JP2888236B2 - Method for producing 1,2-naphthoquinonediazide compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a process for preparing 1,2-naphthoquinonediazide compounds, ultraviolet especially, deep ultraviolet, X
As a component of a radiation-sensitive resin composition suitable as a resist for producing highly integrated circuits that is sensitive to radiation such as rays, electron beams, molecular beams, γ rays, synchrotron radiation, and proton beams.
A method for producing a useful 1,2-naphthoquinonediazide compound .

[0002]

2. Description of the Related Art Positive resists are widely used in the manufacture of integrated circuits because they provide high-resolution resist patterns. However, with the recent increase in the degree of integration of integrated circuits, resists with higher resolution have been developed. A positive resist capable of forming a pattern is desired. That is, when a fine resist pattern is formed by a positive resist, when a latent image formed by exposure is developed with a developing solution composed of an alkaline aqueous solution, a portion where the exposed portion is in contact with the wafer (the bottom of the pattern). It needs to be developed quickly.

[0003]

However, in the case of the conventional positive type resist, when the sense of the resist pattern to be formed becomes 0.8 μm or less, development residue called scum tends to occur, and there is a problem in developability. Was.

[0004] Further, with the improvement of the degree of integration of integrated circuits,
The wafer etching method has shifted from conventional wet etching with large side etching to dry etching with small side etching. In this dry etching, it is necessary that the resist pattern does not change at the time of etching, and thus it is necessary that the heat resistance is good.

Accordingly, an object of the present invention is to effectively suppress the occurrence of scum when forming a resist pattern,
Excellent developability, high sensitivity, heat resistance,
It is to provide a manufacturing method of a particular 1,2-naphthoquinonediazide compounds suitable radiation-sensitive resin composition possible as an excellent positive resist film residual rate.

[0006]

SUMMARY OF THE INVENTION Namely, the present invention is one general formula (1):

[0007]

Embedded image [In the general formula (1), R ^{1 to} R ⁴ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a hydroxyl group, and each of R ^{1 to} R ⁴ is different from each other by at least two kinds. ^May be bonded to each benzene ring as a group, provided that any of R ¹ , R ² and R ⁴ contains at least one hydroxyl group; R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted Or an unsubstituted alkyl group;
a, b and d each independently represent an integer of 0 to 5;
4 of an integer, provided that a, a hydroxy compound at least one of b and d is represented by the non-zero], 1,2
-Naphthoquinonediazide-4-sulfonyl chloride
Or 1,2-naphthoquinonediazide-5-sulfonylk
A general formula (2) consisting of an esterification reaction with a chloride.

[0008]

Embedded image [In the general formula (2), R ¹ ~R ⁴ is a substituted or unsubstituted alkyl group independently, substituted or unsubstituted aryl group or OD group (wherein, D represents a hydrogen atom or a 1,2-naphthoquinonediazide - 4-sulfonyl group or 1,2-na
Shift indicates quinonediazide-5-sulfonyl group), provided that may be attached to the benzene ring as each different two or more kinds group ^{R 1 ~R 4, R 1,} R
Any of ² and R ⁴ contains at least one 1,2-naphthoquinonediazide group; R ⁵ , R ⁶ ,
a, b, c and d are as defined with respect to the general formula (1).] The present invention provides a method for producing a 1,2-naphthoquinonediazide compound represented by the following formula:

[0009] 1,2-Naphthon obtained by the method of the present invention
Non-diazide compounds are components of radiation-sensitive resin compositions.
For example, ( A) an alkali-soluble resin, and (B) the general formula (2) produced by the method described above.
A 1,2-naphthoquinonediazide compound represented by: and a radiation-sensitive resin composition comprising : is excellent in developability and effectively suppresses the generation of scum, high sensitivity, and heat resistance, It can be suitably used as a positive resist excellent in residual film property.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Method for producing 2-naphthoquinonediazide compound The above-mentioned general formula (1) used as a raw material in the production method of the present invention, namely,

[0011]

Embedded image

Wherein R ^{1 to} R ⁴ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
Alternatively, it indicates any of hydroxyl groups, and examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
t-butyl group, cyclohexyl group, hydroxymethyl group, chloromethyl group, bromomethyl group, 2-chloromethyl group, trimethylsilylmethyl group, benzyl group, cumyl group and the like. Among them, methyl group, ethyl group, hydroxy group A methyl group and the like are preferable, and examples of the substituted or unsubstituted aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-hydroxyphenyl group,
-Trimethylsiloxyphenyl group, 4-methoxyphenyl group, 4-acetylphenyl group and the like,
Among them, a phenyl group, a 4-hydroxyphenyl group and the like are preferable.

