JPH09194413A - Pentaphenol compound, production method and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new phenol compound useful as an alkali soluble low molecular weight additive to a photo sensitive resin composition, an intermediate for a photosensitive ingredient, etc. SOLUTION: This compound is a pentaphenol compound expressed by formula I (R<1> -R<5> are each H, 1,2-naphthoquinonediazide-4- or -5-sulfonyl; R<6> -R<14> are each H, a 1-6C alkyl, a 1-6C alkoxy, a 2-6C alkenyl, a 3-6C cycloalkyl; R<15> is H, a 1-6C alkyl, a 2-6C alkenyl, a 3-6C cycloalkyl), e.g. a compound of formula II. The compound of formula I is obtained by carrying out the reaction of a pentaphenol compound of formula III with 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide. The compound of formula III is obtained by carrying out the reaction of a dimethylol compound of formula IV with a phenol compound necessary for obtaining the compound of formula IV. From the compound of formula I or its quinonediazidesulfonic acid ester, a resin having a well balanced properties such as high sensitivity, high resolving power, high heat resistance, various properties of resist, etc., is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pentaphenol-based compound, a method for producing the same, and its application to the resist field.

[0002]

2. Description of the Related Art It is generally known that a compound having a phenolic hydroxyl group is converted to a quinonediazide sulfonate and used as a photosensitizer in a photosensitive resin composition for semiconductor fine processing. That is, when a composition containing a compound having a quinonediazide group and an alkali-soluble resin is applied onto a metal substrate and irradiated with light having a wavelength of 300 to 500 nm, the quinonediazide group is decomposed to generate a carboxyl group, which is insoluble in alkali. The composition is used as a positive resist by taking advantage of the fact that the state changes to an alkali-soluble state. This positive type resist has a feature of being superior in resolution as compared with a negative type resist, and is therefore used for manufacturing various integrated circuits for semiconductors. In recent years, integrated circuits in the semiconductor industry have become finer with higher integration, and nowadays, submicron pattern formation is required. Among them, the lithography process occupies an important position in the production of integrated circuits, and even positive resists are required to have higher resolution, that is, higher γ value.

With respect to resist materials containing a quinonediazide compound and an alkali-soluble resin, many proposals have hitherto been made on combinations of the respective components. For example, Japanese Unexamined Patent Publication No. 1-189644 (= USP 5,153,096) describes the use of a triphenylmethane compound having at least two phenolic hydroxyl groups converted to a quinonediazidesulfonic acid ester as a photosensitizer. . However, even if such a known photosensitizer is used, there is a limit as a resist for the present ultra-fine processing for producing ultra-high integrated circuits, that is, so-called submicron lithography. Therefore, various studies have been conducted on a photosensitizer for improving resist performance such as sensitivity, resolution and heat resistance.

On the other hand, studies have been conducted to improve the sensitivity of resists by using a compound having a phenolic hydroxyl group as an alkali-soluble low molecular weight additive in a photosensitive resin composition containing a quinonediazide compound and an alkali-soluble resin. .

[0005]

The object of the present invention is to use as an alkali-soluble low molecular weight additive in a photosensitive resin composition, and a quinone diazide sulfonate esterified photosensitive agent for the photosensitive resin composition. It is to provide a novel phenolic compound which is useful as a component.

Another object of the present invention is to use such a phenolic compound or a quinonediazide sulfonic acid ester thereof to obtain high sensitivity, high resolution, high heat resistance, good profile, good focus tolerance, small development residue, etc. An object of the present invention is to provide a photosensitive resin composition in which various resist performances are balanced.

[0007]

As a result of intensive studies, the present inventors have found a phenolic compound having a specific structure having five phenolic hydroxyl groups, and this compound has a low alkali solubility in a photosensitive resin composition. The present invention has been completed by finding that it is useful as a molecular weight additive and that excellent results are obtained even when a quinonediazide sulfonate ester of this compound is used as a photosensitizer.

Therefore, the present invention provides a pentaphenol compound represented by the following formula (I).

[0009]

In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of each other represent hydrogen or 1,2-naphthoquinonediazide-4- or -5-sulfonyl, R ⁶ , R ⁷ ,
R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R < ¹¹ >, R <^12> , R <^13> and R < ¹⁴ > are each independently hydrogen, alkyl having 1 to 6 carbons, and 1 to 6 carbons.
Alkoxy, C2-C6 alkenyl, or C6
Represents the following cycloalkyl, R ¹⁵ is hydrogen, 1 to 1 carbon atoms
6 alkyl, alkenyl having 2 to 6 carbons or 6 carbons
Represents the following cycloalkyl:

In the formula (I), R ¹ , R ² , R ³ and R
^A compound in which ⁴ and R ⁵ are all hydrogen, that is, the following formula (Ia)

[0012]

(Wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ have the above meanings)
The pentaphenol compound represented by the following formula (II)

[0014]

The dimethylol compound represented by the formula (wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹⁵ have the above-mentioned meanings) is necessary for obtaining the compound of the formula (Ia). It can be produced by reacting with a phenolic compound.

The pentaphenol compound of formula (Ia) is added to 1,2-naphthoquinonediazide-4- or -5-
By reacting with a sulfonyl halide, the compound of formula (I)
And an ester in which at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is 1,2-naphthoquinonediazide-4- or -5-sulfonyl can be produced.

