JPH0977736A - Method for producing naphthoquinonediazide photosensitive agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce both of loss and metallic content and obtain a naphthoquinonediazide used for positive type resist compositions in a form of a solution. SOLUTION: A phenolic compound of the formula (R<11> to R<18> are each H, OH, a 1-6C alkyl, a 1-6C alkoxy, etc.; R<19> and R<20> are each H, a 1-6C alkyl, a 1-6C cycloalkyl, phenyl, etc.) is subjected to condensation reaction with 1,2- naphthoquinonediazide-4- or -5-sulfonyl halide in an organic solvent having a property separable from water (e.g. methyl amyl ketone) in the presence of a base (e.g. triethylamine) at 10-40 deg.C for 0.5-8hr. Then, the reaction product is washed with water and separated from water layer to provide the objective product. The method is improved in yield and is good in safety, compared with a method for obtaining naphthoquinoneazide-based photosensitive agent as a solid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a naphthoquinonediazide-based photosensitive agent used in, for example, a positive resist composition.

[0002]

2. Description of the Related Art It is known that a compound having a phenolic hydroxyl group is converted into a quinonediazide sulfonic acid ester and used as a photosensitive agent in a positive resist composition for semiconductor fine processing. In the quinonediazide sulfonic acid esterification, 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide is usually used, and a photosensitizer is produced by condensing this with a compound having a phenolic hydroxyl group. . This reaction is generally carried out in a solvent, and as a reaction solvent, it is known to use 1,4-dioxane, acetone, γ-butyrolactone, or a mixture of two or more thereof.
4-dioxane is often used.

On the other hand, since positive resist compositions for semiconductor fine processing do not like the presence of metals, there is also a demand for reduction of metals in naphthoquinonediazide type photosensitizers. It is known that washing with water is effective for reducing the metal content of the naphthoquinonediazide-based photosensitizer. Since the reaction solvents generally used in the past, including 1,4-dioxane, are well soluble in water, the naphthoquinonediazide-based photosensitizer obtained in such a solvent must be once crystallized by adding water. , And thereafter, an operation of repeatedly washing with pure water is performed.

[0004]

However, in the operation of taking out a naphthoquinonediazide-based photosensitizer as a solid substance, it is necessary to pay attention to handling from the viewpoint of safety and disaster prevention, and depending on the type of photosensitizer, the photosensitizer after crystallization may not be used. There were problems such as a longer filtration time due to a smaller particle size, a loss at the stage of solidification, and a lower yield.

The object of the present invention is to produce a naphthoquinonediazide sensitizer by a condensation reaction of a compound having a phenolic hydroxyl group and a naphthoquinonediazide sulfonyl halide, and to reduce the loss of the naphthoquinonediazide sensitizer which is a target product. It is to reduce the metal content and obtain the naphthoquinonediazide sensitizer in the form of a solution.

[0006]

Means for Solving the Problems As a result of intensive studies aimed at achieving such an object, the present inventors have separated a condensation reaction between a compound having a phenolic hydroxyl group and a naphthoquinonediazidesulfonyl halide with water. By carrying out in an organic solvent having a property, even if water is added after the reaction, the target naphthoquinonediazide-based photosensitizer does not precipitate, and thus is obtained in the form of a solution, and can be washed in the form of a solution,
As a result, they have found that the amount of metal can be reduced, and have completed the present invention.

That is, in the present invention, a compound having a phenolic hydroxyl group and 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide are condensed in an organic solvent having a property of separating from water, and then condensed. The present invention provides a method of washing with water to obtain a naphthoquinonediazide-based photosensitizer in the form of a solution of the organic solvent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compound having a phenolic hydroxyl group to be subjected to quinonediazide sulfonic acid esterification in the present invention can be various compounds used for photosensitizing in the field of resist. That is, it is a phenolic compound having at least one, preferably two or more, more preferably three to six phenolic hydroxyl groups in the molecule. Preferable phenolic compounds for quinonediazide sulfonic acid esterification according to the present invention include, for example, compounds represented by the following general formulas (I) to (IV).

