JP2014144950A - Acrylate derivative and alcohol derivative, and production method of the derivatives - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate (alcohol derivative) of an acrylate derivative which is useful as a raw material of a polymeric compound for a resist composition that has excellent lithographic characteristics and forms a resist pattern in a good profile.SOLUTION: The alcohol derivative is expressed by formula (2) described below, and a production method of the derivative is provided. In the formula, R, R, R, Rto Rrepresent H, an alkyl group, a cycloalkyl group or an alkoxy group; Rand Rrepresent H, an alkyl group, a cycloalkyl group or an alkoxy group, or Rand Rare bonded to form an alkylene group, -O- or -S-; and Rrepresents H or an alkyl group or a cyclic hydrocarbon group.

Description

  The present invention relates to an acrylate derivative and an alcohol derivative and a method for producing them.

In lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light and electron beams through a mask on which a predetermined pattern is formed. And performing a developing process to form a resist pattern having a predetermined shape on the resist film. A resist material in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive type, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology.
As a technique for miniaturization, the exposure light source is generally shortened in wavelength (increased energy). Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used. Currently, mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has been started. Further, F ₂ excimer laser of KrF excimer laser or ArF excimer laser than the short wavelength (high energy), an electron beam, is also studied, such as EUV (extreme ultraviolet) and X-ray is performed.

Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern with fine dimensions.
As a resist material satisfying such requirements, a chemically amplified resist composition containing a base material component whose solubility in an alkaline developer is changed by the action of an acid and an acid generator component that generates an acid upon exposure is used. It has been.
For example, as a positive chemically amplified resist composition, a composition containing a resin component (base resin) whose solubility in an alkaline developer is increased by the action of an acid and an acid generator component is generally used. Yes. When a resist film formed using such a resist composition is selectively exposed at the time of resist pattern formation, an acid is generated from the acid generator component in the exposed portion, and the resin component is alkali-developed by the action of the acid. The solubility in the solution increases, and the exposed portion becomes soluble in the alkaline developer.

Currently, as a resist base resin used in ArF excimer laser lithography and the like, a resin having a constitutional unit derived from (meth) acrylic acid ester (acrylic resin) because of its excellent transparency near 193 nm Etc.) are generally used (see, for example, Patent Document 1).
In addition to the base resin and the acid generator, for example, a nitrogen-containing organic compound such as an alkylamine or an alkyl alcoholamine is blended in the chemically amplified resist composition. The nitrogen-containing organic compound acts as a quencher that traps the acid generated from the acid generator, and contributes to the improvement of lithography properties such as the resist pattern shape.
Currently, tertiary amines are generally widely used as the nitrogen-containing organic compounds. Further, with the miniaturization of patterns, various nitrogen-containing organic compounds are used in order to improve process margins and the like when forming isolated patterns (see, for example, Patent Documents 2 and 3).

JP 2003-241385 A JP 2001-166476 A JP 2001-215589 A

In the future, there is a demand for the development of new materials that can be used for lithography applications, as further progress in lithography technology and expansion of application fields are expected. For example, as pattern miniaturization progresses, various lithography characteristics or pattern shapes such as resolution, depth of focus (DOF), line width roughness (LWR), critical dimension uniformity (CDU), etc. There is a need for a resist material that has improved rectangularity and roundness in the case of a hole pattern.
However, in a resist composition using a tertiary amine as a nitrogen-containing organic compound, although the effect of acid diffusion control from the exposed area to the unexposed area and the environmental resistance are recognized, nucleophilicity and basicity are low. When it is too high, it reacts with an ester moiety in the acid generator or the base component contained in the resist composition to cause decomposition, so that there is a problem that storage stability is low and lithography characteristics are also deteriorated.
The resist compositions containing nitrogen-containing organic compounds described in Patent Documents 2 and 3 have not yet been able to satisfy the required lithography characteristics and pattern shapes as the pattern becomes finer.
The present invention has been made in view of the above circumstances, and is an acrylic ester derivative useful as a raw material for a polymer compound for a resist composition that is excellent in lithography properties and can form a resist pattern having a good shape, and its An object is to provide an intermediate (alcohol derivative) and a method for producing the same.

  As a result of intensive studies, the present inventors use, as a base resin, a polymer compound obtained by polymerizing an acrylate derivative containing a specific nitrogen atom-containing group as a quencher for trapping an acid generated from an acid generator. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention provides the following [1] to [5].
[1] The following general formula (1)

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ² , R ³ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom. Represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R ⁴ and R ⁶ are each independently a hydrogen atom, Represents an alkyl group having 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or R ⁴ and R ⁶ are bonded to each other to form an alkylene group having 1 to 3 carbon atoms, —O -, or .R ¹¹ which represents -S- represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms).
An acrylic ester derivative represented by (hereinafter referred to as an acrylic ester derivative (1)).
[2] The following general formula (2)

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined above.)
A method for producing an acrylate derivative (1), which comprises esterifying an alcohol derivative (hereinafter referred to as alcohol derivative (2)).
[3] Alcohol derivative (2).
[4] In the presence of a base, the following general formula (3)

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined above)
A cyclohexene derivative represented by the following formula (hereinafter referred to as cyclohexene derivative (3)) is oxidized to give the following general formula (4):

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined above)
A method for producing an alcohol derivative (2), comprising: obtaining an epoxy derivative represented by formula (hereinafter referred to as an epoxy derivative (4)), and subjecting the obtained epoxy derivative (4) to a base treatment.
[5] A method for producing an epoxy derivative (4), wherein the cyclohexene derivative (3) is oxidized in the presence of a base.

  INDUSTRIAL APPLICABILITY According to the present invention, an acrylate derivative and an intermediate thereof (alcohol derivative) useful as a raw material for a polymer compound for a resist composition that has excellent lithography properties and forms a resist pattern with a good shape, and a method for producing them Can be provided.

[Acrylic acid ester derivative (1)]
The following acrylic ester derivative (1) of the present invention is useful for obtaining a resist composition that is excellent in lithography properties and forms a resist pattern having a good shape.

R ¹ in the acrylate derivative (1) represents a hydrogen atom, a methyl group or a trifluoromethyl group. Among these, R ¹ is preferably a hydrogen atom or a methyl group.
R ² , R ³ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the acrylate derivative (1) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, carbon A cycloalkyl group having 3 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms is represented.
R ⁴ and R ⁶ in the acrylate derivative (1) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Represents an alkoxy group, or R ⁴ and R ⁶ together represent an alkylene group having 1 to 3 carbon atoms, —O—, or —S—.
R ¹¹ in the acrylate derivative (1) represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms.

The alkyl group having 1 to 6 carbon atoms which R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents may be linear or branched. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, n-pentyl group, n-hexyl group and the like can be mentioned. Among these, from the viewpoint of obtaining a resist composition that forms a resist pattern having a good shape, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
Examples of the cycloalkyl group having 3 to 6 carbon atoms which R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent include a cyclopropyl group and a cyclobutyl group , A cyclopentyl group, and a cyclohexyl group.
The alkoxy group having 1 to 6 carbon atoms independently represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be linear or branched. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group and the like can be mentioned. Among these, from the viewpoint of obtaining a resist composition that forms a resist pattern having a good shape, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group is more preferable.
Among the above, the ^{R 2, R 3, R 5} , R 7, R 8, R 9, R 10, and more is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms are preferred, each is hydrogen atom preferable.