The groups R ⁵ and R ⁶ each represent a hydrogen atom or a substituted or unsubstituted alkyl group;
Examples of such substituted or unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl,
n-butyl group, t-butyl group, cyclohexyl group, hydroxymethyl group, chloromethyl group, bromomethyl group, 2
-Chloromethyl group, trimethylsilylmethyl group, benzyl group, cumyl group and the like, among which a methyl group, an ethyl group, a hydroxymethyl group and the like are preferable.

Specific examples of the hydroxy compound represented by the general formula (1) include the following. 1,1-bis (4-hydroxyphenyl) -1- [4-
(4-hydroxybenzyl) phenyl] ethane

[0015]

Embedded image 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1- [4- (4-hydroxybenzyl) phenyl] ethane

[0016]

Embedded image 1,1-bis (3,5-dimethyl-2-hydroxymethyl) -1- [4- (4-hydroxybenzyl) phenyl] ethane

[0017]

Embedded image 1,1-bis (4-hydroxy-3-methylphenyl)
-1- [4- (4-hydroxybenzyl) phenyl] ethane

[0018]

Embedded image 1,1-bis (2,6-dimethyl-4-hydroxyphenyl) -1- [4- (4-hydroxybenzyl) phenyl] ethane

[0019]

Embedded image 1,1-bis (3,4-dihydroxyphenyl) -1-
[4- (4-hydroxybenzyl) phenyl] ethane

[0020]

Embedded image 1,1-bis (4-hydroxyphenyl) -1- [4-
{1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane

[0021]

Embedded image 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl)
-1-methylethyldiphenyl] ethane

[0022]

Embedded image 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl)
-1-methylethyldiphenyl] ethane

[0023]

Embedded image 1,1-bis (4-hydroxy-3-methylphenyl)
-1- [4- {1- (4-hydroxyphenyl) -1-]
Methylethyldiphenyl] ethane

[0024]

Embedded image 1,1-bis (2,6-dimethyl-4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl)
-1-methylethyldiphenyl] ethane

[0025]

Embedded image 1,1-bis (3,4-dihydroxyphenyl) -1-
[4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane

[0026]

Embedded image

The above-mentioned hydroxy compounds can be prepared, for example, by dissolving a substituted or unsubstituted phenol and a substituted or unsubstituted acetophenone in the presence of an acidic catalyst, as disclosed, for example, in DE 1,930,333. It is obtained by condensation below. The reaction product is generally obtained as an oily mixture, but can also be purified by means such as recrystallization. Obtained by the manufacturing method,
General formula (2), that is,

[0028]

Embedded image

[0029] ^{In, R 5, R 6, a} , b, but c and d are as defined for formula ^{(1), R} 1 ~
R ⁴ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group as described with respect to the general formula (1), or an OD group (D is a hydrogen atom or 1,2-naphthoquinonediazide -4-sulfoni
Or 1,2-naphthoquinonediazide-5-sulfo
Indicates a group), provided ^that the one of R 1, ^{R 2} and ^{R 4} 1,2-naphthoquinonediazide-4-sulfonyl
Nil group or 1,2-naphthoquinonediazide-5-sul
Honiru group that contains at least one. In the above, each of the groups R ^{1 to} R ⁴ may be bonded to each benzene ring as two or more different groups.

The 1,2-naphthoquinonediazide compound represented by the general formula (2) is obtained by replacing a part or all of the hydroxyl hydrogen atoms in the hydroxy compound represented by the general formula (1) with an organic group containing a 1,2-quinonediazide group. obtained in a compound obtained by substituting, by the method of the present invention, for example, by the esterification reaction of the hydroxy compound and 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride Rye de be able to. The esterification reaction is preferably performed in the presence of triethylamine.