The pentaphenolic compound represented by the above formula (Ia) is useful as a precursor for quinonediazide sulfonic acid esterification, and the compound itself is used as an alkali-soluble low molecular weight additive for a photosensitive resin composition. It can also be used. Further, in the formula (I),
One of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is 1,2-naphthoquinonediazide-4- or-5-sulfonyl,
A pentaphenol ester in which the rest are hydrogen or 1,2-naphthoquinonediazide-4- or -5-sulfonyl independently of each other is useful as a photosensitizer for a photosensitive resin composition.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the formula (I), R ⁶ , R ⁷ ,
Alkyl represented by ^{R 8, R 9, R 10} , R 11, R 12, R 13, R 14 and R ¹⁵ are methyl, ethyl, propyl, butyl, tert- butyl and the like, those having 1 to 6 carbon atoms And alkenyl can also be vinyl, allyl, etc.
It can have 2 to 6 carbon atoms, and the cycloalkyl can also have 6 or less carbon atoms, such as cyclopentyl and cyclohexyl. Also, R ⁶ ,
Alkoxy represented by ^{R 7, R 8, R 9} , R 10, R 11, R 12, R 13 and R ¹⁴ are methoxy, ethoxy, propoxy, etc., can be of 1 to 6 carbon atoms. R
⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R
Each of ¹⁴ is independently hydrogen, alkyl or alkoxy, and is preferably hydrogen or alkyl having 1 to 4 carbon atoms. It is also advantageous for at least one of R ⁶ and R ⁷ and at least one of R ⁸ and R ^{9 to be} each alkyl. Further R
¹⁵ is advantageously hydrogen or alkyl, especially hydrogen or methyl.

In the formula (I), R ¹ , R ² , R ³ and R
Pentaphenolic ester in which at least one of ⁴ and R ⁵ is 1,2-naphthoquinonediazide-4- or -5-sulfonyl is similar to near or moderate ultraviolet rays or far ultraviolet rays (including excimer laser). It is useful as a photosensitizer sensitive to various radiations, and can be a photosensitive resin composition containing such a photosensitizer together with an alkali-soluble resin. Also, R ¹ , R ² , R in the formula (I)
A pentaphenol compound represented by the above formula (Ia) in which ³ , R ⁴ and R ⁵ are all hydrogen is useful as a precursor of such a photosensitizer, and the compound itself is
It can also be used as an alkali-soluble low molecular weight additive for a photosensitive resin composition containing an alkali-soluble resin and a quinonediazide-based photosensitizer.

A compound in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the formula (I) are all hydrogen, that is, the above formula (Ia)
The pentaphenol compound represented by
It can be produced by subjecting a dimethylol compound represented by to a condensation reaction with a phenolic compound necessary for obtaining a compound of formula (Ia) in the presence of an acidic catalyst. The phenolic compound necessary to obtain the compound of formula (Ia) is specifically represented by the following formulas (III) and (IV).

[0021]

In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have the above-mentioned meanings. By using two different phenolic compounds represented by the formulas (III) and (IV), the formula (Ia)
It is possible to produce a compound in which the benzene ring to which R ¹¹ and R ¹² are bonded and the benzene ring to which R ¹³ and R ¹⁴ are bonded in are different from each other, but in general, a compound represented by the formula (III) or (IV) is used. A compound in which the benzene ring to which R ¹¹ and R ¹² are bonded and the benzene ring to which R ¹³ and R ¹⁴ are bonded in formula (Ia) are advantageously prepared by using only one phenolic compound To be done.

The dimethylol compound represented by the above formula (II), which is the starting material for this reaction, has the following formula (V)

A phenolic group 3 represented by the formula (wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹⁵ have the above-mentioned meanings)
It is obtained by reacting a nucleophile compound with formaldehyde in the presence of an alkali catalyst to form dimethylol. Further, the phenolic trinuclear compound represented by the formula (V) has the following formula (VI)

[0025]

The carbonyl compound represented by the formula (wherein R ¹⁰ and R ¹⁵ have the above-mentioned meanings) is a phenolic compound necessary for obtaining a trinuclear compound of the formula (V) in the presence of an acidic catalyst. It can be produced by a condensation reaction with.
The phenolic compound necessary for obtaining the trinuclear compound of the formula (V) is specifically defined by the following formulas (VII) and (VII
Indicated by I).

[0027]

In the formula, R ⁶ , R ⁷ , R ⁸ and R ⁹ have the above-mentioned meanings. By using two different phenolic compounds represented by the formulas (VII) and (VIII), the formula (V)
A compound in which the benzene ring to which R ⁶ and R ⁷ are bonded and the benzene ring to which R ⁸ and R ⁹ are bonded can be prepared in A compound in which the benzene ring to which R ⁶ and R ⁷ are bonded and the benzene ring to which R ⁸ and R ⁹ are bonded in formula (V) are the same can be advantageously produced by using only one phenolic compound. To be done.

A phenolic trinuclear compound of the formula (V) was prepared by using only the phenolic compound of the formula (VII) in the condensation reaction with the carbonyl compound of the formula (VI), and using this dimethylol compound. When the condensation reaction with only the phenolic compound represented by the formula (III) is carried out,
A pentaphenol compound represented by the following formula (Ib) is obtained.

[0030]

In the formula, R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹² and R ¹⁵ have the above-mentioned meanings.

The reaction of starting from the carbonyl compound of the formula (VI) to the pentaphenolic compound of the formula (Ia) and further to the ester form thereof will be described in sequence below.

As the carbonyl compound of the formula (VI) used in the reaction for producing the phenolic trinuclear compound of the formula (V), the benzene ring is substituted with alkyl or the like within the range corresponding to the definition of the formula. Examples thereof include hydroxybenzaldehydes, alkylhydroxyphenylketones, alkenylhydroxyphenylketones and cycloalkylhydroxyphenylketones. Among them, 2-, 3- or 4-hydroxybenzaldehydes (further, the benzene ring is alkyl And the like, and hydroxyacetophenones such as 2-, 3- or 4-hydroxyacetophenone (wherein the benzene ring may be further substituted with alkyl or the like). Used for. Further, as the phenolic compound represented by the formula (VII) and / or (VIII) condensed with the carbonyl compound, phenol and its nucleus alkyl, alkoxy, alkenyl or Examples thereof include cycloalkyl-substituted compounds, and among them, cresol, xylenol, tert-butylphenol, tert-butylcresol and the like are advantageously used.