Examples of the alkylene group having 1 to 3 carbon atoms formed by combining R ⁴ and R ⁶ include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, and propane-1,1- Examples include a diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group. Among these, a methylene group and an ethane-1,2-diyl group are preferable, and a methylene group is more preferable from the viewpoint of obtaining a resist composition that forms a resist pattern having a good shape.
Among the above, R ⁴ and R ⁶ are each preferably a hydrogen atom, or an alkylene group having 1 to 3 carbon atoms or —O— in which both are bonded, and a methylene group or —O—. More preferably.

The alkyl group having 1 to 6 carbon atoms represented by R ¹¹ may be linear or branched. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s- Examples thereof include a butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. Among these, from the viewpoint of obtaining a resist composition that forms a resist pattern having a good shape, an alkyl group having 1 to 4 carbon atoms is preferable, a branched alkyl group having 3 or 4 carbon atoms is more preferable, and t- A butyl group is more preferable.
Examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms independently represented by R ¹¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantane-1-yl group.
Among these, R ¹¹ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group from the viewpoint of obtaining a resist composition that forms a resist pattern having a good shape. , S-butyl group, t-butyl group, and adamantane-1-yl group are preferable.

In the acrylic ester derivative (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the alcohol derivative (2). , Cyclohexene derivative (3) and epoxy derivative (4), and later diene derivative (5), acrylic acid halide derivative (6) and amine compound (7), respectively.
Specific examples of the acrylate derivative (1) of the present invention are shown below, but are not particularly limited thereto.

As the acrylic ester derivative (1), R ¹ is a hydrogen atom or a methyl group, R ² , R ³ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are all hydrogen atoms; ¹¹ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group or adamantane-1-yl group, and R ⁴ and R ⁴ It is preferable that ⁶ is a methylene group in which both are bonded or —O—.

[Production method of acrylic ester derivative (1)]
Although there is no restriction | limiting in particular in the manufacturing method of acrylic ester derivative (1) of this invention, For example, it can manufacture by the following 1st processes-4th processes.
First step: After reacting a diene derivative (hereinafter referred to as diene derivative (5)) with an acrylic acid halide derivative (hereinafter referred to as acrylic acid halide derivative (6)), an amine compound R ¹¹ NH ₂ ( R ¹¹ is as defined above, and is hereinafter referred to as amine compound (7)) to obtain a cyclohexene derivative (3).
Second step: A step of obtaining an epoxy derivative (4) by reacting the cyclohexene derivative (3) with an organic peroxide in the presence of a basic compound.
Third step: a step of obtaining the alcohol derivative (2) by reacting the epoxy derivative (4) with a basic substance.
Fourth step: A step of producing the acrylic ester derivative (1) by reacting the alcohol derivative (2) with the acrylic acid derivative.
The chemical reaction formulas relating to the first to fourth steps are shown below. In addition, the said diene derivative (5) and acrylic acid halide derivative (6) are the structures described in the following chemical reaction formulas.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰およびＲ¹¹は、前記定義の通りである。Ｘは、塩素原子、臭素原子またはヨウ素原子を表す。）

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are as defined above. X is a chlorine atom Represents a bromine atom or an iodine atom.)

<First step>
First, the 1st process regarding the manufacturing method of a cyclohexene derivative (3) is demonstrated.
The first step is a step of reacting the diene derivative (5) and the acrylic acid halide derivative (6) [hereinafter referred to as first step-1]. And a step of reacting the reaction intermediate obtained in the first step-1 with the amine compound (7) [hereinafter referred to as the first step-2. ].
(First step-1)
Specific examples of the diene derivative (5) used in the first step-1 include butadiene, isoprene, 2,3-dimethylbutadiene, cyclopentadiene, furan and the like.
Specific examples of the acrylic acid halide derivative (6) used in the first step-1 include acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, crotonic acid chloride, crotonic acid bromide, and 3-methyl-2. -Butenoic acid chloride etc. are mentioned.
The amount of the diene derivative (5) used is preferably in the range of 1 to 50 times mol with respect to the acrylic acid halide derivative (6), and more preferably in the range of 1 to 10 times mol from the viewpoint of ease of post-treatment. .

The reaction of the first step-1 is carried out in the presence or absence of a solvent.
The solvent is not particularly limited as long as it does not inhibit the reaction. For example, saturated hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; methylene chloride, dichloroethane, chloroform and benzene chloride Chlorinated hydrocarbon solvents such as: ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, and furan; ester solvents such as methyl acetate, ethyl acetate, and propyl acetate. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
When carried out in the presence of a solvent, the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the diene derivative (5), and from the viewpoint of ease of post-treatment, 0.5 to 20 A range of mass times is more preferable.

The reaction temperature in the first step-1 varies depending on the types of the diene derivative (5) and the acrylic acid halide derivative (6), but is preferably in the range of -30 to 100 ° C, more preferably in the range of -10 to 50 ° C. preferable. Moreover, although there is no restriction | limiting in particular in reaction pressure, Usually, implementing under a normal pressure is preferable.
The reaction time in the first step-1 varies depending on the type and amount of the diene derivative (5) and acrylic acid halide derivative (6), the reaction temperature, etc., but is preferably in the range of about 1 hour to 50 hours.
The reaction in the first step-1 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
The reaction mixture containing the reaction intermediate obtained in the first step-1 can be used as a raw material in the first step-2 as it is without any purification operation, and it is preferable to do so. .

  The method for carrying out the first step-1 is not particularly limited, but an acrylic acid halide derivative (6) and an optional solvent are charged into the reactor, and the desired reaction temperature and desired reaction are added to this mixed solution. A method of dropping the diene derivative (5) under pressure is preferred.

(First step-2)
Specific examples of the amine compound (7) used in the first step-2 include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, cyclohexane. Examples include propylamine, cyclohexylamine, and 1-adamantylamine.
The amount of the amine compound (7) used is preferably in the range of 1 to 10 moles relative to the acrylic acid halide derivative (6) used in the first step-1. From the viewpoint of ease of post-treatment, A range of 5 moles is more preferred. There is no restriction | limiting in particular in the usage form of an amine compound (7), You may use as aqueous solution and may use it with a pure product.

The reaction of the first step-2 is carried out in the presence or absence of a solvent.
The solvent is not particularly limited as long as it does not inhibit the reaction, but the same solvents as those exemplified in the description of the first step-1 can be mentioned. Therefore, when a solvent is used in the first step-1, it is preferable to use the used solvent as it is in the first step-2. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
When carried out in the presence of a solvent, the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the diene derivative (5) used in the first step-1, and the ease of post-treatment. From a viewpoint, the range of 0.5-20 mass times is more preferable.
When the reaction mixture obtained in the first step-1 is used as it is as the raw material of the first step-2, the amount of the solvent may be as it is or may be further added.

