JP2002161068A - Method for producing (meth)acrylic anhydride and method for producing (meth)acrylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To advantageously produce highly pure (meth)acrylic anhydride without causing its polymerization, and to produce highly pure (meth)acrylate in a high yield. SOLUTION: This method for producing the (meth)acrylic anhydride, comprises reacting (meth)acrylic acid with a fatty acid anhydride and then neutralizing and washing the reaction solution with an alkali aqueous solution of pH 7. 5 to 13. 5. The method for producing the (meth)acrylate, comprising reacting the (meth)acrylic anhydride with a secondary or tertiary alcohol in the coexistence of a basic compound having an acidity (pKa) of <=11 in 25 deg.C water.

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 (meth) acrylic anhydride, particularly (meth) acrylic anhydride which is a raw material of a (meth) acrylate monomer which is a raw material of a polymer for a semiconductor resist. The present invention also relates to a method for producing a (meth) acrylate, particularly a (meth) acrylate which is a raw material of a polymer for a semiconductor resist.

[0002]

2. Description of the Related Art As a method for producing (meth) acrylic anhydride, there is a method (Khim. Prom. (Moscow)) obtained by reacting (meth) acrylic acid with (meth) acrylic chloride.
(1969), 45 (11), 822-3) or a method of reacting methacrylic acid with acetic anhydride followed by distillation (Japanese Patent Application Laid-Open No. Sho 62-1582).
No. 37) is known.

However, the method of producing (meth) acrylic anhydride by the reaction of (meth) acrylic acid and (meth) acrylic acid chloride involves the reaction of a special material having corrosion resistance since an acid gas is generated. It is not suitable for implementation on an industrial scale because of the equipment required.

On the other hand, the method of distillation after reacting methacrylic acid and acetic anhydride has no problem with the material of the apparatus.
It is difficult to purify (meth) acrylic anhydride to obtain a high-purity product. In other words, distillation, which is a general purification method, uses (meth) acrylic acid and (meth)
In the latter stage of the process of distilling off the mixed acid anhydride of acrylic acid and acetic acid and unreacted acetic anhydride, the concentrated (meth) acrylic anhydride is exposed to a high temperature under acidic conditions, so that it is extremely easy to polymerize. There is a problem.

A method for producing a (meth) acrylic acid ester from (meth) acrylic anhydride and alcohol is known, but as described above, a high-purity (meth) acrylic anhydride as a raw material is used. Due to the difficulty of production, industrially producing (meth) acrylic esters represented by the following formulas (3) and (4), which are useful as raw material monomers for polymers for semiconductor materials, particularly for semiconductor materials. This method was not suitable. That is, when (meth) acrylic anhydride having low purity is used, there is a problem that only low-purity (meth) acrylic ester can be obtained in low yield by a side reaction or a polymerization reaction.

[0006]

Embedded image (Wherein, R ¹ represents hydrogen or an alkyl group, n and m each independently represent the number of 0 or 1 methylene group, and R ³ represents hydrogen or a methyl group.)

[0007]

Embedded image (In the formula, R ² represents an alkyl group, and R ³ represents a hydrogen or methyl group.)

[0008]

Accordingly, an object of the present invention is to provide (meth) acrylic anhydride, especially (meth) acrylic anhydride which is a raw material of a (meth) acrylate monomer which is a raw material of a polymer for a semiconductor resist. It is an object of the present invention to provide a method for producing a product at a high purity without causing polymerization on an industrial scale. Another object of the present invention is to provide (meth) acrylic acid esters of secondary or tertiary alcohols, particularly (meth) acrylic acid esters of the formulas (3) and (4), which are raw material monomers for polymers for semiconductor resists. And a method for producing these esters in high purity.

[0009]

Means for Solving the Problems The present inventors have proposed (meth)
In a method for producing (meth) acrylic anhydride by a reaction between acrylic acid and a fatty acid anhydride, a highly purified (meth) acrylic acid without distillation is obtained by neutralizing a reaction solution after the reaction with an aqueous alkali solution. The inventors have found that an anhydride can be obtained, which has led to the present invention.

