JPH09110757A - Pentaphenol compound, its intermediate and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound giving a photosensitive resin composition having balanced resist performance such as high sensitivity, high resolution, good profile, good focus allowability and little generation of residues in developing. SOLUTION: This compound is expressed by formula I (R<1> to R<5> are each H or 1,2-naphthoquinonediazido-4- or 5-sulfonyl), e.g. 2,4-bis(4-hydroxy-2,-5- dimethylbenzyl)-3,5,6-trimethylphenol. A compound of formula I wherein all the R<1> to R<5> are H can be produced by condensing triphenol of formula II with formaldehyde in the presence of an alkaline catalyst and reacting the resultant dimethyloltriphenol of formula III with p-cresol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pentaphenol compound useful as a photosensitizer or a precursor thereof, an intermediate thereof, and a method for producing them.

[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, a composition containing a compound having a quinonediazide group and a novolak resin is applied on a metal substrate, and when this is irradiated with light of 300 to 500 nm, the quinonediazide group is decomposed to generate a carboxyl group, and an alkali-insoluble state is converted into an alkali. 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 that it has a higher resolution than a negative resist, it is used for manufacturing various integrated circuits for semiconductors.

[0003] In recent years, integrated circuits in the semiconductor industry have been steadily miniaturized with high integration, and submicron pattern formation is now required. Among them, the lithography process occupies an important position in the production of integrated circuits, and even positive resists are required to have even higher resolution (high γ value).

With respect to a resist material containing a quinonediazide compound and a novolac resin, many proposals have been made in the past regarding combinations of 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 to improve the resist performance such as sensitivity, resolution and heat resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to produce and provide a novel phenolic compound which can be a photosensitizer component of a photosensitive resin composition or a raw material thereof.

Another object of the present invention is to use such a compound to obtain a photosensitive resin composition having a well-balanced resist performance such as high sensitivity, high resolution, good profile, good focus tolerance and small development residue. To provide things.

[0007]

As a result of intensive studies, the inventors of the present invention found a phenolic compound having a specific structure having five phenolic hydroxyl groups, and sensitized this compound by quinonediazide sulfonate esterification. It was found that the above-mentioned object can be achieved by using it as an agent and completed the present invention.

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

[0009]

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵
Independently of one another represent hydrogen or 1,2-naphthoquinonediazide-4- or-5-sulfonyl. The 1,2-naphthoquinonediazide-4- or -5-sulfonyl as used herein means a group represented by any of the following formulas.

[0011]

The invention also relates to R ¹ , R ¹ in formula (I)
2,4-wherein ² , R ³ , R ⁴ and R ⁵ are all hydrogen
Bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -2,5-dimethylbenzyl] -3,
The following formula (II) which can be a precursor of 5,6-trimethylphenol (hereinafter sometimes referred to as “pentaphenol (I)”)

[0013]

2,4-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) represented by
-3,5,6-trimethylphenol (hereinafter sometimes referred to as "dimethylol triphenol (II)"), and further, this dimethylol triphenol (I
The following formula (III) that can be a precursor of I)

[0015]

2,4-bis (4-hydroxy-2,5-dimethylbenzyl) -3,5,6-trimethylphenol (hereinafter sometimes referred to as "triphenol (III)") represented by provide.

The present invention further provides 2,4-bis (hydroxymethyl) -3,5,6-trimethylphenol,
A method for producing triphenol (III) by reacting with 2,5-xylenol is provided, and dimethylol triphenol (II) is produced by reacting triphenol (III) with formaldehyde in the presence of an alkali catalyst. And a method for producing pentaphenol (I) by reacting dimethyloltriphenol (II) with para-cresol,
Furthermore, by reacting pentaphenol (I) with 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide, R ¹ in the formula (I),
At least one of R ² , R ³ , R ⁴ and R ⁵ is 1, 2
Also provided is a method for producing a compound that is naphthoquinonediazide-4- or -5-sulfonyl (hereinafter sometimes referred to as "ester (I)").