The reaction temperature in the first step-2 varies depending on the types of the amine compound (7) and the acrylic acid halide derivative (6), but is preferably in the range of -30 to 100 ° C, more preferably in the range of -10 to 50 ° C. preferable. Moreover, although there is no restriction | limiting in particular in reaction pressure, Usually, implementing under a normal pressure is preferable.
The reaction time in the first step-2 varies depending on the types and amounts of the amine compound (7) and the acrylic acid halide derivative (6), the reaction temperature, etc., but is preferably in the range of about 1 hour to 50 hours.
The reaction in the first step-2 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

  The method for carrying out the first step-2 is not particularly limited, but the reactor is charged with the amine compound (7) and, optionally, a solvent, and this mixture is subjected to a desired reaction temperature and a desired reaction pressure. Thus, a method of dropping the reaction intermediate obtained in the first step-1 is preferable.

Separation and purification of the cyclohexene derivative (3) from the reaction mixture obtained by the above method can be performed by a method generally used for separation and purification of organic compounds.
For example, the cyclohexene derivative (3) can be separated by adding the organic solvent and water after the completion of the reaction in the first step-2, allowing to stand, separating the organic layer and the aqueous layer, and concentrating the organic layer. And if necessary, a highly purified cyclohexene derivative (3) can be obtained by recrystallization, silica gel chromatography, or the like.

<Second step>
Next, the 2nd process regarding the manufacturing method of an epoxy derivative (4) is demonstrated.
Specific examples of the organic peroxide used in the second step include peracetic acid, m-chloroperbenzoic acid, dimethyldioxirane and the like.
The amount of the organic peroxide used is preferably in the range of 1 to 10 moles relative to the cyclohexene derivative (3), and more preferably in the range of 1 to 5 moles from the viewpoint of ease of post-treatment.

Specific examples of the basic compound used in the second step include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; calcium hydroxide and barium hydroxide. Alkaline earth metal hydroxides; alkaline earth metal carbonates such as calcium carbonate and barium carbonate. Among these, alkali metal carbonate is preferable.
The amount of the basic compound used is preferably in the range of 1 to 20 moles relative to the organic peroxide, and more preferably in the range of 1 to 10 moles from the viewpoint of ease of post-treatment.

The reaction in the second step is usually carried out in the presence of a solvent.
The solvent is not particularly limited as long as it does not inhibit the reaction. For example, water; saturated hydrocarbon solvents such as hexane, heptane, cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene; methylene chloride, dichloroethane, chloride Examples include chlorinated hydrocarbon solvents such as benzene; ester solvents such as methyl acetate, ethyl acetate, and isopropyl acetate. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
The amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the cyclohexene derivative (3), and more preferably in the range of 0.5 to 20 times by mass from the viewpoint of ease of post-treatment.

Although the reaction temperature in a 2nd process changes with kinds etc. of an organic peroxide and a cyclohexene derivative (3), the range of -80-100 degreeC is preferable, and the range of -30-50 degreeC is more preferable. Moreover, although there is no restriction | limiting in particular in reaction pressure, Usually, implementing under a normal pressure is preferable.
The reaction time in the second step varies depending on the type and amount of the organic peroxide and cyclohexene derivative (3), the reaction temperature, etc., but is preferably in the range of about 1 hour to 50 hours.
The reaction in the second step is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

The reaction in the second step can be stopped by adding a reducing agent.
Examples of the reducing agent include sodium sulfite, sodium thiosulfate, and sodium hydrogen sulfite.
When adding a reducing agent and stopping reaction of a 2nd process, the addition amount of this reducing agent has the preferable range of 1-5 times mole with respect to an unreacted organic peroxide, and ease of post-processing. From the viewpoint of the above, a range of 1 to 3 moles is more preferable.

  The method for carrying out the second step is not particularly limited, but the reactor is charged with the cyclohexene derivative (3), the basic compound and the solvent, and this mixture is subjected to a desired reaction temperature and a desired reaction pressure. Then, a method of dropping a mixed solution of an organic peroxide and a solvent is preferable.

  Separation and purification of the epoxy derivative (4) from the reaction mixture obtained by the above method can be carried out by methods generally used for separation of organic compounds such as solvent extraction and distillation, and further recrystallization and distillation. The purity can be improved by a method generally used for purification of organic compounds such as sublimation.

<Third step>
Next, the 3rd process regarding the manufacturing method of alcohol derivative (2) is demonstrated.
Specific examples of basic substances used in the third step include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium-t-butoxide, potassium-t-butoxide; hydrogen And alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride. Among these, sodium-t-butoxide, potassium-t-butoxide, and sodium hydride are preferable.
The usage-amount of a basic substance has the preferable range of 1-5 times mole with respect to an epoxy derivative (4), and the range of 1-3 times mole is more preferable from a viewpoint of the ease of post-processing.

The reaction in the third step is usually carried out in the presence of a solvent.
The solvent is not particularly limited as long as it does not inhibit the reaction. For example, saturated hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; diethyl ether, diisopropyl ether, tetrahydrofuran and the like Ether solvent; Alcohol solvents such as methanol, ethanol, t-butanol and the like. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
The amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the epoxy derivative (4), and more preferably in the range of 0.5 to 20 times by mass from the viewpoint of ease of post-treatment.

The reaction temperature in the third step varies depending on the basic substance and the type of the epoxy derivative (4), but is preferably in the range of −80 to 100 ° C., more preferably in the range of −30 to 50 ° C. Moreover, although there is no restriction | limiting in particular in reaction pressure, Usually, implementing under a normal pressure is preferable.
The reaction time in the third step varies depending on the type and amount of the basic substance and the epoxy derivative (4), the reaction temperature, etc., but is generally preferably in the range of 1 hour to 50 hours.
The reaction in the third step is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

The reaction of the third step can be stopped by adding water.
When adding water and stopping reaction of a 3rd process, the addition amount of water has the preferable range of 1-100 times mole with respect to the basic substance to be used, from a viewpoint of the ease of post-processing, 1 The range of ˜50 times mol is more preferable.

  The method for carrying out the third step is not particularly limited, but a basic substance and a solvent are charged into the reactor, and this mixture is mixed with an epoxy derivative (4) under a desired reaction temperature and a desired reaction pressure. ) Is preferably added slowly.

Separation and purification of the alcohol derivative (2) from the reaction mixture obtained by the above method can be performed by methods generally used for separation of organic compounds such as solvent extraction and distillation, and further recrystallization and distillation. The purity can be improved by a method generally used for purification of organic compounds such as sublimation.
Specific examples of the alcohol derivative (2) of the present invention obtained in the third step are shown below, but are not particularly limited thereto.

<4th process>
Next, the 4th process regarding the manufacturing method of an acrylic ester derivative (1) is demonstrated.
The acrylic ester derivative (1) can be obtained by esterifying the alcohol derivative (2). Although there is no restriction | limiting in particular in the method of esterifying alcohol derivative (2), For example, the following method is mentioned.
Method 1: A method of reacting an acrylic acid halide with an alcohol derivative (2) in the presence of a base.
Method 2: A method in which acrylic anhydrides and alcohol derivative (2) are reacted in the presence of a base.
Method 3: A method of reacting acrylic acid and alcohol derivative (2).
Hereinafter, each of the methods 1 to 3 will be described in order.