In this reaction, the phenolic compound of the formula (VII) and / or (VIII) is preferably used in a molar ratio of 2 to 10, more preferably 2 to 5 with respect to the carbonyl compound of the formula (VI). Used in a molar ratio of. If this molar ratio is too low, the selectivity of the reaction will be lowered, and if it is too high, the raw material cost will be high, such being undesirable. When one compound represented by the formula (VII) or (VIII) is used as the phenolic compound, the phenolic compound may be used in the above molar ratio, and is also represented by the formulas (VII) and (VIII). In the case of producing a compound in which the benzene ring to which R ⁶ and R ⁷ are bonded and the benzene ring to which R ⁸ and R ⁹ are bonded in the formula (V) are different from each other, It is preferable to use the phenolic compound in an approximately equimolar amount such that the total of both is in the above molar ratio with respect to the carbonyl compound of the formula (VI).

This reaction is usually carried out in the presence of an acid catalyst. The acid catalyst may be either an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as p-toluenesulfonic acid. The acid catalyst is used usually in an amount of 1 equivalent or less, preferably 0.01 to 0.5 equivalent, based on the carbonyl compound of the formula (VI). This reaction is preferably carried out in a solvent, and the reaction solvent in this case is an aromatic solvent, which is also an aromatic hydrocarbon solvent,
Alternatively, it is preferably an alcohol solvent. Examples of the aromatic hydrocarbon solvent include benzene, toluene and xylene, and among them, toluene is preferably used. Further, as the alcohol solvent, methanol, ethanol,
Examples thereof include isopropanol, and among them, methanol is preferably used. The reaction solvent is generally 0.5 to 5 times by weight, based on the amount of the phenolic compound,
It is preferably used in the range of 1 to 3 times by weight, more preferably 1 to 2 times by weight.

The carbonyl compound represented by the formula (VI) and the formula
The reaction with the phenolic compound represented by (VII) and / or (VIII) is usually in the range of 40 to 120 ° C, preferably 6
It is performed at a temperature in the range of 0 to 100 ° C. for about 2 to 10 hours. This reaction usually proceeds at atmospheric pressure.

By such a reaction, the phenolic trinuclear compound represented by the formula (V) is obtained, and the dimethylolation thereof can be carried out by reacting with formaldehyde in the presence of an alkali catalyst. Examples of the alkali catalyst used here include inorganic bases such as sodium hydroxide, potassium hydroxide and potassium carbonate, and organic bases such as tetramethylammonium hydroxide, and among them, inorganic bases such as sodium hydroxide. Is preferably used. The amount of the alkali catalyst is, based on the phenol-based trinuclear compound represented by the formula (V),
Usually, a range of 0.5 to 6 times by mole, more preferably 1 to 4 times by mole is preferable. If the amount of the alkali catalyst is too small, the reaction time becomes long, and if the amount is too large, the selectivity of the reaction becomes poor. Formaldehyde is usually 1 to 8 mole times, preferably 3 to, the phenol-type trinuclear compound of the formula (V).
6 moles are used.

This reaction is usually carried out in a solvent. As a reaction solvent, tetrahydrofuran, dioxane,
Water, polar solvents such as methanol are preferred, and among them,
Water or a mixed solvent of water and another polar solvent is preferably used. The reaction solvent is phenol-based 3 represented by the formula (V).
It is usually used in an amount of 1 to 10 times by weight, preferably 2 to 6 times by weight, the amount of the nuclear compound. This reaction is usually 0 to 80 ° C.
At a temperature in the range of, preferably in the range of 30 to 50 ° C. If the reaction temperature is too high, the selectivity of the reaction deteriorates, and if it is too low, the reaction becomes slow.

By such a reaction, the dimethylol compound represented by the formula (II) is obtained. By reacting this dimethylol compound with a phenolic compound represented by the formula (III) and / or (IV), a pentaphenolic compound of the formula (Ia) can be obtained. The phenolic compound used in this reaction can be phenol or a nuclear alkyl, alkoxy, alkenyl or cycloalkyl substituted product thereof in a range corresponding to the definition of formula (III) or (IV), and specifically, Phenol, cresol,
Examples include xylenol, tert-butylphenol, tert-butylcresol and the like.

The dimethylol compound of formula (II) and the formula (III)
And / or (IV) in the reaction with the phenolic compound, the phenolic compound generally has a molar ratio of 2 to 50, preferably 4 to 20 with respect to the dimethylol compound of the formula (II). Used in. When only one compound represented by the formula (III) or (IV) is used as the phenolic compound, the phenolic compound may be used in the above molar ratio, and in the formulas (III) and (IV), When two kinds of compounds shown in the formula (Ia) are used to produce a compound in which the benzene ring to which R ¹¹ and R ¹² are bonded and the benzene ring to which R ¹³ and R ¹⁴ are bonded are different, It is preferable to use approximately the same molar amount of the two types of phenolic compounds, so that the total of both is in the above molar ratio with respect to the dimethylol compound of formula (II).

This reaction is usually carried out in the presence of an acid catalyst, which may be an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as p-toluenesulfonic acid.
Of these, p-toluenesulfonic acid is preferably used. The acid catalyst is a dimethylol compound of the formula (II),
It is usually used in an amount of 1 equivalent or less, preferably 0.1 to 0.5 equivalent.