The ester (I) is useful as a photosensitizer which is sensitive to radiation such as near-ultraviolet light or far-ultraviolet light (including excimer laser and the like). Therefore, according to the present invention, the ester (I) is used as an active ingredient. A photosensitizer is also provided. Then, a photosensitive resin composition containing such a photosensitizer together with an alkali-soluble resin can be obtained. Further, in the formula (I), a compound in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ are all hydrogen, that is, pentaphenol (I) is useful as a precursor of the ester (I).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Pentaphenol (I) can be produced, for example, by reacting dimethyloltriphenol (II) with para-cresol. The dimethylol triphenol (II) used as a raw material in this reaction can be produced, for example, by condensing triphenol (III) and formaldehyde in the presence of an alkali catalyst. Further, triphenol (III) is, for example, 2,3-bis (hydroxymethyl) -3,5,6-trimethylphenol obtained by dimethylolation of 2,3,5-trimethylphenol with formaldehyde, which is converted into 2,5-bis (hydroxymethyl) -3,5,6-trimethylphenol. It can be produced by condensing with xylenol. Hereinafter, the reaction of starting from 2,3,5-trimethylphenol to pentaphenol (I) and further to ester (I) will be sequentially described.

The reaction of 2,3,5-trimethylphenol with formaldehyde gives 2,4-bis (hydroxymethyl) -3,5,6-trimethylphenol. In this reaction, formaldehyde is preferably used in a molar ratio in the range of 2 to 10 with respect to 2,3,5-trimethylphenol, and more preferably in a molar ratio in the range of 4 to 8, especially 5 to 6. Is more preferable. If this molar ratio is too high or too low, the selectivity of the reaction tends to decrease. This reaction is carried out in the presence of an alkali catalyst. The alkali catalyst may be either an inorganic base or an organic base, but inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, among which sodium hydroxide is preferably used. The alkali catalyst is generally used in an amount of 0.5 to 5 mole times, preferably 1 to 4 mole times, more preferably 1 to 2 mole times, with respect to 2,3,5-trimethylphenol. . If the amount of the catalyst is too small, the reaction time becomes long, and if it is too large, the selectivity of the reaction becomes poor.

This reaction is generally carried out in a solvent, and a polar solvent such as tetrahydrofuran, dioxane, water or methanol is preferable as the reaction solvent, and water is particularly preferably used. The amount of the solvent is generally in the range of 1 to 10 times by weight, preferably 2 to 6 times by weight, more preferably 3 to 5 times by weight, based on 2,3,5-trimethylphenol. The reaction is preferably charged by adding formaldehyde to a mixture of 2,3,5-trimethylphenol, an alkali catalyst and a reaction solvent.
At this time, formaldehyde is preferably added over 0.5 to 4 hours, more preferably 0.5 to 2 hours, and especially 0.5.
It is preferred to complete the addition of formaldehyde in ~ 1 hour. When formaldehyde is rapidly added, heat generation is intense and the selectivity of the reaction tends to decrease, while if the formaldehyde addition time is too long, by-products tend to increase. Formaldehyde is preferably added by a method of dropping the aqueous solution.

2,4-bis (hydroxymethyl) -3,5,6-trimethylphenol thus obtained is
By reacting with 5-xylenol, triphenol (III) is obtained. In this reaction, 2,5-xylenol is 2,4-bis (hydroxymethyl)-
It is generally used in a molar ratio in the range of 1 to 10, preferably 1.5 to 6 and more preferably 2 to 4 with respect to 3,5,6-trimethylphenol. This reaction is generally performed 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 paratoluenesulfonic acid. Among them, sulfuric acid or paratoluenesulfonic acid is preferable, and sulfuric acid is particularly preferably used. The acid catalyst is used usually in an amount of 1 equivalent or less, preferably 0.01 to 0.5 equivalent, based on 2,4-bis (hydroxymethyl) -3,5,6-trimethylphenol.

