JP4697395B2 - ADAMANTAN DERIVATIVE AND RESIN COMPOSITION USING THE SAME - Google Patents

Description

The present invention has an adamantane skeleton and is excellent in optical properties, heat resistance, acid dissociation properties, etc., and optical materials such as cross-linked resins, optical fibers, optical waveguides, optical disk substrates, and photoresists, raw materials thereof, pharmaceutical and agricultural chemical intermediates And a novel adamantane derivative useful as various industrial products.
The present invention also provides a functional resin composition that 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), and the raw material thereof. And an acrylate compound having an adamantane skeleton.

Since adamantane has a rigid structure and high symmetry, and its derivative exhibits a unique function, a highly functional resin material, pharmaceutical intermediate, optical material (see Patent Documents 1 and 2), photoresist ( It is known that it is useful for, for example, Patent Document 3).
On the other hand, the functional resin composition used in the semiconductor manufacturing process has a good balance of properties 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 a need. When a light source uses a short wavelength light source of KrF excimer laser or later, a chemically amplified resist is generally used, and its composition is generally composed of a functional resin composition as a main ingredient, a photoacid generator, and several types. It is used as a solution containing the additives. Among them, it is important that the functional resin composition as the main agent has the above-mentioned characteristics in a well-balanced manner, and determines the resist performance.

  When a light source uses a short wavelength light source of KrF excimer laser or later, a chemically amplified resist is used. In this case, the functional resin composition as a main ingredient generally has acrylate or the like as a repeating unit. It is a polymer. However, it is not used in a single repeating unit. This is because a single repeating unit cannot satisfy all the characteristics such as etching resistance. Actually, a plurality of repeating units having a functional group for improving each characteristic, that is, two or more kinds of copolymers are used as functional resin compositions. Hydroxystyrene resins are proposed for resists for KrF excimer laser lithography, and acrylic resins based on 2-alkyl-2-adamantyl methacrylate are proposed for resists for ArF excimer laser lithography (see Patent Documents 3 and 4). .

  In particular, miniaturization is progressing rapidly in recent lithography processes. In particular, for each light source, it is required to extend the life to a line width up to about 1/3 of the wavelength. Along with this, demands for resolution and line edge roughness have become stricter as the line width becomes thinner. As a cause thereof, the non-uniformity of the functional resin composition due to greatly different properties of each repeating unit is cited as a cause (see Non-Patent Document 1). Here, an alkali-soluble and etching-resistant resist composition containing an adamantanecarboxylic acid derivative has been proposed (see Patent Document 5). In addition, as a resist composition having features such as low surface roughness during etching and low line edge roughness, acrylic acid containing an acrylate represented by 2- (1-adamantyl) -2-methacryloyloxypropane as a basic skeleton as a resist composition. A copolymer having only an ester derivative as a unit in the main chain has been proposed (see Patent Document 6).

  However, each repeating unit often has only one or two performances required for a chemically amplified resist, that is, performance to improve etching resistance, alkali developability, substrate adhesion, etc. In order to meet strict requirements, 3 types and 4 types of repeating units are used, and the number tends to increase. For this reason, it becomes difficult to satisfy uniformity, and it is difficult to sufficiently satisfy resolution and line edge roughness. There is a real situation.

Under these circumstances, the development of a functional resin composition excellent in alkali developability and substrate adhesion that can achieve an improvement in resolution and line edge roughness without adversely affecting the basic properties as a functional resin composition. There is a strong demand.
Japanese Patent Publication No. 1-53333 JP-A-6-305044 Japanese Patent Laid-Open No. 4-39665 JP 10-319595 A JP 2000-122295 A JP 2003-167346 A SEMICON JAPAN SEMI Technology-ology Symposium 2002, 3-27

An object of the present invention is to provide an adamantane derivative having an adamantane skeleton and having excellent optical properties and the like, and an adamantane derivative useful as a monomer used therein.
Further, 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, as a resist having pattern shape, dry etching resistance, heat resistance, etc. It is an object of the present invention to provide a functional resin composition excellent in alkali developability and substrate adhesion that can achieve an improvement in resolution and line edge roughness without impairing the basic physical properties, and a raw material compound thereof.

  As a result of intensive studies on the above-mentioned problem, the present inventors have found that the adamantane derivative represented by the formula (1) is a compound that meets the above-mentioned purpose, and can be efficiently produced by a specific process. I found out. Further, the present inventors have found that a functional resin composition containing a component represented by formula (3) as a repeating unit and using an adamantane derivative represented by formula (1) as a raw material is useful as a photoresist. did.

(Wherein X is the same or different and represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, or a hydrocarbyl group having a hydroxyl group, a halogen group, a nitrile group, or an ether group, and n ₁ is And R _{1 to} R ₄ are the same or different and each represents an alkyl group or a halogen-containing alkyl group, and Y ₁ and Y ₂ are the same or different and represent a hydrogen atom or formula (2) Represents a group represented by

(R _{5 to} R ₇ are the same or different and each represents a hydrogen atom, an alkyl group, a halogen group or a halogen-containing alkyl group).

