JP2010254639A - Alicyclic ester compound and resin composition produced therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which can accomplish improvement in resolution and line edge roughness without detriment to basic properties as a resist, such as pattern form, dry etching resistance, and heat resistance as a chemically amplified resist sensitive to a KrF excimer laser, an ArF excimer laser, an F<SB>2</SB>excimer laser or a far-ultraviolet radiation typified by EUV and which is excellent in alkali-developing property and in the adhesiveness to a base material; and to provide a raw material compound therefor. <P>SOLUTION: What is provided is an alicyclic ester compound represented by formula (1) (wherein R<SB>1</SB>is hydrogen, methyl, or trifluoromethyl; R<SB>2</SB>to R<SB>4</SB>, which may be the same or different from each other, are methyl or ethyl; Z is a 4-15C divalent hydrocarbon group and together with the carbon atoms to which its terminals are bonded forms a cyclic hydrocarbon, provided that a hydrogen atom or atoms in the hydrocarbon group may be substituted by a halogen atom(s) or an alkoxy group(s)). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention is excellent in optical properties, heat resistance, light transmittance, etc., and is a cross-linked resin, optical fiber, optical waveguide, optical disk substrate, KrF and ArF, F ₂ excimer laser resist, X-ray, electron beam, EUV ( The present invention relates to a functional resin composition that can be used as an optical material such as a chemically amplified resist for extreme ultraviolet light) and its raw materials, pharmaceutical and agrochemical intermediates, and other various industrial products, and an alicyclic ester compound that is a raw material thereof.

  The resin composition for photoresist used in the semiconductor manufacturing process needs to have a well-balanced property such as the property that the irradiated part changes to alkali-soluble by light irradiation, etching resistance, substrate adhesion, and transparency to the light source used. There is. When a short-wavelength light source after the KrF excimer laser is used as a light source, a chemically amplified resist is generally used. The composition is generally composed of a resin composition and a photoacid generator as a main ingredient, and several additions. Used as a solution containing an agent. Among them, it is important that the resin composition as the main component has the above-mentioned properties in a well-balanced manner, and determines the resist performance.

  When the light source uses a short wavelength light source after the KrF excimer laser, a chemically amplified resist is used. In this case, the resin composition as the main component is generally a polymer having acrylate or the like as a repeating unit. It is. However, it is not used in a single repeating unit. This is because a single repeating unit cannot satisfy all of the characteristics such as etching resistance. Actually, a copolymer having a plurality of repeating units each having a functional group for improving each property, that is, two or more types, is used as the resin composition. As such a resin composition, a hydroxystyrene-based resin is proposed for a resist for KrF excimer laser lithography, and an acrylic resin having 2-alkyl-2-adamantyl methacrylate as a basic skeleton is proposed for a resist for ArF excimer laser lithography. (See Patent Documents 1 and 2).

  However, in recent years, the lithography process has been rapidly miniaturized, and it is required to extend the life of each light source to a line width up to about 1/3 of the wavelength. In particular, in ArF excimer laser lithography, further miniaturization is required by applying an immersion technique or introducing a double patterning technique. Along with this, demands for sensitivity, resolution, line edge roughness, etc. have become stricter as the line width becomes thinner.

  In order to solve such problems, various studies have been made such as copolymerization of various acrylate compounds with existing resin monomers, or major changes in the structure of existing resins. For example, a resist composition containing an adamantane derivative having characteristics such as surface roughness during etching and small line edge roughness has been proposed (see Patent Document 3). However, even with such a resist composition, it is actually difficult to sufficiently satisfy the resolution and line edge roughness in thinning.

  Under these circumstances, there is a strong demand for the development of an excellent functional resin composition that can achieve improvement in sensitivity, resolution, and line edge roughness without adversely affecting the basic properties of the resin composition. Among them, it has been shown that the content of alcoholic hydroxyl groups contained in the resin composition tends to improve sensitivity and resolution (see Non-Patent Document 1). As an example of a resin containing a monomer having an alcoholic hydroxyl group, for example, a resin containing 3,5-dihydroxy-1-adamantyl (meth) acrylate has also been proposed (see Patent Document 4). Sensitivity and high resolution are expected. In addition, resist monomers having acid dissociation performance contained in resist polymers usually do not have alcoholic hydroxyl groups, but among them, they have one alcoholic hydroxyl group and have acid dissociation performance. As a resist monomer, 3- (1-hydroxy-1-methylethyl) -1- (1-methacryloyloxy-1-methylethyl) adamantane has been proposed (Patent Document 5). The resolution is expected.

Japanese Patent Laid-Open No. 4-39665 JP 10-319595 A JP 2003-167346 A JP 2000-122295 A JP 2006-016379 A

SPIE, 6923-123 (2008)

The object of the present invention is as a chemically amplified resist sensitive to far ultraviolet rays typified by KrF excimer laser, ArF excimer laser, F ₂ excimer laser or EUV, and as a resist having a pattern shape, dry etching resistance, heat resistance, etc. An object of the present invention is to provide a resin composition excellent in alkali developability and substrate adhesion that can achieve improvement in resolution and line edge roughness without impairing physical properties, and a raw material compound thereof.

