JP3424225B2 - Radiation-sensitive resin composition and coating formed therefrom - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive resin composition and a film formed therefrom . More specifically, as a positive resist for manufacturing a circuit such as a semiconductor integrated circuit (hereinafter referred to as “IC”) or a thin film transistor (hereinafter referred to as “TFT”) circuit for a liquid crystal display (hereinafter referred to as “LCD”), or an interlayer. Radiation-sensitive resin composition suitable as a material for forming a permanent film such as an insulating film and a protective film for a color filter, and a radiation-sensitive resin composition formed therefrom
Regarding coating .

[0002]

2. Description of the Related Art In recent years, in the manufacture of semiconductor integrated circuits, there has been a demand for a radiation-sensitive resin composition used as a resist having high resolution and high sensitivity.

That is, in the manufacture of ICs, a resist capable of obtaining a high resolution of submicron or less may be required, but on the other hand, a resolution of the order of several μm to several tens of μm can be obtained, and particularly large. There is a strong demand for a high-sensitivity resist that exhibits a high yield even if the throughput is increased by using a silicon wafer having a reduced diameter.

In addition, for example, in the step of etching a silicon wafer in the manufacture of ICs, a wet etching method that allows batch processing in large quantities is often used. For this reason, the resist pattern formed is in close contact with the substrate. It is required to have chemical resistance and chemical resistance so that it is not affected by the etching solution. Further, when an ion implantation process or the like is added, heat resistance capable of withstanding high temperature heating is required.

Conventionally, a positive resist containing a novolac resin and a 1,2-quinonediazide compound has been known as a resist used in the manufacture of ICs. However, although this positive resist has excellent resolution, it has sufficient characteristics with respect to chemical resistance to withstand wet etching as described above, sensitivity, adhesion to substrate, heat resistance, etc. It cannot be said that

In the LCD which has been rapidly developed in recent years, an active matrix type LCD (hereinafter referred to as "AM
"-LCD") is regarded as a favorite next-generation display device to replace a cathode ray tube because of its quick response speed, and a large display screen area is desired. A like this
A resist is used for forming the TFT circuit of the M-LCD as in the case of the IC.

Further, when manufacturing an LCD, a permanent film such as an interlayer insulating film or a protective film for a color filter, which is conventionally formed by using a thermosetting resin composition, should be formed by a composition similar to that of a resist. Attempts have been made to

The permanent film of such an LCD is required to have chemical resistance, adhesion to a substrate, heat resistance, transparency in the visible light region, and the like. However, the above-mentioned novolac resin and quinonediazide compound are required. The conventional positive resists containing the above cannot form a sufficiently satisfactory permanent film in terms of chemical resistance, adhesion to a substrate, heat resistance and the like.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new radiation sensitive resin composition and a coating film formed from it . Another object of the present invention is IC, L
A positive type for manufacturing circuits such as TFT circuits for CDs, which is excellent in chemical resistance, sensitivity, developability, residual film rate, heat resistance and adhesion to the substrate and can be developed by a developing solution containing an alkaline aqueous solution. A radiation-sensitive resin composition suitable as a resist and a coating film formed from the same.

Still another object of the present invention is to form a permanent film such as an interlayer insulating film of LCD, a color filter protective film, a circuit protective film, etc., which has heat resistance and adhesion to a substrate. To provide a radiation-sensitive resin composition capable of providing a permanent film having excellent properties, transparency in the visible light region, chemical resistance, and the like, and a coating film formed from the same.

[0011]

The above objects and advantages of the present invention are as follows: [A] (a-1) polymerized units of unsaturated carboxylic acid and (a-2) the following general formula [I]

[0012]

[Chemical 2]

