KR20130103649A - Acrylic ester derivative, alcohol derivative, and method for producing same - Google Patents

Abstract

(식 중, R¹ 은 수소 원자, 메틸기 또는 트리플루오로메틸기를 나타내고, R², R³, R⁵, R⁷, R⁸, R⁹, R¹⁰ 은 각각 독립적으로, 수소 원자, 탄소수 1 ∼ 6 의 알킬기, 탄소수 3 ∼ 6 의 시클로알킬기 또는 탄소수 1 ∼ 6 의 알콕시기를 나타낸다. R⁴ 및 R⁶ 은 각각 독립적으로, 수소 원자, 탄소수 1 ∼ 6 의 알킬기, 탄소수 3 ∼ 6 의 시클로알킬기 혹은 탄소수 1 ∼ 6 의 알콕시기를 나타내거나, 또는 R⁴ 및 R⁶ 은 양자가 결합하여 탄소수 1 ∼ 3 의 알킬렌기, -O-, 혹은 -S- 를 나타낸다. R¹¹ 은, 수소 원자, 탄소수 1 ∼ 6 의 알킬기, 탄소수 3 ∼ 10 의 고리형 탄화수소기를 나타낸다)Provided are acrylic acid ester derivatives and intermediates thereof (alcohol derivatives) which are excellent as lithographic properties and are useful as raw materials for polymer compounds for resist compositions for forming resist patterns of good shape, and methods for producing them. Specifically, the acrylate ester derivative represented by the following general formula.

(In 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> , R <^10> respectively independently represents a hydrogen atom and C1-C An alkyl group of 6, a cycloalkyl group of 3 to 6 carbon atoms or an alkoxy group of 1 to 6 carbon atoms, R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, or carbon atoms Or an alkoxy group of 1 to 6, or R ⁴ and R ⁶ Both are bonded to each other to represent an alkylene group having 1 to 3 carbon atoms, -O-, or -S-. R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms)

Description

Acrylate esters and alcohol derivatives and methods for their preparation {ACRYLIC ESTER DERIVATIVE, ALCOHOL DERIVATIVE, AND METHOD FOR PRODUCING SAME}

The present invention relates to acrylic acid ester derivatives and alcohol derivatives and methods for their preparation.

The lithography technique forms, for example, a resist film made of a resist material on a substrate, and selectively exposes the resist film with radiation such as light or electron beam through a mask having a predetermined pattern, thereby performing development processing. By implementing, it has a process of forming a resist pattern of a predetermined shape in the said resist film. The resist material which changes to the characteristic which the exposed part changes by the characteristic which melt | dissolves in a developing solution is positive type, and the resist material which changes by the characteristic which the exposed part does not melt | dissolve in a developing solution is called negative type.

BACKGROUND ART [0002] In recent years, in the manufacture of semiconductor devices and liquid crystal display devices, patterns are being rapidly miniaturized by advances in lithography technology.

As a method of miniaturization, shortening of wavelength (high energy) of the exposure light source is generally performed. Specifically, ultraviolet rays typified by g-line and i-line have conventionally been used, but mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers is now disclosed. In addition, studies have been conducted on F ₂ excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays and the like which are shorter in wavelength (high energy) than KrF excimer lasers and ArF excimer lasers.

Resist materials are required to have lithography properties such as sensitivity to resolution of these exposure light sources and resolving ability to reproduce patterns of fine dimensions.

As a resist material that satisfies such a requirement, a chemically amplified resist composition containing a base component whose solubility in an alkaline developer is changed by the action of an acid and an acid generator component which generates an acid by exposure is used.

For example, as a positive chemically amplified resist composition, one containing a resin component (base resin) in which solubility in an alkaline developer is increased by the action of an acid and an acid generator component are generally used. Such a resist film formed by using a resist composition, when selective exposure is performed at the time of forming a resist pattern, an acid is generated from an acid generator component in the exposed portion, and the action of the acid causes the acid component to react with the alkaline developer. Solubility increases and an exposure part becomes soluble with respect to alkaline developing solution.

Currently, as a base resin of a resist used in ArF excimer laser lithography, etc., since it is excellent in transparency in the vicinity of 193 nm, resin (acrylic resin) etc. which have a structural unit derived from (meth) acrylic acid ester in a principal chain, etc. This is generally used (for example, refer patent document 1).

In addition to the base resin and the acid generator, for example, a compound containing a nitrogen-containing organic compound such as alkylamine or alkyl alcohol amine in the chemically amplified resist composition is carried out. The nitrogen-containing organic compound acts as a quencher to trap the acid generated from the acid generator, contributing to the improvement of lithography characteristics such as resist pattern shape.

Currently, tertiary amines are generally used widely as the nitrogen-containing organic compounds. Moreover, in order to improve the process margin etc. at the time of formation of an isolated pattern with refinement | miniaturization of a pattern, various nitrogen-containing organic compounds are used (for example, refer patent document 2 and 3).

Japanese Patent Application Laid-Open No. 2003-241385 JP 2001-166476 A Japanese Unexamined Patent Publication No. 2001-215689

In the future, new advances in lithography technology, expansion of applications, and the like are expected, and there is a demand for developing new materials that can be used for lithography applications. For example, as the pattern refines, various lithographic characteristics or pattern shapes (e.g., line patterns, such as resolution, depth of focus (DOF), line with roughness (LWR), marginal dimensional uniformity (CDU) There is a demand for a resist material having improved rectangularity and roundness in a hole pattern).

However, in the resist composition using the tertiary amine as the nitrogen-containing organic compound, the effect of controlling the acid diffusion from the exposure region to the unexposed region and the environmental resistance is observed. In order to cause decomposition by reacting with the ester site in the acid generator or the base component contained in the composition, there is a problem that the storage stability is low and the lithographic characteristics are also reduced.

The resist compositions containing the nitrogen-containing organic compounds described in Patent Literatures 2 and 3 did not still satisfy the lithography characteristics and pattern shapes required as the pattern was refined.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent lithographic properties and is useful as a raw material of a polymer compound for a resist composition capable of forming a resist pattern having a good shape, and an intermediate thereof (alcohol derivative) and its preparation. The task is to provide a method.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors can solve the said subject by using as a base resin the high molecular compound obtained by superposing | polymerizing the acrylic acid ester derivative containing a specific nitrogen atom containing group as a quencher which traps the acid generated from an acid generator. It was found out and completed the present invention.

That is, this invention provides the following [1]-[5].

[1] A compound represented by the following general formula (1)

[Formula 1]

(In 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> , R <^10> respectively independently represents a hydrogen atom and C1-C An alkyl group of 6, a cycloalkyl group of 3 to 6 carbon atoms or an alkoxy group of 1 to 6 carbon atoms, R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, or carbon atoms Or an alkoxy group of 1 to 6 or 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 represents a hydrogen atom or 1 to 6 carbon atoms. Alkyl group, C3-10 cyclic hydrocarbon group)

Acrylic ester ester represented by (Hereinafter, it is called an acrylic ester derivative (1).).

[2] the following general formula (2)

[Formula 2]

^{(Wherein, R 2, R 3, R} 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 are the same as defined above)

Alcohol derivative represented by the following (hereinafter referred to as alcohol derivative (2))

A method for producing an acrylate ester derivative (1), characterized in that esterification is carried out.

[3] alcohol derivatives (2).

