JPS62276536A - Radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved visibility, without reducing the performance of a resist by incorporating an anthraquinone compd. having alkylamino group to the titled composition. CONSTITUTION:The titled composition contains the anthraquinone compd. having the alkylamino group. The anthraquinone compd. having the alkylamino group is composed of a dyestuff which has at least one of the alkylamino group binded to the anthraquinone skeleton. Thus, the resist film having the high visibility is formed, and the handling of a glass substrate or an ITO substrate makes easy after coating, even in case of using the glass substrate or the ITO substrate, without damaging inherent characteristics of the radiation sensitive resin composition.

Description

[Detailed Description of the Invention] 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a radiation-sensitive resin composition, and more particularly, the present invention relates to a radiation-sensitive resin composition, and more particularly, to a radiation-sensitive resin composition that can be used without changing the original characteristics of the radiation-sensitive resin composition. ,
The present invention relates to a radiation-sensitive resin composition suitable for a resist with excellent visibility.

[Conventional technology]

In recent years, integrated circuit manufacturing methods have made remarkable progress, and there is a strong demand for improvements to the equipment and peripheral materials used for this purpose.In the field of resists, there is a desire to develop resists that are easy to handle and have high resolution. .

Conventionally, in the production of integrated circuits, a mixture of a diazide compound and a cyclized polyisoprene compound has been mainly used as a negative resist, and a mixture of a quinone diazide compound and a novolak resin has been used as a positive resist. A resist made of a mixture of these materials is naturally colored yellow, and there is no problem when such a resist is used on a silicon substrate. When applied to a substrate (substrate), it is difficult to handle because it is difficult to visually confirm whether the resist has been applied, and there are many operational problems when manufacturing liquid crystal display elements and the like.

In addition, radiation-sensitive resin compositions containing dyes have also been proposed (Japanese Patent Publication No. 37562/1983, Japanese Patent Application Laid-Open No. 59/1983).
142538, etc.). All of these are caused by so-called halation (on a highly reflective substrate such as aluminum, when irradiated with ultraviolet rays, the ultraviolet rays reflected from the substrate surface go around to areas where it is not desired to be irradiated with ultraviolet rays, resulting in the production of integrated circuits). This is a technology to prevent the phenomenon of inability to accurately reproduce the fine patterns required for resist printing, and currently no technology has been proposed that improves visibility without degrading resist performance. be.

[Problem that the invention seeks to solve]

The present invention was made against the background of the above-mentioned conventional technical problems, and it is possible to coat a radiation-sensitive resin composition on a glass substrate or a substrate on which ITO is vapor-deposited (ITO substrate) without impairing the original characteristics of the radiation-sensitive resin composition. It is an object of the present invention to provide a radiation-sensitive resin composition suitable for a resist that has visibility even when it is exposed to light.

[Means for solving problems]

That is, the present invention provides a radiation-sensitive resin composition characterized in that it contains an anthraquinone compound having an alkylamino group.

The anthraquinone compound having an alkylamino group used in the present invention is a dye having at least one alkylamino group in the anthraquinone skeleton, for example, a 9,10-anthraquinone skeleton represented by the following general formula (1). Compounds having the following can be mentioned.

(In the formula, R1 and Rg are the same or different, and are a hydrogen atom, an amino group, a sulfoxyl group, a halogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms, a carboxyl group, a nitro group, or an alkyl group having 1 to 10 carbon atoms) Specific examples of anthraquinone compounds (hereinafter sometimes simply referred to as "anthraquinone compounds") that have an amino group and a small number of such alkylamino groups (of which one is the above-mentioned alkylamino group) include the following: Compounds can be mentioned.

OO O○ OO ○ , O, 0, 0, 0, 0, 0・z 0 , ○ , ○
OO, 0
, 0, 0, ○ 00
, ○
,0 1 0
,0,
○, 0.

U
00 Hz N Hz 011i
! 1 0 CH2NH, ○ II l lII
I IIOCHz N
Hz , 0111I OC82NN, , 0 ○ +1 t ■□ t OQ Two or more of the above anthraquinone compounds can also be used in combination.

Note that these anthraquinone compounds are preferably compounds that satisfy the following conditions.

(1) Dissolve in ketone or ester solvents.

