JPH08240911A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE: To obtain a radiation sensitive resin compsn. hardly causing a change in the dimensions of a pattern and having superior focus latitude and heat resistant transparency by using a polymer contg. specified units each having a carboxyl group, a radiation sensitive acid generating compd. and a compd. having an acid-crosslinkable group. CONSTITUTION: This radiation sensitive resin compsn. contains a polymer contg. structural units each having at least one carboxyl group represented by formula I, an acid generating compd. which generates an acid when irradiated and a crosslinkable compd. having one or more groups which are crosslinked by the generated acid. In the formula I, each of R<1> -R<4> is H, 1-10C alkyl, 6-20C aryl, carboxyl or a group represented by formula II, III, IV, etc., and at least one of R<1> -R<4> is a group represented by the formula II, III, IV, etc. In the formula II-IV, each of n1-n3 is an integer of 1-5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition, and more specifically, to negatives sensitive to radiation such as ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, and proton beams. A radiation-sensitive resin composition suitable as a mold resist.

[0002]

2. Description of the Related Art In recent years, in the field of semiconductor industry, miniaturization of patterns has been required with the progress of high integration. Therefore, development of resists capable of forming patterns with higher resolution has been actively conducted. ing.

As the negative resist, an acid generating compound which generates an acid by receiving radiation and a cross-linking agent such as methylol melamine and alkoxy melamine are added based on polyhydroxystyrene or novolac resin. A chemically amplified negative resist has been developed. However, for these chemically amplified negative resists, for example, due to process reasons, the time between irradiation and subsequent heat treatment (hereinafter also referred to as “PEB treatment”) is performed. It has been pointed out that the size of the obtained pattern is remarkably changed by changing the temperature or the heating temperature of the PEB process. Furthermore, these chemically amplified negative resists are
There is a drawback that it cannot be used as an optical material such as a protective film of a liquid crystal color filter or a microlens because the color changes due to heat treatment.

[0004]

The present invention has been made based on the above circumstances, and its purpose is to:
Regardless of the length of time from the irradiation of radiation to the PEB treatment or the heating temperature of the PEB treatment, the dimensional change of the obtained pattern is small, and it has excellent focus tolerance and heat-resistant transparency. It is to provide a radioactive resin composition. Another object of the present invention is high sensitivity,
It is an object of the present invention to provide a radiation-sensitive resin composition having excellent storage stability, high resolution and high residual film rate, and capable of forming a pattern having excellent heat resistance and adhesion to a substrate.

[0005]

The radiation-sensitive resin composition of the present invention receives a component (A) composed of a polymer containing a carboxyl group-containing structural unit represented by the following formula (1) and radiation. Component (B) comprising an acid-generating compound which generates an acid by the above, and component (C) comprising a compound having at least one group capable of being crosslinked by the action of the acid generated from the component (B). Is characterized by.

[0006]

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The radiation-sensitive resin composition of the present invention will be specifically described below. The radiation-sensitive resin composition of the present invention comprises a component (A) composed of a specific polymer and an acid-generating compound (B) which generates an acid upon receiving radiation.
What contains the component and the (C) component which consists of a compound (henceforth a "crosslinkable compound") which has at least one group which can be crosslinked by the action of the acid generated from this (B) component. Is.

<Component (A)> The polymer (hereinafter referred to as “specific polymer”) used as the component (A) is a carboxyl group-containing structural unit represented by the above formula (1) (hereinafter, referred to as “specific polymer”).
It is referred to as "a specific carboxyl group-containing structural unit". ) As an essential structural unit, even a polymer having only this specific carboxyl group-containing structural unit as a repeating unit is a polymer having a specific carboxyl group-containing structural unit and another structural unit. May be.

The specific carboxyl group-containing structural unit is obtained by cleaving the polymerizable double bond of the monomer represented by the following formula (4) (hereinafter referred to as "specific monomer").

[0010]

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Specific examples of the specific monomer include unsaturated carboxylic acids or unsaturated dicarboxylic acids having a group represented by the formula (2a) such as 3-butenoic acid, 4-pentenoic acid and itaconic acid; (Meth) acryloyloxyacetic acid, 3-
(Meth) acrylates of hydroxy fatty acid having a group represented by the formula (2b) such as (meth) acryloyloxypropionic acid, 2- (meth) acryloyloxypropionic acid, and 4- (meth) acryloyloxybutanoic acid;
4- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 2- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxyphthalic acid, 3- (meth) acryloyloxyphthalic acid, 4- (meth) acryloyloxyisophthalic acid, 5
-(Meth) acryloyloxyisophthalic acid, 2- (meth) acryloyloxyterephthalic acid, and the like (meth) acrylates of an aromatic hydroxycarboxylic acid having a group represented by the formula (2c); succinic acid mono (2- ( (Meth) acryloyloxy) ethyl, phthalic acid mono (2- (meth))
Acryloyloxy) ethyl, isophthalic acid mono (2-
(Meth) acryloyloxy) ethyl, terephthalic acid mono (2- (meth) acryloyloxy) ethyl, tetrahydrophthalic acid mono (2- (meth) acryloyloxy) ethyl, tetrahydroisophthalic acid mono (2- (meth) acryloyloxy) Mono (meth) acryloyloxyethyl esters of dicarboxylic acids having a group represented by formula (2d) such as ethyl and tetrahydroterephthalic acid mono (2- (meth) acryloyloxy) ethyl;

