JP2011016738A - Method for producing (meth)acrylate compound - Google Patents

Abstract

A monomer used for the synthesis of a resist compound, which has a group having a norbornene skeleton, a (meth) acryloyl group involved in polymerization, and a linking group arranged between these groups It aims at providing the method of manufacturing an acid ester compound simply, suppressing the production | generation of a by-product.
An acid addition step in which a specific lower carboxylic acid having a terminal halogen group is added to a specific norbornene derivative in the absence of a solvent to obtain an ester intermediate, the ester intermediate and (meth) acrylic A method for producing a (meth) acrylic acid ester compound comprising an esterification step of esterifying an acid.
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Description

  The present invention relates to a method for producing a (meth) acrylic acid ester compound.

In the field of microfabrication in the manufacture of semiconductor elements and liquid crystal elements, miniaturization is progressing rapidly due to advances in lithography technology. Such miniaturization is brought about especially by shortening the wavelength of irradiation light. Specifically, the wavelength of irradiation light has changed from conventional ultraviolet rays represented by g-line (wavelength: 438 nm) and i-line (wavelength: 365 nm) to DUV (Deep Ultra Violet).
Further, with the shortening of the wavelength of irradiation light and electron beam as described above, there is a demand for a high-resolution resist that can handle such irradiation light and electron beam.

As a high-resolution resist, a “chemically amplified resist” containing a photoacid generator is known, and diversification and high functionality of monomers used for the production of such resist compounds are progressing.
For example, a (meth) acrylic acid ester compound having a norbornene skeleton is known as a monomer that can impart dry etching resistance to a resist compound. As a method for producing the compound, a method in which (meth) acrylic acid is directly added to a norbornene derivative in the presence of a sulfonic acid having a fluorine-containing substituent is disclosed (for example, Patent Document 1).

  A compound having a norbornene skeleton, a (meth) acryloyl group involved in polymerization, and a substituent that exhibits various functions such as an acid leaving group and a lactone group, the (meth) acryloyl group and the substitution A (meth) acrylic acid ester compound in which a linking group is arranged between groups is known. As described above, the resist performance is further improved by using, as a monomer, a (meth) acrylic acid ester compound in which the distance from the polymer main chain to the substituent is increased. As a method for producing the compound, after condensing an alcohol derivative having a substituent that exhibits a function and an acid halide of a monohalocarboxylic acid, these are combined with (meth) acrylic acid in the presence of a deoxidizing agent. The method of making it react is shown (for example, patent document 2).

JP 2004-59436 A JP-A-2005-331918

However, in the production method described in Patent Document 2, it is necessary to use an alcohol derivative having a substituent that exhibits a function. The synthesis of the alcohol derivative may require several steps, and the entire production process is often complicated.
In addition, the method of directly adding (meth) acrylic acid to the norbornene derivative in the production method described in Patent Document 1 can be applied to the production of the (meth) acrylic acid ester compound having a linking group described above. However, in this method, when a carboxylic acid other than (meth) acrylic acid is added, the reactivity decreases because the carboxylic acid is difficult to dissolve in a low polarity solvent such as hexane. In addition, since a sulfonic acid having a fluorine-containing substituent is used, a solvent having low acid stability cannot be used. For example, when an aromatic compound such as toluene is used as a solvent, a Friedel-Crafts type reaction proceeds and a by-product is generated.

  The present invention is a monomer used for the synthesis of a resist compound, which has a group having a norbornene skeleton, a (meth) acryloyl group involved in polymerization, and a linking group arranged between these groups (meth) It aims at providing the method of suppressing the production | generation of a by-product and manufacturing easily an acrylic ester compound.

The present invention employs the following configuration in order to solve the above problems.
[1] An ester intermediate represented by the following formula (3) by adding a lower carboxylic acid represented by the following formula (2) to the norbornene derivative represented by the following formula (1) in the absence of a solvent. An esterification step of obtaining an (meth) acrylic acid ester compound represented by the following formula (4) by an esterification reaction of the ester intermediate and (meth) acrylic acid ( A method for producing a (meth) acrylate compound.