That is, the present invention comprises a step of reacting (meth) acrylic acid with a fatty acid anhydride, and a step of neutralizing and washing the reaction solution after the reaction with an aqueous alkaline solution having a pH of 7.5 to 13.5. (Meth) acrylic anhydride.

In this method, it is preferable that the reaction solution is previously dissolved in a low-polarity solvent before the neutralization washing step.

The (meth) acrylic anhydride produced by this method is suitable as a raw material of a (meth) acrylic ester monomer which is a raw material of a polymer for a semiconductor resist.

[0013] The present invention also relates to a method in which the (meth) acrylic anhydride produced by the above-mentioned method and a secondary or tertiary alcohol have an acidity (pKa) of 1 in water at 25 ° C.
This is a method for producing a (meth) acrylic ester having an esterification step of reacting in the presence of one or less basic compounds.

The secondary or tertiary alcohol is preferably an alcohol represented by the following formula (1) or (2), and the (meth) acrylic acid ester produced at this time is represented by the following formula: (3) or a (meth) acrylate represented by the following formula (4) is preferable.

[0015]

Embedded image (In the formula, R ¹ is hydrogen or an alkyl group, and n and m each independently represent the number of 0 or 1 methylene group.)

[0016]

Embedded image (In the formula, R ² represents an alkyl group.)

[0017]

Embedded image (Wherein, R ¹ represents hydrogen or an alkyl group, n and m each independently represent the number of 0 or 1 methylene group, and R ³ represents hydrogen or a methyl group.)

[0018]

Embedded image (In the formula, R ² represents an alkyl group and R ³ represents a hydrogen or a methyl group.) At this time, the produced (meth) acrylate is a (meth) acrylate represented by the above formula (3). In some cases, a higher purity is obtained by washing the (meth) acrylate obtained after the esterification step with a low-polar solvent and further adding a washing step of washing with an acidic aqueous solution and / or an alkaline aqueous solution. Can be

When the (meth) acrylate to be produced is the (meth) acrylate represented by the formula (4), the (meth) acrylate obtained after the esterification step is converted to an alkaline By adding a washing step of washing with an aqueous solution and further washing with an acidic aqueous solution, a product with higher purity can be obtained. Furthermore, a higher purity (meth) acrylate can be obtained by thin-film distillation of the (meth) acrylate thus washed.

The (meth) acrylate produced by the method of the present invention is suitable as a raw material for a polymer for a semiconductor resist.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (meth) acrylic anhydride is produced by reacting (meth) acrylic acid with a fatty acid anhydride. Here, “(meth) acrylic acid” is a general term for acrylic acid and methacrylic acid, as is commonly used. The fatty acid anhydride used in the present invention is preferably a compound represented by the following structural formula.

[0022]

Embedded image (In the formula, R ⁴ represents an alkyl group.) Here, R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms, and two R ⁴ may be different from each other. Is preferred.

At this time, the reaction temperature is -30 ° C to 120 ° C.
Is preferable, and 0 ° C to 100 ° C is more preferable. The higher the reaction temperature, the faster the reaction rate, and the lower the reaction temperature, the more the side reaction can be suppressed. The reaction is preferably carried out while removing the by-produced fatty acid out of the system under reduced pressure. This reaction can be carried out without a solvent, but if necessary, an inert solvent may be used. Examples of the inert solvent include n-hexane, toluene, xylene and the like.

In the reaction, a catalyst may be used if necessary, and examples thereof include phosphoric acid, potassium acetate, and sulfuric acid.

Further, in order to prevent polymerization during the reaction, it is preferable to appropriately use a polymerization inhibitor.

In the present invention, the reaction solution after the reaction step is adjusted to pH
Neutralize with an alkaline aqueous solution of 7.5-13.5. Further, prior to the neutralization step, it is preferable that the reaction solution is previously dissolved in a low-polarity solvent. When a low-polarity solvent is used in the reaction, the solvent may be used as it is, but may be removed.

As the low-polarity solvent, a solvent which can dissolve (meth) acrylic anhydride, has low solubility in water, and can be easily separated from (meth) acrylic anhydride by distillation.

