JP2005029520A - Polymerizable adamantane derivative, macromolecular compound, resin composition for photoresist, and method for producing semiconductor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymerizable monomer capable of imparting adhesion to a substrate, proper hydrophilicity and transparency to a polymer for a photoresist. <P>SOLUTION: The polymerizable adamantane derivative is represented by formula (1a) or (1b) (wherein, R<SP>1</SP>and R<SP>2</SP>are each a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group; R<SP>3</SP>is a fluorine atom or a fluoroalkyl group; and the ring in the formula may have a substituent). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymerizable adamantane derivative useful as a monomer component for a photoresist resin used when performing microfabrication of a semiconductor, a polymer compound containing a repeating unit corresponding to a polymerizable adamantane derivative having a specific structure, The present invention relates to a photoresist resin composition containing a polymer compound and a method for producing a semiconductor using the resin composition.

  The photoresist resin used in the semiconductor manufacturing process is soluble in an alkali developer by desorbing due to an acid generated from a photoacid generator upon exposure to a portion showing adhesion to a substrate such as a silicon wafer. This part is necessary. In addition, the photoresist resin needs to have resistance to dry etching.

  Conventionally, an alicyclic hydrocarbon skeleton containing a lactone ring is known as a structure that provides substrate adhesion and has dry etching resistance (see Patent Document 1). Moreover, an alicyclic hydrocarbon skeleton containing a tertiary carbon atom has been proposed as a structure that imparts acid detachability and has dry etching resistance (see Patent Document 2). Therefore, by copolymerizing these two skeleton monomers, it is possible to obtain a polymer in which the functions necessary for the photoresist resin are integrated. Such a copolymer has substrate adhesion, acid detachment property, and dry etching resistance, but has a very low polarity and low hydrophilicity because it has an alicyclic hydrocarbon skeleton. Problems such as being difficult to dissolve in the solvent and difficult to dissolve in the alkali developer after the exposure are likely to occur, and the performance balance as a resist resin is poor.

On the other hand, lithography exposure light sources used for semiconductor manufacturing have become shorter in wavelength year by year, and have shifted from KrF excimer lasers with a wavelength of 248 nm to ArF excimer lasers with a wavelength of 193 nm. _Two excimer lasers are promising. Resins used for conventional resists for KrF excimer laser exposure and ArF excimer laser exposure do not exhibit sufficient transparency to vacuum ultraviolet light (light having a wavelength of 190 nm or less). Therefore, several high molecular compounds containing fluorine atoms in the molecule have been proposed as such highly transparent resins for vacuum ultraviolet light (Patent Documents 3 to 9, etc.). However, even these resins do not necessarily have sufficient transparency (transparency) to vacuum ultraviolet light. In addition, few resins have a good balance of properties such as acid detachability, dry etching resistance, substrate adhesion, and solubility (hydrophilicity) in resist solvents and alkaline developers.

JP 2000-26446 A JP-A-9-73137 Japanese Patent Laid-Open No. 2002-6501 JP 2002-155118 A JP 2002-179731 A JP 2002-220419 A JP 2002-293840 A JP 2002-327013 A JP 2003-2925 A

  An object of the present invention is to provide a novel polymerizable adamantane derivative capable of imparting substrate adhesion, hydrophilicity and transparency to a polymer for photoresist, a polymer compound containing a repeating unit corresponding to a specific polymerizable adamantane derivative, It is providing the resin composition for photoresists containing a high molecular compound, and the manufacturing method of the semiconductor using this resin composition.

  Another object of the present invention is to provide a novel polymerizable monomer that can be easily copolymerized with other monomers for imparting various functions required as a photoresist.

  Still another object of the present invention is to use a polymer compound excellent in substrate adhesion and hydrophilicity, or these characteristics and transparency, a resin composition for photoresist containing the polymer compound, and the resin composition. Another object of the present invention is to provide a semiconductor manufacturing method.

  Another object of the present invention is to provide a polymer compound having well-balanced properties such as transparency to light used for exposure, substrate adhesion, moderate hydrophilicity, acid detachment properties, and etching resistance, and the polymer. An object of the present invention is to provide a photoresist resin composition containing a compound and a method for producing a semiconductor using the resin composition.

  Still another object of the present invention is to provide a photoresist resin composition capable of forming a fine pattern with high accuracy, and a semiconductor manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventors have found a novel polymerizable monomer having an adamantane skeleton, and by subjecting this monomer to polymerization, the substrate adhesion and hydrophilicity are improved. Excellent and high polymer compound with high transparency to light with a wavelength of 300 nm or less, particularly vacuum ultraviolet light, and transparency to light used for exposure and moderate hydrophilicity by copolymerization with other monomers The present inventors have found that a polymer compound having a good balance of various properties such as acid detachability, etching resistance and substrate adhesion can be produced. The present invention has been completed based on these findings.

（式中、Ｒ¹、Ｒ²は、それぞれ、水素原子、フッ素原子、アルキル基又はフルオロアルキル基を示し、Ｒ³はフッ素原子又はフルオロアルキル基を示す。式中の環は置換基を有していてもよい）
で表される重合性アダマンタン誘導体を提供する。 That is, the present invention provides the following formula (1a) or (1b)

(In the formula, R ¹ and R ² each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and R ³ represents a fluorine atom or a fluoroalkyl group. The ring in the formula has a substituent. May be)
A polymerizable adamantane derivative represented by the formula:

（式中の環は置換基を有していてもよい）
で表されるアダマンタノール類と、下記式（３）

（式中、Ｒ¹、Ｒ²は、それぞれ、水素原子、フッ素原子、アルキル基又はフルオロアルキル基を示し、Ｒ³はフッ素原子又はフルオロアルキル基を示す）
で表される不飽和カルボン酸又はその反応性誘導体とを反応させて、下記式（1a）又は（1b）

（式中、Ｒ¹、Ｒ²、Ｒ³は前記に同じ。式中の環は置換基を有していてもよい）
で表される化合物を得ることを特徴とする重合性アダマンタン誘導体の製造法を提供する。 The present invention also provides the following formula (2a) or (2b)

(The ring in the formula may have a substituent)
An adamantanol represented by the following formula (3)

(Wherein R ¹ and R ² each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and R ³ represents a fluorine atom or a fluoroalkyl group)
Is reacted with an unsaturated carboxylic acid represented by the following formula (1a) or (1b)

(In the formula, R ¹ , R ² and R ³ are the same as above. The ring in the formula may have a substituent)
A method for producing a polymerizable adamantane derivative, characterized in that a compound represented by the formula:

（式中、Ｒ¹、Ｒ²、Ｒ⁴は、それぞれ、水素原子、フッ素原子、アルキル基又はフルオロアルキル基を示し、ｎは０又は１を示す。但し、ｎ＝１の時は、Ｒ⁴はフッ素原子又はフルオロアルキル基である。式中の環は置換基を有していてもよい）
で表される重合性アダマンタン誘導体に対応する繰り返し単位を含む高分子化合物を提供する。 The present invention further includes the following formula (4a) or (4b):

(Wherein R ¹ , R ² and R ⁴ each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and n represents 0 or 1, provided that when n = 1, R ⁴ Is a fluorine atom or a fluoroalkyl group, and the ring in the formula may have a substituent)
The high molecular compound containing the repeating unit corresponding to the polymerizable adamantane derivative represented by these is provided.

