JP4594695B2 - Method for producing adamantane derivative - Google Patents

Description

  The present invention relates to a method for producing an adamantane derivative, and more particularly to a method for efficiently producing alkylsulfonyloxy-substituted adamantyl (meth) acrylates useful as monomers for functional resins such as photosensitive resins in the field of photolithography.

Adamantane has a structure in which four cyclohexane rings are condensed into a cage shape, is a highly symmetric and stable compound, and its derivative exhibits a unique function. It is known to be useful as a raw material for the above. For example, since it has optical characteristics, heat resistance, etc., it has been attempted to use it for an optical disk substrate, an optical fiber, a lens, or the like (for example, see Patent Document 1 and Patent Document 2).
In addition, an attempt has been made to use adamantane esters as a resin material for a photoresist by utilizing its acid sensitivity, dry etching resistance, ultraviolet transmittance, and the like (see, for example, Patent Document 3).
On the other hand, in recent years, with the progress of miniaturization of semiconductor elements, further miniaturization is required in the lithography process in the manufacture thereof. Therefore, it is compatible with short-wavelength irradiation light such as KrF, ArF or F ₂ excimer laser light. Various methods for forming a fine pattern using the above-described photoresist material have been studied. The appearance of a new photoresist material capable of dealing with short-wavelength irradiation light such as the excimer laser light is desired. Conventionally, monomers having a hydroxyl group introduced therein are known (see, for example, Patent Document 4), but a photoresist material having a functional functional group that has not been known is desired.

JP-A-6-305044 Japanese Patent Laid-Open No. 9-302077 Japanese Patent Laid-Open No. 4-39665 JP-A-63-33350

Under such circumstances, the present inventors have previously described a novel methanesulfonyloxy-substituted adamantyl (meth) useful as a monomer of a functional resin (photosensitive resin or the like) in the field of photolithography and an intermediate of the monomer. An acrylate was found (Japanese Patent Application No. 2004-29034).
However, since a polymer is produced during the reaction in the production process of the novel methanesulfonyloxy-substituted adamantyl (meth) acrylates, the yield is reduced, and a step for removing the polymer is necessary. There were problems in handling, such as the precipitation of the polymer produced in the purification step of (meth) acrylates and the attachment to the apparatus, which required time for purification.
The present invention produces alkylsulfonyloxy substituted (meth) adamantyl acrylates, which are adamantane derivatives useful as monomers for functional resins such as photosensitive resins in the field of photolithography, with good yield without any problems in handling. It is intended to provide a method.

As a result of intensive studies to achieve the above object, the present inventors have found that an adamantane compound and a sulfonyl compound, which are raw materials for the alkylsulfonyloxy-substituted adamantyl (meth) acrylates, in an organic solvent having a low dielectric constant. It has been found that, by reacting, the target (meth) acrylates can be produced in a high yield and the production of the polymer can be suppressed, so that the handling is improved. The present invention has been completed based on such knowledge.
That is, the present invention relates to the general formula (I)

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a CF ₃ group, Y represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or two Ys formed together. And a plurality of Y may be the same or different, k represents an integer of 0 to 14, and m and n independently represent an integer of 0 to 4.)
An adamantane compound represented by general formula (II)

(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkylphenyl group, or a CF ₃ group, and X represents a hydroxyl group or a halogen atom.)
The sulfonyl compound represented by the general formula (III) is reacted in an organic solvent having a dielectric constant of 8 or less at 20 ° C.