Examples of such a low-polarity solvent include hydrocarbon solvents, and in particular, n-hexane and n-hexane.
Aliphatic hydrocarbons such as heptane and n-pentane, and aromatic hydrocarbons such as toluene are preferred. Solvent amount is (meta)
The amount is usually 1 to 30 times, preferably 5 to 20 times the weight of the acrylic anhydride. The larger the amount of the low-polarity solvent, the higher the neutralization effect of the alkaline aqueous solution, and the smaller the amount, the lower the cost.

The lower the pH of the aqueous alkali solution, the lower the (meth)
Acrylic anhydride decomposition is reduced. The alkali used is not particularly limited, and examples thereof include aqueous solutions of hydroxides and carbonates of sodium and potassium. The neutralization washing is performed at least once, and is repeated as appropriate depending on the amount of the remaining impurities. Excessive neutralization cleaning leads to loss of (meth) acrylic anhydride, so the neutralization cleaning ends when the remaining impurities become less than the allowable amount.

As an industrial neutralization washing operation, for example,
There is a method in which the solution is poured into a container provided with a mechanism capable of draining from the lower part, an aqueous alkali solution is added with stirring, the mixture is sufficiently stirred, the mixture is allowed to stand, and after separating, the aqueous layer (lower layer) is drained.

In the neutralization washing step, it is preferable to wash with an aqueous alkali solution and then with water as necessary.

After the neutralization and washing step, a mixed solution mainly comprising (meth) acrylic anhydride and a low-polar solvent is obtained. For example, the low-polar solvent is distilled off and concentrated to remove the (meth) acrylic anhydride. Obtainable. Since the acid such as (meth) acrylic acid has already been removed at this time, polymerization hardly occurs even when heated.

The (meth) acrylic anhydride thus produced is suitable as a raw material of a (meth) acrylic ester monomer which is a raw material of a polymer for a semiconductor resist because it has few impurities.

In the present invention, the (meth) acrylic anhydride produced in this manner and the secondary or tertiary alcohols have an acidity (pKa) of 1 in water at 25 ° C.
This is a method for producing a (meth) acrylate ester which is reacted in the presence of one or less basic compounds. This method is the second
A lactone alcohol represented by the formula (1) or an adamantyl alcohol represented by the formula (2), which is a secondary or tertiary alcohol, represented by the formula (3) or the formula (4) It is suitable for producing (meth) acrylic esters.

In the lactone alcohols represented by the formula (1), R ¹ is hydrogen or an alkyl group, and the number of carbon atoms in the case of the alkyl group is not particularly limited. In light of the above, R ¹ is preferably hydrogen or an alkyl group having 1 to 5 carbon atoms. Particularly, R ¹ is preferably hydrogen or a linear alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.

In the adamantyl alcohols represented by the formula (2), R ² is an alkyl group, and the number of carbon atoms is not particularly limited.
To 5 are preferable, and particularly, a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group,
-Butyl groups are preferred.

The acidity (pK) of a basic compound used as a catalyst in this ester synthesis reaction in water at 25 ° C.
a) is 11 or less, preferably 6 to 11. As the basic compound, amines and a heterocyclic nitrogen-containing compound in which a nitrogen atom may be a member forming a ring are preferable. For example, triethylamine (pKa = 10.7)
2), pyridine (pKa = 5.42), 2,6-dimethylpyridine (pKa = 6.90), triethylenetetramine (pKa = 3.25, 6.56, 9.08, 9.7)
4), triethanolamine (pKa = 7.76), piperazine (pKa = 5.59, 9.71) and the like.

The amount of the basic compound used is preferably changed as appropriate in accordance with the type of the secondary or tertiary alcohol to be subjected to the reaction, but the starting alcohol is a lactone represented by the above formula (1). In the case of alcohols, it is usually 0.1 to 3 mol, preferably 0.5 to 2 mol, per 1 mol of the lactone alcohol represented by the formula (1). When the raw material alcohol is an adamantyl alcohol represented by the formula (2), the adamantyl alcohol represented by the formula (2) is usually 0.1 to 3 mol, preferably 0.5 to 3 mol per mol of the adamantyl alcohol. 2 moles.