Here, in the present invention, in order to sufficiently exhibit the function for improving the developability of the 1,2-naphthoquinonediazide compound of the general formula (2), the average condensation rate of the esterification reaction [( Number of esterified phenolic hydroxyl groups / Number of phenolic hydroxyl groups before reaction) × 10
0] (hereinafter referred to as “average condensation rate”) is usually 100%
Or less, preferably 50% or less, more preferably 30%
It is as follows.

Radiation-Sensitive Resin Composition Next, the 1,2-naphthoquino obtained by the method of the present invention.
The composition using the diazide compound will be described in the order of components. (A) an alkali-soluble resin need for an alkali-soluble resin (hereinafter, "resin (A)"
), For example, a novolak resin, a resol resin, polyvinylphenol or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, a carboxyl group-containing methacrylic acid-based resin, and the like. Is preferably used. Among the novolak resins, the following general formula (3):

[0033]

Embedded image (Wherein, n represents an integer of 1 to 3) is particularly preferably obtained by polycondensing a phenol and an aldehyde represented by the following formula:

The preferred phenols include, for example, o-cresol, m-cresol, p-cresol,
2,3-xylenol, 2,4-xylenol, 2,5
-Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol,
3,4,5-trimethylphenol and the like can be mentioned, among which o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are preferable. .
These phenols are used alone or in combination of two or more.

Examples of the aldehydes to be polycondensed with the above phenols include formaldehyde, trioxane, baraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde. , M-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m
-Chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde,
Examples thereof include pn-butylbenzaldehyde and furfural, and formaldehyde is particularly preferably used. These aldehydes may be used alone or
It can be used in combination of more than one kind. The amount of the aldehyde used is 0.7 to 1 mol of the phenol.
It is preferably 3 mol, more preferably 0.8 to 1.5 mol.

For the polycondensation of phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. The use amount of these acidic catalysts is usually 1 × 10
^{−5 to} 5 × 10 ⁻¹ mol.

In the polycondensation reaction, water is usually used as a reaction medium. However, when the phenol used for the polycondensation does not dissolve in the aqueous solution of the aldehyde and becomes a heterogeneous system from the beginning of the reaction, the reaction medium is used. May be used as a hydrophilic solvent. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol, and butanol; and cyclic ethers such as tetrahydrofuran and dioxane. The amount of the reaction medium used is usually 20 to 100 parts by weight of the reaction raw material.
1000 parts by weight.

The temperature of the polycondensation can be appropriately adjusted according to the reactivity of the reaction raw materials.
° C, preferably 70 to 130 ° C. As the method of the polycondensation reaction, a method in which phenols, aldehydes, acidic catalysts, etc. are charged at once, and a method in which phenols, aldehydes, etc. are added as the reaction proceeds in the presence of an acidic catalyst, should be adopted. Can be. After the completion of the polycondensation reaction,
In order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the system, the temperature of the reaction system is generally set to 130 to 2
The temperature is raised to 30 ° C. and reduced pressure, for example, 20 to 50 mmHg
Volatile components are distilled off to the extent that the resin (A) obtained is recovered.

The resin (A) used in the present invention preferably has a weight average molecular weight in terms of polystyrene (hereinafter referred to as "Mw") of 2,000 to 20,000, and 3,000 to 15,000. It is more preferred that there be. When Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer,
Further, the developability and sensitivity tend to decrease, and when Mw is less than 2,000, the heat resistance tends to decrease. In order to obtain a resin (A) having a high Mw, the resin obtained above was dissolved in a good solvent such as ethyl cellosolve acetate, dioxane, methanol, and ethyl acetate, and then dissolved in water, n-hexane, and n-hexane. What is necessary is just to mix a poor solvent such as heptane, and then separate the resin solution layer to be deposited, and recover the high molecular weight resin (A).

[0040] (B) 1,2 The naphthoquinonediazide component (B) of the diazide compounds set Narubutsu, obtained by the manufacturing method described above, represented by 1,2-naphthoquinonediazide compound in the general formula (2) ( Hereinafter, "naphthoquinonediazide compound (B)" is used. The naphthoquinonediazide compound (B) is used per 100 parts by weight of the resin (A).
It is preferable to use 0.5 to 90 parts by weight, particularly 2 to 50 parts by weight.

[0041] Other ingredients hydroxy compound group forming compound, can be formulated as required, the hydroxy compound represented by the general formula (1). Specific examples of the hydroxy compound are as described above. When the hydroxy compound is blended, the blending amount is determined based on the resin (A) 1
It is preferable to use 0.5 to 90 parts by weight, particularly 2 to 50 parts by weight, per 100 parts by weight.