(Wherein R ¹ is a hydrogen atom, a methyl group or a CF ₃ group, R ² is an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkylphenyl group, or a CF ₃ group, and Y is an alkyl having 1 to 10 carbon atoms A group, a halogen atom, a hydroxyl group, or two Ys formed together represent ═O. Further, a plurality of Ys may be the same or different, k represents an integer of 0 to 14, and m , N independently represents an integer of 0-4.)
A method for producing an adamantane derivative characterized by having a structure represented by:

Alkylsulfonyloxy-substituted adamantyl (meth) acrylates that are adamantane derivatives produced by the method of the present invention are useful as monomers for functional resins such as photosensitive resins in the field of photolithography. Further, it is considered that the compatibility with PAG (photoacid generator) which is one component of the resist agent mixed solution is improved, so that a homogeneous film can be formed, and thereby the surface roughness after exposure (LER: resist side surface). The effect of improving the unevenness, LWR: waviness when the wiring is viewed from directly above can be expected.
Further, the adamantane derivative can be produced in a high yield by the method of the present invention, and the production of the polymer can be suppressed, so that the handling can be improved, and it can be produced efficiently and advantageously industrially. .

The adamantane derivative produced by the method of the present invention is a compound represented by the general formula (III). Hereinafter, the compound and the production method will be described.
First, an adamantane derivative produced by the method of the present invention has a general formula (III)

Alkylsulfonyloxy-substituted adamantyl (meth) acrylates having a structure represented by:
In the general formula (III), R ¹ is a hydrogen atom, a methyl group or a CF ₃ group, R ² is an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkylphenyl group, or a CF ₃ group, and Y is 1 carbon atom. -10 which is formed by combining 10 to 10 alkyl groups, halogen atoms, hydroxyl groups or two Ys together. Moreover, several Y may be the same and may differ. k shows the integer of 0-14, m and n show the integer of 0-4 independently. Note that when m is 0 and n is 0, a structure in which oxygen is directly bonded to an adamantyl group is shown.
In the above, examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. Either linear or branched may be used. Examples of the alkylphenyl group include a methylphenyl group, an ethylphenyl group, and a propylphenyl group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  Examples of the adamantane derivative represented by the general formula (III) include 3-methanesulfonyloxy-1-adamantyl methacrylate, 3-methanesulfonyloxy-1-adamantyl acrylate, 3-methanesulfonyloxy-1-adamantyl 2-tri Fluoromethyl acrylate, 1-methanesulfonyloxy-4-adamantyl methacrylate, 1-methanesulfonyloxy-4-adamantyl acrylate, 1-methanesulfonyloxy-4-adamantyl 2-trifluoromethyl acrylate, 3-methanesulfonyloxymethyl-1 -Adamantylmethyl methacrylate, 3-methanesulfonyloxymethyl-1-adamantylmethyl acrylate, 3-methanesulfonyloxymethyl-1-adamantylmethyl 2-to Fluoromethyl acrylate, 3-methanesulfonyloxy - perfluoro-1-adamantyl methacrylate, 3-methanesulfonyloxy - perfluoro-1-adamantyl acrylate, and the like.

Next, the manufacturing method of the adamantane derivative of this invention is demonstrated.
That is, the production method of the present invention is carried out by reacting the adamantane compound represented by the general formula (I) with the sulfonyl compound represented by the general formula (II).
Examples of the adamantane compound represented by the general formula (I) of the raw material include 3-hydroxy-1-adamantyl methacrylate, 3-hydroxy-1-adamantyl acrylate, 3-hydroxy-1-adamantyl 2-trifluoromethyl acrylate, 1 -Hydroxy-4-adamantyl methacrylate, 1-hydroxy-4-adamantyl acrylate, 1-hydroxy-4-adamantyl 2-trifluoromethyl acrylate, 3-hydroxymethyl-1-adamantylmethyl methacrylate, 3-hydroxymethyl-1-adamantyl Methyl acrylate, 3-hydroxymethyl-1-adamantylmethyl 2-trifluoromethyl acrylate, 3-hydroxy-perfluoro-1-adamantyl methacrylate, 3-hydroxy There may be mentioned hydroxyl group-containing adamantyl acrylates such as -perfluoro-1-adamantyl acrylate.
In addition, the sulfonyl compound represented by the general formula (II) is preferably a compound in which X is a halogen atom rather than a hydroxyl group from the viewpoint of reactivity, and in particular from an industrial viewpoint, a chlorine atom is preferable. Examples of the sulfonyl compound include methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, p-toluenesulfonyl chloride, trifluoromethanesulfonyl chloride, and the like. Among these, methanesulfonyl chloride is preferable.
The charging ratio of the adamantane compound and the sulfonyl compound is preferably in the range of 1 to 1.5 mol of the sulfonyl compound with respect to 1 mol of the adamantane compound.