The reaction is preferably carried out in a solvent, and the reaction solvent in this case is preferably an alcohol solvent such as methanol or an aromatic solvent. As the aromatic solvent, aromatic hydrocarbons such as benzene,
Toluene, xylene, etc. are mentioned, and among them, toluene is preferably used. The reaction solvent, for example, the aromatic solvent, based on the amount of the phenolic compound as the reaction raw material,
Generally 0.5 to 5 times by weight, preferably 1 to 3 times by weight,
More preferably, it is used in the range of 1 to 2 times by weight. The reaction is usually in the range from 10 ° C to the boiling point, preferably 15
It is carried out at a temperature in the range of -60 ° C for about 2-3 hours. This reaction usually proceeds under atmospheric pressure.

When the reaction is carried out near room temperature in an aromatic solvent, the reaction proceeds with the progress of the reaction, and when the reaction is carried out at a temperature higher than that, by cooling to near room temperature after completion of the reaction, the desired product is obtained. A pentaphenol-based compound of formula (Ia) precipitates as crystals. By taking out the crystals, a crude product is obtained, and then any purification operation can be performed. For example, since this compound has a low solubility in an aromatic solvent at room temperature, it can be purified by performing crystallization from an aromatic solvent or repeating it as necessary. The crystallization solvent used in this case may be the same as or different from that used in the reaction.

When the pentaphenol compound of the formula (Ia) is used as it is as an alkali-soluble low molecular weight additive or a quinonediazide sulfonate ester is used as a photosensitizer in a photosensitive resin composition for semiconductor production,
It is preferable to dissolve the crude product in a solvent having a solubility in water of 9 g / 100 g or less and then wash and separate the solution to reduce the metal content. Here, that the solubility in water is 9 g / 100 g or less means that the maximum amount soluble in 100 g of water at 20 ° C. is 9 g or less. The solvent used here preferably has a solubility of the pentaphenol compound represented by the formula (Ia) at 20 ° C. of 1 g / 100 g or more. Such solvents include, for example,
Examples thereof include acetic acid esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, and ketones such as methyl isobutyl ketone and 2-heptanone. Among them, ethyl acetate is preferably used. In the solution containing the pentaphenol compound of the formula (Ia) in which the metal is reduced in this way, an aromatic solvent may be further added to crystallize the desired product. The aromatic solvent used here may be the same as or different from that used in the reaction, but toluene is preferably used.

Specific examples of the pentaphenol-based compound of the formula (Ia) thus obtained include those shown below.

[0046]

[0047]

[0048]

[0049]

The pentaphenol compound represented by the formula (Ia) can be used as an alkali-soluble low molecular weight additive in a photosensitive resin composition containing an alkali-soluble resin and a quinonediazide-type photosensitizer.
A quinonediazide sulfonic acid ester can be used as a photosensitizer.

In the case of quinonediazide sulfonic acid esterification, various sulfonic acid derivatives having a 1,2-quinonediazide skeleton are used as an esterifying agent, preferably 1,2-naphthoquinonediazide-4- or-
5-sulfonyl halide is used. The halogen constituting the sulfonyl halide can be, for example, chlorine or bromine, but is usually preferably chlorine, and therefore 1,2-naphthoquinonediazide-4- or -5
-Sulfonyl chloride is preferably used as esterifying agent. In addition, 1,2-naphthoquinonediazide-
It is also possible to use a mixture of 4-sulfonyl halide and 1,2-naphthoquinonediazide-5-sulfonyl halide. In the esterification reaction, the 1,2-naphthoquinonediazide-4- and / or -5-sulfonylhalide is usually used in a molar ratio of 1.2 to 5, and preferably to the pentaphenol compound represented by the formula (Ia). It is used in a molar ratio of 1.4 to 2.5.

This esterification reaction is usually carried out in the presence of a dehydrohalogenating agent. The dehydrohalogenating agent is generally a basic compound such as sodium carbonate,
An inorganic base such as sodium hydrogen carbonate, ethylamine,
Ethanolamine, diethylamine, diethanolamine, triethylamine, N, N-dimethylaniline,
Mention may be made of amines such as N, N-diethylaniline. The dehydrohalogenating agent is a 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide,
Usually a molar ratio of 1.05-1.5, preferably 1.05-1.2,
More preferably, it is used in a molar ratio of 1.1 to 1.2.

The esterification reaction is usually carried out in a solvent. Examples of the reaction solvent include ethers, lactones, and aliphatic ketones, among which dioxolane,
It is preferably selected from 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, acetone and 2-heptanone. These can be used alone or in combination of two or more, and 1,4-dioxane is particularly preferable. The reaction solvent is usually in the range of 2 to 6 times by weight, based on the total amount of the pentaphenol compound represented by the formula (Ia) and the quinonediazidesulfonyl halide,
It is preferably used in an amount of 3 to 5 times by weight, more preferably 4 to 5 times by weight.

This esterification reaction proceeds sufficiently under normal pressure near room temperature, and generally, a temperature in the range of 20 to 30 ° C. is adopted and is carried out for about 2 to 10 hours.

After completion of the reaction, neutralize with an acid such as acetic acid,
After filtering the solid, the filtrate is mixed with a dilute aqueous acid solution, for example, an aqueous acetic acid solution having a concentration of about 0.1 to 2% by weight.
The target ester begins to precipitate. The ester can be taken out by filtering, washing and drying this.

In this esterification reaction, although it depends on the molar ratio of the 1,2-naphthoquinonediazidesulfonyl halide used, R ¹ , R ² in the formula (I),
Any one of R ³ , R ⁴ and R ⁵ becomes a quinonediazidesulfonyl (monoester), any two of them become a quinonediazidesulfonyl (diester), and any three of them become a quinonediazidesulfonyl. Obtained as a mixture of two or more kinds (triester), those in which any four of them are quinonediazidesulfonyl (tetraester), and those in which all five of them are quinonediazidesulfonyl (pentaester). To be This mixture can usually be used as it is as a photosensitive agent.