(2) λ□8 is in the range of 450 to 700 nm, and its absorbance is 0.5 or more (20 mg/l cm, acetone).

In the radiation-sensitive resin composition of the present invention, the anthraquinone compound (1) is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 7% by weight of the entire solid content of the composition.
If it is less than 0.1% by weight, visibility is poor, while if it exceeds 10% by weight, sensitivity decreases (depending on the amount of injection).

Next, examples of the radiation-sensitive resin composition in which the anthraquinone compound having an alkylamino group is blended in the present invention include, for example, a positive radiation-sensitive resin composition comprising an alkali-soluble resin and a quinonediazide compound. .

Examples of the alkali-soluble resin include phenol,
Alkali-soluble novolac resins obtained by addition condensation of phenols such as cresol, ethylphenol, xylenol, p-phenylphenol, resorcinol, pyrogallol, and phloroglucinol with aldehydes such as formaldehyde, acetaldehyde, and henzaldehyde, and hydroxyl Styrene or α
- Mention may be made of polymers of hydroxystyrene derivatives such as methylhydroxystyrene.

Alkali-soluble novolak resins are produced by condensing phenols and aldehydes in the presence of an acidic catalyst in a conventional manner. Examples of the acidic catalyst used in this case include oxalic acid, acetic acid, hydrochloric acid, and sulfuric acid, and these are usually used in an amount smaller than the stoichiometric equivalent of the aldehyde to be subjected to the reaction. The condensation reaction is preferably carried out at 80 to 150°C, particularly 95 to 120°C, under a pressure of 1 to 3 atmospheres, and is usually completed in about 1 to 7 hours.

Further, the number average molecular weight of the alkali-soluble novolak resin in terms of polystyrene is preferably 400 to 900, particularly 5
00-900 is preferable.

The polymer of hydroxystyrene or hydroxystyrene derivative is composed of hydroxystyrene, hydroxystyrene derivative, etc., for example, an azo compound such as azobisisobutyronitrile, or a peroxide such as benzoyl peroxide or lauroyl peroxide. A method of radical polymerization in the presence of a radical generator, in which hydroxyl groups contained in hydroxystyrene and hydroxystyrene derivatives are silylated or acetylated, and this product is subjected to radical polymerization in the presence of the radical generator, or n-butyllithium, 5ec-butyl It is produced by polymerizing in the presence of an anionic polymerization initiator such as lithium or sodium naphthalene, followed by desilylation or deacetylation.

These polymers of hydroxystyrene or hydroxystyrene derivatives may be copolymers with other polymerizable monomers. In this case, examples of seven polymers that can be copolymerized include styrene monomers such as styrene and aminostyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, acrylic acid, methyl acrylate, and acrylic acid. Examples include (meth)acrylic acid monomers such as ethyl ester, diene monomers such as butadiene and isoprene, and these monomers may be copolymerized in combination of 2 fffi or more. The preferred (co)polymerization ratio of hydroxystyrene or hydroxystyrene derivative in the (co)polymer of hydroxystyrene or hydroxystyrene derivative is 3
0 to 100 mol%, particularly preferably 40 to 100 mol%
It is.

Moreover, the weight average molecular weight of the (co)polymer of hydroxystyrene and/or a hydroxystyrene derivative in terms of polystyrene is preferably 3,000 to 30,000.

Among the alkali-soluble resins, m-cresol is
Alkali-soluble novolak resin obtained by condensing formaldehyde with a cresol isomer mixture containing 5 to 97% by weight and 3 to 55% by weight of p-cresol, especially 0-
Preferred is an alkali-soluble novolac resin obtained by condensing formaldehyde with a cresol isomer mixture containing only m-cresol and p-cresol without containing cresol. Particularly preferred are those obtained by condensation at a ratio of 3 to 45,155.

The alkali-soluble resin may be one imparted with radiation sensitivity, for example, a 1.2-naphthoquinone diazido-4-sulfonyl group, a 1,2-naphthoquinone di-7dido-5-sulfonyl group, Alkali-soluble novolak resins into which quinonediazide sulfonyl groups such as 1,2-benzoquinonediazide-4-sulfonyl groups have been introduced, polymers of hydroxystyrene or hydroxystyrene derivatives having four quinonediazide sulfonyl groups, etc., may be used. From the viewpoint of alkali solubility, the alkali-soluble resin imparted with radiation sensitivity preferably has a content of quinonediazide sulfonyl groups of 10% by weight or less, particularly 1 to 8% by weight.