[4] In the presence of a base, the following general formula (3)

(3)

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are the same as defined above)

Cyclohexene derivatives (hereinafter referred to as cyclohexene derivatives (3))

Is oxidized to the following general formula (4)

[Formula 4]

^{(Wherein, R 2, R 3, R} 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 are the same as defined above)

An epoxy derivative (hereinafter referred to as an epoxy derivative (4)) is obtained, and the epoxy derivative (4) obtained is subjected to a base treatment, characterized in that the method for producing an alcohol derivative (2).

[5] A process for producing an epoxy derivative (4), wherein the cyclohexene derivative (3) is oxidized in the presence of a base.

According to the present invention, it is possible to provide an acrylate ester derivative, an intermediate thereof (alcohol derivative) and a production method thereof, which are excellent as lithography properties and are useful as a raw material for a polymer compound for a resist composition that forms a resist pattern having a good shape.

[Acrylic acid ester derivative (1)]

In order to obtain the resist composition which is excellent in the lithography characteristic and forms the resist pattern of a favorable shape, the following acrylic acid ester derivative (1) of this invention is useful.

[Chemical Formula 5]

R ¹ in the acrylate ester derivative (1) represents a hydrogen atom, a methyl group or a trifluoromethyl group. Among these, as R ¹ , a hydrogen atom or a methyl group is preferable.

R <^2> , R <^3> , R <^5> , R <^7> , R <^8> , R <^9> and R <^10> in the said acrylic acid ester derivative (1) are respectively independently a hydrogen atom, a C1-C6 alkyl group, and a C3-C6 cycloalkyl group Or a C1-C6 alkoxy group is shown.

R ⁴ and R ⁶ in the acrylate ester derivative (1) each independently represent a hydrogen atom, 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, or R ⁴ And R ⁶ are bonded to each other to represent an alkylene group having 1 to 3 carbon atoms, -O-, or -S-.

R <^11> in the said acrylate ester derivative (1) represents a hydrogen atom, a C1-C6 alkyl group, and a C3-C10 cyclic hydrocarbon group.

As a C1-C6 alkyl group which R <^2> , R <^3> , R <^4> , R <^5> , R <^6> , R <^7> , R <^8> , R <^9> and R <^10> respectively independently represent, linear or branched chain may be sufficient, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, n-pentyl group, n-hexyl group, etc. are mentioned. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable from a viewpoint of obtaining the resist composition which forms the resist pattern of a favorable shape.

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ Examples of the cycloalkyl group having 3 to 6 carbon atoms each independently represent a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

As a C1-C6 alkoxy group which R <^2> , R <^3> , R <^4> , R <^5> , R <^6> , R <^7> , R <^8> , R <^9> , and R <^10> represent each independently, they may be linear or branched chain form, For example, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, etc. are mentioned. Among these, a C1-C3 alkoxy group is preferable and a methoxy group is more preferable from a viewpoint of obtaining the resist composition which forms the resist pattern of a favorable shape.

Among these, as R <^2> , R <^3> , R <^5> , R <^7> , R <^8> , R <^9> , R <^10> , a hydrogen atom or a C1-C6 alkyl group is preferable, and it is more preferable that all are hydrogen atoms.

Examples of the alkylene group having 1 to 3 carbon atoms formed by bonding of R ⁴ and R ⁶ include methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, A propane-1, 2-diyl group and a propane-1, 3- diyl group are mentioned. Among these, from a viewpoint of obtaining the resist composition which forms the resist pattern of a favorable shape, a methylene group and an ethane- 1, 2- diyl group are preferable, and a methylene group is more preferable.

Among the above, as R ⁴ and R ⁶ , all are hydrogen atoms, or preferably an alkylene group having 1 to 3 carbon atoms or —O— bonded to each other, and more preferably a methylene group or —O—.

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- A butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. are mentioned. Among these, a C1-C4 alkyl group is preferable from a viewpoint of obtaining the resist composition which forms the resist pattern of a favorable shape, A branched C3-C4 alkyl group is more preferable, and t-butyl group is still more preferable.

As a C3-C10 cyclic hydrocarbon group which R <^11> represents each independently, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantan-1-yl group, etc. are mentioned, for example.

Among the above, R ¹¹ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a s-butyl group from the viewpoint of obtaining a resist composition forming a resist pattern having a good shape. , t-butyl group and adamantan-1-yl group are preferable.

In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in the acrylate ester derivative (1) are alcohol derivatives (2) and cyclo The same as those in the hexene derivative (3) and the epoxy derivative (4) and the diene derivative (5), the acrylate halide derivative (6) and the amine compound (7) which follow.

Although the specific example of the acrylate ester derivative (1) of this invention is shown below, it is not specifically limited to these.

[Formula 6]

[Formula 7]

[Formula 8]

As the acrylate 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, and R ¹¹ is a hydrogen atom, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group or adamantan-1-yl group, and R ⁴ and R ⁶ are both methylenes bonded to each other; Group or -0-.

[Method for producing acrylic ester derivative (1)]

Although there is no restriction | limiting in particular in the manufacturing method of the acrylate ester derivative (1) of this invention, For example, it can manufacture by the following 1st process-4th process.

First step: After reacting a diene derivative (hereinafter referred to as diene derivative (5)) and an acrylic acid halide derivative (hereinafter referred to as acrylic acid halide derivative (6)), the amine compound R ¹¹ NH ₂ (R ¹¹ is defined above). Hereinafter, the process of obtaining a cyclohexene derivative (3) by making it react with an amine compound (7).

2nd process: The process of obtaining an epoxy derivative (4) by making cyclohexene derivative (3) react with organic peroxide in presence of a basic compound.

3rd process: The process of obtaining an alcohol derivative (2) by making an epoxy derivative (4) react with a basic substance.

4th process: The process of manufacturing an acrylate ester derivative (1) by making an alcohol derivative (2) react with an 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 the acrylate halide derivative (6) are the structures described in the following chemical reaction formulas.

[Chemical Formula 9]

(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 the same as defined above. X is a chlorine atom or a bromine atom. Or iodine atom)

<1st process>

First, the 1st process regarding the manufacturing method of the cyclohexene derivative (3) is demonstrated.

The first step is a step of reacting the diene derivative (5) with the acrylic acid halide derivative (hereinafter referred to as first step-1) and the reaction intermediate obtained in the first step-1 with the amine compound (7). It has a process to make it [it calls it a 1st process-2 hereafter].

(First step-1)

Specific examples of the diene derivative (5) used in the first step-1 include butadiene, isoprene, 2,3-dimethylbutadiene, cyclopentadiene, and furan.

As a specific example of the acrylic acid halide derivative (6) used at the 1st process-1, acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, crotonic acid chloride, crotonic acid bromide, 3-methyl-2- Butene acid chloride, and the like.

As for the usage-amount of the diene derivative (5), the range of 1-50 times mole is preferable with respect to the halide acrylate derivative (6), and the range of 1-10 times mole is more preferable from the viewpoint of the ease of post-processing.

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. Examples of the solvent include, but are not limited to, saturated hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene: methylene chloride, dichloroethane, chloroform, Chlorinated hydrocarbon solvents such as benzene chloride; Ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran and furan; Ester solvent, such as methyl acetate, ethyl acetate, and propyl acetate, etc. are mentioned. A solvent may be used individually by 1 type, and may mix and use 2 or more types.

When performing in presence of a solvent, the usage-amount of a solvent has a preferable range of 0.5-100 mass times with respect to diene derivative (5), and the range of 0.5-20 mass times is more preferable from the viewpoint of the ease of post-processing. .