This reaction is preferably carried out in a solvent, in which case the reaction solvent is preferably an aromatic solvent, either an aromatic hydrocarbon solvent or an alcohol solvent, also methanol. Examples of the aromatic hydrocarbon solvent include benzene, toluene and xylene, and among them, toluene is preferably used. The reaction solvent is generally in the range of 0.5 to 5 times by weight, preferably 1 to 3 times by weight, and more preferably 1 based on the amount of 2,5-xylenol.
It is used in the range of up to 2 times by weight. The reaction is usually carried out at a temperature in the range of 10 ° C to the boiling point, preferably in the range of 15 to 60 ° C for about 2 to 3 hours. This reaction usually proceeds at atmospheric pressure.

After completion of the reaction, it is preferable to reduce the metal content by adding a solvent having a water solubility of 9 g / 100 g or less to the reaction mass and then performing water separation. Here, the solubility in water of 9 g / 100 g or less means
It means that the maximum amount that can be dissolved in 100 g of water at 20 ° C. is 9 g or less. The solvent used here preferably has a solubility of triphenol (III) at 20 ° C. of 1 g / 100 g or more. 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.

In the solution containing triphenol (III) thus reducing the amount of metal, 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.

By reacting the triphenol (III) thus obtained with formaldehyde, dimethylol triphenol (II) can be obtained. In this reaction, formaldehyde is preferably used in a molar ratio of 2 to 10 with respect to triphenol (III), more preferably 4 to 8, and most preferably 5 to 6. . If this molar ratio is too high or too low, the selectivity of the reaction tends to decrease. This reaction is carried out in the presence of an alkali catalyst. The alkali catalyst may be either an inorganic base or an organic base, but inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, among which sodium hydroxide is preferably used. The alkali catalyst is generally 0.5 to 6 mole times, preferably 2 to 5 times the triphenol (III).
It is used in a molar amount, more preferably in a range of 3 to 4 times. If the amount of the catalyst is too small, the reaction time becomes long, and if it is too large, the selectivity of the reaction becomes poor.

This reaction is generally carried out in a solvent, and the reaction solvent is preferably a polar solvent such as tetrahydrofuran, dioxane, water or methanol, and among them, a mixed solvent of water and tetrahydrofuran is preferably used.
The amount of the solvent is generally in the range of 1 to 10 times by weight, preferably 2 to 6 times by weight, more preferably 3 to 5 times by weight, based on triphenol (III). The reaction temperature is generally in the range of 10 to 60 ° C, preferably 30 to 50 ° C, more preferably 35 to 45 ° C. If the reaction temperature is too high, the selectivity of the reaction will decrease, and if the temperature is too low, the reaction will be slow. The reaction was charged with triphenol
A method of adding formaldehyde to a mixture of (III), an alkali catalyst and a reaction solvent is preferable. At this time, formaldehyde is preferably added over 0.5 to 4 hours, more preferably 0.5 to 2 hours, and particularly preferably 0.5 to 1 hour, to complete the addition of formaldehyde. When formaldehyde is rapidly added, heat generation is intense and the selectivity of the reaction tends to decrease, while if the formaldehyde addition time is too long, by-products tend to increase. Formaldehyde is preferably added by a method of dropping the aqueous solution.

By reacting the dimethyloltriphenol (II) thus obtained with para-cresol,
Pentaphenol (I) is obtained. In this reaction, para-cresol is generally used in a molar ratio of 2 to 50, preferably 4 to 20, and more preferably 8 to 20 with respect to dimethyloltriphenol (II). At this time, it is preferable to use an acid catalyst. The acid catalyst may be either an inorganic acid or an organic acid. 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 used in an amount of 1 equivalent or less with respect to dimethyloltriphenol (II), preferably 0.1.
Used in the range of up to 0.5 equivalent.

This reaction is preferably carried out in a solvent, in which case the reaction solvent is preferably an aromatic solvent, which is also an aromatic hydrocarbon solvent. Examples of the aromatic hydrocarbon solvent include benzene, toluene and xylene, and among them, toluene is preferably used. The reaction solvent, such as an aromatic solvent, is generally in the range of 0.5 to 5 times by weight, preferably 1 to 3 times by weight, more preferably 1 to 2 times by weight, based on the amount of para-cresol. Used in. The reaction is usually carried out at a temperature in the range of 10 ° C to the boiling point, preferably in the range of 15 to 60 ° C for about 2 to 3 hours. This reaction usually proceeds at atmospheric pressure.