[0009]

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R
¹⁶ , R ¹⁷ and R ¹⁸ each independently represent hydrogen, a hydroxyl group, alkyl having 6 or less carbon atoms, cycloalkyl having 6 or less carbon atoms or alkoxy having 6 or less carbon atoms, and R ¹⁹ and R ²⁰ each independently, Hydrogen, alkyl having 6 or less carbon atoms, 6 carbon atoms
The following cycloalkyl, or hydroxyl group, alkyl having 6 or less carbon atoms, cycloalkyl having 6 or less carbon atoms and 6 carbon atoms
Represents phenyl optionally substituted with a substituent selected from the group consisting of the following alkoxy:

[0011]

[0012] In the formula, R ²¹ and R ²² are independently of each other, represent hydrogen, hydroxyl or alkyl having 6 or less carbon atoms, R ^23,
R ²⁴ , R ²⁵ and R ²⁶ independently represent hydrogen or alkyl having 6 or less carbons, or R ²³ and R ²⁴ together, and R ²⁵ and R ²⁶ together, each represents Forming a cycloalkane ring having 6 or less carbon atoms together with the carbon atom to be bonded;

[0013]

In the formula, R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent hydrogen or alkyl having 6 or less carbon atoms, and m
And n independently represent an integer of 0 to 3, but m + n ≧
2 and Y is -C ( ^R35 ) ( ^R36 )-or -C ( ^R37 ) (R
³⁸ ) -Ar-C (R ³⁹ ) (R ⁴⁰ )-, wherein R ³⁵ ,
R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are independently of each other hydrogen, alkyl having 6 or less carbon atoms, cycloalkyl having 6 or less carbon atoms, hydroxyl group, alkyl having 6 or less carbon atoms, and 6 carbon atoms. Represents a phenyl which may be substituted with a substituent selected from the group consisting of cycloalkyl and alkoxy having 6 or less carbon atoms, and Ar is substituted with a substituent selected from the group consisting of alkyl having 6 or less carbon atoms and hydroxyl group Represents optionally substituted phenylene;

[0015]

In the formula, R ⁴¹ and R ⁴² each independently represent hydrogen, alkyl having 6 or less carbon atoms or aryl having 10 or less carbon atoms, and q and r each independently represent an integer of 0 to 3, q + r ≧ 2.

Compounds having a phenolic hydroxyl group, such as compounds represented by the above general formulas (I) to (IV),
2-naphthoquinonediazide-4- or -5-sulfonic acid ester is obtained by condensing such a compound having a phenolic hydroxyl group with 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide. Here, as the sulfonyl halide, sulfonyl chloride is particularly preferably used.

This reaction is usually performed in the presence of a base. Examples of the base used here include amines such as trimethylamine, triethylamine, triethanolamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, and inorganic bases such as sodium carbonate and sodium hydrogencarbonate. Can be The base is 1,2-
The molar ratio of naphthoquinonediazide-4- or -5-sulfonyl halide is usually 1 to 1.5, preferably 1.0.
Used in a molar ratio of 5 to 1.3.

In the present invention, an organic solvent having a property of separating from water is used as a reaction solvent for the esterification reaction.
Examples of the organic solvent include n-hexane and n-hexane.
Aliphatic hydrocarbons such as heptane, cyclohexane,
Alicyclic hydrocarbons such as cyclopentane, toluene,
Aromatic hydrocarbons such as xylene, ethers such as diethyl ether, dichloromethane, chloroform,
Carbon tetrachloride, halogenated aliphatic hydrocarbons such as ethylene dichloride, chlorobenzene, halogenated aromatic hydrocarbons such as dichlorobenzene, ethyl acetate, butyl acetate, esters such as amyl acetate, methyl isobutyl ketone, Ketones such as methyl amyl ketone,
Examples thereof include glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether propionate. Such an organic solvent must be one that is liquid at room temperature, as is clear from the term "solvent," and must have a property of separating from water, as is clear from the definition of the present invention. Of these, the use of a solvent that can serve as a solvent for the positive resist composition is advantageous because the naphthoquinonediazide-based photosensitive agent obtained in the form of a solution can be directly applied to the preparation of the positive resist composition. In particular, ketones or glycol ether esters having a property of separating from water are preferably used.