Although the reaction temperature in 1st process-1 differs also according to the kind of diene derivative (5), acrylate halide derivative (6), etc., the range of -30-100 degreeC is preferable and the range of -10-50 degreeC Is more preferable. Moreover, there is no restriction | limiting in particular in reaction pressure, Usually, it is preferable to carry out under normal pressure.

Although reaction time in 1st process-1 differs also with the kind, usage-amount, reaction temperature, etc. of the diene derivative (5) and the acrylate halide derivative (6), the range of 1 hour-50 hours is preferable generally.

It is preferable to perform reaction in 1st process-1 in inert gas atmosphere, such as nitrogen and argon.

The reaction liquid mixture containing the reaction intermediate obtained in 1st process-1 can be used as a raw material of 1st process-2 without performing a purification operation in particular, and it is preferable to do so.

Although it does not restrict | limit especially as an implementation method of 1st process-1, The acrylic acid halide derivative (6) and a solvent are inject | poured into a reactor as needed, and this mixture liquid is made into a diene derivative (5) under desired reaction temperature and desired reaction pressure. ) Is preferable.

(Step 1-2)

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, cyclopropylamine, cyclohexylamine, 1-adamantylamine, etc. are mentioned.

As for the usage-amount of an amine compound (7), the range of 1-10 times mole is preferable with respect to the acrylic acid halide derivative (6) used at 1st process-1, and the range of 1-5 times mole from a viewpoint of the ease of post-processing. Is more preferable. There is no restriction | limiting in particular in the use form of an amine compound (7), It may be used as aqueous solution, and may be used as it is pure.

The reaction of the first step-2 is carried out in the presence or absence of a solvent.

Although there is no restriction | limiting in particular as a solvent unless it inhibits reaction, The thing similar to the solvent illustrated in description of 1st process-1 is mentioned. Therefore, when using a solvent in 1st process-1, it is preferable to use the used solvent as it is in 1st process-2. A solvent may be used individually by 1 type, and may mix and use 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 mass times with respect to the diene derivative (5) used in the first step-1, and 0.5 to 20 mass from the viewpoint of ease of post-treatment. The range of the double is more preferable.

When using the reaction liquid obtained in 1st process-1 as a raw material of 1st process-2, the quantity of a solvent may be sufficient as it may be further added.

Although the reaction temperature in 1st process-2 differs also depending on the kind of amine compound (7), an acrylate halide derivative (6), etc., the range of -30-100 degreeC is preferable and the range of -10-50 degreeC Is more preferable. Moreover, there is no restriction | limiting in particular in reaction pressure, Usually, it is preferable to carry out under normal pressure.

Although the reaction time in 1st process-2 differs also with the kind, usage-amount, reaction temperature, etc. of an amine compound (7) and an acrylate halide derivative (6), the range of 1 hour-50 hours is preferable generally.

It is preferable to perform reaction in 1st process-2 in inert gas atmosphere, such as nitrogen and argon.

Although not particularly limited, the amine compound (7) and the solvent are optionally injected into the reactor, and the mixture is obtained in the first step-1 under the desired reaction temperature and the desired reaction pressure. The method of dropping the reaction intermediate is preferred.

Separation and purification of the cyclohexene derivative (3) from the reaction mixture obtained by the above method can be carried out by a method generally used for separation and purification of organic compounds.

For example, after completion | finish of reaction of 1st process-2, after adding an organic solvent and water, it stops still, and it divides into an organic layer and an aqueous layer, and can concentrate a cyclohexene derivative (3) by concentrating an organic layer. And the cyclohexene derivative (3) of high purity can be obtained by refine | purifying by recrystallization, silica gel column chromatography, etc. as needed.

&Lt; Second Step &

Next, the 2nd process regarding the manufacturing method of the epoxy derivative (4) is demonstrated.

Specific examples of the organic peroxide used in the second step include peracetic acid, m-chloro perbenzoic acid, dimethyldioxirane and the like.

As for the usage-amount of an organic peroxide, the range of 1-10 times mole is preferable with respect to cyclohexene derivative (3), and the range of 1-5 times mole is more preferable from the viewpoint of the ease of post-processing.

As a specific example of the basic compound used at a 2nd process, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; Alkaline earth metal carbonates, such as calcium carbonate and barium carbonate, etc. are mentioned. Among these, alkali metal carbonate is preferable.

The use amount of the basic compound is preferably in the range of 1 to 20 times the mole, and more preferably 1 to 10 times the mole from the viewpoint of ease of post-treatment with respect to the organic peroxide.

The reaction of 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 and cyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene and xylene: chlorinated hydrocarbon solvents such as methylene chloride, dichloroethane and benzene chloride; Ester solvent, such as methyl acetate, ethyl acetate, and isopropyl acetate, is mentioned. A solvent may be used individually by 1 type, and may mix and use 2 or more types.

As for the usage-amount of a solvent, the range of 0.5-100 mass times is preferable with respect to cyclohexene derivative (3), and the range of 0.5-20 mass times is more preferable from the viewpoint of the ease of post-processing.

Although the reaction temperature in a 2nd process changes also with the kind of organic peroxide, cyclohexene derivative (3), etc., the range of -80-100 degreeC is preferable and the range of -30-50 degreeC is more preferable. Moreover, there is no restriction | limiting in particular in reaction pressure, Usually, it is preferable to carry out under normal pressure.

Although the reaction time in a 2nd process changes also with kinds, usage-amount, reaction temperature, etc. of organic peroxide and cyclohexene derivative (3), the range of 1 to 50 hours is preferable generally.

It is preferable to perform reaction in a 2nd process in inert gas atmosphere, such as nitrogen and argon.

The reaction of the second step can be stopped by adding a reducing agent.

As a reducing agent, sodium sulfite, sodium thiosulfate, sodium hydrogen sulfite, etc. are mentioned, for example.

When adding a reducing agent and stopping reaction of a 2nd process, the addition amount of the reducing agent has the preferable range of 1-5 times mole with respect to an unreacted organic peroxide, and 1-3 times from the viewpoint of the ease of post-processing. The range of mole is more preferable.

Although it does not restrict | limit especially as an implementation method of a 2nd process, The cyclohexene derivative (3), a basic compound, and a solvent are inject | poured into a reactor, and this liquid mixture is mixed with the organic peroxide and a solvent at a desired reaction temperature and desired reaction pressure. The method of dropping is preferable.

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

<Third process>

Next, the 3rd process concerning the manufacturing method of alcohol derivative (2) is demonstrated.

Specific examples of the basic substance used in the third step include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium-t-butoxide and potassium-t-butoxide. ; Alkali metal hydrides, such as lithium hydride, sodium hydride, and potassium hydride, etc. are mentioned. Among these, sodium-t-butoxide, potassium-t-butoxide and sodium hydride are preferable.

As for the usage-amount of a basic substance, the range of 1-5 times mole is preferable with respect to an epoxy derivative (4), and the range of 1-3 moles is more preferable from a viewpoint of the ease of post-processing.

The reaction of the third process 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. Examples thereof include saturated hydrocarbon solvents such as hexane, heptane and cyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene and xylene: ether solvents such as diethyl ether, diisopropyl ether and tetrahydrofuran; Alcohol solvents, such as methanol, ethanol, and t-butanol, etc. are mentioned. A solvent may be used individually by 1 type, or may mix and use F, 2 or more types.