(Method 1)
Specific examples of the acrylic acid halides used in Method 1 include acrylic acid chloride, methacrylic acid chloride, 2-trifluoromethylacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, and 2-trifluoromethylacrylic acid bromide. Can be mentioned. Among these, acrylic acid chloride, methacrylic acid chloride, and 2-trifluoromethylacrylic acid chloride are preferable from the viewpoint of availability.
The amount of acrylic acid halides used is preferably in the range of 1 to 10 moles relative to the alcohol derivative (2), and more preferably in the range of 1 to 5 moles from the viewpoint of ease of post-treatment.

Specific examples of the base used in Method 1 are not particularly limited as long as they neutralize the by-product acid. For example, pyridine, 2-methylpyridine, 2-methyl-5-ethylpyridine, 2,6- Nitrogen-containing heterocyclic aromatic compounds such as dimethylpyridine; amines such as triethylamine, triethylenetetramine, triethanolamine, piperazine, diazabicyclo [2.2.2] octane; bicarbonates of alkali metals such as sodium hydrogencarbonate, etc. Is mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The amount of the base used is preferably in the range of 1 to 10 moles relative to the alcohol derivative (2), and more preferably in the range of 1 to 5 moles from the viewpoint of ease of post-treatment.

The reaction of Method 1 is carried out in the presence or absence of a solvent.
The solvent is not particularly limited as long as it does not inhibit the reaction. For example, saturated hydrocarbon solvents such as hexane, heptane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; such as methylene chloride, dichloroethane, and benzene chloride. Chlorinated hydrocarbon solvents; ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, and furan; nitrile solvents such as acetonitrile and benzonitrile; ester solvents such as methyl acetate, ethyl acetate, and propyl acetate; 2-butanone, 4-methyl- Examples thereof include ketone solvents such as 2-pentanone. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
When carried out in the presence of a solvent, the amount of the solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the alcohol derivative (2), and from the viewpoint of ease of post-treatment, 0.5 to 20 A range of mass times is more preferable.

In the reaction of method 1, a polymerization inhibitor can be used to prevent polymerization.
Examples of the polymerization inhibitor include phenolic polymerization inhibitors such as hydroquinone and p-methoxyphenol; N, N′-diisopropyl-p-phenylenediamine, N, N′-di-2-naphthyl-p-phenylenediamine, N -Amine polymerization inhibitors such as phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine; 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamide And N-oxyl-based polymerization inhibitors such as -2,2,6,6-tetramethylpiperidine-N-oxyl. A polymerization inhibitor can be used alone or in combination of two or more. When a polymerization inhibitor is used, the amount used is not particularly limited and may be determined as appropriate.

Method 1 can also be carried out by adding an activator such as 4-dimethylaminopyridine.
The reaction temperature in Method 1 varies depending on the type of the alcohol derivative (2) and the acrylic halide, and whether or not an activator is used, but is generally in the range of −50 to 100 ° C., from the viewpoint of reaction rate and polymerization inhibition. A range of −30 to 80 ° C. is more preferable. The reaction pressure is not particularly limited, but it is usually preferable to carry out the reaction under normal pressure.
The reaction time in Method 1 varies depending on the type, amount used, reaction temperature, and the like of the base, the alcohol derivative (2) and the acrylic acid halide, but is preferably in the range of about 1 hour to 50 hours.
Method 1 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

  The method for carrying out method 1 is not particularly limited, but the reactor is charged with the alcohol derivative (2), a base, and optionally a solvent, a polymerization inhibitor, and an activator. A method of dropping acrylic acid halides at a temperature and a desired reaction pressure is preferred.

(Method 2)
Specific examples of the acrylic anhydrides used in Method 2 include acrylic anhydride, methacrylic anhydride, 2-trifluoromethyl acrylic anhydride, pivalic anhydride, pivalic anhydride, Examples include 2-trifluoromethylacrylic acid pivalic acid anhydride, acrylic acid methanesulfonic acid anhydride, methacrylic acid methanesulfonic acid anhydride, and 2-trifluoromethylacrylic acid methanesulfonic acid anhydride.
The amount of acrylic anhydrides used is preferably in the range of 1 to 10 moles relative to the alcohol derivative (2), and more preferably in the range of 1 to 5 moles from the viewpoint of ease of post-treatment.

  Examples of the base used in Method 2 include the same bases as those exemplified in Method 1. A base may be used individually by 1 type and may be used in mixture of 2 or more types. The amount of the base used is preferably in the range of 1 to 10 moles relative to the alcohol derivative (2), and more preferably in the range of 1 to 5 moles from the viewpoint of ease of post-treatment.

The reaction of Method 2 is carried out in the presence or absence of a solvent.
There is no restriction | limiting in particular as long as reaction is not inhibited, The same thing as the solvent illustrated by the method 1 is mentioned. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
When carried out in the presence of a solvent, the amount of solvent used is preferably in the range of 0.5 to 100 times by mass with respect to the diene derivative (5), and 0.5 to 20 mass from the viewpoint of ease of post-treatment. A range of double is more preferable.

  In the reaction of Method 2, a polymerization inhibitor can be used to prevent polymerization. Examples of the polymerization inhibitor include the same polymerization inhibitors as those exemplified in Method 1. A polymerization inhibitor can be used alone or in combination of two or more. When a polymerization inhibitor is used, the amount used is not particularly limited and may be determined as appropriate.

Method 2 can also be carried out by adding an activator such as 4-dimethylaminopyridine.
The reaction temperature in Method 2 varies depending on the types of the alcohol derivative (2) and acrylic anhydrides and whether or not an activator is used, but is generally preferably in the range of −50 to 100 ° C. From the reaction rate and polymerization inhibition, The range of 30-80 degreeC is more preferable. The reaction pressure is not particularly limited, but it is usually preferable to carry out the reaction under normal pressure.
The reaction time in Method 2 varies depending on the type and amount of the base, alcohol derivative (2) and acrylic anhydride, the reaction temperature, etc., but is preferably in the range of about 1 to 50 hours.
Method 2 is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

(Method 3)
The acrylic acid used in Method 3 is acrylic acid, methacrylic acid or 2-trifluoromethyl acrylic acid. The amount of acrylic acid used is preferably in the range of 1 to 50 times mol with respect to the alcohol derivative (2), and more preferably in the range of 1 to 20 times mol from the viewpoint of ease of post-treatment.

  In Method 3, an acid catalyst is usually used. Examples of the acid catalyst include solid acid catalysts such as sulfuric acid, p-toluenesulfonic acid monohydrate, and acidic ion exchange resins. When using an acid catalyst other than the solid acid catalyst, the amount used is preferably in the range of 0.001 to 2 moles, more preferably in the range of 0.01 to 1 moles, relative to the alcohol derivative (2). . When a solid acid catalyst is used as the acid catalyst, the amount used may be appropriately set according to the amount used of the alcohol derivative (2).