Wherein R ¹ is a hydrogen atom or a methyl group. R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a carboxy group, or R ² and R ³ are linked to form a ring having 3 to 6 carbon atoms or a ring containing a hetero atom, X is a halogen group, and n is an integer of 1 to 3.

  According to the production method of the present invention, a (meth) acrylic acid ester compound having a group having a norbornene skeleton, a (meth) acryloyl group involved in polymerization, and a linking group arranged between these groups, The production of by-products can be suppressed and the production can be simplified.

  Hereinafter, an example of an embodiment of a method for producing a (meth) acrylic acid ester compound of the present invention will be shown and described in detail. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acryloyl group” means acryloyl group or methacryloyl group.

  In the production method of the present invention, an ester intermediate represented by the following formula (3) is prepared by adding a lower carboxylic acid represented by the following formula (2) to a norbornene derivative represented by the following formula (1). And an esterification step of esterifying the ester intermediate with (meth) acrylic acid. According to the production method, a group having a norbornene skeleton represented by the following formula (4), a (meth) acryloyl group involved in polymerization, and a linking group arranged between these groups (meth) An acrylate compound is obtained.

R ² and R ³ in the formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a carboxy group, or R ² and R ³ are connected to each other. To form a ring having 3 to 6 carbon atoms or a hetero atom having 3 to 6 carbon atoms.
Examples of the ring containing a hetero atom include a lactone ring containing an oxygen atom, a furan ring, and a pyran ring. That is, assuming that the ^{R 2} and ^{R 3} are linked _{is, -CO-O-CH 2 -} , - CH 2 -O-CH 2 -, - CH 2 -O- (CH 2) 2 - , and the like .
R ² and R ^3, from the viewpoint of improving the adhesion of the resist compound to the silicon wafer, with either one of R ² and R ³ are hydrogen atom, and the other is cyano group, or, R ² and R It is preferable that ³ is connected to form a lactone ring containing an oxygen atom.

X in the formula (2) is a halogen group. Examples of the halogen group include a chloro group and a bromo group. Of these, a chloro group is preferred from the viewpoint of availability and cost.
N in said Formula (2) is an integer of 1-3. n is preferably 1 to 2 and more preferably 1 from the viewpoint that the glass transition point (Tg) of the resist compound can be easily prevented from decreasing.

X in Formula (3) and the formula (4), n, ^{R 2} and ^{R 3} are the same X, n, and ^{R 2} and ^{R 3} in the formula (1) and the formula (2).
R ¹ in the formula (4) is a hydrogen atom or a methyl group.
Hereinafter, each compound represented by the formulas (1) to (4) is referred to as a norbornene derivative (1), a lower carboxylic acid (2), an ester intermediate (3), and an ester compound (4).

(Acid addition process)
In the acid addition step, the lower carboxylic acid (2) having a halogen group at the terminal is added to the norbornene derivative (1) in the presence of sulfonic acids and without solvent. By this addition reaction, an ester intermediate (3) having a halogen group at the terminal is obtained. In the production method of the present invention, the production of by-products can be suppressed by performing the addition reaction in the acid addition step in the absence of a solvent. Therefore, a high purity ester compound (4) can be easily produced through the subsequent esterification step.
In this specification, “under no solvent” means a reaction diluent such as an organic solvent for dissolving a raw material compound or a catalyst used in the production of a normal (meth) acrylic ester compound (involved in the reaction). Means that substantially no compound is used. Here, “substantially (no solvent) is used” ideally means that no solvent is contained, but this does not mean that only, for example, a solvent derived from the above raw material compound or the like There is a case where it may be mixed, and this is also an intention that can be included.