(Wherein X is the same or different and represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, or a hydrocarbyl group having a hydroxyl group, a halogen group, a nitrile group, or an ether group, and n ₁ is And R _{1 to} R ₄ are the same or different and each represents an alkyl group or a halogen-containing alkyl group, and Y ₃ and Y ₄ are the same or different and represent a hydrogen atom or formula (4) Indicate)

(R _{5 to} R ₇ are the same or different and each represents a hydrogen atom, an alkyl group, a halogen group or a halogen-containing alkyl group).

  The functional resin composition of the present invention was excellent in etching resistance and could form a fine pattern with high accuracy. In addition, it has excellent adhesion to the substrate and has alkali solubility. According to the functional resin composition of the present invention, a fine pattern can be formed with high accuracy.

  First, the adamantane derivative of the present invention and the functional resin composition using it as a raw material will be described. The synthesis of the compound represented by the formula (1) is carried out by introducing a carboxyl group into the adamantane ring of the adamantane represented by the formula (5), the 1,3-adamantane dicarboxylic acid represented by the formula (6) and its It can be synthesized from where the derivative is obtained.

Wherein Y ₅ and Y ₆ are the same or different and each represents a hydrogen atom, a hydroxyl group or a halogen group, and X is the same or different and each represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group or a hydroxyl group. And a hydrocarbyl group having a group, a halogen group, a nitrile group, or an ether group, and n ₁ represents an integer of ₁ to 14.)

(Wherein X is the same or different and represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, or a hydrocarbyl group having a hydroxyl group, a halogen group, a nitrile group, or an ether group. N ₁ is 1; Represents an integer of ~ 14.)

  Examples of the adamantane represented by the formula (5) include adamantane and 1,3-substituted adamantane. As 1,3-substituted adamantane, 1,3-adamantanediol, 1,3-dibromoadamantane, 1-bromo-3-hydroxyadamantane, 1,3-dichloroadamantane, 1-chloro-3-hydroxyadamantane, 1-hydroxy Examples include -3-adamantanecarboxylic acid, 1-bromo-3-adamantanecarboxylic acid, and 1-chloro-3-adamantanecarboxylic acid. When 1,3-substituted adamantane is used, particularly when 1,3-adamantanediols are used, the 1,3-adamantane dicarboxylic acids represented by formula (6) and the compounds thereof can be obtained with high selectivity and high yield. A derivative is obtained.

  Examples of the method for introducing a carboxyl group into the adamantane include a method of reacting with carbon monoxide and oxygen in the presence of a protonic acid. When the reaction is carried out in the presence of a protonic acid, the reaction can be carried out smoothly and the target compound can be obtained with high selectivity and yield. This protonic acid may be used as a solvent. Protic acids include organic acids (organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and tartaric acid, organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid), inorganic Acids (eg, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) are included.

  Moreover, the method of using formic acid etc. as a carbon monoxide source instead of carbon monoxide is mentioned. For example, it is known that formic acid decomposes in concentrated sulfuric acid to generate carbon monoxide. In addition, instead of oxygen, a raw material that already contains the necessary oxygen atom, such as 1,3-adamantanediol, is used as a raw material, or an acid having an oxidizing property such as sulfuric acid or nitric acid is used as a proton acid. In some cases, oxygen need not be used.

  The carboxyl group introduction reaction is performed in an inert organic solvent. Examples of the organic solvent include organic carboxylic acids such as acetic acid, nitriles such as acetonitrile and benzonitrile, amides such as formamide, acetamide, dimethylformamide and dimethylacetamide, alcohols such as t-butanol and t-amyl alcohol, Aliphatic hydrocarbons such as hexane and octane, aromatic hydrocarbons such as benzene, halogenated hydrocarbons, nitro compounds, esters such as ethyl acetate, ethers such as diethyl ether, diisopropyl ether and dioxane, and mixed solvents thereof Can be mentioned. The above carboxylation reaction proceeds smoothly even under relatively mild conditions. The reaction temperature is, for example, −78 to 200 ° C., preferably about 0 to 100 ° C., and the reaction is usually performed at about 10 to 80 ° C. in many cases. The reaction can be carried out at normal pressure or under pressure.

  Carbon monoxide and oxygen used in the carboxylation reaction may be pure carbon monoxide or oxygen, or may be diluted with an inert gas. Air or ozone can also be used as an oxygen source. The amount of carbon monoxide used is selected from the range of 1 equivalent to the substrate (in this case, when 2 carboxyl groups are introduced, 2 mol of carbon monoxide is used per 1 mol of the substrate) to 1000 equivalents. It is preferably 1.5 to 100 equivalents, more preferably about 2 to 10 equivalents. The same applies when formic acid is used instead of carbon monoxide. The usage-amount of oxygen can be selected from the range of 0-1000 equivalent with respect to a substrate, Preferably it is 0-100 equivalent, More preferably, it is 0-12 equivalent.

  Among the above methods, the method using 1,3-adamantanediol as an adamantane raw material, concentrated sulfuric acid as a protonic acid, and formic acid as a carbon monoxide source can be handled in a simple and mild liquid phase reaction. In addition, the desired 1,3-adamantanecarboxylic acid derivative can be obtained with high selectivity and high yield.