  In the reaction of method 3, a polymerization inhibitor can be used to prevent polymerization. Examples of the polymerization inhibitor include the same polymerization inhibitors as those exemplified in Method 1. A polymerization inhibitor can be used alone or in combination of two or more. When a polymerization inhibitor is used, the amount used is not particularly limited and may be determined as appropriate.

The reaction temperature in Method 3 varies depending on the type of the alcohol derivative (2) and acrylic acid, but is generally preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 100 ° C. The reaction pressure is not particularly limited, but it is usually preferable to carry out the reaction under normal pressure.
The reaction time in Method 3 varies depending on the types and amounts of the base, alcohol derivative (2) and acrylic acids, the reaction temperature, etc., but is preferably in the range of about 1 hour to 50 hours.

  Since the reaction of Method 3 is an equilibrium reaction, it is preferable to carry out the reaction while removing by-product water from the reaction system in order to sufficiently proceed the reaction. As a method of removing water, for example, a method of removing water from a device such as a decanter using a solvent that forms an azeotrope with water such as hexane or toluene, or a water adsorbent such as molecular sieves is used. The method etc. are mentioned.

  Separation and purification of the acrylate derivative (1) from the reaction mixture obtained in the above-mentioned method 1, 2 or 3 can be carried out by methods generally used for separation of organic compounds such as solvent extraction and distillation. Further, the purity can be improved by a method generally used for purification of organic compounds such as recrystallization, distillation, sublimation and the like.

[Polymer compound]
A polymer obtained by polymerizing the acrylic ester derivative (1) of the present invention alone or a copolymer obtained by copolymerizing the acrylic ester derivative (1) and another polymerizable compound is used for a photoresist composition. It is useful as a high molecular compound.
Specific examples of other polymerizable compounds (hereinafter referred to as copolymerization monomers) that can be copolymerized with the acrylate derivative (1) include compounds represented by the following chemical formulas. However, it is not particularly limited to these.

In the above formulas (I) to (XII), R ¹² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹³ represents a polymerizable group. R ¹⁴ represents a hydrogen atom or —COOR ¹⁵ , and R ¹⁵ represents an alkyl group having 1 to 3 carbon atoms. R ¹⁶ represents an alkyl group.

In the comonomer, the alkyl group having 1 to 3 carbon atoms independently represented by R ¹² and R ¹⁵ includes a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkyl group represented by R ¹⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. Examples of the polymerizable group represented by R ¹³ include an acryloyl group, a methacryloyl group, a vinyl group, and a crotonoyl group.

The polymer compound can be produced by radical polymerization according to a conventional method. In particular, a method for synthesizing a polymer compound having a small molecular weight distribution includes living radical polymerization.
A general radical polymerization method includes a radical polymerization initiator and a solvent, and, if necessary, one or more kinds of acrylic ester derivatives (1) and, if necessary, one or more kinds of the above copolymerization monomers. Accordingly, the polymerization is carried out in the presence of a chain transfer agent.
The method for carrying out radical polymerization is not particularly limited, and conventional methods such as those used in the production of acrylic polymer compounds such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization can be used.

Examples of the radical polymerization initiator include hydroperoxide compounds such as t-butyl hydroperoxide and cumene hydroperoxide; di-t-butyl peroxide, t-butyl-α-cumyl peroxide, di-α-cumyl peroxide and the like. Dialkyl peroxide compounds; diacyl peroxide compounds such as benzoyl peroxide and diisobutyryl peroxide; and azo compounds such as 2,2′-azobisisobutyronitrile and dimethyl-2,2′-azobisisobutyrate.
The amount of the radical polymerization initiator used can be appropriately selected according to the polymerization conditions such as the acrylic ester derivative (1), copolymerization monomer, chain transfer agent, solvent used in the polymerization reaction, the amount of solvent used, and the polymerization temperature. Is the total amount of all polymerizable compounds [acrylic ester derivative (1) and comonomer, and so on. ] Usually, the range of 0.005 to 0.2 mol is preferable with respect to 1 mol, and the range of 0.01 to 0.15 mol is more preferable.

  Examples of the chain transfer agent include thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, and mercaptopropionic acid. When a chain transfer agent is used, the amount used is usually preferably in the range of 0.005 to 0.2 mol, more preferably in the range of 0.01 to 0.15 mol, per 1 mol of all polymerizable compounds. preferable.

The solvent is not particularly limited as long as the polymerization reaction is not inhibited. For example, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene Glycol ethers such as glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether; esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, propyl acetate; acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone , Methyl amyl ketone, cyclopentanone, cyclohexa Ketones, such as emissions diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethers such as 1,4-dioxane.
The usage-amount of a solvent is the range of 0.5-20 mass parts normally with respect to 1 mass part of all the polymeric compounds, and it is preferable that it is the range of 1-10 mass parts from a viewpoint of economical efficiency. .

The polymerization temperature is usually 40 to 150 ° C., and preferably 60 to 120 ° C. from the viewpoint of the stability of the polymer compound to be produced.
The time for the polymerization reaction varies depending on the polymerization conditions such as the acrylic ester derivative (1), the comonomer, the polymerization initiator, the type and amount of the solvent used, and the temperature of the polymerization reaction, but usually 30 minutes to 48 hours. The range of 1 hour to 24 hours is more preferable.

The polymer compound thus obtained can be isolated by ordinary operations such as reprecipitation. The isolated polymer compound can be dried by vacuum drying or the like.
Examples of the solvent used in the reprecipitation operation include aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene and xylene; methylene chloride, chloroform, chlorobenzene, dichlorobenzene, and the like. Nitrogenated hydrocarbons such as nitromethane; Nitriles such as acetonitrile and benzonitrile; Ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and 1,4-dioxane; Ketones such as acetone and methyl ethyl ketone; Carboxyls such as acetic acid Acid; Esters such as ethyl acetate and butyl acetate; Carbonates such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; Methanol, ethanol, propanol, isopropyl alcohol Include water; alcohols such as butanol.

[Photoresist composition]
A photoresist composition is prepared by blending the polymer compound, an organic solvent and a photoacid generator, and a basic compound and additives as necessary.
As the photoacid generator, a photoacid generator conventionally used for a chemically amplified resist can be used.
Furthermore, a surfactant, a sensitizer, an antihalation agent, a shape improver, a storage stabilizer, an antifoaming agent, and the like can be added to the photoresist composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these examples.

<Example 1> First step (first step-1)
217.2 g (2.400 mol) of acryloyl chloride and 520 g of toluene were charged into a 3 L flask having an internal volume of 2 L equipped with a thermometer, a stirrer, a nitrogen introducing tube and a dropping funnel, and the internal temperature was cooled to 0 ° C. To this mixed solution, 190.4 g (2.880 mol) of cyclopentadiene was added dropwise from the dropping funnel over 1 hour. After completion of dropping, the mixture was stirred at 0 ° C. for 1 hour to prepare a reaction intermediate solution.
(First step-2)
T-butylamine 201.1 g (2.750 mol) and toluene 513 g were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a dropping funnel, and the internal temperature was cooled to 0 ° C. . The reaction intermediate solution obtained in the first step-1 was added dropwise to the mixture from the dropping funnel over 1 hour 30 minutes, and then the internal temperature was raised to 25 ° C.
To the obtained reaction mixture, 1800 ml of ethyl acetate and 300 ml of water were added, stirred for 30 minutes, and allowed to stand for liquid separation to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure to obtain a concentrate.
750 ml of ethyl acetate and 250 ml of hexane were added to the concentrate and heated to 40 ° C. to dissolve the concentrate. After cooling to 2 ° C. with stirring, the precipitated crystals were collected by filtration. The obtained crystals were dried under reduced pressure, and 124.3 g (0.643 mol; yield 26.8%) of Nt-butylbicyclo [2.2.1] hept-5-ene-2-carboxamide having the following characteristics: Got.