  In this reaction, a base is generally used as a catalyst. As a base, sodium amide, triethylamine, tributylamine, trioctylamine, pyridine, N, N-dimethylaniline, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5 4.0] undecene-7 (DBU), sodium hydroxide, potassium hydroxide, sodium hydride, potassium carbonate, silver oxide, sodium methoxide, potassium t-butoxide and the like. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, an organic solvent having a dielectric constant of 8 or less at 20 ° C. is used as the solvent for the above reaction. By using such a low dielectric constant solvent, the target alkylsulfonyloxy-substituted adamantyl (meth) acrylates can be produced in high yield, and the production of polymers can be suppressed, so that the handling is also improved. The As this solvent, those having a solubility of the raw material adamantane compound at the reaction temperature of 0.5% by mass or more, preferably 5% by mass or more are suitably used.
Specific examples of such solvents include hydrocarbon solvents such as toluene, n-hexane, n-heptane, and cyclohexane, ester solvents such as ethyl acetate, these solvents, diethyl ether, tetrahydrofuran, and the like. A mixed solvent with an ether solvent can be mentioned. These solvents may be used alone or in a combination of two or more. The amount of the solvent is preferably such that the concentration of the raw material adamantane compound in the reaction mixture is 0.5% by mass or more, desirably 5% by mass or more. At this time, the raw material adamantane compound may be in a suspended state, but is preferably dissolved. Moreover, it is desirable to remove the water | moisture content in a solvent before use.

The reaction temperature is usually in the range of −200 to 100 ° C., preferably −50 to 50 ° C. Within this temperature range, the reaction rate does not decrease, the reaction time does not become too long, and the by-product of the polymer does not increase.
The reaction pressure is usually 0.01 to 10 MPa in absolute pressure, preferably in the range of normal pressure to 1 MPa. Within this pressure range, a special pressure-resistant device is not necessary, there is no safety problem, and it is industrially advantageous.
The reaction time is usually in the range of 1 minute to 24 hours, preferably 5 minutes to 6 hours.

As a specific production method, the raw material adamantane compound and sulfonyl compound are reacted in the above-mentioned organic solvent having a low dielectric constant in the presence of a base, and after the reaction, the salt is removed by washing with water. Isolate the oxy-substituted adamantyl (meth) acrylates.
For purification of the target reaction product, distillation, crystallization, column separation, etc. can be employed, and a purification method may be selected depending on the properties of the product and the type of impurities.
The obtained compound was identified by gas chromatography (GC), liquid chromatography (LC), gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR). ), A melting point measuring device or the like.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, about the value of the dielectric constant of a solvent, it is a numerical value from the organic synthetic chemistry association new edition solvent pocket book (Ohm company), Teruzo Asahara et al. Solvent handbook (Kodansha Scientific), and dielectric constant of mixed solvent (Example 5). The rate is a numerical value calculated by the addition rule.

Example 1
A stirrer, a dropping funnel and a thermometer were attached to a 200 mL glass reactor, and 10.0 g (42 mmol) of adamantate HM (manufactured by Idemitsu Kosan Co., Ltd .: 3-hydroxy-1-adamantyl methacrylate), 8.8 mL of triethylamine (63 Mmol) and 84.0 mL of toluene, and the mixture was immersed in a 25 ° C. water bath and stirred. Methanesulfonyl chloride 4.0mL (50mmol) was dripped here over 35 minutes. Thereafter, the mixture was further stirred for 25 minutes. 10 mL of water was added thereto to deactivate unreacted methanesulfonyl chloride. A part of the reaction solution was taken and subjected to GPC measurement to determine the production ratio of the target product and the polymer. The remaining reaction solution was transferred to a 200 mL separatory funnel, 40 mL of water was added and washed with water, and then the organic layer was washed with 50 mL of 1 milmol / mL hydrochloric acid and then with 50 mL of water. The polymer did not precipitate during the liquid separation operation. After adding anhydrous magnesium sulfate 6.0g (50 mmol) and dehydrating, magnesium sulfate was removed by filtration. The filtrate was attached to an evaporator and toluene was distilled off, and then the resulting viscous product was cooled to 0 ° C. and crystallized. After washing this with a small amount of n-hexane, the crystals were separated by filtration and dried under reduced pressure until a constant weight was obtained, to obtain the target adamantane derivative (3-methanesulfonyloxy-1-adamantyl methacrylate). Table 1 shows the results of the yield (mol%) of the target product relative to the starting adamantane compound, the purity (mass%) by gas chromatography, and the polymer production ratio (mass%) by GPC measurement.