  The 1,3-adamantane dicarboxylic acids obtained by the above method are represented by the formula (8) to the formula (11), as they are represented by the formula (7) or by introducing a protecting group. To obtain a 1,3-adamantane dialkyl alcohol compound (hereinafter referred to as an adamantane dialcohol compound) represented by the formula (12) by reacting with an organometallic compound or an organic compound / metal such as alkyl lithium and Grignard reagent. be able to.

Wherein Y ₇ and Y ₈ are the same or different and each represents a hydrogen atom or a hydrocarbyl group, and X is the same or different and represent a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, a hydroxyl group, a halogen group, And a hydrocarbyl group having a group, a nitrile group, or an ether group, and n ₁ represents an integer of ₁ to 14.)

(In the formula, R ₈ represents a hydrocarbon group, a halogen-containing alkyl group, and Z represents a halogen atom.)

(Wherein X is the same or different and represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, or a hydrocarbyl group having a hydroxyl group, a halogen group, a nitrile group, or an ether group, and n ₁ is And represents an integer of _{1 to} 14. R _{1 to} R ₄ are the same or different and each represents an alkyl group or a halogen-containing alkyl group.

  As the organometallic compound, known compounds such as alkyl lithium and Grignard reagent can be used. In addition, a Barbier reaction in which a halogenated compound / metal (lithium or magnesium) for deriving an organometallic compound is used in one pot can be used (hereinafter, formula (8) to formula (11) are referred to as organometallic compounds). ). For example, when synthesizing 1,3-di (2-hydroxy-2-propyl) adamantane, the corresponding organometallic compound is a reagent for introducing a methyl group such as methyllithium or methylmagnesium bromide. The reaction with the alkyllithium and the Grignard reagent can be carried out according to the usual Grignard reaction. The amount of alkyllithium or Grignard reagent used is 1 equivalent (in this case, the molar amount of the required alkyl group to 1 mol of raw material) to 10 equivalents, preferably 1 equivalent to 2 equivalents, relative to the above compound. use. Further, the amount of the organometallic compound is increased according to the number of carboxylic acid groups and hydroxyl groups. The reaction is performed, for example, in ethers such as diethyl ether and tetrahydrofuran. The reaction temperature is, for example, -20 to 150 ° C, preferably about 0 to 100 ° C.

  A conventional method can be used for introducing the protective group for the carboxyl group. Examples of the protecting group for the carboxyl group include an alkoxy group (alkoxy group such as methoxy, ethoxy, t-butoxy group), an aralkyloxy group (benzyloxy group, p-methoxybenzyloxy, diphenylmethyloxy, benzhydryloxy group). Etc.), N-hydroxysuccinimide groups and the like can be used.

  The target compound represented by the formula (1) is obtained by an esterification reaction between the adamantane dialcohol compound produced by the above reaction and (meth) acrylic acid or a derivative thereof (hereinafter, acrylic acid compound). The adamantane dialcohols may be used as they are, as shown by the formula (13), or by replacing the hydroxyl group with an alkali metal such as lithium or sodium or magnesium halide. The esterification reaction with the acrylic acid compound represented by formula (14) or formula (15) can be performed by a conventional method using an acid catalyst, a base catalyst, or a transesterification catalyst.

(Wherein X is the same or different and represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, or a hydrocarbyl group having a hydroxyl group, a halogen group, a nitrile group, or an ether group, and n ₁ is R _{1 to} R ₄ are the same or different and each represents an alkyl group or a halogen-containing alkyl group, and Y ₉ and Y ₁₀ are the same or different and represent a hydrogen atom or potassium, sodium, lithium Alkali metal such as magnesium halide)

(In the formula, R _{5 to} R ₇ are the same or different and each represents a hydrogen atom, an alkyl group, a halogen group, or a halogen-containing alkyl group, and Y ₁₁ represents a hydroxyl group, an alkoxy group, or a halogen group.)

(In the formula, R _{5 to} R ₇ are the same or different and each represents a hydrogen atom, an alkyl group, a halogen group, or a halogen-containing alkyl group.)

  Specific examples of the acrylic acid compound include acid compounds such as acrylic acid, methacrylic acid, 2-fluoroacrylic acid, trifluoroacrylic acid and 2- (trifluoromethyl) acrylic acid, acrylic acid chloride, methacrylic acid chloride, 2 -Acrylic acid halides such as fluoroacrylic acid chloride, trifluoroacrylic acid chloride, 2- (trifluoromethyl) acrylic acid chloride, methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate , T-butyl methacrylate, methyl trifluoroacrylate, ethyl trifluoroacrylate, isopropyl trifluoroacrylate, tert-butyl trifluoroacrylate, methyl pentafluoromethacrylate, ethyl pentafluoromethacrylate, pen Isopropyl fluoromethacrylate, pentafluoromethacrylate-t-butyl, methyl 2-fluoroacrylate, ethyl 2-fluoroacrylate, isopropyl 2-fluoroacrylate, 2-t-butyl acrylate, 2- (trifluoro Acrylic esters such as methyl) methyl acrylate, 2- (trifluoromethyl) ethyl acrylate, isopropyl 2- (trifluoromethyl) acrylate, 2- (trifluoromethyl) acrylate-t-butyl, acrylic Acrylates such as sodium acid, sodium methacrylate, sodium 2-fluoroacrylate, sodium trifluoroacrylate, sodium 2- (trifluoromethyl) acrylate, anhydrous acrylic acid, anhydrous methacrylic acid, anhydrous perfluoroacrylic acid Anhydride, perfluoro methacrylic acid, 2,2'-difluoro acrylic anhydride, 2-fluoro-acrylic anhydride, acrylic anhydride such as 2-trifluoromethyl acrylic acid anhydride. The amount used is 1 to 100 equivalents relative to the raw material (the required acryloyloxy group content is 1 equivalent), preferably 1 to 10 equivalents. If it is less than that, the yield decreases, and if it is more than that, it is not economical.

