JPH09157350A - Resin composition and its cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation-sensitive resin compsn. and a cured product thereof which are suitable as a negative-working resist by incorporating a specified copolymer, a phenolic compd., a melamine compd., and an onium salt. SOLUTION: A copolymer (A) of an unsatd. carboxylic acid (a) with an epoxy-contg. radical polymerizable compd. (b) and other radical-polymerizable compd. (c), a phenolic compd. (B), a melamine (C) represented by formula I (wherein R1 to R6 represent each H or CH2 OR; R represents H or a 1-6C alkyl), and an onium salt (D), represented by formula II [wherein X represents formula III (wherein R13 to R22 represent H, a halogen, nitro, an alkoxy, a 1-20C aliph. group optionally having OH in its structure OH, an ether, an ester or the like); R7 represents a 1-10C alkyl; R8 to R12 represent each H, OH, a 1-13C aliph. group, a halogen or the like; (n) is 1 to 2; Z represents BF4 , PF6 of the like] capable of functioning as a light acid generator, are mixed together so that the amts. of the components (B), (C), and (D) are respectively 5 to 200 pts.wt., 1 to 100 pts.wt., and 0.001 to 30 pts.wt. based on 100 pts.wt. component (A).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive resin composition and a cured product thereof. Specifically, semiconductor integrated circuits that are sensitive to radiation such as ultraviolet rays, electron beams, and X-rays, LC
The present invention relates to a radiation-sensitive resin composition suitable as a negative resist for forming a D TFT circuit or a mask for forming a circuit.

[0002]

2. Description of the Related Art Positive resists, which are a combination of a quinonediazide compound and a novolac resin, give a pattern of high resolution and are therefore widely used in the manufacture of integrated circuits. In recent years, in the field of the semiconductor industry, patterns have become finer with the progress of higher integration, and high-resolution resists have been actively developed. However, in the actual manufacturing process, the ratio of processing steps requiring submicron resolution is about 10 to 20% of the whole,
The resolution required in the rough process, which occupies most of the rest, is on the order of several microns to several tens of microns. The resist used in these rough processes is strongly required to have high sensitivity rather than high resolution. Furthermore, in the rough process, since the etching process of the base substrate is often performed by the wet etching method that enables large-scale batch processing, the dry etching resistance required in the case of the reactive ion etching method is more preferable than that of the substrate. Adhesion and chemical resistance that is not affected by etchant are important. In addition, the resist used in the rough process is required to have heat resistance that can withstand high temperature heating in the ion implantation process and the like. Poly-type resist, which is a combination of quinonediazide compound and novolac resin, is excellent in terms of resolution and reactive ion etching resistance, but it is often the case in terms of sensitivity, adhesion to substrate, and heat resistance. A shortage has been pointed out.

Such a situation also applies to the field of the liquid crystal display (LCD) industry, which has seen rapid development in recent years. Among the liquid crystal displays, the active matrix (AM) type LCD, which is built into each thin film transistor (TFT) for each pixel, is regarded as the favorite of the next-generation display device that changes to CRT because of its fast response speed. The screen area is steadily increasing. The design rule of the TFT of AM-LCD is about several microns, and the resolution that the resist for rough process has is sufficient for manufacturing, but because of the use of a substrate larger than that used for semiconductor manufacturing, As long as a positive resist containing a combination of a quinonediazide compound and a novolac resin is used, the above-mentioned sensitivity,
Problems such as adhesion to the substrate and heat resistance will become more prominent.

[0004]

An object of the present invention is to provide a radiation sensitive resin composition and a cured product thereof. Another object of the present invention is to provide a radiation-sensitive resin composition for a negative resist, which is excellent in sensitivity, residual film rate, heat resistance, and adhesion to a substrate, and a cured product thereof.