［式（5a）中、環Ｚ¹は下記式（6a）、（6b）、（6c）、（6d）、（6e）、（6f）、（6g）又は（6h）

（式中、Ｙ¹はアルキレン基、酸素原子又は硫黄原子を示し、Ｙ²、Ｙ³、Ｙ⁴、Ｙ⁵は、それぞれ、アルキレン基、酸素原子、硫黄原子又は無結合を示す。ａ、ｃ、ｄ、ｅは、それぞれ、０〜３の整数を示し、ｂは１又は２を示す。式中の環は置換基を有していてもよい）
で表される何れかの環を示し、Ｗ¹は２価の炭化水素基を示す。Ｒ⁵、Ｒ⁶、Ｒ⁷は、それぞれ、水素原子、フッ素原子、アルキル基又はフルオロアルキル基を示す。ｐは０又は１を示し、ｑは１〜８の整数を示す。ｑが２以上の場合、ｑ個の括弧内の基は同一であってもよく異なっていてもよい。式（5b）中、Ｒ⁸は置換基を有していてもよいアルキル基を示す。Ｒ⁵、Ｒ⁶、Ｒ⁷は前記に同じ。ｒは１〜８の整数を示す。ｒが２以上の場合、ｒ個の括弧内の基は同一であってもよく異なっていてもよい］
で表されるアクリル酸エステル系単量体［但し、式（4a）、（4b）で表される化合物を除く］に対応する繰り返し単位、下記式（7a）又は（7b）

［式（7a）中、環Ｚ²は下記式（6a）、（6b）、（6c）、（6d）、（6e）、（6f）、（6g）又は（6h）

（式中、Ｙ¹はアルキレン基、酸素原子又は硫黄原子を示し、Ｙ²、Ｙ³、Ｙ⁴、Ｙ⁵は、それぞれ、アルキレン基、酸素原子、硫黄原子又は無結合を示す。ａ、ｃ、ｄ、ｅは、それぞれ、０〜３の整数を示し、ｂは１又は２を示す。式中の環は置換基を有していてもよい）
で表される何れかの環を示し、Ｗ²は２価の炭化水素基を示す。Ｒ⁹、Ｒ¹⁰及びＲ¹¹は、同一又は異なって、水素原子又は有機基を示す。環Ｚ²、Ｗ²、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹のうち少なくとも２つは、互いに結合して、隣接する１又は２以上の原子と共に環を形成していてもよい。ｓは０又は１を示し、ｔは１〜８の整数を示す。ｔが２以上の場合、ｔ個の括弧内の基は同一であってもよく異なっていてもよい。式（7b）中、Ｒ¹²は置換基を有していてもよいアルキル基を示し、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は、同一又は異なって、水素原子又は有機基を示す。Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵のうち少なくとも２つは、互いに結合して、隣接する１又は２以上の原子と共に環を形成していてもよい。ｕは１〜８の整数を示す。ｕが２以上の場合、ｕ個の括弧内の基は同一であってもよく異なっていてもよい］
で表されるビニルエーテル系単量体［但し、式（4a）、（4b）で表される化合物を除く］に対応する繰り返し単位、下記式（8a）又は（8b）

［式（8a）、（8b）中、Ｙ⁶、Ｙ⁷は、それぞれ、アルキレン基、酸素原子、硫黄原子又は無結合を示す。Ｙ⁸は酸素原子又は−ＮＨ−基を示す。ｆは０〜３の整数を示す。式中の環を構成する原子は置換基を有していてもよい）
で表される環状不飽和単量体に対応する繰り返し単位などを含んでいてもよい。 This polymer compound may further contain a repeating unit having an acid-eliminating function. In addition, the polymer compound further has the following formula (5a) or (5b)

[In the formula (5a), the ring Z ¹ is represented by the following formula (6a), (6b), (6c), (6d), (6e), (6f), (6g) or (6h)

(Wherein Y ¹ represents an alkylene group, an oxygen atom or a sulfur atom, and Y ² , Y ³ , Y ⁴ and Y ⁵ represent an alkylene group, an oxygen atom, a sulfur atom or no bond, respectively. A, c , D and e each represent an integer of 0 to 3, and b represents 1 or 2. The ring in the formula may have a substituent.
And W ¹ represents a divalent hydrocarbon group. R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group. p represents 0 or 1, and q represents an integer of 1 to 8. When q is 2 or more, the groups in q parentheses may be the same or different. In formula (5b), R ⁸ represents an alkyl group which may have a substituent. R ⁵ , R ⁶ and R ⁷ are the same as above. r shows the integer of 1-8. when r is 2 or more, the groups in r parentheses may be the same or different.]
A repeating unit corresponding to an acrylate monomer represented by the formula (excluding compounds represented by formulas (4a) and (4b)), the following formula (7a) or (7b)

[In the formula (7a), ring Z ² represents the following formula (6a), (6b), (6c), (6d), (6e), (6f), (6g) or (6h)

(Wherein Y ¹ represents an alkylene group, an oxygen atom or a sulfur atom, and Y ² , Y ³ , Y ⁴ and Y ⁵ represent an alkylene group, an oxygen atom, a sulfur atom or no bond, respectively. A, c , D and e each represent an integer of 0 to 3, and b represents 1 or 2. The ring in the formula may have a substituent.
And W ² represents a divalent hydrocarbon group. R ⁹ , R ¹⁰ and R ¹¹ are the same or different and each represents a hydrogen atom or an organic group. At least two of the rings Z ² , W ² , R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring together with one or more adjacent atoms. s represents 0 or 1, and t represents an integer of 1 to 8. When t is 2 or more, the groups in t parentheses may be the same or different. In formula (7b), R ¹² represents an alkyl group which may have a substituent, and R ¹³ , R ¹⁴ and R ¹⁵ are the same or different and represent a hydrogen atom or an organic group. At least two of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring together with one or more adjacent atoms. u represents an integer of 1 to 8. When u is 2 or more, the groups in u parentheses may be the same or different.]
A repeating unit corresponding to a vinyl ether monomer represented by the formula (excluding compounds represented by formulas (4a) and (4b)), the following formula (8a) or (8b)

[In formulas (8a) and (8b), Y ⁶ and Y ⁷ each represent an alkylene group, an oxygen atom, a sulfur atom, or no bond. Y ⁸ represents an oxygen atom or a —NH— group. f shows the integer of 0-3. (The atoms constituting the ring in the formula may have a substituent)
A repeating unit corresponding to the cyclic unsaturated monomer represented by

  The present invention also provides a resin composition for photoresist comprising at least the polymer compound and a photoacid generator.

  The present invention further provides a method for producing a semiconductor, comprising a step of applying the photoresist resin composition to a substrate or a substrate to form a resist coating film, and forming a pattern through exposure and development.

  The vinyl ether monomer, vinyl ether compound, and vinyl ester compound in this specification include compounds in which a hydrogen atom of a vinyl group is substituted with a substituent. In addition, the α, β-unsaturated carboxylic acid ester monomer may be referred to as an acrylic acid ester monomer or an acrylic monomer for convenience. The “organic group” in the present specification is used in a broad sense including not only a carbon atom-containing group but also a nonmetal atom-containing group such as, for example, a halogen atom, a nitro group, or a sulfonic acid group.

  ADVANTAGE OF THE INVENTION According to this invention, the novel polymerizable monomer which can provide board | substrate adhesiveness, moderate hydrophilicity, and transparency to the polymer for photoresists is provided. In addition, it is possible to impart substrate adhesion, moderate hydrophilicity, and transparency to the polymer, as well as novel polymerizability that can be easily copolymerized with other monomers to provide various functions required as a photoresist. Monomers are provided.

  The polymer compound of the present invention is excellent in substrate adhesion and hydrophilicity, and has high transparency to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light. Moreover, various properties such as transparency to light used for exposure, hydrophilicity, acid detachment, etching resistance, and substrate adhesion can be exhibited in a balanced manner. Therefore, according to a photoresist resin composition containing the polymer compound and a semiconductor manufacturing method using the resin composition, a fine pattern can be formed with high accuracy.