The thus esterified compound can be advantageously used as a photosensitizer which is sensitive to radiation such as near to moderate ultraviolet rays and far ultraviolet rays (including excimer laser). This photosensitizer exhibits a particularly high effect when it is combined with an alkali-soluble resin such as a novolac resin to form a photosensitive resin composition for a positive resist.

In the formula (I), R ¹ , R ² , R ³ and R
^A compound in which ⁴ and R ⁵ are all hydrogen, that is, a compound of formula (I
When the pentaphenol compound represented by a) is used as an alkali-soluble low molecular weight additive in a photosensitive resin composition, this additive is used in combination with an alkali-soluble resin and a quinonediazide-based photosensitizer.

A photosensitive resin composition is formed whether the pentaphenol compound of the formula (Ia) is used as an alkali-soluble low molecular weight additive or when it is used as a photosensitizer by converting it into a quinonediazide sulfonic acid ester. The alkali-soluble resin is preferably a novolac resin obtained by condensing a compound having at least one phenolic hydroxyl group and an aldehyde in the presence of an acid catalyst. The type of novolac resin is not particularly limited, and various types used in the resist field can be used. Examples of the phenolic compound that is a raw material of the novolac resin include m-cresol, p-cresol, o-cresol, 2,5-xylenol, 3,5-
Examples include xylenol, 3,4-xylenol, 2,3,5-trimethylphenol, 2-tert-butyl-5-methylphenol and tert-butylhydroquinone. As the aldehyde which is the other raw material of the novolac resin, formaldehyde, acetaldehyde, benzaldehyde, glyoxal, salicylaldehyde and the like can be mentioned. In particular, formaldehyde is industrially mass-produced as an aqueous solution of about 37% by weight, which is convenient.

One or two of these phenolic compounds
The novolak resin can be obtained by condensing one or more species and one or more species of aldehydes in the presence of an acid catalyst. As the acid catalyst, an organic acid, an inorganic acid, a divalent metal salt or the like is used, and specific examples thereof include oxalic acid, acetic acid and p.
-Toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, zinc acetate and the like. The condensation reaction can be performed according to a conventional method, for example, at a temperature in the range of 60 to 120 ° C. for 2 to 30
It takes about an hour. The reaction may be performed in a bulk or in a suitable solvent.

The resulting novolak resin is subjected to gel permeation chromatography (GP) by subjecting it to an operation such as fractionation for the purpose of reducing the development residue of the resist.
In the pattern by C) (using a UV254 nm detector), the area ratio of the components having a polystyrene-equivalent molecular weight of 900 or less is 25% or less with respect to the total pattern area excluding the pattern area of the unreacted phenolic compound, and further Two
It is preferably set to 0% or less. When fractionation is performed, a novolac resin is used as a good solvent, for example, alcohol such as methanol or ethanol, acetone or methyl ethyl ketone, ketone such as methyl isobutyl ketone, ethylene glycol ether such as ethyl cellosolve, and ethylene such as ethyl cellosolve acetate. Dissolving in glycol ether ester, cyclic ether such as tetrahydrofuran, etc., and pouring this solution into water to precipitate high molecular weight components, or this solution,
A method of mixing with a poor solvent such as pentane, hexane, or heptane to perform liquid separation can be adopted.

It is effective to add an alkali-soluble phenolic compound having a molecular weight of 900 or less to the novolak resin which has been subjected to such a fractionation operation to increase the high molecular weight component,
As such an alkali-soluble compound, a pentaphenol compound of formula (Ia) can be used. When the pentaphenol-based compound of formula (Ia) is converted into a quinonediazide sulfonic acid ester and used as a photosensitizer, another phenol-based compound having a molecular weight of 900 or less can be used as an additive. Is preferably one having at least two phenolic hydroxyl groups in its molecular structure.
-275955 (= EP-A-358,871), JP-A-2-2560, and the like. When an alkali-soluble phenolic compound having a molecular weight of 900 or less is used, it is 3 to 4 based on the total solid content in the photosensitive resin composition.
It is preferably contained in the range of 0% by weight.

When the pentaphenol-based compound of formula (Ia) is used as an alkali-soluble low molecular weight additive in the photosensitive resin composition, the quinonediazide-based photosensitizer constituting the photosensitive resin composition is a compound having a phenolic hydroxyl group. It can be an o-quinonediazide sulfonate. The phenolic compound to be esterified with a quinonediazide sulfonate is preferably one having at least two phenolic hydroxyl groups in the molecule, and examples thereof include polyhydroxybenzophenones such as trihydroxybenzophenone, tetrahydroxybenzophenone and pentahydroxybenzophenone; 4,4-trimethyl-2 ', 4', 7-trihydroxyflavan, 2,4
4-trimethyl-2 ', 3', 4 ', 7,8-pentahydroxyflavan, 4- (1', 2 ', 3', 4 ',
4'a, 9'a-hexahydro-6'-hydroxyspiro [cyclohexane-1,9'-xanthene] -4'a
-Yl) resorcinol, 4- (1 ', 2', 3 ',
4 ', 4'a, 9'a-Hexahydro-6'-hydroxy-5'-methylspiro [cyclohexane-1,9'-
Xanthene] -4'a-yl) -2-methylresorcinol, such as polyhydroxyflavans, 2 to
A compound having 6 benzene rings bonded with an aliphatic hydrocarbon-based linking group and having at least two phenolic hydroxyl groups in the molecule can be used. Such a phenolic compound is condensed with an o-quinonediazide sulfonyl halide such as 1,2-naphthoquinonediazide-4- or -5-sulfonyl chloride,
Can be a photosensitizer. Of course, even when the pentaphenol compound of formula (Ia) is used as an alkali-soluble low molecular weight additive, the pentaphenol compound of formula (Ia) converted to a quinonediazide sulfonate is used as a photosensitizer. You can also These photosensitizers may be used alone or in combination of two or more.