  In order to react the adamantane dialcohol compound and the acrylic acid compound quickly and in a high yield, it is preferable that an additive is present. When an acid halide or an acrylic anhydride is used as the acrylic acid compound, it is desirable that a base compound is present as an additive. That is, when an acid halide compound or acrylic acid anhydride represented by acrylic acid chloride or methacrylic acid chloride, acrylic acid anhydride or methacrylic acid anhydride is used as the acrylic acid compound, the reaction proceeds rapidly when a base compound is present together. Thus, the target substance can be obtained in high yield. In this case, the target substance can be obtained in a sufficiently high yield even if it is easily desorbed by the acid catalyst. As the base compound to be added, an amine compound is desirable as the organic base. Examples include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, diisopropylamine, tri-n-propylamine, n-butylamine, di-n-butylamine, diisobutyl. Amine, tri-n-butylamine, diphenylamine, 1,5-diazabicyclo [4.3.0] nonene-5, 1,5-diazabicyclo [5.4.0] undecene-5, diazabicyclo [2.2.2] Examples include amines such as octane, and triethylamine is particularly effective. In addition, anilines such as aniline, methylaniline, dimethylaniline, toluidine, anisidine, chloroaniline, bromoaniline, nitroaniline and aminobenzoic acid, pyridines such as dimethylaminopyridine, nitrogen containing pyrroles, quinolines and piperidines Heterocyclic compounds, metal alkoxides such as sodium methoxide, lithium methoxide, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, trimethyl-n-propylammonium hydroxide, ethylammonium sulfate, trimethylammonium nitrate, An amine sulfate such as anilinium chloride, nitrate, chloride, an inorganic base such as sodium bicarbonate, and a Grignard reagent such as ethyl magnesium bromide may be present in the reaction solution.

  The amount of these additives used is preferably 10 equivalents or less relative to the raw material. No more addition effect. There are no particular restrictions on the method of adding the base compound. Although it may be charged in advance before adding the acrylic acid compound, or may be added after charging the acrylic acid compound, it is usually desirable to add it dropwise at the same time as the acrylic acid compound. In that case, it is desirable to control the reaction temperature so that the reaction temperature does not rise abnormally, because the progress of the side reaction can be suppressed. A solvent having high solubility of the raw material and the target substance is desirable. Examples thereof include halogen compounds such as dichloromethane, chloroform and 1,2-dichloroethane, ether compounds such as tetrahydrofuran, diethyl ether and methyl t-butyl ether, and hydrocarbon compounds such as benzene and hexane. The reaction temperature is -70 to 200 ° C, preferably -50 to 80 ° C. When it is lower than −70 ° C., the reaction rate is lowered, and when it is higher than 200 ° C., it becomes difficult to control the reaction or side reaction proceeds to lower the yield.

  When an acrylic acid compound typified by acrylic acid or methacrylic acid is used as the acrylic acid compound, a production method by removing by-product water during the reaction with an azeotropic or dehydrating agent using an acid catalyst is desirable. . A Dean-Stark water separator or the like can be used to remove water by azeotropic distillation. As the acid catalyst, sulfuric acid or the like is preferable as the inorganic acid, and benzenesulfonic acid or p-toluenesulfonic acid is preferable as the organic acid. Known dehydrating agents can be used, such as concentrated sulfuric acid, boron trifluoride etherate, trifluoroacetic anhydride, dicyclohexylcarbodiimide, 2-halobenzothiazolium fluoroborate, 2-halogenated pyridinium salt, triphenylphosphine. / Carbon tetrachloride, thionyl chloride / base compound and the like are preferable.

  As the solvent, when water to be generated is removed by azeotropic distillation, a solvent that has low compatibility with water and high solubility of the target substance and is inert to the reaction of the present invention is selected. Moreover, in order to remove water by-produced during the reaction, it is preferable to use a solvent azeotropic with water. Examples of such organic solvents include, for example, aliphatic hydrocarbons having 6 to 10 carbon atoms such as hexane, heptane, octane, nonane, decane, and the like and 6 to 6 carbon atoms such as cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane. 10 alicyclic hydrocarbons and aromatic hydrocarbons such as benzene, toluene and xylene. When using a dehydrating agent, nitriles such as acetonitrile and benzonitrile, amides such as formamide, acetamide, dimethylformamide and dimethylacetamide, halogenated hydrocarbons, nitro compounds, esters such as ethyl acetate, diethyl ether, diisopropyl And ethers such as ether and dioxane. These solvents can be used alone or in a system in which two or more solvents are mixed. The solvent is used in a proportion of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, with respect to 1 part by weight of the raw material. The reaction temperature in the present invention is the azeotropic temperature of the organic solvent used and water in the case of azeotropic dehydration. When using a dehydrating agent, it is not restricted to this. When the reaction temperature is lower than 60 ° C., the reaction rate is remarkably reduced. When the reaction temperature is higher than 150 ° C., the selectivity of the target substance is reduced.

