JPH09110761A - Production of tetraphenol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tetraphenol compound in high selectivity, purity and yield without causing the inclusion of reaction solvent into the product. SOLUTION: 4,4'-Methylenebis[2-(4-hydroxybenzyl)-3,6-dimethylphenol] of the formula can be produced by reacting (A) 4,4'-methylenebis(2- hydroxymethyl-3,6-dimethylphenol) with (B) phenol at a molar ratio of 1:(5-50) in 0.25-10mol (based on 1mol of the component B) of an alcohol-containing reaction solvent (preferably a solvent essentially composed exclusively of an alcohol) using 0.01-1mol (based on 1mol of the component A) of an acidic catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to 4,4′-methylenebis [2- (4-hydroxybenzyl) -3,6-dimethyl useful as a raw material or an additive for a photosensitizer in a resist for semiconductor fine processing, for example. Phenol]. 4, which is the object of the present invention
4'-methylenebis [2- (4-hydroxybenzyl)
-3,6-dimethylphenol] has the structure of the following formula (I), and is hereinafter referred to as "tetraphenol (I)" for simplicity.
There is that.

[0002]

[0003]

2. Description of the Related Art The use of quinonediazide sulfonic acid ester of tetraphenol (I) as a photosensitizer for a resist composition for semiconductor fine processing is disclosed in JP-A-6-16780.
5 (= EP-A-573,056), in which 4,4'-methylenebis (2-hydroxymethyl-
Tetraphenol (I) is produced by reacting 3,6-dimethylphenol) with phenol in an aqueous solvent in the presence of an acid catalyst. This publication also describes crystallizing tetraphenol (I) obtained by the reaction from a mixed solution of toluene and ethyl acetate.

[0004]

DISCLOSURE OF THE INVENTION As a result of continuing research on the synthesis of tetraphenol (I), the present inventors have come to recognize that further improvement is required in reaction selectivity, yield and the like. . Further, the tetraphenol (I) obtained as described above contains about 15% by weight of a crystallization solvent, and the solvent cannot be sufficiently removed even by usual drying, so that the quantitative purity becomes low. It has been found.

Therefore, an object of the present invention is to provide tetraphenol (I) with high selectivity, high purity and high yield.
Is to manufacture. Another object of the present invention is to produce tetraphenol (I) without incorporating a solvent.

As a result of further intensive studies aimed at achieving such an object, the present inventors have found that the use of a specific reaction solvent gives favorable results, and the tetraphenol (I It was also found that the carry-in of a solvent can be avoided by subjecting (1) to a specific treatment, and the present invention has been completed.

[0007]

That is, the present invention is as follows.
4'-methylenebis (2-hydroxymethyl-3,6-
A method for producing tetraphenol (I) by reacting dimethylphenol) and phenol in a molar ratio of 1: 5 to 50 in a reaction solvent containing an alcohol in the presence of an acid catalyst. is there.

The tetraphenol (I) thus obtained can be azeotropically removed by heating the solvent incorporated therein by heating it together with isopropyl alcohol and water. Is preferred.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the reaction of the present invention, phenol is used in a molar ratio of 5 to 50 with respect to 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol). Is 10 to 30, and further 10
The range of 20 is more preferable. This reaction is carried out in the presence of an acid catalyst, and the acid catalyst may be either an inorganic acid or an organic acid, but preferable examples include hydrochloric acid, sulfuric acid and paratoluenesulfonic acid, and among them, paratoluenesulfonic acid. Is preferably used. The acid catalyst is
4,4'-methylenebis (2-hydroxymethyl-3,
6-dimethylphenol), and is preferably used in a range of 0.01 to 1 mol times, and more preferably 0.05 to 0.3.
It is more preferable to use it in a molar ratio, especially in the range of 0.1 to 0.2.

By carrying out this reaction in an alcohol solvent, the reaction of the phenol to the para position is promoted and the selectivity of the target substance is improved. The alcohol used as a reaction solvent is a lower alcohol such as methanol, ethanol,
It may be isopropyl alcohol, butyl alcohol, or the like, or a mixture thereof, but among them, methanol is preferably used. In the present invention, it is preferable to use only alcohol as a reaction solvent, but in some cases, water may be present in addition to water produced by the reaction. The alcohol as a reaction solvent is preferably used in a range of 0.25 to 10 times by mole, more preferably 0.4 to 5 times by mole, and especially 0.5 to 2 times that of phenol.
It is more preferable to use it in a molar range.

Further, by carrying out the reaction in the alcohol solvent as described above, 4,4'-methylenebis (2
-Hydroxymethyl-3,6-dimethylphenol)
Can be used even if the purity is low.
4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) having a purity in the range of -100% can be used. 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) is usually
It is produced by condensing 2,5-xylenol and formaldehyde in the presence of a base catalyst, and a high degree of purification treatment is required to increase its purity. This is advantageous because tetraphenol (I) can be produced in high purity without performing a high-level purification treatment.