4- (4'-vinylbenzyloxy) benzoic acid, 4- (3'-vinylbenzyloxy) benzoic acid,
4- (2'-vinylbenzyloxy) benzoic acid, 4-
(3'-Vinylbenzyloxy) phenylacetic acid, 4-
(3'-Vinylbenzyloxy) phenylacetic acid, 4-
(2'-Vinylbenzyloxy) phenylacetic acid, phthalic acid mono-4'-vinylbenzyl, phthalic acid mono-3'-
Vinylbenzyl, mono-2'-vinylbenzyl phthalate, mono-4'-vinylbenzyl isophthalate, mono-3'-vinylbenzyl isophthalate, mono-2'-vinylbenzyl isophthalate, tetrahydrophthalic acid mono-
4'-Vinylbenzyl, tetrahydrophthalic acid mono-
3'-Vinylbenzyl, tetrahydrophthalic acid mono-
2'-vinylbenzyl, mono-4-vinylbenzyl succinate, mono-3-vinylbenzyl succinate, mono-2-vinylbenzyl succinate, mono-4'-vinylbenzyl 1,2,3-benzenetricarboxylic acid, 1,4,4-benzenetricarboxylic acid mono-4′-vinylbenzyl,
1,3,5-benzenetricarboxylic acid mono-4'-vinylbenzyl, 1,2,3-benzenetricarboxylic acid mono-3'-vinylbenzyl, 1,2,4-benzenetricarboxylic acid mono-3'-vinylbenzyl , 3,3,5-benzenetricarboxylate mono-3′-vinylbenzyl,
1,2,3-benzenetricarboxylic acid mono-2'-vinylbenzyl, 1,2,4-benzenetricarboxylic acid mono-2'-vinylbenzyl, 1,3,5-benzenetricarboxylic acid mono-2'-vinylbenzyl Vinyl benzyl ether or vinyl benzyl ester having a group represented by formula (2e) such as; monomethyl, monoethyl, monopropyl, mono-i-propyl, monobutyl, mono-sec-butyl, mono-tert-itaconic acid. Examples thereof include monoalkyl esters of unsaturated carboxylic acids having a group represented by the formula (2f) such as butyl and a carboxyl group.

Of these, unsaturated dicarboxylic acids are itaconic acid; unsaturated dicarboxylic acid monoesters are itaconic acid monomethyl, monoethyl,
Monopropyl or mono-i-propyl, monobutyl ester; as methacrylates or acrylates of hydroxy fatty acid, (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropionic acid or 2- (meth) acryloyloxypropionic acid; As the methacrylate or acrylate of aromatic hydroxycarboxylic acid, 4- (meth) acryloyloxybenzoic acid; as the monomethacryloyloxyethyl ester or monoacryloyloxyethyl ester of dicarboxylic acid, succinic acid mono (2- (meth)) is used. Acryloyloxy) ethyl, mono (2- (meth) acryloyloxy) ethyl phthalate or mono (2- (meth) acryloyloxy) ethyl tetrahydroterephthalate; carboxyl group-containing vinyl Examples of the rubenzyl ethers or esters include 4- (4′-vinylbenzyloxy) benzoic acid, 4- (4′-vinylbenzyloxy) phenylacetic acid, mono-4′-vinylbenzyl phthalate, and mono-4 succinate. -Vinylbenzyl, 1,4,3-benzenetricarboxylic acid mono-4'-vinylbenzyl, 1,2,4-benzenetricarboxylic acid mono-4'-vinylbenzyl or 1,3,5-benzenetricarboxylic acid mono-4 '-Vinylbenzyl can be mentioned as a preferred one. The specific polymer may have one or more structural units in which the polymerizable double bonds of these specific monomers are cleaved.

The specific polymer has another structural unit in addition to the specific carboxyl group-containing structural unit for the purpose of improving transparency, alkali solubility adjustment, heat resistance, water resistance, solvent resistance, adhesion and the like. May be. Other structural units include copolymerizable monomers (hereinafter simply referred to as “copolymerizable monomers”) copolymerizable with a specific monomer, such as unsaturated acid anhydrides and epoxy group-containing unsaturated compounds. A structural unit in which a polymerizable double bond of a compound or other radically polymerizable compound is cleaved can be mentioned.

Specific examples of the unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride and methyl-5-norbornene. 2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride And dimethyltetrahydrophthalic anhydride.

Specific examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-n-propylglycidyl (meth) acrylate and α-n-butylglycidyl (meth). ) Epoxy group-containing (meth) such as acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate
Acrylates; epoxy group-containing unsaturated aliphatic compounds such as allyl glycidyl ether, 2-vinylcyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene oxide; vinylglycidyl ether, 2-vinylbenzylglycidyl ether, 3-vinyl Benzyl glycidyl ether, 4-vinyl benzyl glycidyl ether, α-methyl-2-vinyl benzyl glycidyl ether, α-methyl-3-vinyl benzyl glycidyl ether, α-methyl-4-vinyl benzyl glycidyl ether, 2,3-diglycidyl Oxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene,
2,3,4-triglycidyloxymethylstyrene,
2,3,5-triglycidyloxymethylstyrene,
2,3,6-triglycidyloxymethylstyrene,
3,4,5-triglycidyloxymethylstyrene,
Examples thereof include glycidyl ethers such as 2,4,6-triglycidyloxymethylstyrene.

Specific examples of the above other radically polymerizable compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, butadiene, 2,3-dimethylbutadiene and isoprene. Olefins; p-methoxystyrene, pt
Substituted styrenes such as ert-butoxystyrene, chloromethylstyrene; methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, i-propyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, (meth)
Acrylic acid-tert-butyl, (meth) acrylic acid-
2-ethylhexyl, lauryl (meth) acrylate,
Dodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate,
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, adamantyl acrylate (meth),
Allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, cyclopentyl (meth) acrylate, furyl (meth) acrylate, ( Tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenesyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate , (Meth) acrylate perfluoroethyl, (meth) acrylate perfluoro-n-propyl,
(Meth) acrylates such as perfluoro-i-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate;
(Meth) acrylic acid amides such as acrylic acid amide, (meth) acrylic acid-N, N-dimethylamide, (meth) acrylic acid-N, N-dipropylamide, (meth) acrylic acid anilide; acrylonitrile, acrolein , Methacrylonitrile, vinyl chloride, vinylidene chloride, N-
Examples thereof include compounds such as vinylpyrrolidone and vinyl acetate.