  As a result of intensive studies on the above problems, the present inventors have found that the alicyclic ester compound represented by the formula (1) has an acid-dissociable tertiary ester group in the acid-dissociating alicyclic skeleton. Therefore, the acid-dissociable group is expected to be easily removed during alkali development, and it was found that the compound is suitable for the above purpose. Also, a functional resin composition produced using an alicyclic ester compound represented by the formula (1) as a raw material, that is, a functional resin composition containing a resin containing a component represented by the formula (2) in a repeating unit. As a result, the inventors have found that usefulness as a photoresist is expected, and have reached the present invention.

（式中、Ｒ₁は、水素原子、メチル基またはトリフルオロメチル基を示し、Ｒ₂〜Ｒ₄は、同一または異なって、メチル基またはエチル基を示し、Ｚは、炭素数４〜１５の２価の炭化水素基を示し、両端で結合する炭素原子と共に環状の炭化水素を形成する。炭化水素基においては、水素原子がハロゲン原子、アルコキシ基で置換されていても良い。） That is, the present invention is an alicyclic ester compound represented by the following formula (1).

(In the formula, R ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group, R _{2 to} R ₄ are the same or different and represent a methyl group or an ethyl group, and Z represents a carbon number of 4 to 15) (A divalent hydrocarbon group, which forms a cyclic hydrocarbon together with carbon atoms bonded at both ends. In the hydrocarbon group, the hydrogen atom may be substituted with a halogen atom or an alkoxy group.)

（式中、Ｒ₁は、水素原子、メチル基またはトリフルオロメチル基を示し、Ｒ₂〜Ｒ₄は、同一または異なって、メチル基またはエチル基を示し、Ｚは、炭素数４〜１５の２価の炭化水素基を示し、両端で結合する炭素原子と共に環状の炭化水素を形成する。炭化水素基においては、水素原子がハロゲン原子、アルコキシ基で置換されていても良い。） Moreover, this invention is a functional resin composition containing resin which contains the component represented by following formula (2) in a repeating unit.

(In the formula, R ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group, R _{2 to} R ₄ are the same or different and represent a methyl group or an ethyl group, and Z represents a carbon number of 4 to 15) (A divalent hydrocarbon group, which forms a cyclic hydrocarbon together with carbon atoms bonded at both ends. In the hydrocarbon group, the hydrogen atom may be substituted with a halogen atom or an alkoxy group.)

The alicyclic ester compounds of the present invention are useful as cross-linked resins, optical materials such as optical fibers, optical waveguides, optical disk substrates, and photoresists, raw materials thereof, pharmaceutical / agrochemical intermediates, and other various industrial products. In addition, the functional resin composition of the present invention can be used as a resist raw material for KrF, ArF, and F ₂ excimer lasers, and a chemically amplified resist for X-rays, electron beams, and EUV (extreme ultraviolet light). The resist resin composition is excellent in etching resistance, has excellent adhesion to the substrate, has alkali solubility, and can be expected to form a pattern with high sensitivity and resolution with high accuracy. .

2 is a graph showing a ¹ H-NMR spectrum of a white solid finally obtained in Example 1. FIG. 2 is a graph showing a ¹³ C-NMR spectrum of a white solid finally obtained in Example 1. FIG. 2 is a graph showing an IR spectrum of a white solid finally obtained in Example 1. FIG. 2 is a graph showing a ¹ H-NMR spectrum of a pale yellow liquid finally obtained in Example 2. FIG. 4 is a graph showing a ¹³ C-NMR spectrum of a pale yellow liquid finally obtained in Example 2. FIG. 4 is a graph showing an IR spectrum of a pale yellow liquid finally obtained in Example 2. FIG. 4 is a graph showing a ¹ H-NMR spectrum of a pale yellow liquid finally obtained in Example 3. FIG. 4 is a graph showing a ¹³ C-NMR spectrum of a pale yellow liquid finally obtained in Example 3. FIG. 6 is a graph showing an IR spectrum of a pale yellow liquid finally obtained in Example 3. 4 is a graph showing a ¹ H-NMR spectrum of a pale yellow liquid obtained in Example 4. 4 is a graph showing a ¹³ C-NMR spectrum of a pale yellow liquid obtained in Example 4. It is a graph which shows IR spectrum of the pale yellow liquid obtained in Example 4.

Hereinafter, the present invention will be described in more detail. The alicyclic ester compound of the present invention is represented by the following general formula (1).

Here, R ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R _{2 to} R ₄ are the same or different and represent a methyl group or an ethyl group, preferably a methyl group. Z represents a divalent hydrocarbon group having 4 to 15 carbon atoms and forms a cyclic hydrocarbon together with carbon atoms bonded at both ends. In the hydrocarbon group, the hydrogen atom may be substituted with a halogen atom or an alkoxy group. Examples of the cyclic hydrocarbon to be formed include cyclopentane, cyclohexane, cycloheptane, cyclooctane, bicyclo [2.2.1] heptane, 1,1,7-trimethylbicyclo [2.2.1] heptane, bicyclo [ 2.2.2] Octane, bicyclo [3.3.1] nonane, bicyclo [4.4.0] decane, tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclo [4.4.0] .1, ^2,5 . 1 ^7,10 ] dodecane, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10 . ^0,8 ] pentadecane, adamantane and the like. Among them, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, 1,1,7-trimethylbicyclo [2.2.1] heptane, and adamantane are available because of the availability of ketone compounds as raw materials. preferable.

