JPH09110751A - Method for producing pentanuclear novolak compound - Google Patents

Abstract

(57) [Abstract] [Problem] Formula (I) (In the formula, ^one of R ^{1 to} R ⁵ represents a hydroxyl group, and R ^{6 to} R ¹⁰
Of ¹ represents a hydroxyl group, and the rest of R ^{1 to} R ¹⁰ independently of each other represents hydrogen, alkyl having 1 to 6 carbons or a hydroxyl group), and industrially advantageously produces a pentanuclear novolak compound. SOLUTION: 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol is used as a raw material, and a mononuclear compound corresponding to both terminals of the formula (I) is used. Phenolic compound, 1: 2-50
The pentanuclear novolak compound (I) is produced by reacting in the presence of an acid catalyst at a molar ratio of.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a pentanuclear novolak compound represented by the following formula (I), which is useful as a raw material or an additive for a photosensitizer in a resist for semiconductor fine processing, for example.

[0002]

Where R ¹ , R ² , R ³ , R ⁴ and R ⁵
One of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents a hydroxyl group, and R ¹ , R ² , R ³ , R ⁴ ,
The rest of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently of each other represent hydrogen, alkyl having 1 to 6 carbons or a hydroxyl group.

[0004]

It is generally known that a compound having a phenolic hydroxyl group is converted to a quinonediazide sulfonic acid ester and used as a photosensitizer in a resist composition for semiconductor fine processing. That is, when a composition comprising a compound having a quinonediazide group and a novolac resin is applied on a metal substrate and irradiated with light of 300 to 500 nm, the quinonediazide group is decomposed to form a carboxyl group, which is alkali-insoluble. The composition is used as a positive resist by taking advantage of the fact that the composition becomes soluble. Since such a positive resist has a feature of excellent resolution, it is used for manufacturing various integrated circuits for semiconductors. Further, a compound having a phenolic hydroxyl group is used as an alkali-soluble low molecular weight additive in a resist composition for semiconductor fine processing,
Research is also being conducted to increase the sensitivity of resists.

Various phenolic compounds have been proposed as raw materials for such sensitizers or alkali-soluble low molecular weight additives. For example, JP-A-5-323597 (= E
PA-570,884) discloses compounds in which three phenolic nuclei are linked by two aliphatic linking groups. In addition,
Japanese Patent Publication No. 6-167805 (= EP-A-573,056) discloses a compound in which four or more phenol nuclei are bound by an aliphatic linking group.

[0006]

[Patent Document 1] Japanese Patent Application Laid-Open No. 6-167805
The publication also partially describes a pentanuclear novolak compound corresponding to the above formula (I), which is the object of the present invention,
As a specific synthetic method thereof, a method starting from a methylol compound of the compound having a phenol nucleus at both ends in the formula (I) is disclosed. However, in the case of such a method, there are problems that the amount of by-products increases and the purification of the target product becomes complicated.

The inventors of the present invention have shown that 5 represented by the above formula (I)
In order to industrially produce a nuclear novolak compound, as a result of continued intensive research, by using a specific dimethylol compound, high purity, high yield, and high selectivity,
The present invention was completed by finding that this pentanuclear novolak compound can be produced.

[0008]

Means for Solving the Problems That is, the present invention is
6-bis (4-hydroxy-3-hydroxymethyl-
2,5-dimethylbenzyl) -4-methylphenol and the phenolic compound necessary to form the compound of formula (I) in a molar ratio of 1: 2 to 50 in the presence of an acid catalyst. The present invention provides a method for producing a pentanuclear novolak compound represented by the formula (I) by reacting.

Here, the phenolic compound necessary for producing the compound of formula (I) means the following formulas (II) and (II
I) means the one shown.

[0010]

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above.
By using different phenolic compounds of the formulas (II) and (III), it is possible to produce compounds having different terminals in the formula (I).
Alternatively, by using only one type of phenolic compound represented by the formula (III), a compound having the same both terminals in the formula (I) can be produced.