The alkali-soluble resin imparted with radiation sensitivity includes the alkali-soluble resin, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-benzoquinonediazide. It is produced by condensing quinone diazide sulfonyl chloride such as -4-sulfonyl chloride in an appropriate solvent, if necessary in the presence of a basic catalyst.

Two or more types of the alkali-soluble resins can be used in combination, but when used in combination, it is preferable that the resins have compatibility with each other. Examples of combinations of two or more alkali-soluble resins include alkali-soluble novolak resin and hydroxystyrene polymer, alkali-soluble novolak resin and α-
Examples include methyl hydroxystyrene polymer, an alkali-soluble novolak resin that is made with an alkali-soluble novolac resin and radiation-sensitive, and an alkali-soluble novolak resin that is made with a hydroxystyrene polymer and has radiation-sensitivity.

Examples of the quinonediazide compound to be mixed with the alkali-soluble resin include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 2-naphthoquinonediazide 5.
Examples include mono- or polyhydroxybenzene or the fi-sulfonic acid esters of these compounds.

Specific examples of hydroxybenzene include p
-Cresol, resorcinol, pyrogallol, phloroglucinol, etc.

Furthermore, as a quinonediazide compound, for example, it is represented by the following general formula (i) [wherein n is an integer of 1 to 3, and R9 represents an alkyl group, an aryl group, a -(poly)hydroxyaryl group, or an aralkyl group]. 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1゜2-naphthoquinonediazide-5
A 1°2-quinonediazide compound obtained by condensing -sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride can also be used.

As a compound represented by general formula (1), for example, 2.3
．． 4-trihydroxyphenylmethylketone, 2.3.
4-trihydroxyphenylethyl ketone, 2,3.4
-1-lyhydroxyphenylbutyl ketone, 2,3.4
-1-lihydroxyphenyl-n-hexyl ketone, 3
, 4.5-trihydroxyphenylmethylketone, 3.
4.5-trihydroxyphenylethyl ketone, 3,4
．． 5-trihydroxyphenylbutylketone, 3.4゜5-trihydroxyphenyl-n-hexylketone, 2
, 4.6-1-lyhydroxyphenylmethylketone, 2
, 4.6-) lyhydroxyphenylethyl ketone, 2,
4.6-trihydroxyphenylbutylketone, 2,4
．． 6-dolyhydroxyphenyl-n-hexylketone,
2,3.41-lyhydroxyphenyldecyl ketone,
2.3.4-trihydroxybenzophenone, 2,4.
6-trihydroxybenzophenone, 2,3.4-1-
Lihydroxydiphenylhenzylketone, 3,4゜5-trihydroxyphenylhenzylketone, 2゜4.6-drihydroxyphenylbenzylketone, 2.4-dihydroxyphenylpropylketone, 2.4-dihydroxyphenyl -n-hexylketone, 2.4-dihydroxybenzophenone, 2°3.4.4'-tetrahydroxyhensiphenone, 2.4,6.4'-tetrahydroxyhensiphenone, 2. 4. Examples include 2', 4'-tetrahydroxyhensiphenone.

Further, as the quinonediazide compound, for example, 2.4.
2',4'-tetrahydroxy-6,6'-dimethyl-diphenylmethane, 2,6.2'.

6'-tetrahydroxy-3,5,3', 5'-tetrachloro-diphenylmethane, 2,2'-dihydroxy-
4,4'-dimethyl-diphenylmethane-(1,1)
, 2.2'-dihydroxy-4゜4'-dimethoxy-diphenylethane-(1,1) 2.4.2', 4'-tetrahydroxy-diphenylethane-(1,1), 2.2
'-Dihydroxy-4,4'-dimethoxy-triphenylmethane, 2.2'-dihydroxy-dinaphthylmethane, 2°4.2',4'-tetrahydroxy-diphenyl sulfoxide, 2. 4. 2',4'-tetrahydroxy-6,6'-dimethyl-diphenylethane-(
1,1) ,2. 4. 2', 4'-tetrahydroxy-6,6'-dicarbomethoxydiphenylmethane, 2. 4. 2', 4'-tetrahydroxy-
6,6'-dimethyl-triphenylmethane, 2.4.2
',4'-tetrahydroxy-diphenylpropane-(
1,1), 2,4.2', 4'-tetrahydroxy-diphenyl-n-butane-(1,1), 2,4.2', 4
',6'-pentahydroxy-triphenylmethane, 2
, 4.2'.