  When an acrylic acid compound such as methyl acrylate or methyl methacrylate is used as the acrylic acid compound, the corresponding alcohol (methanol in the case of a methoxy group, ethanol in the case of an ethoxy group) is known such as distillation To remove it from the reaction system to obtain the target substance. Examples of the metal and derivatives thereof include metals such as tin, titanium, germanium, zinc, lead, cobalt, iron, zirconium, manganese, antimony, and potassium, and derivatives thereof. Derivatives are preferably halogen compounds, oxides, carbonates, metal alkoxides, carboxylates and the like. The reaction temperature 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, halogen compounds such as dichloromethane, chloroform, 1,2-dichloroethane, ether compounds such as tetrahydrofuran, diethyl ether, methyl t-butyl ether, hydrocarbon compounds such as benzene, toluene, hexane, heptane, acetonitrile, etc. A nitrile compound is mentioned.

  Further, the esterification reaction may be carried out after the hydroxyl group of the adamantane dialcohol compound is converted to an alcoholate state with an alkali metal such as lithium or sodium, an alkyl lithium such as butyl lithium, or a Grignard reagent such as ethyl magnesium bromide. . 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. Further, after the reaction between 1,3-adamantane dicarboxylic acid and its derivative and the organometallic compound, such a state is obtained, and the esterification reaction can be carried out as it is without taking out the adamantane dialcohol. The reaction time in the esterification of the present invention requires 0.5 to 1000 hours, preferably 1 to 100 hours. The reaction time depends on the reaction temperature, the esterification method, etc., and is determined according to the desired yield, and is not limited to the above range.

  A polymerization inhibitor may be added during the esterification step. The polymerization inhibitor is not particularly limited as long as it is general, and 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. As addition amount, it is 0.001 to 10 weight% with respect to an acrylic acid compound, Preferably it is 0.01 to 1 weight%.

  After completion of the reaction, the reaction solution is washed with water to remove excess acrylic acid compounds, acids, bases and other additives. At this time, the washing water may contain an appropriate inorganic salt such as sodium chloride or sodium bicarbonate. Moreover, unreacted acrylic acid compounds are removed by alkali washing. Examples of the alkali cleaning include an aqueous sodium hydroxide solution, a potassium hydroxide solution, and aqueous ammonia, but there are no particular restrictions on the alkaline component used. 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. Further, when washing, an organic solvent may be added to the reaction solution according to the physical properties of the compound represented by the formula (1). The organic solvent to be added may be the same as that used in the reaction or may be different, but it is usually desirable to use a solvent with a low polarity that is easily separated from water.

  Each reaction step in the present invention can be carried out under normal pressure, reduced pressure or increased pressure. 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, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization and column chromatography, or a separation means combining these.

  The compound represented by the formula (1) thus produced is specifically 2-methacryloyloxy-2- (3- (2-methacryloyloxy-2-propyl) -1-adamantyl) propane. 2-acryloyloxy-2- (3- (2-acryloyloxy-2-propyl) -1-adamantyl) propane, 2-perfluoroacryloyloxy-2- (3- (2-perfluoroacryloyl) Oxy-2-propyl) -1-adamantyl) propane, 2- (α-trifluoro) acryloyloxy- (3- (2- (α-trifluoro) acryloyloxy-2-propyl) -1-adamantyl) Propane, 2- (meth) acryloyloxy-2- (3- (2- (meth) acryloyloxy-2-propyl) -5-hydro Xyl-1-adamantyl) propane, 2- (meth) acryloyloxy-2- (3- (2- (meth) acryloyloxy-2-butyl) -1-adamantyl) butane, 2- (meth) acryloyl Oxy-3- (3- (2- (2- (meth) acryloyloxy-3-pentyl) -1-adamantyl) pentane, 2- (meth) acryloyloxy-2- (3- (2- (meth) acryloyl) Oxy-2-propyl) -5,7-dimethyl-1-adamantyl) propane, 2- (meth) acryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane, 2 -Hydroxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane and the like. Particularly, as a raw material of the functional resin composition, 2-methacryloyloxy-2- (3- (2-methacryloyloxy-2-propyl) -1-adamantyl) propane, 2-acryloyloxy-2- (3 -(2-acryloyloxy-2-propyl) -1-adamantyl) propane, 2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane, 2-acryloyl Oxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane is preferred.

  The functional resin composition of the present invention can be produced by homopolymerizing or copolymerizing these repeating units. In polymerization, generally, a repeating unit is dissolved in a solvent, a catalyst is added, and a polymerization reaction is performed 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. In the polymerization of the functional resin composition of the present invention, radical polymerization using a radical generator such as azoisobutyronitrile, ionic polymerization using a catalyst such as alkyl lithium, and the like are common. The method can be performed according to a conventional method.