Other 1,2-quinonediazide compound compositions include the naphthoquinonediazide compound (B) described above.
Other 1,2-naphthoquinonediazide compounds can be blended. Such 1,2-quinonediazide compounds include, for example, 1,2-benzoquinonediazide-4
-Sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

Specifically, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-
Sulfonate, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-
Sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-
5-sulfonic acid ester, 3'-methoxy-2,3,
4,4'-tetrahydroxybenzophenone-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 3 '
Polyhydroxybenzophenone such as methoxy-2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester
1,2-naphthoquinonediazidosulfonic acid ester,
1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl)
Hydrogen atoms of hydroxyl groups of ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester and a novolak resin or a resol resin (hereinafter simply referred to as “resin (B)”), for example, 20 to 100 mol% per hydrogen atom 1,2-naphthoquinonediazide-4-sulfonyl group, preferably 1,2-naphthoquinonediazido-5-sulfonyl group, etc. Quinonediazidesulfonic acid esters.

The resin (B) is obtained by condensation of a phenol and an aldehyde. Examples of the phenol include phenol, 1-phenol and phenol used in the synthesis of the resin (A). Naphthol, 2-naphthol and the like can be used. As the aldehydes, those used in the synthesis of the resin (A) can be used. The amount of the aldehyde used is preferably 0.1 to 3 mol, more preferably 0.2 to 1.5 mol, per 1 mol of the phenol. In this condensation, an alkaline catalyst can be used in addition to the acidic catalyst used for the synthesis of the resin (A).

The Mw of the resin (B) is usually 10,000, in view of the easiness of the esterification reaction and the solubility in a solvent.
It is preferably 0 or less, more preferably 200 to 2,000. Particularly preferably, it is 300 to 1,000. Examples of the 1,2-quinonediazidosulfonic acid ester of the resin (B) include phenol / formaldehyde condensed novolak resin, m-cresol / formaldehyde condensed novolak resin, p-
Cresol / formaldehyde condensed novolak resin, o
Cresol / formaldehyde condensed novolak resin,
1,2-benzoquinonediazide such as m-cresol / p-cresol / formaldehyde condensed novolak resin
Examples thereof include 4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester.

In the composition of the present invention, the amount of the 1,2-quinonediazide compound is usually 3 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the resin (A).
Although it is parts by weight, the total amount of the 1,2-quinonediazidosulfonyl groups in the composition is usually adjusted to 5 to 25% by weight, preferably 10 to 20% by weight.

Other Various Compounding Agents In the composition of the present invention , various compounding agents such as a sensitizer, a surfactant and a dissolution promoter can be compounded. The sensitizer is compounded for improving the sensitivity of the composition. Examples of such a sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazine-3. (4H)-
Ons, 10H-pyrido- (3,2-b)-(1,4)
-Benzothiazines, urazoles, hydantoins,
Examples include parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. The compounding amount of these sensitizers depends on the resin (A)
It is usually 50 parts by weight or less for 100 parts by weight.

The surfactant is compounded for improving the coating property and the developing property of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether and polyoxyethylene stearyl ether. ,
Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, EFTOP EF301, EF303, EF352 (trade names,
Shin-Akita Chemical Co., Ltd.), Megafax F171, F17
2, F173 (trade name, manufactured by Dainippon Ink), Florado FC430, FC431 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-38
2, SC-101, SC-102, SC-103, SC
-104, SC-105, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymer polyfluoro-No. 75, no. 9
5 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.).
The content of these surfactants is 100% of the solid content of the composition.
It is usually 2 parts by weight or less per part by weight.

The dissolution accelerator is added to promote the solubility of the composition in a developer and to improve sensitivity and developability. Examples of such a dissolution promoter include 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 3,5-dimethyl-4, 4'-dihydroxydiphenylmethane, bisphenol A, 3,5-
Dimethyl-2 ', 4-dihydroxydiphenylmethane,
1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane, an alkali-soluble novolak resin having a weight average molecular weight (Mw) of 2,000 or less in terms of polystyrene, and the like. . The amount of these dissolution promoters is usually 50 parts by weight or less based on 100 parts by weight of the resin (A).