[0005]

The present invention provides a copolymer (A) of an unsaturated carboxylic acid (a), a radical-polymerizable compound (b) containing an epoxy group and another radical-polymerizable compound (c). ), A phenolic compound (B), a melamine (C) represented by the general formula (1), and

[0006]

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(In the formula, R _{1 to} R ₆ may be the same or different and each represents a hydrogen atom or a —CH ₂ OR group, and R represents a hydrogen atom or a C _{1 to} C ₆ alkyl group.) General formula (II)

[0008]

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{Wherein X is a group represented by the formula (III)

[0010]

[Chemical 6]

(In the formula, R _{13 to} R ₂₂ are each a hydrogen atom,
In the structure of halogen atom, nitro group, alkoxy group, C _{1 to} C ₂₀ , hydroxyl group, ether group, ester group, (meth)
It is a group selected from any of an acryloyl group, an epoxy group or an aliphatic group which may have an allyl group, a phenyl group, a phenoxy group and a thiophenoxy group. ) R
₇ is a C _{1 to} C ₁₀ alkyl group, R _{8 to} R ₁₂ are hydrogen atom, hydroxyl group, C _{1 to} C ₁₅ aliphatic group, halogen atom, nitro group, alkoxy group, ester group, phenyl group and Is a group selected from the groups represented by formula (III), n is 1 to 2, Z is BF ₄ , PF ₆ , SbF ₆ ,
AsF ₆ , p-toluene sulfonate or trifluoromethane sulfonate is shown. } The resin composition containing the onium salt (D) which functions as a photo-acid generator represented by these, and its hardened | cured material.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The components of the present invention will be described below. 1. Component (A) (hereinafter referred to as "copolymer"): The copolymer used in the present invention is soluble in an alkaline aqueous solution,
Moreover, it is a copolymer that can be crosslinked by heating. The copolymer (A) is obtained by radically copolymerizing an unsaturated carboxylic acid (a) and a radical-polymerizable compound (b) containing an epoxy group with another radical-polymerizable compound (c) in a solvent. Is obtained by Examples of the unsaturated carboxylic acid (a) include methacrylic acid,
Acrylic acid, maleic acid, itaconic acid, 1,4-cyclohexenedicarboxylic acid, o-, m-, p-vinylbenzoic acid and the like can be mentioned. Preferred are methacrylic acid and acrylic acid. These unsaturated carboxylic acids may be used either individually or in combination of two or more. The proportion of unsaturated carboxylic acid in the copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. If the unsaturated carboxylic acid content is less than 5% by weight, the obtained copolymer becomes difficult to dissolve in an alkaline aqueous solution, resulting in a decrease in sensitivity and deterioration of developability. Solubility in the alkaline aqueous solution becomes too high, causing a reduction in the residual film rate in the unexposed area.

As the radically polymerizable compound (b) containing an epoxy group, glycidyl (meth) acrylate,
α-ethylglycidyl (meth) acrylate, α-n-
Propylglycidyl (meth) acrylate, α-n-butylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, α-ethyl-6,7-
Epoxyheptyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether, etc. can be mentioned, Preferably glycidyl (meth) acrylate and vinyl glycidyl ether can be mentioned.
These radically polymerizable compounds containing an epoxy group can be used alone or in combination of two or more kinds. The proportion of the radically polymerizable compound containing an epoxy group in the copolymer is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. If the amount of the radically polymerizable compound containing an epoxy group is less than 5% by weight, the heat resistance of the pattern obtained from the composition will not be sufficient, and if it exceeds 70% by weight, the storage stability of the leucopolymer will be improved. Becomes worse.

