JPH0899922A - Polyhydric phenol compound, its production and use - Google Patents

Abstract

PURPOSE: To obtain a new polyhydric phenol compound producible in high purity by simple reaction, useful as an intermediate for a sensitive agent for a resist composition and an alkali-soluble component for the resist composition. CONSTITUTION: 1,2,3-Trihydroxy-4-(4-hydroxy-2,5-dimethylbenzyl)benzene is expressed by the formula. The compound is obtained by reacting 4-hydroxy- methyl-2,5-dimethylphenol with pyrogallol. The molar ratio of pyrogallol to 4-hydroxy-methyl-2,5-dimethylphenol is 1-3 and the reaction is preferably carried out in the presence of an acid catalyst. The amount of water as a reaction solvent is preferably 0.25 5 pts.wt. based on 1 pt.wt. of pyrogallol. The reaction product is preferably purified by crystallization from an aromatic solvent or an aqueous solution of an alcohol. A positive type resist composition containing the compound has excellent balance of properties such as sensitivity, resolving power, γ value and profile and no scum in development and is suitable for fine processing of semiconductor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenol compound useful as a component of a resist composition, a method for producing the same, and its application to a resist composition.

[0002]

2. Description of the Related Art Many polyhydric phenol compounds have been known so far, for example, JP-A-55-162728 (= USP 4,51).
4,334) and JP-A-62-84035 (= USP 4,894,432) describe a polyhydric phenol compound having a plurality of benzene rings. However, such a known polyphenol compound requires a long production process, and the product obtained by the reaction has a low purity, which makes it difficult to purify it to a high purity.

On the other hand, many studies have been conducted for converting a polyhydric phenol compound into a quinonediazide sulfonic acid ester and using it as a photosensitizer in a resist composition for semiconductor fine processing [for example, JP-A-6-167805 (= EP. -A-5
73, 056), etc.), and the use of the polyphenol compound itself as an additive which is an alkali-soluble component in such a resist composition is also being conducted [eg, JP-A-2-2560, 3-200253. Bulletin, etc.].

[0004]

An object of the present invention is to produce and provide a novel diphenylmethane-based polyhydric phenol compound with high purity by a simple reaction.

Another object of the present invention is to provide a diphenylmethane type polyhydric phenol compound useful as one component in a resist composition for semiconductor fine processing.

[0006]

As a result of intensive studies, the present inventors have found an aromatic tetrahydroxy compound having a specific structure, and this compound can be easily obtained in high purity and is a component of a resist composition. As a result, the present invention has been completed, and the present invention has been completed.

Therefore, the present invention, from one aspect,
2,3-trihydroxy-4- (4-hydroxy-2,
5-dimethylbenzyl) benzene. This compound has a structure of the following formula (I), and may be hereinafter referred to as compound (I) for simplicity.

[0008]

The present invention also provides, from another aspect, a method for producing compound (I) by reacting 4-hydroxymethyl-2,5-dimethylphenol with pyrogallol.

From another aspect, the present invention also provides a resist additive containing compound (I) as an active ingredient, and further provides a resist composition containing compound (I). .

The compound (I) according to the present invention can be easily produced in high purity by the reaction of 4-hydroxymethyl-2,5-dimethylphenol and pyrogallol. At this time, it is preferable to use pyrogallol in a molar ratio of 1 to 3 with respect to 4-hydroxymethyl-2,5-dimethylphenol, and more preferably in a molar ratio of 1 to 2.

The reaction is accelerated by the use of acid catalysts. The acid catalyst may be either an inorganic acid or an organic acid, and examples thereof include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and p-toluenesulfonic acid. Hydrochloric acid, sulfuric acid or p-toluenesulfonic acid is preferably used, and more preferably p-toluenesulfonic acid is used. The acid catalyst is usually 0.01 to 0.1 mol times, preferably 0.01 times, the amount of pyrogallol.
It is used in an amount of up to 0.05 mol times, and more preferably within a range of 0.01 to 0.03 mol times.

The reaction is usually carried out in a solvent, and water is preferably used as the reaction solvent. The reaction solvent, especially water, is generally in the range of 0.25 to 5 times by weight, preferably 0.5 to 2 times by weight, more preferably 0.8 to 1.2 times by weight, based on the amount of pyrogallol. Used in double range.

The reaction is generally carried out at atmospheric pressure, eg 10
It is carried out at a temperature of -60 ° C. The reaction temperature is preferably as low as possible within the range in which the raw materials are dissolved. In this reaction,
It is preferable that 4-hydroxymethyl-2,5-dimethylphenol is gradually or dividedly added to an aqueous solution containing pyrogallol and an acid catalyst, for example, over 0.5 to 2 hours.