The range of 0.5-100 mass times is preferable with respect to the epoxy derivative (4), and, as for the usage-amount of a solvent, the range of 0.5-20 mass times is more preferable from a viewpoint of the ease of post-processing.

Although the reaction temperature in a 3rd process changes also with kinds of basic substance, epoxy derivative (4), etc., the range of -80-100 degreeC is preferable and the range of -30-50 degreeC is more preferable. Moreover, there is no restriction | limiting in particular in reaction pressure, Usually, it is preferable to carry out under normal pressure.

Although the reaction time in a 3rd process changes also with kinds of basic substance and epoxy derivative (4), usage-amount, reaction temperature, etc., the range of 1 hour-50 hours is preferable generally.

It is preferable to perform reaction in a 3rd process in inert gas atmosphere, such as nitrogen and argon.

The reaction of the third step can be stopped by adding water.

When water is added to stop the reaction of the third step, the amount of water added is preferably in the range of 1 to 100 times the molar amount to the basic substance to be used, and in the range of 1 to 50 times the mole from the viewpoint of ease of post-treatment. Is more preferable.

Although it does not restrict | limit especially as an implementation method of a 3rd process, The method of inject | pouring a basic substance and a solvent into a reactor, and slowly adding an epoxy derivative (4) to this liquid mixture under desired reaction temperature and desired reaction pressure is preferable. .

Separation and purification of the alcohol derivative (2) from the reaction mixture obtained in the above method can be carried out by a method generally used for separation of organic compounds such as solvent extraction and distillation, and further recrystallization, distillation, sublimation and the like. Purity can be improved by the method generally used for the purification of the organic compound of.

Although the specific example of the alcohol derivative (2) of this invention obtained at the 3rd process is shown below, it is not specifically limited to these.

[Formula 10]

[Formula 11]

[Chemical Formula 12]

<4th process>

Next, the 4th process regarding the manufacturing method of an acrylate ester derivative (1) is demonstrated.

An acrylate ester derivative (1) is obtained by esterifying an alcohol derivative (2). Although there is no restriction | limiting in particular in the method of esterifying an alcohol derivative (2), For example, the following method is mentioned.

Method 1: Reaction of acrylic acid halides and alcohol derivative (2) in presence of a base.

Method 2: Reacting acrylic acid anhydride and alcohol derivative (2) in presence of a base.

Method 3: Reaction of acrylic acid and alcohol derivative (2).

Hereinafter, each of the methods 1-3 is explained in order.

(Method 1)

As an example of the acrylic acid halides used by the method 1, acrylic acid chloride, methacrylic acid chloride, 2-trifluoromethylacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide, 2-trifluoromethylacrylic acid bromide, etc. are mentioned. Can be. Among these, acrylic acid chloride, methacrylic acid chloride, and 2-trifluoromethylacrylic acid chloride are preferable from the viewpoint of availability.

The use amount of acrylic acid halides is preferably in the range of 1 to 10 times mole, and more preferably in the range of 1 to 5 times mole from the viewpoint of ease of post-treatment with respect to the alcohol derivative (2).

Specific examples of the base to be used in the method 1 include, but are not particularly limited as long as it neutralizes the by-product acid, for example, pyridine, 2-methylpyridine, 2-methyl-5-ethylpyridine, 2,6-dimethylpyridine, and the like. Nitrogen-containing heterocyclic aromatic compounds; Amines such as triethylamine, triethylenetetramine, triethanolamine, piperazine, diazabicyclo [2.2.2] octane;

Hydrogen carbonate of alkali metals, such as sodium hydrogencarbonate, etc. are mentioned. These may be used singly or in combination of two or more kinds.

The range of 1-10 times mole is preferable with respect to an alcohol derivative (2), and, as for the usage-amount of a base, the range of 1-5 times mole is more preferable from a viewpoint of the ease of post-processing.

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. Examples thereof include saturated hydrocarbon solvents such as hexane, heptane and cyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene and xylene; Chlorinated hydrocarbon solvents such as methylene chloride, dichloroethane and benzene chloride:

Ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran and furan;

Nitrile solvents such as acetonitrile and benznitrile; Ester solvents such as methyl acetate, ethyl acetate, and propyl acetate; And ketone solvents such as 2-butanone and 4-methyl-2-pentanone. A solvent may be used individually by 1 type, and may mix and use 2 or more types.

When implementing in presence of a solvent, the range of 0.5-100 mass times is preferable with respect to an alcohol derivative (2), and, as for the usage-amount of a solvent, the range of 0.5-20 mass times is more preferable from a viewpoint of the ease of post-processing. .

The reaction of the method 1 can also use a polymerization inhibitor, in order to prevent superposition | polymerization.

As a polymerization inhibitor, For example, Phenol-type polymerization inhibitors, such as hydroquinone and p-methoxyphenol; N, N'-diisopropyl-p-phenylenediamine, N.N'-di-2-naphthyl-p-phenylenediamine, N-phenyl-N '-(1,3-dimethylbutyl) -p Amine polymerization inhibitors such as -phenylenediamine; N-oxyl, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl and 4-acetamide-2,2,6,6-tetramethylpiperidine-N-oxyl A system polymerization inhibitor is mentioned. A polymerization inhibitor may be used individually by 1 type, and may mix and use 2 or more types. When using a polymerization inhibitor, the usage-amount is not specifically limited, What is necessary is just to determine suitably.

Method 1 can also be carried out by adding an activator such as 4-dimethylaminopyridine.

Although the reaction temperature in the method 1 changes with kinds of alcohol derivative (2) and acrylic acid halides, and the use of an activator, the range of -50-100 degreeC is generally preferable, and a reaction rate and a viewpoint of polymerization inhibition The range of -30-80 degreeC is more preferable. Moreover, there is no restriction | limiting in particular in reaction pressure, Usually, it is preferable to carry out under normal pressure.

Although the reaction time in the method 1 differs also with the kind, usage-amount, reaction temperature, etc. of a base, an alcohol derivative (2), and acrylate halides, the range of 1 hour-50 hours is preferable generally.

It is preferable to perform Method 1 in inert gas atmosphere, such as nitrogen and argon.

The method of carrying out Method 1 is not particularly limited, but an alcohol derivative (2), a base, and a solvent, a polymerization inhibitor, and an activator are injected into the reactor as desired, and the mixture is subjected to a desired reaction temperature and a desired reaction pressure. And a method of dropping acrylic acid halides is preferable.

(Method 2)

As an example of acrylic acid anhydride used by the method 2, acrylic anhydride, methacrylic anhydride, 2-trifluoromethyl acrylic anhydride, acrylic acid pivalic anhydride, methacrylic acid pivalic anhydride, 2-trifluoromethyl acrylic acid blood Dispersed anhydride, acrylate methanesulfonic anhydride, methacrylate methanesulfonic anhydride, 2-trifluoromethyl acrylate methanesulfonic anhydride, etc. are mentioned.

As for the usage-amount of acrylic acid anhydride, the range of 1-10 times mole is preferable with respect to alcohol derivative (2), and the range of 1-5 times mole is more preferable from the viewpoint of the ease of post-processing.

As a base used by the method 2, the thing similar to the base illustrated by the method 1 is mentioned. A base may be used individually by 1 type, and may mix and use 2 or more types. The range of 1-10 times mole is preferable with respect to an alcohol derivative (2), and, as for the usage-amount of a base, the range of 1-5 times mole is more preferable from a viewpoint of the ease of post-processing.

