It is 40%, preferably 0.1 to 40%, more preferably 1 to 25%. Containing a polyhydric phenol compound is preferable because the visible light transmittance of the resulting film increases and the performance as a transparent cured resin pattern is improved. Moreover, when the addition amount of a polyhydric phenol compound (E) exists in the said range, there exists a tendency for visible light transmittance | permeability not to fall to the extent which is a problem practically, and it is preferable.

  Examples of the crosslinking agent (F) include methylol compounds.

  Examples of the methylol compound include alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins. Here, as the alkoxymethylated melamine resin, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, etc., as alkoxymethylated urea resin, for example, methoxymethylated Examples include urea resins, ethoxymethylated urea resins, propoxymethylated urea resins, butoxymethylated urea resins. The above crosslinking agents may be used alone or in combination of two or more.

  In the radiation sensitive resin composition of this invention, when it contains a crosslinking agent (F), the content is 0.1-15% by mass fraction with respect to solid content of a radiation sensitive resin composition. Preferably there is. When the content of the crosslinking agent (F) is in the above range, the visible light transmittance of the obtained film is increased, and the performance as a transparent cured resin pattern is preferably improved.

  Examples of the polymerizable monomer (G) include a polymerizable monomer capable of radical polymerization upon heating, a polymerizable monomer capable of cationic polymerization, and the like, and preferably a polymerizable monomer capable of cationic polymerization. .

  Examples of the polymerizable monomer capable of radical polymerization include compounds having a polymerizable carbon-carbon unsaturated bond, which may be a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, or 3 It may be a polyfunctional polymerizable monomer such as a polymerizable monomer having higher functionality.

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

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

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

  Examples of the polymerizable monomer capable of cationic polymerization include polymerizable monomers having a cationic polymerizable functional group such as a vinyl ether group, a propenyl ether group, and an oxetanyl group. Specific examples of the compound containing a vinyl ether group include: Examples include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether and the like. As a compound containing a propenyl ether group, 4- (1-propenyloxymethyl) -1,3 -Dioxolan-2-one and the like, and compounds containing an oxetanyl group include bis {3- (3-ethyloxetanyl) methyl} ether, 1,4-bis {3- (3-ethyloxetanyl) methoxy} benzene, 1,4- {3- (3-ethyloxetanyl) methoxy} methylbenzene, 1,4-bis {3- (3-ethyloxetanyl) methoxy} cyclohexane, 1,4-bis {3- (3-ethyloxetanyl) methoxy} methyl Examples include cyclohexane and 3- (3-ethyloxetanyl) methylated novolak resin.

  In the radiation sensitive resin composition of this invention, when using the said polymerizable monomer (G), this can be used individually or in combination of 2 or more types, respectively. When the polymerizable monomer (G) is contained, the content thereof is preferably 0.1 to 20% by mass fraction with respect to the solid content of the radiation-sensitive resin composition.

The radiation-sensitive resin composition of the present invention is usually used after being mixed with a solvent (H) and diluted. Examples of the solvent (H) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Esters such as methyl 2-hydroxyisobutanoate, ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone. Preferable solvents include methyl 2-hydroxyisobutanoate, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and among them, methyl 2-hydroxyisobutanoate is preferable.
The solvent (H) is used alone or in combination of two or more, and the content thereof is usually 50 to 95% by mass fraction with respect to the total amount of the radiation sensitive resin composition, preferably Is 60-90%.

  The radiation-sensitive resin composition of the present invention may contain various other components as necessary, such as surfactants, antioxidants, dissolution inhibitors, ultraviolet absorbers, adhesion improvers, electron donors, and the like. Additives can also be included.

  The radiation-sensitive resin composition of the present invention includes, for example, a structural unit derived from an unsaturated carboxylic acid (a1) and a structural unit derived from an unsaturated compound having an oxetanyl group (excluding the unsaturated carboxylic acid). a solution in which the copolymer (A) containing a2) is dissolved in the solvent (H), a solution in which the quinonediazide compound (B) is dissolved in the solvent (H), and an onium salt comprising a hexafluoroantimonate anion and an onium cation. It can manufacture by the method of mixing the solution which melt | dissolved the cationic polymerization initiator (C) containing in the solvent (H), respectively. Moreover, you may add a solvent (H) after mixing. After mixing, it is preferable to filter to remove solids not dissolved in the solvent. For example, it is preferable to filter using a filter having a pore size of 3 μm or less, preferably 0.1 μm or more and 2 μm or less. The solvent used for each component may be the same or different as long as it is compatible.