Compound (I) is produced by such a reaction. For example, when water is used as the reaction solvent, the compound (I) precipitates as the reaction progresses or after the reaction is cooled to around room temperature. If this is subjected to solid-liquid separation, a crude product of compound (I) is obtained, and this crude product is preferably further purified. Purification can be performed by any means, but purification by crystallization is particularly preferably adopted. For example, crystallization from an aromatic solvent such as benzene, toluene or xylene, crystallization from an aqueous solution containing an alcohol such as methanol or ethanol, and the like can be adopted. When crystallization from an aromatic solvent is adopted, toluene is preferably used. When crystallization from an alcohol aqueous solution is adopted, an alcohol aqueous solution of preferably 30 to 60% by weight, more preferably 30 to 40% by weight, especially an aqueous methanol solution is used.

The compound (I) thus obtained is, for example, 1,2-naphthoquinonediazide-4- or -5-sulfonic acid chloride, 1,2-benzoquinonediazide-4.
It can be esterified by reaction with o-quinonediazide sulfonic acid halide such as sulfonic acid chloride and used as a photosensitizer component of a positive resist composition containing an alkali-soluble novolac resin. Separately from this, in compound (I) itself, in a positive resist composition containing a photosensitizer composed of an o-quinonediazide sulfonic acid ester of an aromatic polyhydroxy compound and an alkali-soluble novolak resin, a low molecular weight alkali-soluble component is added. Can also be used as an additive. These positive resist compositions are sensitive to radiation such as ultraviolet rays and deep ultraviolet rays (including excimer lasers) and are used for fine processing of semiconductors.

The alkali-soluble novolac resin constituting the resist composition contains at least 1 phenolic hydroxyl group.
The compound is obtained by condensing an individual compound and an aldehyde in the presence of an acid catalyst, and the type thereof is not particularly limited, and various types used in the resist field can be used. Examples of the phenolic compound which is a raw material of the novolac resin include o-cresol and m.
-Cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol,
2,3,5-trimethylphenol, 2-t-butyl-
5-methylphenol and the like can be mentioned. Further, as the aldehyde which is the other raw material of the novolac resin,
Aliphatic aldehydes such as formaldehyde, acetaldehyde, glyoxal, and aromatic aldehydes such as benzaldehyde and salicylaldehyde are mentioned. In particular, formaldehyde is industrially mass-produced as a 37% by weight aqueous solution and is preferably used.

One or two of such phenolic compounds
The novolak resin is obtained by condensing one or more species and one or more species of aldehydes in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, oxalic acid, acetic acid, organic acids such as p-toluenesulfonic acid, and divalent metal salts such as zinc acetate. 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 about 2 to 30 hours. The reaction may be carried out in bulk or in a suitable solvent.

The resulting novolak resin is subjected to a gel permeation chromatography (GPC) (using a UV 254 nm detector) pattern by subjecting to operations such as fractionation for the purpose of reducing the development residue of the resist. In the above, it is preferable that 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. Furthermore, the area ratio of the components having a polystyrene-equivalent molecular weight of 900 or less is 20
It is more preferable to set it to be not more than%. When fractionation is carried out, the novolak resin obtained by condensation is treated with 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, ethyl cellosolve acetate. Dissolve in ethylene glycol ether ester such as, or ether such as tetrahydrofuran, and then pour this solution into water to precipitate the high molecular weight component, or mix this solution with a poor solvent such as pentane, hexane or heptane. Then, a method of separating the liquid can be adopted.

When the compound (I) is used as an additive for a resist composition, the photosensitizer constituting the resist composition is an o-quinonediazide sulfonic acid ester of an aromatic polyhydroxy compound. Aromatic polyhydroxy compounds to be esterified include, for example, polyhydroxybenzophenones such as trihydroxybenzophenone, tetrahydroxybenzophenone and pentahydroxybenzophenone, 2,4,4-trimethyl-2 ′, 4 ′, 7.
-Trihydroxyflavan, 2,4,4-trimethyl-
2 ', 3', 4 ', 7,8-pentahydroxyflavan, 6-hydroxy-4a- (2,4-dihydroxyphenyl) -1,2,3,4,4a, 9a-hexahydroxanthene-9- Polyhydroxyflavans such as spiro-1'-cyclohexane, and other compounds having 2 to 4 benzene rings bonded by an aliphatic hydrocarbon-based linking group and having 2 or more aromatic hydroxyl groups it can. As a more specific photosensitizer, for example, JP-A-2-2352
(= USP 5,124,228), JP-A-2-103543 (= EP-A-36
3,978), JP-A-2-269351 (= USP 5,290,656),
JP-A-3-185447 (= USP 5,283,155), JP-A-4-5
0851 (= USP 5,188,920), JP-A-4-295472
(= EP-A-505,987), JP-A-5-323597 (= EP-A-57
0,884), JP-A-6-167805 (= EP-A-573,056) and the like.