The reaction of Method 2 is carried out in the presence or absence of a solvent.

As a solvent, there is no restriction | limiting in particular unless the reaction is 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 mix and use 2 or more types.

When performing in the presence of a solvent, the range of 0.5-100 mass times is preferable with respect to diene derivative (5), and, as for the usage-amount of a solvent, the range of 0.5-20 mass times is more preferable from a viewpoint of the ease of post-processing.

The reaction of the method 2 can also use a polymerization inhibitor, in order to prevent superposition | polymerization. As a polymerization inhibitor, the thing similar to the polymerization inhibitor illustrated by the method 1 is mentioned. A polymerization inhibitor may be used individually by 1 type, and may mix and use 2 or more types. When using a polymerization inhibitor, the usage-amount is not specifically limited, What is necessary is just to determine suitably.

Method 2 can also be carried out by adding an activator such as 4-dimethylaminopyridine.

The reaction temperature in the method 2 varies depending on the type of the alcohol derivative (2) and the acrylic anhydride and the presence or absence of the use of the activator. The range of -50 to 100 ° C is generally preferable, and from the reaction rate and polymerization inhibition- The range of 30-80 degreeC is more preferable. Moreover, there is no restriction | limiting in particular in reaction pressure, Usually, it is preferable to carry out under normal pressure.

Although the reaction time in the method 2 differs also with the kind, usage-amount, reaction temperature, etc. of a base, an alcohol derivative (2), and acrylic acid anhydrides, the range of 1 to 50 hours is preferable generally.

It is preferable to perform method 2 in inert gas atmosphere, such as nitrogen and argon.

(Method 3)

Acrylic acids used in Method 3 are acrylic acid, methacrylic acid or 2-trifluoromethylacrylic acid. The range of 1-50 times mole is preferable with respect to an alcohol derivative (2), and, as for the usage-amount of acrylic acid, the range of 1-20 times mole is more preferable from a viewpoint of the ease of post-processing.

In method 3, an acid catalyst is usually used. As an acid catalyst, solid acid catalysts, such as a sulfuric acid, p-toluenesulfonic acid monohydrate, and an acidic ion exchange resin, are mentioned, for example. When using acid catalysts other than a solid acid catalyst, the usage-amount of the alcohol derivative (2) is preferably in the range of 0.001 to 2 times mole, and more preferably in the range of 0.01 to 1 time mole. When using a solid acid catalyst as an acid catalyst, the usage-amount may be suitably set according to the usage-amount of an alcohol derivative (2).

The reaction of the method 3 can also use a polymerization inhibitor, in order to prevent superposition | polymerization. As a polymerization inhibitor, the thing similar to the polymerization inhibitor illustrated by the method 1 is mentioned. A polymerization inhibitor may be used individually by 1 type, and may mix and use 2 or more types. When using a polymerization inhibitor, the usage-amount is not specifically limited, What is necessary is just to determine suitably.

Although the reaction temperature of the method 3 changes with kinds of alcohol derivative (2) and acrylic acid, the range of 30-150 degreeC is preferable generally, and the range of 50-100 degreeC is more preferable. Moreover, there is no restriction | limiting in particular in reaction pressure, Usually, it is preferable to carry out under normal pressure.

Although the reaction time in the method 3 changes also with kinds, usage-amount, reaction temperature, etc. of a base, an alcohol derivative (2), and acrylic acid, the range of 1 hour-50 hours is preferable generally.

Since the reaction of the method 3 is an equilibrium reaction, in order to fully advance reaction, it is preferable to carry out, removing the by-product water from a reaction system. As a method of removing water, for example, using a solvent which forms an azeotropic mixture with water, such as hexane and toluene, removing water from an apparatus such as a decanter, and a method such as molecular The method of using a water adsorbent, etc. are mentioned.

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

[Polymer compound]

The polymer obtained by polymerizing the acrylate ester derivative (1) of the present invention alone or the copolymer obtained by copolymerizing the acrylate ester derivative (1) with another polymerizable compound is useful as a high molecular compound for a photoresist composition.

As a specific example of the other polymeric compound (henceforth a copolymerization monomer) which can be copolymerized with an acrylate ester derivative (1), the compound etc. which are represented by the following chemical formula are mentioned, for example, It is not specifically limited to these. .

[Chemical Formula 13]

R <^12> represents a hydrogen atom or a C1-C3 alkyl group in said Formula (I)-(XII), and R <^13> shows a polymeric group. R <^14> represents a hydrogen atom or -COOR <^15> , R <^15> represents a C1-C3 alkyl group. In addition, R ¹⁶ represents an alkyl group.

In a copolymerization monomer, a methyl group, an ethyl group, n-propyl group, and isopropyl group are mentioned as a C1-C3 alkyl group which R <^12> and R <^15> respectively independently represent. As an alkyl group which R <^16> represents, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group etc. are mentioned, for example. Moreover, as a polymeric group which R <^13> represents, an acryloyl group, a methacryloyl group, a vinyl group, a crotonoyl group, etc. are mentioned, for example.

The high molecular compound can be prepared by radical polymerization, according to a conventional method. Especially as a method of synthesizing a high molecular compound with a small molecular weight distribution, living radical polymerization etc. are mentioned.

A general radical polymerization method polymerizes one or more types of acrylate ester derivatives (1) as needed and one or more types of said copolymerization monomers as needed in the presence of a radical polymerization initiator and a solvent, and a chain transfer agent as needed.

There is no restriction | limiting in particular in the implementation method of radical polymerization, The conventional method used when manufacturing an acryl-type high molecular compound, such as a solution polymerization method, an emulsion polymerization method, suspension polymerization method, a bulk polymerization method, can be used.

As said radical polymerization initiator, For example, hydroperoxide compounds, such as t-butyl hydroperoxide and cumene hydroperoxide; Dialkyl peroxide compounds such as di-t-butyl peroxide, t-butyl-α-cumyl peroxide and di-α-cumyl peroxide; Diacyl peroxide compounds such as benzoyl peroxide and diisobutyryl peroxide; Azo compounds, such as 2,2'- azobisisobutyronitrile and dimethyl-2,2'- azobisisobutyrate, etc. are mentioned.

Although the usage-amount of a radical polymerization initiator can be suitably selected according to superposition | polymerization conditions, such as the acrylate ester derivative (1) used for a polymerization reaction, a copolymerization monomer, a chain transfer agent, the kind and usage-amount of a solvent, and a polymerization temperature, a prepolymerizable compound [acrylic acid ester derivative It is the total amount of (1) and a copolymerization monomer, and it is the same below] With respect to 1 mol, the range of 0.005-0.2 mol is preferable normally, and the range of 0.01-0.15 mol is more preferable.

Examples of the chain transfer agent include thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, and mercaptopropionic acid. When using a chain transfer agent, the range of 0.005-0.2 mol is normally preferable with respect to 1 mol of prepolymerizable compounds, and its range of 0.01-0.15 mol is more 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, and ethylene glycol monomethyl ether. Glycol ethers such as propionate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate and diethylene glycol dimethyl ether; Esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, and propyl acetate; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone and cyclohexanone; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, and the like.

The amount of the solvent used is usually in the range of 0.5 to 20 parts by mass with respect to 1 part by mass of the prepolymerizable compound, and from the viewpoint of economical efficiency, it is preferably in the range of 1 to 10 parts by mass.

Polymerization temperature is 40-150 degreeC normally, and it is preferable that it is the range of 60-120 degreeC from a viewpoint of the stability of the high molecular compound produced | generated.