Further, 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol used as another reaction raw material in the present invention is represented by the following formula (IV): It has a structure and may be hereinafter referred to as "dimethylol (IV)" for simplicity.

[0013]

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Dimethylol (IV) is, for example,
2,6-bis (4-hydroxy-2,5-dimethylbenzyl) -4-methylphenol and formaldehyde,
It can be produced by reacting in the presence of an alkali catalyst. In addition, 2,6-bis (4-hydroxy-2,5-
Dimethylbenzyl) -4-methylphenol is obtained by converting para-cresol into dimethylol with formaldehyde.
6-bis (hydroxymethyl) -4-methylphenol can be produced by condensing this with 2,5-xylenol.

According to the present invention, dimethylol (IV)
The reaction with the phenolic compound (II) and / or (III) gives the pentanuclear novolak compound (I).
At this time, the phenolic compound is used in a molar ratio of 2 to 50 with respect to dimethylol (IV), and this molar ratio is preferably 4 to 20 and more preferably 6 to 20. When the amount of the phenolic compound is small, the selectivity of the reaction becomes poor, while when the amount is large, the extraction yield decreases. Further, in the present invention, dimethylol (I
The purity of V) is not significantly affected, and
-Bis (4-hydroxy-2,5-dimethylbenzyl)
The product obtained by the reaction of -4-methylphenol and formaldehyde can also be used without much purification. Generally, dimethylol (IV) having a purity in the range of 65 to 100% by weight can be used.

The reaction between dimethylol (IV) and a phenolic compound is carried out in the presence of an acid catalyst, which is an inorganic acid such as hydrochloric acid or sulfuric acid, formic acid, acetic acid, propionic acid or paratoluenesulfonic acid. Although any of such organic acids may be used, among them, a mineral acid such as hydrochloric acid or sulfuric acid or paratoluenesulfonic acid is preferable, and paratoluenesulfonic acid is particularly preferably used. The acid catalyst is usually 1 equivalent or less, preferably 0.01-1, relative to dimethylol (IV).
It is used in an equivalent amount, more preferably in the range of 0.1 to 0.5 equivalent amount. If the amount of the acid catalyst is too small, the reaction time tends to be long, and if the amount is too large, the selectivity of the reaction tends to be poor.

This reaction is preferably carried out in a solvent,
The reaction solvent in this case may be alcohols, water, an aromatic solvent and the like, but among them, an aromatic solvent, which is also an aromatic hydrocarbon solvent, is preferable. Examples of alcohols include lower alcohols such as methanol, ethanol, isopropyl alcohol and butyl alcohol, and examples of aromatic hydrocarbon solvents include benzene, toluene and xylene. Among them, toluene is preferably used. To be The reaction solvent, such as an aromatic solvent, is a phenolic compound (II) or (II
Based on the total amount of I), it is generally in the range of 0.5 to 5 times by weight, preferably 1 to 3 times by weight, more preferably 1 to
It is used in the range of 2 times by weight. If the amount of solvent is too large,
If the amount is too small, the selectivity of the reaction tends to be poor.

The reaction is preferably charged by adding dimethylol (IV) to a mixture of a phenolic compound, an acid catalyst and a reaction solvent. At this time, the dimethylol (IV) is preferably added over 0.01 to 12 hours, more preferably 0.5 to 4 hours, and more preferably 1 to 2 hours. The reaction is usually 10 ° C
To reflux temperature, preferably at a temperature in the range of 15 to 50 ° C. This reaction usually proceeds under atmospheric pressure, and is 2 to 5 except for the addition time of dimethylol (IV).
It takes about an hour.

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 certain pentanuclear novolak compound (I)
Crystals will precipitate. By taking out these crystals, a crude product is obtained, which can then be subjected to any purification means. For example, since this compound has a low solubility in an aromatic solvent at room temperature, it can be purified by performing crystallization from the aromatic solvent or repeating it if necessary. The crystallization solvent used in this case may be the same as or different from that used in the reaction.