  In order to form a transparent cured resin pattern using the radiation sensitive resin composition of the present invention, for example, a layer (1) made of the radiation sensitive resin composition of the present invention is formed on a substrate (2) ( 1 (a)), the layer (1) is exposed to radiation (4) through a positive mask (3), exposed (FIG. 1 (b)), and then developed (FIG. 1 (c)). ).

  Examples of the substrate (2) include resin substrates such as a transparent glass plate and a silicon wafer, as well as a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. A CCD or TFT circuit, a color filter, a transparent electrode, or the like may be formed in advance on the substrate.

  The layer (1) comprising the radiation-sensitive resin composition can be formed by an ordinary method, for example, a method of applying the radiation-sensitive resin composition of the present invention on the substrate (2). Coating is performed by a known coating method such as a coating method using a liquid-saving coater such as a spin coating method (spin coating method), a casting coating method, a roll coating method, a slit & spin coating method, or a slit coating method. Done. After coating, the radiation-sensitive resin composition layer (1) is formed by drying by heating (hereinafter sometimes referred to as pre-baking) or drying under reduced pressure to volatilize the solvent. A radiation sensitive resin composition layer (1) consists of solid content of a radiation sensitive resin composition, and hardly contains a volatile component. Moreover, the thickness of this radiation sensitive resin composition layer is about 1.5-5 micrometers, for example.

  Next, the radiation-sensitive resin composition layer (1) is irradiated with radiation (4) through a positive mask (3). The pattern of the positive mask (3) is appropriately selected according to the target pattern of the transparent cured resin pattern. As the radiation, for example, light rays such as g-line and i-line are used. The radiation is preferably irradiated using, for example, a mask aligner or a stepper (not shown).

  Development is performed after the exposure. Development can be performed by, for example, a method of bringing the radiation-sensitive resin composition layer (1) after exposure into contact with a developer. As the developer, an alkaline aqueous solution is used as usual. As an alkaline aqueous solution, an aqueous solution of an alkaline compound is used as usual, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

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

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

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

  Examples of the nonionic surfactant include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, and polyoxyethylene alkyl aryl ether, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters. , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

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

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

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

  In order to bring the radiation-sensitive resin composition layer (1) into contact with the developer, for example, the substrate (2) on which the radiation-sensitive resin composition layer (1) is formed may be immersed in the developer. Of the radiation-sensitive resin composition layer (1), the radiation-irradiated region (12) irradiated with radiation in the previous exposure is dissolved in the developer by the development, and the radiation-unirradiated region (not irradiated with radiation) ( 11) remains without dissolving in the developer to form pattern (5).

  Since the radiation sensitive resin composition of this invention contains a quinonediazide compound (B), even if the time which makes a radiation sensitive resin composition layer (1) contact with a developing solution is short, a radiation irradiation area | region (11) is. Easily dissolves and is removed. Moreover, since it contains a quinonediazide compound (B), even if the time during which the radiation-sensitive resin composition layer (1) is brought into contact with the developer becomes long, the radiation non-irradiated region (12) dissolves in the developer and disappears. There is nothing to do.

  After development, it is usually washed with water and dried. After drying, the obtained pattern (5) is further irradiated with radiation. Irradiation is usually performed directly on the pattern formed on the substrate without using a mask, but it is preferable to irradiate the entire surface of the pattern with radiation. Moreover, you may perform irradiation of a radiation from a substrate back surface. The radiation to be irradiated here is preferably ultraviolet rays or deep ultraviolet rays containing radiation having a wavelength of 250 to 330 nm, and the irradiation amount per unit area is usually larger than the irradiation amount in the exposure through the previous mask.