The norbornene derivative (1) can be easily synthesized by a known technique by utilizing the Diels-Alder reaction between cyclohexadiene and the corresponding olefins.
Further, as described in Japanese Patent No. 4116282, after performing Diels-Alder reaction of cyclohexadiene and maleic anhydride, one of the carbonyl groups of the obtained adduct is reduced with a reducing agent such as sodium borohydride. By doing so, it is possible to synthesize one in which R ² and R ³ are linked to form a lactone ring containing an oxygen atom.
Lower carboxylic acid (2) can be obtained as a commercial product. However, the lower carboxylic acid (2) may be synthesized using a known technique.

  The amount of the lower carboxylic acid (2) used is preferably 1.0 equivalent to 4.0 equivalents, more preferably 1.5 equivalents to 2.5 equivalents, relative to the norbornene derivative (1). preferable. If the usage-amount of lower carboxylic acid (2) is 1.5 equivalent or more, an addition reaction will advance easily. Further, if the amount of the lower carboxylic acid (2) used is 4.0 equivalents or less, the amount of the necessary base used can be reduced when neutralizing the excess lower carboxylic acid (2). It is advantageous in terms of cost.

The sulfonic acids act as a catalyst for the addition reaction.
Examples of sulfonic acids include methanesulfonic acid and trifluoromethanesulfonic acid. Of these, trifluoromethanesulfonic acid is preferred from the viewpoint of reaction rate.
The amount of sulfonic acids used is preferably 0.01 equivalents or more and 0.1 equivalents or less, more preferably 0.03 equivalents or more and 0.07 equivalents or less, relative to the norbornene derivative (1). If the amount of the sulfonic acid used is 0.01 equivalent or more, the addition reaction is likely to proceed. Moreover, if the usage-amount of sulfonic acids is 0.1 equivalent or less, control of reaction heat is easy.

The reaction temperature of the addition reaction is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 130 ° C. or lower. If reaction temperature is 50 degreeC or more or 80 degreeC or more, an addition reaction will advance easily. Moreover, if reaction temperature is 150 degrees C or less or 130 degrees C or less, it is easy to control reaction rate.
The ester intermediate (3) obtained by the addition reaction described above can be purified by known purification methods such as crystallization, distillation and various chromatography.

(Esterification process)
In the esterification step, the ester intermediate (3) having a halogen group at the terminal obtained in the acid addition step is reacted with (meth) acrylic acid. By the esterification reaction, an ester compound (4) having a linking group, that is, — (CH) _n —CO—O— is obtained.
The esterification reaction is preferably performed in an inert solvent such as toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide.

  The amount of (meth) acrylic acid used is preferably 1.0 equivalent or more and 2.0 equivalent or less, and 1.0 equivalent or more and 1.5 equivalent or less, relative to the ester intermediate (3). More preferred. If the usage-amount of (meth) acrylic acid is 1.0 equivalent or more, esterification reaction will advance easily and the yield of ester compound (4) will improve. Moreover, if the usage-amount of (meth) acrylic acid is 2.0 equivalent or less, refinement | purification of the ester compound (4) obtained will become easy.

The esterification reaction is preferably performed in the presence of a deoxidizer.
Examples of the deoxidizer include organic bases such as triethylamine and pyridine, inorganic bases such as potassium carbonate and sodium hydroxide, and mixtures thereof.
The use amount of the deoxidizer is preferably 1.0 equivalent or more and 5.0 equivalent or less, more preferably 1.0 equivalent or more and 3.0 equivalent or less, with respect to the ester intermediate (3). . If the usage-amount of a deoxidizer is 1.0 equivalent or more, esterification reaction will advance easily. Moreover, if the usage-amount of a deoxidizer is 5.0 equivalent or less, the neutralization process after reaction can be skipped.

  The reaction temperature of the esterification reaction is preferably −30 ° C. or higher and 200 ° C. or lower, and more preferably 0 ° C. or higher and 100 ° C. or lower. If reaction temperature is -30 degreeC or more, esterification reaction will advance easily. Moreover, if reaction temperature is 200 degrees C or less, it will be easy to control reaction rate.