Next, the other radically polymerizable compound (c) will be described. Generally, when radical polymerization of an unsaturated carboxylic acid and a radically polymerizable compound containing an epoxy group is carried out in a two-component system, the carboxyl group and the epoxy group react during the polymerization reaction to cause gelation. Therefore, in order to obtain the copolymer I, it is necessary to suppress the gelation by copolymerizing another radically polymerizable compound as the third component. Examples of the other radically polymerizable compound (c) having such a purpose include olefins such as butadiene, 2,3-dimethylbutadiene and isoprene, styrene, α-,
o-, m-, p-methylstyrene, p-methoxystyrene, p-tert-butoxystyrene, chloromethylstyrene, methyl (meth) acrylate, ethyl, n-propyl, i-propyl, n-butyl, sec -Butyl,
tert-butyl, 2-ethylhexyl, lauryl, dodecyl, dicyclopentanyl, isobornyl, cyclohexyl, 2-methylcyclohexyl, dicyclohexyl, adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, cyclopentyl, furyl, cresyl, 1,1,1. 1-trifluoroethyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-i-propyl, triphenylmethyl ester, amide of (meth) acrylic acid, N, N of (meth) acrylic acid
-Dimethylamide acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, N-
Examples thereof include vinylpyrrolidone and vinyl acetate. Preferably, styrene, butadiene, p-tert
-Butoxystyrene, (meth) acrylic acid tert-butyl ester, (meth) acrylic acid dicyclopentenyl ester, (meth) acrylic acid benzyl ester and the like can be mentioned. These radically polymerizable compounds can be used alone or in combination of two or more kinds. The proportion of the other radically polymerizable compound in the copolymer is preferably 10 to 70% by weight, more preferably 20 to 60% by weight. If the proportion of the other radically polymerizable compound is less than 10% by weight, gelation is likely to occur during the polymerization reaction, and if it exceeds 70% by weight, the solubility of the copolymer I in an aqueous alkaline solution is lowered, The heat resistance of the composition may deteriorate.

Examples of the solvent used for producing the copolymer include alcohols such as methanol, ethanol, propanol and butanol; cyclic ethers such as tetrahydrofuran and dioxane; and aromatic compounds such as benzene, toluene and xylene. Hydrocarbons, DM
Aprotic polar solvents such as F and N-methylpyrrolidone, acetic acid esters such as ethyl acetate and butyl acetate, glycol ethers such as diethylene glycol dimethyl ether, and cellosolve acetates such as methyl cellosolve acetate. The amount of these reaction media used is usually 20 per 100 parts by weight of the reaction raw material.
１０００1000 parts by weight.

Examples of the polymerization initiator include 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (2,4-methylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile)
Examples thereof include azo compounds such as benzoyl peroxide, lauroyl peroxide, ter-butylperoxypivalate, and organic peroxides such as 1,1-bis (ter-butylperoxy) cyclohexane, and hydrogen peroxide. The copolymer (A) used in the present invention is prepared by charging each of the components (a), (b) and (c) in the reaction medium in the above-mentioned use ratio and reacting at a reaction temperature of 60 to 100 ° C. The reaction time is preferably 3 to 20 hours.

Copolymer (A) used in the present invention
The polystyrene reduced weight average molecular weight is usually 2,000.
0-100,000, preferably 5000-50000
It is. If the average molecular weight is less than 2000, the pattern shape,
The residual film rate, developability and heat resistance are deteriorated. When it exceeds 100,000, the pattern shape and developability are deteriorated, and particularly the sensitivity is deteriorated.