When the pentaphenol compound of the formula (Ia) is converted into a quinonediazide sulfonic acid ester and used as a photosensitizer, a 1,2-quinonediazide sulfonic acid ester of another phenol compound is used in combination, if necessary. be able to. The quinone diazide sulfonic acid ester used in combination can also be the quinone diazide sulfonic acid ester of the phenolic compound exemplified above, and more specifically, the compounds described in JP-A-5-204148 and JP-A-5-323597. The compounds described in JP-A No. 6-167805 (= EP-A-573,056) and the like can be mentioned.

In the present invention, the total amount of the photosensitizers, including the case where a plurality of photosensitizers are used in combination, is in the range of 10 to 50% by weight based on the total solid content in the photosensitive resin composition. It is preferably contained.

The resist solution containing the photosensitive resin composition is prepared by mixing and dissolving each component in a solvent.
The solvent used here is preferably one which dissolves each component, has an appropriate drying rate, and gives a uniform and smooth coating film after the solvent is evaporated. Such solvents include glycol ether esters such as propylene glycol monomethyl ether acetate, ethyl cellosolve acetate and methyl cellosolve acetate, esters such as ethyl pyruvate, n-amyl acetate and ethyl lactate,
Ketones such as 2-heptanone, cyclic esters such as γ-butyrolactone, others described in JP-A-2-220056, JP-A-4-362645, JP-A-4-367863. And the like described in the publication. As the solvent, each compound may be used alone or in combination of two or more kinds.

The resist solution or photosensitive resin composition thus obtained may further contain a small amount of resin or dye as an additive, if necessary.

[0068]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the used amount are based on weight unless otherwise specified.

Synthesis Example 1: Preparation of 4,4 '-(4-hydroxybenzylidene) di-2,6-xylenol In a 1 liter four-necked flask, 145.30 g of 2,6-xylenol and 36-hydroxybenzaldehyde 36 were charged. .3
1 g, 5.66 g of p-toluenesulfonic acid and 236.10 g of methanol were charged and dissolved, the temperature was raised to the reflux temperature, and the mixture was further stirred at that temperature for 8 hours. After the reaction,
600 g of ethyl acetate was charged, washed with water and then concentrated.
The concentrated mass was charged with 500 g of toluene, cooled to 20 ° C., filtered, and the filtered product was rinsed with 400 g of toluene.
The filtrate was dried under reduced pressure at 60 ° C for a whole day and night to give 4,4'-
103.49 g (purity 96.8%) of (4-hydroxybenzylidene) di-2,6-xylenol was obtained. Yield 96.7
%.

Synthesis Example 2: Dimethylolation of 4,4 '-(4-hydroxybenzylidene) di-2,6-xylenol A 500 ml four-necked flask was charged with 4 of 96.8% purity obtained in Synthesis Example 1. , 4 '-(4-hydroxybenzylidene)
Di-2,6-xylenol (34.84 g), sodium hydroxide (6.0 g), water (69.69 g) and methanol (29.87 g) were charged and dissolved, and the temperature was adjusted to 45 ° C. 24.13 g of 37.3% formalin was added dropwise thereto over 1 hour, and the mixture was further stirred for 7 hours after completion of the dropping. After completion of the reaction, the mixture was neutralized with 27.0 g of glacial acetic acid, cooled to 25 ° C, and filtered. Filter 1 water
Rinse with 00g, then vacuum dry at 60 ° C for 24 hours,
4,4 '-[4-hydroxy-3,5-bis (hydroxymethyl) benzylidene] di-2,6-xylenol 3
6.8 g (purity 65.5%) was obtained. Yield 60.7%.

Synthesis Example 3: Preparation of Compound of Formula (9) In a 100 ml four-necked flask, 0.76 g of p-toluenesulfonic acid, 21.63 g of p-cresol and 2 parts of toluene were added.
1.63 g was charged and the temperature was adjusted to 40 ° C., to which 4,4 ′-[4-hydroxy-3,5-bis (hydroxymethyl) benzylidene] having a purity of 65.5% obtained in Synthesis Example 2 was added.
8.17 g of di-2,6-xylenol was divided into 10 parts, charged in 1 hour, and then reacted at the same temperature for 2 hours.
After completion of the reaction, the mixture was filtered and rinsed with 100 g of toluene. The filtrate obtained was mixed with 100 g of toluene and 200 of ethyl acetate.
It was charged into a mixed liquid of g at 60 ° C. and dissolved, and 200 g of ion-exchanged water was further added and stirred to separate the liquid. Then 1%
200 g of an oxalic acid aqueous solution was charged, stirred, and separated to perform demetalization. Next, after washing with 200 g of ion-exchanged water four times, the oil layer was concentrated. To the concentrated mass was added 100 g of toluene, cooled to 20 ° C., filtered, and rinsed with 100 g of toluene. The obtained filtered product was dried under reduced pressure at 60 ° C. for one day to obtain 4,4 ′-[4-hydroxy-3,5-bis (2-hydroxy-5-methylbenzyl) benzylidene] di-2,6-xylenol [ The compound represented by the formula (9): hereinafter referred to as "compound (9)"] was obtained in an amount of 4.16 g (quantitative purity: 93.29%). 4,
The yield based on 4 '-[4-hydroxy-3,5-bis (hydroxymethyl) benzylidene] di-2,6-xylenol was 50.3%.

Mass spectrometry: FD-MS 588 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 2.03 (s, 12H); 2.10 (s, 6H); 3.72 (s, 4H); 4.92 (s, 1H) 6.52 (s, 4H); 6.66 (s, 2H); 6.68 (d, J = 8.25 Hz, 2H); 6.69 (d, J = 1.65 Hz, 2H); 6.78 (dd, J = 1.65 Hz, 8.25 Hz , 2H); 7.92 (s, 2H); 8.20 (s, 1H); 9.31 (s, 2H).