Among them, the unsaturated acid anhydride is maleic anhydride, itaconic anhydride or citraconic anhydride; the epoxy group-containing unsaturated compound is glycidyl (meth) acrylate, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether; other radically polymerizable compounds include styrene, α-methylstyrene, p-tert-butoxystyrene, butadiene, methyl (meth) acrylate, -tert-butyl (meth) acrylate, ( Preference is given to dicyclopentanyl methacrylate, benzyl (meth) acrylate or N-vinylpyrrolidone. These copolymerizable monomers can be used alone or in combination of two or more kinds.

The proportion of other structural units in the specific polymer is preferably 90% by weight or less, and particularly preferably 80% by weight or less. When this ratio exceeds 90% by weight, the polymer has a small ratio of the specific carboxyl group-containing structural unit, so that the alkali solubility is lowered, and moreover, sufficient crosslink density cannot be obtained, and the sensitivity is lowered. And the residual film rate may decrease.

The specific polymer is usually produced by radical polymerization of a specific monomer or a specific monomer and a copolymerizable monomer in a polymerization solvent. In addition, if necessary, these may be polymerized in a state where the functional groups of the specific monomer and the copolymerizable monomer are protected, and then deprotection treatment may be performed.

Examples of the polymerization solvent used for producing the specific polymer include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol; cyclic ethers such as tetrahydrofuran and dioxane; benzene, toluene, xylene and the like. Aromatic hydrocarbons; amide-based protic polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone;
Esters such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate; methyl 3-methoxypropionate, 2
-Alkoxy esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, (Di) glycol dialkyl esters such as diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether,
(Di) glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether; glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate Cyclohexanone, methyl ethyl ketone,
Examples thereof include ketones such as methyl isobutyl ketone and 2-heptanone. These polymerization solvents can be used alone or in combination of two or more kinds.

The ratio of the polymerization solvent and the reaction raw material is not particularly limited, but is usually 20 to 1000 parts by weight of the polymerization solvent with respect to 100 parts by weight of the reaction raw material.

Examples of the polymerization initiator for radical polymerization include 2,2'-azobisisobutyronitrile,
Azo compounds such as 2,2′-azobis- (2,4-methylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, tert. -Butyl peroxypivalate, 1,1-bis- (tert-
There may be mentioned organic peroxides such as butylperoxy) cyclohexane or hydrogen peroxide. When a peroxide is used as a polymerization initiator, it may be used as a redox polymerization initiator in combination with a reducing agent.

The specific polymer has a polystyrene-converted weight average molecular weight of usually 1,000 to 20,000, preferably 2,000 to 70,000. When a specific polymer having a polystyrene-reduced weight average molecular weight of less than 1000 is used, the shape of the obtained pattern becomes poor, the residual film rate of the pattern decreases, or the heat resistance of the pattern decreases. There are cases. On the other hand, when a specific polymer having a polystyrene-reduced weight average molecular weight of more than 20,000 is used, the radiation-sensitive resin composition may have poor coatability or developability, and the resulting pattern The shape of may become defective.

<Component (B)> As the acid-generating compound which generates an acid upon receiving the radiation which is the component (B),
For example, trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts and the like can be used.

Examples of the trichloromethyl-s-triazines include tris (2,4,6-trichloromethyl) -s-triazine and 2-phenyl-bis (4,6-).
Trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -bis (4,6-trichloromethyl) -s
-Triazine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) ) -Bis (4,6-
Trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl)-
s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2
-(3-Methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-
Triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy) -Β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(3-Methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxy-β-styryl) -bis (4,6-trichloromethyl)
-S-triazine, 2- (3,4,5-trimethoxy-
β-styryl) -bis (4,6-trichloromethyl)-
s-Triazine, 2- (4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) ) -S-Triazine, 2-
(3-Methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine and the like can be mentioned.

Examples of the diaryliodonium salts include, for example, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfone. Nato, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium Li trifluoroacetate, 4-methoxyphenyl phenyl iodonium -p- toluenesulfonate, bis (4-tert- butylphenyl) iodonium tetrafluoroborate, bis (4-tert
-Butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t
ert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate and the like.

Examples of the above triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium trifluoroacetate Phenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate Four
-Methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoro Examples thereof include arsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate and the like.

Among these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine and 2- (4-methoxyphenyl)-. Screw (4,6-
Trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl)
-S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) -bis (4.
6-trichloromethyl) -s-triazine; diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate or 4-methoxyphenylphenyliodonium trifluoroacetate; Examples of the triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4
-Phenylthiophenyldiphenyltrifluoromethanesulfonate or 4-phenylthiophenyldiphenyltrifluoroacetate can each be mentioned as preferred.

The proportion of the component (B) used is 10 parts of the component (A).
0.001 to 30 parts by weight relative to 0 parts by weight, particularly,
It is preferably 0.01 to 10 parts by weight. The use ratio of the component (B) is 0.0 with respect to 100 parts by weight of the component (A).
If the amount is less than 01 parts by weight, the amount of acid generated by receiving radiation is small, so that the crosslinking of the molecules of the component (A) does not proceed sufficiently, the residual film rate after development processing, and the heat resistance of the obtained pattern. Properties, chemical resistance, adhesion to the substrate, etc. may decrease. On the other hand, the proportion of the component (B) used is (A)
If the amount exceeds 30 parts by weight based on 100 parts by weight of the component, the composition tends to have low sensitivity.