Phenolic Compound (B) Examples of the phenolic compound used in the composition of the present invention include phenol, o-, m-, p-cresol, phenol novolac, cresol novolac, hydroquinone, catechol, resorcinol and pyrogallol. , Gallic acid, phlorogricinol, bisphenol A, P, S, F, AF, methylenebisphenol, 4,
4'-ethylidene bisphenol, 4,4'-cyclohexylidene bisphenol, 4,4 '-(1-phenylethylidene) bisphenol, 4,4'-(1-phenylethylidene) bisphenol, 4,4 '-(1- Methylethylidene) bis [2- (2-propenyl) phenol], 4,4'-oxybisphenol, 4,4'-
4 "-ethylidyne tris [2-methylphenol],
4,4 '-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-(3,4-diolbenzylidene) bis [2,6-dimethylphenol], 4,4 '[ (3,4-Dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4′-
[(4-hydroxyphenyl) methylene] bis [2,6
-Dimethylphenol], 2,2 '-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol] ], 4, 4'-
[(2-hydroxyphenol) methylene] bis [2,2
4,6-trimethylphenol], 4,4 ', 4 ",
4 "'-(1,2-ethanedilidene) tetrakis [2-
Methylphenol], 4,4 ', 4 ", 4"'-(1,
4-Phenylenedimethyridine) tetrakis (2,6-dimethylphenol), 4,4'-isopropylidene bis [2-fluorophenol], 4,4 '-[(4-fluorophenyl) methylene] bis [2-fluoro Phenol], 4,4 '-(phenylmethylene) bis [2-fluorophenol], 4,4'-[(4-fluorophenyl) methylene] bisphenol], bis (2,4-dihydroxyphenyl) methane, bis (P-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, 2,2-bis (2,3,4-dihydroxyphenyl) propane, 1 , 1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane,
4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Methane, 2, 3,
4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4 ′ -Tetrahydroxybenzophenone, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3
4,4'-tetrahydroxy-3'-methoxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, 2,4,6,3', 4 ', 5'-hexahydroxybenzophenone, etc. And preferably bisphenol A, P, S, F, AF, 4,4'-
(1-Phenylethylidene) bisphenol, 1,1,
3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4 '[1- [4- [1-
[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol A, 1,1,1-tri- (p-hydroxyphenyl) ethane and the like can be mentioned. These may be used alone or as a mixture of two or more.

The amount of the phenolic compound added is usually 5 to 200 parts by weight per 100 parts by weight of the copolymer (A),
Preferably it is 20 to 100 parts by weight. This addition amount is 5
When the amount is less than the weight part, the crosslinking between the phenolic compound and the melamines becomes insufficient, so that the swelling at the time of development becomes severe and the patterning is difficult. On the other hand, when it exceeds 200 parts by weight, the film forming property as a film cannot be maintained.

Melamines (C) represented by the general formula (I) (hereinafter referred to as "melamines") Melamines include, for example, hexamethylolmelamine, hexabutyrolmelamine, partially methylolated melamine and alkylation thereof. Body, tetramethylol benzoguanamine,
Partially methylolated benzoguanamine and its alkylated products can be mentioned. The amount of these melamines added is 1 to 10 parts by weight with respect to 100 parts by weight of the copolymer I.
It is 0 part by weight, preferably 5 to 50 parts by weight. If the addition amount is less than 1 part by weight, the crosslinking of the system is insufficient and patterning becomes difficult. On the other hand, if the amount exceeds 100 parts by weight, the alkali solubility of the entire composition becomes too high, which causes a problem that the residual film rate after development decreases.

Examples of onium salts (D) include onium salts represented by the general formula (II). The onium salt represented by the general formula (II) can be synthesized by the following method. For example, an acridone compound represented by the general formula (IV)

[0022]