（式中、Ｒ₂〜Ｒ₄は、同一または異なって、メチル基またはエチル基を示す。）

（式中、Ｚは、炭素数４〜１５の２価の炭化水素基を示し、両端で結合する炭素原子と共に環状の炭化水素を形成する。炭化水素基においては、水素原子がハロゲン原子、アルコキシ基で置換されていても良い。）

（式中、Ｒ₂〜Ｒ₄は、同一または異なって、メチル基またはエチル基を示し、Ｚは、炭素数４〜１５の２価の炭化水素基を示し、両端で結合する炭素原子と共に環状の炭化水素を形成する。炭化水素基においては、水素原子がハロゲン原子、アルコキシ基で置換されていても良い。）

（式中、Ｒ₁は、水素原子、メチル基またはトリフルオロメチル基を示し、Ｙは、ハロゲン基またはアルコキシ基を示す。）

（式中、Ｒ₁は、水素原子、メチル基またはトリフルオロメチル基を示す。） In the alicyclic ester compound of the formula (1) of the present invention, for example, a base is allowed to act on the corresponding acetate ester (3) to prepare a metal enolate, and further a nucleophilic addition reaction is performed on the carbonyl compound of the formula (4). A step of obtaining an alcohol compound represented by formula (5), and esterifying the alcohol compound represented by formula (5) with a (meth) acrylic acid derivative represented by formula (6) or formula (7) It can synthesize | combine by the process to make.

(In formula, R < ₂ > -R < ₄ > is the same or different and shows a methyl group or an ethyl group.)

(In the formula, Z represents a divalent hydrocarbon group having 4 to 15 carbon atoms and forms a cyclic hydrocarbon together with carbon atoms bonded at both ends. In the hydrocarbon group, a hydrogen atom is a halogen atom, an alkoxy group. It may be substituted with a group.)

Wherein R _{2 to} R ₄ are the same or different and each represents a methyl group or an ethyl group, Z represents a divalent hydrocarbon group having 4 to 15 carbon atoms, and is cyclic with carbon atoms bonded at both ends (In the hydrocarbon group, the hydrogen atom may be substituted with a halogen atom or an alkoxy group.)

(In the formula, R ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and Y represents a halogen group or an alkoxy group.)

(In the formula, R ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group.)

  The base used in preparing the metal enolate of the acetate represented by the formula (3) includes lithium diisopropylamide, lithium hexamethyldisilazide, sodium hexamethyldisilazide, potassium hexamethyldisilazide, sodium amide , Potassium amide, metal amides such as lithium 2,2,6,6-tetramethylpiperidine, sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, etc. Metal hydrides such as alkoxide, sodium hydride, lithium hydride, potassium hydride, calcium hydride, n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, phenyllithium, Alkyl metal compounds such as chill bromide can be exemplified lithium, sodium, and metal such as potassium.

  Solvents for preparing the metal enolate include tetrahydrofuran, diethyl ether, di-n-butyl ether, 1,4-dioxane, ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, methyl t-butyl ether, hexane, heptane, Preferred are alicyclic hydrocarbons such as octane, nonane, decane, cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, trialkylbenzene, ethylbenzene, and cumene. Can be used alone or in admixture. The reaction temperature and reaction time for preparing the metal enolate vary greatly depending on the base to be used. However, when lithium diisopropylamide, which is a representative base, is used, the reaction temperature is preferably -80 ° C to 0 ° C, and the reaction time is 0.00. About 5 to 2 hours are preferable. In order to maintain the activity of the base and the generated metal enolate, the reaction is preferably performed in an atmosphere of an inert gas such as dry nitrogen or argon.

Next, an alcohol compound represented by the above formula (5) is synthesized by reacting the prepared metal enolate with the carbonyl compound of the above formula (4). Examples of the carbonyl compound to be reacted include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, bicyclo [2.2.1] heptan-2-one (norcamphor), 1,1,7-trimethylbicyclo [2 2.1] heptan-2-one (camphor), bicyclo [2.2.2] octanone, bicyclo [3.3.1] nonanone, bicyclo [4.4.0] decanone, tricyclo [5.2. 1.0 ^2,6 ] decanone, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanone, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10 . 0 ^4,8] pentadecanone, can be exemplified ketones such as 2-adamantanone. Of these, cyclopentanone, cyclohexanone, norcamphor, camphor, and 2-adamantanone are preferred because of the availability of carbonyl compounds. The carbonyl compound of the above formula (4) is preferably used in a proportion of 0.5 to 2.0 mol, more preferably 0.8 to 1.2 mol, relative to 1 mol of metal enolate. It is preferable. The reaction solvent is tetrahydrofuran, diethyl ether, di-n-butyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethers such as methyl t-butyl ether, hexane, heptane, octane, nonane, decane, Preferred are cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, trialkylbenzene, ethylbenzene, and cumene. These solvents may be used alone or in combination. Can be used. Although the reaction temperature and reaction time vary depending on the carbonyl compound and metal enolate used, the reaction temperature is preferably −80 to 30 ° C. and the reaction time is preferably about 0.5 to 20 hours.

  Next, the target compound of the formula (5) is obtained by an esterification reaction between the alcohol compound represented by the formula (5) and the (meth) acrylic acid derivative represented by the formula (6) or the formula (7). The alicyclic ester compound 1) is synthesized.