[Polymerized adamantane derivative]
The polymerizable adamantane derivative of the present invention is represented by the formula (1a) or (1b). These compounds are polymerized at the double bond sites shown in the formula to give polymer compounds. Since these compounds have an adamantane skeleton, they can impart etching resistance to the polymer, and since they have a hydroxyl group in the adamantane ring, they have substrate adhesion and / or hydrophilicity (resist solvent or alkali development). Solubility in a liquid). Moreover, since it has a fluorine atom or a fluoroalkyl group at the α-position of the carbonyl group of the ester, it can impart high transparency to light with a wavelength of 300 nm or less, particularly vacuum ultraviolet light, to the polymer. Furthermore, various monomers used for imparting various functions required as a photoresist (for example, acid detachability, substrate adhesion, transparency, etching resistance, etc.), such as other acrylate ester-based monomers. It is easy to copolymerize with monomers and vinyl ether monomers. Therefore, by using these compounds, for example, it is easy to obtain a polymer compound that is excellent in transparency to vacuum ultraviolet light and the like and has a good balance of properties such as acid detachability, substrate adhesion, hydrophilicity, and etching resistance. Can be prepared.

In the formulas (1a) and (1b), R ¹ and R ² each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and R ³ represents a fluorine atom or a fluoroalkyl group. Examples of the alkyl group include 1 to 1 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups. Examples include about 15 linear or branched alkyl groups.

  Examples of the fluoroalkyl group include a linear or branched fluoroalkyl group having about 1 to 15 carbon atoms in which at least one hydrogen atom of the alkyl group is substituted with a fluorine atom. Representative examples of such fluoroalkyl groups include, for example, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl. , Heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, nonafluorobutyl, tridecafluorohexyl, henicosafluorodecyl group, etc. .

R ¹ and R ² are each preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. R ³ is preferably a fluorine atom or a C 1-3 fluoroalkyl group (particularly a trifluoromethyl group).

  In the formulas (1a) and (1b), the adamantane ring in the formula may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, a hydroxy (halo) alkyl group which may be protected with a protecting group, and a protecting group. Protected with an amino group which may be protected with, a carboxyl group which may be protected with a protecting group, a sulfo group which may be protected with a protecting group, an oxo group, a nitro group, a cyano group, or a protecting group And a good acyl group.

Examples of the halogen atom include fluorine, chlorine, bromine atom and the like. Examples of the alkyl group include C _1-10 alkyl groups (preferably C _1-5 alkyl) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, and decyl groups. Group). Examples of the haloalkyl group include C _1-10 haloalkyl groups (preferably, C _1-5 haloalkyl groups) such as chloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl groups. . Examples of the aryl group include phenyl and naphthyl groups. The aromatic ring of the aryl group is, for example, a halogen atom such as a fluorine atom, a C _1-4 alkyl group such as a methyl group, a C _1-5 haloalkyl group such as a trifluoromethyl group, a C _1-4 such as a hydroxyl group or a methoxy group. It may have a substituent such as an alkoxy group such as an alkoxy group, an amino group, a dialkylamino group, a carboxyl group or a methoxycarbonyl group, an acyl group such as a nitro group, a cyano group or an acetyl group. Examples of the hydroxy (halo) alkyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, 1-hydroxy-1-methylethyl group, 2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl group [Preferably, a hydroxy-C _1-4 alkyl group, a hydroxy-C _1-4 haloalkyl group, and the like].

Examples of the hydroxyl protecting group in the hydroxyl group or hydroxy (halo) alkyl group include protecting groups commonly used in the field of organic synthesis, for example, alkyl groups (for example, C _1-4 alkyl such as methyl and t-butyl groups). Group), alkenyl group (for example, allyl group), cycloalkyl group (for example, cyclohexyl group), aryl group (for example, 2,4-dinitrophenyl group), aralkyl group (for example, benzyl group); Substituted methyl group (eg, methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuran Nyl group, 1-hydroxyalkyl group (for example, 1-hydroxyethyl group) A group capable of forming an acetal or hemiacetal group with a hydroxyl group; an acyl group (for example, a C _1-6 aliphatic acyl group such as formyl, acetyl, propionyl, butyryl, isobutyryl, pivaloyl group); an acetoacetyl group An aromatic acyl group such as a benzoyl group), an alkoxycarbonyl group (eg, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group), an aralkyloxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted silyl group ( For example, when there are two or more hydroxyl groups (including hydroxymethyl groups) in the molecule, a divalent hydrocarbon group (for example, methylene, ethylidene) which may have a substituent. Isopropylidene, cyclopentylidene, cyclohexylidene, Njiriden group, etc.), and others.

Examples of the protecting group for the amino group include an alkyl group, an aralkyl group, an acyl group, and an alkoxycarbonyl group exemplified as the protecting group for the hydroxyl group. Examples of the protecting group for carboxyl group and sulfo group include alkoxy groups (for example, C _1-6 alkoxy groups such as methoxy, ethoxy and butoxy groups), cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, Examples include a trialkylsilyloxy group, an amino group which may have a substituent, a hydrazino group, an alkoxycarbonylhydrazino group, an aralkylcarbonylhydrazino group, and the like.

Examples of the acyl group include C _1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; aromatic acyl groups such as acetoacetyl groups and benzoyl groups. As the protecting group for the acyl group, a protecting group conventionally used in the field of organic synthesis can be used. Examples of the protected form of the acyl group include acetal (including hemiacetal).

  Representative examples of the polymerizable adamantane derivative represented by the formula (1a) include 1- (2-trifluoromethyl-2-propenoyloxy) -3,5-dihydroxyadamantane, 1- (2-fluoro-2 -Propenoyloxy) -3,5-dihydroxyadamantane, 1- (2-trifluoromethyl-2-propenoyloxy) -3,5,7-trihydroxyadamantane, and the like. Further, as representative examples of the polymerizable adamantane derivative represented by the formula (1b), 1- (2-trifluoromethyl-2-propenoyloxy) -3-hydroxyadamantane, 1- (2-fluoro-2) -Propenoyloxy) -3-hydroxyadamantane, 1- (2-trifluoromethyl-2-propenoyloxy) -3-hydroxy-5,7-dimethyladamantane, and the like.

  The polymerizable adamantane derivative represented by the formula (1a) or (1b) includes an adamantanol represented by the formula (2a) or (2b) and an unsaturated carboxylic acid represented by the formula (3). Or it can obtain by making it react with the reactive derivative. The sign in the formula has the same meaning as described above.

  Examples of the reactive derivative of the unsaturated carboxylic acid represented by the formula (3) include acid halides (acid chloride, acid bromide, etc.), acid anhydrides, esters (methyl ester, ethyl ester, etc.) and the like.

  In this reaction, when an unsaturated carboxylic acid represented by the formula (3) is used as the one raw material in the reaction, an acid such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, strong acidic ion exchange resin is used as a catalyst. Used. The reaction is preferably carried out in a solvent inert to the reaction such as toluene. Further, the reaction rate can be increased by carrying out the reaction while distilling off the by-produced water. When the unsaturated carboxylic acid represented by the formula (3) is reacted with the adamantanol represented by the formula (2a), 1 mol of the adamantanol represented by the formula (2a) is used. On the other hand, it is usually about 0.1 to 10 mol, and when reacted with the adamantanol represented by the formula (2b), with respect to 1 mol of the adamantanol represented by the formula (2b), Usually, it is about 0.5 to 2 mol. The reaction temperature varies depending on the type of raw material used in the reaction, but is generally about 20 to 150 ° C.

  In the above reaction, when an acid halide or acid anhydride of an unsaturated carboxylic acid represented by the formula (3) is used as one raw material for the reaction, the reaction is usually performed in the presence of a base. Examples of the base that can be used include organic bases such as triethylamine and pyridine, and inorganic bases such as sodium hydroxide, sodium carbonate, and sodium bicarbonate. Although the usage-amount of a base is about 1-1.5 equivalent normally with respect to the acid halide or acid anhydride of unsaturated carboxylic acid represented by Formula (3), you may use a large excess amount. The reaction is preferably carried out in a solvent inert to the reaction such as toluene, methylene chloride, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide and the like. Further, an organic base such as pyridine may be used as a solvent. The use amount of the acid halide or acid anhydride of the unsaturated carboxylic acid represented by the formula (3) is usually 0.9 with respect to 1 mol of the adamantanols represented by the formula (1a) or the formula (1b). Although it is about -1.3 mol, a large excess amount may be used. The reaction temperature varies depending on the type of raw material used for the reaction, but is generally about -10 ° C to 100 ° C.