The lower limit of the reaction temperature of the ester synthesis reaction is usually at least -20 ° C, preferably at least 10 ° C, more preferably at least 40 ° C. The upper limit of the reaction temperature is usually 120 ° C.
Or less, preferably 100 ° C. or less, more preferably 80 ° C.
It is as follows. As the reaction temperature is lower, side reactions are suppressed.

Although the reaction time is not particularly limited, the target product is obtained as much as possible in consideration of the production ratio of the decomposition product of the target product (meth) acrylate and the secondary or tertiary alcohol. It is preferable that the setting is made such that The reaction time is usually 5 to 50 hours, preferably 1 hour.
0-40 hours. As the reaction time is shorter, side reactions are suppressed.

In the ester synthesis reaction, if necessary, a solvent inert to the reaction, such as a halogenated hydrocarbon, ether, ketone, or aromatic hydrocarbon, may be used. In order to prevent polymerization, a polymerization inhibitor such as hydroquinone and hydroquinone monomethyl ether and oxygen are preferably present.

When the thus obtained (meth) acrylate is a monomer having a high polarity such as the (meth) acrylate represented by the formula (3), this is dissolved in a polar solvent and By washing with a low-polarity solvent as a solvent, unreacted (meth) acrylic anhydride can be removed. The solvent does not need to be special, and as the polar solvent, for example, a water-methanol mixed solvent,
Water, methanol, ethylene glycol and the like, and examples of the low-polar solvent include aliphatic hydrocarbons such as n-hexane, n-heptane and n-pentane, and aromatic hydrocarbons such as toluene. Can be When a water-methanol mixed solvent is used, methanol is distilled off from the water-methanol mixed layer, and the (meth) acrylate represented by the formula (3) can be extracted with a suitable solvent such as ethyl acetate. .

Since the extract contains a basic compound such as an amine used as a catalyst and an acidic by-product such as (meth) acrylic acid, the extract is washed with an acidic aqueous solution and / or an alkaline aqueous solution. Examples of the acidic aqueous solution include a sulfuric acid aqueous solution, and examples of the alkaline aqueous solution include a sodium hydroxide aqueous solution. PH of these aqueous solutions
Is too high or too low, the (meth) acrylate represented by the formula (3) may be decomposed. Therefore, a weakly acidic or weakly basic region having a pH of 4 to 10 is preferable. Finally, it is appropriately washed with a neutral aqueous solution such as an aqueous sodium chloride solution.

On the other hand, when the obtained (meth) acrylate is a low-polarity monomer such as the (meth) acrylate represented by the formula (4), this is dissolved in a low-polarity solvent which is a poor solvent. The unreacted (meth) acrylic anhydride can be removed by washing with an alkaline aqueous solution. The low-polarity solvent does not need to be special, and examples thereof include aliphatic hydrocarbons such as n-hexane, n-heptane and n-pentane, and aromatic hydrocarbons such as toluene. The type of the alkaline aqueous solution used is not particularly limited, and examples thereof include an aqueous sodium hydroxide solution and an aqueous sodium hydrogen carbonate solution.
The (meth) acrylic ester washed with an alkaline aqueous solution is washed with an acidic aqueous solution since a basic catalyst such as an amine is present. The acidic aqueous solution used is not particularly limited, and examples thereof include a sulfuric acid aqueous solution. P of acidic aqueous solution
If H is too low, the (meth) acrylic acid ester represented by the formula (4) may be decomposed. Therefore, a weakly acidic region having a pH of 4 or more is preferable. Finally, it is appropriately washed with a neutral aqueous solution such as an aqueous sodium chloride solution.

The thus obtained (meth) acrylic ester represented by the formula (3) or (4) can be further subjected to thin-film distillation to reduce metal impurities to 50 ppb or less. The thin-film evaporator used at this time does not need to be a special one, and a general one can be used. This thin film distillation is usually performed at 100 to 200 ° C./1 to
It is preferable to carry out at 1500 Pa.

The (meth) acrylic acid ester thus produced is suitable as a (meth) acrylic acid ester monomer which is a raw material of a polymer for a semiconductor resist because it has few impurities.

[0047]

EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The analysis in the examples was performed by gas chromatography (hereinafter referred to as GC) and ¹ H-NMR.