  The alcohol compound represented by the formula (5) can be used for the reaction as it is, or it can be used by replacing the hydrogen of the hydroxyl group with an alkali metal such as lithium or sodium or magnesium halide. The esterification reaction with the (meth) acrylic acid derivative represented by formula (6) or formula (7) can be performed by a conventional method using a base catalyst or a transesterification catalyst.

  Specific examples of (meth) acrylic acid derivatives include acrylic acid halides such as acrylic acid chloride, methacrylic acid chloride, 2- (trifluoromethyl) acrylic acid chloride, methyl acrylate, ethyl acrylate, and n-butyl acrylate. , Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl 2- (trifluoromethyl) acrylate, ethyl 2- (trifluoromethyl) acrylate, or n- (2- (trifluoromethyl) acrylate Examples include acrylic acid esters such as butyl, and acrylic acid anhydrides such as acrylic acid anhydride, methacrylic acid anhydride, and 2-trifluoromethyl acrylic acid anhydride. Among these, acrylic acid chloride, methacrylic acid chloride, methyl acrylate, methyl methacrylate, acrylic anhydride and methacrylic anhydride are preferable. The amount used is preferably 0.5 to 10 moles, more preferably 0.8 to 2 moles per mole of the alcohol compound represented by formula (5). When the amount used is less than 0.5 mol, the yield decreases, and when the amount used is more than 10 mol, it is not economical.

  In the reaction between the alcohol compound represented by formula (5) and the (meth) acrylic acid derivative, it is preferable to add a base compound. Examples of the basic compound to be added include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, diisopropylamine, tri-n-propylamine, n-butylamine, di-n. -Butylamine, diisobutylamine, tri-n-butylamine, diphenylamine, 1,5-diazabicyclo [4.3.0] nonene-5, 1,5-diazabicyclo [5.4.0] undecene-5, diazabicyclo [2. 2.2] Amines such as octane, aniline, methylaniline, dimethylaniline, toluidine, anisidine, chloroaniline, bromoaniline, nitroaniline, pyridine and dimethylaminopyridine are preferred.

  The amount of these amines used is preferably 0.2 to 20 moles, more preferably 0.5 to 2 moles per mole of the alcohol compound represented by the formula (5). The amines may be charged in advance before adding the (meth) acrylic acid derivative, may be added after the (meth) acrylic acid derivative is charged, or added simultaneously with the (meth) acrylic acid derivative. You may add while.

  The alcohol compound represented by the formula (5) undergoes an esterification reaction after being converted to an alcoholate state with a base such as an alkali metal such as lithium or sodium, an alkyl lithium such as butyl lithium, or a Grignard reagent such as ethyl magnesium bromide. You can go. That is, the OH group that is a hydroxyl group may be converted to an OX group (X is Li, Na, MgBr, MgCl, etc.) and then esterified. The reaction solvent is tetrahydrofuran, diethyl ether, di-n-butyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethers such as methyl t-butyl ether, hexane, heptane, octane, nonane, decane, Preferred are cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, trialkylbenzene, ethylbenzene, and cumene. These solvents may be used alone or in combination. Can be used. The reaction temperature and reaction time for esterification vary greatly depending on the base and reaction solvent used, but the reaction temperature is preferably -80 to 100 ° C, more preferably 0 to 60 ° C. The reaction time is preferably about 0.5 to 50 hours, more preferably about 1 to 10 hours.

  When acrylic esters such as methyl acrylate and methyl methacrylate are used as (meth) acrylic acid derivatives, the corresponding alcohol (methanol in the case of methoxy group, ethanol in the case of ethoxy group) is distilled. The target substance is obtained by performing reaction at a temperature higher than that of the esterification reaction while removing it from the reaction system by a known method such as. Examples of the metal added as a catalyst and derivatives thereof include metals such as tin, titanium, germanium, zinc, lead, cobalt, iron, zirconium, manganese, antimony, potassium, and derivatives thereof. Derivatives are preferably halogen compounds, oxides, carbonates, metal alkoxides, carboxylates and the like. The reaction temperature at this time is 0 to 200 ° C, preferably 50 to 150 ° C. When the temperature is lower than 0 ° C., the reaction rate decreases, and when the temperature is higher than 200 ° C., side reactions proceed and the yield decreases. When removing the corresponding alcohol out of the reaction system by distillation, a method of reacting near the boiling point of the corresponding alcohol can be mentioned. As the solvent, a raw material and a target substance having high solubility and inert to the reaction are desirable. As such, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, tetrahydrofuran, diethyl ether, di-n-butyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Ethers such as methyl-t-butyl ether, hexane, heptane, octane, nonane, decane, cyclohexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, and other alicyclic hydrocarbons, benzene, toluene, xylene, trialkylbenzene, ethylbenzene , Aromatic hydrocarbons such as cumene, and nitriles such as acetonitrile.

  A polymerization inhibitor may be added during the esterification step. The polymerization inhibitor is not particularly limited as long as it is a general one. 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxyl Amine aluminum salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, N, N'-dimethyl-p Nitroso compounds such as nitrosoaniline, sulfur-containing compounds such as phenothiazine, methylene blue, 2-mercaptobenzimidazole, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, 4 -Hydro Amines such as sidiphenylamine and aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone and hydroquinone monomethyl ether, methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s -Phenols such as butylcatechol and 2,2-methylenebis- (6-t-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexane oxime and p-quinone dioxime, di Examples thereof include alkylthiodipropinates. The amount added is 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic acid derivative.