The reaction was prepared by adding 4,4'-methylenebis (2) to a mixture of phenol, an acid catalyst and a reaction solvent.
-Hydroxymethyl-3,6-dimethylphenol) is preferably added. At this time, 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) is preferably added over 0.01 to 12 hours, more preferably 0.5 to 4 hours, especially 4,4'-methylenebis (2-hydroxymethyl-
It is preferred to finish the addition of 3,6-dimethylphenol).

The reaction is generally in the range from 10 ° C to the boiling point, preferably 12-60 ° C, more preferably 15 ° C.
It is carried out at a temperature in the range of ~ 35 ° C. This reaction usually proceeds under atmospheric pressure and is carried out for about 2 to 5 hours except the addition time of 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol).

After completion of the reaction, tetraphenol (I) is in a state of being dissolved in an alcohol solvent. If necessary, after neutralizing with a base such as aqueous ammonia, tetraphenol (I) may be added. I) can be taken out as a solid. For example, a method in which a poor solvent is added to the reaction solution or a solution obtained by neutralizing the solution and crystallization is performed can be adopted. The crystallization solvent used here is an aromatic solvent, which is also an aromatic hydrocarbon solvent such as benzene, toluene,
Examples thereof include xylene, and among them, toluene is preferably used. In addition, aromatic solvents and esters or ketones such as ethyl acetate, methyl isobutyl ketone,
A mixed solvent with acetone or the like is also preferably used.

Tetraphenol (I) thus obtained
Can be used as a photosensitizer in a resist composition for semiconductor production after being converted to a quinonediazide sulfonate, and this tetraphenol (I) itself is also used as an alkali-soluble additive in a resist composition for semiconductor production. You can also Thus, when tetraphenol (I) is used as a component or raw material of a resist composition for semiconductor production, the crude product obtained by the reaction is dissolved in a solvent having a solubility in water of 9 g / 100 g or less. It is preferable to reduce the metal content by washing and separating with water. Here, the solubility in water is 9g
"/ 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 tetraphenol (I) of 1 g / 100 g or more at 20 ° C. Examples of such a solvent include ethyl acetate, n-butyl acetate, acetic acid esters such as isoamyl acetate, ketones such as methyl isobutyl ketone and 2-heptanone, and the like.
Among them, ethyl acetate is preferably used.

In the solution containing tetraphenol (I) whose 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 previous crystallization, but toluene is preferably used.

The resulting tetraphenol (I) may also be further subjected to any purification means. In particular, since the reaction solvent and / or the crystallization solvent incorporated in the product can be removed azeotropically by heating with isopropyl alcohol and water, such an operation is preferably adopted. In this case, isopropyl alcohol is preferably used in a proportion of 0.3 to 5 times by weight that of water.

[0018]

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. The percentages given in the examples are by weight unless otherwise stated.

Example 1 A 5-liter four-necked flask was charged with sodium carbonate 18
Charge 2.9g and 808.5g of water to dissolve, then 2,
808.5 g of 5-xylenol was charged and the temperature was adjusted to 40 ° C. 2378.5% formalin 2148.5 g was dripped there over 1 hour. After finishing the dropping, while checking the physical properties of the reaction mass,
404.6 g of methyl isobutyl ketone was charged and stirred for 7 hours. After completion of the reaction, it was neutralized with 220.8 g of 90% acetic acid aqueous solution and cooled with stirring. When the temperature reaches 25 ° C, stop stirring, remove the supernatant liquid, and then deionize water 330
0 g was charged and stirred for 1 hour, the stirring was stopped again, and the supernatant was removed. After repeating the washing with ion-exchanged water and the removal of the supernatant twice, the ion-exchanged water 3
300 g was charged, the mixture was stirred for 1 hour, filtered, and then rinsed with 4290 g of ion-exchanged water. The obtained filtrate is 45
After drying under reduced pressure at ℃ for 24 hours, 4,4'-methylenebis (2
-Hydroxymethyl-3,6-dimethylphenol) 1
013.1 g (purity 65.6%) was obtained. Yield 63.5%.