  The ester compound (4) obtained by this esterification step can be taken out by a post-treatment usually used when taking out the product from the reaction solution after the esterification reaction. Furthermore, it can also be purified by known purification methods such as chromatography, recrystallization, distillation and the like.

  According to the manufacturing method of this invention demonstrated above, the production | generation of a by-product can be suppressed and the ester compound (4) which has a coupling group can be easily manufactured in a short process. This is because, in the production method of the present invention, the norbornene derivative (1) is subjected to the addition reaction of the lower carboxylic acid (2) having a halogen group at the terminal in the absence of a solvent. This is because it is possible to suppress the generation of by-products.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
The reaction reagents and monomers used in the examples were used as they were without purifying commercially available products unless otherwise specified.
[Identification of ester intermediate (3) and ester compound (4)]
The ester intermediate (3) and ester compound (4) obtained in this example were identified by ¹ H-NMR measurement. The measurement uses GSX-400 type FT-NMR (trade name) manufactured by JEOL Ltd., puts a deuterated chloroform solution having a sample concentration of about 5% by mass into a test tube having a diameter of 5 mm, a measurement temperature of 40 ° C., The measurement frequency was 400 MHz, and the integration was performed 16 times in the single pulse mode.

[Example 1]
First, a norbornene derivative (1) was synthesized by the method described in Japanese Patent No. 4116282.
After Diels-Alder reaction of cyclohexadiene and maleic anhydride, one of the carbonyl groups of the obtained adduct was reduced with sodium borohydride as a reducing agent, and represented by the following formula (1-1). 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one (hereinafter referred to as “derivative (1-1)”) was synthesized.

(Acid addition process)
Subsequently, addition reaction of the lower carboxylic acid (2) with respect to the derivative (1-1) was performed.
A derivative (1-1) (100 g) and monochloroacetic acid (126 g), which is a lower carboxylic acid (2), are charged into a flask equipped with a dropping funnel, a condenser, a thermometer, a nitrogen gas inlet, and a stirrer. Then, the temperature of the flask was changed to 60 ° C to melt the derivative (1-1) and monochloroacetic acid, and stirring was started until the internal temperature reached 100 ° C. Heated. Subsequently, trifluoromethanesulfonic acid (10.0 g), which is a sulfonic acid, was dropped from the dropping funnel over 2 hours, and after completion of the dropping, the addition reaction was carried out by maintaining the internal temperature at 100 ° C. for 3 hours.
After confirming the disappearance of the derivative (1-1) by gas chromatography (hereinafter referred to as “GC”), the mixture was cooled to an internal temperature of 50 ° C., toluene (100 g) was added, and the internal temperature was further 25 ° C. Until cooled. Next, 50 g of water was added to the flask, and then saturated sodium bicarbonate water was added until the pH of the aqueous layer reached 8, to neutralize trifluoromethanesulfonic acid and excess monochloroacetic acid. Subsequently, the organic layer was separated using a separatory funnel, and the aqueous layer was extracted twice with ethyl acetate (350 g). Thereafter, the obtained organic layer was washed twice with saturated brine (100 g), toluene and ethyl acetate were distilled off with an evaporator, and purified by simple distillation under reduced pressure (distillation temperature: 170 to 175 ° C., distillation pressure: 27 ~ 53 Pa).
By the above operation, 1-chloroacetic acid 8- (4-oxatricyclo [5.2.1.0 ^2,6 ] -8 represented by the following formula (3-1), which is a light orange oily liquid. -Decanyl-3-one) (hereinafter referred to as “intermediate (3-1)”) and 1-chloroacetic acid 9- (4-oxatricyclo [5] represented by the following formula (3-1 ′) .2.1.0 ^2,6 ] -8-decanyl-3-one) (hereinafter referred to as “intermediate (3-1 ′)”) (lactone ring and monochloroacetic acid relative to norbornene ring) A mixture (114 g, acquisition yield 70.9%) of each group of endo and exo isomer combinations (4 types) was obtained.