  In the above reaction, when an unsaturated carboxylic acid ester represented by the formula (3) is used as one raw material in the reaction, it is preferable to use a transesterification catalyst as a catalyst. As the transesterification catalyst, those commonly used in the field of organic synthesis such as metal compounds such as aluminum compounds and titanium compounds can be used. The reaction is preferably carried out in a solvent inert to the reaction such as toluene. The reaction may be carried out while distilling off alcohol produced as a by-product in the reaction. The amount of the unsaturated carboxylic acid ester represented by the formula (3) is usually 0.9 to 1.3 mol with respect to 1 mol of the adamantanol represented by the formula (1a) or the formula (1b). However, a large excess amount may be used. The reaction temperature varies depending on the raw material to be used, but generally can be appropriately selected from the range of about 20 to 150 ° C. In any method, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like.

[Polymer compound]
The polymer compound of the present invention contains a repeating unit (monomer unit) corresponding to the polymerizable adamantane derivative represented by the formula (4a) or (4b). The repeating unit may be one type or two or more types. Such a polymer compound can be obtained by subjecting the polymerizable adamantane derivative represented by the formula (4a) or (4b) to polymerization.

In the formula (4a) or (4b), R ⁴ represents a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and n represents 0 or 1. R ¹ and R ² are the same as described above. However, when n = 1, R ⁴ is a fluorine atom or a fluoroalkyl group. Examples of the alkyl group and fluoroalkyl group for R ⁴ include the same alkyl groups and fluoroalkyl groups as those described above for R ¹ and R ² . R ⁴ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms. When n is 0, a hydrogen atom is particularly preferable. When n is 1, Particularly preferred are a fluorine atom and a fluoroalkyl group having 1 to 3 carbon atoms (such as a trifluoromethyl group). The ring in formula (4a) or (4b) may have a substituent similar to the substituent that the ring in formula (1a) or (1b) may have.

Of the compounds represented by the formula (4a) or (4b), the compound in which n is 1 corresponds to the compound represented by the formula (1a) or (1b). Among the compounds represented by the formula (4a) or (4b), the compound in which n is 0 belongs to the vinyl ether monomer. This vinyl ether monomer is polymerized at a double bond site shown in the formula to give a polymer compound. Since this vinyl ether monomer has an adamantane skeleton, it can impart etching resistance to the polymer, and since it has a hydroxyl group in the adamantane ring, the polymer has substrate adhesion and / or hydrophilicity (resist solvent). And solubility in an alkaline developer). In particular, a compound in which at least one of R ¹ , R ² and R ⁴ is a fluorine atom or a fluoroalkyl group can impart high transparency to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light, to the polymer. Furthermore, this vinyl ether monomer is easily copolymerized with various monomers used for imparting various functions required as a photoresist. Therefore, for example, it is possible to easily prepare a polymer compound that is excellent in transparency to, for example, vacuum ultraviolet light and has a good balance of properties such as acid detachability, substrate adhesion, hydrophilicity, and etching resistance.

  Representative examples of the vinyl ether monomer include 3-vinyloxy-1-adamantanol, 5-vinyloxy-1,3-adamantanediol, 7-vinyloxy-1,3,5-adamantanetriol, 3,5- Examples include dimethyl-7-vinyloxy-1-adamantanol.

The vinyl ether monomer can be produced by a known method or by utilizing a known reaction. The vinyl ether monomer comprises vinyl esters such as vinyl acetate and vinyl propionate, and adamantanol represented by the formula (2a) or (2b) in the presence of an iridium compound catalyst, and Preferably, the adamantanol can be obtained by vinyl etherification by reacting in the presence of a base. For example, 5-vinyloxy-1,3-adamantanediol can be produced from vinyl acetate and 1,3,5-adamantanetriol. This reaction is carried out in the presence or absence of a solvent. The usage-amount of vinylesters is about 0.1-5 mol with respect to 1 mol of adamantanols, for example. As the iridium compound catalyst, for example, an organic iridium catalyst such as di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) [Ir (cod) Cl] ₂ ) can be used. The usage-amount of an iridium compound catalyst is 0.0001-1 mol with respect to 1 mol of adamantanols, Preferably it is about 0.001-0.3 mol. As the base, for example, an inorganic base such as sodium carbonate can be used. The usage-amount of a base is 0.001-3 mol with respect to 1 mol of adamantanols, Preferably it is about 0.005-2 mol. The reaction temperature can be appropriately selected according to the type of reaction components and the like, and is, for example, about 50 to 150 ° C. The reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like.

  In addition to the repeating unit corresponding to the polymerizable adamantane derivative represented by the above formula (4a) or (4b), the polymer compound of the present invention has various functions required as a resist in a sufficiently balanced manner, You may have another repeating unit. Such other repeating units can be produced by copolymerizing a polymerizable unsaturated monomer corresponding to the repeating unit and the polymerizable adamantane derivative. Examples of the other repeating unit include a repeating unit that improves the substrate adhesion and / or hydrophilic function, a repeating unit that has an acid detachment function, a repeating unit that has an etching resistance function, and a repeating unit that increases transparency. Is mentioned. In preparing the polymer compound of the present invention, a monomer used for smoothly progressing copolymerization or making the copolymer composition uniform can be used as a comonomer.

  Repeating units that enhance substrate adhesion or hydrophilic function can be introduced into the polymer by using a polymerizable unsaturated monomer having a polar group as a comonomer. Examples of the polar group include a hydroxyl group that may have a protective group, a carboxyl group that may have a protective group, an amino group that may have a protective group, and a protective group. Examples thereof include a sulfo group and a lactone ring-containing group. As the protecting group, those commonly used in the field of organic synthesis (for example, the protecting groups exemplified above) can be used. As the polymerizable unsaturated monomer having a polar group, a compound known in the resist field can be used.

  The repeating unit having an acid-eliminating function is, for example, (1) a hydrocarbon group having a tertiary carbon, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, etc., adjacent to the oxygen atom constituting the ester. (Meth) acrylic acid ester derivatives to which is bonded, and (2) hydrocarbon groups (alicyclic hydrocarbon groups, aliphatic hydrocarbon groups, groups to which these are bonded, etc.) adjacent to the oxygen atom constituting the ester. And a —COOR group (R represents a tertiary hydrocarbon group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, or the like) bonded to the hydrocarbon group directly or via a linking group. (Meth) acrylic acid ester derivatives and the like can be introduced into the polymer by using them as comonomers. Note that a carbon atom having at least one hydrogen atom bonded to the tertiary carbon adjacent position of the tertiary hydrocarbon group in R must be present. As such a (meth) acrylic acid ester derivative, a known compound in the resist field can be used.

As a representative example of the polymerizable unsaturated monomer other than the polymerizable adamantane derivative used for imparting various functions as a resist to the polymer compound of the present invention, it is represented by the formula (5a) or (5b). Acrylate monomers (excluding compounds represented by formulas (4a) and (4b)). In formula (5a), ring Z ¹ is any ^one of the above formulas (6a), (6b), (6c), (6d), (6e), (6f), (6g) or (6h) Represents a ring, and W ¹ represents a divalent hydrocarbon group. The ring in the formula may have a substituent. R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group. p represents 0 or 1, and q represents an integer of 1 to 8. When q is 2 or more, the groups in q parentheses may be the same or different. In formula (5b), R ⁸ represents an alkyl group which may have a substituent. R ⁵ , R ⁶ and R ⁷ are the same as above. r shows the integer of 1-8. When r is 2 or more, the groups in r parentheses may be the same or different.