When the reaction is carried out near room temperature in an aromatic solvent, the reaction proceeds as the reaction proceeds, 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. Crystals of certain pentaphenol (I) are deposited. 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.

Further, when this compound is converted to a quinonediazide sulfonic acid ester as described below to be used as a photosensitizer in a photosensitive resin composition for semiconductor production, a solvent having a solubility in water of 9 g / 100 g or less is used. After the crude product is dissolved, it is preferably washed with water and separated to reduce the metal content. Here, the solubility in water is 9
The term "g / 100g or less" means that the maximum amount that can be dissolved in 100g of water at 20C is 9g or less. The solvent used here preferably has a solubility of pentaphenol (I) at 20 ° C. of 1 g / 100 g or more. 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.

In the solution containing pentaphenol (I) thus reduced in metal, 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.

Pentaphenol (I) thus obtained
Is, for example, quinonediazide sulfonic acid esterification,
It can be a photosensitizer. For esterification,
Although various sulfonic acid derivatives having a 1,2-quinonediazide skeleton can be used, 1,2-naphthoquinonediazide-4- or -5-sulfonylhalide is preferably used. The halogen constituting the sulfonyl halide can be, for example, chlorine or bromine,
Usually chlorine is preferred and therefore 1,2-
Naphthoquinonediazide-4- or -5-sulfonyl chloride is preferably used as the esterifying agent.
Further, a mixture of 1,2-naphthoquinonediazide-4-sulfonyl halide and 1,2-naphthoquinonediazide-5-sulfonyl halide can also be used.

In the esterification reaction, 1,2-naphthoquinonediazide-4- and / or -5-sulfonyl halide is usually used in an amount of 1.2 with respect to pentaphenol (I).
It is used in a molar ratio of from 5 to 5, preferably from 1.4 to 4, and more preferably from 1.4 to 2.5.

This reaction is usually carried out in the presence of a dehydrohalogenating agent. The dehydrohalogenating agent is generally a basic compound, for example, an inorganic base such as sodium carbonate or sodium hydrogen carbonate, ethylamine, ethanolamine, diethylamine, diethanolamine, triethylamine, N, N-dimethylaniline, N, N. -Amines such as diethylaniline. The dehydrohalogenating agent is 1,2-naphthoquinonediazide-4-
Or for -5-sulfonyl halide, usually 1.05
It is used in a molar ratio of 1.5, preferably 1.05 to 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 in the range of 2 to 6 times by weight, preferably 3 to 3 based on the total amount of pentaphenol (I) and quinonediazide sulfonyl halide.
It is used in an amount of 5 times by weight, more preferably 4 to 5 times by weight.

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.

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

The thus esterified compound can be advantageously used as a photosensitizer sensitive to radiation such as near-ultraviolet light or far-ultraviolet light (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.

If desired, 1,2-quinonediazide sulfonic acid ester of another phenolic compound may be used in combination. Specific examples of the quinonediazide sulfonic acid ester used in combination include the compounds described in JP-A-5-204148 and JP-A-5-323597 (= EP-A-57).
0,884), JP-A-6-167805 (= EP-
A-573,056), a compound of the following formula (IV)

[0042]

(In the formula, one of R ¹¹ and R ¹² is —OQ ⁴
The other of R ¹¹ and R ¹² , R ¹³ , R ¹⁴ and R
¹⁵ independently represents hydrogen, alkyl having 6 or less carbon atoms, cycloalkyl having 6 or less carbon atoms, alkenyl having 6 or less carbon atoms, alkoxy having 6 or less carbon atoms or halogen;
R ¹⁶ and R ¹⁷ each independently represent hydrogen, alkyl having 6 or less carbon atoms or alkenyl having 6 or less carbon atoms,
Or both of them together at the terminal form a cycloalkane ring having 6 or less carbon atoms together with the carbon atom to which they are bonded; ^one of Q ¹ , Q ² , Q ³ and Q ⁴ represents o-quinonediazidesulfonyl. , The rest, independently of one another, represent hydrogen or o-quinonediazidesulfonyl).