(Esterification process)
Using the mixture obtained in the acid addition step, esterification reaction with methacrylic acid was performed.
In a flask equipped with a dropping funnel, thermometer, nitrogen gas inlet, and stir bar, methacrylic acid (7.30 g), potassium carbonate (11.8 g) as a deoxidizer, potassium iodide (2.80 g), dimethyl After formamide (100 g) was added and purged with nitrogen, stirring was started and the internal temperature was adjusted to 25 ° C. Separately, a solution was prepared by dissolving a mixture (15.6 g) of the intermediate (3-1) and the intermediate (3-1 ′) in dimethylformamide (50.0 g). It put in the dropping funnel and it was dripped over 15 minutes in the said flask. After completion of dropping, the esterification reaction was carried out by maintaining the internal temperature at 25 ° C. for 4 hours.
After confirming the disappearance of intermediate (3-1) and intermediate (3-1 ′) by GC, water (100 g) and toluene (100 g) were added, the organic layer was separated with a separatory funnel, and the aqueous layer Was extracted twice with toluene (100 g). Thereafter, the organic layer was washed twice with saturated brine (50 g), dimethylformamide and toluene were distilled off with an evaporator, and purified with a silica gel column (silica gel 400 g, developing solvent was n-hexane: ethyl acetate = 2: 1). ).
Through the above operation, the compound (4-1) represented by the following formula (4-1) and the compound (4-1 ′) represented by the following formula (4-1 ′) are colorless and transparent oily liquids. (16.4 g, acquisition yield 89.0%) was obtained.

[Example 2]
In the acid addition step, chloroacetic acid addition reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed from 100 ° C. to 90 ° C. and the holding time was changed from 3 hours to 11 hours. At a retention time of 3 hours, 49.8% of the derivative (1-1) remained as a percentage of GC area, and at a retention time of 11 hours, the derivative (1-1) disappeared by GC.
Thereafter, the intermediate was purified in the same manner as in Example 1, and esterification with methacrylic acid was carried out in the esterification step. As a result, the compound (1) was a colorless and transparent oily liquid with the same yield as in Example 1. A mixture of 4-1) and the compound (4-1 ′) was obtained.

[Comparative Example 1]
In the acid addition step, monochloroacetic acid addition reaction was performed in the same manner as in Example 1 except that 300 mL of toluene was added to the flask. When the disappearance of the derivative (1-1) was confirmed by GC, the derivative (1-1) was completely disappeared, but 17.0% of a by-product in which toluene and monochloroacetic acid reacted was produced in an area percentage. It was.

As described above, in the production method of the present invention in which the addition reaction is performed in the absence of a solvent in the acid addition step, the production of a byproduct is suppressed and a (meth) acrylic acid ester compound having a linking group is easily produced. I was able to.
On the other hand, in Comparative Example 1 in which the addition reaction was performed in a solvent, a large amount of by-products were generated.

  The production method of the present invention can easily produce a (meth) acrylic acid ester compound that can be suitably used for the production of a resist compound that can cope with irradiation light with a short wavelength, so that in the production of a semiconductor element or a liquid crystal element This is very useful in the field of microfabrication.

Claims (1)

An acid for obtaining an ester intermediate represented by the following formula (3) by subjecting a norbornene derivative represented by the following formula (1) to a lower carboxylic acid represented by the following formula (2) in the absence of a solvent. Additional process;
Esterification reaction of the ester intermediate and (meth) acrylic acid to obtain a (meth) acrylic acid ester compound represented by the following formula (4);
The manufacturing method of the (meth) acrylic acid ester compound which has this.

Wherein R ¹ is a hydrogen atom or a methyl group. R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a carboxy group, or R ² and R ³ are linked to form a ring having 3 to 6 carbon atoms or a ring containing a hetero atom, X is a halogen group, and n is an integer of 1 to 3.