When this compound is converted to a quinonediazide sulfonic acid ester to be used as a photosensitizer in a resist composition for semiconductor production, the solubility in water is 9 g / 10.
After dissolving the above crude product in a solvent of 0 g or less, it is preferable to reduce the metal content by washing and separating. 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 has a solubility of the pentanuclear novolak compound (I) at 20 ° C. of 1 g.
/ 100 g or more is preferable. Examples of such a solvent 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.

The solution containing the pentanuclear novolak compound (I) thus reduced in metal can be further crystallized by adding an aromatic solvent. The aromatic solvent used here may be the same as or different from that used in the reaction, but toluene is preferably used.

The pentanuclear novolak compound (I) thus obtained can be used, for example, as an alkali-soluble low molecular weight additive in a resist composition for semiconductor production, and is also converted into a sensitizer by quinone diazide sulfonic acid esterification. be able to. In the latter esterification, 1,2-quinonediazide sulfonyl halide, 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, one or more of 1,2-quinonediazidesulfonyl chloride is an esterifying agent. Is preferably used as.

This esterification reaction is usually carried out in the presence of a dehydrohalogenating agent. Examples of the dehydrohalogenating agent include generally basic compounds such as sodium carbonate, inorganic bases such as sodium hydrogencarbonate, ethylamine, ethanolamine, diethylamine, diethanolamine, triethylamine, N, N-dimethylaniline, N, N-dimethylaniline, and the like. Examples include amines such as N-diethylaniline. The dehydrohalogenating agent is usually used in a molar ratio of 1.05-1.5, preferably 1.05-1.5, with respect to 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide.
It is used in a molar ratio of 1.2, more preferably 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 used in a range of 2 to 6 times by weight, preferably 3 to 5 times by weight, based on the total amount of the pentanuclear novolak compound (I) and the quinonediazidesulfonyl halide.

This esterification reaction proceeds sufficiently under normal pressure even 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.

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

[0028]

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 indicating the content or the amount used are based on weight unless otherwise specified.

Reference Example 1: Preparation of dimethylol (IV) 2,6-bis (4-hydroxy-2,5-dimethylbenzyl) -4-methylphenol 263.6 parts, sodium hydroxide 67.2 parts, water 1169 .3 parts and 107.5 parts of tetrahydrofuran were charged into a four-necked flask and dissolved,
The temperature was adjusted to 40 ° C. 340.9 parts of 37% formalin was added dropwise thereto over 1 hour, and then the mixture was stirred at the same temperature for 2 hours. After completion of the reaction, the mixture was neutralized with 134.4 parts of 90% acetic acid aqueous solution and then cooled to 25 ° C. The precipitated crystals were filtered and rinsed with 1000 parts of ion-exchanged water. The obtained filtered product was dried under reduced pressure at 45 ° C for a whole day and night to give 2,6-bis (4
-Hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol 265 parts (purity 8
0%).

Mass spectrum: MS 436 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.9
5 (s, 3H); 2.05 (s, 6H); 2.10 (s, 6H); 3.78 (s, 4
H); 4.65 (s, 4H); 5.23 (brs, 2H); 6.31 (s, 2H); 6.7
0 (s, 2H); 8.18 (brs, 1H); 8.60 (brs, 2H).