Examples thereof include compounds represented by (described in Japanese Patent Application No. 7-58826 filed by the present applicant).

In the present invention, including such other quinonediazide sulfonic acid ester, when used, the photosensitizing agent is used in an amount of 10 to 50% by weight based on the total solid content in the photosensitive resin composition. It is preferably contained in the range.

The alkali-soluble novolac resin constituting the photosensitive resin composition is obtained by condensing a compound having at least one phenolic hydroxyl group and an aldehyde in the presence of an acid catalyst, and its type is The material is not particularly limited, and various materials used in the resist field can be used. Examples of the phenolic compound that is a raw material of the novolac resin include metacresol and
Para-cresol, ortho-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol,
2,3,5-trimethylphenol, 2-t-butyl-
5-methylphenol, t-butylhydroquinone and the like. 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 and is preferably used.

Novolak resins can be obtained by condensing one or more of these phenolic compounds and one or more of aldehydes in the presence of an acid catalyst. As the acid catalyst, organic acids, inorganic acids, divalent metal salts and the like are used, and specific examples thereof include oxalic acid, acetic acid, paratoluenesulfonic 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
It takes about 30 hours. 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 carried out, a novolak 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 also 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 the alkali-soluble phenolic compound having a molecular weight of 900 or less, those having two or more phenolic hydroxyl groups in the molecular structure are preferable, for example, JP-A-2-275955 (= EP-A-358,871) and JP-A-2-2560. And the like described in the publication. When an alkali-soluble phenolic compound having a molecular weight of 900 or less is used, it is preferably contained in the range of 3 to 40% by weight based on the total solid content in the photosensitive resin composition.

The resist solution containing the photosensitive resin composition is prepared by mixing and dissolving a photosensitizer and a novolac resin, or, if necessary, an alkali-soluble phenolic compound having a molecular weight of 900 or less in a solvent.
The solvent used here preferably has an appropriate drying rate and gives a uniform and smooth coating film after the solvent evaporates. 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, and 2-heptanone. Ketones, cyclic esters such as γ-butyrolactone, those described in JP-A-2-220056, JP-A-4-362645, JP-A-4-3
No. 67863, and the like. 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.

[0052]

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: Dimethylolation of 2,3,5-trimethylphenol A 2 liter four-necked flask was charged with 13,3,5-trimethylphenol (136.19 g), sodium hydroxide (48.0 g) and water (480 g). It melt | dissolved and temperature-controlled at 40 degreeC.
486.91 g of 37% formalin was added dropwise thereto over 1 hour, and the mixture was further stirred at the same temperature for 3 hours. After the reaction was completed, neutralize with 180.15 g of 90% acetic acid aqueous solution and then 25
Cooled to ° C and filtered. The filtrate was extracted with 1000 g of ethyl acetate, the ethyl acetate layer was washed with water and then concentrated. The concentrated mass was charged with 500 g of toluene, cooled to 20 ° C., filtered, and rinsed with 400 g of toluene. The obtained filtered product was dried under reduced pressure at 45 ° C for a whole day and night to obtain 100 g of 2,4-bis (hydroxymethyl) -3,5,6-trimethylphenol (purity 90%). Yield 45.9%.

Mass Spectrometry: MS 196 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 2.0
6 (s, 3H); 2.19 (s, 3H); 2.21 (s, 3H); 4.41 (d, J =
8.2 Hz, 2H); 4.43 (t, J = 8.2 Hz, 1H); 4.62 (s, 2
H); 5.41 (brs, 1H); 8.80 (brs, 1H).