  Among such acrylate monomers, when a compound containing a fluorine atom in the molecule is used as a comonomer, transparency to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light, can be enhanced. In addition, when using an acrylate monomer having an alicyclic carbocycle, the etching resistance of the polymer can be improved, and an acrylate monomer having a polar group in the molecule is used. In some cases, substrate adhesion and / or hydrophilicity can be improved. Furthermore, an acrylate ester monomer in which a tertiary carbon atom is bonded to an oxygen atom constituting the ester bond, or a hydrocarbon group (alicyclic hydrocarbon group) adjacent to the oxygen atom constituting the ester bond , An aliphatic hydrocarbon group, a group in which these are bonded, and the like, and -COOR group (R is a tertiary hydrocarbon group, 2-tetrahydrofuranyl group or 2-tetrahydropyranyl group) In the case of using an acrylate ester monomer in which a group or the like is bonded directly or via a linking group, an acid-eliminating function can be imparted. These acrylic monomers can be used alone or in combination of two or more.

Examples of the alkylene group in Y ¹ , Y ² , Y ³ , Y ⁴ , and Y ⁵ in the formulas (6a), (6b), (6d), and (6e) include methylene, ethylene, propylene, and trimethylene groups. And a linear or branched alkylene group having 1 to 3 carbon atoms (preferably 1 or 2). Examples of the substituent that the ring in formulas (6a) to (6h) may have include the same groups as the substituent that the adamantane ring in formula (1a) or (1b) may have. Can be mentioned. Preferable substituents include, for example, a fluorine atom, a fluoroalkyl group (for example, a C _1-10 fluoroalkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl group, etc., particularly C _1-5 fluoro Alkyl groups, etc.), alkyl groups (for example, C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups, especially C _1-5 alkyl groups) and the like. The number of substituents in each ring is about 0 to 5, preferably about 0 to 3. When there are two or more ring substituents, they may be bonded to each other to form a 4-membered or more ring, for example, a cycloalkane ring or a lactone ring, together with the carbon atoms constituting the ring.

In formula (5a), the divalent hydrocarbon group in W ¹ is a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of two or more thereof. Hydrocarbon groups. One or more monovalent hydrocarbon groups (aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or hydrocarbon group in which two or more of these are bonded) are bonded to these hydrocarbon groups. It may be. The divalent hydrocarbon group includes a hydrocarbon group having a substituent. Examples of the substituent include the same groups as the substituent that the adamantane ring in the formula (1a) or (1b) may have.

  Representative examples of divalent hydrocarbon groups include, for example, alkylene groups such as methylene, methylmethylene, ethylmethylene, dimethylmethylene, ethylmethylmethylene, ethylene, propylene, trimethylene, and tetramethylene groups; alkenylene groups such as propenylene groups Cycloalkylene group such as 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene group; cyclopropylene, cyclopentylidene, cyclohexylidene group; And arylene groups such as a phenylene group; benzylidene groups; and groups in which at least one of hydrogen atoms of these groups is substituted with a fluorine atom.

（式中、Ｒ¹⁶及びＲ¹⁷は、同一又は異なって、水素原子又は炭化水素基を示す。Ｒ¹⁶及びＲ¹⁷は、互いに結合して、隣接する炭素原子と共に脂環式環を形成していてもよい）
で表される基が含まれる。 Preferred examples of W ¹ include, for example, the following formula (9)

(In the formula, R ¹⁶ and R ¹⁷ are the same or different and each represents a hydrogen atom or a hydrocarbon group. R ¹⁶ and R ¹⁷ are bonded to each other to form an alicyclic ring together with adjacent carbon atoms. May be)
The group represented by these is included.

As the hydrocarbon group in R ¹⁶ and R ¹⁷ , an aliphatic hydrocarbon group (an alkyl group having about 1 to 20 carbon atoms, an alkenyl group having about 2 to 20 carbon atoms, an alkynyl group having about 2 to 20 carbon atoms, etc.), An alicyclic hydrocarbon group (a cycloalkyl group having about 3 to 20 members, a cycloalkenyl group having about 3 to 20 members, a bridged cyclic hydrocarbon group, etc.), an aromatic hydrocarbon group (having about 6 to 14 carbon atoms) Aromatic hydrocarbon groups and the like, and groups in which two or more of these are bonded. The hydrocarbon group includes a hydrocarbon group having a substituent. Examples of the substituent include the same groups as the substituent that the adamantane ring in formula (1a) or (1b) may have.

R ¹⁶ and R ¹⁷ are preferably a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl group, etc. A linear or branched alkyl group having about 1 to 15 carbon atoms (preferably about 1 to 12 carbon atoms); trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trimethyl Fluoro-1- (trifluoromethyl) ethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, nonafluorobutyl, 2,2,3 , 3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4-hexafluorobutyl, undecafluoropentyl, 2 , 2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, tridecafluorohexyl, 2,2, 3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, penta Decafluoroheptyl, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl, 2,2,3,3,4,4,5 5,6,6,7,7-dodecafluoroheptyl, heptadecafluorooctyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Pentadecafluorooctyl, nonadecafluorononyl, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadeca Lorononyl, henicosafluorodecyl, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluoro A linear or branched fluoroalkyl group having about 1 to 15 carbon atoms (preferably about 1 to 10 and more preferably about 1 to 5) such as a decyl group; having a substituent such as a cyclopentyl group or a cyclohexyl group A cycloalkyl group which may be substituted; a bridged cyclic group which may have a substituent such as a norbornan-2-yl group and an adamantan-1-yl group. Examples of the substituent that the cycloalkyl group and the bridged cyclic group may have include the same substituents that the ring in the formulas (6a) to (6h) may have.

Examples of the alkyl group and fluoroalkyl group in R ⁵ , R ⁶ , and R ⁷ are the same as the alkyl group and fluoroalkyl group in R ¹ and R ² , respectively. R ⁵ is preferably a hydrogen atom, a fluorine atom, a C 1-3 alkyl group such as a methyl group, or a C 1-3 fluoroalkyl group such as a trifluoromethyl group. R ⁶ and R ⁷ are each preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms such as a methyl group, or a fluoroalkyl group having 1 to 3 carbon atoms such as a trifluoromethyl group, and particularly preferably a hydrogen atom. .

In formula (5b), examples of the alkyl group for R ⁸ include carbon numbers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, octyl, and decyl groups. Examples thereof include a linear or branched alkyl group having about 1 to 20 (preferably 1 to 10 carbon atoms). Examples of the substituent that the alkyl group may have include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an oxo group, a hydroxyl group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, Aralkyloxy group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted It may have an amino group, a sulfo group, an aromatic hydrocarbon group, a heterocyclic group, or the like. The hydroxyl group or carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.

（式中、環Ｚ¹、Ｒ⁵、Ｒ⁶、Ｒ⁷は前記に同じ。Ｒ¹⁸、Ｒ¹⁹はそれぞれ、Ｒ¹⁶、Ｒ¹⁷と同じである。Ｒ²⁰は水素原子、フッ素原子、アルキル基又はフルオロアルキル基を示す）
で表される化合物が好ましい。 Among the compounds represented by the formula (5a), the following formula (5a-1) or (5a-2)

(In the formula, rings Z ¹ , R ⁵ , R ⁶ and R ⁷ are the same as above. R ¹⁸ and R ¹⁹ are the same as R ¹⁶ and R ¹⁷ , respectively. R ²⁰ is a hydrogen atom, a fluorine atom or an alkyl group. Or a fluoroalkyl group)
The compound represented by these is preferable.

Examples of the alkyl group and fluoroalkyl group in R ²⁰ are the same as the alkyl group and fluoroalkyl group in R ¹ and R ² , respectively.