<Component (C)> Specific examples of the crosslinkable compound which is the component (C) include melamine resin, benzoguanamine resin, glycoluril resin, urea resin, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, and alkoxy. Examples thereof include methylated glycoluril resin and alkoxymethylated urea resin. The above-mentioned alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin and alkoxymethylated urea resin are methylol melamine resin, methylol benzoguanamine resin, methylol glycoluril resin and methylol urea resin. Obtained by converting the group to an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group and a butoxymethyl group. Of these resins, alkoxymethylated melamine resins and alkoxymethylated benzoguanamine resins are mentioned as preferred crosslinkable compounds. As the crosslinkable compounds, Cymel 300 and 30
1, the same 303, the same 370, the same 325, the same 327, the same 70
1, the same 266, the same 267, the same 238, the same 1141, the same 2
72, 202, 1156, 1158, 112
3, Same 1170, Same 1174, Same UFR65, Same 300
(Above, Mitsui Cyanamid Co., Ltd.), Nikarac M
x-750, Mx-032, Mx-706, Mx
-708, Mx-40, Mx-31, Ms-1
1, those commercially available under the trade name of the same Mw-30 (above, manufactured by Sanwa Chemical Co., Ltd.) can be preferably used. These crosslinkable compounds can be used alone or in combination of two or more kinds.

The proportion of component (C) used is 10 parts of component (A).
It is preferably 1 to 100 parts by weight, particularly 5 to 50 parts by weight, relative to 0 parts by weight. If the proportion of the component (C) used is less than 1 part by weight relative to 100 parts by weight of the component (A), the crosslinking of the system may be insufficient, which may make it difficult to form a pattern. . On the other hand, when the proportion of the component (C) used exceeds 100 parts by weight with respect to 100 parts by weight of the component (A), the alkali solubility of the composition as a whole becomes excessive, and the residual film rate after the development processing is increased. Will decrease.

<Other Components> The radiation-sensitive resin composition of the present invention may contain a sensitizer. Examples of the sensitizer include coumarins having a substituent at the 3-position and / or the 7-position, flavones, dibenzalacetones, dibenzalcyclohexanes, chalcones, xanthenes, thioxanthenes, Porphyrins, phthalocyanines, acridines, anthracenes and the like can be used. The proportion of the sensitizer used is 100 for the component (A).
30 parts by weight or less, preferably 0.1 to 30 parts by weight
It is 20 parts by weight or less.

The radiation-sensitive resin composition of the present invention contains two or more epoxy groups in the molecule mainly for the purpose of improving the heat resistance and adhesion of the pattern or the coating property of the composition. Compounds can be added. Examples of the compound containing two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin, aliphatic poly Examples thereof include glycidyl ether.

The bisphenol A type epoxy resins are commercially available as Epicoat 1001 and 1
002, 1003, 1004, 1007, 10
09, 1010, 828 (all manufactured by Yuka Shell Epoxy Co., Ltd.) are available as Epicoat 807 (Okaka Shell Epoxy Co., Ltd.) as bisphenol F type epoxy resins.
Manufactured by Yuka Shell Epoxy Co., Ltd., EPPN201, 202 (above).
Nippon Kayaku Co., Ltd. and the like are used as cresol novolac type epoxy resins, EOCN-102, EOCN-10.
3S, EOCN-104S, EOCN-1020, EO
CN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like as a cycloaliphatic epoxy resin are CY175, CY177, CY179 (or more. , CI
BA-GEIGY A. G), ERL-4234, E
RL-4299, ERL-4221, ERL-4206
(Above, manufactured by U.C.C.), Shoredyne 509 (manufactured by Showa Denko KK), Araldite CY-182, and CY-.
192, CY-184 (above, CIBA-GEIGY
A. G), Epicron 200, 400 (above, Dainippon Ink and Chemicals, Inc.), Epicoat 871, 87.
2 (above, Yuka Shell Epoxy Co., Ltd.), ED-56
61, ED-5662 (above, manufactured by Celanese Coating Co., Ltd.), and the like, as an aliphatic polyglycidyl ether, Epolite 100MF (Kyoeisha Oil and Fat Chemical Co., Ltd.)
Manufactured by Nippon Oil & Fats Co., Ltd., and the like.

Among these, preferred are bisphenol A type epoxy resin, phenol novolac type epoxy resin and cresol novolac type epoxy resin.

Most of the compounds exemplified above are high molecular weight compounds, but the molecular weight of this compound is not particularly limited, and for example, low molecular weight compounds such as glycidyl ether of bisphenol A or bisphenol F are used. You can also do it. The proportion of such a compound containing two or more epoxy groups in the molecule is usually 100 parts by weight or less, preferably 5 parts by weight, relative to 100 parts by weight of the component (A).
It is 0 parts by weight or less.

Further, in the radiation-sensitive resin composition of the present invention, a surfactant can be added in order to improve the coatability (for example, prevention of striation) and the developability. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and other polyoxyethylene. Aryl ethers, polyethylene glycol dilaurate,
Nonionic surfactants such as polyethylene glycol dialkyl esters such as polyethylene glycol distearate; Ftop EF301, EF303, E
F352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F172, F173 (above manufactured by Dainippon Ink and Chemicals), Florard FC430, FC43
1 (above, Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, SC
-102, SC-103, SC-104, SC-10
5, SC-106 (above, manufactured by Asahi Glass Co., Ltd.) and other commercially available fluorine-based surfactants; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (Co) Polymer Polyflow No. 57, 95 (manufactured by Kyoei Yushi Kagaku Kogyo Co., Ltd.) and other commercially available surfactants can be used.

The ratio of these surfactants to be used is usually 2 parts by weight or less, preferably 1 part by weight or less, relative to 100 parts by weight of the solid content in the composition.

In addition, in the radiation-sensitive resin composition of the present invention, an adhesion aid such as a silane coupling agent can be added to improve the adhesion to the substrate, and the heat resistance can be improved. For this purpose, an unsaturated compound such as polyvalent acrylate may be added. Further, in the radiation-sensitive resin composition of the present invention, an antistatic agent, a storage stabilizer, an antihalation agent, an antifoaming agent, a pigment, a thermal acid generator, etc. may be added, if necessary.