(In the formula, R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₄ is 1 carbon atom.
~ 5 alkyl groups, m and n independently of one another
It is an integer of 5. ) A copolymer containing polymerized units of a compound represented by the formula (hereinafter, also referred to as "copolymer [A]"),
[B] 2,3,4-trihydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,4,6-trihydroxybenzophenone-1,2-na
Futoquinonediazide-5-sulfonate, 2,
2 ', 4,4'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,3,4,3'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,3,4,4'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,3,4,2'-tetrahydroxy-4'-methylben
Zophenone-1,2-naphthoquinonediazide-5-sul
Fonate ester, 2,3,4,4'-tetrahydroxy-
3'-methoxybenzophenone-1,2-naphthoquinone
Diazide-5-sulfonic acid ester, 2,3,4,2 ′,
6'-Pentahydroxybenzophenone-1,2-naphth
Toquinonediazide-5-sulfonate, 3,4,
5,2 ', 4'-pentahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,4,6,3 ', 4', 5'-hexahydroxybenzoph
Enone-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 3,4,5,3 ', 4', 5'-hexahydro
Xybenzophenone-1,2-naphthoquinonediazide-
5-sulfonic acid ester, bis (2,4-dihydroxy
Phenyl) methane-1,2-naphthoquinonediazide-5
-Sulfonic acid ester, bis (p-hydroxyphenyl)
) Methane-1,2-naphthoquinonediazide-5-sul
Fonate ester, tri (p-hydroxyphenyl) meta
1,2-naphthoquinonediazide-5-sulfonic acid
Steal 1,1,1-tri (p-hydroxyphenyl) eth
Tan-1,2-naphthoquinonediazide-5-sulfonic acid
Ester, bis (2,3,4-trihydroxyphenyl)
Methane-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 2,2-bis (2,3,4-trihydroxy
Phenyl) propane-1,2-naphthoquinonediazide-
5-sulfonic acid ester, 1,1,3-tris (2,5-
Dimethyl-4-hydroxyphenyl) -3-phenylphenol
Lopan-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 4,4 '-[1- [4- [1- [4-hydr
Roxyphenyl] -1-methylethyl] phenyl] ethyl
Ridene] bisphenol-1,2-naphthoquinone diazide
De-5-sulfonic acid ester, bis (2,5-dimethyl)
-4-hydroxyphenyl) -2-hydroxyphenyl
Methane-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 3,3,3 ', 3'-tetramethyl-1,1'
-Spiroindene-5,6,7,5 ', 6', 7'-hexa
Nol-1,2-naphthoquinonediazide-5-sulfone
Acid ester and 2,2,4-trimethyl-7,2 ', 4'
-Trihydroxyflavan-1,2-naphthoquinonedia
1, selected from zido-5-sulfonate
2-quinonediazide compound, and acid by heating [C]
Generating a cationic polymerization catalyst, the radiation-sensitive resin composition and which is characterized by containing the formed therefrom
Achieved by the membrane . Hereinafter, the present invention will be described in detail, with which other objects, advantages and effects of the present invention will be apparent.

First, each component contained in the radiation-sensitive resin composition according to the present invention will be described below. In the present invention, the term “radiation” is used as a concept including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, proton beam rays and the like.

Copolymer [A] The copolymer [A] used in the present invention is a polymer unit of an unsaturated carboxylic acid (a-1) and a compound (a-2) represented by the above general formula [I]. Other radically polymerizable compound (hereinafter, referred to as "other radicals") containing the polymerized unit of as a copolymerization component and copolymerizable with the unsaturated carboxylic acid (a-1) and the compound (a-2) as necessary. Also referred to as a “polymerizable compound”) (a-3) may be further contained as a copolymerization component.

The unsaturated carboxylic acid (a-1) used in the present invention is preferably an unsaturated carboxylic acid having an ethylenically unsaturated double bond.

Specific examples of the unsaturated carboxylic acid (a-1) include methacrylic acid, acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid and p-vinylbenzoic acid. Carboxylic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 1,4
-Cyclohexene dicarboxylic acid, 3-vinylphthalic acid,
4-vinylphthalic acid, methyl-5-norbornene-2,
Examples of the dicarboxylic acid include 3-dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid and dimethyltetrahydrophthalic acid.
Of these, methacrylic acid, acrylic acid, itaconic acid and the like are preferably used.

In the present invention, the unsaturated carboxylic acid (a
As -1), a partially esterified product or partially amidated product of the above unsaturated carboxylic acid in which a part of the carboxylic acid group remains free, for example, a half ester or a half amide of an unsaturated dicarboxylic acid can also be used. . As the half ester or half amide of such unsaturated carboxylic acid, monomethyl itaconate, monobutyl itaconate and the like are preferably used. These unsaturated carboxylic acids can be used alone or in combination of two or more kinds.

The compound (a-2) used in the present invention is
It is represented by the above general formula [I]. In the formula [I], R
_{1 to} R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ is an alkyl group having 1 to 5 carbon atoms, m and n are each independently an integer of 1 to 5 is there. The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a se group.
Examples thereof include c-butyl group, tert-butyl group, pentyl group and the like.

The compound represented by the general formula [I] (a-
Specific examples of 2) include, for example, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, and p.
-Vinylbenzyl methyl ether, o-vinylbenzyl ethyl ether, m-vinylbenzyl ethyl ether,
p-vinylbenzyl ethyl ether, o-vinylbenzyl propyl ether, m-vinyl benzyl propyl ether, p-vinyl benzyl propyl ether, o-vinyl benzyl isopropyl ether, m-vinyl benzyl isopropyl ether, p-vinyl benzyl isopropyl ether, o -Vinylbenzyl butyl ether, m-
Vinyl benzyl butyl ether, p-vinyl benzyl butyl ether, o-vinyl benzyl isobutyl ether, m-vinyl benzyl isobutyl ether, p-vinyl benzyl isobutyl ether, o-vinyl benzyl-
tert-butyl ether, m-vinylbenzyl-te
rt-butyl ether, p-vinylbenzyl-tert
Butyl ether, α-methyl-o-vinylbenzyl methyl ether, α-methyl-m-vinylbenzyl methyl ether, α-methyl-p-vinylbenzyl methyl ether, 2,3-dimethoxymethylstyrene, 2,4-dimethoxymethylstyrene 2,5-dimethoxymethylstyrene, 2,6-dimethoxymethylstyrene, 2,3,4-trimethoxymethylstyrene, 2,3,5-trimethoxymethylstyrene, 2,3,6-trimethoxymethylstyrene, 3,4,5-trimethoxymethylstyrene, 2,4,6
-Trimethoxymethylstyrene and the like can be mentioned.