Further, the composition of the present invention may contain a dye or a pigment for visualizing the latent image in the irradiated area and reducing the influence of halation upon irradiation, and improving the adhesiveness. For this purpose, an adhesion aid may be added. Further, if necessary, a storage stabilizer, an antifoaming agent and the like can be added.

Preparation of Composition and Pattern Formation The composition of the present invention comprises the above resin (A) and 1,2-
The naphthoquinonediazide compound (B) and, if necessary, other 1,2-quinonediazide compounds and various compounding agents are dissolved in a solvent such that the solid content concentration becomes 20 to 40% by weight, and the pore diameter is about 0.2 μm. It is prepared by filtration through a filter.

Examples of the solvent used in this case include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate, and propylene glycol propyl. Ether acetate, toluene, xylene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, 2
Ethyl-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate,
Methyl 3-ethoxypropionate can be used. These organic solvents are used alone or in combination of two or more. Further, N-methylformamide,
N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, caproic acid, caprylic Add a high boiling point solvent such as acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. Can also.

The composition of the present invention is applied to, for example, a silicon wafer or a wafer coated with aluminum or the like by spin coating, flow coating, roll coating or the like to form a photosensitive layer, and a predetermined mask pattern is formed. The pattern is formed by irradiating the photosensitive layer with radiation and developing with a developer. When the composition of the present invention is used as a positive resist, the composition is coated on a wafer or the like, prebaked and exposed, and then heated at 70 to 140 ° C., and thereafter, The effect of the present invention can be further improved by developing.

Developer The developer of the composition of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, diamine, and the like. -N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -
7-undecene, 1,5-diazabicyclo- [4.3.
0] -5-Nonane or the like is used in an alkaline aqueous solution obtained by dissolving an alkaline compound such that the concentration is usually 1 to 10% by weight, preferably 2 to 5% by weight. Further, a suitable amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol or a surfactant may be added to the developer. When development is performed using a developing solution composed of such an alkaline aqueous solution, rinsing is generally continued with water.

[0055]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples. The measurement of Mw and the evaluation of the resist in the examples were performed by the following methods.

[0056] Mw: Toyo Soda Co., Ltd. GPC column (G2000H ₆ 2 this, G
3000H ₆ 1 present, using G4000H ₆ 1 present), flow rate 1.5 ml / min, eluent tetrahydrofuran, analytical conditions of column temperature 40 ° C., as measured by gel permeation chromatography method using monodisperse polystyrene as the standard.

Sensitivity: The exposure time was changed with a Nikon-NSR-1505G4D reduction projection exposure machine (lens numerical aperture; 0.45).
Exposure is performed using g-line having a wavelength of 436 nm, or the exposure time is changed using a Nikon-NSR-1505i6A reduction projection exposure machine (numerical aperture of lens: 0.45), and i-line having a wavelength of 365 nm is used. Exposure is performed, and then development is performed using a 2.4% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution at 25 ° C. for 60 seconds, rinsing with water, and drying to form a resist pattern on a wafer. Exposure time for forming a line and space pattern (1LIS) with a width of 1: 1
This is referred to as “optimal exposure time”).

Resolution: The dimension of the minimum resist pattern resolved when exposed for the optimal exposure time was measured.

Residual film ratio: The thickness of the pattern after development at the optimum exposure time was divided by the thickness of the resist film before development, and this value was multiplied by 100 to give a unit of%.

Developability: The degree of scum and residual development was examined.

Heat resistance: The wafer on which the resist pattern was formed was placed in a clean oven, and the temperature at which the pattern began to collapse was measured.

Pattern shape: Using a scanning electron microscope, the lower side A and upper side B of a rectangular cross section after development of a 0.6 μm resist pattern were measured,
When 0.85 ≦ B / A ≦ 1, the pattern shape was determined to be good. However, in the case where the pattern shape has a skirt or a reverse tapered shape, it is determined that the pattern is defective even if B / A is within the above range.