The following compounds are illustrated as typical examples of the compound represented by the formula (5a-1). As a typical compound in which the ring Z ¹ is a ring represented by the formula (6a), for example, 2- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] norbornane, 2- [1- (2-trifluoromethyl-2-propenoyloxy) -1,2-dimethylpropyl] norbornane, 2- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methyl Pentyl] norbornane, 2,3-bis (trifluoromethyl) -5- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylpentyl] norbornane, 1,2,3,3,4 , 5,5,6,6,7,7-undecafluoro-2- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylpentyl] norbornane, 2- [3,3, 3-to Lifluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methylpropyl] norbornane, 2- [3,3,4,4,5,5,6,6,7,7,8, 8,9,9,10,10,10-heptadecafluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methyldecyl] norbornane, 2- [3,3,3-trifluoro- 1- (2,2,2-trifluoroethyl) -1- (2-trifluoromethyl-2-propenoyloxy) propyl] norbornane, 2- [3,3,3-trifluoro-1- (2, 2,2-trifluoroethyl) -1- (2-trifluoromethyl-2-propenoyloxy) propyl] -2-trifluoromethylnorbornane, 3- [3,3,4,4,5,5,6 , 6,7,7,8,8 9,9,10,10,10- heptadecafluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methyldecyl] - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodecane, 2- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylpentyl] -7-oxabicyclo [2.2.1] is R ^5, such as triisocyanate Examples thereof include compounds that are fluoromethyl groups, and compounds corresponding to the aforementioned compounds in which R ⁵ is a fluorine atom, a hydrogen atom, or a methyl group.

As a typical compound in which the ring Z ¹ is a ring represented by the formula (6b), for example, 1- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] cyclohexane, 1- [2,2,2-trifluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] cyclohexane, 1- [3,3,4,4,5,5, 6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methyldecyl] cyclohexane, 3- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] -tricyclo [6.2.1.0 ^2,7 ] undecane, 3- [2,2,2-trifluoro- 1- (2-trifluoromethyl-2-propyl Penoiruokishi) -1-methylethyl] - tricyclo [6.2.1.0 ^{2, 7]} undecane, 3- [3,3,4,4,5,5,6,6,7,7,8,8 , 9,9,10,10,10-heptadecafluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methyldecyl] -tricyclo [6.2.1.0 ^2,7 ] undecane compound R ^5, such as a trifluoromethyl group, and R ⁵ is a fluorine atom, such as compounds corresponding to the compound is a hydrogen atom or a methyl group.

As a representative compound in which the ring Z ¹ is a ring represented by the formula (6c), for example, 1- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] adamantane, 1- [2,2,2-trifluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] adamantane, 1-fluoro-3- [1- (2-trifluoromethyl) -2-propenoyloxy) -1-methylethyl] adamantane, 1,3-difluoro-5- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] adamantane, 1,3 , 5-trifluoro-7- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] adamantane, 2,2,3,4,4,5,6,6,7, 8, 8, 9 , 9,10,10-pentadecafluoro-1- [1- (2-trifluoromethyl-2-propenoyloxy) -1-methylethyl] adamantane, 1- [3,3,3-trifluoro-1 -(2-trifluoromethyl-2-propenoyloxy) -1-methylpropyl] adamantane, 1- [3,3,4,4,5,5,6,6,7,7,8,8-dodeca Fluoro-1- (2-trifluoromethyl-2-propenoyloxy) -1-methyloctyl] adamantane, 1- [3,3,3-trifluoro-1- (2,2,2-trifluoroethyl) A compound in which R ⁵ is a trifluoromethyl group, such as -1- (2-trifluoromethyl-2-propenoyloxy) propyl] adamantane, and the compound in which R ⁵ is a fluorine atom, a hydrogen atom, or a methyl group; And corresponding compounds.

The following compounds are illustrated as typical examples of the compound represented by the formula (5a-2). As a typical compound in which the ring Z ¹ is a ring represented by the formula (6a), for example, 2- (2,2,2-trifluoroethyl) -2- (2-trifluoromethyl-2-propene Noyloxy) norbornane, 2-nonafluorobutyl-5- (2-trifluoromethyl-2-propenoyloxy) -5-methylnorbornane, 2,3,3,4,4,5,5,6-octafluoro -8- (2-trifluoromethyl-2-propenoyloxy) -8-methyltricyclo [5.2.1.0 ^2,6 ] decane, 2- (2-trifluoromethyl-2-propenoyloxy) ) Norbornane, 3-hydroxy-4- (2-trifluoromethyl-2-propenoyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-hydroxy-8- (2-trifluoromethyl-2-propenoyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-hydroxymethyl-8- (2-trifluoromethyl-2-propenoyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-hydroxymethyl-9- (2-trifluoromethyl-2-propenoyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 8-hydroxy-3- (2-trifluoromethyl-2-propenoyloxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 9-hydroxy-3- (2-trifluoromethyl-2-propenoyloxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 2-nonafluorobutyl-5- (2-trifluoromethyl-2-propenoyloxy) norbornane, 2-tridecafluorohexyl-5- (2-trifluoromethyl-2-propenoyl) Oxy) norbornane, 2-tridecafluorohexyl-5- (2-trifluoromethyl-2-propenoyloxy) -7-oxabicyclo [2.2.1] heptane, 3-tridecafluorohexyl-8- ( 2-trifluoromethyl-2-propenoyloxy) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane, 2,3,3,4,4,5,5,6- octafluoro-8- (2-trifluoromethyl-2-propenoyloxy) tricyclo [5.2.1.0 ^2,6 ] decane, 2,3,3,4,4,5,5,6-octafluoro-8- (2-trifluoromethyl-2-propenoyloxy) -10-oxatricyclo [5.2 .1.0 ^2,6] decane, 2,3,3,4,4,5,5,6,6,7- decafluoro-9- (2-trifluoromethyl-2-propenoyloxy) tricyclo [ 6.2.1.0 ^{2, 7]} compounds wherein R ⁵ is a trifluoromethyl group, such as undecane, and R ⁵ is fluorine atom, and the like corresponding compound to the compound is a hydrogen atom or a methyl group.

Representative compounds in which ring Z ¹ is a ring represented by formula (6b) include, for example, 1- (2-trifluoromethyl-2-propenoyloxy) cyclopentane, 1- (2-trifluoromethyl) -2-propenoyloxy) cyclohexane, cis-5- (2-trifluoromethyl-2-propenoyloxy) -1,1,3-trimethylcyclohexane, trans-5- (2-trifluoromethyl-2-prope Noyloxy) -1,1,3-trimethylcyclohexane, 2- (2-trifluoromethyl-2-propenoyloxy) -1-isopropyl-4-methylcyclohexane, 3- (2-trifluoromethyl-2-propene Noiruokishi) tricyclo [6.2.1.0 ^{2, 7]} undecane, 4- (2-trifluoromethyl-2-propenoyloxy) Torishi B [6.2.1.0 ^{2, 7]} undecane, 2- (2-trifluoromethyl-2-propenoyloxy) -7-oxabicyclo [3.2.1] octan-6-one, 1- Nonafluorobutyl-4- (2-trifluoromethyl-2-propenoyloxy) cyclohexane, 1-tridecafluorohexyl-4- (2-trifluoromethyl-2-propenoyloxy) cyclohexane, 2-tridecafluoro Hexyl-6- (2-trifluoromethyl-2-propenoyloxy) perhydronaphthalene, 1,1,2,2,3,3,3a, 7a-octafluoro-5- (2-trifluoromethyl-2 -Propenoyloxy) perhydroindene, 1,1,2,2,3,3,4,4,4a, 8a-decafluoro-6- (2-trifluoromethyl-2-pro Penoiruokishi) compound wherein R ⁵ is a trifluoromethyl group, such as decalin, and R ⁵ is fluorine atom, and the like corresponding compound to the compound is a hydrogen atom or a methyl group.