<Formation of Pattern> By using the radiation-sensitive resin composition of the present invention, a pattern can be formed, for example, as follows. First, the radiation-sensitive resin composition is dissolved in a solvent so that the solid content thereof is 5 to 60% by weight, and the composition solution is obtained by filtering the solution with a filter having a pore size of 0.2 to 10 μm. Prepare. Then, the composition solution is applied to the surface of a substrate such as a silicon wafer and prebaked to remove the solvent to form a coating film of the radiation-sensitive resin composition. Then, the formed coating film is subjected to radiation irradiation treatment and then PEB treatment. After that, a pattern is formed by performing a development process to remove the unirradiated portion.

In the above, as the solvent for preparing the composition solution, the same solvents as those exemplified as the above-mentioned polymerization solvent used for producing the specific polymer can be used. Further, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, It is also possible to add a high boiling point solvent such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and carbitol acetate.

As the method of applying the composition solution to the substrate, various methods such as a spin coating method, a flow coating method and a roll coating method can be adopted. The prebaking conditions include, for example, a heating temperature of 50 to 150 ° C. and a heating time of 30 seconds.
It is 600 seconds. Is mentioned. As the radiation used for the radiation treatment, i-rays with a wavelength of 365 nm, 43
Examples thereof include ultraviolet rays such as 6 nm g-ray, far ultraviolet rays such as KrF excimer laser having a wavelength of 248 nm and ArF excimer laser having a wavelength of 193 nm, and charged particle beams such as X-rays such as synchrotron radiation and electron rays.

The developer used in the developing treatment is, for example, sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo (5.4.0) -7
-Undecene, 1,5-diazabicyclo (4.3.0)
An alkaline aqueous solution obtained by dissolving -5-nonane or the like can be used. It is also possible to use a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, or a surfactant added to this alkaline aqueous solution in an appropriate amount. The development processing time is, for example, 10 to 300.
It is a second, and as a developing method, a puddle method, a dipping method, a rocking dipping method, or the like can be used.

[0045]

EXAMPLES Examples of the radiation-sensitive resin composition of the present invention will be described below, but the present invention is not limited thereto. Further, in the following, the polystyrene-reduced weight average molecular weight of the polymer is measured using a GPC chromatograph HLC-8020 manufactured by Tosoh Corporation, and the ratio of the structural unit in the polymer is ¹ manufactured by JEOL Ltd. H-N
It was measured using an MR spectrometer EX-90.

[Synthesis of Specific Polymer] <Synthesis Example 1> In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 30.0 g of monobutyl itaconic acid as a specific monomer, copolymerizable 70.0 g of styrene as a monomer, 6.0 g of N, N′-azobisisobutyronitrile as a polymerization initiator, and 100.0 of propylene glycol monomethyl ether as a polymerization solvent.
After charging g, purging the inside of the separable flask with nitrogen gas for 30 minutes, the separable flask was immersed in an oil bath, the internal temperature was kept at 80 ° C., and polymerization was carried out for 6 hours while stirring to give a polymer. A solution was obtained. The polymer solution was poured into 10 liters of hexane to precipitate the polymer, which was further purified by reprecipitation using tetrahydrofuran / hexane twice, and then dried under reduced pressure at 25 ° C. for 12 hours to give a white color. Powdered polymer (A
1) was obtained. The specific carboxyl group-containing structural unit in this polymer (A1) is a group represented by the formula (1) in which R ¹ and R ³ are hydrogen atoms, R ² is a group represented by —CH ₂ COOC ₄ H ₉ , and R ⁴ is a carboxyl group. It is the base. Further, the polystyrene reduced weight average molecular weight of the polymer (A1) is 0.
It was 93 × 10 ⁴ , and the weight ratio of the structural unit derived from monobutyl itaconate to the structural unit derived from styrene in the polymer (A1) was 77:23.

<Synthesis Example 2> Stirrer, cooling pipe, nitrogen introducing pipe
And in a separable flask equipped with a thermometer
Monosuccinic acid mono (2-methacryloyloxy)
6) Ethyl 60.0 g, methacrylic acid as a copolymerizable monomer
Methyl acetate 40.0 g, N, N'-a as a polymerization initiator
With 3.0 g of zobisisobutyronitrile and a polymerization solvent
Then propylene glycol monomethyl ether 200.
0 g was charged, otherwise the same as in Synthesis Example 1
A powdery polymer (A2) was obtained. In this polymer (A2)
The specific carboxyl group-containing structural unit in the formula (1) is
And R¹And R³Is a hydrogen atom, R²Is a methyl group, R
^FourIs -COO- (CH ₂)₂Of the group represented by -COOH
Things. Also, the polystyrene conversion of the polymer (A2)
Weight average molecular weight is 3.87 × 10^FourAnd the polymer (A
2) Succinic acid mono (2-methacryloyloxy)
Si) To the structural unit derived from ethyl and methyl methacrylate
The ratio with the derived structural unit is 58:42 by weight.
It was.

<Synthesis Example 3> In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 60.0 g of mono (2-methacryloyloxy) ethyl phthalate as a specific monomer, copolymerizable 40.0 g of methyl methacrylate as a monomer, 3.0 g of N, N′-azobisisobutyronitrile as a polymerization initiator, and propylene glycol monomethyl ether 200.
A polymer (A3) was obtained as a white powder in the same manner as in Synthesis Example 1 except that 0 g was charged. The specific carboxyl group-containing structural unit in this polymer (A3) has the same formula (1) as R ¹ and R ³ are hydrogen atoms, R ² is a methyl group, and R ² is a methyl group.
⁴ is a group represented by the following chemical formula 4.

[0049]

[Chemical 4]

The polystyrene reduced weight average molecular weight of the polymer (A3) was 3.06 × 10 ⁴ , and the polymer (A3)
The ratio of the structural unit derived from mono (2-methacryloyloxy) ethyl phthalate to the structural unit derived from methyl methacrylate in 3) was 57:43 by weight.