When the compound (I) is used as an additive for the resist composition, its amount is preferably in the range of 3 to 40% by weight based on the total solid content in the resist composition. Further, the amount of the photosensitizer in the resist composition is preferably in the range of 10 to 50% by weight based on the amount of total solids in the resist composition.

Preparation of the resist solution containing the compound (I)
It is carried out by mixing the photosensitive agent, the novolac resin and the compound (I) or, if necessary, other components with a solvent and dissolving them. The solvent used here preferably has an appropriate drying rate and gives a uniform and smooth coating film after the solvent is evaporated. Examples of such a solvent include glycol ether esters such as propylene glycol monomethyl ether acetate, ethyl cellosolve acetate and methyl cellosolve acetate, n-amyl acetate, ethyl acetate, ethyl lactate, ethyl pyruvate and γ-butyrolactone. Esters, ketones such as 2-heptanone, and others described in JP-A-2-220056, JP-A-4-362645, JP-A-4-367863, etc. Can be mentioned. As the solvent, each compound may be used alone or in combination of two or more kinds.

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

[0024]

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,% and parts representing the content or the addition amount are based on weight unless otherwise specified.

Reference Example: Production of Novolac Resin In a four-necked flask having an internal volume of 1000 ml, 148.5 g of m-cresol, 121.5 g of p-cresol, 252 g of methyl isobutyl ketone, 37.0 g of 10% aqueous oxalic acid solution.
Then, 84.8 g of a 90% aqueous acetic acid solution was charged, and 129.5 g of 37% formalin was added dropwise over 40 minutes while heating and stirring in an oil bath at 100 ° C., and the reaction was further performed for 15 hours. Then, it was washed with water and dehydrated to obtain 466 g of a methyl isobutyl ketone solution containing 42.3% of novolak resin. The polystyrene reduced weight average molecular weight by GPC was 4,300.

450 g of this solution was charged into a 5-liter bottomed separable flask, 909.6 g of methyl isobutyl ketone and 996.1 g of n-heptane were added, and the mixture was stirred at 60 ° C. for 30 minutes and then left to stand, The layers were separated. 2-heptanone was added to the lower layer mass obtained by liquid separation.
0 g was added, methyl isobutyl ketone and n-heptane were removed by an evaporator, and novolak resin 2-
A heptanone solution was obtained. The polystyrene reduced weight average molecular weight by GPC was 9,000, and the area ratio in the polystyrene reduced molecular weight range of 900 or less was 14% with respect to the entire pattern area.

Example 1 Pyrogallol 1009 was placed in a 5-liter three-necked flask.
g, p-toluenesulfonic acid 30.43 g and water 1009
Then, while maintaining the temperature at 35 ° C., 761 g of 4-hydroxymethyl-2,5-dimethylphenol was added portionwise in 1.5 hours. Subsequently, the mixture was kept at the same temperature for 1.5 hours, cooled to room temperature, and the precipitated crystals were filtered. The filtered material was poured into a mixed solution of 400 g of toluene and 2400 g of ethyl acetate to dissolve it, and then it was washed with ion-exchanged water to demetallize, concentrated, filtered, dried, and further dried under reduced pressure all day and night. , 2,3-trihydroxy-4- (4-hydroxy-2,5-dimethylbenzyl) benzene [compound (I)] was obtained in an amount of 450 g.

Mass spectrum: MS 260 ¹ H-NMR (acetone) δ (ppm): 2.11 (s, 6H);
3.74 (s, 2H); 6.16 (d, J = 8.5 Hz, 1H); 6.27 (d, J =
8.5 Hz, 1H); 6.62 (s, 1H); 6.80 (s, 1H); 7.54 (br
s, 4H).