Of these, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl ethyl ether, m-vinylbenzyl ethyl ether, p-
Vinylbenzyl ethyl ether and the like are preferably used. These compounds (a-2) can be used alone or in combination of two or more kinds.

Specific examples of the other radically polymerizable compound (a-3) used in the present invention include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, and α-n-propyl (meth). Glycidyl acrylate,
Glycidyl α-n-butyl (meth) acrylate 3,4
-Epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,
Epoxy group-containing radical polymerization of 7-epoxyheptyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3-vinyl cyclohexene oxide, etc. Compounds; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-i-propyl, (meth) acrylic acid-n-butyl, (meth) Acrylic acid-sec-butyl, (meth) acrylic acid-ter-
Butyl, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, dodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (meth) ) Dicyclohexyl acrylate, (meth)
Adamantyl acrylate, allyl (meth) acrylate,
Probagyl (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, permethacrylate acrylate Fluoroethyl, (meth) acrylic acid perfluoro-n-propyl, (meth) acrylic acid perfluoro-i
-Propyl, triphenylmethyl (meth) acrylate,
Cumyl (meth) acrylate, (meth) acrylic acid-2-
Hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-amide, (meth) acrylic acid-N, N-dimethylamide, (meth) acrylic acid-N, N-dipropylamide, ( (Meth) acrylic acid-
(Meth) acryloyl group-containing radically polymerizable compounds such as anilide and (meth) acrylonitrile;

Acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl acetate, styrene, α
-Methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene,
p-methoxymethylstyrene, p-tert-butoxystyrene, chloromethylstyrene, butadiene, 2,3
-Vinyl group-containing radically polymerizable compounds such as dimethyl butadiene and isoprene; unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and itaconic acid diethyl.

Of these, glycidyl (meth) acrylate, styrene, α-methylstyrene, p-tertbutoxystyrene, dicyclopentanyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, Butadiene and isoprene are preferably used. By using these compounds as a copolymerization component, the alkali solubility of the polymer,
The glass transition temperature, the dielectric constant, and the like can be controlled, and as a result, the performance as a resist such as resolution and residual film ratio, and the performance as a permanent film such as transparency and heat resistance may be improved. These compounds (a-3) can be used alone or in combination of two or more kinds.

The copolymer [A] used in the present invention can be obtained by copolymerizing each of the above compounds. The copolymer contains the polymerized units of the unsaturated carboxylic acid (a-1) in an amount of preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight, and preferably the polymerized units of the compound (a-2). Is 5 to 90% by weight, particularly preferably 20 to 50% by weight, and the polymerized units of the other radically polymerizable compound (a-3) are preferably 70% by weight or less, particularly preferably 2%.
It is contained in an amount of 0 to 60% by weight.

When the content of the polymerized units of unsaturated carboxylic acid (a-1) is less than 5% by weight, the resulting coating film has a reduced solubility in a developing solution containing an alkaline aqueous solution, resulting in poor developability, resulting in sensitivity. May decrease. Meanwhile, 50% by weight
When it exceeds, the solubility of the obtained coating film in an alkaline aqueous solution becomes too large, and the residual film rate of the obtained resist pattern may deteriorate. In addition, the compound (a-2)
If the content of the polymerized units is less than 5% by weight, the resulting coating may have insufficient crosslink density and may be inferior in heat resistance and chemical resistance. On the other hand, if it exceeds 90% by weight, the obtained coating may have an alkaline aqueous solution. There is a case where the solubility of the composition is deteriorated to deteriorate the developability and the sensitivity is decreased. Furthermore, the content of the polymerized units of the other radically polymerizable compound (a-3) is 70% by weight.
If it exceeds, the balance of the solubility of the polymer in a developing solution composed of an alkaline aqueous solution may become poor, and patterning may become difficult.

The copolymer [A] used in the present invention has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of usually 2 × 10 ³ to 1 × 10 ⁵ , preferably 5 ×.
It is preferably 10 ^{3 to} 5 × 10 ⁴ . Mw is 2 × 1
When it is less than 0 ³ , the resulting coating may have poor developability, residual film rate, etc., and may be inferior in pattern shape, heat resistance, etc. On the other hand, when it exceeds 1 × 10 ⁵ , the sensitivity may be lowered. The pattern shape may be inferior.

The copolymer [A] used in the present invention as described above includes the unsaturated carboxylic acid (a-1), the compound (a-2) represented by the general formula [I], and in some cases. Although it can be obtained by copolymerizing the other radically polymerizable compound (a-3) by various polymerization methods, the method of copolymerizing in a solvent in the presence of a catalyst (polymerization initiator) is preferable.

Specific examples of the solvent used for the copolymerization include alcohols such as methanol, ethanol, propanol and butanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate; ethylene. Glycol ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene Glico Propylene glycol alkyl ether acetates such as propyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketone, cyclohexanone, 2-
Ketones such as heptanone and 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate,
Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Esters such as methyl 3-ethoxypropionate, ethyl acetate and butyl acetate; aprotic polar solvents such as dimethylformamide and N-methyl-2-pyrrolidone. These solvents are polymerizable compounds [(a-1), (a-2) and (a
-3)] in total of 10 to 10 parts by weight, usually 20 to 10
Used in an amount of 00 parts by weight.