<Synthesis Example 4> In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 60.0 g of mono (2-methacryloyloxy) ethyl tetrahydrophthalate was copolymerized as a specific monomer. 40.0 g of methyl methacrylate as a polymerizable monomer, 3.0 g of N, N′-azobisisobutyronitrile as a polymerization initiator, and 200.0 g of propylene glycol monomethyl ether as a polymerization solvent were charged. A white powdery polymer (A4) was obtained in the same manner as in 1. The specific carboxyl group-containing structural unit in this polymer (A4) is
In the formula (1), R ¹ and R ³ are hydrogen atoms, R ² is a methyl group, and R ⁴ is a group represented by the following chemical formula 5.

[0052]

Embedded image

The polystyrene reduced weight average molecular weight of the polymer (A4) was 2.81 × 10 ⁴ , and the polymer (A4)
The ratio of the structural unit derived from mono (2-methacryloyloxy) ethyl tetrahydrophthalate to the structural unit derived from methyl methacrylate in 4) is 6 by weight.
It was 0:40.

Synthesis Example 5 In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 60.0 g of 4- (4'-vinylbenzyloxy) benzoic acid as a specific monomer was added. Benzyl methacrylate 40.0 g as a polymerizable monomer, N, N'-azobisisobutyronitrile 10.0 g as a polymerization initiator, and propylene glycol monomethyl ether 100.0 as a polymerization solvent.
g was charged, and otherwise the same as in Synthesis Example 1 to obtain a white powder polymer (A5). Specific carboxyl group-containing structural unit in the polymer (A5), in formula ^{(1), R 1, R} 2 and R ³ are hydrogen atoms, R ⁴ is represented by the following Chemical Formula 6
Is a group represented by.

[0055]

[Chemical 6]

The polystyrene-reduced weight average molecular weight of the polymer (A5) was 1.54 × 10 ⁴ , and the polymer (A5)
The ratio of the structural unit derived from 4- (4′-vinylbenzyloxy) benzoic acid to the structural unit derived from benzyl methacrylate in 5) was 50:50 by weight.

<Synthesis Example 6> 60.0 g of 4- (4'-vinylbenzyloxy) phenylacetic acid as a specific monomer was placed in a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer. 40.0 g of benzyl methacrylate as a polymerizable monomer, 10.0 g of N, N'-azobisisobutyronitrile as a polymerization initiator, and propylene glycol monomethyl ether 10 as a polymerization solvent.
A white powdery polymer (A6) was obtained in the same manner as in Synthesis Example 1 except that 0.0 g was charged. This polymer (A6)
The specific carboxyl group-containing structural unit in is represented by the formula (1)
In the formula, R ¹ , R ² and R ³ are hydrogen atoms and R ⁴ is a group represented by the following chemical formula 7.

[0058]

[Chemical 7]

The polystyrene reduced weight average molecular weight of the polymer (A6) was 1.67 × 10 ⁴ ,
The ratio of the structural unit derived from 4- (4′-vinylbenzyloxy) phenylacetic acid to the structural unit derived from benzyl methacrylate in 6) was 53:47 by weight.

<Synthesis Example 7> Mono-4′-vinylbenzyl phthalate 6 as a specific monomer was placed in a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer.
Charge 0.0 g, benzyl methacrylate 40.0 g as a copolymerizable monomer, N, N′-azobisisobutyronitrile 10.0 g as a polymerization initiator, and propylene glycol monomethyl ether 100.0 g as a polymerization solvent. A white powdery polymer (A7) was obtained in the same manner as in Synthesis Example 1 except for the above. The specific carboxyl group-containing structural unit in this polymer (A7) is represented by R in the formula (1).
¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is a group represented by the following chemical formula 8.

[0061]

Embedded image

The polystyrene reduced weight average molecular weight of the polymer (A7) was 2.33 × 10 ⁴ ,
The ratio of the structural unit derived from mono-4′-vinylbenzyl phthalate to the structural unit derived from benzyl methacrylate in 7) was 57:43 by weight.

<Synthesis Example 8> Mono-4-vinylbenzyl succinate 60.60 as a specific monomer was placed in a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer.
0 g, methyl methacrylate 40. as a copolymerizable monomer.
0 g, 10.0 g of N, N′-azobisisobutyronitrile as a polymerization initiator, and 100.0 g of propylene glycol monomethyl ether as a polymerization solvent were charged,
Otherwise in the same manner as in Synthesis Example 1, a white powder polymer (A8) was obtained. The specific carboxyl group-containing structural unit in this polymer (A8) has the same structure as R ¹ in the formula (1),
R ² and R ³ are hydrogen atoms, and R ⁴ is a group represented by the following chemical formula 9.

[0064]

[Chemical 9]

The polystyrene reduced weight average molecular weight of the polymer (A8) was 1.22 × 10 ⁴ , and the polymer (A8)
The ratio of the structural unit derived from mono-4-vinylbenzyl succinate to the structural unit derived from methyl methacrylate in 8) was 55:45 by weight.

<Synthesis Example 9> Mono-4-vinylbenzyl succinate 60.60 as a specific monomer was placed in a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer.
0 g, 4-vinylbenzyl acetate 40.0 g as a copolymerizable monomer, N, N′-azobisisobutyronitrile 10.0 g as a polymerization initiator, and propylene glycol monomethyl ether 100.0 g as a polymerization solvent. A white powdery polymer (A9) was obtained in the same manner as in Synthesis Example 1 except for charging. The specific carboxyl group-containing structural unit in this polymer (A9) is the same as that of the polymer (A8). The polystyrene reduced weight average molecular weight of the polymer (A9) is 2.22 × 10 ⁴ , and the structural unit derived from mono-4-vinylbenzyl succinate and the 4-vinylbenzyl acetate are in the polymer (A9). The ratio with the derived structural unit was 58:42 by weight.