Separately, in an 8-liter four-necked flask, 54.0 g of paratoluenesulfonic acid and 3244.0 of phenol.
and 1077.4 g of methanol were charged and the temperature was adjusted to 20 ° C. There, 4,4 'of 65.6% purity obtained above
-977.7 g of methylenebis (2-hydroxymethyl-3,6-dimethylphenol) was divided into 10 parts, and 3 hours were taken for 1 hour.
It was added over 0 minutes, and then the reaction was continued for 2 hours. After completion of the reaction, the solution was neutralized with 58.0 g of 25% aqueous ammonia and then concentrated, and then 120.0 g of methanol was charged. Next, the temperature was raised to 60 ° C., and at the same temperature, 2326.7 g of toluene and 581.7 g of ethyl acetate were charged, cooled to 40 ° C., and stirred for 6 hours. Then filtered and toluene 2617.6
and a mixed solution of 290.8 g of ethyl acetate and rinsed to obtain 960.5 g of a filtrate. This filtered material was dissolved in 1921.2 g of ethyl acetate, and after further charging 480.3 g of toluene and 1120.7 g of ion-exchanged water and stirring,
Separated. Next, demetalization was carried out by charging 1120.7 g of a 1% aqueous oxalic acid solution, stirring and separating the solution.
Furthermore, after washing with 110.7 g of ion-exchanged water was repeated 4 times, the oil layer was concentrated. Toluene 1 in concentrated mass
398.5 g was charged and cooled to 20 ° C., and stirring was stopped.

The supernatant liquid was removed, and toluene 11 was added thereto.
A mixed solution of 69.1 g and 129.9 g of ethyl acetate was charged and stirred for 30 minutes, then the stirring was stopped and the supernatant was removed. The procedure of washing with a mixed solution of toluene / ethyl acetate and the removal of the supernatant was repeated 4 times, and then 1587.7 g of isopropyl alcohol and 1587.7 g of ion-exchanged water were charged into the remaining mass and the mixture was concentrated. To the concentration residue,
714.5 g of isopropyl alcohol and 1667.1 g of ion-exchanged water were charged and concentrated again. The concentrated residue was charged with 119.8 g of ion-exchanged water, cooled to 40 ° C., filtered, and rinsed with 119.8 g of ion-exchanged water. The obtained filtered product was dried under reduced pressure at 45 ° C. for one day to obtain 4,4 ′.
-Methylenebis [2- (4-hydroxybenzyl)-
3,4.6-Dimethylphenol] 384.6 g was obtained. The quantitative purity was 96.8%, and the yield based on 2,5-xylenol was 24.8%. The yield based on 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) was 39.1%.

Mass spectrometry: MS 468 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.9
5 (s, 6H); 2.07 (s, 6H); 3.64 (brs, 2H); 3.92 (s, 4
H); 6.41 (s, 2H); 6.61 (d, J = 8.6 Hz, 4H); 6.88 (d,
J = 8.6 Hz, 4H); 7.95 (s, 2H); 9.07 (s, 1H).

Example 2 733.2 g of 2,5-xylenol, 6 of sodium hydroxide
To a mixture of 0.0 g and 540 g of water at 70-75 ° C,
1622 g of 37% formalin was added dropwise over 3 hours.
After the addition, the mixture was stirred at the same temperature for 4 hours. After cooling to 55 ° C., 172 g of 36% hydrochloric acid was added and stirred for 10 minutes,
Then, 1500 g of methyl isobutyl ketone was added to completely dissolve the reaction mixture. Next, at the same temperature, deionized water 15
0 g was added for washing, and the layers were separated. The obtained oil layer was concentrated, 500 g of toluene was added, and the mixture was stirred overnight at room temperature.
The precipitated crystals were filtered and the resulting cake was washed with toluene 80
It was washed with 0 g to obtain 425.1 g of wet cake. Ethyl acetate (425 g) and toluene (300 g) were added to this wet cake, and the mixture was washed by stirring at 75 to 80 ° C. for 2 hours. Next, after concentrating the solvent, add 500 g of toluene and add 75
It was washed by stirring at -80 ° C for 1 hour. It was then cooled to room temperature and filtered. The cake obtained is toluene 800
After mixing and stirring with g to wash, filter, dry,
4'-methylenebis (2-hydroxymethyl-3,6-
193.5 g (purity 95%) of dimethylphenol was obtained. Yield 19.4%.

Separately, 5.40 g of paratoluenesulfonic acid,
A mixture of 324.4 g of phenol and 107.7 g of methanol was thermostated at 20 ° C. There, purity 9 obtained above
67.5 g of 5% 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) was divided into 10 parts, charged over 1 hour and 30 minutes, and further reacted for 2 hours. After completion of the reaction, the mixture was neutralized with 5.8 g of 25% aqueous ammonia and then concentrated, and then 12.0 g of methanol was charged. Next, the temperature was raised to 60 ° C., and at the same temperature, toluene 23 was added.
2.7 g and ethyl acetate 58.2 g were charged, and the mixture was cooled to 40 ° C. and stirred for 6 hours. After that, it is filtered and toluene 26
Rinsing with a mixed solution of 1.8 g and ethyl acetate 29.1 g yielded 115.3 g of filtrate. This filtered material was dissolved in 230.5 g of ethyl acetate, 57.6 g of toluene and 134.5 g of ion-exchanged water were charged, and the mixture was stirred and then separated. Next, 134.5 g of a 1% aqueous oxalic acid solution was charged, stirred, and then liquid-separated to remove metal. Furthermore, after washing with 134.5 g of ion-exchanged water was repeated 4 times, the oil layer was concentrated. To the concentrated mass was charged 167.8 g of toluene, cooled to 20 ° C., and stirring was stopped.