Example 1 Preparation of Triphenol (III) In a 5 liter four-necked flask, 5.88 g of sulfuric acid, 2,5-
293.2 g of xylenol and 293.2 g of methanol were charged and the temperature was adjusted to 30 ° C. There, 90% of purity 2,
4-Bis (hydroxymethyl) -3,5,6-trimethylphenol (117.75 g) was divided into 10 portions, charged in 1 hour, and then reacted at the same temperature for 2 hours. After completion of the reaction, 500 g of toluene and 1000 g of ethyl acetate were charged, 1000 g of ion-exchanged water was further charged, and the mixture was stirred and then separated. After that, 1000 g of a 1% oxalic acid aqueous solution was charged into the oil layer, and the mixture was stirred and separated to remove metal. Next, after washing with 1000 g of ion-exchanged water four times, the oil layer was concentrated. To the concentrated mass, 500 g of toluene was added, cooled to 20 ° C., filtered, and rinsed with 200 g of toluene. The filtered substance was charged into 500 g of ethyl acetate and dissolved, and the oil layer was concentrated. The concentrated mass was charged with 500 g of toluene, cooled to 20 ° C., filtered, and rinsed with 200 g of toluene.
The obtained filtered product was dried under reduced pressure at 45 ° C. for 24 hours to obtain 2,4
-Bis (4-hydroxy-2,5-dimethylbenzyl)
98.6 g (quantitative purity 99.38%) of -3,5,6-trimethylphenol was obtained. The yield based on 2,4-bis (hydroxymethyl) -3,5,6-trimethylphenol was 44.8%.

[0056] Mass spectrometry: MS 404 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
1 (s, 3H); 1.89 (s, 6H); 2.00 (s, 3H); 2.12 (s, 3
H); 2.22 (s, 6H); 3.68 (s, 2H); 3.78 (s, 2H); 6.08
(s, 1H); 6.15 (s, 1H); 6.58 (s, 1H); 6.60 (s, 1H);
7.80 (s, 1H); 8.80 (s, 1H); 8.85 (s, 1H).

Example 2: Preparation of dimethyloltriphenol (II) 2,4-bis (4-hydroxy-2,5-dimethylbenzyl) -3,5,6-trimethylphenol was added to a 500 ml four-necked flask. 40.45g, sodium hydroxide 1
4.40 g, water 144 g and tetrahydrofuran 14.4
0 g was charged and dissolved, and the temperature was adjusted to 40 ° C. 37 there
% Formalin (48.69 g) was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 3 hours. After the reaction, 90
The mixture was neutralized with 18.02 g of aqueous acetic acid solution, cooled to 25 ° C., and filtered. The filtered product was dissolved in a mixed solution of 100 g of ethyl acetate and 14.40 g of tetrahydrofuran, washed with water, and the oil layer was concentrated. 100 g of toluene was charged to the concentrated mass, cooled to 20 ° C., and then filtered to obtain 10 parts of toluene.
Rinse with 0 g. The obtained filtered product was dried under reduced pressure at 45 ° C for a whole day and night to give 2,4-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -3,5.
36.8 g (purity 75%) of 6-trimethylphenol was obtained. Yield 59.4%.

Mass Spectrometry: MS 464 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.7
8 (s, 3H); 1.93 (s, 6H); 2.01 (s, 3H); 2.13 (s, 3
H); 2.26 (s, 6H); 3.71 (s, 2H); 3.81 (s, 2H); 4.67
(s, 4H); 5.22 (brs, 2H); 6.08 (s, 1H); 6.13 (s, 1
H); 7.78 (brs, 1H); 8.46 (brs, 1H); 8.47 (brs, 1H).

Example 3: Preparation of pentaphenol (I) In a 200 ml four-necked flask, 0.57 g of paratoluenesulfonic acid, 38.93 g of paracresol and 3 of toluene.
8.93 g was charged and the temperature was adjusted to 30 ° C. Then, 10.94 g of 2,4-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -3,5,6-trimethylphenol having a purity of 75% obtained in Example 2 was added thereto. The mixture was divided, charged for 1 hour and 30 minutes, and then reacted at the same temperature for another 2 hours. After the reaction was completed, the precipitated crystals were filtered and rinsed with 100 g of toluene. The filtered material was charged into a mixed solution of 100 g of toluene and 200 g of ethyl acetate at 60 ° C. to dissolve the filtered material, and further 200 ion-exchanged water was added.
g was charged, stirred, and then separated. To the oil layer, 200 g of a 1% oxalic acid aqueous solution was added, and the mixture was stirred and separated to remove metal. 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,
Rinse with 100 g of toluene. The obtained filtrate is 45
After drying under reduced pressure at ℃ for 24 hours, 2,4-bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl)-
10.3 g (quantitative purity 94.9%) of 2,5-dimethylbenzyl] -3,5,6-trimethylphenol was obtained. 2,
4-bis (4-hydroxy-3-hydroxymethyl-
The yield based on 2,5-dimethylbenzyl) -3,5,6-trimethylphenol was 68.0%.