In this invention, the following are mentioned as a raw material of a copolymer with the compound represented by Formula (1). 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 2- (meth) acryloyloxy-2- (1-adamantyl) propane, 2- (meth) acryloyloxy Adamantyl acrylate derivatives such as 2- (1-adamantyl) butane and 3- (meth) acryloyloxy-3- (1-adamantyl) pentane, hydroxystyrene, α-methylstyrene, 4-t-butoxystyrene, 4- Hydroxystyrene derivatives such as t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2-t-butoxycarbonylethyloxy) styrene, t-butyl (meth) acrylate, (meth) acrylic acid Isobornyl, tris (meth) acrylic acid Rhodecanyl, β- (meth) acryloyloxy γ-butyrolactone, β- (meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acrylic Royloxy-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 ] nonane-3-one), 6- (meth) acryl Royloxy 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one and the like can be mentioned. Other repeating units may be present alone or in combination of two or more.

  The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) of the functional resin composition of the present invention is preferably 1,000 to 150,000, more preferably 3. , 100,000 to 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, a functional resin composition can be used individually or in mixture of 2 or more types.

  The functional resin composition of the present invention contains the above polymer compound for functional resin composition and a photoacid generator in a solvent. Commonly used resin solvents include, for example, 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, etc. 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 Ethylene glycol mono, such as glycol monomethyl ether and ethylene glycol monoethyl ether Examples include alkyl ethers such as alkyl ethers, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, esters such as ethyl acetate and ethyl lactate, alcohols such as cyclohexanol and 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 acid 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.

  Examples of the photoacid generator that can be used in the far ultraviolet region include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, and diazomethane compounds. Among these, onium salt compounds such as sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, and pyridinium salts are suitable for an ArF excimer laser having a laser wavelength of 193 nm.

  Specific examples of photoacid generators that can be suitably used for an ArF excimer laser wavelength of 193 nm include triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, and (hydroxyphenyl). ) Benzylmethylsulfonium toluenesulfonate, diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, and the like.

  An acid diffusion controlling 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 an acid 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; trialkylamines such as triethylamine Aromatic amines such as aniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, etc .; amine compounds such as ethylenediamine, formamide, N, In addition to amide compounds such as N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, urea compounds such as urea, imidazoles such as imidazole and benzimidazole, pyridines such as pyridine and 4-methylpyridine, 1 , 4-Diazabicyclo [2 2.2] 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 Industry), 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 functional 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, metal, or plastic. Then, a resist film is formed by coating on a substrate such as glass or ceramic. In some cases, after a heat treatment at a temperature of about 50 ° C. to 200 ° C. in advance, exposure is performed through a predetermined mask pattern. The thickness of the coating film is, for example, about 0.1 to 20 μm, preferably about 0.3 to 2 μm. For the exposure, light of various wavelengths, such as ultraviolet rays and X-rays, can be used. For example, as a light source, an F ₂ excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), or a KrF excimer laser (wavelength 248 nm). ) And other extreme ultraviolet rays, extreme ultraviolet rays (wavelength 13 nm), X-rays, electron beams and the like are appropriately selected and used. Further, the exposure conditions such as the exposure amount are appropriately selected according to the composition of the functional resin composition, the type of each additive, and the like.

  In the present invention, 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-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane was carried out by the method described later. First, 100 g of 1,3-dihydroxyadamantane was synthesized from adamantane by the method described in JP-A No. 2002-167342. Next, 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane and 800 g of 96% sulfuric acid were charged into a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser, and 300 g of formic acid was added for 1 hour. The solution was added dropwise, and then reacted at 25 ° C. for 10 hours. The precipitated crystals were separated by filtration and washed with water to obtain 140 g of 1,3-adamantane dicarboxylic acid. Next, 140 g of 1,3-adamantane dicarboxylic acid, 12 g of 96% sulfuric acid, 200 g of methanol, and 1000 mL of 1,2-dichloroethane were added to a four-necked flask equipped with a stirrer, a thermometer, and a Dimroth condenser. Reacted for hours.

  After the reaction, the organic layer and the aqueous layer were separated, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution. The organic layer was concentrated, and the resulting crystals were filtered to obtain 150 g of methyl 1,3-adamantane dicarboxylate. Next, 100 g of methyl 1,3-adamantane dicarboxylate and 500 mL of tetrahydrofuran are charged into a four-necked flask equipped with a stirrer, a thermometer, a Dimroth cooler, and a dropping funnel, and 600 mL of a 3M methylmagnesium bromide / diethyl ether solution is added. It was added dropwise over time. Then, it stirred at 25 degreeC for 3 hours, water was added, reaction was stopped, and the organic layer and the water layer were isolate | separated. The organic layer was concentrated to obtain 90 g of 1,3-adamantane diisopropanol.

Next, 90 g of 1,3-adamantane diisopropanol and 100 mL of 1,2-dichloroethane were charged into a five-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser, and two dropping funnels, and 63 g of methacrylic acid chloride and 81 g of triethylamine were added. It was dripped simultaneously over 1 hour. Then, it stirred at 25 degreeC for 3 hours, water was added and reaction was stopped. The organic layer and the aqueous layer are separated, and the organic layer is washed with ion-exchanged water, filtered and concentrated, purified by silica gel column chromatography, and 2-methacryloyloxy-2- ( 80 g of 3- (2-hydroxy-2-propyl) -1-adamantyl) propane was obtained (referred to as compound A. Identified by ¹ H-NMR and ¹³ C-NMR, see FIGS. 1 and 2).