The purity of the product was calculated from the peak area of GC according to the following equation.

Purity (%) = (A / B) × 100 where A is the peak area of the target product (meth) acrylic anhydride or (meth) acrylate,
Represents the sum of the areas of all peaks.

The actual yield was calculated by the following equation.

Actual yield (%) = (C / D) × 100 where C is the number of moles of the desired product (calculated by multiplying the weight of the product by the purity and dividing by the molecular weight of the desired product) , D represent the number of moles of the starting material alcohols or (meth) acrylic acid.

Example 1 (Synthesis of methacrylic anhydride) 8.61 g (0.1 mol) of methacrylic acid and acetic anhydride were placed in a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver. 7.66 g (0.075 mol), phosphoric acid 0.037
g (3.8 × 10 ⁻⁴ mol), 4-hydroxy-2,
0.009 g of 2,6,6-tetramethyl-piperidine-N-oxyl (hereinafter, referred to as HO-TEMPO) was charged and heated and stirred at 60 ° C. for 20 hours. After cooling the reaction solution, 75 ml of n-hexane was added, and the mixture was washed twice with 75 ml of water, and a saturated aqueous solution of sodium hydrogencarbonate (pH = 7.8) was added.
1) The mixture was neutralized and washed 5 times with 75 ml, washed once with 75 ml of water, and the hexane layer was concentrated to obtain 1.67 g of methacrylic anhydride having a purity of 97%. The actual yield based on the raw material methacrylic acid of methacrylic anhydride was 21%.

(Synthesis of γ-butyrolactone-3-yl methacrylate) 6 g (52.5 mmol) of β-hydroxy-γ-butyrolactone was placed in a glass flask equipped with a stirrer, two dropping funnels, a thermometer, and a Dimroth condenser.
12.9 g (78.8 mmol) of 97% pure methacrylic anhydride obtained by the above method, 6.4 g of pyridine
(81.4 mmol), 40 g of 2-butanone, HO-T
0.02 g of EMPO was charged and heated and stirred at 50 ° C. for 22 hours. 2-Butanone was distilled off from the reaction solution, and 130 ml of methanol and 200 ml of water were added.
Washed twice with 0 ml. In the aqueous layer where methanol was concentrated,
Extraction was performed by adding 160 ml of ethyl acetate and 4 g of sodium chloride. The organic layer was washed twice with 160 ml of a 2% aqueous sodium hydrogen carbonate solution, once with a 2% aqueous sulfuric acid solution, and once with a 1% aqueous sodium chloride solution. The ethyl acetate layer was concentrated and γ-butyrolactone-3 having a purity of 91% was obtained. 5.8 g of -yl methacrylate were obtained. Raw material β-hydroxy-γ of the obtained γ-butyrolactone-3-yl methacrylate
-The actual yield based on butyrolactone was 59%. The ¹ H-NMR spectrum data of the obtained γ-butyrolactone-3-yl methacrylate was as follows.

¹ H-NMR (CDCl ₃ ) 2.1 (3H, s), 2.8 (1H, d,
J = 18.4Hz), 3.0 (1H, dd, J = 6.8Hz, 18.4Hz), 4.5 (1H, d, J
= 10.8Hz), 4.7 (1H, dd, J = 4.8Hz, 10.8Hz), 5.6 (1H, dd, J
= 4.8 Hz, 6.8 Hz), 5.8 (1H, s), 6.3 (1H, s) (Distillation of γ-butyrolactone-3-yl methacrylate) γ-butyrolactone-3- having a purity of 91% obtained by the above method. 29 g of ilmethacrylate in a thin-film still
Vacuum distillation was performed at 34 to 140 ° C./27 to 200 Pa. At that time, 4-hydroxy-2,2,6,6 was used as a polymerization inhibitor.
A compound obtained by adding an average of 6 moles of ethylene oxide to the 4-position of 6-tetramethyl-piperidine-N-oxyl is 1
000 ppm was added. Distilled γ-butyrolactone
The amount of 3-yl methacrylate was 25 g. The impurity content in the distillate is 1.2% (the chlorine content is 0.68 pp
m), the actual yield was 51% (based on β-hydroxy-γ-butyrolactone). Also, γ-butyrolactone-
Na, M which are trace metals in 3-yl methacrylate
The contents of g, K, Ca, Mn, Fe and Cu were respectively 100 ppb or more before the thin film distillation, but were 50 ppb or less for each element after the thin film distillation.