Example 1 Preparation of 2,6-bis [4-hydroxy-3- (4-hydroxybenzyl) -2,5-dimethylbenzyl] -4-methylphenol

A 1-liter four-necked flask was charged with 11.41 g of p-toluenesulfonic acid, 150.6 g of phenol and 300 g of toluene, and the temperature was adjusted to 40 ° C., and the purity obtained in Reference Example 1 was 80%. 2,6-bis (4
-Hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol (87.31 g)
The mixture was divided, charged for 1 hour and 30 minutes, and then reacted at the same temperature for another 3 hours. After completion of the reaction, it is filtered and toluene 2
Rinse with 00g. The filtrate obtained was mixed with toluene 20
A mixed solution of 0 g and 1000 g of ethyl acetate was charged and dissolved at 60 ° C., 1000 g of ion-exchanged water was further added, and the mixture was stirred and separated. After that, 1000% 1% oxalic acid aqueous solution
Demetalization was carried out by charging g, stirring, and separating. Next, after washing with 1000 g of ion-exchanged water four times, the oil layer was concentrated. Toluene 100 in concentrated mass
g, cooled to 20 ° C., filtered, and then toluene 200
rinsed with g.

The obtained filtered product was dried under reduced pressure at 45 ° C. for a whole day and night to give 2,6-bis [4-hydroxy-3- (4-hydroxybenzyl) -2,5-dimethylbenzyl] -4-.
42.5 g (quantitative purity 96.8%) of methylphenol was obtained. The yield based on 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol was 43.7%.

Mass Spectrometry: MS 588

Example 2: 2,6-bis [4-hydroxy-3- (4-hydroxy-3-methylbenzyl)-
Production of 2,5-dimethylbenzyl] -4-methylphenol

A 1-liter four-necked flask was charged with 1.9 g of paratoluenesulfonic acid, 86.5 g of orthocresol and 177 g of toluene, and the temperature was adjusted to 30 ° C.
Then, 21.83 g of 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol having a purity of 80% obtained in Reference Example 1 was divided into 10 parts, The mixture was charged in 1 hour and 30 minutes, and then reacted at the same temperature for another 3 hours. After the reaction was completed, it was filtered and rinsed with 100 g of toluene. The obtained filtered product was charged and dissolved in a mixed liquid of 100 g of toluene and 200 g of ethyl acetate at 60 ° C., 200 g of ion-exchanged water was further added, and the mixture was stirred and separated. After that, 200 g of 1% oxalic acid aqueous solution
Was charged, stirred, and separated to demetalize. Next, after washing with 200 g of ion-exchanged water four times, the oil layer was concentrated. Toluene 100g in concentrated mass
And cooled to 20 ° C., filtered, and then toluene 100 g
I rinsed with.

The filtrate obtained was dried under reduced pressure at 45 ° C. for one day to obtain 2,6-bis [4-hydroxy-3- (4-hydroxy-3-methylbenzyl) -2,5-dimethylbenzyl] -4. -Methylphenol 15.5g (quantitative purity 9
(5.2%). 2,6-bis (4-hydroxy-3
-Hydroxymethyl-2,5-dimethylbenzyl) -4
-The yield based on methylphenol was 59.8%.

Mass spectrum: MS 616 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.9
2 (s, 6H); 2.02 (s, 9H); 2.12 (s, 6H); 3.74 (s, 4
H); 3.88 (s, 4H); 6.25 (s, 2H); 6.60 (d, J = 7.9 H
z, 2H); 6.66 (s, 2H); 6.67 (d, J = 7.9 Hz, 2H); 6.7
8 (s, 2H); 7.94 (s, 2H); 8.10 (s, 1H); 8.91 (s, 2
H).

Example 3: 2,6-bis [4-hydroxy-3- (4-hydroxy-2-methylbenzyl)-
Production of 2,5-dimethylbenzyl] -4-methylphenol

A 1 liter four-necked flask was charged with 1.14 g of paratoluenesulfonic acid, 25.95 g of metacresol and 54.19 g of toluene and the temperature was adjusted to 30 ° C.
Then, 13.10 g of 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol having a purity of 80% obtained in Reference Example 1 was divided into 10 parts, The mixture was charged in 1 hour and 30 minutes, and then reacted at the same temperature for another 3 hours. After the reaction was completed, it was filtered and rinsed with 100 g of toluene. The obtained filtered product was charged and dissolved in a mixed liquid of 100 g of toluene and 200 g of ethyl acetate at 60 ° C., 200 g of ion-exchanged water was further added, and the mixture was stirred and separated. After that, 200 g of 1% oxalic acid aqueous solution
Was charged, stirred, and separated to demetalize. Next, after washing with 200 g of ion-exchanged water four times, the oil layer was concentrated. Toluene 100g in concentrated mass
And cooled to 20 ° C., filtered, and then toluene 100 g
I rinsed with.