The supernatant liquid was removed and toluene 14 was added thereto.
A mixed solution of 0.3 g and ethyl acetate (15.6 g) was charged and stirred for 30 minutes, then the stirring was stopped and the supernatant was removed. The procedure of washing with a mixed solution of toluene / ethyl acetate and the removal of the supernatant was repeated four times, and then 190.5 g of isopropyl alcohol and 190.5 g of ion-exchanged water were charged into the remaining mass and the mixture was concentrated. 85.7 g of isopropyl alcohol and 200 g of deionized water in the concentrated residue
Was charged and concentrated again. Ion-exchanged water 14 in the concentrated residue
2.9 g was charged, the mixture was cooled to 40 ° C., filtered, and then rinsed with 142.9 g of ion-exchanged water. The obtained filtered product was dried under reduced pressure at 45 ° C. for a day and night to obtain 46.1 g of 4,4′-methylenebis [2- (4-hydroxybenzyl) -3,6-dimethylphenol]. The quantitative purity was 96.9%, and the yield based on 2,5-xylenol was 9.1%. The yield based on 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) is 47.0.
%Met.

Comparative Example 188 g phenol, 46 g water and 0.9 g 96% sulfuric acid.
While keeping the mixture of 30 to 35 ° C., 4,4′-methylenebis (2 having a purity of 95% obtained in the first half of Example 2 was obtained.
-Hydroxymethyl-3,6-dimethylphenol) 3
1.6 g was charged in 30 portions every 30 minutes. After the completion of charging, the mixture was stirred at the same temperature for 2 hours. Then toluene 2
A mixture of 00 ml, 200 ml of ethyl acetate and 300 ml of water was added to wash and separate the layers. The obtained oil layer was concentrated, 9.3 g of ethyl acetate and 186 g of toluene were added, and the mixture was stirred overnight at room temperature. The precipitated crystals were filtered, and the obtained cake was mixed with 60 ml of toluene with stirring and washed.
Next, after filtration, the obtained cake was dissolved in 32.7 g of acetone at 50 to 55 ° C., 68 g of toluene was added, and then acetone was concentrated and then filtered. The obtained cake was dissolved in acetone, toluene was added thereto, and then acetone was concentrated and then filtered. The cake obtained is mixed with toluene and stirred to wash, and the cake after filtration is dried,
18.5 g of 4,4'-methylenebis [2- (4-hydroxybenzyl) -3,6-dimethylphenol] was obtained.
The quantitative purity was 80.5%, and the yield based on 2,5-xylenol was 6.4%. The yield based on 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) was 33.5%.

[0027]

INDUSTRIAL APPLICABILITY According to the present invention, tetraphenol (I) can be produced with high selectivity, high purity and high yield. In particular, if the crude product after the reaction is heated with isopropyl alcohol and water, the solvent is azeotropically removed, and tetraphenol (I) can be obtained with a small solvent uptake. According to the present invention, the raw material 4,4'-methylenebis (2-hydroxymethyl-
Even if the purity of 3,6-dimethylphenol) is low, good results can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 37/72 C07C 37/72 37/78 37/78 37/84 37/84 // C07B 61 / 00 300 C07B 61/00 300 (72) Inventor Haruki Ozaki 3-98 Kasugadeka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (9)

[Claims] 1. The presence of an acid catalyst in a reaction solvent containing alcohol in a molar ratio of 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) and phenol in a ratio of 1: 5 to 50. A method for producing 4,4'-methylenebis [2- (4-hydroxybenzyl) -3,6-dimethylphenol], which comprises reacting below. 2. The method according to claim 1, wherein the reaction solvent consists essentially of alcohol. 3. The reaction solvent for phenol is 0.25-1.
The method according to claim 1 or 2, which is used in an amount of 0 mol times. 4. The acid catalyst according to claim 1, wherein the acid catalyst is used in an amount of 0.01 to 1 mole times that of 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol). Method. 5. A 4,4'-methylenebis (2-hydroxymethyl-3,6-dimethylphenol) is added to a mixture of phenol, an acid catalyst and a reaction solvent over 0.01 to 12 hours. The method according to any one of to 4. 6. The method according to any one of claims 1 to 5, comprising a step of taking out the reaction product as a solid. 7. The method according to claim 6, wherein the product is crystallized from a crystallization solvent containing an aromatic solvent. 8. The method according to claim 6, 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. 9. The method according to claim 1, wherein the product is heated with isopropyl alcohol and water to azeotropically remove the solvent incorporated therein.