<Synthesis of Resin A> Synthesis Example 1 A flask equipped with a stirrer, a condenser and a thermometer was charged with 67.6 g (0.63 mol) of m-cresol 10.0 g (0,0 g) of 2,3,5-trimethylphenol. 0.073 mol) p-cresol 31.8 g (0.29 mol) 37% by weight aqueous formaldehyde solution 107.1 g (formaldehyde: 1.32 mol) and oxalic acid dihydrate 1.33 g (1.06 × 10 ⁻²⁾ ), The flask was immersed in an oil bath, polycondensation was carried out for 30 minutes with stirring while maintaining the internal temperature at 100 ° C., and then 17.5 g (0.16 mol) of m-cresol and 2,3 , 5-trimethylphenol (40.0 g, 0.29 mol) was added, and polycondensation was further carried out for 40 minutes. Then, the oil bath temperature was raised to 180 ° C., and simultaneously the pressure in the flask was reduced to 30 to 50 mmHg, and water, oxalic acid, unreacted formaldehyde, m-cresol, p-talesol and 2,3,5-trimethylphenol were used. Was removed.
Then, the molten resin was returned to room temperature and collected. This resin is referred to as resin (A1).

Synthesis Example 2 Resin (A1) was dissolved in ethyl cellosolve acetate so as to have a solid content of 20% by weight, and twice the amount of methanol and an equal amount of water with respect to the weight of this resin solution were added and stirred. And left. After being separated into two layers by standing, the resin solution layer (lower layer) was taken out, concentrated, dehydrated, and dried to collect the resin. This resin is converted into a resin (A
2).

Synthesis Example 3 In an autoclave, 69.2 g (0.64 mol) of m-cresol 21.8 g (0.16 mol) of 2,3,5-trimethylphenol 61.0 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde: 0) .75 mol) Oxalic acid dihydrate (6.3 g, 0.05 mol), water (52.6 g) and dioxane (182 g) were charged, and the autoclave was immersed in an oil bath.
The mixture was condensed for 6 hours while stirring at a temperature of ℃ C. After the reaction, the temperature was returned to room temperature, and the contents were taken out into a beaker. After separating into two layers in this beaker, take out the lower layer,
Concentrated, dehydrated and dried to recover the resin. This resin is referred to as resin (A3).

Synthesis Example 4 In the same flask as used in Synthesis Example 1, m-cresol 13.0 g (0.12 mol) p-cresol 32.4 g (0.3 mol) 3,5-xylenol 39. 0 g (0.32 mol) 37 wt% aqueous formaldehyde solution 56.9 g (formaldehyde: 0.70 mol) and oxalic acid dihydrate 0.083 g (6.59 × 10 ⁻⁴ mol) were charged, and the flask was placed in an oil bath. After stirring for polycondensation for 30 minutes while keeping the internal temperature at 100 ° C., 51.9 g (0.48 mol) of m-talesol and 9.77 g (0.08 mol) of 3,5-dimethylphenol were further added. ) Is continuously charged into the flask as the reaction proceeds.
The polycondensation was performed for 5 minutes. Thereafter, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (A4).

Synthesis Example 5 In an autoclave, 69.2 g (0.64 mol) of m-cresol, 19.5 g (0.16 mol) of 3,5-xylenol 58.4 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde: 0.72 mol) ) Oxalic acid dihydrate 0.90 g (7.14 × 10 ⁻³ mol) 54.4 g of water and 228 g of dioxane were charged and polycondensation was performed for 10 hours, and a resin was recovered in the same manner as in Synthesis Example 3. This resin is referred to as resin (A5).

Synthesis Example 6 In a flask similar to that used in Synthesis Example 1, 26.0 g (0.24 mol) of m-cresol 78.2 g (0.64 mol) of 3,5-xylenol 37% by weight aqueous solution of formaldehyde 14.6 g (formaldehyde: 1.80 mol) and oxalic acid dihydrate 0.164 g (1.30 × 10 ⁻³ mol) were charged, the flask was immersed in an oil bath, and the internal temperature was maintained at 100 ° C. After performing polycondensation for 30 minutes with stirring, 104 g (0.96 mol) of m-cresol and 20.0 g (0.16 mol) of 3,5-xylenol were further added, and the mixture was further reacted for 70 minutes. Then, the oil bath temperature was increased to 180 ° C., and at the same time, the pressure in the flask was increased to 30 ° C.
The pressure was reduced to ４０40 mmHg to remove water, oxalic acid, unreacted formaldehyde, m-cresol and 3,5-xylenol. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (A6).