¹ H-NMR (270 MHz, CDCl ₃ , TMS, ppm) δ: 6.24 (1H, m), 5.97 (1H, m), 5.20 (1H, br), 3.09 (1H, s ), 2.90 (1H, s), 2.77 (1H, m), 1.86 (1H, m), 1.42 (1H, m), 1.35 (9H, s), 1.39 -1.30 (2H, m)

<Example 2> Second step An Nt-butylbicyclo [2.2.1] hepta-5 was added to a 2 L three-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a dropping funnel. En-2-carboxamide 50.0 g (0.259 mol), methylene chloride 250 g, potassium carbonate 121.6 g (0.880 mol) and water 550 g were charged, and the internal temperature was cooled to 0 ° C. To this mixed solution, 75.9 g (0.440 mol) of m-chloroperbenzoic acid and 1559 g of methylene chloride were added dropwise from a dropping funnel over 20 minutes. After stirring at 0-7 ° C. for 4 hours, 22 g of a saturated aqueous sodium sulfite solution was added and stirred for 30 minutes. After allowing to stand and liquid separation, the organic layer was washed twice with 400 ml of water. The obtained organic layer was concentrated under reduced pressure to obtain a concentrate.
554 g of diisopropyl ether and 222 g of hexane were added to the concentrate, the internal temperature was raised to 50 ° C. to dissolve the concentrate, and the mixture was cooled to 2 ° C., and the precipitated crystals were collected by filtration. The obtained crystals were dried under reduced pressure, and 26.4 g (0.126 mol; yield 48. Nt-butyl-5,6-epoxybicyclo [2.2.1] hept-2-carboxamide having the following characteristics: 6%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS, ppm) δ: 5.31 (1H, br), 3.12 (2H, m), 2.60 (1H, s), 2.52 (1H, s ), 2.04 (1H, m), 1.92 (1H, m), 1.59 (1H, m), 1.35 (9H, s), 1.39-1.30 (2H, m)

<Comparative Example 1>
In Example 2, when an experiment was conducted in the same manner except that 121.6 g (0.880 mol) of potassium carbonate was not used, Nt-butyl-5,6-epoxybicyclo [2.2.1] hepta- Only 0.5 g (0.002 mol; yield 0.8%) of 2-carboxamide was obtained.

<Example 3> Third step 61.0 g (0.544 mol) of potassium tert-butoxide and 1045 g of tert-butanol were charged into a 2 L three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube. The temperature was raised to 50 ° C. Nt-butyl-5,6-epoxybicyclo [2.2.1] hept-2-carboxamide 56.9 g (0.272 mol) was added to this mixture over 1 hour. Subsequently, after the internal temperature was cooled to 25 ° C., 620 g of 3.9 mass% hydrochloric acid and 1900 ml of ethyl acetate were added and stirred for 30 minutes. After allowing to stand and liquid separation, the organic layer was washed twice with 400 ml of water. The obtained organic layer was concentrated under reduced pressure to obtain a concentrate.
30 g of methanol and 820 g of diisopropyl ether were added to the resulting concentrate, and the internal temperature was raised to 50 ° C. to dissolve the concentrate. Subsequently, after cooling to 0 ° C., the precipitated crude crystals were collected by filtration. 200 g of ethyl acetate and 200 g of diisopropyl ether were added to the obtained crude crystals, and the internal temperature was raised to 50 ° C. to dissolve the crude crystals. Subsequently, after cooling to 0 ° C., the precipitated crystals were collected by filtration. The obtained crystals were dried under reduced pressure, and 24.9 g of Nt-butyl-6-hydroxyhexahydro-2-oxo-3,5-methano-4H-cyclopenta [2,3-b] pyrrole having the following characteristics ( 0.119 mol; yield 43.8%).

¹ H-NMR (270 MHz, CDCl ₃ , TMS, ppm) δ: 3.63 (1H, s), 3.55 (1H, m), 2.85 (1H, m), 2.44 (1H, br ), 2.35 (1H, m), 2.25 (1H, m), 2.00-1.78 (2H, m), 1.42 (9H, s), 1.50-1.35 ( 2H, m)

<Example 4> Fourth step (Method 1)
Nt-butyl-6-hydroxyhexahydro-2-oxo-3,5-methano-4H-cyclopenta was added to a 500 mL three-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a dropping funnel. [2,3-b] pyrrole (34.1 g, 0.163 mol), methylene chloride (340 ml) and triethylamine (29.8 g, 0.294 mol) were charged, and the internal temperature was cooled to -40 ° C. To this mixed liquid, 20.5 g (0.196 mol) of methacrylic acid chloride was dropped from a dropping funnel over 1 hour. To the reaction mixture, 12 ml of methanol was added, followed by 120 ml of water, and then stirred for 30 minutes. After allowing to stand and liquid separation, the aqueous layer was extracted four times with 50 ml of methylene chloride. The resulting methylene chloride layers were combined and concentrated under reduced pressure.
The resulting concentrated liquid was purified by silica gel column chromatography, and Nt-butylhexahydro-2-oxo-3,5-methano-4H-cyclopenta [2,3-b] pyrrole-6 having the following characteristics: Ir = methacrylic acid 17.2 g (0.062 mol; yield 38.0%) was obtained.

¹ H-NMR (270 MHz, CDCl ₃ , TMS, ppm) δ: 6.11 (1H, s), 5.59 (1H, m), 4.67 (1H, m), 3.70 (1H, m ), 2.93 (1H, m), 2.51 (1H, m), 2.32 (1H, m), 1.95 (3H, s), 1.90 (1H, m), 1.85 (1H, m), 1.64 (1H, m), 1.47 (1H, m), 1.40 (9H, s)

<Reference example>
Using the monomers (1) to (7) represented by the following chemical formulas, the following polymer compounds were synthesized.

The monomer (2) was synthesized by the method shown below.
(Synthesis of monomer (2))
In a three-necked flask with an internal volume of 500 ml, under a nitrogen atmosphere, 20 g (105.14 mmol) of alcohol, 30.23 g (157.71 mmol) of ethyldiisopropylaminocarbodiimide hydrochloride and 0.6 g of dimethylaminopyridine shown in the following chemical reaction formula 300 ml of a tetrahydrofuran (THF) solution of (5 mmol) was added. Thereto was added 16.67 g (115.66 mmol) of the carboxylic acid compound shown in the following chemical reaction formula under ice-cooling (0 ° C.), and the mixture was stirred at room temperature for 12 hours.
After stopping the reaction by adding 50 ml of water, the reaction solvent was concentrated under reduced pressure, and the organic layer obtained by extraction three times with ethyl acetate was washed with water, saturated sodium bicarbonate, hydrochloric acid aqueous solution with a concentration of 1 mol / L. Washed in the order. The product obtained by distilling off the solvent under reduced pressure was dried to obtain monomer (2).