Synthetic Example 4: Production of Compound of Formula (7) The same moles of phenol were used in place of p-cresol in Synthetic Example 3, and the same procedure as in Synthetic Example 3 was repeated to obtain 4,4 '.
-[4-Hydroxy-3,5-bis (4-hydroxybenzyl) benzylidene] di-2,6-xylenol [Compound represented by the formula (7): hereinafter, "Compound (7)"
]] Was obtained. The structure was confirmed by mass spectrometry and nuclear magnetic resonance spectroscopy.

Synthesis Example 5: Quinonediazide sulfonic acid esterification of compound (7) In a 100 ml four-necked flask, 0.408 g of the compound (7) obtained in Synthesis Example 4, 1,2-naphthoquinonediazide-
5-Sulfonyl chloride (0.392 g) and 1,4-dioxane (4.0 g) were charged and the temperature was adjusted to 25 ° C. There,
Triethylamine (0.177 g) was added dropwise over 1 hour, and the reaction was further continued for 3 hours. After completion of the reaction, acetic acid 0.04
It was neutralized with g and filtered. The filtrate was added to a mixed solution of 0.25 g of acetic acid and 25 g of ion-exchanged water and stirred for 1 hour, and the precipitated crystals were filtered and washed with water. The obtained filtered product was dried under reduced pressure at 45 ° C. overnight to obtain 0.70 g of a photosensitizer. This is the photosensitizer (7 '). The yield based on compound (7) was 93.7.
%Met.

Reference Example: Production of Novolac Resin A four-necked flask was charged with 148.5 parts of m-cresol, 121.5 parts of p-cresol and 252 of methyl isobutyl ketone.
, 10% oxalic acid aqueous solution 37.0 parts and 90% acetic acid aqueous solution 84.8 parts were charged, and 37.0% formalin 129.5 parts was added dropwise over 40 minutes while heating and stirring in an oil bath at 100 ° C. Then, the reaction was continued for another 15 hours. Next, it was washed with water and dehydrated to obtain 466 parts of a methyl isobutyl ketone solution containing 42.3% of a novolak resin. The weight average molecular weight in terms of polystyrene measured by GPC was 4,300.

450 parts of this solution was placed in a bottomable separable flask, and methyl isobutyl ketone 90 was added.
After adding 9.6 parts and n-heptane 996.1 parts and stirring at 60 degreeC for 30 minutes, it stood still and liquid-separated. To the lower layer mass obtained by liquid separation, 380 parts of 2-heptanone was added, and methyl isobutyl ketone and n-heptane were removed by an evaporator to obtain a 2-heptanone solution of novolak resin. The weight average molecular weight in terms of polystyrene by GPC is 9,000, and the molecular weight in terms of polystyrene is 900.
The area ratio in the following range is 14% with respect to the entire pattern area.
Met.

Application Example 1 15 parts by weight of the 2-heptanone solution of the novolak resin obtained in the Reference Example, and compound (9) as an additive in an amount of 3.9
Parts, 4,4'-methylenebis [2- (4-
Hydroxybenzyl) -3,6-dimethylphenol]
(Has the following structure)

[0078]

5 parts of a condensate of 1,2-naphthoquinonediazide-5-sulfonyl chloride in a molar ratio of 1: 2,
As another sensitizer, 4- (1 ', 2', 3 ', 4',
4'a, 9'a-hexahydro-6'-hydroxyspiro [cyclohexane-1,9'-xanthene] -4'a
-Yl) resorcinol (having a structure of the following formula)

[0080]

1 part of a condensate of 1,2-naphthoquinonediazide-5-sulfonyl chloride in a molar ratio of 1: 3,
And 2-heptanone, the total amount of 2-heptanone is 5
It mixed so that it might become 0 parts, and melt | dissolved. The pore size of this liquid is 0.2
A resist solution was prepared by filtering with a μm fluororesin filter.

On a silicon wafer washed by a conventional method,
Using a spin coater, apply the above resist solution so that the film thickness after drying would be 1.1 μm, and apply 90 on a hot plate.
Bake at ℃ for 1 minute. Next, a reduction projection exposure machine with an exposure wavelength of 365 nm (i-line) [Nikon Products, NS
R 2005i 9C, NA = 0.57], and the exposure amount was changed stepwise. Next, the wafer was baked on a hot plate at 110 ° C. for 1 minute. This is the developer "SOP
It was developed for 1 minute with D "[Sumitomo Chemical Co., Ltd. product] to obtain a positive pattern.
The evaluation was performed as follows, and the results are shown in Table 1.

Effective Sensitivity: The line and space pattern of 0.50 μm was displayed at an exposure amount of 1: 1.

Resolution: The dimension of the line-and-space pattern, which was separated with no film loss, was measured by observing with a scanning electron microscope at an exposure amount (effective sensitivity) at which the line-and-space pattern became 1: 1.

Focus (depth of focus): The width of the focus at which the 0.40 μm line-and-space pattern was separated at the effective sensitivity without film loss was measured by observing with a scanning electron microscope.

Scum: The presence or absence of scum (development residue) was observed with a scanning electron microscope.

When the profile (cross-sectional shape) of the 0.45 μm line-and-space pattern at the effective sensitivity was observed with a scanning electron microscope, the pattern was cut vertically.