Synthesis example 1
2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane 60 g, 2-methyl-2-adamantyl methacrylate 70 g, methacryloyloxy-γ-butyrolactone 30 g, azobisisobuty After dissolving 6 g of ronitrile in 160 g of methyl isobutyl ketone, the reaction temperature was maintained at 70 ° C. in a nitrogen atmosphere and polymerization was performed for 16 hours. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to solidify and purify the produced resin, and the produced white powder was filtered and dried at 50 ° C. under reduced pressure overnight. The obtained resin had Mw of 11,500 and Mw / Mn of 1.6. As a result of ¹³ C-NMR analysis, 2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane: 2-methyl-2-adamantyl methacrylate: methacryloyloxy-γ-butyrolactone copolymer molar ratio was 30:50:20. This resin was referred to as Resin A.

Synthesis example 2
2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane 50 g, methacryloyloxy-γ-butyrolactone 30 g, and azobisisobutyronitrile 3 g were dissolved in methyl isobutyl ketone 80 g. Then, polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to solidify and purify the produced resin, and the produced white powder was filtered and dried at 50 ° C. under reduced pressure overnight. The obtained resin had Mw of 12,300 and Mw / Mn of 1.5. As a result of ¹³ C-NMR analysis, 2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-Adamantyl) propane: methacryloyloxy-γ-butyrolactone copolymer molar ratio was 60:40. This resin was designated as Resin B.

Synthesis example 3
After dissolving 50 g of 2-methyl-2-adamantyl methacrylate, 50 g of 3-hydroxy-1-adamantyl methacrylate, 40 g of methacryloyloxy-γ-butyrolactone and 6 g of azobisisobutyronitrile in 160 g of methyl isobutyl ketone, The reaction temperature was kept at 70 ° C. and polymerization was carried out for 16 hours. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to solidify and purify the produced resin, and the produced white powder was filtered and dried at 50 ° C. under reduced pressure overnight. The obtained resin had Mw of 11,000 and Mw / Mn of 1.6. As a result of ¹³ C-NMR analysis, 2-methyl-2-adamantyl methacrylate: 3-hydroxy-1-adamantyl methacrylate: methacryloyloxy -Γ-butyrolactone was 40:35:25. This resin was designated as Resin C.

Example 2
About resin A obtained in Synthesis Example 1, 100 parts by weight and 10 parts by weight of triphenylsulfonium hexafluoroantimonate are mixed with ethyl lactate as a solvent to prepare a resin composition for photoresist having a resin concentration of 15% by weight. did. This photoresist resin composition was applied to a silicon wafer by a spin coating method to form a photosensitive layer having a thickness of 0.5 μm. After pre-baking on a hot plate at a temperature of 100 ° C. for 150 seconds, using an ArF excimer laser with a wavelength of 193 nm, exposure was performed at a dose of 20 mJ / cm ² through a mask, followed by post-baking at a temperature of 100 ° C. for 60 seconds. Next, the film was developed with a 0.3M tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water to obtain a 0.20 μm line and space pattern.

Example 3
The same operation as in Example 2 was performed except that the resin B obtained in Synthesis Example 2 was used instead of the resin A, and the obtained pattern was evaluated.

Comparative Example 1
The same operation as in Example 2 was performed except that the resin C obtained in Synthesis Example 3 was used instead of the resin A, and the obtained pattern was evaluated.
For the resists formed of the resins A, B, and C, the difference (line edge roughness) between the widest and narrowest line width was examined by SEM. As a result, the resin A containing 2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane has a small line edge roughness and accurately forms a fine pattern. I was able to. Good results were also obtained for Resin B containing 2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane and having a reduced number of components. Further, when the etching rate with respect to CF ₄ gas was examined on the obtained film after pre-baking using a reactive etching apparatus, a good result was obtained. Moreover, in the observation by SEM, since peeling of a pattern etc. was not seen, it has confirmed that it was excellent also in the board | substrate adhesiveness. Line edge roughness, etching rate, and substrate adhesion were all superior to the existing resin C.

Substrate adhesion: By observing peeling by SEM, superiority or inferiority was given in the order of ◎, ○, △.

Example 4
Synthesis of 2-methacryloyloxy-2- (3- (2-methacryloyloxy-2-propyl) -1-adamantyl) propane was carried out by the method described later. First, 100 g of 1,3-dihydroxyadamantane was synthesized from adamantane by the method described in JP-A No. 2002-167342. Next, 100 g of 1,3-dihydroxyadamantane, 500 mL of 1,2-dichloroethane, and 800 g of 96% by weight sulfuric acid were charged into a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a Dimroth condenser, and 300 g of formic acid was added. The solution was added dropwise over a period of time, and then reacted at 25 ° C. for 10 hours. The precipitated crystals were separated by filtration and washed with water to obtain 140 g of 1,3-adamantane dicarboxylic acid.