(Synthesis of polymer compound (A) -1)
In a three-necked flask connected with a thermometer and a reflux tube, monomer (1) 11.77 g (69.23 mmol), monomer (2) 15.00 g (47.47 mmol), monomer (3) 16.58 g (63.63 mmol). 29 mmol), 4.65 g (27.96 mmol) of monomer (4), 3.27 g (13.85 mmol) of monomer (5) and 0.55 g (1.98 mmol) of monomer (7) were dissolved in 76.91 g of methyl ethyl ketone. As a result, a monomer mixture was obtained.
Dimethyl azobisisobutyrate (22.1 mmol) as a polymerization initiator was added to and dissolved in the obtained monomer mixture. The mixture thus obtained was added dropwise to 42.72 g of methyl ethyl ketone heated to 78 ° C. in a nitrogen atmosphere over 3 hours. After completion of dropping, the reaction solution was heated and stirred for 4 hours, and then cooled to room temperature.
The obtained polymerization solution is dropped into a large amount of n-heptane to precipitate a polymer, and the precipitated white powder is filtered off, washed with a mixed solvent of n-heptane / isopropyl alcohol, dried, and polymerized. 43 g of compound (A) -1 was obtained.
The weight average molecular weight (Mw), molecular weight dispersity (Mw / Mn), and copolymer composition ratio determined by ¹³ C-NMR (600 MHz) of this polymer compound (A) -1 (each constituent unit in the polymer compound) The ratio (molar ratio) is shown in Table 1.

(Synthesis of polymer compound (A) -2 to (A) -6)
In the synthesis of the polymer compound (A) -1, the experiment was conducted in the same manner except that the proportion of the constituent units of each polymer compound was changed as shown in Table 1, whereby the polymer compound (A)- 2- (A) -6 was synthesized. Table 1 shows the weight average molecular weight (Mw) and molecular weight dispersity (Mw / Mn) of the polymer compounds (A) -2 to (A) -6.

(Synthesis of polymer compound (A) -7)
In a three-necked flask connected with a thermometer and a reflux tube, monomer (2) 32.32 g (102.29 mmol), monomer (6) 11.93 g (34.10 mmol), monomer (5) 8.05 g ( 34.10 mmol) and 0.95 g (3.41 mmol) of monomer (7) were dissolved in 106.77 g of methyl ethyl ketone to obtain a monomer mixture.
To the resulting monomer mixture, dimethyl azobisisobutyrate (17.3 mmol) was added and dissolved as a polymerization initiator. The mixed solution thus obtained was added dropwise over 3 hours to 67.00 g of methyl ethyl ketone [67.1 g (255.73 mmol) of monomer (3) dissolved in advance] heated to 80 ° C. in a nitrogen atmosphere. After completion of dropping, the reaction solution was heated and stirred for 2 hours, and then the reaction solution was cooled to room temperature.
The obtained polymerization solution was dropped into a large amount of n-heptane, the polymer was precipitated, the precipitated white powder was filtered off, washed sequentially with an n-heptane / 2-propanol mixed solvent and methanol, It was made to dry and the polymer compound (A) -7 65g was obtained.
The weight average molecular weight (Mw), molecular weight dispersity (Mw / Mn), and copolymer composition ratio determined by ¹³ C-NMR measurement (600 MHz) of this polymer compound (A) -7 (each component in the polymer compound) The unit ratio (molar ratio) is shown in Table 1.

(Synthesis of polymer compound (A) -8 to (A) -12)
In the synthesis of the polymer compound (A) -7, an experiment was conducted in the same manner except that the proportion of the constituent units of each polymer compound was changed as shown in Table 1, so that the polymer compound (A)- 8- (A) -12 was synthesized. Table 1 shows the weight average molecular weight (Mw) and the molecular weight dispersity (Mw / Mn) of the polymer compounds (A) -8 to (A) -12.

(Synthesis of fluorine-containing polymer compound (C) -1)
In a three-necked flask connected with a thermometer and a reflux tube, 15.00 g (54.32 mmol) of monomer (c1) and 5.21 g (23.28 mmol) of monomer (c2) were added to 114.52 g of THF and dissolved to obtain monomer. A mixture was obtained.
To the obtained monomer mixture, dimethyl azobisisobutyrate (4.66 mmol) was added and dissolved as a polymerization initiator. The mixture thus obtained was heated and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere, and then cooled to room temperature.
After concentrating the obtained polymerization liquid under reduced pressure, it is dropped into a large amount of n-heptane to precipitate a polymer, and the precipitated polymer is filtered, washed and dried to obtain a fluorine-containing polymer compound (C ) -1 (5.6 g) was obtained.
This fluorine-containing polymer compound (C) -1 had a weight average molecular weight (Mw) of 25000 and a molecular weight dispersity (Mw / Mn) of 1.5. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the polymer compound) determined by ¹³ C-NMR measurement (600 MHz) was 1 / m = 80/20.

<Preparation of resist composition>
Each component shown in Tables 2-3 was mixed and dissolved to prepare a positive resist composition.

In Table 2, the numerical value in [] shows a compounding quantity (part by mass). Moreover, the symbol in Table 2 shows the following, respectively.
(A) -1: polymer compound (A) -1
(A) -2: polymer compound (A) -2
(A) -3: polymer compound (A) -3
(A) -4: polymer compound (A) -4
(A) -5: polymer compound (A) -5
(A) -6: polymer compound (A) -6
(B) -1: Compound represented by the following chemical formula (B) -1 (B) -2: Compound represented by the following chemical formula (B) -2 (B) -3: In the following chemical formula (B) -3 Compound (B) -4: Compound (C) -1 represented by the following chemical formula (B) -4: Fluorine-containing polymer compound (C) -1
(C) -2: a fluorine-containing polymer compound represented by the following chemical formula (C) -2 (synthesized by the method described in JP 2008-134607 A. Mw = 8000, Mw / Mn = 1.47)
(C) -3: a fluorine-containing polymer compound represented by the following chemical formula (C) -3 (Mw = 8600, Mw / Mn = 1.39, composition ratio 1 / m = 54.2 / 45.8 (mol) ratio))
(D) -1: Tri-n-pentylamine (D) -2: Triethanolamine (D) -3: Compound (E) -1 represented by the following chemical formula (D) -3: Salicylic acid (S)- 1: γ-butyrolactone (S) -2: mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / cyclohexanone = 45/30/25 (mass ratio)

In Table 2, the numerical value in [] shows a compounding quantity (part by mass). Moreover, the symbol in Table 2 shows the following, respectively. The same symbols as in Table 1 are as in the annotations in Table 1.
(A) -7: Polymer compound (A) -7
(A) -8: Polymer compound (A) -8
(A) -9: polymer compound (A) -9
(A) -10: polymer compound (A) -10
(A) -11: polymer compound (A) -11
(A) -12: polymer compound (A) -12
(B) -5: Compound represented by the following chemical formula (B) -5 (B) -6: Compound represented by the following chemical formula (B) -6 (S) -3: Propylene glycol monomethyl ether acetate / propylene glycol Monomethyl ether = 6/4 (mass ratio) mixed solvent

<Evaluation of lithography characteristics (1)>
Using the resist compositions 1 to 14, a resist pattern was formed by the following resist pattern forming method, and the lithography characteristics were evaluated.