4'-Tetrahydroxy-diphenylcyclohexane-
(1,1), 2,2-dihydroxy-4°4'-dimethoxy-diphenylmethane, 2,4°2',4'-tetradroxy-diphenylpentane-(1,1), 2.
4. 2', 4'-tetradroxy-diphenylpropane-(2,2), 2°4.2', 4'-tetradroxy-triphenylmethane, 2,2'-dihydroxy-5,5'-dibromo-diphenylmethane, 2 ,2'-
Dihydroxy-5,5'-dichloro-diphenylethane (1,1), 2,2'-dihydroxy-5,5'-dibromo-diphenylethane (1,1), etc.,
naphthoquinonediazide-4-sulfonyl chloride, 1,
A 1,2-quinonediazide compound obtained by a condensation reaction with 2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-benzoquinonediazide-5-sulfonyl chloride can be used.

Furthermore, 3.5-dihydroxybenzoic acid lauryl, 2.
3.4-1-lyhydroxybenzoic acid phenyl, 3,4.
A (poly)hydroxybenzoic acid alkyl ester or aryl ester such as propyl 5-trihydroxybenzoate or phenyl 3,4.5-trihydroxybenzoate is combined with 1,2-1-phthoquinonediazide 4-sulfonyl chloride, 1° 2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-benzoquinonediazide-5-
1゜2- obtained by condensation reaction with sulfonyl chloride
Quinonediazide compounds can be used.

The amount of the quinonediazide compound to be added is determined based on the alkali solubility, heat resistance, plasma etching resistance, solubility of unirradiated areas, and range of irritability against radiation when the resulting positive radiation-sensitive resin composition is used as a resist. resin 100
The amount per part by weight is preferably 10 to 40 parts by weight, particularly preferably 15 to 35 parts by weight.

The positive radiation-sensitive resin composition may contain a sensitizer, if necessary. Examples of the sensitizer include hensitriazole and its halides, 5-methylbenzotriazole and its halides, 5,6
-Simethylbenzotriazole and its halide, 1.2-naphthotriazole and its halide, cyclohexyltriazole and its halide, 1.2.3-triazole and its halide,
1,2,4-triazole and its halides, 4
．． Triazoles such as 5-dicyano-1,2,3-triazole and its halides; indazoles such as indazole and its halides, 5-nitroindazole and its halides, 6-aminoindazole and its halides; imidazole and imidazole tR such as its halide, 4-azabenzimidazole and its halide; 2 H-
Pyrido(3,2-b)-1,4-oxazine-3(4
H) ons, 10H-pyrido C3,2-b) (1,4)
-benzothiazines; uraduls; hydantoins;
Barbylic acids; glycine anhydrides; 1-hydroxybenzotriazoles; alloxanes and maleimides are used. These compounds may be derivatives of these compounds, that is, these compounds, and examples of derivatives of these compounds include 1-methylurazole, ■-phenylurazol, and 3-methylurazol. , 3-p-triurazole, 5,5-diphenylhydantoin, 5.5-dimethylhydantoin, 5-methyl-5-phenylhydantoin, 5-methyl-5-p
-Tolylhydantoin, 1-methylhydantoin, 1-
Phenylhydantoin, 1-methyl-5-methylhydantoin, 5-methylhydantoin, 5-ethyl-5-p
-Tolylhydantoin, 5,5-diethylhydantoin, 5-ethyl-5-p-tolylbarbylic acid, 5-nitrobarbyl M, 5,5-dimethylbarbyl!
, 5.5-diphenylbarbic acid, 1-methylglycine, 1-phenylglycine, 2-methylglycine, 2
．． Examples include 2-dimethylglydine, 5-methyl-1-hydroxybenzotriazole, 5,6-dimethyl-1-hydroxybenzotriazole, 1-methylalloxane, 1-phenylloxane, and 3-phenylmaleimide.