<Synthesis Example 10> Stirrer, cooling pipe, nitrogen introduction
In a separable flask equipped with a tube and thermometer,
Mono-4-vinylbenzyl succinate 6 as constant monomer
0.0 g, 4-vinylbenzyl group as a copolymerizable monomer
40.0 g of lysidyl ether, N as a polymerization initiator,
10.0 g of N'-azobisisobutyronitrile, and
Propylene glycol monomethyl ether as a polymerization solvent
100.0 g of the raw material was charged, and otherwise the same as in Synthesis Example 1.
Thus, a white powder polymer (A10) was obtained. This polymer
Specific carboxyl group-containing structural unit in (A10)
Are the same as those of the polymer (A8). Also the polymer
The polystyrene reduced weight average molecular weight of (A10) is 2.2.
2 x 10 ^FourAnd succinic acid in the polymer (A10)
Structural units derived from mono-4-vinylbenzyl and 4-bi
Structural units derived from nylbenzyl glycidyl ether and
Was 64:36 by weight.

<Synthesis Example 11> Stirrer, cooling tube, nitrogen introduction
In a separable flask equipped with a tube and thermometer,
Mono-4-vinylbenzyl succinate 6 as constant monomer
0.0 g, benzyl methacrylate as a copolymerizable monomer
40.0 g, N, N'-azobisiso as a polymerization initiator
Butyronitrile (10.0 g) and professional solvent for polymerization
Prepare 100.0 g of pyrene glycol monomethyl ether
Except that the weight of the white powder was the same as in Synthesis Example 1.
A coalescence (A11) was obtained. In this polymer (A11)
The specific carboxyl group-containing structural unit is a polymer (A8)
It is the same as the one. In addition, the polymer (A11)
Len equivalent weight average molecular weight is 2.22 × 10 ^FourAnd is heavy
Mono-4-vinylben succinate in coalesced (A11)
Structural unit derived from zir and derived from benzyl methacrylate
The ratio with the structural unit is 55:45 by weight.
Was.

<Synthesis Example 12> Stirrer, cooling tube, nitrogen introduction
In a separable flask equipped with a tube and thermometer,
Mono-4-vinylbenzyl succinate 6 as constant monomer
0.0 g, dicyclomethacrylate as copolymerizable monomer
Hexyl 40.0 g, N, N'-azo as polymerization initiator
With 10.0 g of bisisobutyronitrile and a polymerization solvent
And propylene glycol monomethyl ether 100.
0 g was charged, otherwise the same as in Synthesis Example 1
A powdery polymer (A12) was obtained. This polymer (A12)
The specific carboxyl group-containing structural unit in is a polymer
It is the same as that of (A8). Further, the polymer (A12)
Polystyrene-converted weight average molecular weight is 1.22 × 10 ^Four
And succinic acid mono-4-in the polymer (A12)
Structural units derived from vinylbenzyl and dimethacrylate
The ratio with the structural unit derived from chlorhexyl is the weight ratio.
It was 55:45.

<Synthesis Example of Polymer for Comparison> 4-vinylbenzoic acid 100.0 as a monomer was placed in a separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer.
g, N, N′-azobisisobutyronitrile 10.0 g as a polymerization initiator, and propylene glycol monomethyl ether 200.0 g as a polymerization solvent. Other than that, the same procedure as in Synthesis Example 1 was performed to compare white powders. A polymer (A13) was obtained. The polystyrene reduced weight average molecular weight of this comparative polymer (A13) was 2.55 × 10 ⁴ .

Example 1 As the component (A), the polymer (A
1) 100 parts by weight, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine 2 parts by weight as the component (B), and hexamethoxymethylol as the component (C). After dissolving 20 parts by weight of "Cymel 300 (manufactured by Mitsui Cyanamid Co., Ltd.)", which is a melamine resin, in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 30% by weight, a membrane having a pore size of 0.2 μm is obtained. By filtering with a filter, the radiation-sensitive resin composition solution (R
1) was obtained.

<Examples 2 to 12> In Example 1,
Radiation-sensitive resin composition solution (R2) of the present invention in the same manner except that the polymer (A2) to polymer (A12) are used instead of the polymer (A1) as the component (A), respectively.
A radiation sensitive resin composition solution (R12) was obtained.

Example 13 100 parts by weight of the polymer (A9) as the component (A), 10 parts by weight of triphenylsulfonium trifluoromethanesulfonate as the component (B), and hexamethoxymethylolmelamine resin as the component (C). The radiation-sensitive resin composition solution (R13) of the present invention was obtained by mixing 20 parts by weight of "CYMEL 300" which is the above and 5 parts by weight of 9-hydroxymethylanthracene as a sensitizer.

<Examples 14 to 16> In Example 14, the polymer (A10), the polymer (A11), and the polymer (A12) were used as the component (A) instead of the polymer (A9). Other than the above, the radiation-sensitive resin composition solution (R14) to the radiation-sensitive resin composition (R1) of the present invention are similarly prepared.
6) was obtained.

Comparative Example 1 A comparative radiation sensitive resin composition solution (R17) was prepared in the same manner as in Example 1 except that the comparative polymer (A13) was used in place of the polymer (A1). Got

Using these composition solutions, patterns were formed by the following method, and the performance of the radiation sensitive resin composition was evaluated for the following items.

(1) Pattern formation: Each of the above composition solutions was applied onto a silicon substrate having a diameter of 4 inches by a spin coating method so as to have a thickness of 2.0 μm,
A coating film was formed by prebaking at 90 ° C. for 2 minutes on a hot plate. Then, for this coating,
After performing radiation irradiation treatment with an NSR1505i6A reduction projection exposure machine (manufactured by Nikon Corporation, NA = 0.45, λ = 365 nm) at an optimum depth of focus, PEB treatment was performed on a hot plate at 80 ° C. for 2 minutes. Then 2.38
A pattern was formed by performing development processing at 25 ° C. for 1 minute using an aqueous solution of tetramethylammonium hydroxide by weight, washing with water and drying.

(2) Performance Evaluation of Radiation Sensitive Resin Composition: [Sensitivity] In the above pattern forming step, the irradiation time of the radiation is changed to perform the radiation irradiation treatment.
The irradiation time required for the pattern line width to be 2.0 μm under the condition that a projected image of a 0 μm line-and-space (L / S) pattern is formed (hereinafter referred to as “optimum radiation irradiation time”). I asked. [Resolution] With respect to the pattern formed by performing the radiation irradiation treatment at the optimum radiation irradiation time, the dimension of the smallest space pattern that was resolved was measured using a scanning electron microscope. [Developability] The formed pattern is observed by a scanning electron microscope to check the surface roughness of the line part and the presence or absence of undeveloped residue (scum) in the space part. It was evaluated as x.