  After completion of the reaction, the reaction solution is washed with washing water to remove excess (meth) acrylic acid derivatives, acids, bases and other additives. At this time, the washing water may contain an appropriate inorganic salt such as sodium chloride or sodium bicarbonate. Further, unreacted (meth) acrylic acid derivatives are removed by alkali washing. For the alkali cleaning, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, an aqueous sodium hydrogen carbonate solution, aqueous ammonia, or the like can be used, but the alkaline component used is not particularly limited. In addition, acid cleaning may be performed to remove metal impurities. Examples of acid cleaning include inorganic acids such as aqueous hydrochloric acid, aqueous sulfuric acid, and aqueous phosphoric acid, and organic acids such as aqueous oxalic acid. Moreover, you may add an organic solvent to a reaction liquid in the case of washing | cleaning. The organic solvent to be added may be the same as that used for the reaction or may be different, but it is usually preferable to use a solvent having a small polarity that is easily separated from water.

  Each said reaction process for manufacturing the alicyclic ester compound of this invention can be performed under a normal pressure, pressure reduction, or pressurization. The reaction can be carried out by a conventional method such as batch, semi-batch or continuous. In each step, each derivative may be isolated, or may be used in the next step as it is without isolation. After completion of the reaction, it can be easily separated and purified by a conventional method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, purification by activated carbon, or a combination of these. .

  The resin contained in the functional resin composition of the present invention can be produced by homopolymerizing the alicyclic ester compound obtained as described above or copolymerizing it with other raw materials. In the polymerization, generally, the alicyclic ester compound obtained as described above, and in the case of copolymerization, the alicyclic ester compound and other raw materials to be copolymerized are dissolved in a solvent, and a catalyst is obtained. And the polymerization reaction is carried out while heating or cooling. The polymerization reaction depends on the type of initiator, the starting method such as heat and light, the polymerization conditions such as temperature, pressure, concentration, solvent and additives. As the polymerization, radical polymerization using a radical generator such as azoisobutyronitrile and ionic polymerization using a catalyst such as alkyl lithium are generally used. The method can be performed according to a conventional method.

In the present invention, examples of other raw materials that form a copolymer with the compound represented by the formula (1) include the following. 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2- (meth) acryloyloxy-2- (1-adamantyl) propane, 2- (meth) acryloyloxy 2- (1-adamantyl) butane, 3- (meth) acryloyloxy-3- (1-adamantyl) pentane, 3-hydroxy-1-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl ( Adamantyl acrylate derivatives such as (meth) acrylate, hydroxystyrene, α-methylstyrene, 4-t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2-t- Butoxycarbonylethyloxy) styrene etc. Droxystyrene derivatives, t-butyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, β- (meth) acryloyloxy γ-butyrolactone, β- (meth) acryloyl Oxy β-methyl-γ-butyrolactone, α- (meth) acryloyloxy γ-butyrolactone, α- (meth) acryloyloxy α-methyl-γ-butyrolactone, α- (meth) acryloyloxy γ, γ-dimethyl -Γ-butyrolactone, 5- (meth) acryloyloxy 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (= 9- (meth) acryloyloxy 2-oxatricyclo [4.2.1.0 ^4,8 ] nonan-3-one), 6- (meth) acryloyloxy 3-oxatricyclo [ 4.3.1.1 ^4,8 ] undecan-2-one, 2-methyl-2- (meth) acryloyloxycyclopentane, 2-ethyl-2- (meth) acryloyloxycyclopentane and the like. These raw materials can be present alone or in combination of two or more.

  The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) of the resin contained in the functional resin composition of the present invention is preferably 1,000 to 150,000. More preferably, it is 3,000-100,000. The ratio (Mw / Mn) of Mw of the functional resin composition to the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1-10. , Preferably 1-5. In this invention, resin contained in a functional resin composition can be used individually or in mixture of 2 or more types.

  The functional resin composition of the present invention usually contains a photoacid generator and a solvent in addition to the above resin. Examples of commonly used solvents include linear ketones such as 2-pentanone and 2-hexanone, cyclic ketones such as cyclopentanone and cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Propylene glycol monoalkyl acetates, ethylene glycol monomethyl ether acetate, ethylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, ethylene glycol Ethylene glycol monoal such as monomethyl ether and ethylene glycol monoethyl ether Ethers, diethylene glycol dimethyl ether, diethylene glycol alkyl ethers such as diethylene glycol diethyl ether, ethyl acetate, esters such as ethyl lactate, cyclohexanol, alcohols such as 1-octanol, ethylene carbonate, and γ- butyrolactone. These solvents can be used alone or in admixture of two or more.

  Photoacid generators can be used as acid generators for chemically amplified resist compositions depending on the wavelength of the exposure light, while considering the thickness range of the resist coating film and its own light absorption coefficient. Can be appropriately selected. A photo-acid generator can be used individually or in combination of 2 or more types. The amount of the photoacid generator used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight per 100 parts by weight of the resin.

  Usable photoacid generators include, for example, onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, diazomethane compounds, and the like. Of these, onium salt compounds such as sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, and pyridinium salts are preferred.

KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂
Specific examples of photoacid generators that can be suitably used for excimer laser (wavelength: 157 nm), extreme ultraviolet light (wavelength: 13 nm), X-rays, electron beams, and the like include triphenylsulfonium triflate and triphenyl. Examples include sulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, and diphenyliodonium hexafluoroantimonate. .

  An acid diffusion control agent having an action of controlling an undesired chemical reaction in a non-exposed region by controlling a diffusion phenomenon in the resist film of an acid generated from a photoacid generator by exposure can be blended. As the acid diffusion controller, a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment in the resist pattern forming step is preferable. Examples of such nitrogen-containing organic compounds include monoalkylamines such as n-hexylamine, n-heptylamine and n-octylamine; dialkylamines such as di-n-butylamine; trialkyls such as triethylamine. Amines; aromatic amines such as aniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline and diphenylamine; amine compounds such as ethylenediamine, formamide, N Amide compounds such as N, dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, urea compounds such as urea, imidazoles such as imidazole and benzimidazole, pyridines such as pyridine and 4-methylpyridine, 1,4-diazabicyclo [ .2.2] octane and the like can be mentioned. The compounding amount of the acid diffusion controller is usually 15 parts by weight or less, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight per 100 parts by weight of the resin.

  Furthermore, in the functional resin composition of the present invention, if necessary, various additive components used in conventional chemically amplified resist compositions such as surfactants, quenchers, sensitizers, halation, and the like. Various additives such as an inhibitor, a storage stabilizer, and an antifoaming agent can be contained. Preferred sensitizers include, for example, carbazoles, benzophenones, rose bengals, anthracenes and the like.

  Examples of usable surfactants include nonionic surfactants such as polyoxyethylene lauryl ether and polyethylene glycol dilaurate, as well as surfactants marketed under the following trade names: Megafax F173 (Dainippon Ink, Inc.) Chemical Industries), L-70001 (Shin-Etsu Chemical Co., Ltd.), F-top EF301, EF303, EF352 (Tochem Products), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass), KP341 (manufactured by Shin-Etsu Chemical), Polyflow No. 75, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution prepared as described above is applied by an appropriate application means such as a spin coater, a dip coater, or a roller coater, for example, a silicon wafer, a metal, A resist film is formed by coating on a substrate such as plastic, glass, ceramic, etc., and after a heat treatment at a temperature of about 50 ° C. to 200 ° C. in some cases, exposure is performed through a predetermined mask pattern. The thickness of the resist film is, for example, about 0.01 to 20 μm, preferably about 0.02 to 1 μm. For exposure, light of various wavelengths, such as ultraviolet rays and X-rays, can be used. For example, as a light source, F ₂
Far ultraviolet rays such as excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), extreme ultraviolet rays (wavelength 13 nm), X-rays, electron beams, etc. are appropriately selected and used. Moreover, exposure conditions, such as exposure amount, are suitably selected according to the compounding composition of a radiation sensitive resin composition, the kind of each additive, etc.

  In order to stably form a high-precision fine pattern, it is preferable to perform heat treatment at a temperature of 50 to 200 ° C. for 30 seconds or more after exposure. In this case, if the temperature is less than 50 ° C., there is a possibility that the variation in sensitivity depending on the type of the substrate spreads. Then, a predetermined resist pattern is formed by developing with an alkali developer usually at 10 to 50 ° C. for 10 to 200 seconds, preferably at 20 to 25 ° C. for 15 to 90 seconds.

  Examples of the alkali developer include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo- [5. 4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and the like, usually with a concentration of 1 to 10% by weight, preferably 1 to 3% by weight. An alkaline aqueous solution so dissolved is used. In addition, a water-soluble organic solvent and a surfactant can be appropriately added to the developer composed of the alkaline aqueous solution.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Example 1
<Synthesis of 2-t-butoxycarbonylmethyl-2-adamantanol>
Under a nitrogen atmosphere, 15.5 ml (110 mmol) of diisopropylamine and 80 ml of anhydrous tetrahydrofuran were placed in a flask and cooled to −70 ° C. in a dry ice / acetone bath. While stirring with a magnetic stirrer, 39.8 ml (105 mmol) of a 2.64M n-butyllithium / n-hexane solution was dropped from an isobaric dropping funnel over 1 hour. After stirring for 20 minutes, a solution of 13.4 ml (100 mmol) of t-butyl acetate in 40 ml of anhydrous tetrahydrofuran was added dropwise over 30 minutes. After stirring for 1 hour, a solution of 2-adamantanone 15.0 g (100 mmol) in anhydrous tetrahydrofuran 50 ml was added dropwise over 30 minutes. The temperature was gradually raised to room temperature over 3 hours. After stirring for 30 minutes, 40 ml of a 20 wt% ammonium chloride aqueous solution was added, and 50 ml of water and 100 ml of toluene were further added to separate the layers. Further, it was washed with 100 ml of water, filtered through 5C filter paper, and concentrated to obtain 25.9 g of a white solid (GC purity 99.2%, yield 97%). The obtained white solid was confirmed to be the target product by ¹ H, ¹³ C-NMR and IR.