Example 2 (Synthesis of 2-methyl-2-adamantyl methacrylate) 2-Methyl-2-adamantanol was placed in a glass flask equipped with a stirrer, two dropping funnels, a thermometer, and a Dimroth condenser. 23. 6 g (0.1 mol) of methacrylic anhydride having a purity of 97% obtained by the method of Example 1
1 g (0.15 mol), 15.7 g of triethylamine
(0.155 mol), dimethylaminopyridine 0.6
g (0.005 mol), toluene 70 ml, HO-T
0.005 g of EMPO was charged and heated and stirred at 50 ° C. for 31 hours. The reaction mixture contains 2-methyl-2 with a yield of about 40%.
-It was confirmed that adamantyl methacrylate was produced. This was purified by silica gel column chromatography to obtain 9.1 g of 2-methyl-2-adamantyl methacrylate.

The purity of the obtained 2-methyl-2-adamantyl methacrylate was 99%, and the actual yield was 39% (2-
Methyl-2-adamantanol).

The ¹ H-NMR spectrum data of the product was as follows.

¹ H-NMR (CDCl ₃ ) 1.6-2.4 (20H, m), 5.5 (1H,
s), 6.1 (1H, s) [Example 3] (Synthesis of methacrylic anhydride) In a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver, 8.61 g (0%) of methacrylic acid was added. .1 mol), acetic anhydride 7.66 g (0.075 mol), phosphoric acid 0.037
g (3.8 × 10 ⁻⁴ mol), HO-TEMPO0.0
Then, the mixture was heated and stirred at 60 ° C. for 20 hours. After cooling the reaction solution, 75 ml of n-hexane was added, and 75 ml of water was added.
l twice, and 10% aqueous sodium hydroxide solution (pH
= 13.2) The mixture was neutralized and washed three times with 75 ml, washed once with 75 ml of water, and the hexane layer was concentrated to obtain 2.45 g of methacrylic anhydride having a purity of 97%. The actual yield based on the raw material methacrylic acid of methacrylic anhydride was 31%.

Example 4 (Synthesis of Polymer for Semiconductor Resist) Under a nitrogen atmosphere, 20.0 parts of 1,4-dioxane was placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer.
The temperature of the hot water bath was raised to 80 ° C. while stirring. 29.3 parts of 2-methacryloyloxy-2-methyladamantane (abbreviation: MAdMA) obtained by the method of Example 2, and β-methacryloyloxy-γ-butyrolactone (abbreviation: HGBMA) obtained by the method of Example 1. A monomer solution obtained by mixing 2 parts, 62.5 parts of 1,4-dioxane and 1.9 parts of azobisisobutyronitrile was dropped into the flask at a constant speed over 6 hours, and then the mixture was heated at 80 ° C. The temperature was maintained for 2 hours. Next, the obtained reaction solution was diluted about 2-fold with tetrahydrofuran, and added dropwise to about 10-fold amount of methanol while stirring to obtain a white precipitate (copolymer A-1). The obtained precipitate was separated by filtration and dried under reduced pressure at 60 ° C. for about 40 hours.

The weight average molecular weight of the obtained copolymer was 1
1,000, copolymer composition ratio MAdMA / HGBMA =
It was 50/50 mol%.

100 parts of the obtained copolymer, 2 parts of triphenylsulfonium triflate as a photoacid generator, N
0.1 parts of isopropyl methacrylamide, propylene glycol monomethyl ether acetate 5 as a solvent
After mixing 00 parts to make a uniform solution, the pore size is 0.1 μm
The solution was filtered through a membrane filter of No. 1 to prepare a resist composition solution. Then, after spin coating each composition solution on a silicon wafer, using a hot plate,
Prebake at 120 ° C. for 60 seconds to form a film having a thickness of 0.5 μm
Was formed. Next, after exposure using an ArF excimer laser exposure machine, post exposure bake was performed at 120 ° C. for 60 seconds using a hot plate. Then, it is developed at room temperature using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, washed with pure water, and dried.
A resist pattern was formed. The obtained resist pattern has a sensitivity of 5.8 mJ / cm ² , a resolution of 0.13 μm,
The resist shape was good.