  The pattern (5) thus formed is preferable in that the heat treatment and solvent resistance of the transparent cured resin pattern are improved by further heat treatment (hereinafter sometimes referred to as post-bake). . The heating is performed by a method in which the substrate after development and irradiation with radiation is heated with a heating device such as a hot plate or a clean oven. The heating temperature is usually about 150 ° C to 250 ° C, preferably about 180 ° C to 240 ° C, and the heating time is usually about 5 minutes to 120 minutes, preferably about 15 minutes to 90 minutes. By heating, the pattern is further cured and a stronger transparent cured resin pattern is formed.

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

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Synthesis example 1
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A1. This resin A1 had a weight average molecular weight in terms of polystyrene of 15,000.
6.4 g of methacrylic acid
11.7 g of cyclohexyl methacrylate
17.7 g of 3-ethyl-3-methacryloxymethyloxetane
Methyl 2-hydroxyisobutanoate 83.3g
Azobisisobutyronitrile 0.9g

Synthesis example 2
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A2. The polystyrene equivalent weight average molecular weight of this resin A2 was 15,000.

6.8 g of methacrylic acid
13.7 g of N-phenylmaleimide
17.8 g of 3-ethyl-3-methacryloxymethyloxetane
Methyl 2-hydroxyisobutanoate 89.5g
Azobisisobutyronitrile 0.9g

Synthesis example 3
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A3. This resin A3 had a polystyrene equivalent weight average molecular weight of 15,000.

6.8 g of methacrylic acid
14.2 g of N-cyclohexylmaleimide
17.8 g of 3-ethyl-3-methacryloxymethyloxetane
90.7 g of methyl 2-hydroxyisobutanoate
Azobisisobutyronitrile 0.9g

In addition, the measurement conditions of said polystyrene conversion weight average molecular weight are as follows.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL, TSK-GELG4000HXL in-line column temperature; 40 ° C
Mobile phase solvent; tetrahydrofuran flow rate; 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6% by mass (solvent: tetrahydrofuran)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Example 1
(A) Resin A1 (100 parts by mass),
(B) Formula (4)

（式中、Ｑ⁴は、式（４−１）で示される置換基を示す。）

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

A compound represented by (22 parts by mass),
(C) sulfonium salt hexafluoroantimonate [Sun Aid SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.)] (2 parts by mass),
(G) Methyl 2-hydroxyisobutanoate (429 parts by mass) was mixed at 23 ° C., and then pressure filtered through a cartridge filter made of polytetrafluoroethylene having a pore size of 1.0 μm, and the radiation-sensitive resin composition was filtrated. Got as.

  The radiation-sensitive resin composition obtained above is spin-coated on a 4-inch silicon wafer (2), and heated (prebaked) at 100 ° C. for 2 minutes using a hot plate, the radiation-sensitive resin composition layer (1 ) And the film thickness was measured using a film thickness meter [Lambda Ace (Dainippon Screen Mfg. Co., Ltd.)], and it was 2.6 μm (FIG. 1 (a)).

  Thereafter, an i-line stepper [NSR-1755i7A (NA = 0.5) (manufactured by Nikon Corporation)] was used for the obtained radiation-sensitive resin composition layer (1) through a positive mask (3). Radiation (4) was 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 μm in a transparent cured resin pattern with an interval of 9 μm was used.

After the exposure, after developing by immersing in an aqueous solution of tetramethylammonium hydroxide at 23 ° C. (containing 0.2 parts by mass of tetramethylammonium hydroxide in 100 parts by mass) for 70 seconds, washing with ultrapure water, Dried. In the pattern after development, assuming that the exposure amount in the mask exposure in which the diameter of the contact hole is 3 μm is effective sensitivity, the effective sensitivity is 79 mJ / cm ² , and the angle θ formed by the cross section of the pattern and the substrate is 90 It was a degree. After drying, the whole surface was irradiated with radiation using a DUV lamp [UXM-501MD (manufactured by Ushio Co., Ltd.)] (intensity of 300 mJ / cm ^{2 based on a} wavelength of 313 nm), and 30 ° C. at 220 ° C. in a clean oven. By heating for a minute, a transparent cured resin pattern (5) was 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 was determined by forming a transparent cured resin film on the transparent glass substrate [# 1737 (manufactured by Corning)] by the above method except that the exposure step using a stepper was not performed, and the microspectrophotometer [OSP-200 ( Olympus Optical Co., Ltd.)]. The film thickness was measured with a film thickness meter [DEKTAK3 (manufactured by ULVAC)]. The average light transmittance at a wavelength of 400 to 750 nm per 1 μm of the obtained transparent cured resin film was 99.3% and showed high transparency, and no coloring was observed. The angle θ formed by the cross section of the cured resin pattern and the substrate was 54 degrees. Further, the substrate on which the transparent cured resin pattern was formed was immersed in methyl ethyl ketone or N-methylpyrrolidone (23 ° C.) for 30 minutes and subjected to a solvent resistance test. As a result, no change was observed before and after the immersion.