As a typical compound in which the ring Z ¹ is a ring represented by the formula (6c), for example, 2- (2,2,2-trifluoroethyl) -2- (2-trifluoromethyl-2-propene Noyloxy) adamantane, 1-fluoro-4- (2-trifluoromethyl-2-propenoyloxy) -4-methyladamantane, 1,3-difluoro-6- (2-trifluoromethyl-2-propenoyloxy) ) -6-methyladamantane, 1- (2-trifluoromethyl-2-propenoyloxy) adamantane, 2- (2-trifluoromethyl-2-propenoyloxy) adamantane, 2- (2-trifluoromethyl- 2-propenoyloxy) -2-methyladamantane, 2-ethyl-2- (2-trifluoromethyl-2-propenoyloxy) adamantane, 5- (2-trifluoromethyl-2-propenoyloxy) -1,3-dimethyladamantane, 1-carboxy-3- (2-trifluoromethyl-2-propenoyloxy) adamantane, 1-amino-3- (2 -Trifluoromethyl-2-propenoyloxy) adamantane, 3- (2-trifluoromethyl-2-propenoyloxy) -1-nitroadamantane, 3- (2-trifluoromethyl-2-propenoyloxy)- 1-sulfoadamantane, 1-t-butyloxycarbonyl-3- (2-trifluoromethyl-2-propenoyloxy) adamantane, 1- (2-trifluoromethyl-2-propenoyloxy) -4-oxoadamantane A compound in which R ⁵ is a trifluoromethyl group, and the like, and R ⁵ is a fluorine atom, a hydrogen atom or a methyl group And a compound corresponding to the above-mentioned compound which is a sulfur group.

As a typical compound in which the ring Z ¹ is a ring represented by the formula (6d), for example, 8- (2-trifluoromethyl-2-propenoyloxy) -4-oxatricyclo [5.2. ^1.02,6 ] decane-3,5-dione, 4- (2-trifluoromethyl-2-propenoyloxy) -11-oxapentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadecane-10,12-dione compounds R ⁵ is a trifluoromethyl group, such as, and R ⁵ is fluorine atom, and the like corresponding compound to the compound is a hydrogen atom or a methyl group.

Examples of the compound in which the ring Z ¹ is a ring represented by the formula (6e) include α- (2-trifluoromethyl-2-propenoyloxy) -γ-butyrolactone, β- (2-trifluoromethyl-2). -Propenoyloxy) -γ-butyrolactone, γ- (2-trifluoromethyl-2-propenoyloxy) -γ-butyrolactone, α- (2-trifluoromethyl-2-propenoyloxy) -γ, γ- Dimethyl-γ-butyrolactone, α- (2-trifluoromethyl-2-propenoyloxy) -α, γ, γ-trimethyl-γ-butyrolactone, 8- (2-trifluoromethyl-2-propenoyloxy)- 4-oxatricyclo [5.2.1.0 ^{2, 6]} decan-3-one, 9- (2-trifluoromethyl-2-propenoyloxy) -4-oxatricyclo [5.2 1.0 ^{2, 6]} R ^5, such as decane-3-one compound is a trifluoromethyl group, and R ⁵ is fluorine atom, and the like corresponding compound to the compound is a hydrogen atom or a methyl group.

As a compound in which the ring Z ¹ is a ring represented by the formula (6f), for example, 4- (2-trifluoromethyl-2-propenoyloxy) -2,7-dioxabicyclo [3.3.0] Examples thereof include compounds such as octane-3,6-dione, wherein R ⁵ is a trifluoromethyl group, and compounds corresponding to the compound wherein R ⁵ is a fluorine atom, a hydrogen atom or a methyl group.

As a compound in which the ring Z ¹ is a ring represented by the formula (6g), for example, 5- (2-trifluoromethyl-2-propenoyloxy) -3-oxatricyclo [4.2.1.0 ^{4 , 8} ] nonan-2-one, 5-methyl-5- (2-trifluoromethyl-2-propenoyloxy) -3-oxatricyclo [4.2.1.0 ^4,8 ] nonane-2- one, 9-methyl-5- (2-trifluoromethyl-2-propenoyloxy) -3- oxatricyclo [4.2.1.0 ^{4, 8]} is R ^5, such as nonane-2-one tri Examples thereof include compounds that are fluoromethyl groups, and compounds corresponding to the aforementioned compounds in which R ⁵ is a fluorine atom, a hydrogen atom, or a methyl group.

As a compound in which the ring Z ¹ is a ring represented by the formula (6h), for example, 6- (2-trifluoromethyl-2-propenoyloxy) -3-oxatricyclo [4.3.1.1 ^{4 , 8} ] undecan-2-one, 8- (2-trifluoromethyl-2-propenoyloxy) -6-hydroxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2- R ⁵ such as on, 6- (2-trifluoromethyl-2-propenoyloxy) -8-hydroxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one Examples thereof include compounds that are fluoromethyl groups, and compounds corresponding to the aforementioned compounds in which R ⁵ is a fluorine atom, a hydrogen atom, or a methyl group.

Representative examples of the compound represented by the formula (5b) include, for example, methyl 2-trifluoromethyl-2-propenoate, ethyl 2-trifluoromethyl-2-propenoate, 2-trifluoromethyl-2-propenoic acid Propyl, isopropyl 2-trifluoromethyl-2-propenoate, s-butyl 2-trifluoromethyl-2-propenoate, t-butyl 2-trifluoromethyl-2-propenoate, 2-trifluoromethyl-2- Hexyl propenoate, 2-trifluoromethyl-2-propenoic acid (2-hydroxyethyl), trifluoromethyl 2-trifluoromethyl-2-propenoate, 2-trifluoromethyl-2-propenoic acid (2,2, 2-trifluoroethyl), 2-trifluoromethyl-2-propenoic acid (2,2,3,3,3-pentafluoropropyl) 2-trifluoromethyl-2-propenoic acid (2,2,3,3-tetrafluoropropyl), 2-trifluoromethyl-2-propenoic acid (2,2,3,3,4,4,4- Heptafluorobutyl), 2-trifluoromethyl-2-propenoic acid (2,2,3,3,4,4-hexafluorobutyl), 2-trifluoromethyl-2-propenoic acid (2,2,3,3) 3,4,4,5,5,5-nonafluoropentyl), 2-trifluoromethyl-2-propenoic acid (2,2,3,3,4,4,5,5-octafluoropentyl), 2 -Trifluoromethyl-2-propenoic acid (2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl), 2-trifluoromethyl-2- Propenoic acid (2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluoroheptyl), 2-trifluoromethyl-2-propenoic acid (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl), 2-trifluoromethyl-2-propenoic acid (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9) , 10,10,11,11-icosafluoroundecyl), 2-trifluoromethyl-2-propenoic acid (2,2,2-trifluoro-1-trifluoromethylethyl), 2-trifluoromethyl- 2-propenoic acid (1,2,2,2-tetrafluoro-1-trifluoromethylethyl), 2-trifluoromethyl-2-propenoic acid [1,1-bis (trifluoromethyl) ethyl], 2- Trifluoromethyl-2-propenoic acid (1-trifluoro (Romethyl-1-methylethyl), 2-trifluoromethyl-2-propenoic acid (2,2,2-trifluoro-1-trifluoromethyl-1-phenylethyl), 2-trifluoromethyl-2-propenoic acid Examples thereof include a compound in which R ⁵ is a trifluoromethyl group such as (1-trifluoromethyl-1-phenylethyl) and a compound corresponding to the compound in which R ⁵ is a fluorine atom, a hydrogen atom or a methyl group.