<Synthesis of 2-t-butoxycarbonylmethyl-2-adamantyl methacrylate>
Under a nitrogen atmosphere, 5.0 g (22.1 mmol) of 2-t-butoxycarbonylmethyl-2-adamantanol synthesized as described above and 20 ml of anhydrous tetrahydrofuran were charged into a flask, and −60 ° C. in a dry ice / acetone bath. Cooled to. While stirring with a magnetic stirrer, 8.8 ml (23.2 mmol) of a 2.64M n-butyllithium / n-hexane solution was added dropwise over 10 minutes and stirred for 20 minutes. After gradually raising the temperature to room temperature over 1.5 hours, 2 ml of pyridine was added. Under ice cooling, a solution of 3.2 g (30.9 mmol) of methacrylic acid chloride / 10 ml of anhydrous tetrahydrofuran was added dropwise over 20 minutes. The mixture was stirred overnight while gradually raising the temperature. After separation by adding 50 ml of water and 50 ml of heptane, the mixture was further washed with 50 g of 5 wt% sulfuric acid aqueous solution, 50 ml of water, 50 g of 5 wt% sodium hydroxide aqueous solution and 50 ml of water. After filtration through 5A filter paper, the solution was concentrated and purified by silica gel column chromatography. 1.34 g of the target product was obtained as a white solid (yield 18%). The structure of the obtained white solid was confirmed by ¹ H, ¹³ C-NMR, and IR (see FIGS. 1 to 3).

(Example 2)
<Synthesis of 1-t-butoxycarbonylmethyl-1-cyclohexanol>
Under a nitrogen atmosphere, 12.6 ml (89.6 mmol) of diisopropylamine and 60 ml of anhydrous tetrahydrofuran were placed in a flask and cooled to −70 ° C. in a dry ice / acetone bath. While stirring with a magnetic stirrer, 32.3 ml (85.3 mmol) of a 2.64M n-butyllithium / n-hexane solution was dropped from an isobaric dropping funnel over 10 minutes. After stirring for 20 minutes, a solution of t-butyl acetate 12.0 ml (89.6 mmol) in anhydrous tetrahydrofuran 20 ml was added dropwise over 30 minutes. After stirring for 30 minutes, a solution of 9.3 ml (89.6 mmol) of cyclohexanone in 15 ml of anhydrous tetrahydrofuran was added dropwise over 30 minutes. The temperature was gradually raised to 0 ° C. over 3 hours. After stirring at room temperature overnight, 50 ml of water, 20 ml of toluene and 50 ml of heptane were added to separate the layers. Furthermore, it was washed twice with 50 g of 5 wt% aqueous sodium hydroxide solution and 50 ml of water. After filtration through 5C filter paper, concentration was performed to obtain 17.88 g of the desired product as a pale yellow liquid (GC purity 99.2%, yield 98%). The desired product was confirmed by ¹ H, ¹³ C-NMR and IR.

<Synthesis of 1-t-butoxycarbonylmethyl-1-cyclohexyl methacrylate>
Under a nitrogen atmosphere, 5.0 g (23.3 mmol) of 1-t-butoxycarbonylmethyl-1-cyclohexanol synthesized as described above and 15 ml of anhydrous tetrahydrofuran were charged into a flask, and −60 ° C. in a dry ice / acetone bath. Cooled to. While stirring with a magnetic stirrer, 9.3 ml (24.5 mmol) of a 2.64M n-butyllithium / n-hexane solution was added dropwise over 10 minutes and stirred for 20 minutes. The temperature was gradually raised to room temperature over 2 hours. Cool to −30 ° C. and add 1 ml of pyridine. Further, 3.41 g (32.6 mmol) of methacrylic acid chloride / 10 ml of anhydrous tetrahydrofuran was added dropwise over 10 minutes. The temperature was gradually raised to room temperature and stirred overnight. After separation by adding 50 ml of water and 50 ml of heptane, the mixture was further washed with 50 g of 5 wt% sulfuric acid aqueous solution, 50 ml of water, 50 g of 5 wt% sodium hydroxide aqueous solution and 50 ml of water. After filtration through 5A filter paper, the solution was concentrated and purified by silica gel column chromatography. 4.63 g of the target product was obtained as a pale yellow liquid (yield 70%). The structure of the obtained pale yellow liquid was confirmed by ¹ H, ¹³ C-NMR, and IR (see FIGS. 4 to 6).

(Example 3)
<Synthesis of 1-t-butoxycarbonylmethyl-1-cyclopentanol>
Under a nitrogen atmosphere, 12.6 ml (89.6 mmol) of diisopropylamine and 60 ml of anhydrous tetrahydrofuran were placed in a flask and cooled to −70 ° C. in a dry ice / acetone bath. While stirring with a magnetic stirrer, 32.3 ml (85.3 mmol) of a 2.64M n-butyllithium / n-hexane solution was dropped from an isobaric dropping funnel over 10 minutes. After stirring for 20 minutes, a solution of t-butyl acetate 12.0 ml (89.6 mmol) in anhydrous tetrahydrofuran 20 ml was added dropwise over 30 minutes. After stirring for 30 minutes, a solution of 8.3 ml (89.6 mmol) of cyclopentanone in 15 ml of anhydrous tetrahydrofuran was added dropwise over 30 minutes. The temperature was gradually raised to 0 ° C. over 3 hours. After stirring at room temperature overnight, 50 ml of water and 100 ml of heptane were added to separate the layers. Furthermore, it was washed with 50 ml of water, 50 ml of 20 wt% ammonium chloride aqueous solution, 50 g of 5 wt% sodium hydroxide aqueous solution and 50 ml of water. After filtration through 5C filter paper, concentration was performed to obtain 15.68 g of the desired product as a pale yellow liquid (GC purity 98.2%, yield 92%). The desired product was confirmed by ¹ H, ¹³ C-NMR and IR.