Mass spectrometry: MS 644 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.8
1 (s, 3H); 2.01 (s, 12H); 2.11 (s, 6H); 2.16 (s, 3
H); 2.29 (s, 3H); 3.72 (s, 2H); 3.82 (s, 2H); 3.90
(s, 4H); 6.10 (s, 1H); 6.18 (s, 1H); 6.38 (s, 1H);
6.40 (s, 1H); 6.70 (d, J = 7.1 Hz, 2H); 6.75 (d, J =
7.1 Hz, 2H); 7.93 (brs, 3H); 9.24 (brs, 2H).

Example 4: Quinonediazide sulfonate esterification In a 100 ml four-necked flask, 2,4-bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl)] was added.
-2,5-Dimethylbenzyl] -3,5,6-trimethylphenol 0.97 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 0.81 g and 1,4
-Preparing 8.87 g of dioxane and adjusting the temperature to 25 ° C. Triethylamine 0.36 g was added dropwise thereto over 1 hour,
After that, the reaction was further continued for 3 hours. After completion of the reaction, acetic acid 0.0
Neutralized with 9 g and filtered. The filtrate was added to a mixed solution of 0.5 g of acetic acid and 50 g of ion-exchanged water and stirred for 1 hour, and then the precipitated crystals were filtered and washed. The obtained filtered product was dried under reduced pressure at 45 ° C. for one day to obtain 1.65 g of a photosensitizer. The yield based on 2,4-bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -2,5-dimethylbenzyl] -3,5,6-trimethylphenol was 97.1%. It was

Analysis value of main component Mass analysis: MS 1108 ¹ H-NMR (dimethyl sulfoxide) δ (ppm): 1.7
9 (s, 3H); 1.95 (s, 12H); 2.00 (s, 3H); 2.04 (s, 6
H); 2.17 (s, 3H); 3.70 (s, 2H); 3.80 (s, 2H); 3.87
(s, 2H); 3.90 (s, 2H); 6.10 (s, 1H); 6.17 (s, 1H);
6.40 (s, 1H); 6.45 (s, 1H); 6.65 (d, J = 7.8 Hz, 2
H); 6.90 (d, J = 7.8 Hz, 2H); 7.44 (d, J = 7.4 Hz, 2
H); 7.69 (t, J = 7.2 Hz, 2H); 7.76 (d, J = 7.4 Hz, 2
H); 7.91 (brs, 3H); 8.26 (d, J = 7.2 Hz, 2H); 8.61
(d, J = 7.2 Hz, 2H).

Reference Example 2: Production of novolac resin In a four-necked flask, 148.5 parts of meta-cresol, 121.5 parts of para-cresol, and 252 of methyl isobutyl ketone were prepared.
, 10% oxalic acid aqueous solution 37.0 parts and 90% acetic acid aqueous solution 84.8 parts were charged, and 37% formalin 129.5 parts was added dropwise over 40 minutes while heating and stirring in an oil bath at 100 ° C., and thereafter. 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 separable flask with a bottom, and methyl isobutyl ketone 90 was added.
9.6 parts and n-heptane 996.1 parts are added, and the temperature is 60 ° C.
After stirring for 30 minutes, the mixture was allowed to stand and liquid was separated. 380 parts of 2-heptanone was added to the lower layer mass obtained by liquid separation,
Methyl isobutyl ketone and n-heptane were removed by an evaporator to obtain a 2-heptanone solution of the novolak resin. The polystyrene reduced weight average molecular weight by GPC is 9000, and the polystyrene reduced molecular weight is 9
The area ratio in the range of 00 or less is 1 with respect to the entire pattern area.
4%.