Although the time of a polymerization reaction changes with superposition | polymerization conditions, such as an acrylate ester derivative (1), a copolymerization monomer, a polymerization initiator, the kind and usage-amount of a solvent, the temperature of a polymerization reaction, etc., the range of 30 minutes-48 hours is preferable normally. And, the range of 1 hour-24 hours is more preferable.

The high molecular compound obtained in this way can be isolated by normal operation, such as reprecipitation. The isolated high molecular compound may be dried by vacuum drying or the like.

As a solvent used by operation of reprecipitation, For example, Aliphatic hydrocarbons, such as a pentane and a hexane; Alicyclic hydrocarbons such as cyclohexane; Aromatic hydrocarbons such as benzene and xylene; Halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene and dichlorobenzene; Nitrated 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; Carboxylic acids such as acetic acid; Esters such as ethyl acetate and butyl acetate; Carbonates, such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; Alcohols such as methanol, ethanol, propanol, isopropyl alcohol and butanol; Water can be heard.

[Photoresist Composition]

A photoresist composition is prepared by blending the polymer compound, an organic solvent, a photoacid generator, and, if necessary, a basic compound and an additive.

As the photo acid generator, a photo acid generator commonly used in conventional chemically amplified resists can be used.

Moreover, surfactant, a sensitizer, an antihalation agent, a shape improver, a storage stabilizer, an antifoamer, etc. can be mix | blended with a photoresist composition.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

Example 1 First Process

(First step-1)

217.2 g (2.400 mol) of acryloyl chloride and 520 g of toluene were injected into a 2-liter three-necked flask equipped with a thermometer, a stirring device, a nitrogen inlet tube, and a dropping funnel, and the internal temperature was cooled to 0 ° C. . 190.4 g (2.880 mol) of cyclopentadienes were dripped at this mixed liquid over 1 hour from the dropping funnel. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 1 hour to prepare a reaction intermediate solution.

(Step 1-2)

201.1 g (2.750 mol) of t-butylamine and 513 g of toluene were injected | thrown-in to the internal volume 2 L three neck flask provided with the thermometer, the stirring apparatus, the nitrogen inlet tube, and the dropping funnel, and the internal temperature was cooled to 0 degreeC. . The reaction intermediate solution obtained by the said 1st process-1 was dripped at this mixed liquid over 1 hour 30 minutes from the dropping funnel, and internal temperature was heated up at 25 degreeC.

1800 ml of ethyl acetate and 300 ml of water were added to the obtained reaction mixture, and after stirring for 30 minutes, the mixture was stopped and separated, and an organic layer was obtained. 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 the concentrate was heated to 40 DEG 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 a reduced pressure to obtain 124.3 g (0.643 mol; yield 26.8%) of N-t-butylbicyclo [2.2.1] hepta-5-ene-2-carboxamide having the following characteristics.

[Formula 14]

Example 2 Second Step

50.0 g (0.259 mol) of Nt-butyl bicyclo [2.2.1] hepta-5-ene-2-carboxamide in a 2-liter three-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a dropping funnel. ), 250 g of methylene chloride, 121.6 g (0.880 mol) of potassium carbonate and 550 g of water were injected, and the internal temperature was cooled to 0 ° C. 75.9 g (0.440 mol) of m-chloro perbenzoic acid and 1559 g of methylene chloride were dripped at this liquid mixture over 20 minutes from the dropping funnel. After stirring at 0-7 degreeC for 4 hours, 22 g of saturated sodium sulfite aqueous solution was added, and it stirred for 30 minutes. After stopping still and separating, 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, the concentrate was dissolved, and then cooled to 2 ° C, and the precipitated crystals were collected by filtration. The obtained crystals were dried under reduced pressure to obtain 26.4 g (0.126 mol; yield 48.6%) of N-t-butyl-5,6-epoxybicyclo [2.2.1] hepta-2-carboxamide having the following characteristics.

[Formula 15]

&Lt; Comparative Example 1 &

In Example 2, the same experiment was conducted except that 121.6 g (0.880 mol) of potassium carbonate was used. As a result, Nt-butyl-5,6-epoxybicyclo [2.2.1] hepta-2-carbox 0.5 g (0.002 mol: 0.8% of yield) of mead only was obtained.

Example 3 Third Step

61.0 g (0.544 mol) of potassium-t-butoxide and 1045 g of t-butanol were injected | thrown-in to the internal volume 2 L three neck flask provided with the thermometer, the stirring apparatus, and the nitrogen inlet tube, and it heated up at 50 degreeC. To this mixed solution, 56.9 g (0.272 mol) of N-t-butyl-5,6-epoxybicyclo [2.2.1] hepta-2-carboxamide was added over 1 hour. Then, after cooling internal temperature at 25 degreeC, 620g of 3.9 mass% hydrochloric acid and 1900 ml of ethyl acetate were added, and it stirred for 30 minutes. After stopping still and separating, the organic layer was washed twice with 400 ml of water. The obtained organic layer was concentrated under reduced pressure to obtain a concentrate.

Methanol 30g and diisopropyl ether 820g were added to the obtained concentrate, the internal temperature was heated up at 50 degreeC, and the concentrate was dissolved. Then, after cooling to 0 degreeC, the precipitated crude crystal was collected by filtration. 200 g of ethyl acetate and 200 g of diisopropyl ether were added to the obtained crude crystal, and the internal temperature was raised to 50 ° C to dissolve the crude crystal. Then, after cooling to 0 degreeC, the precipitated crystal | crystallization was filtrated. The obtained crystal was dried under reduced pressure, and 24.9 g (0.119 mol) of Nt-butyl-6-hydroxyhexahydro-2-oxo-3,5-methano-4H-cyclopenta [2,3-b] pyrrole having the following characteristics: Yield 43.8%).

[Chemical Formula 16]

Example 4 Fourth Step (Method 1)

In a 500 mL three-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube and a dropping funnel, Nt-butyl-6-hydroxyhexahydro-2-oxo-3,5-methano-4H-cyclopenta 34.1 g (0.163 mol) of [2,3-b] pyrrole, 340 ml of methylene chloride and 29.8 g (0.294 mol) of triethylamine were injected and the internal temperature was cooled to -40 ° C. 20.5 g (0.196 mol) of methacrylic acid chlorides were dripped at this mixed liquid over 1 hour from the dropping funnel. 12 mL of methanol was added to the reaction mixture, and then 120 mL of water was added, followed by stirring for 30 minutes. After stopping still and separating, the aqueous layer was extracted four times with 50 ml of methylene chloride. The methylene chloride layers obtained were combined and concentrated under reduced pressure.

The obtained concentrate was purified by silica gel column chromatography to obtain Nt-butylhexahydro-2-oxo-3,5-methano-4H-cyclopenta [2,3-b] pyrrole-6-yl- having the following characteristics. 17.2 g (0.062 mol; yield 38.0%) of methacrylic acid was obtained.

[Chemical Formula 17]

<Reference example>

The polymer compound shown below was synthesize | combined using the monomer (1)-(7) shown by following formula.

[Chemical Formula 18]

In addition, the monomer (2) was synthesize | combined by the method shown below.