The filtrate obtained was dried under reduced pressure at 45 ° C. for a whole day and night to give 2,6-bis [4-hydroxy-3- (4-hydroxy-2-methylbenzyl) -2,5-dimethylbenzyl] -4. -Methylphenol 4.86 g (quantitative purity 9
4.5%). 2,6-bis (4-hydroxy-3
-Hydroxymethyl-2,5-dimethylbenzyl) -4
-The yield based on methylphenol was 31.1%.

Mass spectrometry: MS 616 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
2 (s, 6H); 1.98 (s, 3H); 2.13 (s, 6H); 2.28 (s, 6
H); 3.82 (brs, 8H); 6.24 (d, J = 8.2 Hz, 2H); 6.25
(s, 2H); 6.38 (d, J = 8.2 Hz, 2H); 6.58 (s, 2H); 6.7
2 (s, 2H); 7.11 (d, J = 7.9 Hz, 2H); 7.49 (d, J =
7.9 Hz, 2H); 8.12 (brs, 1H).

Example 4: 2,6-bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl)-
Production of 2,5-dimethylbenzyl] -4-methylphenol

A 1-liter four-necked flask was charged with 1.90 g of para-toluenesulfonic acid, 86.5 g of para-cresol and 176.83 g of toluene, and the temperature was adjusted to 30 ° C. There, 2,6-of 80% purity obtained in Reference Example 1
Bis (4-hydroxy-3-hydroxymethyl-2,5
-Dimethylbenzyl) -4-methylphenol 21.83
g was divided into 10 parts, charged for 1 hour and 30 minutes, and then reacted at the same temperature for 3 hours. After completion of the reaction, the mixture was filtered and rinsed with 200 g of toluene. The obtained filtered material was charged and dissolved in a mixed solution of 200 g of toluene and 400 g of ethyl acetate at 60 ° C., 400 g of ion-exchanged water was further added, and the mixture was stirred and separated. Then, 1% oxalic acid aqueous solution 400
Demetalization was carried out by charging g, stirring, and separating. Next, after washing with 400 g of ion-exchanged water four times, the oil layer was concentrated. Toluene 200g in concentrated mass
And cooled to 20 ° C., filtered, and then toluene 200 g
I rinsed with.

The obtained filtered product was dried under reduced pressure at 45 ° C. for a whole day and night to give 2,6-bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -2,5-dimethylbenzyl] -4. -Methylphenol 22.87g (quantitative purity 9
4.6%). 2,6-bis (4-hydroxy-3-
Hydroxymethyl-2,5-dimethylbenzyl) -4-
The yield based on methylphenol was 87.6%.

Mass spectrum: MS 616 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
8 (s, 6H); 1.95 (s, 3H); 2.03 (s, 6H); 2.13 (s, 6
H); 3.78 (s, 4H); 3.88 (s, 4H); 6.28 (s, 2H); 6.32
(s, 2H); 6.68 (d, J = 8.2 Hz, 2H); 6.70 (s, 2H); 6.7
4 (d, J = 8.2 Hz, 2H); 7.95 (brs, 2H); 8.12 (brs, 1
H); 9.20 (brs, 2H).