Comparative Example 1
A stirrer, a dropping funnel and a thermometer were attached to a 200 mL glass reactor, and 10.0 g (42 mmol) of adamantate HM (produced by Idemitsu Kosan: 3-hydroxy-1-adamantyl methacrylate), 8.8 mL of triethylamine (63 Mmol) and 84 mL of tetrahydrofuran were added, and the mixture was immersed in a water bath at 25 ° C. and stirred. Methanesulfonyl chloride 4.0mL (50mmol) was dripped here over 35 minutes. Thereafter, the mixture was further stirred for 25 minutes. 10 mL of water was added thereto to deactivate unreacted methanesulfonyl chloride. A part of the reaction solution was taken and subjected to GPC measurement to determine the production ratio of the target product and the polymer. The remaining reaction solution was transferred to a 300 mL separatory funnel, and 100 mL of diethyl ether and 40 mL of water were added and washed with water. At that time, the polymer was deposited and adhered to the separatory funnel, and the separatory funnel cock was clogged with the polymer when the organic layer and the aqueous layer were separated. The organic layer was then washed with 50 mL of 1 milmol / mL hydrochloric acid and then with 50 mL of water. After adding anhydrous magnesium sulfate 6.0g (50 mmol) and dehydrating, magnesium sulfate was removed by filtration. The filtrate was attached to an evaporator and the solvent was distilled off, and then the resulting viscous product was cooled to 0 ° C. and crystallized. After washing this with a small amount of n-hexane, the crystals were separated by filtration and dried under reduced pressure until a constant weight was obtained to obtain the desired product. Table 1 shows the results of yield of the target product, purity by gas chromatography, and polymer production ratio by GPC measurement.

Example 2
A stirrer, a dropping funnel and a thermometer were attached to a 200 mL glass reactor, and 10.0 g (42 mmol) of adamantate HM (produced by Idemitsu Kosan: 3-hydroxy-1-adamantyl methacrylate), 8.8 mL of triethylamine (63 Mmol) and 42 mL of toluene were added and cooled to 5 ° C. in an ice bath with stirring. Methanesulfonyl chloride 4.0mL (50 mmol) was dripped here over 3 minutes. Thereafter, the mixture was further stirred for 5 minutes. 10 mL of water was added thereto to deactivate unreacted methanesulfonyl chloride. A part of the reaction solution was taken and subjected to GPC measurement to determine the production ratio of the target product and the polymer. The remaining reaction solution was transferred to a 200 mL separatory funnel, 40 mL of water was added and washed with water, and then the organic layer was washed with 50 mL of 1 mmol / mL hydrochloric acid and then with 50 mL of water. The polymer did not precipitate during the liquid separation operation. After adding anhydrous magnesium sulfate 6.0g (50 mmol) and dehydrating, magnesium sulfate was removed by filtration. The filtrate was attached to an evaporator and toluene was distilled off, and then the resulting viscous product was cooled to 0 ° C. and crystallized. This was washed with a small amount of n-hexane, and then the crystals were separated by filtration and dried under reduced pressure until a constant weight was obtained. Table 1 shows the results of yield of the target product, purity by gas chromatography, and polymer production ratio by GPC measurement.