(Synthesis of Monomer (2))

Into a 500 mL three-necked flask, 20 g (105.14 mmol) of alcohol, 30.23 g (157.71 mmol) of ethyldiisopropylaminocarbodiimide hydrochloride, and dimethylaminopyridine O, which are represented in the following chemical reaction formula under a nitrogen atmosphere. 3OmL of a .6 g (5 mmol) tetrahydrofuran (THF) solution was added. 16.67 g (115.66 mmol) of the carboxylic acid compound shown in the following chemical reaction formula were added there under ice-cooling (O degreeC), and it stirred at room temperature for 12 hours.

After the reaction was stopped by adding 50 ml of water, the reaction solvent was concentrated under reduced pressure, and the organic layer obtained by extracting three times with ethyl acetate was prepared in the order of water, saturated sodium hydrogencarbonate, and aqueous hydrochloric acid at a concentration of 1 mol / L. Washed. The product obtained by distilling a solvent off under reduced pressure was dried and the monomer (2) was obtained.

[Chemical Formula 19]

(Synthesis of Polymer Compound (A) -1)

In a three-necked flask with a thermometer and reflux tube, 11.77 g (69.23 mmol) of monomer (1), 15.00 g (47.47 mmol) of monomer (2), 16.58 g (63.29 mmol) of monomer (3) 4) 4.65 g (27.96 mmol), monomer (5) 3.27 g (13.85 mmol), and monomer (7) 0.55 g (1.98 mmol) were dissolved in 76.91 g of methyl ethyl ketone to obtain a monomer mixture.

Dimethyl azobisisobutyrate (22.1 mmol) was added and dissolved in the obtained monomer liquid mixture as a polymerization initiator. The liquid mixture obtained in this way was dripped at 42.72 g of methyl ethyl ketone heated at 78 degreeC in nitrogen atmosphere over 3 hours. After completion of the dropwise addition, the reaction solution was heated and stirred for 4 hours, and then cooled to room temperature.

The resulting polymer solution was added dropwise to a large amount of n-heptane, the polymer was precipitated, and the precipitated white powder was separated by filtration, washed with an n-heptane / isopropyl alcohol mixed solvent, and dried to give a high molecular compound (A)- 43 g of 1 was obtained.

Copolymer composition ratio determined by the weight average molecular weight (Mw), molecular weight dispersion degree (Mw / Mn), and ¹³ C-NMR (60 MHz) of the polymer compound (A) -1 (a ratio (molar ratio) of each structural unit in the polymer compound) ) Is shown in Table 1.

(Synthesis of Polymer Compound (A) -2 to (A) -6)

In the synthesis of the above-mentioned high molecular compound (A) -1, except that the ratio of the structural unit of each high molecular compound was changed as shown in Table 1, experiment was carried out similarly, and high molecular compound (A) -2-(A ) -6 was synthesized. Polymer Compound (A)

It shows in Table 1 about the weight average molecular weight (Mw) and molecular weight dispersion degree (Mw / Mn) of -2-(A) -6.

(Synthesis of Polymer Compound (A) -7)

In a three-necked flask connected with a thermometer and a reflux tube, 32.32 g (102.29 mmol) of monomer (2), 11.93 g (34.10 mmol) of monomer (6), 8.05 g (34.10 mmol) of monomer (5), and 0.95 g (3.41 mmol) of monomers (7) were dissolved in 106.77 g of methyl ethyl ketone to obtain a monomer liquid mixture.

Dimethyl azobisisobutyrate (17.3 mmol) was added to the obtained monomer liquid mixture as a polymerization initiator to dissolve it. The liquid mixture thus obtained was added dropwise to 67.00 g of methyl ethyl ketone (preliminarily dissolved 67.1 g (255.73 mmol) of monomer (3)) heated to 80 ° C. under nitrogen atmosphere over 3 hours. After completion of the dropwise addition, the reaction solution was heated and stirred for 2 hours, after which the reaction solution was cooled to room temperature.

The resulting polymer solution was added dropwise to a large amount of n-heptane, the polymer was precipitated, and the precipitated white powder was separated by filtration, washed sequentially with n-heptane / 2-propanol mixed solvent and methanol, and dried to obtain a high molecular compound. 65 g of (A) -7 was obtained.

Copolymer composition ratio obtained by weight average molecular weight (Mw), molecular weight dispersion degree (Mw / Mn), and ¹³ C-NMR measurement (60 MHz) of this high molecular compound (A) -7 (ratio of each structural unit in the polymer compound (molar ratio )) Is shown in Table 1.

(Synthesis of Polymer Compound (A) -8 to (A) -12)

In the synthesis of the above-mentioned high molecular compound (A) -7, except for changing the ratio of the structural unit of each high molecular compound as shown in Table 1, experiment was carried out similarly, and high molecular compound (A) -8-(A ) -12 was synthesized. Table 1 shows the weight average molecular weight (Mw) and the molecular weight dispersion degree (Mw / Mn) of the high molecular 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 a monomer mixture.

Dimethyl azobisisobutyrate (4.66 mmol) was added and dissolved in the obtained monomer liquid mixture as a polymerization initiator. The liquid mixture thus obtained was heated and stirred at 80 ° C. for 6 hours in a nitrogen atmosphere, and then cooled to room temperature.

After concentrating the obtained polymer liquid under reduced pressure, it was dripped at large quantity of n-heptane, the polymer was precipitated, the precipitated polymer was isolate | separated by filtration, washing | cleaning, and drying, and 5.6g of fluorine-containing high molecular compound (C) -1 was obtained. .

The weight average molecular weight (Mw) of this fluoropolymer compound (C) -1 was 250OO, and molecular weight dispersion degree (Mw / Mn) was 1.5. Moreover, the copolymerization composition ratio (ratio of each structural unit in a polymer compound (molar ratio)) calculated | required by ¹³ C-NMR measurement (60 MHz) was l / m = 80/20.

[Chemical Formula 20]

&Lt; Preparation of resist composition >

Each component shown in Tables 2-3 was mixed and melt | dissolved, and the positive resist composition was prepared.

In Table 2, the numerical value in [] shows a compounding quantity (mass part). In addition, the symbol in Table 2 represents the following, respectively.

(A) -1: high molecular compound (A) -1

(A) -2: high molecular compound (A) -2

(A) -3: high molecular compound (A) -3

(A) -4: high molecular compound (A) -4

(A) -5: high molecular compound (A) -5

(A) -6: high molecular compound (A) -6

(B) -1: the compound represented by chemical formula (B) -1 shown below

(B) -2: the compound represented by chemical formula (B) -2 shown below

(B) -3: the compound represented by chemical formula (B) -3 shown below

(B) -4: the compound represented by chemical formula (B) -4 shown below

(C) -1: Fluorine-containing high molecular compound (C) -1

(C) -2: A fluorine-containing polymer compound represented by the following general formula (C) -2 (synthesized by the method described in JP2008-134607 A. Mw = 8000, Mw / Mn = 1.47)

(C) -3: Fluorine-containing high molecular compound represented by the following general formula (C) -3 (Mw = 8600, Mw / Mn = 1.39, composition ratio l / m = 54.2 / 45.8 (molar ratio))

(D) -1: tri-n-pentylamine

(D) -2: triethanolamine

(D) -3: the compound represented by chemical formula (D) -3 shown below

(E) -1: 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)

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

In Table 2, the numerical value in [] shows a compounding quantity (mass part). In addition, the symbol in Table 2 represents the following, respectively. In addition, about the same symbol as in Table 1, it is as showing in the comment of Table 1.