As the catalyst, those generally known as radical polymerization initiators can be widely used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile,
2'-azobis (2,4-dimethylvaleronitrile),
Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1,1′-bis (t-butyl) Peroxy)
Organic peroxides such as cyclohexane and hydrogen peroxide can be used. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox type polymerization initiator. Further, in the above copolymerization, a molecular weight modifier such as α-methylstyrene dimer may be added.

The copolymer [A] has a carboxyl group derived from the unsaturated carboxylic acid (a-1) and an alkoxymethylol group derived from the compound (a-2) represented by the general formula [I]. It has an alkali-soluble property and a self-crosslinking property. Further, the copolymer [A] has an appropriate solubility in an alkaline aqueous solution, and gives a radiation-sensitive resin composition excellent in high sensitivity, high residual film rate, developability and the like. Furthermore, the resist pattern obtained by using the copolymer [A] is excellent in various properties such as heat resistance, adhesion to a substrate, transparency in the visible light range, and chemical resistance.

[B] 1,2-quinonediazide compound

The 1,2-quinonediazide compound used in the present invention, 2, 3,4-trihydroxy benzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, 4,6-trihydroxy benzophenone - 1,
2-naphthoquinonediazide-5-sulfonic acid ester le,
2, 2 ', 4,4'-tetrahydroxy-benzophenone -
1,2-naphthoquinonediazide-5-sulfonic acid ester , 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester , 2,3,4,4'-tetrahydroxy benzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, 3,4,2'- tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide -
5-sulfonic acid ester, 2, 3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester le,

[0034] 2, 3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3, 4,5,2', 4'-pentahydroxybenzophenone -1, 2-naphthoquinone diazide-
5-sulfonic acid ester le, 2, 4,6,3 ', 4', 5'-
Hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3, 4,5,3 ',
4 ', 5'-hexahydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester Lumpur,

The bi scan (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid <br/> ester le, bi scan (p- hydroxyphenyl) methane -
1,2-naphthoquinonediazide-5-sulfonic acid ester
Le, Application Benefits (p- hydroxyphenyl) methane-1,2
Naphthoquinonediazide-5-sulfonic acid ester Lumpur,

[0036] 1, 1,1-tri (p- hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester le, bi scan (2,3,4-hydroxyphenyl) methane-1,2 - naphthoquinonediazide-5-sulfonic acid ester le, 2, 2-bis (2,3,4-hydroxyphenyl) propane 1,2-naphthoquinonediazide-5-sulfonic acid ester le, 1, 1,3-tris (2,5-Dimethyl-4-hydroxyphenyl) -3-
Phenylpropane-1,2-naphthoquinonediazide-5
- sulfonic acid ester Lumpur,

[0037] 4, 4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester le, bi- scan (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl methane-1,2-naphthoquinonediazide-5-sulfonic acid ester le, 3, 3,3 ', 3'-tetramethyl-1,1 '
- spiroindene -5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester le and 2, 2,4-trimethyl -7,2 ',
4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester le and the like.

[0038] Of these, 2, 3,4-trihydroxy benzophenone-1,2-naphthoquinonediazide-5
Sulfonic acid ester , 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5
-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 , 2,2,4-trimethyl-
7,2 ', 4'-trihydroxy flavan-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1, 1, 1
-Tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like are preferably used. These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

[C] Cation weight that generates an acid by heating
As the cationic polymerization catalyst capable of generating an acid by applying heat in case the catalyst present invention, sulfonium salts, benzothiazolium salts,
Onium salts such as ammonium salts and phosphonium salts are used. Of these, sulfonium salts and benzothiazolium salts are preferable.

Specific examples of the sulfonium salt include 4
-Acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4-
(Benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4-
Alkylsulfonium salts such as (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate; benzyl-4 -Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2 -Methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonet DOO, benzyl-3-chloro-4-
Monobenzylsulfonium salts such as hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-
4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4
-Methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-
Dibenzylsulfonium salts such as butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate; p-chlorobenzyl-
4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p
-Nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate,
3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-
Substituted benzylsulfonium salts such as chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; the following formulas (1) to (7)
The sulfonium salt represented by

[0042]

[Chemical 3]

Specific examples of the above benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate and 3 Benzyl such as-(p-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate Examples thereof include benzothiazolium salts.

Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium Hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate and the like are preferably used. These commercial products include San-Aid SI-L85 and SI-L11.
0, SI-L145, SI-L150, SI-L
160 (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. These compounds can be used alone or in combination of two or more kinds.

Other Components The radiation-sensitive resin composition of the present invention may contain a sensitizer for the 1,2-quinonediazide compound for the purpose of further improving sensitivity. As such a sensitizer,
2H-pyrido- (3,2-b) -1,4-oxazine-3
(4H) -one, 10H-pyrido- (3,2-b) -1,
4-benzothiazine, urazoles, hydantoins,
Examples thereof include barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, and maleimides. The sensitizer is used in an amount of usually 100 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the 1,2-quinonediazide compound, if necessary.