Example 2 Pyrogallol 1009 was placed in a 5-liter three-necked flask.
g, p-toluenesulfonic acid 30.43 g and water 1009
Then, while maintaining the temperature at 35 ° C., 761 g of 4-hydroxymethyl-2,5-dimethylphenol was added portionwise in 1.5 hours. Subsequently, the mixture was kept at the same temperature for 1.5 hours, cooled to room temperature, and the precipitated crystals were filtered. The filtrate was added to 1160 g of methanol at 50 ° C. to completely dissolve it, and then 1740 g of ion-exchanged water was added, and then cooled to 20 ° C. to precipitate crystals, which were filtered, dried, and dried under reduced pressure for a whole day and night. 1,2,3-trihydroxy-
500 g of 4- (4-hydroxy-2,5-dimethylbenzyl) benzene [compound (I)] was obtained.

As a result of mass spectrometry and nuclear magnetic resonance analysis, it was confirmed that the compound obtained here was the same as that obtained in Example 1.

Example 3 15 parts by weight of a 2-heptanone solution of the novolak resin obtained in Reference Example in terms of solid content, 4,4'-methylenebis [2- (4-hydroxybenzyl) -3,6- Dimethylphenol] and 1,2-naphthoquinonediazide-5
5 parts of a condensate with a molar ratio of 1: 2 with sulfonic acid chloride,
Similarly, 6-hydroxy-4a- (2,4- as a photosensitizer
Dihydroxyphenyl) -1,2,3,4,4a, 9a-hexahydroxanthene-9-spiro-1'-cyclohexane (having the structure of the following formula)

[0032]

1 part of a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride in a molar ratio of 1: 3, 3.9 parts of compound (I) as an additive and 2 parts of 2-heptanone. -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.

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 will be 1.1 μm, and apply 90 on a hot plate.
Bake at 1 ° C for 1 minute. Next, a reduction projection exposure tool with an exposure wavelength of 365 nm (i-line) [Nikon Products, NS
R 1755i 7A, NA = 0.5) was used, and the exposure amount was changed stepwise for exposure. Next, the wafer was baked on a hot plate at 110 ° C. for 1 minute. This is the developer "SOPD"
The product was developed for 1 minute with [Sumitomo Chemical Co., Ltd. product] to obtain a positive pattern. The positive pattern was evaluated 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 dose of 1: 1.

Resolution: The dimension of the line-and-space pattern, which is separated without film loss, was measured with a scanning electron microscope at an exposure amount (effective sensitivity) at which the line-and-space pattern became 1: 1.

Profile: 0.45 in effective sensitivity
The cross-sectional shape of the μm line and space pattern was observed with a scanning electron microscope.

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

Γ value: The normalized film thickness (= remaining film thickness / initial film thickness) was plotted against the logarithm of the exposure amount, the inclination θ was determined, and tan θ was taken as the γ value.

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

[0041]

[Table 1]

[0042]

The 1,2,3-trihydroxy-4- (4-hydroxy-2,5-dimethylbenzyl) benzene according to the present invention is converted into an o-quinonediazide sulfonic acid ester and becomes a photosensitizer for a resist composition. In addition, it is also useful as an alkali-soluble component of a resist composition in the form of a tetrahydroxy compound as it is. This compound can be produced in high purity by a simple reaction. In addition, a positive resist composition containing this compound has an excellent balance of various performances such as sensitivity, resolution, γ value, and profile, and is free from scum (development residue) during development, and is suitable for fine processing of semiconductors. It is a thing.

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Claims (9)

[Claims] 1. 1,2,3-Trihydroxy-4- (4-
Hydroxy-2,5-dimethylbenzyl) benzene. 2. 1,2-, 3-Trihydroxy-4- (4-hydroxy-2,5-dimethylbenzyl), characterized in that 4-hydroxymethyl-2,5-dimethylphenol is reacted with pyrogallol. Benzene production method. 3. The method according to claim 2, wherein pyrogallol is used in a molar ratio of 1 to 3 with respect to 4-hydroxymethyl-2,5-dimethylphenol, and the reaction is carried out in the presence of an acid catalyst. 4. The method according to claim 2, wherein water is used as a reaction solvent. 5. The method according to claim 4, wherein water is used in an amount of 0.25 to 5 times by weight the amount of pyrogallol. 6. The method according to claim 2, wherein the reaction product is purified by crystallization from an aromatic solvent or an aqueous alcohol solution. 7. 1,2,3-Trihydroxy-4- (4-
A resist additive containing hydroxy-2,5-dimethylbenzyl) benzene as an active ingredient. 8. 1,2,3-Trihydroxy-4- (4-
A resist composition comprising hydroxy-2,5-dimethylbenzyl) benzene. 9. The composition according to claim 8, which further comprises an alkali-soluble novolac resin and an o-quinonediazide sulfonic acid ester-based photosensitizer and is of a positive type.