(A) -7: high molecular compound (A) -7

(A) -8: high molecular compound (A) -8

(A) -9: high molecular compound (A) -9

(A) -1O: high molecular compound (A) -1O

(A) -11: high molecular compound (A) -11

(A) -12: high molecular compound (A) -12

(B) -5: the compound represented by chemical formula (B) -5 shown below

(B) -6: the compound represented by chemical formula (B) -6 shown below

(S) -3: Mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 6/4 (mass ratio)

(25)

<Evaluation of lithography characteristics (1)>

Using the said resist compositions 1-14, the resist pattern was formed by the resist pattern formation method shown below, and the lithographic characteristic was evaluated.

(Formation of resist pattern)

An organic antireflection film having a film thickness of 90 nm is coated on a 12-inch silicon wafer by applying an organic antireflection film composition "ARC95" (manufactured by Brewer Science Co., Ltd.) using a spinner, firing and drying at 205 ° C for 60 seconds on a hot plate. Formed.

And the resist composition 1-14 was apply | coated using the spinner on this organic type anti-reflective film, and it bakes (PAB) process after application | coating on 120 degreeC and 60 second conditions on a hotplate, and dried, and a film thickness A 95 nm resist film was formed.

Next, the said resist is made through ArP immersion exposure apparatus "NSR-S609B" (made by Nikon Corporation, NA (number of openings) = 1.07, cross pole, immersion medium: water) through a mask pattern (6% halftone). ArF excimer laser (193 nm) was selectively irradiated to the film.

Then, a post-exposure bake (PEB) treatment was performed at 95 ° C. for 60 seconds, and an alkali development treatment was further performed at 23 ° C. with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 10 seconds, after which pure water was used. Water rinsing was carried out for 30 seconds, dewatering and drying were performed.

As a result, also in any example, the 1: 1 line and space (L / S) pattern of 50 nm of line width was obtained. The optimum exposure dose Eop (mJ / cm 2) in which the L / S pattern was formed was determined to be an index of sensitivity. The results are shown in Table 4.

(Evaluation of Depth of Focus (DOF))

In the above Eop, the focal point can be properly shifted up and down so that the L / S pattern of 1: 1 described above can be formed within the range of the dimensional change rate of 50 nm ± 5% (ie, 47.5 to 52.5 nm) of the target dimension. The depth (unit: micrometer) was calculated | required. The results are shown in Table 4.

(Evaluation of LWR)

In the 1: 1 L / S pattern formed from the above Eop, the line width was 50 in the longitudinal direction of the line by means of a measuring SEM "S-9380" (scanning electron microscope, acceleration voltage 300 V, manufactured by Hitachi, Ltd.). It measured in several places and calculated | required the triple value (3s) of the standard deviation (s) from the result as a measure which shows 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.

As mentioned above, the resist compositions 1-10 obtained using the acrylate ester derivative (1) which concerns on this invention have favorable DOF and LWR, and are excellent in lithography characteristic compared with the resist compositions 11-14 which are not, It was confirmed that a resist pattern having a good shape can be formed.

<Evaluation of lithography characteristics (2)>

Using the resist compositions 16-28, the resist pattern was formed by the resist pattern formation method shown below, and the lithographic characteristic was evaluated.

(Formation of resist pattern)

An organic antireflection film having a thickness of 89 nm was coated on a 12-inch silicon wafer by applying an organic antireflection film composition "ARC29A" (manufactured by Brewer Science Co., Ltd.) using a spinner, baking on a hot plate for 60 seconds and drying for 60 seconds. Formed.

And the resist composition 16-28 was apply | coated using the spinner on this organic type anti-reflective film, respectively, apply | coated after baking on 90 degreeC and 60 second conditions on a hotplate, PAB treatment, and dried, and a film thickness A 100 nm resist film was formed.

Next, the mask pattern (6% halftone) was performed by ArF liquid immersion exposure apparatus "NSR-S609B" (Nikon Corporation, NA (opening number) = 1.07, Conventional (0.97) w / o POLANO, liquid immersion medium: water). Through this, an ArF excimer laser (193 nm) was selectively irradiated to the resist film.

Then, post-exposure bake (PEB) was performed at 80 ° C. for 60 seconds, and an alkali development treatment was performed at 23 ° C. for 20 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution, followed by using pure water. Water rinse was performed for 30 seconds, dehydrated, and dried.

As a result, also in any example, a dense contact hole pattern (CH pattern) in which holes having 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) at which the CH pattern is formed was obtained and used as an index of sensitivity. The results are shown in Table 5.

(Evaluation of the CDU)

In the CH pattern formed in the above Eop, the diameter (CD) of 100 holes in each CH pattern was measured, and from the results, three times (3s) of the standard deviation (s) was used as a measure of CD uniformity (CDU). Calculated. The results are shown in Table 5.

The smaller the value of 3s, the higher the critical dimension uniformity of the hole.

(Evaluation of roundness)

The CH pattern formed in the said Eop was observed from the air, and by the length measurement SEM "S-9380" (made by Hitachi, Ltd.), the distance of 24 directions from the center of the hole to the outer edge of 100 holes in each CH pattern was measured. It measured, and computed the triple value (3s) of the standard deviation (s) calculated from the result as a measure which shows roundness. The results are shown in Table 5.

The smaller the value of 3s, the higher the roundness of the hole.

As mentioned above, the resist compositions 16-24 obtained using the acrylate ester derivative (1) which concerns on this invention are excellent in lithography characteristic, since CDU is favorable and roundness is high compared with the resist compositions 25-28 which are not, It was confirmed that a resist pattern having a good shape can be formed.

Industrial availability

The acrylate ester derivative (1) of the present invention is useful as a raw material of a polymer compound for a resist composition which is excellent in lithography properties and forms a resist pattern having a good shape. Moreover, the alcohol derivative (2) of this invention is useful as a synthetic intermediate of this acrylic acid ester derivative (1).

Claims (5)

(1)
[Formula 1]

(In 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> , R <^10> respectively independently represents a hydrogen atom and C1-C An alkyl group of 6, a cycloalkyl group of 3 to 6 carbon atoms or an alkoxy group of 1 to 6 carbon atoms, R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, or carbon atoms represents an alkoxy group of 1 to 6, or R ⁴ and R ⁶ are both a bond to represent a alkylene group, -O-, -S- or a group having a carbon number of 1 to 3. R ¹¹ is a hydrogen atom, a group having 1 to 6 carbon atoms An alkyl group and a C3-C10 cyclic hydrocarbon group are shown.)
Acrylic ester ester represented by. General formula (2)
(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.)
The following general formula (1) characterized by esterifying an alcohol derivative represented by
(3)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are as defined above.)
The manufacturing method of the acrylic acid ester derivative represented by these. General formula (2)
[Chemical 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.)
Alcohol derivative represented by. In the presence of a base, the following general formula (3)
[Chemical Formula 5]

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the same as defined above)
The cyclohexene derivative represented by the above is oxidized, and the following general formula (4)
[Chemical Formula 6]

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are the same as defined above)
The epoxy derivative represented by the following is obtained, and the epoxy derivative obtained is subjected to a base treatment, characterized by the following general formula (2)
(7)

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are the same as defined above)
The manufacturing method of the alcohol derivative shown by. In the presence of a base, the following general formula (3)
[Chemical Formula 8]

^{(Wherein, R 2, R 3, R} 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11 are the same as defined above)
To oxidize the cyclohexene derivative represented by the following general formula (4)
[Chemical Formula 9]

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ are the same as defined above)
The manufacturing method of the epoxy derivative shown by