Comparative Example 1 (Synthesis of Methacrylic Anhydride) In a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver, 8.61 g (0.1 mol) of methacrylic acid, acetic anhydride 7.66 g (0.075 mol), phosphoric acid 0.037
g (3.8 × 10 ⁻⁴ mol), HO-TEMPO0.0
Then, the mixture was heated and stirred at 60 ° C. for 20 hours. After cooling the reaction solution, 75 ml of n-hexane was added, and 75 ml of water was added.
2 times with 20% aqueous sodium hydroxide solution (pH
= 13.7) Washed neutralized with 75 ml, washed once with 75 ml of water, and concentrated the hexane layer to obtain 0.26 g of methacrylic anhydride having a purity of 97%. The actual yield of methacrylic anhydride based on the starting material methacrylic acid was 3.3%.

Comparative Example 2 (Synthesis of Methacrylic Anhydride) In a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver, 138 g (1.6 mol) of methacrylic acid and 123 g of acetic anhydride ( 1.2 mol), phosphoric acid 0.78 g (0.0
08 mol), and HO-TEMPO 0.14 g were charged.
Heating under reduced pressure was performed at an internal temperature of 83 to 104 ° C./17.3 to 2.7 kPa. After distilling off acetic acid and methacrylic acid as a raw material,
An attempt was made to remove methacrylic anhydride by distillation, but polymerization occurred inside the flask and methacrylic anhydride could not be obtained.

Comparative Example 3 (Synthesis of γ-butyrolactone-3-yl methacrylate) In a glass flask equipped with a stirrer, two dropping funnels, a thermometer, and a Dimroth condenser, 3-hydroxy-γ was placed under a nitrogen stream. -Butyrolactone 245 g (2.4 mo
l), methylene chloride (1600 ml) was charged, and methacryloyl chloride (300 g, 2.9 mol) was added to one of the dropping funnels.
l) and 313 g of triethylamine (3.1 m
ol). After the inside of the glass flask was replaced with nitrogen, it was cooled to −60 to −70 ° C. in a dry ice-acetone bath. While stirring the inside of the glass flask, triethylamine and methacrylic acid chloride were added dropwise while adjusting the amount of triethylamine to methacrylic acid chloride so as to be a small excess. After completion of the dropwise addition, stirring was continued for 3 hours.
To the reaction solution, 820 ml of water was added, a small amount of celite was added, and the filtered filtrate was washed three times with 820 ml of water using a separating funnel, 200 g of magnesium sulfate was added and dried, and the filtered filtrate was concentrated to obtain crude γ. 475 g of -butyrolactone-3-yl methacrylate were obtained. This was distilled under reduced pressure at 134 to 140 ° C./27 to 200 Pa using a thin film evaporator.
At that time, 4-hydroxy-2,2,2 was used as a polymerization inhibitor.
6,6-tetramethyl-piperidine-N-oxyl 4
A compound having an average of 6 moles of ethylene oxide added thereto was added at 1000 ppm. The distilled γ-butyrolactone-3-yl methacrylate was 209 g (1.19 m
ol). The impurity content in the distillate is 3.0%
(The chlorine content is 36 ppm) and the actual yield is 50% (β-
Hydroxy-γ-butyrolactone). The ¹ H-NMR spectrum data of the product was as follows.

¹ H-NMR (CDCl ₃ ) 2.1 (3H, s), 2.8 (1 H, d, J = 18,
4Hz), 3.0 (1H, dd, J = 6.8Hz, 18.4Hz), 4.5 (1H, d, J = 10.8Hz),
4.7 (1H, dd, J = 4.8Hz, 10.8Hz), 5.6 (1H, dd, J = 4.8Hz, 6.8H
z), 5.8 (1H, s), 6.3 (1H, s) The γ-butyrolactone-3-yl methacrylate obtained by this method contains 50 times or more chlorine as compared with that of Example 1. Γ-butyrolactone of Example 1 was used as a raw material for a semiconductor resist in which low chlorine was desired.
It is inferior to 3-yl methacrylate.