In addition, for the purpose of improving developability, storage stability, coating properties, etc., the positive radiation-sensitive resin composition may contain natural resins such as rosin, schlag, etc., styrene and maleic anhydride, if necessary. Copolymers, copolymers of styrene and acrylic acid, methacrylic acid or their alkyl esters, copolymers of acrylic acid or methacrylic acid and their alkyl esters or hydroxyalkyl esters, acrylic acid polymers, vinylpyrrolidone Synthetic resins such as polymers, surfactants, and plasticizers such as diethyl phthalate, diisopropyl phthalate, and di-t-butyl phthalate may be blended.

Another example of the radiation-sensitive resin composition used in the present invention is a negative-tone radiation-sensitive resin composition comprising a cyclized product of a conjugated diene polymer and a radiation crosslinking agent.

The cyclized product of the conjugated diene polymer is a cyclized product of a polymer or copolymer having a unit represented by the following general formula (11) in the polymer chain.

RZOCR21 (wherein R'' to R21 are the same or different, a hydrogen atom,
Alkyl groups, such as methyl, ethyl, butyl, propyl, etc., or aryl groups. ) Specific examples of the unit represented by general formula (11) include cis-1,4-butadiene unit, trans-1゜4-butadiene unit, cis-1,4-isoprene unit, trans-
1,4-isoprene unit, cis-1,4-pentadiene unit, trans-1,4-pentadiene unit, l,4-
Examples of these conjugated diene units include 2-phenylbutadiene units, 1,2-butadiene units, 3.4-isoprene units, 1,2-pentadiene units, and 3.4-2-phenylbutadiene units. Examples of monomer units that can be copolymerized with styrene units include vinyl aromatic compound units such as styrene units and α-methylstyrene units, and olefin units such as ethylene units, propylene units, and isobutylene units. The cyclized products of these conjugated diene polymers include cis-1,4-isoprene units, trans-1,4-isoprene units, 3.4-isoprene units, cis-1,4-butadiene units, trans-1 ，
A cyclized product of a polymer or copolymer having at least one unit selected from 4-butadiene units and 1,2-butadiene units is preferred, and a cyclized product of an isoprene polymer or a butadiene polymer is particularly preferred. The amount of residual double bonds in the cyclized product of the conjugated diene polymer is not particularly limited, but is preferably 5 to 95%, particularly preferably 10 to 90%, and most preferably 15 to 50%.

In addition, the amount of remaining double bonds is It is represented by (*: Measured by NMR).

The radiation crosslinking agent is not particularly limited as long as it is a radiation crosslinking agent that is soluble in a solvent, and may be an and-based photosensitive substance such as 4,4'-diazidostilbene, p-phenylenebisazide, .4'-Diazidobenzophenone, 4,4'-diazidophenylmethane, 4,4'-diazidochalcone, 2,6-bis(4'-azidobenzal)cyclohexanone, 2,6-bis(4'-azidobenzal) )-4-methylcyclocyclohexanone, 4,4'
-Diazido diphenyl, 4,4'-diazide-3゜3'
-dimethyldiphenyl, 2,7-diazide chalcone, etc. can be used. These radiation crosslinking agents are preferably used by adding 0.1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, per 100 parts by weight of the cyclized product of the conjugated diene polymer. be done.

When using the radiation-sensitive resin composition of the present invention as a resist, it is coated on a substrate to be microfabricated, for example, electron beams, ultraviolet rays, far ultraviolet rays, X-rays, visible light, neutron beams, molecular beams, ion beams, etc. A pattern can be formed by partially irradiating radiation such as a line through a mask pattern or reticle and developing it.

The radiation-sensitive resin composition of the present invention may be applied to a substrate by, for example, dissolving the radiation-sensitive resin composition of the present invention in a suitable organic solvent, and applying the same by spin coating, flow coating, or roll coating. An example of this method is to apply it using a method. Examples of the solvent used in this case include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Glycol ethers such as diethylene glycol monoethyl ether and diethylene glycol dibutyl ether, cellosolve esters such as methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, acetonylacetone, acetophenone, and isophorone; ethers such as hensyl ethyl ether, 1,2-dibutoxyethane, and dihexyl ether; fatty acids such as caproic acid and caprylic acid; ■-octatool, 1 Alcohols such as -nonanol, ■-decanol, hensyl alcohol, ethyl acetate, butyl acetate, 2-ethylhexyl acetate, hensyl octate, benzyl benzoate, diethyl oxalate, dibutyl oxalate, diethyl malonate, dibutyl maleate, maleic acid Examples include esters such as diethyl, dimethyl phthalate, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, butyl lactate, and lactones such as T-butyrolactone. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent used varies depending on the required film thickness when applying the radiation-sensitive resin composition solution, but is generally 100 to 2,000 parts by weight, preferably 300 parts by weight, per 100 parts by weight of the solid content of the composition. ~1.500 parts by weight.