Example 5: Preparation of 2,6-bis [4-hydroxy-3- (4-hydroxy-2,5-dimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol

In a 1 liter four-necked flask, 11.41 g of para-toluenesulfonic acid and 19,5-xylenol 19 were added.
5.47 g and 235 g of toluene were charged and the temperature was adjusted to 40 ° C. Then, 87.31 g of 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol having a purity of 80% obtained in Reference Example 1 was divided into 10 parts, The mixture was charged in 1 hour and 30 minutes, and then reacted at the same temperature for another 3 hours. After completion of the reaction, the mixture was filtered and rinsed with 200 g of toluene. The obtained filtered product was charged and dissolved in a mixed liquid of 200 g of toluene and 1000 g of ethyl acetate at 60 ° C., and further ion-exchanged water 10
00 g was added, and the mixture was stirred and separated. Thereafter, 1000 g of a 1% oxalic acid aqueous solution was charged, and the mixture was stirred and separated to perform demetalization. Next, after washing with 1000 g of ion-exchanged water four times, the oil layer was concentrated. To the concentrated mass was added 500 g of toluene, cooled to 20 ° C., filtered, and rinsed with 500 g of toluene.

The obtained filtrate was dried under reduced pressure at 45 ° C. for one day to obtain 2,6-bis [4-hydroxy-3- (4-hydroxy-2,5-dimethylbenzyl) -2,5-dimethylbenzyl]. 34.8 g of -4-methylphenol (quantitative purity 95.6%) was obtained. 2,6-bis (4-hydroxy-
3-hydroxymethyl-2,5-dimethylbenzyl)-
The yield based on 4-methylphenol was 32.3%.

Mass spectrometry: MS 644 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
0 (s, 6H); 1.88 (s, 6H); 1.95 (s, 3H); 2.13 (s, 6
H); 2.25 (s, 6H); 3.75 (s, 4H); 3.78 (s, 4H); 6.16
(s, 2H); 6.26 (s, 2H); 6.58 (s, 2H); 6.77 (s, 2H);
7.89 (brs, 2H); 8.15 (brs, 1H); 8.80 (brs, 2H).

Example 6: Preparation of 2,6-bis [4-hydroxy-3- (2-hydroxy-3,5-dimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol

In a 1 liter four-necked flask, 1.9 g of paratoluenesulfonic acid and 9,773 of 2,4-xylenol were added.
g and 199.3 g of toluene were charged and the temperature was adjusted to 30 ° C. 80% pure 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-obtained in Reference Example 1)
Dimethylbenzyl) -4-methylphenol 21.83 g
Was divided into 10 parts, charged for 1 hour and 30 minutes, and then reacted at the same temperature for another 3 hours. After completion of the reaction, the mixture was filtered and rinsed with 100 g of toluene. The obtained filtered product was charged and dissolved in a mixed liquid of 100 g of toluene and 200 g of ethyl acetate at 60 ° C., 200 g of ion-exchanged water was further added, and the mixture was stirred and separated. After that, 200 g of 1% oxalic acid aqueous solution
Was charged, stirred, and separated to demetalize. Next, after washing with 200 g of ion-exchanged water four times, the oil layer was concentrated. Toluene 100g in concentrated mass
And cooled to 20 ° C., filtered, and then toluene 100 g
I rinsed with.

The obtained filtered product was dried under reduced pressure at 45 ° C. for one day to obtain 2,6-bis [4-hydroxy-3- (2-hydroxy-3,5-dimethylbenzyl) -2,5-dimethylbenzyl]. 22.86 g (quantitative purity 95.1%) of 4-methylphenol was obtained. 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl)
The yield based on -4-methylphenol was 84.3%.

Mass spectrometry: MS 644 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
8 (s, 6H); 1.95 (s, 3H); 2.00 (s, 6H); 2.12 (s, 12
H); 3.77 (s, 4H); 3.88 (s, 4H); 6.19 (s, 2H); 6.26
(s, 2H); 6.68 (s, 2H); 6.72 (s, 2H); 8.05 (brs, 2
H); 8.14 (brs, 1H); 8.18 (brs, 2H).