Example 2
(C) Radiation sensitivity was changed in the same manner as in Example 1 except that Sun Aid SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.) was changed to Sun Aid SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.). A resin composition was obtained.

The same operation as in Example 1 was performed to form a transparent cured resin pattern on the substrate. The 3 μm contact hole pattern was resolved with an effective sensitivity of 89 mJ / cm ² , and the angle θ formed by the developed pattern cross section and the substrate was 90 degrees. The light transmittance measured in the same manner as in Example 1 was as high as 99.3%, and no coloration was observed. The angle θ formed by the cross section of the cured resin pattern after the heat treatment and the substrate was 52 degrees. In the same solvent resistance test as in Example 1, no change was observed in the coating film before and after immersion.

Example 3
(C) Radiation-sensitive operation was carried out in the same manner as in Example 1 except that Sun-Aid SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.) was changed to Adekaoptomer SP-170 (Asahi Denka Kogyo Co., Ltd.). A functional resin composition was obtained.

The same operation as in Example 1 was performed to form a transparent cured resin pattern on the substrate. The 3 μm contact hole pattern was resolved at an effective sensitivity of 100 mJ / cm ² , and the angle θ formed by 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 as high as 99.3%, and no coloration was observed. The angle θ formed by the cross section of the cured resin pattern after the heat treatment and the substrate was 57 degrees. In the same solvent resistance test as in Example 1, no change was observed in the coating film before and after immersion.

Example 4
(C) Radiation-sensitive operation was carried out in the same manner as in Example 1 except that Sun-Aid SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.) was changed to Adekaoptomer SP-172 (manufactured by Asahi Denka Kogyo Co., Ltd.). A functional resin composition was obtained.

Except that the entire exposure performed after development is performed using an ultra-high pressure mercury lamp [USH-250D (USHIO Co., Ltd.)] over the entire surface (intensity at a wavelength of 365 nm is 300 mJ / cm ² ). The same operation as 1 was performed to form a transparent cured resin pattern on the substrate. A 3 μm contact hole pattern was resolved with 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 by 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 as high as 99.3%, and no coloration was observed. The angle θ formed by the cross section of the cured resin pattern after the heat treatment and the substrate was 56 degrees. In the same solvent resistance test as in Example 1, no change was observed in the coating film before and after immersion.

Example 5
(A) A radiation-sensitive resin composition was obtained in the same manner as in Example 4 except that resin A1 (100 parts by mass) was changed to (A) resin A2 (100 parts by mass).

The same operation as in Example 4 was performed to form a transparent cured resin pattern on the substrate. A 3 μm contact hole pattern was resolved with an effective sensitivity of 120 mJ / cm ² . 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 by the cross section of the pattern after development and the substrate was 90 degrees. The light transmittance measured by operating in the same manner as in Example 1 was as high as 99.5%, and no coloring was observed. The angle θ formed by the cross section of the cured resin pattern after the heat treatment and the substrate was 66 degrees. In the same solvent resistance test as in Example 1, no change was observed in the coating film before and after immersion.

Example 6
(A) A radiation-sensitive resin composition was obtained in the same manner as in Example 4 except that resin A1 (100 parts by mass) was changed to (A) resin A3 (100 parts by mass).