The radiation-sensitive resin composition of the present invention also comprises
For the purpose of further improving the heat resistance and the adhesion to the substrate, a compound having at least two epoxy groups in the molecule and having no radical polymerizability may be contained. Examples of such compounds include Epicoat 1001 and Epicoat 100.
2, ibid 1003, ibid 1004, ibid 1007, ibid 100
9, 1010, 828 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.) and other bisphenol A type epoxy resins;
Epicoat 807 (trade name; Yuka Shell Epoxy Co., Ltd.)
Bisphenol F type epoxy resin such as; Epicoat 152, 154 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.) Epoxy resin; EOCN102, 103S, 104S, 10
20, 1025, 1027 (trade name; Nippon Kayaku Co., Ltd.)
Cresol novolac type epoxy resin such as Epicoat 180S75 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.); Epicoat 1032H60 and XY-4000.
(Trade name; manufactured by Yuka Shell Epoxy Co., Ltd.) and other polyphenol type epoxy resins; CY-175, 177, 179, Araldite CY-182, 192, 184.
(Trade name; manufactured by Ciba Geigy), ERL-423
4, 4299, 4221, 4206 (trade name; U.C.C.
Made by the company), Shodyne 509 (trade name; Showa Denko KK)
Manufactured by Epicron 200, 400 (trade name; manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661,
Same as 5662 (trade name; Celanese Coating Co., Ltd.)
Made) and other cycloaliphatic epoxy resins; Epolite 100
MF (Kyoeisha Oil and Fat Chemical Co., Ltd.), Epiol TM
Examples thereof include aliphatic polyglycidyl ethers such as P (manufactured by NOF CORPORATION).

These compounds are copolymers [A] 100
It is optionally used in an amount of 50 parts by weight or less based on parts by weight.

Further, the radiation-sensitive resin composition of the present invention comprises
A surfactant may be added for the purpose of preventing striation (after coating streaks) and improving the developability.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dilaurate, polyoxyethylene distearate, etc. Nonionic surfactants such as oxyethylene dialkyl esters; Ftop EF301, 303, 352 (Shin-Akita Kasei Co., Ltd.)
Made), Megafac F171, F172, F173
(Manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-
430, FC-431 (manufactured by Sumitomo 3M Ltd.),
Asahi Guard AG710, Surflon S-382, S
C-101, SC-102, SC-103, SC
-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) and the like; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, 95 (Kyoeisha) (Meth) acrylic acid copolymer-based surfactants such as those manufactured by Yushi Kagaku Kogyo Co., Ltd. may be mentioned. The above surfactant is 2% by weight or less, preferably 1% by weight based on the solid content of the radiation-sensitive resin composition.
It is optionally used in an amount of not more than wt%.

In addition, the radiation-sensitive resin composition of the present invention may contain an adhesion aid for the purpose of further improving the adhesion to the substrate. As such an adhesion aid,
Examples thereof include functional silane coupling agents. Further, the radiation-sensitive resin composition according to the present invention may contain an antistatic agent, a storage stabilizer, a defoaming agent, a pigment, a dye and the like, if necessary.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention comprises the above-mentioned copolymer [A], 1,2-quinonediazide compound, a latent acid generator and, if necessary, other components. However, with respect to 100 parts by weight of the copolymer [A], the 1,2-quinonediazide compound [B] is preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, and the latent acid generator [C]. ], Preferably 0.1 to 50 parts by weight, particularly preferably 1 to 10 parts by weight
It is desirable to include parts by weight.

When the amount of the 1,2-quinonediazide compound in the radiation sensitive resin composition is less than 5 parts by weight based on 100 parts by weight of the copolymer [A], a coating film formed from the composition. May cause difficulty in patterning due to development due to a small difference in solubility between the radiation-irradiated part and the non-irradiated part. On the other hand, when it exceeds 100 parts by weight, 1,2-quinonediazide compound is sufficient for short-time irradiation. The sensitivity may be lowered without being decomposed into. When the amount of the latent acid generator is less than 0.1 part by weight with respect to 100 parts by weight of the copolymer [A], the amount of acid generated during heating is small, so that the crosslinking density of the system is sufficient. And the chemical resistance may decrease. On the other hand, if it exceeds 50 parts by weight, the latent acid generator may be precipitated in the resin composition solution during storage.

The radiation-sensitive resin composition of the present invention can be easily prepared by uniformly mixing the above components, and is usually dissolved in a suitable solvent and used in the form of a solution. For example, by dissolving the copolymer [A] in a solvent and mixing the 1,2-quinonediazide compound, the latent acid generator and, if necessary, other components in a predetermined ratio, the solution state A radiation sensitive resin composition can be prepared.

As the solvent, the same solvent as that used for producing the copolymer [A] can be used. Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-
Methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate. It is also possible to use a solvent such as γ-butyrolactone, ethylene carbonate, propylene carbonate or phenyl cellosolve acetate.