In the case of the above-mentioned positive radiation-sensitive resin, examples of the developer used when forming a resist pattern of the radiation-sensitive resin composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, silicic acid, etc. Aqueous solutions of inorganic alkalis such as sodium, sodium metasilicate, trisodium phosphate, sodium hydrogen phosphate, n-propylamine, di-n-propylamine, di-n-butylamine, methyldiethylamine, pyrrole, 2,5- water of amines such as dimethylpyrrole, β-picoline, collidine, piperidine, piperazine, triethylenediamine)
liquid, aqueous solutions of alcohol amines such as dimethylethanolamine, triethanolamine, diethylhydrocylamine, tetramethylammonium hydroxide,
Examples include an aqueous solution such as tetraethylammonia hydroxide or a developer containing aqueous ammonia as a main ingredient. These developers may contain surfactants, stabilizers such as sodium sulfite and ammonium sulfite, alcohol, Hydrophilic organic solvents such as ketones, esters, and ethers, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetra-n-butylammonium hydroxide, tetra-n
-Butylammonium chloride, trimethylbenzylammonium hydroxide, trimethylhensylammonium iosite, tetrapentylammonium hydroxide, tetrapentylammonium bromide, etc. can be added.

Further, as the developer for the negative radiation-sensitive resin composition, benzene, toluene, xylene, n-hebutane, cyclohexane, ethylcyclohexane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, decalin, etc. Examples include organic solvents such as methanol, ethanol, acetone, ethyl ether, n-butyl acetate, n-amyl acetate, and dioxane, and mixed solvents obtained by mixing these organic solvents in an appropriate ratio.

Note that the developability can be further improved by adding a surfactant, such as an aliphatic ester nonionic surfactant, to these developers. Examples of aliphatic ester nonionic surfactants include those with an HLBI of ~5 such as sorbitan trioleate, sorbitan sesquioleate, sorbitan monooleate, sorbitan distearate, sorbitan distearate, stearic acid monoglyceride, and oleic acid monoglyceride. can be mentioned.

Furthermore, after development, methanol, ethanol, acetone,
Rinsing may be performed using ethyl ether, n-butyl acetate, n-amyl acetate, dioxane, or the like.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 After charging 65 g of m-cresol and 35 g of p-cresol into a 500 mf Mitsuro separable flask,
66 ml of 37% by weight formalin aqueous solution and 0.0 oxalic acid
4 g was added, and the separable flask was immersed in an oil bath while stirring, and the reaction was carried out for 10 hours while maintaining the reaction temperature at 100'C.

After the reaction was completed, water was distilled off by reducing the pressure to 300 smHg, and the internal temperature was further raised to 130'C to remove unreacted substances. Next, the molten alkali-soluble novolac resin, which was a reaction product, was returned to room temperature and collected. Next, 15 g of this alkali-soluble novolac resin, 2.4□ 6
- Trihydroxybenzophenone - After dissolving 3.0 g of 1,2-naphthoquinonediazide-5-sulfonic acid triester and 0.6 g of 1,4-diethylaminoanthraquinone in 75 g of ethyl cellosolve acetate, the pore size was 0.
．． A solution of the radiation-sensitive resin composition of the present invention was prepared by filtering through a 2 μm membrane filter.

Comparative Example 1 C, I, Solvent Lend 23 (C, [, So
A solution of a radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that 0.6 g of Ivent Red 23) was used.

Comparative Example 2 A solution of a radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that no colorant was used.