Example 3
The target product was obtained in the same manner as in Example 2 except that 42 mL of toluene was changed to 84 mL in Example 2. The polymer did not precipitate in the process of liquid separation. Table 1 shows the results of yield of the target product, purity by gas chromatography, and polymer production ratio by GPC measurement.

Example 4
The target product was obtained in the same manner as in Example 2 except that toluene was changed to ethyl acetate in Example 2. The polymer did not precipitate in the process of liquid separation. Table 1 shows the results of yield of the target product, purity by gas chromatography, and polymer production ratio by GPC measurement.

Example 5
The target product was obtained in the same manner as in Example 2 except that toluene was changed to a mixed solvent of 22 mL of cyclohexane and 22 mL of tetrahydrofuran in Example 2. The polymer did not precipitate in the process of liquid separation. Table 1 shows the results of yield of the target product, purity by gas chromatography, and polymer production ratio by GPC measurement.

Comparative Example 2
A stirrer, a dropping funnel and a thermometer were attached to a 200 mL glass reactor, and 10.0 g (42 mmol) of adamantate HM (produced by Idemitsu Kosan: 3-hydroxy-1-adamantyl methacrylate), 8.8 mL of triethylamine (63 Mmol) and 42 mL of tetrahydrofuran were added and cooled to 5 ° C. in an ice bath with stirring. Methanesulfonyl chloride 4.0mL (50 mmol) was dripped here over 3 minutes. Thereafter, the mixture was further stirred for 5 minutes. 10 mL of water was added thereto to deactivate unreacted methanesulfonyl chloride. A part of the reaction solution was taken and subjected to GPC measurement to determine the production ratio of the target product and the polymer. The remaining reaction solution was transferred to a 300 mL separatory funnel, and 100 mL of diethyl ether and 40 mL of water were added and washed with water. At that time, polymer precipitated and adhered to the separatory funnel. The organic layer was then washed with 50 mL of 1 mmol / mL hydrochloric acid and then with 50 mL of water. After adding anhydrous magnesium sulfate 6.0g (50 mmol) and dehydrating, magnesium sulfate was removed by filtration. The filtrate was attached to an evaporator and the solvent was distilled off, and then the resulting viscous product was cooled to 0 ° C. and crystallized. After washing this with a small amount of n-hexane, the crystals were separated by filtration and dried under reduced pressure until a constant weight was obtained to obtain the desired product. Table 1 shows the results of yield of the target product, purity by gas chromatography, and polymer production ratio by GPC measurement.

Comparative Example 3
The target product was obtained in the same manner as in Example 2 except that toluene was changed to methylene chloride in Example 2. Polymer was deposited in the process of liquid separation. Table 1 shows the results of yield of the target product, purity by gas chromatography, and polymer production ratio by GPC measurement.

Claims (3)

Formula (I)

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a CF ₃ group, Y represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or two Ys formed together. And a plurality of Y may be the same or different, k represents an integer of 0 to 14, and m and n independently represent an integer of 0 to 4.)
An adamantane compound represented by general formula (II)

(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkylphenyl group, or a CF ₃ group, and X represents a hydroxyl group or a halogen atom.)
The sulfonyl compound represented by the general formula (III) is reacted in an organic solvent having a dielectric constant of 8 or less at 20 ° C.

(In the formula, R ¹ is a hydrogen atom, a methyl group or a CF ₃ group, R ² is an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkylphenyl group, or a CF ₃ group, and Y is an alkyl having 1 to 10 carbon atoms. A group, a halogen atom, a hydroxyl group, or two Ys formed together represents ═O. A plurality of Ys may be the same or different, k represents an integer of 0 to 14, and m , N independently represents an integer of 0-4.)
A method for producing an adamantane derivative, characterized by having a structure represented by: The organic solvent is at least one organic solvent selected from hydrocarbon solvents, ester solvents, and hydrocarbon solvents and / or mixed solvents of ester solvents and ether solvents. A method for producing the adamantane derivative as described. The method for producing an adamantane derivative according to claim 1 or 2, wherein a reaction temperature in the organic solvent is -200 to 100 ° C.