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(Wherein R ₇ is a C ₁ -C ₁₀ alkyl group,
R ₈ to R ₁₂ are each a hydrogen atom, a hydroxyl group, C ₁ -C ₁₅
Aliphatic groups, halogen atoms, nitro groups, alkoxy groups,
It is a group selected from an ester group and a phenyl group. ) And a substituted or unsubstituted diphenyl sulfoxide compound using a known reaction for forming a sulfonium salt (1 below)
Method), 2) a corresponding substituted or unsubstituted sulfonium salt is previously synthesized, and then a method of converting and introducing a substituent (hereinafter referred to as 2) method) can be used. First, the method 1) will be specifically described. The onium salts represented by the formula (II) include acridone compounds represented by the formula (IV) (for example, N-butyl-2-chloro-9-acridone, N-ethyl-2-chloro-9-).
Acridone, N-butyl-2-methyl-9-acridone, N-ethyl-1-ethyl-2-chloro-9-acridone, N-methyl-2-ethoxy-9-acridone, N
-Phenyl-2-ethyl-9-acridone, N-butyl-1-methyl-2-propoxy-9-acridone, N-
Ethyl-2,4-diethyl-9-acridone, N-ethyl-2,4-dipropyl-9-acridone, N-methyl-2-isopropyl-9-acridone, N-butyl-1.
Examples include -propyl-9-acridone and N-phenyl-2-nitro-9-acridone. ) And a substituted or unsubstituted diphenyl sulfoxide compound (eg,
Diphenyl sulfoxide, 4,4′-difluorodiphenyl sulfoxide, 2,2′-difluorodisenyl sulfoxide, 3,3′-difluorodiphenyl sulfoxide, 4,2′-difluorodiphenyl sulfoxide,
4,4'-dibromodiphenyl sulfoxide, 4,4 '
-Dichlorodiphenyl sulfoxide, 2,2 ', 4,
4'-tetrachlorodiphenyl sulfoxide, 4,4 '
-Dimethyldiphenylsulfoxide, 4,4'-diethyldiphenylsulfoxide, 4-methylthiodiphenylsulfoxide, 4-phenylthiodiphenylsulfoxide, etc.) by known methods, for example, dehydrating agents (for example, phosphorus pentoxide, concentrated sulfuric acid, acetic anhydride, etc.) ) And a solvent such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc., the condensation reaction is carried out at room temperature to 100 ° C., and trifluoromethanesulfonate or p-toluenesulfonate is taken out. Or,
These reaction liquids are, for example, NaSbF ₆ , NaPF ₆ ,
NaAsF ₆ , NaBF ₄ , KSbF ₆ , KPF ₆ , K
The onium salt can be obtained by dropping into an aqueous solution of AsF ₆ , or the like.

The method 2) will be described in detail. An onium salt synthesized by the method 1), for example, the formula (V)

[0025]

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[0026] (wherein, wherein R ₇ to R ₁₂ are the same as R ₇ to R ₁₂ in the formula (IV), A is a halogen atom, Z is the formula (I
It is the same as Z in I). In a known method, for example, in the presence of a basic compound (eg, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.), a large excess of mono- or polyalcohols (eg, methanol, ethanol, Carbitol, ethylene glycol,
Polyethylene glycol, propylene glycol, glycerin, trimethylolpropane, 1,4-butanediol, glycidol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, allyl alcohol, etc.) at room temperature to 150 ° C. If necessary, by reacting in the presence of an organic solvent such as dimethyl sulfoxide, the halide portion of the halide compound, for example

[0027]

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[0028]

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[0029]

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It is possible to obtain sulfonium salts converted to substituents such as Specific examples of the sulfonium salts thus obtained are, for example,

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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Preferred examples include: The amount of these onium salts added is such that the copolymer (A) 1
It is 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight with respect to 00 parts by weight. If the addition amount is less than 0.001 part by weight, the amount of acid generated by exposure is small, so that the crosslinking of the phenol compound and the melamines does not proceed sufficiently, the residual film rate after development, the heat resistance of the pattern, and the chemical resistance are descend. Further, if the addition amount exceeds 30 parts by weight, the sensitivity is lowered.

In the composition of the present invention, a compound containing two or more epoxy groups in the molecule other than the copolymer (A) can be blended mainly for the purpose of improving heat resistance and adhesion. Examples of the compound containing two or more epoxy groups in the molecule include Yuka Shell Epoxy Co., Ltd.
Manufactured by Epicoat 1001, 1002, 1003, 100
Bisphenol A type epoxy resin such as 4, Epicoat 8
07 (Yukaka Shell Epoxy Co., Ltd., bisphenol F
Epoxy resin) Epicoat 152, 154 (Phenolnoholak type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), EOCN-102, 103S, 104S, 10
20, 1025, 1027 (Nippon Kayaku Co., Ltd., cresol novolac type epoxy resin), Epolite 100M
F (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.), Epiol TMP
Aliphatic polyglycidyl ethers such as (manufactured by NOF CORPORATION) can be used. The addition amount of these epoxy compounds is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the copolymer (A).

Further, the composition of the present invention may contain an adhesion aid for improving the adhesion to the substrate. In addition, an antistatic agent, a storage stabilizer, an antihalation agent, an antifoaming agent and the like can be added to the composition of the present invention, if necessary.