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; ethyl cellosolve acetate, from the viewpoint of solubility and ease of forming a coating film.
Ethylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; esters such as ethyl lactate and ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; Ketones such as 2-heptanone are preferably used.

The radiation-sensitive resin composition of the present invention is applied to an object to be coated as a solution dissolved in a solvent so that the solid content concentration is preferably 20 to 40% by weight. The radiation-sensitive resin composition solution prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.2 μm. The radiation-sensitive resin composition solution thus prepared has excellent long-term storage stability.

Method of Use The above radiation sensitive resin composition solution is applied on the surface of a substrate,
A coating film can be formed by removing the solvent by heating. As a method of applying the radiation-sensitive resin composition solution to the surface of the substrate, various methods such as a spray method, a roll coating method and a spin coating method can be adopted.

Next, the formed coating film is heated (prebaked). The heating conditions vary depending on the type of each component, the mixing ratio, etc., but are usually 10 to 6 at 60 to 120 ° C.
It is about 00 seconds.

Next, the heated coating film is irradiated with radiation through a mask having a predetermined pattern, and then developed with a developing solution,
Remove unnecessary parts. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-
n-Propylamine, triethylamine, methyldiethylamine, N-methylpyrrolidone, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4. It is possible to use an alkaline aqueous solution containing alkalis such as 0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonane. The alkaline water-soluble concentration is usually 0.1 to 2.5% by weight, preferably 0.2 to 0.5% by weight. Further, in the alkaline aqueous solution, a water-soluble organic solvent such as methanol or ethanol,
An aqueous solution containing a suitable amount of a surfactant or the like may be used as the developing solution.

The developing time is usually from 30 to 180 seconds, and the developing method may be any of a puddle method and a dipping method. After the development, washing with running water is performed for 30 to 90 seconds, and air drying with compressed air or compressed nitrogen is performed to remove moisture on the substrate and form a patterned film. Thereafter, the patterned coating is irradiated with radiation from a high-pressure mercury lamp or the like over the entire surface to leave 1,2-
The quinonediazide compound is completely decomposed. Then, with a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on a hot plate, or 30 to 30 in an oven.
By performing heat treatment for 90 minutes, a patterned crosslinked coating film is obtained.

[0060]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

Synthesis of Copolymer [A] Synthesis Example 1 (Synthesis of Copolymer [A-1]) A separable flask equipped with a stirrer, a cooling pipe, a nitrogen introducing pipe, and a thermometer is shown in Table 1. Charge compound 3
After purging with nitrogen for 0 minutes, the separable flask was immersed in an oil bath and the internal temperature was kept at 80 ° C. to carry out a polymerization reaction for 4 hours. The solid content concentration of the obtained polymer solution was 40.5% by weight, and it was confirmed that the polymerization reaction proceeded 100%. The Mw of the copolymer [A-1] is 1.12 × 1.
It was 0 ⁴ . In addition, Mw is GPC (gel permeation chromatography) (Tosoh Corporation HLC-8).
020) is the polystyrene-reduced molecular weight (hereinafter the same). The results are shown in Table 1.

Synthesis Examples 2-5 (Copolymers [A-2]-[A
Synthesis of -6]) Copolymers [A-2] to [A-2] in the same manner as in Synthesis Example 1 except that each component and solvent shown in Table 1 were charged in the amounts shown in Table 1. A-6] containing a polymer solution was obtained. Table 1 shows the solid content concentration and Mw of each of the obtained polymer solutions.

[0063]

[Table 1]

Preparation of Radiation-Sensitive Resin Composition Example 1 100 parts by weight (solid content) of the copolymer [A-1] obtained in Synthesis Example 1 4,4 as a 1,2-quinonediazide compound
4 '-[1- [4- [1- [4-hydroxyphenyl]]
-1-Methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5
-Condensation product with sulfonic acid chloride (2 mol) ([B-
1]) 30 parts by weight and 1.0 part by weight of San-Aid SI-L150 (manufactured by Sanshin Chemical Industry Co., Ltd.) as a latent acid generator are mixed to give a solid content concentration of 35% by weight of diethylene glycol ethyl. After being dissolved in methyl ether, it was filtered through a Millipore filter having a pore size of 0.45 μm to prepare a radiation sensitive resin composition solution.

Examples 2 to 17 and Comparative Examples 1 to 2 A radiation sensitive resin composition solution was prepared in the same manner as in Example 1 except that the components shown in Table 3 were replaced. did.

In Table 3, the abbreviations of the components show the following compounds. [B-1] ... 4,4 '-[1- [4- [1- [4-
Hydroxyphenyl] -1-methylethyl] phenyl]
Ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol)
Condensation product with [B-2] ... 1,1,3-Tris (2,5-dimethyl-4-hydroxyphenyl-3-phenyl) propane (1 mol) and 1,2-naphthoquinonediazide-5 Condensate with sulfonic acid chloride (1.9 mol) [B-3] ... 2,3,4-trihydroxybenzophenone (1 mol) and 1,2-naphthoquinonediazide-5
Sulfonic acid chloride (2.6 mol) and condensates of [C-1] ··· sulfonium salts; San-Aid SI-L
150 (manufactured by Sanshin Chemical Industry Co., Ltd.) [C-2] ... Methyl trifluoromethanesulfonate (p-hydroxyphenyl) (p-methylbenzyl) sulfonium