[0066]

According to the present invention, (meth) acrylic anhydride, in particular, (meth) acrylic acid ester monomer which is a raw material of a polymer for a semiconductor resist (meth) acrylic ester monomer
Acrylic anhydride can be industrially produced with high purity without polymerization.

According to the present invention, the (meth) acrylic acid ester of a secondary or tertiary alcohol, particularly the (meth) acrylate of the formulas (3) and (4), which are the starting monomers for the polymer for semiconductor resists, Acrylic esters can be produced in high yields and these esters can be produced in high purity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 307/33 C08F 20/18 C08F 20/18 20/28 20/28 C07B 61/00 300 // C07B 61 / 00 300 C07D 307/32 Q (72) Inventor Okuta Minami 1-6-1, Konan, Minato-ku, Tokyo F-term in Mitsubishi Rayon Co., Ltd. (reference) 4C037 FA10 4H006 AA02 AC47 AC48 AD16 BA51 BA80 BB11 BB31 BB43 BC10 BC53 BD70 BE10 BJ30 BS10 BS80 KA06 4H039 CA66 CD40 4J100 AL08P BA11P BC09P BC53P CA01 JA38

Claims (10)

[Claims] 1. A method comprising: reacting (meth) acrylic acid with a fatty acid anhydride; and neutralizing and washing the reaction solution after the reaction with an aqueous alkaline solution having a pH of 7.5 to 13.5. A method for producing (meth) acrylic anhydride. 2. The method for producing (meth) acrylic anhydride according to claim 1, wherein the reaction solution is previously dissolved in a low-polarity solvent before the neutralization washing step. 3. The (meth) acrylic anhydride according to claim 1, wherein the produced (meth) acrylic anhydride is a raw material of a (meth) acrylate monomer which is a raw material of a polymer for a semiconductor resist. Production method. 4. The acidity (pKa) of a (meth) acrylic anhydride produced by the method according to claim 1 or 2 and a secondary or tertiary alcohol in water at 25 ° C.
A method for producing a (meth) acrylic acid ester, comprising an esterification step of reacting in the coexistence of a basic compound having a value of 11 or less. 5. The secondary or tertiary alcohol is a compound represented by the following formula (1) or (2):
The (meth) acrylate to be produced is represented by the following formula (3)
5. The method for producing a (meth) acrylate according to claim 4, wherein the method is a (meth) acrylate represented by the following formula (4). 6. Embedded image (Wherein, R ¹ is a hydrogen or alkyl group, and n and m each independently represent the number of 0 or 1 methylene group.) (In the formula, R ² represents an alkyl group.) (In the formula, R ¹ represents a hydrogen or an alkyl group, n and m each independently represent the number of 0 or 1 methylene group, and R ³ represents a hydrogen or a methyl group.) (In the formula, R ² represents an alkyl group, and R ³ represents a hydrogen or methyl group.) 6. The method according to claim 5, wherein the esterification step is performed at a reaction temperature of 80 ° C. or lower. 7. The (meth) acrylate to be produced is a (meth) acrylate represented by the formula (3), wherein the (meth) acrylate obtained after the esterification step has a low polarity. The method for producing a (meth) acrylate according to claim 6, further comprising a washing step of washing with a solvent and further washing with an acidic aqueous solution and / or an alkaline aqueous solution. 8. The (meth) acrylate to be produced is a (meth) acrylate represented by the formula (4), and the (meth) acrylate obtained after the esterification step is an alkaline aqueous solution. 7. A washing step of washing with an acidic aqueous solution.
The method for producing the (meth) acrylic ester according to the above. 9. The method for producing a (meth) acrylate according to claim 7, wherein the (meth) acrylate obtained after the washing step is subjected to thin-film distillation. 10. The produced (meth) acrylic acid ester is a raw material of a polymer for a semiconductor resist.
10. The method for producing a (meth) acrylic ester according to any of 9.