By using such an organic solvent which has a property of separating from water, purification can be carried out by washing and separating the liquid after the reaction, thus eliminating the need for filtration of the photosensitizer, improving yield and ensuring safety. The effect of being played is exhibited. Further, according to the present invention, the reaction time tends to be shortened as compared with the case where 1,4-dioxane is used as the reaction solvent, although it varies depending on the kind of the solvent used. The reaction solvent is usually in the range of 2 to 10 times by weight, preferably 3 times, based on the total amount of the compound having a phenolic hydroxyl group and 1,2-naphthoquinonediazide-4- or -5-sulfonylhalide.
It is used in the range of up to 6 times by weight.

In the present invention, it is preferable to use a solvent having a property of separating liquid from water alone, but two or more solvents having a property of separating liquid from water are used within a range not impairing the object of the present invention. Use in combination with the above, other solvent,
For example, water-soluble ethers such as 1,4-dioxane and tetrahydrofuran, water-soluble esters such as γ-butyrolactone, and amides such as N-methylpyrrolidone can be used in combination. Even when a mixed solvent is used, it is preferable that the amount of the solvent having a property of separating from water is 50% by weight or more, further 70% by weight or more, or 80% by weight or more, based on the total amount of the solvent.

The esterification reaction proceeds at around room temperature under normal pressure, and a temperature in the range of 10 to 40 ° C. is generally adopted. The reaction time varies depending on the type of the compound having a phenolic hydroxyl group and the naphthoquinonediazidosulfonyl halide, but is usually in the range of about 0.5 to 8 hours.

After completion of the reaction, if necessary, after neutralization with an acid such as acetic acid, the salt of the base used for neutralizing the hydrogen halide produced by the reaction is filtered or water is added to the above-mentioned salt. The naphthoquinonediazide-based photosensitizer can be obtained in the form of a solution by transferring the salt of (1) to the aqueous layer to remove it, and further washing with water for metal removal and liquid separation. After that, it is generally preferable to carry out concentration in order to remove water contained in the solvent and to obtain a concentration necessary for producing a positive resist composition.

[0024]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 In a 1 liter four-necked flask, 4,4'-methylenebis [2- (4-hydroxybenzyl) -3,6-dimethylphenol] (having the structure of the following formula)

[0026]

56.91 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 702.0 g of methyl amyl ketone were charged to complete dissolution. While stirring at 20 to 30 ° C, 31.64 g of triethylamine was added dropwise thereto over 2 hours. After the completion of dropping, the mixture was stirred at the same temperature for 2 hours, then charged with 7.84 g of acetic acid, and heated at 30 ° C.
For 1 hour. The reaction mixture is then filtered,
The filter residue was washed with 70.0 g of methyl amyl ketone. The filtrate and the washing solution were combined, washed with 716.0 g of ion-exchanged water, and separated. Wash with this ion-exchanged water and separate the liquid 5
After repeated times, the resulting photosensitizer methyl amyl ketone solution was concentrated at 45 ° C. to obtain 304.4 g of a photosensitizer A solution.
I got

Comparative Example 1 In a 1-liter four-necked flask, 4,4'-methylenebis [2- (4-hydroxybenzyl) -3,6-dimethylphenol] (compound having the structure shown in Example 1) was added. 5
9.24 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride (70.0 g) and 1,4-dioxane (646.25 g) were charged and suspended. 20-30 there
31.63 g of triethylamine was added dropwise over 2 hours while stirring at ℃. After completion of dropping, the mixture was stirred at the same temperature for 6 hours, then 7.82 g of acetic acid was charged, and the mixture was further stirred at 30 ° C. for 1 hour. The reaction mixture is then filtered and the filtration residue is
-Washed with 70.0 g of dioxane. The filtrate and the washing solution were poured into a mixed solution of 28.65 g of acetic acid and 2865 g of ion-exchanged water, stirred for 30 minutes and allowed to stand for 30 minutes to precipitate crystals, and the supernatant was removed by suction. The obtained crystals were washed by stirring with 3719 g of ion-exchanged water, allowed to stand for 30 minutes to precipitate the crystals, and the supernatant was removed by suction. This washing with ion-exchanged water and suction removal of the supernatant liquid were repeated twice, followed by filtration and washing with 1508 g of ion-exchanged water. 283.1 g of the obtained wet cake was dried at 40 ° C.
3.24 g of Photosensitizer B was obtained.