Evaluation of Radiation-sensitive Resin Composition The radiation-sensitive resin compositions obtained in Examples and Comparative Examples were evaluated by forming a patterned coating film as described below. The results are shown in Table 3. (I) A 4-inch silicon wafer was coated with the radiation-sensitive resin composition solution obtained in each example using a spinner, and then heated on a hot plate at 90 ° C. for 4 minutes to give a film thickness of 4.0 μm. Was formed. (Ii) The obtained coating film was used as NSR-17 manufactured by Nikon Corporation.
55i7A reduction projection exposure machine (NA = 0.50, λ = 36
After changing the exposure time by 5 nm) and exposing it,
A 5% by weight aqueous solution of tetramethylammonium hydroxide was used for development for 1 minute at 25 ° C., rinsed with water, and drying to form a patterned coating film on the silicon wafer.

The evaluation items and evaluation methods are shown below. [Sensitivity] The exposure time required for obtaining a patterned film having a line width of 2.0 μm in the patterned film formed as described above (hereinafter referred to as “optimum exposure time”) was determined. [Resolution] The dimension of the smallest space pattern resolved at the optimum exposure time was measured with a scanning electron microscope. The [residual film rate] (film thickness after development / film thickness before development) × 100 was determined, and 90% or more was ◯ and less than 90% was x. [Developability] The presence or absence of surface roughness of the patterned film after development and the development residue (scum) in the space portion was observed with a scanning electron microscope. When scum is not recognized, it is marked as ○,
When it was recognized, it was designated as x.

[Pattern shape] The cross-sectional shape of the patterned coating film at the optimum exposure time was observed with a scanning electron microscope. Table 2 shows the evaluation criteria of the cross-sectional shape. When the shape was square or rectangular like A, it was evaluated as good (∘), and when it was observed that it was different from the shape of A such as B or C, it was evaluated as bad (x).

[0070]

[Table 2]

[Optimal curing temperature and heat resistance] About 100 μm ×
A silicon wafer on which a 100 μm patterned coating is formed is exposed to 6 m of ultraviolet light having a light intensity of 5 mw at 365 nm.
After irradiation for 0 seconds, use a hot plate at each temperature for 15
Heated for minutes. The silicon wafer on which the cross-linked patterned film was formed was immersed in dimethyl sulfoxide at 80 ° C. for 15 minutes. The temperature at which no surface roughness was observed and the rate of change in film thickness before and after immersion was less than 5% was defined as the optimum curing temperature.
The patterned coating film heated at the optimum curing temperature was further heated for 1 hour, and the temperature at which the film loss due to thermal decomposition was 3% or more was investigated. When this temperature was 30 ° C. or higher than the optimum curing temperature, it was evaluated as ◯, 10 ° C. or higher and lower than 30 ° C. was evaluated as Δ, and less than 10 ° C. was evaluated as x.

[Light Transmittance] A patterned coating of about 100 μm × 100 μm was formed on a Corning 7059 glass substrate and heated at an optimum curing temperature. 4 of this pattern
The light transmittance from 00 nm to 780 nm was measured, and those having a minimum transmittance of 90% or more were evaluated as ◯, 80% or more and less than 90% as Δ, and less than 80% as ×.

[Adhesiveness] A silicon wafer with a thermal oxide film of 0.66 μm was used to form a 5.0 μmL / S pattern film, and the film was heated at the optimum curing temperature for 5 minutes on a hot plate. The heated silicon wafer is dipped in a 6: 1 (volume ratio) mixed solution of a 40 wt% ammonium fluoride aqueous solution and a 50 wt% hydrogen fluoride aqueous solution at 25 ° C. for 6 minutes to form an underlayer of the patterned film. Cut (Table 2
The difference in the pattern width between the uppermost part and the lowermost part of the pattern shape indicated by is observed by a scanning electron microscope, and a value of less than 1.0 μm is indicated by ◯, a value of 1.0 μm or more and less than 1.3 μm is indicated by Δ, and 1.3
μm or more was defined as x.

[Storage Stability] The radiation-sensitive resin composition solution was stored at 5 ° C. for 3 months, then a patterned coating film was formed by the above-mentioned method, and the same evaluation as above was carried out. The results with the resin composition were compared. The radiation-sensitive resin composition immediately after preparation was judged to be good when the same evaluation result was obtained.

[0075]

[Table 3]

[0076]

The radiation-sensitive resin composition according to the present invention is
It is possible to form a coating (pattern) having excellent sensitivity, developability, residual film rate, heat resistance, adhesion to a substrate, and transparency, and particularly excellent chemical resistance. Such a radiation-sensitive resin composition of the present invention is a semiconductor integrated circuit (IC).
And not only thin film transistor (TFT) circuits for liquid crystal displays (LCDs), but also positive resists for making masks for circuit manufacturing, and also for permanent films such as interlayer insulating films and color filter protective films. It is also suitable as a material.