Application Example 15 parts by weight of a 2-heptanone solution of the novolac resin obtained in Reference Example 2 in terms of solid content, 1,3-bis [1 as an additive
3.9 parts of-(2,4-dihydroxyphenyl) -1-methylethyl] benzene and 5 parts of the photosensitizer obtained in Example 4
Part, 1,2,3-trihydroxy-as another photosensitizer
1 part of a condensate of 4- (4-hydroxy-2,5-dimethylbenzyl) benzene and 1,2-naphthoquinonediazide-5-sulfonyl chloride in a molar ratio of 1: 4, and 2-heptanone were Heptanone was mixed and dissolved so that the total amount was 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 would be 1.1 μm, and apply 90
Bake at ℃ 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], 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. Each positive pattern was evaluated as follows, and each result was obtained.

Effective sensitivity: The exposure amount (effective sensitivity) at which the line-and-space pattern of 0.50 μm became 1: 1 was 250 msec.

Resolution: The dimension of the line-and-space pattern, which is separated with no film loss at an exposure amount (effective sensitivity) at which the line-and-space pattern becomes 1: 1 is 0.35 μm when measured with a scanning electron microscope. It was

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

Focus (depth of focus): The width of the focus at which the 0.40 μm line-and-space pattern is separated at the effective sensitivity without film loss is observed by a scanning electron microscope,
When measured, it was 1.5 μm.

Scum: The presence or absence of scum (development residue) was observed with a scanning electron microscope, and no scum was observed.

Γ value: The normalized film thickness (= remaining film thickness / initial film thickness) is plotted with respect to the logarithm of the exposure amount, the inclination θ is obtained, and tan θ is taken as the γ value, and this γ value is 7.61. there were.

[0073]

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 at least one of R ⁵ and 1,2-naphthoquinonediazidesulfonyl is useful as a photosensitizer for a photosensitive resin composition, and R ¹ , R ² , R 5
Those in which ³ , R ⁴ and R ⁵ are all hydrogen are useful as precursors for the sensitizer. Then, a photosensitive resin composition containing the above-mentioned photosensitizer which has been esterified with 1,2-naphthoquinonediazide sulfonate is excellent in sensitivity and resolution for semiconductor fine processing, and has no development residue. Will be taken.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 303/28 C07C 303/28 309/76 7419-4H 309/76 G03F 7/022 G03F 7/022 // C07B 61/00 300 C07B 61/00 300

Claims (10)

[Claims] (1) Formula (I) (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently of each other hydrogen or 1,2-naphthoquinonediazide-4-
Or a pentaphenol-based compound represented by -5). 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. 4-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -3,5
6-trimethylphenol. 5. 2,4-bis (4-hydroxy-2,5-)
Dimethylbenzyl) -3,5,6-trimethylphenol. 6. 2,4-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylbenzyl) -3,5
2,4-bis [4-hydroxy-, characterized by reacting 6-trimethylphenol and para-cresol
3- (2-hydroxy-5-methylbenzyl) -2,5
-Dimethylbenzyl] -3,5,6-trimethylphenol production method. 7. A 2,4-bis [4-hydroxy-3- (2
-Hydroxy-5-methylbenzyl) -2,5-dimethylbenzyl] -3,5,6-trimethylphenol,
The method for producing a compound according to claim 3, which comprises reacting with 1,2-naphthoquinonediazide-4- or -5-sulfonylhalide. 8. A 2,4-bis (4-hydroxy-2,5-)
2,4-bis (4-hydroxy-3-hydroxymethyl-2,5-dimethyl), characterized in that dimethylbenzyl) -3,5,6-trimethylphenol and formaldehyde are reacted in the presence of an alkali catalyst. Method for producing benzyl) -3,5,6-trimethylphenol. 9. A 2,4-bis (hydroxymethyl) -3,
2,4-bis (4-) characterized in that 5,6-trimethylphenol is reacted with 2,5-xylenol.
Hydroxy-2,5-dimethylbenzyl) -3,5,6
-Method for producing trimethylphenol. 10. 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-sulfonyl, the rest independently of one another, hydrogen or 1,2
-A naphthoquinone diazide-4- or -5-sulfonyl) -containing photosensitizer containing a pentaphenol-based compound as an active ingredient.