Synthesis Example 7 In a flask similar to that used in Synthesis Example 1, 95.2 g (0.88 mol) of m-cresol 2,44.4 g (0.18 mol) of 2,3,5-trimethylphenol 37 weight 154 g (formaldehyde: 1.90 mol) and 1.82 g (0.014 mol) of oxalic acid dihydrate were charged into the flask, and the flask was immersed in an oil bath and stirred while maintaining the internal temperature at 100 ° C. Polycondensation was performed for 90 minutes, and then 23.8 g (0.22 mol) of m-cresol and 97.6 g (0.72 mol) of 2,3,5-trimethylphenol were further added, and polycondensation was further performed for 60 minutes. Then, the oil bath temperature was raised to 180 ° C., and simultaneously the pressure in the flask was reduced to 30 to 40 mmHg, and water, oxalic acid, unreacted formaldehyde, m-cresol and 2,3,5
-The trimethylphenol was removed. Next, Synthesis Example 1
The resin was recovered in the same manner as described above. This resin is converted into a resin (A
7).

Synthesis Example 8 Resin (A7) was dissolved in ethyl cellosolve acetate so as to have a solid content of 20% by weight, and 1.8 times methanol and an equal amount of water were added to the weight of the resin solution. And left to stir. After being separated into two layers by leaving to stand, the resin solution layer (lower layer) is taken out, concentrated,
After dehydration and drying, the resin was recovered. This resin is referred to as resin (A8).

<Synthesis of Resin B> Synthesis Example 9 In a flask similar to that used in Synthesis Example 1, m-cresol 108.0 g (1.00 mol) 24.3 g of 37% by weight aqueous formaldehyde solution (formaldehyde: 0. 30 mol) and oxalic acid dihydrate 0.30 g (2.40 × 10 ⁻³ mol) were charged, the flask was immersed in an oil bath, and polycondensation was performed for 40 minutes while maintaining the internal temperature at 100 ° C. Next, the resin (A
The resin was recovered in the same manner as in the synthesis of 1). This resin,
It is called resin (B1).

Synthesis Example 10 In a flask similar to that used in Synthesis Example 1, m-cresol 64.9 g (0.06 mol) p-cresol 43.3 g (0.40 mol) 37% by weight aqueous formaldehyde solution 3 g (formaldehyde: 0.25 mol) and oxalic acid dihydrate 0.30 g (2.40 × 10 ⁻³ mol) were charged, and the flask was immersed in an oil bath for 30 minutes while maintaining the internal temperature at 100 ° C. Polycondensation was performed. Next, Synthesis Example 1
The resin was recovered in the same manner as described above. The resin (B)
2).

<Abbreviation of hydroxy compound> In the following, 1,1-bis (4-hydroxyphenyl) -1- [4-
{1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane is compound (A1), 1,1-bis (4-hydroxyphenyl) -1- [4- (4-hydroxybenzyl) phenyl] ethane Is abbreviated as compound (A2).

<Synthesis of 1,2-naphthoquinonediazide compound (B)> Example 1 42.5 g (0.10 mol) of compound (A1) was placed in a flask equipped with a stirrer, a dropping funnel and a thermometer under light shielding. 53.7 g (0.20 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 100 g of dioxane were charged and dissolved with stirring. Then, the flask was immersed in a water bath controlled at 30 ° C. When the internal temperature became constant at 30 ° C, 22.3 g (0.22 mol) of triethylamine was added to the solution, and the internal temperature did not exceed 35 ° C. Was slowly dropped using a dropping funnel as described above. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid to cause precipitation, and then the precipitate was collected by filtration at 40 ° C.
The product was dried all day and night with a heating vacuum dryer controlled by the above-mentioned method to obtain a compound. The obtained compound is called compound (B1).

Example 2 42.5 g (0.10 mol) of compound (A1) 67.2 g (0.25 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 27.8 g (0.275 mol) of triethylamine ) Was used in the same manner as in Example 1 to obtain a compound (B2).

Example 3 42.5 g (0.10 mol) of compound (A1) 53.7 g (0.20 mol) of 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 22.3 g (0.22 mol) of triethylamine ) Was used in the same manner as in Example 1 to obtain a compound (B3).

Example 4 39.6 g (0.10 mol) of compound (A2) 53.7 g (0.20 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 22.3 g (0.22 mol) of triethylamine ) Was used in the same manner as in Example 1 to obtain a compound (B4).