As a method of applying the composition of the present invention to a substrate such as a silicon wafer, a predetermined amount of Copolymer I, a phenolic compound, melamines, onium salts and various compounding agents, for example, solid concentration A method may be mentioned in which 20 to 40% by weight is dissolved in a solvent, filtered through a filter of about 0.2 μm, and then applied by spin coating, roll coating, or the like. As the solvent used in this case, ethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol alkyl ethers such as monoethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and other propylene glycol alkyl ether acetates, toluene, xylene, etc. Aromatic hydrocarbons, methyl ethyl ketone, cyclohexanone, 2-heptanone, methyl imebutyl ketone, and other ketones, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, esters such as 3-methyl-3-methoxybutylacetate are used. be able to. These solvents can be used alone or as a mixture. Further, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1
-Nonanol benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
It is also possible to add a high boiling solvent such as γ-butyrolactone, propylene carbonate, phenyl cellosolve acetate and carbitol acetate.

The developer of the composition of the present invention is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkaline water such as aqueous ammonia, ethylamine, n-propylamine. Primary amines such as diethylamine, di-n
Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, secondary amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Quaternary ammonium salt or pyrrole, piperidine, 1,8-diazabicyclo- (5,4,0) -7-undecene, 1,5-diazabicyclo- (4,3,0),
An alkaline aqueous solution prepared by dissolving cyclic amines such as 5-nonane is used. In addition, a water-soluble organic solvent, for example, alcohols such as methanol and ethanol or a surfactant may be added to the developer in an appropriate amount.

When the composition of the present invention is used as a negative resist, the composition of the present invention is applied to a silicon substrate in an amount of 1 to 5 μm.
The film was spin-coated to a film thickness of 70 ° C., prebaked at 70 to 100 ° C. for several minutes on a hot plate, then exposed by an exposure device, and post-baked at 90 to 150 ° C. for several minutes on the hot plate. 20 ~ with tetramethylammonium hydroxide aqueous solution with a concentration of 0.1 ~ 3%
It was developed at 40 ° C. for 1 minute. Rinse with water and dry to form a pattern on the silicon substrate.

[0042]

EXAMPLES The present invention is described below by dividing it into synthetic examples and examples, but the present invention is not limited to these synthetic examples and examples. (Synthesis Example of Copolymer (A)) Synthesis Example 1 In a separable flask, 1.0 g of butadiene, 10 g of styrene, 20 g of methacrylic acid, 29 g of dicyclopentanyl methacrylate, 40 g of glycidyl methacrylate,
Charge 4 g of N-N'-azobisisobutyronitrile and 300 g of diethylene glycol dimethyl ether, and add 30
After purging with nitrogen for 1 minute, heat and keep at 80 ° C for 3
The polymerization reaction was carried out for a time, then the reaction solution was added to 10 liters of methanol, and the resulting precipitate was thoroughly washed with methanol. It was dried under reduced pressure at 50 ° C. to obtain a copolymer (A-1) which was a white resin powder. The weight average molecular weight of this copolymer (A-1) was 2.11 × 10 ⁴ .

Synthesis Example 2 A separable flask was charged with 5 g of butadiene and 10 styrene.
g, methacrylic acid 20 g, dicyclopentanyl methacrylate 25 g, glycidyl methacrylate 40 g, N-
After charging 4 g of N'-azobisisobutyronitrile and 300 g of diethisan glycol dimethyl ether and purging with nitrogen for 30 minutes, the polymerization reaction was carried out for 4 hours while heating and keeping at 80 ° C, and then the reaction solution was added to 10 liters of methanol. The precipitate obtained by adding to the above was thoroughly washed with methanol. It was dried under reduced pressure at 50 ° C. to obtain a copolymer (A-2) as a white resin powder. The weight average molecular weight of this copolymer (A-2) was 1.51 × 10 ⁴ .