Preferred embodiments of the radiation-sensitive resin composition of the present invention detailed above are described below. 1. The copolymer according to claim 1, wherein the copolymer further contains (a-3) a polymer unit of another radical-polymerizable compound copolymerizable with the unsaturated carboxylic acid and the alkoxy-group-containing radical-polymerizable compound. Radiation-sensitive resin composition. 2. The copolymer [A] contains 5 to 50% by weight of the component (a-1), 5 to 90% by weight of the component (a-2), and (a-
3) A composition obtained by copolymerizing 5 to 70% by weight of the component. 3. The component (a-1) of the copolymer [A] is at least one selected from methacrylic acid or acrylic acid, and the component (a-2) is o-vinylbenidyl methyl ether or m-vinylbenzyl. At least one selected from methyl ether and p-vinylbenzyl methyl ether
And a component (a-3) is at least one of glycidyl methacrylate, dicyclopentanyl methacrylate, styrene and isoprene. 4. A composition in which the polystyrene reduced weight average molecular weight of the copolymer (A) is 2 × 10 ³ to 1 × 10 ⁵ . 5. A composition in which the latent acid generator is an onium salt that generates an acid when heated. 6. The composition according to the above 5, wherein the onium salt is at least one of a sulfonium salt and a benzothiazolium salt. 7. 5 to 100 parts by weight of 1,2-quinonediazide compound, more preferably 10 to 50 parts by weight, and 0.1 to 50 parts by weight of latent acid generator based on 100 parts by weight of the copolymer [A]. , More preferably 1 to 10 parts by weight.

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Masayuki Endo 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-7-5682 (JP, A) JP-A 5-158232 (JP, A) JP-A-2-264954 (JP, A) JP-A-8-15858 (JP, A) JP-A-9-146276 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (5)

(57) [Claims] 1. A polymerized unit of [A] (a-1) unsaturated carboxylic acid and (a-2) the following general formula [I]: (In the formula, R _{1 to} R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₄ is an alkyl group having 1 to 5 carbon atoms, and m and n are independently of each other. An integer of 1 to 5), a copolymer containing polymerized units of a compound represented by [B] 2,3,4-trihydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,4,6-trihydroxybenzophenone-1,2-na
Futoquinonediazide-5-sulfonate, 2,
2 ', 4,4'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,3,4,3'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,3,4,4'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,3,4,2'-tetrahydroxy-4'-methylben
Zophenone-1,2-naphthoquinonediazide-5-sul
Fonate ester, 2,3,4,4'-tetrahydroxy-
3'-methoxybenzophenone-1,2-naphthoquinone
Diazide-5-sulfonic acid ester, 2,3,4,2 ′,
6'-Pentahydroxybenzophenone-1,2-naphth
Toquinonediazide-5-sulfonate, 3,4,
5,2 ', 4'-pentahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,4,6,3 ', 4', 5'-hexahydroxybenzoph
Enone-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 3,4,5,3 ', 4', 5'-hexahydro
Xybenzophenone-1,2-naphthoquinonediazide-
5-sulfonic acid ester, bis (2,4-dihydroxy
Phenyl) methane-1,2 Nafutoki Nonjiajido -5
-Sulfonic acid ester, bis (p-hydroxyphenyl)
) Methane-1,2-naphthoquinonediazide-5-sul
Fonate ester, tri (p-hydroxyphenyl) meta
1,2-naphthoquinonediazide-5-sulfonic acid
Steal 1,1,1-tri (p-hydroxyphenyl) eth
Tan-1,2-naphthoquinonediazide-5-sulfonic acid
Ester, bis (2,3,4-trihydroxyphenyl)
Methane-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 2,2-bis (2,3,4-trihydroxy
Phenyl) propane-1,2-naphthoquinonediazide-
5-sulfonic acid ester, 1,1,3-tris (2,5-
Dimethyl-4-hydroxyphenyl) -3-phenylphenol
Lopan-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 4,4 '-[1- [4- [1- [4-hydr
Roxyphenyl] -1-methylethyl] phenyl] ethyl
Ridene] bisphenol-1,2-naphthoquinone diazide
De-5-sulfonic acid ester, bis (2,5-dimethyl)
-4-hydroxyphenyl) -2-hydroxyphenyl
Methane-1,2-naphthoquinonediazide-5-sulfone
Acid ester, 3,3,3 ', 3'-tetramethyl-1,1'
-Spiroindene-5,6,7,5 ', 6', 7'-hexa
Nol-1,2-naphthoquinonediazide-5-sulfone
Acid ester and 2,2,4-trimethyl-7,2 ', 4'
-Trihydroxyflavan-1,2-naphthoquinonedia
1, selected from among zido-5-sulfonates
A radiation-sensitive resin composition comprising a 2-quinonediazide compound and [C] a cationic polymerization catalyst that generates an acid when heated . 2. A radiation-sensitive resin composition for producing a mask used for producing a circuit.
The radiation-sensitive resin composition according to. 3. The radiation-sensitive resin composition according to claim 1, which is used for an interlayer insulating film. 4. The radiation-sensitive resin composition according to claim 1, which is used for a protective film for a color filter. 5. A coating film formed from the radiation-sensitive resin composition according to any one of claims 1 to 4.