Test Example 1 (11) The compositions prepared in Example 1, Comparative Example 1, and Comparative Example 2 were each spin-coated onto a glass substrate, and then shaken for 2 minutes on a hot plate kept at 90°C to form a film. A resist film with a thickness of 1.3 m was obtained.The visibility of the obtained resist film was observed and the results are shown in Table 1.

(2) Using a (IL/IS) test pattern mask with equal line width and space width on the resist 1 film obtained in step 11 above, mask aligner PLA-501F (Canon After irradiating for 1.5 seconds with
．． The resist pattern was developed using a 0% by weight aqueous solution at 21° C. for 1 minute, and rinsed with running water to form a resist pattern.

Next, the residual film rate and resolution of the obtained resist pattern were measured. The results are shown in Table 1.

(3) After leaving the resist film obtained in (1) above at 25°C for 4 days, a resist pattern was formed in the same manner as in (2) above, and the remaining film rate and resolution of the obtained resist pattern were measured. . The results are shown in Table 1.

(4) After storing the compositions prepared in Example 1, Comparative Example 1, and Comparative Example 2 at 25°C for 3 months,
A resist pattern was formed in the same manner as in 1). Next, the residual film rate and resolution of the obtained resist pattern were measured. The results are shown in Table 1.

Table 1 In Table 1, O indicates good visibility and × indicates poor visibility.

Example 2 Isoprene polymer (99% of cis-1,4 bonds, 1% of 3,4-bonds, [η]
(30℃, in toluene) = 4.7Li1/g) 125
xylene 2,37, which was dehydrated after replacing with nitrogen.
5 g was added under a nitrogen stream, a stirrer was attached, the mixture was heated to 80°C in an oil bath, and the mixture was mixed for about 10 hours to form a homogeneous solution. Next, while maintaining the temperature of the reaction system at 80° C., 9.1 mmol of fluorosulfuric acid was added and stirred for 30 minutes.

Then, about 12 ml of water was added to the solution while stirring, and the oil bath was removed to cool the solution to stop the reaction.

In order to prevent gelation of the product, 1.25 g of 2,6-tert-butyl-p-cresol was added, and the product was precipitated and collected in a large excess of methanol, washed with methanol, and then dried. The recovered cyclized product was [η] (30°C, in toluene) = 0.64 gd! /g, remaining double bond amount 20%
It was a cyclized product of Cyclized product 30 thus obtained
g, 0.6 g of 2,6-bis-(4'-azidobenzal)cyclohexanone and 0.3 g of 1,4-dibutylaminoanthraquinone were added and dissolved in xylene to obtain a composition with a solid content concentration of 12% by weight. was prepared.

Comparative Example 3 A composition was prepared in the same manner as in Example 2, except that 1,4-dibutylaminoanthraquino was not used.

Test Example 2 (1) The compositions prepared in Example 2 and Comparative Example 3 were
After spin-coating each onto a glass substrate, it was dried for 15 minutes in a clean oven kept at 80°C to a film thickness of 1 μm.
A resist film of m was obtained. The visibility of the obtained resist film was observed and the results are shown in Table 2.

(2) The resist film obtained in tl) above was irradiated for 0.9 seconds using the same test pattern mask and mask aligner as in (2) of Test Example 1, and then n-hebutane was used as a developer. After development was performed using a mixed solvent of and m-xylene (volume ratio -80:20) to form a resist pattern, the resist pattern was rinsed using n-butyl acetate.

Next, the residual film rate and resolution of the obtained resist pattern were measured. The results are shown in Table 2.

(3) The compositions prepared in Example 2 and Comparative Example 3 were
After storing at 5° C. for 3 months, a resist pattern was formed in the same manner as in (1) above. Next, the residual film rate and resolution of the obtained resist pattern were measured. The results are shown in Table 2.

The resist film made of the composition obtained in Example 2 of Table 2 was colored green and had extremely excellent visibility.

〔Effect of the invention〕

The radiation-sensitive resin composition of the present invention can be applied to glass substrates or IT without impairing the original properties of the radiation-sensitive resin composition.
Even when used on an Oi board, a highly visible resist film can be formed, making it easy to handle glass substrates or ITO substrates after application of the present composition. Furthermore, the radiation-sensitive resin composition of the present invention also has excellent storage stability.

Claims (1)

[Claims] (1) A radiation-sensitive resin composition containing an anthraquinone compound having an alkylamino group.