Example 7: Preparation of 2,6-bis [4-hydroxy-3- (4-hydroxy-3,5-dimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol

The same operation as in Example 6 was repeated except that the same amount of 2,6-xylenol was used in place of 2,4-xylenol in Example 6, to obtain 2,6-bis [4-hydroxy-3-). 25.86 g (quantitative purity 96.4%) of (4-hydroxy-3,5-dimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol was obtained. 2,6-
Bis (4-hydroxy-3-hydroxymethyl-2,5
The yield based on -dimethylbenzyl) -4-methylphenol was 96.6%.

Mass spectrum: MS 644 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.9
2 (s, 12H); 2.05 (s, 12H); 2.14 (s, 3H); 3.77 (s, 4
H); 3.88 (s, 4H); 6.25 (s, 2H); 6.60 (s, 4H); 6.66
(s, 2H); 8.12 (brs, 5H).

Example 8: Preparation of 2,6-bis [4-hydroxy-3- (4-hydroxy-2,6-dimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol

The same operation as in Example 6 was repeated except that the same amount of 3,5-xylenol was used instead of 2,4-xylenol in Example 6, to give 2,6-bis [4-hydroxy-3-). There were obtained 15.86 g (quantitative purity 93.8%) of (4-hydroxy-2,6-dimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol. 2,6-
Bis (4-hydroxy-3-hydroxymethyl-2,5
The yield based on -dimethylbenzyl) -4-methylphenol was 57.7%.

Mass spectrum: MS 644 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
5 (s, 6H); 1.88 (s, 3H); 1.92 (s, 6H); 2.06 (s, 6
H); 2.12 (s, 6H); 3.70 (s, 4H); 3.96 (s, 4H); 6.12
(s, 2H); 6.32 (s, 2H); 6.47 (s, 2H); 6.61 (s, 2H);
7.94 (s, 2H); 8.02 (s, 1H); 9.40 (s, 2H).

Example 9: Preparation of 2,6-bis [4-hydroxy-3- (2-hydroxy-4,5-dimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol

In a 1 liter four-necked flask, 1.14 g of paratoluenesulfonic acid and 58.6 of 3,4-xylenol were added.
4 g and 119.6 g of toluene were charged and the temperature was adjusted to 30 ° C., and 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-bis (2-hydroxy-3-hydroxymethyl-2,5-) obtained in Reference Example 1 and having a purity of 80%.
Dimethylbenzyl) -4-methylphenol 13.10 g
Was divided into 10 parts, charged for 1 hour and 30 minutes, and then reacted at the same temperature for another 3 hours. After completion of the reaction, the mixture was filtered and rinsed with 100 g of toluene. The obtained filtered product was charged and dissolved in a mixed liquid of 100 g of toluene and 200 g of ethyl acetate at 60 ° C., 200 g of ion-exchanged water was further added, and the mixture was stirred and separated. After that, 200 g of 1% oxalic acid aqueous solution
Was charged, stirred, and separated to demetalize. Next, after washing with 200 g of ion-exchanged water four times, the oil layer was concentrated. Toluene 100g in concentrated mass
And cooled to 20 ° C., filtered, and then toluene 100 g
I rinsed with.

The obtained filtered product was dried under reduced pressure at 45 ° C. for one day to obtain 2,6-bis [4-hydroxy-3- (2-hydroxy-4,5-dimethylbenzyl) -2,5-dimethylbenzyl]. 6.86 g of 4-methylphenol (quantitative purity 95.8%) was obtained. 2,6-bis (4-hydroxy-
3-hydroxymethyl-2,5-dimethylbenzyl)-
The yield based on 4-methylphenol was 42.5%.

Mass spectrometry: MS 644 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
2 (s, 6H); 1.91 (s, 6H); 1.94 (s, 3H); 2.06 (s, 6
H); 2.14 (s, 6H); 3.75 (s, 4H); 3.82 (s, 4H); 6.26
(s, 2H); 6.27 (s, 2H); 6.58 (s, 2H); 6.70 (s, 2H);
7.94 (s, 2H); 8.12 (s, 1H); 9.08 (s, 2H).