<Synthesis of Another 1,2-Quinone Diazide Compound> Synthesis Example 11 10.0 g of resin (B2) 16.6 g of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 6.86 g of triethylamine were used. A quinonediazide compound (I) was obtained in the same manner as in Synthesis Example 11.

Examples 5 to 14, Comparative Examples 1 to 3 Resin (A), naphthoquinonediazide compound (B), optionally hydroxy compounds A1, A2, other quinonediazide compounds, and a solvent were mixed as shown in Table 1. Then, after making a homogeneous solution, the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution of the composition of the present invention. The obtained solution is applied on a silicon wafer having a silicon oxide film by using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a 1.2 μm-thick resist film. Exposure, using a wavelength of 436 nm (g-line) or 365 nm (i-line) as described above, developing, rinsing and drying, and then sensitivity, resolution, residual film ratio, developability, heat resistance of the resist film. Evaluation was made on the properties and pattern shapes. Table 2 shows the results.

Examples 5 to 11 and Comparative Examples 1 and 2
Irradiates g-rays, Examples 12 to 14 and Comparative Example 3
Irradiated i-line.

[0081]

[Table 1]

[0082]

[Table 2]

Note: Each addition amount is shown in parts by weight. Note: Quinonediazide compounds (II) to (IV)
Is: (II); a condensate of 1 mol of 2,3,4-trihydroxybenzophenone and 3.0 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride. (III); 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-
Condensate with 3.6 mol of 5-sulfonic acid chloride. (IV); 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5
-Condensates with 4.0 moles of sulfonic chloride. Note: The dissolution accelerator is as follows. (S1); 1,1,1-tris (4-hydroxyphenyl) ethane (S2); 1,1-bis (4-hydroxyphenyl)-
1-phenylethane (S3); m-cresol 108.0 g (1.00 mol), 37% by weight formaldehyde aqueous solution 20.3 g
(Formaldehyde: 0.25 mol) and oxalic acid 2
An alkali-soluble novolak resin (M) synthesized in the same manner as in Synthesis Example 1 except that 0.30 g (2.40 × 10 ⁻³ mol) of hydrate was charged and the internal temperature was maintained at 100 ° C. and condensed for 30 minutes.
w = 520) Note: The types of solvents are as follows. (Α); ethyl cellosolve acetate. (Β); ethyl 2-hydroxypropionate.

[0084]

According to the present invention, 1,2 can be obtained by the production method of the present invention.
-Naphthoquinonediazide compound as alkali-soluble resin
The radiation-sensitive resin composition formed in combination is effectively suppressed in generation of scum and is excellent in developability, high sensitivity, and heat resistance, and can be suitably used as a positive resist excellent in residual film property. .

Continuation of Front Page (72) Inventor Chozo Okuda 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-4-37551 (JP, A) JP-A-4-25358 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 317/14 C07C 315/04 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the general formula (1): [In the general formula (1), R ^{1 to} R ⁴ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a hydroxyl group, and each of R ^{1 to} R ⁴ is different from each other by at least two kinds. ^May be bonded to each benzene ring as a group, provided that any of R ¹ , R ² and R ⁴ contains at least one hydroxyl group; R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted Or an unsubstituted alkyl group;
a, b and d each independently represent an integer of 0 to 5;
An integer of 4 wherein at least one of b and d is not 0], and 1,2-
Naphthoquinonediazide-4-sulfonyl chloride or
Is 1,2-naphthoquinonediazide-5-sulfonyl chloride
A general formula (2) comprising an esterification reaction with a ride : [In the general formula (2), R ¹ ~R ⁴ is a substituted or unsubstituted alkyl group independently, substituted or unsubstituted aryl group or OD group (wherein, D represents a hydrogen atom or a 1,2-naphthoquinonediazide - 4-sulfonyl group or 1,2-na
And each of R ^{1 to} R ⁴ may be bonded to a benzene ring as two or more different groups, provided that R ¹ , R 2
Any of ² and R ⁴ contains at least one 1,2-naphthoquinonediazide group; R ⁵ , R ⁶ , a,
b, c and d are as defined with respect to the general formula (1).] A method for producing a 1,2-naphthoquinonediazide compound represented by the formula: 2. The method according to claim 1, wherein the esterification reaction is performed in the presence of triethylamine.