[Pattern shape] The cross-sectional shape of the pattern formed by performing the radiation irradiation treatment for the optimum radiation irradiation time is observed with a scanning electron microscope,
When the width of the upper surface 2 of the pattern 1 and the width of the lower surface 3 of the pattern 1 are substantially the same as shown in FIG.
When the width of the upper surface 2 of the pattern 1 is smaller than the width of the lower surface 3 of the pattern 1 as shown in FIG.
When the width of the lower surface 3 of the pattern 1 is smaller than the width of the upper surface 2 of the pattern 1 as shown in FIG. [Residual film rate] The film thickness d1 of the pattern after the development treatment was measured, and the ratio of the film thickness d1 to the film thickness d of the initial coating film (d
1 / d) × 100 was calculated, and when the ratio was 90 or more, it was evaluated as ◯, when it was 70 or more and less than 90, it was evaluated as Δ, and when it was 70 or less, it was evaluated as x.

[Dependency of leaving after radiation irradiation until PEB treatment] In the above pattern forming step,
PEB after leaving for 2 hours after radiation treatment
A pattern is formed in the same manner except that the treatment is performed,
In this case, the optimum radiation irradiation time Ed is obtained, and the change rate with respect to the optimum radiation irradiation time E when the heat treatment is performed immediately after the radiation irradiation processing {(E-Ed) / E} × 100
(%) Is calculated, and if the change rate is less than 20%,
The case of 20% or more and less than 30% was evaluated as Δ, and the case of 30% or more was evaluated as x. [PEB Temperature Dependence] In the above pattern forming step, a pattern is formed in the same manner except that PEB treatment is performed at 90 ° C. and 100 ° C., and optimum radiation irradiation times E ₉₀ and E ₁₀₀ in these cases are obtained. , 90 ℃
Change rate of the optimum radiation irradiation time E ₁₀₀ when the PEB processing is performed at 100 ° C. with respect to the optimum radiation irradiation time E ₉₀ when the PEB processing is performed at {(E ₉₀ −E ₁₀₀ ) / E ₉₀ } ×
100 (%) was calculated, and when the rate of change was less than 20%, it was evaluated as ◯, when it was 20% or more and less than 30%, it was evaluated as Δ, and when it was 30% or more, it was evaluated as x. [Focus Tolerance] In the above pattern forming step, the radiation irradiation time is fixed to the optimum radiation irradiation time, and N
A pattern is formed in the same manner except that the radiation depth is changed by changing the depth of focus of the SR1505i6A reduction projection exposure machine, the pattern has a good cross-sectional shape, and the pattern has a dimension of 1.8 to 2.2 μm. When the depth of focus is 4.0 μm or more, ◯ is calculated as 3.9.
When it was less than μm, it was evaluated as x.

[Heat Resistant Transparency] In the above pattern forming step, a pattern was formed in the same manner except that a glass substrate (# 7059 manufactured by Corning Inc.) was used instead of the silicon substrate. The substrate on which this pattern was formed was heat-treated in a clean oven at 200 ° C. for 2 hours. For this heat-treated substrate, wavelengths of 380-7
The light transmittance at 80 nm was measured, and the case where the lowest value of the light transmittance was 90% or more was evaluated as ◯, and the case where it was 89% or less was evaluated as x. [Solvent resistance] In the above pattern forming step, instead of the silicon substrate, a glass substrate (manufactured by Corning Inc.,
A pattern was formed in the same manner except that # 7059) was used. The substrate on which this pattern was formed was divided into 4 parts, and each was immersed in acetone, isopropyl alcohol, ethyl lactate and dimethylsulfoxide for 1 minute, and then the film thickness of the pattern was measured. On the other hand, 90% or more was evaluated as ◯, and 89% or less was evaluated as x. The above results are shown in Table 1.

[0082]

[Table 1]

In the solvent resistance column of Table 1 above, A is acetone, I is isopropyl alcohol, E is ethyl lactate, and D is dimethyl sulfoxide.

Radiation-sensitive resin composition solution (R1) obtained in Examples 1 to 16 to radiation-sensitive resin composition solution (R1)
When 6) was stored at 25 ° C. for 3 months and the above performance evaluation was performed, the same results as those shown in Table 1 were obtained, and these radiation-sensitive resin compositions have excellent storage stability. Was confirmed to have

[0085]

INDUSTRIAL APPLICABILITY The radiation-sensitive resin composition of the present invention has a dimension of a pattern obtained regardless of the length of time from the irradiation of radiation to the PEB treatment and the heating temperature of the PEB treatment. The change is small, and the focus tolerance and the heat-resistant transparency are excellent. Further, the radiation-sensitive resin composition of the present invention forms a pattern having high sensitivity, excellent storage stability, high resolution and high residual film rate, and excellent heat resistance and adhesion to a substrate. can do. Further, the radiation-sensitive resin composition of the present invention is suitable as a resist for producing a protective film for a liquid crystal color filter, an optical material such as a microlens, a semiconductor integrated circuit, a TFT circuit for LCD, a mask for making an integrated circuit, and the like. Can be used for.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a cross-sectional shape model for evaluating a pattern used in performance evaluation of a radiation-sensitive resin composition of an example.

[Explanation of symbols]

 1 pattern 2 upper surface 3 lower surface 4 substrate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Bessho 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A component (A) consisting of a polymer containing a structural unit containing a carboxyl group represented by the following formula (1), and a component (B) consisting of an acid generating compound which generates an acid when exposed to radiation. A compound having at least one group capable of being crosslinked by the action of an acid generated from the component (B) (C)
A radiation-sensitive resin composition, comprising: Embedded image