Synthesis Example 3 In a separable flask, 5 g of butadiene, 5 g of styrene,
Methacrylic acid 16g, dicyclopentanyl methacrylate 34g, glycidyl methacrylate 40g, NN '
After charging 4 g of azobisisobutyronitrile and 200 g of diethylene glycol dimethyl ether and purging with nitrogen for 30 minutes, the polymerization reaction was carried out for 4 hours while heating and maintaining at 80 ° C., and then the reaction solution was added to 10 liters of methanol. The obtained precipitate was thoroughly washed with methanol. It was dried under reduced pressure at 50 ° C. to obtain a copolymer (A-3) as a white resin powder. The weight average molecular weight of this copolymer (A-3) was 1.73 × 10 ⁴ .

(Synthesis Example of Onium Salt (C)) Synthesis Example 4 10.0 parts of N-butyl-2-chloro-9-acridone (manufactured by Kurogane Kasei Co., Ltd.), 4,4'-difluorodiphenyl sulfoxide 9 .2 parts, 6.0 parts of acetic anhydride and 43.1 parts of methanesulfonic acid were charged, and the reaction was carried out at 25 ° C. for about 8 hours with stirring. Then, the reaction mixture was mixed with NaS.
A yellow solid deposited by dripping little by little into 2000 parts of an aqueous solution of bF ₆ (dissolving 9.5 parts of NaSbF ₆ ) was filtered and washed with water. 25.2 parts of a yellow solid were obtained. The melting point of the product was 166 to 170 ° C. and the elemental analysis values were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 46.92 46.96 Hydrogen 3.00 2.99 Sulfur 43.19 43.23 Nitrogen 1.89 1.89 Antimony 16.38 16.41 Fluorine 20 .43 20.49 Chlorine 4.77 4.78 Based on this production method,

[0046]

Embedded image A sulfonium salt of

Synthesis Example 5 N-butyl-2-chloro-9-acridone 10.0 parts,
4,4'-Difluorodiphenyl sulfoxide 9.2
Parts, acetic anhydride 6.0 parts and perfluoromethanesulfonic acid 43.1 parts were charged and the reaction was carried out for about 8 hours with stirring at 25 ° C., then 1000 parts of water and 500 parts of propylene carbonate were charged to this reaction mixture. After stirring for 1 hour, the organic layer was thoroughly washed with water, and propylene carbonate was distilled off under reduced pressure to obtain 20.8 parts of a yellow solid. The elemental analysis values were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 54.96 54.91 Hydrogen 3.52 3.54 Sulfur 9.81 9.78 Nitrogen 2.16 2.14 Fluorine 14.50 14.48 This production Structural formula based on the method

[0048]

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A sulfonium salt (D-2) of was obtained.

Examples 1 to 6 and Comparative Examples 1 and 2 The components were blended according to Table 1 and filtered through a membrane filter having a pore size of 0.2 μm to prepare the composition of the present invention. Each composition was spin-coated on a silicon substrate to a film thickness of 2.0 μm, and prebaked at 90 ° C. for 2 minutes on a hot plate. Then, the negative film was placed on the coating film, and irradiated with ultraviolet rays of 400 mJ / cm ² using an exposure device, and then heat-cured at 100 ° C. for 2 minutes on a hot plate. Development was carried out for 1 minute at 25 ° C. in an aqueous tetramethylammonium hydroxide solution having the concentration shown in Table 1.
It was washed with water and dried to obtain a test piece having a pattern formed on a silicon substrate. The performance evaluation shown below was performed using this test piece. Developability: The surface roughness of the line portion after development and the presence or absence of development residual in the space portion were examined. Pattern shape: The cross-sectional shape of the resist pattern of the test piece was examined, and the cross-sectional shape was good or bad. X ... The cross-sectional shape was poor. Heat resistance: The test piece was heated on a hot plate at 10 ° C. intervals for 5 minutes, and the temperature at which the resist pattern thermally deformed was examined. 180 ° C or higher is ○, 170 ° C to 140 ° C is △, 14
The temperature of 0 ° C or lower was marked with x. Residual film rate: (film thickness after development / initial film thickness) × 100 is obtained 9
0 or more was evaluated as ◯, and 89 or less was evaluated as x.