Example 2 In a 1-liter four-necked flask, 4- [1 ', 2',
3 ', 4', 4'a, 9'a-hexahydro-6'-hydroxy-5'-methylspiro [cyclohexane-1,
9'-xanthene] -4'a-yl] -2-methylresorcinol (having a structure of the following formula)

[0030]

53.76 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride (70.0 g) and methyl amyl ketone (616.0 g) were charged and dissolved. While stirring at 20 to 30 ° C, 31.64 g of triethylamine was added dropwise thereto over 2 hours. After completion of the dropping, the mixture was stirred at the same temperature for 2 hours, and then 10.64 g of acetic acid was added, and
Stirred for an additional hour at ° C. The reaction mixture was then filtered and the filter residue was washed with 70.0 g of methyl amyl ketone.
The filtrate and the washing solution were combined, washed with 760.0 g of ion-exchanged water, and separated. Wash with this ion-exchanged water and separate the liquid 5
After repeated times, the resulting solution of photosensitizer in methyl amyl ketone was concentrated at 45 ° C. to give a solution of photosensitizer C in 327.1
g was obtained.

Comparative Example 2 A 4-liter 1-liter four-necked flask was charged with 4- [1 ', 2',
3 ', 4', 4'a, 9'a-hexahydro-6'-hydroxy-5'-methylspiro [cyclohexane-1,
9'-xanthene] -4'a-yl] -2-methylresorcinol (the compound whose structure is shown in Example 2) was added to 53.7
4 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 70.0 g and 1,4-dioxane 61
6.0 g was charged and suspended. Thereto, 31.66 g of triethylamine was added dropwise over 2 hours while stirring at 20 to 30 ° C. After completion of dropping, the mixture was stirred at the same temperature for 6 hours, then 11.30 g of acetic acid was charged, and the mixture was further stirred at 30 ° C. for 1 hour. Next, the reaction mixture was filtered, and the filtration residue was washed with 70.0 g of 1,4-dioxane. The filtrate and washings were mixed with acetic acid 3
It was poured into a mixed solution of 1.66 g and ion-exchanged water 3197 g and stirred for 30 minutes. The precipitated crystals were filtered, and the obtained cake was washed with 3575 g of ion-exchanged water. This washing with ion-exchanged water was repeated 3 times. 281.5 g of the obtained wet cake was dried at 40 ° C. to obtain 110.71 g of Photosensitizer D.

The yields of the above Examples and Comparative Examples are shown in Table 1.
Shown in

[0034]

[Table 1]

[0035]

According to the present invention, a compound having a phenolic hydroxyl group is converted to 1,2-naphthoquinonediazide-4- or -5.
-When converting to a sulfonic acid ester, it is possible to use an organic solvent that has a property of separating liquid from water to allow purification by water separation after the reaction, and obtain a naphthoquinonediazide-based photosensitizer in the form of a solution of the organic solvent It is the one. Therefore, the present invention has an effect of improving yield and ensuring safety as compared with a method of obtaining a naphthoquinonediazide-based photosensitizer as a solid. In particular, if a reaction solvent that can also serve as a solvent for the desired photosensitizer as a component of a positive resist composition is used,
The resulting photosensitizer solution can be applied to the preparation of the resist composition as it is, which is more effective. Therefore, the method of the present invention is extremely useful for producing a naphthoquinonediazide-based photosensitizer.

Claims (4)

[Claims] A compound having a phenolic hydroxyl group and 1,
2-naphthoquinonediazide-4- or -5-sulfonyl halide is condensed in an organic solvent having a property of separating from water, and then washed with water to form a naphthoquinonediazide-based photosensitizer in the form of a solution of the organic solvent. And a method for producing a naphthoquinonediazide-based photosensitizer. 2. The method according to claim 1, wherein the 1,2-naphthoquinonediazide-4- or -5-sulfonyl halide is 1,2-naphthoquinonediazide-4- or -5-sulfonyl chloride. 3. The method according to claim 1, wherein the organic solvent is a ketone having a property of separating from water. 4. The method according to claim 1, wherein the organic solvent is a glycol ether ester.