The same operation as in Example 4 was performed to form a transparent cured resin pattern on the substrate. A 3 μm contact hole pattern was resolved with 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.
The angle θ formed by 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 as high as 99.3%, and no coloration was observed. The angle θ formed by the cross section of the cured resin pattern after the heat treatment and the substrate was 72 degrees. In the same solvent resistance test as in Example 1, no change was observed in the coating film before and after immersion.

Comparative Example 1
(C) The same procedure as in Example 1 was carried out except that the sun aid SI-100 (manufactured by Sanshin Chemical Industry Co., Ltd.) was used with a sulfonium salt hexafluorophosphate [Sun Aid SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.)]. As a result, a radiation sensitive resin composition was obtained.

The same operation as in Example 1 was performed to form a transparent cured resin pattern on the substrate. The 3 μm contact hole pattern was resolved with an effective sensitivity of 75 mJ / cm ² , and the angle θ formed by the cross section of the pattern after development and the substrate was 90 degrees, but the pattern melted by heat treatment to form a transparent resin pattern I couldn't. The light transmittance measured by operating in the same manner as in Example 1 was 99.3%, and no coloring was observed. In the same solvent resistance test as in Example 1, a 5% increase in film thickness was observed after coating.

  When the radiation-sensitive resin composition of the present invention is used, it is possible to form a transparent cured resin pattern that is not colored and has a high visible light transmittance and sufficient solvent resistance. Can be formed.

It is a schematic diagram which shows the process of forming a transparent cured resin pattern using the radiation sensitive resin composition of this invention. θ: Angle between the ridgeline of the cross section and the substrate surface in the cross section perpendicular to the substrate of the pattern

Explanation of symbols

1: Radiation sensitive resin composition layer 11: Radiation non-irradiated area
12: Radiation irradiation area 2: Substrate 3: Positive mask 4: Radiation 5: Transparent cured resin pattern

Claims (9)

Copolymer (A) containing a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group (excluding unsaturated carboxylic acid) as the binder resin ), A quinonediazide compound (B) represented by the general formula (4) and a radiation-sensitive resin composition containing a salt composed of a hexafluoroantimonate anion and an onium cation as the cationic polymerization initiator (C).

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

  The radiation-sensitive resin composition according to claim 1, wherein the cationic polymerization initiator (C) is an iodonium salt or a sulfonium salt. Content of copolymer (A) containing structural unit (a1) derived from unsaturated carboxylic acid and structural unit (a1) derived from unsaturated compound having oxetanyl group (excluding unsaturated carboxylic acid) However, the solid content of the quinonediazide compound (B) represented by the general formula (4) is 50 to 94.99% by mass with respect to the solid content of the radiation-sensitive resin composition. The content of the cationic polymerization initiator (C), which is an onium salt consisting of hexafluoroantimonate and an onium cation, is 5% to 40% by mass with respect to the solid content. The radiation-sensitive resin composition according to claim 1 or 2, which has a fraction of 0.01 to 10%.   The copolymer (A) is further composed of a structural unit (a31) derived from a carboxylic acid ester having an olefinic double bond, a structural unit (a32) derived from an aromatic vinyl compound, and a structural unit derived from a vinyl cyanide compound. The radiation sensitive resin composition according to any one of claims 1 to 3, comprising at least one structural unit (a3) selected from the group consisting of (a33) and a structural unit (a34) derived from an N-substituted maleimide compound. .   The copolymer (A) further includes a structural unit (a31) derived from a carboxylic acid ester, a structural unit (a32) derived from an aromatic vinyl compound, and a structural unit (a33) derived from a vinyl cyanide compound. The radiation sensitive resin composition in any one of Claims 1-3 containing the at least 1 sort (s) of structural unit (a3) chosen.   The transparent cured resin pattern formed with the radiation sensitive resin composition in any one of Claims 1-5. The radiation-sensitive resin composition according to any one of claims 1 to 5 is applied to a substrate, after being irradiated with radiation through a mask, developed to form a predetermined pattern, followed by Toru you irradiated A method for producing a brightly cured resin pattern. The radiation including radiation of a wavelength of 250～330Nm, method for producing a transparent cured resin pattern 請 Motomeko 7, wherein you irradiates the pattern after development.   The manufacturing method of the transparent cured resin pattern of Claim 7 or 8 which heats after irradiating a radiation.

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