Next, 140 g of 1,3-adamantane dicarboxylic acid, 12 g of 96% sulfuric acid, 200 g of methanol, and 1000 mL of 1,2-dichloroethane were added to a four-necked flask equipped with a stirrer, a thermometer, and a Dimroth condenser. Reacted for hours. After the reaction, the organic layer and the aqueous layer were separated, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution. The organic layer was concentrated, and the resulting crystals were filtered to obtain 150 g of methyl 1,3-adamantane dicarboxylate. Next, 100 g of methyl 1,3-adamantane dicarboxylate and 500 mL of tetrahydrofuran are charged into a four-necked flask equipped with a stirrer, a thermometer, a Dimroth cooler, and a dropping funnel, and 600 mL of a 3M methylmagnesium bromide / diethyl ether solution is added. It was added dropwise over time. Then, it stirred at 25 degreeC for 3 hours, water was added, reaction was stopped, and the organic layer and the water layer were isolate | separated. The organic layer was concentrated to give 90 g of 1,3-adamantane diisopropanol (identified by ¹ H-NMR and ¹³ C-NMR).

Next, 90 g of 1,3-adamantane diisopropanol and 100 mL of 1,2-dichloroethane were charged into a five-necked flask equipped with a stirrer, a thermometer, a Dimroth cooler, and two dropping funnels, and 126 g of methacrylic acid chloride and 162 g of triethylamine were added. It was dripped simultaneously over 1 hour. Then, it stirred at 25 degreeC for 3 hours, water was added and reaction was stopped. The organic layer and the aqueous layer are separated, and the organic layer is washed with ion-exchanged water, filtered and concentrated, purified by silica gel column chromatography, and 2-methacryloyloxy-2- ( 80 g of 3- (2-methacryloyloxy-2-propyl) -1-adamantyl) propane (identified by ¹ H-NMR and ¹³ C-NMR, referred to as compound B) was obtained (see FIGS. 3 and 4). ).

Moreover, 10 g of 2-methacryloyloxy-2- (3- (2-hydroxy-2-propyl) -1-adamantyl) propane was obtained (identified by ¹ H-NMR and ¹³ C-NMR).
The effect of adding Compound B was examined. As a base resin, a terpolymer of 2-methyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, and methacryloyloxy-γ-butyrolactone was used. 2-methyl-2-adamantyl methacrylate 50 g, 3-hydroxy-1-adamantyl methacrylate 50 g, methacryloyloxy-γ-butyrolactone 40 g, and azobisisobutyronitrile 6 g are dissolved in methyl isobutyl ketone 160 g, and compound B 1 g Added. The polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After polymerization, the reaction solution was dropped into a large amount of n-hexane to solidify and purify the produced resin, and the produced white powder was filtered and dried overnight at 50 ° C. under reduced pressure to copolymerize Compound B. A resin was obtained. Moreover, the resin which does not add a compound was also obtained for the comparison.

About two kinds of obtained resins, 100 parts by weight and 10 parts by weight of triphenylsulfonium hexafluoroantimonate are mixed with ethyl lactate as a solvent to prepare a resin composition for photoresist having a resin concentration of 15% by weight. did. This photoresist resin composition was applied to a silicon wafer by a spin coating method to form a photosensitive layer having a thickness of 0.5 μm. After pre-baking on a hot plate at a temperature of 100 ° C. for 150 seconds, using an ArF excimer laser with a wavelength of 193 nm, exposure was performed at a dose of 20 mJ / cm ² through a mask, followed by post-baking at a temperature of 100 ° C. for 60 seconds. Next, the film was developed with a 0.3M tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water to obtain a 0.20 μm line and space pattern. As a result, a pattern with higher contrast was obtained with the resin to which compound B was added than with the resin to which nothing was added.

The adamantane derivative of the present invention is useful as a cross-linked resin, 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).

¹ H-NMR of compound A in Example 1, 270 MHz, CDCl ₃ ¹³ C-NMR of compound A in Example 1, 270 MHz, CDCl ₃ ¹ H-NMR of compound B in Example 4, 270 MHz, CDCl ₃ ¹³ C-NMR of compound B in Example 4, 270 MHz, CDCl ₃

Claims (2)

The compound represented by Formula (1).
(Wherein X is the same or different and represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, or a hydrocarbyl group having a hydroxyl group, a halogen group, a nitrile group, or an ether group, and n ₁ is And R _{1 to} R ₄ are the same or different and each represents an alkyl group, and Y ₁ and Y ₂ are the same or different and represent a hydrogen atom or a group represented by the formula (2). And at least one of the formulas (2).
(R _{5 to} R ₇ are the same or different and each represents a hydrogen atom or an alkyl group). The functional resin composition which contains the component represented by Formula (3) in a repeating unit.
(Wherein X is the same or different and represents a hydrogen atom, an alkyl group, a halogen-containing alkyl group, a halogen group, or a hydrocarbyl group having a hydroxyl group, a halogen group, a nitrile group, or an ether group, and n ₁ is Represents an integer of _{1 to} 14. R _{1 to} R ₄ are the same or different and each represents an alkyl group, and Y ₃ and Y ₄ are the same or different and represent a hydrogen atom or formula (4), and at least one Is the formula (4).)
(R5 to R7 are the same or different and each represents a hydrogen atom or an alkyl group).