Application Example 2 15 parts by weight of a 2-heptanone solution of the novolac resin obtained in Reference Example, in terms of solid content, 1,3-bis [1-
(2,4-Dihydroxyphenyl) -1-methylethyl] benzene (having a structure of the following formula)

[0089]

3 parts, 5 parts of the photosensitizer (7 '), another 4- (1', 2 ', same as that used in the application example 1)
3 ', 4', 4'a, 9'a-Hexahydro-6'-hydroxyspiro [cyclohexane-1,9'-xanthene] -4'a-yl) resorcinol and 1,2-naphthoquinonediazide-5-sulfonyl Using 1 part of a condensate with a molar ratio of 1: 3 with chloride and 2-heptanone, 2
-Heptanone was mixed and dissolved in a total of 50 parts. This solution was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist solution.

Using this resist solution, a positive pattern was prepared and evaluated in the same manner as in Application Example 1, and the results are shown in Table 1. Further, when the profile (cross-sectional shape) of the 0.45 μm line-and-space pattern at the effective sensitivity was observed with a scanning electron microscope, the pattern was cut vertically.

[0092]

[Table 1]

[0093]

Among the pentaphenol compounds represented by the formula (I) according to the present invention, R ¹ , R ² , R ³ and R ^{4 are}
And one in which at least one of R ⁵ is 1,2-naphthoquinonediazidesulfonyl is useful as a photosensitizer for a photosensitive resin composition, and R ¹ , R ² , R ³ , R ⁴
And those in which R ⁵ are all hydrogen are useful as a precursor of the above-mentioned photosensitizer and also as an alkali-soluble low molecular weight additive for a photosensitive resin composition. And
A photosensitive resin composition containing this alkali-soluble low molecular weight additive, or a photosensitive resin composition containing the above-mentioned photosensitive agent which has been 1,2-naphthoquinonediazide sulfonate ester is used for semiconductor microfabrication and has high sensitivity and resolution. Excellent,
Further, the resist performances are well balanced, such as no development residue.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 61/06 LMR C08L 61/06 LMR 101/00 LSY 101/00 LSY G03F 7/022 G03F 7 / 022

Claims (12)

[Claims] (1) Formula (I) (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of each other represent hydrogen or 1,2-naphthoquinonediazide-4- or -5-sulfonyl, and R ⁶ , R ⁷ , R ⁸ , R
⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independent of each other,
Hydrogen, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, alkenyl having 2 to 6 carbons or cycloalkyl having 6 or less carbons, R ¹⁵ is hydrogen, alkyl having 1 to 6 carbons, carbon A pentaphenol compound represented by alkenyl having 2 to 6 or cycloalkyl having 6 or less carbon atoms. 2. The compound according to claim ¹ , wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are all hydrogen. 3. At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is 1,2-naphthoquinonediazide-4-or-
The compound according to claim 1, which is 5-sulfonyl. 4. A method according to claim 1, wherein R ¹⁵ is hydrogen or methyl.
The compound according to any one of the above. 5. Formula (Ia) (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ each independently represent hydrogen, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, alkenyl having 2 to 6 carbons, or cycloalkyl having 6 or less carbons;
¹⁵ represents hydrogen, alkyl having 1 to 6 carbons, alkenyl having 2 to 6 carbons, or cycloalkyl having 6 or less carbons) and is represented by the formula (II) A dimethylol compound represented by the formula (wherein R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹⁵ have the above meanings), and a phenolic compound necessary for obtaining the compound of formula (Ia) The method as described above, characterized by reacting with 6. The formula (I) (In the formula, ^one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is 1,
2-naphthoquinonediazide-4-or-5 represents a sulfonyl, rest, independently of one another represent hydrogen or 1,2-naphthoquinonediazide-4-or ^{5-sulfonyl, R 6, R 7, R} 8, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³
And R ¹⁴ each independently represent hydrogen, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, alkenyl having 2 to 6 carbons or cycloalkyl having 6 or less carbons, and R ¹⁵ is hydrogen or carbon. A alkylphenol having 1 to 6 carbon atoms, an alkenyl having 2 to 6 carbon atoms or a cycloalkyl having 6 or less carbon atoms is represented by the formula (Ia) (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ and R ¹⁵ have the above-mentioned meanings), and a pentaphenol compound represented by the above is reacted with 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide. . 7. The formula (I) (In the formula, ^one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is 1,
2-naphthoquinonediazide-4-or-5 represents a sulfonyl, rest, independently of one another represent hydrogen or 1,2-naphthoquinonediazide-4-or ^{5-sulfonyl, R 6, R 7, R} 8, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³
And R ¹⁴ each independently represent hydrogen, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, alkenyl having 2 to 6 carbons or cycloalkyl having 6 or less carbons, and R ¹⁵ is hydrogen or carbon. A photosensitizer containing a pentaphenol ester represented by C 1-6 alkyl, C 2-6 alkenyl or C 6 or less cycloalkyl) as an active ingredient. 8. The photosensitizer according to claim 7, which is used as a mixture with an alkali-soluble resin. 9. A photosensitive resin composition comprising an alkali-soluble resin and the photosensitizer according to claim 7. 10. The alkali-soluble resin is a novolak resin obtained by condensation of a phenolic compound and an aldehyde, and the area ratio in the range of 900 or less in terms of polystyrene equivalent molecular weight in the gel permeation chromatography pattern is unreacted. The composition according to claim 9, which is 25% or less with respect to the total pattern area excluding the pattern area of the phenolic compound. 11. A formula (Ia) (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ each independently represent hydrogen, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, alkenyl having 2 to 6 carbons, or cycloalkyl having 6 or less carbons;
¹⁵ represents hydrogen, an alkyl having 1 to 6 carbons, an alkenyl having 2 to 6 carbons or a cycloalkyl having 6 or less carbons), which is an alkali-soluble photosensitive resin composition containing a pentaphenol compound as an active ingredient. Additive. 12. A photosensitive resin composition comprising an alkali-soluble resin, a quinonediazide-based photosensitizer and the alkali-soluble additive according to claim 11.