<Synthesis of 1-t-butoxycarbonylmethyl-1-cyclopentyl methacrylate>
In a nitrogen atmosphere, 5.0 g (25.0 mmol) of 1-t-butoxycarbonylmethyl-1-cyclopentanol synthesized as described above and 15 ml of anhydrous tetrahydrofuran were charged into a flask and −60 in a dry ice / acetone bath. Cooled to ° C. While stirring with a magnetic stirrer, 9.9 ml (26.2 mmol) of a 2.64M n-butyllithium / n-hexane solution was added dropwise over 10 minutes and stirred for 20 minutes. The temperature was gradually raised to room temperature over 2 hours. Cool to −30 ° C. and add 1 ml of pyridine. Further, a solution of 3.66 g (35.0 mmol) of methacrylic acid chloride / 10 ml of anhydrous tetrahydrofuran was added dropwise over 10 minutes. The temperature was gradually raised to room temperature and stirred overnight. After separation by adding 50 ml of water and 50 ml of heptane, the mixture was further washed with 50 g of 5 wt% sulfuric acid aqueous solution, 50 ml of water, 50 g of 5 wt% sodium hydroxide aqueous solution and 50 ml of water. After filtration through 5A filter paper, the solution was concentrated and purified by silica gel column chromatography. 4.42 g of the target product was obtained as a pale yellow liquid (yield 66%). About the obtained light yellow liquid, the structure was confirmed by < ¹ > H, < ¹³ > C-NMR, and IR (refer FIGS. 7-9).

Example 4
<Synthesis of 2-t-butoxycarbonylmethyl-2- (1,1,7-trimethylbicyclo [2.2.1] heptyl) methacrylate>
Under a nitrogen atmosphere, 5.8 ml (41.0 mmol) of diisopropylamine and 30 ml of anhydrous tetrahydrofuran were placed in a flask and cooled to −70 ° C. in a dry ice / acetone bath. While stirring with a magnetic stirrer, 15.5 ml (41.0 mmol) of a 2.64M n-butyllithium / n-hexane solution was dropped from an isobaric dropping funnel over 10 minutes. After stirring for 20 minutes, a solution of t-butyl acetate 5.5 ml (41.0 mmol) in anhydrous tetrahydrofuran 20 ml was added dropwise over 30 minutes. After stirring for 30 minutes, a solution of 5.67 g (37.3 mmol) of d-camphor in 15 ml of anhydrous tetrahydrofuran was added dropwise over 30 minutes. The temperature was gradually raised to 0 ° C. over 3 hours. After stirring at room temperature overnight, 30 ml of water and 30 ml of heptane were added to separate the layers.
After concentration of the organic phase, 15 ml of anhydrous tetrahydrofuran was added under a nitrogen atmosphere, and the mixture was cooled to −60 ° C. in a dry ice / acetone bath. While stirring with a magnetic stirrer, 15.5 ml (41.0 mmol) of a 2.64M n-butyllithium / n-hexane solution was added dropwise over 10 minutes and stirred for 20 minutes. The temperature was gradually raised to room temperature over 2 hours. Cool to −30 ° C. and add 3 ml of pyridine. Further, 7.8 g (74.6 mmol) of methacrylic acid chloride was added dropwise over 10 minutes. The temperature was gradually raised to room temperature and stirred overnight. After separation by adding 50 ml of water and 50 ml of heptane, the mixture was further washed with 50 g of 5 wt% sulfuric acid aqueous solution, 50 ml of water, 50 g of 5 wt% sodium hydroxide aqueous solution and 50 ml of water. After filtration through 5A filter paper, the solution was concentrated and purified by silica gel column chromatography. 1.82 g of the target product was obtained as a pale yellow liquid (yield 15%). The structure of the obtained pale yellow liquid was confirmed by ¹ H, ¹³ C-NMR, and IR (see FIGS. 10 to 12).

Claims (3)

An alicyclic ester compound represented by the formula (1).

(In the formula, R ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group, R _{2 to} R ₄ are the same or different and represent a methyl group or an ethyl group, and Z represents a carbon number of 4 to 15) (A divalent hydrocarbon group, which forms a cyclic hydrocarbon together with carbon atoms bonded at both ends. In the hydrocarbon group, the hydrogen atom may be substituted with a halogen atom or an alkoxy group.)   Z together with carbon atoms bonded at both ends forms an adamantane, bicyclo [2.2.1] heptane, 1,7,7-trimethylbicyclo [2.2.1] heptane, cyclopentane, or cyclohexane ring Item 1. An alicyclic ester compound according to Item 1. The functional resin composition containing resin which contains the component represented by Formula (2) in a repeating unit.

(In the formula, R ₁ represents a hydrogen atom, a methyl group or a trifluoromethyl group, R _{2 to} R ₄ are the same or different and represent a methyl group or an ethyl group, and Z represents a carbon number of 4 to 15) (A divalent hydrocarbon group, which forms a cyclic hydrocarbon together with carbon atoms bonded at both ends. In the hydrocarbon group, the hydrogen atom may be substituted with a halogen atom or an alkoxy group.)

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