[0051]

[Table 1] Table 1-1 Example 1 2 3 4 5 6 Copolymer (A-1) 100 100 obtained in Synthesis Example 1 Copolymer (A-2) 100 100 obtained in Synthesis Example 2 Copolymer (A-3) 100 100 1,1,1-tri (p-hydroxyphenyl) ethane 100 100 100 Bisphenol A 100 100 100 Cymel 300 * 3 20 20 20 Cymel 370 * 4 20 20 20 Synthesis example 4 Obtained onium salt (D-1) 3 3 3 Synthesis example 5 Obtained onium salt (D-2) 2 2 2 Diethylene glycol methyl ether Developer concentration 0.24 0.24 0.24 0.24 0.30 0.30 Developability Good Good Good Good Good Good Pattern shape ○ ○ ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ Remaining film rate ○ ○ ○ ○ ○ ○ Table 1-2 Comparative example * 1 * 2 1 2 Copolymer obtained in Synthesis example 1 ( A-1) Copolymer (A-2) obtained in Synthesis Example 2 Copolymer (A-3) 1,1,1-tri (p-hydroxyphenyl) ethane obtained in Synthesis Example 3 Bisphenol A Cymel 300 * 3 Cymel 370 * 4 Synthesis Example 4 Obtained onium salt (D-1) Synthesis Example 5 Obtained onium salt (D-2) Diethylene glycol methyl ether Developer concentration 2.38 2.38 Good developability Good pattern shape × × Heat resistance × × Residual film rate × ×

Note) * 1: manufactured by Tokyo Ohka Kogyo Co., Ltd.
Evaluation was performed using OFPR-800. * 2: OFPR-5000 manufactured by Tokyo Ohka Kogyo Co., Ltd.
Was evaluated using. * 3 Cymel 300: Mitsui Cyanamid Co., Ltd.
Made by melamine resin * 4 Cymel 370: Mitsui Cyanamid Co., Ltd.
Made of melamine resin

As is clear from the results in Table 1, the composition of the present invention is excellent in the residual film rate and the pattern shape, and the cured product is excellent in heat resistance.

[0054]

EFFECT OF THE INVENTION A resin composition having excellent residual film rate and heat resistance and a cured product thereof can be obtained.

Claims (2)

[Claims] 1. A copolymer (A) of an unsaturated carboxylic acid (a), a radical-polymerizable compound (b) containing an epoxy group, and another radical-polymerizable compound (c), and a phenolic compound (B). A melamine (C) represented by the general formula (I): (In the formula, R _{1 to} R ₆ may be the same or different and each represents a hydrogen atom or a —CH ₂ OR group, and R represents a hydrogen atom or a C _{1 to} C ₆ alkyl group) and the general formula. (II) embedded image {In the formula, X is a group represented by the formula (III): (In the formula, R _{13 to} R ₂₂ are each a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, and a structure of C _{1 to} C ₂₀ ,
It is a group selected from any of a hydroxyl group, an ether group, an ester group (meth) acryloyl group, an aliphatic group which may have an epoxy group or an allyl group, a phenyl group, a phenoxy group and a thiophenoxy group. ) R ₇ is C ₁ ~
C ₁₀ alkyl group, R _{8 to} R ₁₂ are each a hydrogen atom,
A group selected from a hydroxyl group, a C _{1 to} C ₁₅ aliphatic group, a halogen atom, a nitro group, an alkoxy group, an ester group, a phenyl group and a group represented by the formula (III), n is 1 to 2 and Z. Is BF ₄ , PF ₆ , SbF ₆ , AsF ₆ ,
Indicates p-toluene sulfonate or trifluoromethane sulfonate. } The resin composition containing the onium salt (D) which functions as a photo-acid generator represented by these. 2. A cured product of the resin composition according to claim 1.