(Formation of resist pattern)
By applying an organic antireflective coating composition “ARC95” (produced by Brewer Science) on a 12-inch silicon wafer using a spinner and baking and drying at 205 ° C. for 60 seconds on a hot plate, An organic antireflection film having a thickness of 90 nm was formed.
Then, each of the resist compositions 1 to 14 is applied onto the organic antireflection film using a spinner, and after application, a baking (PAB) treatment is performed on a hot plate at 120 ° C. for 60 seconds, followed by drying. As a result, a resist film having a thickness of 95 nm was formed.
Next, an ArF immersion exposure apparatus “NSR-S609B” (manufactured by Nikon Corporation, NA (numerical aperture) = 1.07, Cross pole, immersion medium: water) is passed through a mask pattern (6% halftone). The resist film was selectively irradiated with an ArF excimer laser (193 nm).
Then, a post-exposure baking (PEB) treatment is performed at 95 ° C. for 60 seconds, an alkali development treatment is further performed at 23 ° C. with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 10 seconds, and then pure water is used. Then, water rinsing was performed for 30 seconds, followed by shaking off and drying.
As a result, in each example, a 1: 1 line and space (L / S) pattern having a line width of 50 nm was obtained. The optimum exposure amount Eop (mJ / cm ² ) at which the L / S pattern is formed was determined and used as an index of sensitivity. The results are shown in Table 4.

(Evaluation of depth of focus (DOF))
In the above Eop, the focal point is appropriately shifted up and down, and the above-mentioned 1: 1 L / S pattern can be formed within the range of the dimensional change rate of the target dimension 50 nm ± 5% (ie, 47.5 to 52.5 nm). (Unit: μm) was determined. The results are shown in Table 4.

(Evaluation of LWR)
In the L / S pattern of 1: 1 formed by the above Eop, the line width was measured by the length measurement SEM “S-9380” (scanning electron microscope, acceleration voltage 300 V, manufactured by Hitachi, Ltd.). The measurement was performed at 50 points in the direction, and from the result, a triple value (3 s) of the standard deviation (s) was calculated as a scale indicating LWR. The results are shown in Table 4.
The smaller the value of 3s, the smaller the roughness of the line width, which means that a more uniform width L / S pattern was obtained.

  From the above, the resist compositions 1 to 10 obtained by using the acrylic ester derivative (1) according to the present invention are better in both DOF and LWR than the resist compositions 11 to 14 that are not. It was confirmed that a resist pattern having excellent lithography characteristics and a good shape can be formed.

<Evaluation of lithography characteristics (2)>
Using the resist compositions 16 to 28, a resist pattern was formed by the following resist pattern forming method, and the lithography characteristics were evaluated.

(Formation of resist pattern)
By applying an organic antireflection film composition “ARC29A” (produced by Brewer Science Co., Ltd.) on a 12-inch silicon wafer using a spinner, baking on a hot plate at 205 ° C. for 60 seconds and drying, An organic antireflection film having a thickness of 89 nm was formed.
Then, each of the resist compositions 16 to 28 is applied onto the organic antireflection film using a spinner, and after application, a baking (PAB) treatment is performed on the hot plate at 90 ° C. for 60 seconds, followed by drying. As a result, a resist film having a thickness of 100 nm was formed.
Next, using an ArF immersion exposure apparatus “NSR-S609B” (Nikon Corporation, NA (numerical aperture) = 1.07, Conventional (0.97) w / oPOLANO, immersion medium: water), a mask pattern ( The resist film was selectively irradiated with ArF excimer laser (193 nm) through 6% halftone).
Then, post-exposure baking (PEB) is performed at 80 ° C. for 60 seconds, and further, an alkali development treatment is performed for 20 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C., and then pure water is used. Water rinsing was performed for 30 seconds, followed by shaking off and drying.
As a result, in each of the examples, a dense contact hole pattern (CH pattern) in which holes with a hole diameter of 90 nm were arranged at equal intervals (pitch 140 nm) was obtained. The optimum exposure dose Eop (mJ / cm ² ; sensitivity) for forming the CH pattern was determined and used as an index of sensitivity. The results are shown in Table 5.

(Evaluation of CDU)
In the CH pattern formed by the above Eop, the diameter (CD) of 100 holes in each CH pattern is measured, and from the result, the standard deviation (s) three times (3 s) is obtained as the CD uniformity ( It was calculated as a scale indicating CDU). The results are shown in Table 5.
The smaller the value of 3s, the higher the critical dimension uniformity of the holes.

(Evaluation of roundness)
The CH pattern formed in the above Eop is observed from above, and the length measurement SEM “S-9380” (manufactured by Hitachi, Ltd.) is used to measure 100 holes in each CH pattern from the center of the hole to the outer edge. The distance in 24 directions was measured, and a value (3s) three times the standard deviation (s) calculated from the results was calculated as a scale indicating roundness. The results are shown in Table 5.
The smaller this 3s value, the higher the roundness of the hole.

  As described above, the resist compositions 16 to 24 obtained using the acrylic ester derivative (1) according to the present invention have a good CDU and roundness compared to the resist compositions 25 to 28 that are not. Therefore, it was confirmed that a resist pattern having excellent lithography characteristics and a good shape can be formed.

  The acrylic ester derivative (1) of the present invention is excellent as a lithographic property and is useful as a raw material for a polymer compound for a resist composition that forms a resist pattern having a good shape. The alcohol derivative (2) of the present invention is useful as a synthetic intermediate for the acrylate derivative (1).

Claims (3)

The following general formula (2)

(In the formula, R ² , R ³ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclohexane having 3 to 6 carbon atoms. An alkyl group or an alkoxy group having 1 to 6 carbon atoms, R ⁴ and R ⁶ are bonded to each other to represent an alkylene group having 1 to 3 carbon atoms, —O—, or —S—, and R ¹¹ is a carbon atom. Represents an alkyl group having 1 to 6 carbon atoms and a cyclic hydrocarbon group having 3 to 10 carbon atoms.)
An alcohol derivative represented by In the presence of a base, the following general formula (3)

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined in claim 1).
A cyclohexene derivative represented by the following general formula (4) is oxidized:

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined in claim 1).
An epoxy derivative represented by the formula (2) is obtained, and the obtained epoxy derivative is treated with a base:

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined in claim 1).
The manufacturing method of the alcohol derivative shown by these. In the presence of a base, the following general formula (3)

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined in claim 1).
A cyclohexene derivative represented by the following formula (4) is oxidized:

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined in claim 1).
The manufacturing method of the epoxy derivative shown by these.