Example 10: Preparation of 2,6-bis [4-hydroxy-3- (4-hydroxy-2,3,6-trimethylbenzyl) -2,5-dimethylbenzyl] -4-methylphenol

A 1 liter four-necked flask was charged with 1.14 g of paratoluenesulfonic acid, 43.58 g of 2,3,5-trimethylphenol and 88.69 g of toluene, and the temperature was adjusted to 30 ° C. Purity 80 obtained in Example 1
%, 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol (8.73 g) was divided into 10 parts and charged in 1 hour and 30 minutes.
Then, the mixture was reacted at the same temperature for 3 hours. After completion of the reaction, the mixture was filtered and rinsed with 100 g of toluene. The obtained filtered product was charged and dissolved in a mixed solution of 100 g of toluene and 200 g of ethyl acetate at 60 ° C., and further ion-exchanged water 200
g was added, and the mixture was stirred and separated. Thereafter, 200 g of a 1% oxalic acid aqueous solution was charged, and the mixture was stirred and separated to perform demetalization. Next, wash with 200 g of deionized water 4
After several rounds, 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 filtrate thus obtained was dried under reduced pressure at 45 ° C. for a whole day and night to give 2,6-bis [4-hydroxy-3- (4-hydroxy-2,3,6-trimethylbenzyl) -2,5-.
Dimethylbenzyl] -4-methylphenol 6.86g
(Quantitative purity 94.5%) was obtained. The yield based on 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol was 60.2%.

Mass spectrometry: MS 672 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
5 (s, 6H); 1.88 (s, 3H); 1.95 (s, 6H); 2.04 (s, 6
H); 2.12 (s, 12H); 3.70 (s, 4H); 3.98 (s, 4H); 6.16
(s, 2H); 6.42 (s, 2H); 6.64 (s, 2H); 8.12 (s, 1H);
8.18 (brs, 2H); 8.24 (brs, 2H).

The compounds obtained in Examples 1 to 10 have the following structures, respectively.

[0070]

[0071]

[0072]

According to the present invention, 5 represented by the formula (I)
A nuclear novolak compound can be produced with high selectivity, high purity and high yield. And 5 obtained in this way
The nuclear novolak compound is useful as a raw material of a photosensitizer or an alkali-soluble low molecular weight additive in a resist composition for semiconductor production.

Claims (8)

[Claims] 1. A 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol and a phenolic system necessary for producing a compound of the following formula (I): A compound of formula (I), characterized in that it is reacted with a compound in a molar ratio of 1: 2 to 50 in the presence of an acid catalyst. (Wherein ^one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents a hydroxyl group, one of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents a hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R
The rest of ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently of each other represent hydrogen, an alkyl having 1 to 6 carbons or a hydroxyl group). 2. The acid catalyst is present in an amount of 0.01 to 1 equivalent based on 2,6-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -4-methylphenol. the method of. 3. The method according to claim 1, wherein the reaction is carried out in a solvent. 4. The method according to claim 3, wherein the reaction solvent is selected from alcohols, water and aromatic solvents. 5. The method according to claim 3 or 4, wherein the reaction solvent is used in an amount of 0.5 to 5 times the weight of the starting phenolic compound. 6. A mixture of a starting phenolic compound, an acid catalyst and a reaction solvent is charged with 2,6-bis (4-hydroxy-).
3-hydroxymethyl-2,5-dimethylbenzyl)-
The method according to any one of claims 3 to 5, wherein 4-methylphenol is added over 0.01 to 12 hours. 7. The method according to claim 1, wherein the product is crystallized from an aromatic solvent. 8. The method according to claim 1, wherein the product is dissolved in a solvent having a water solubility of 9 g / 100 g or less, and water separation is performed to reduce the metal content.