In the acrylic monomer, (1) among the compounds represented by the formula (5a), the ring Z ¹ is represented by the formula (6d), (6e), (6f), (6g) or (6h). A ring compound, (2) among the compounds represented by formula (5a), ring Z ¹ is a ring represented by (6a), (6b) or (6c), and ring Z ¹ has the above polarity A compound in which a group or a group containing a polar group is bonded, or W ¹ is a group containing a polar group, (3) R ⁸ is a group containing a polar group among the compounds represented by formula (5b) The compound forms a repeating unit having substrate adhesion and / or hydrophilic function by being subjected to copolymerization as a comonomer.

In the acrylic monomer, (1) among the compounds represented by the formula (5a), a compound having a tertiary carbon atom in the oxygen atom —O— constituting the ester bond shown in the formula [ For example, a compound represented by the formula (5a-1) or (5a-2)], (2) among the compounds represented by the formula (5a), a —COOR group (R is tertiary) in the ring Z ¹ A compound in which a hydrocarbon group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group or the like is bonded directly or via a linking group, (3) among the compounds represented by the formula (5b), R ^Of the compounds in which ⁸ is a tertiary hydrocarbon group and (4) the compound represented by formula (5b), R ⁸ is a —COOR group (where R is a tertiary hydrocarbon group, a 2-tetrahydrofuranyl group or 2 -A tetrahydropyranyl group or the like) is bonded directly or via a linking group A repeating unit having an acid-eliminating function is formed by copolymerization as a mer.

  The acrylic monomer can be produced by a known method or by using a known reaction. Further, in accordance with the method shown as the method for producing the compound represented by the above formula (1a) or (1b), a fluorine atom-containing or non-containing unsaturated carboxylic acid or a reactive derivative thereof (acid halide, acid anhydride) The corresponding acrylic monomer can be obtained by reacting a hydroxy compound with a hydroxy compound in the presence of a base, an acid catalyst, a transesterification catalyst or the like.

Other representative examples of the polymerizable unsaturated monomer other than the polymerizable adamantane derivative represented by the formula (4a) or (4b) used for imparting various functions as a resist to the polymer compound of the present invention Specific examples include vinyl ether monomers represented by the formula (7a) or (7b) [excluding compounds represented by the formulas (4a) and (4b)]. In formula (7a), ring Z ² is any one of the above formulas (6a), (6b), (6c), (6d), (6e), (6f), (6g) or (6h) Represents a ring, and W ² represents a divalent hydrocarbon group. R ⁹ , R ¹⁰ and R ¹¹ are the same or different and each represents a hydrogen atom or an organic group. At least two of the rings Z ² , W ² , R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring together with one or more adjacent atoms. s represents 0 or 1, and t represents an integer of 1 to 8. When t is 2 or more, the groups in t parentheses may be the same or different. In formula (7b), R ¹² represents an alkyl group which may have a substituent, and R ¹³ , R ¹⁴ and R ¹⁵ are the same or different and represent a hydrogen atom or an organic group. At least two of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring together with one or more adjacent atoms. r shows the integer of 1-8. When r is 2 or more, the groups in r parentheses may be the same or different.

  By copolymerizing such a vinyl ether monomer, particularly a vinyl ether monomer having an alicyclic carbon ring, the etching resistance of the polymer can be improved. Further, by using a vinyl ether monomer having a polar group in the molecule, it is possible to improve substrate adhesion and / or hydrophilicity. When a compound containing a fluorine atom in the molecule is used as a comonomer, the transparency to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light can be enhanced. These vinyl ether monomers can be used alone or in combination.

（式中、Ｒ²¹及びＲ²²は、同一又は異なって、水素原子又は炭化水素基を示す。Ｒ²¹及びＲ²²は、互いに結合して、隣接する炭素原子と共に脂環式環を形成していてもよい）
で表される基が含まれる。 Examples of the divalent hydrocarbon group for W ² include the same divalent hydrocarbon groups as those described above for W ¹ . Preferred examples of W ² include, for example, the following formula (10)

(In the formula, R ²¹ and R ²² are the same or different and each represents a hydrogen atom or a hydrocarbon group. R ²¹ and R ²² are bonded to each other to form an alicyclic ring together with adjacent carbon atoms. May be)
The group represented by these is included.

As the hydrocarbon group in R ²¹ and R ²² , an aliphatic hydrocarbon group (an alkyl group having about 1 to 20 carbon atoms, an alkenyl group having about 2 to 20 carbon atoms, an alkynyl group having about 2 to 20 carbon atoms, etc.), An alicyclic hydrocarbon group (a cycloalkyl group having about 3 to 20 members, a cycloalkenyl group having about 3 to 20 members, a bridged cyclic hydrocarbon group, etc.), an aromatic hydrocarbon group (having about 6 to 14 carbon atoms) Aromatic hydrocarbon groups and the like, and groups in which two or more of these are bonded. The hydrocarbon group includes a hydrocarbon group having a substituent. Examples of the substituent include the same substituents that the divalent hydrocarbon group in W ¹ may have.

R ²¹ and R ²² are preferably hydrogen atoms; C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups (particularly C _1-5 alkyl groups); substituents such as cyclopentyl groups and cyclohexyl groups. A cycloalkyl group optionally having a substituent; a bridged cyclic group optionally having a substituent such as a norbornan-2-yl group and an adamantan-1-yl group. Examples of the substituent that the cycloalkyl group and the bridged cyclic group may have include the same substituents that the ring in the formulas (6a) to (6h) may have.

In the formula (7a), examples of the organic group for R ⁹ , R ¹⁰ and R ¹¹ include a halogen atom, a hydrocarbon group, a heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxy group). Carbonyl group, cycloalkyloxycarbonyl group, etc.), carboxyl group, substituted or unsubstituted carbamoyl group, cyano group, nitro group, sulfur acid group, sulfur acid ester group, acyl group (aliphatic acyl group such as acetyl group; benzoyl group) Etc.), alkoxy groups (C _1-6 alkoxy groups such as methoxy groups, ethoxy groups, etc.), N, N-disubstituted amino groups (N, N-dimethylamino groups, piperidino groups, etc.), etc. And a group in which two or more of these are bonded, and the carboxyl group is protected with a known or commonly used protective group in the field of organic synthesis. It may be. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Of these organic groups, a hydrocarbon group, a heterocyclic group, and the like are preferable.

The hydrocarbon group and the heterocyclic group also include a hydrocarbon group and a heterocyclic group having a substituent. Examples of the hydrocarbon group include the same hydrocarbon groups as those described above for R ¹² and R ¹³ . Preferred hydrocarbon groups include C _1-10 alkyl groups, C _2-10 alkenyl groups, C _2-10 alkynyl groups, C _3-15 cycloalkyl groups, C _6-10 aromatic hydrocarbon groups, C _3-15 A cycloalkyl-C _1-4 alkyl group, a C _7-14 aralkyl group and the like are included. These hydrocarbon groups may have a substituent, and examples of the substituent include the same substituents that the divalent hydrocarbon group in W ¹ may have.

The heterocyclic ring constituting the heterocyclic group in R ^{9 and the} like includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocyclic ring include a heterocyclic ring containing an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. The heterocyclic group includes an alkyl group (for example, a C _1-4 alkyl group such as methyl and ethyl groups), a cycloalkyl group, an aryl group (for example, , Phenyl, naphthyl group, etc.).

Preferred R ⁹ , R ¹⁰ and R ¹¹ include a hydrogen atom and a hydrocarbon group (for example, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _3-15 cycloalkyl group, C _6-10 aromatic hydrocarbon group, C _3-12 cycloalkyl-C _1-4 alkyl group, C _7-14 aralkyl group, etc.). R ⁹ , R ¹⁰ and R ¹¹ are particularly preferably a C _1-3 alkyl group such as a hydrogen atom or a methyl group.

The ring formed by combining at least two of the rings Z ² , W ² , R ⁹ , R ¹⁰ and R ¹¹ together with one or more adjacent atoms includes a non-aromatic carbocycle or heterocycle. included.

Typical examples of the vinyl ether compound represented by the formula (7a) include the following compounds. Examples of vinyl ether compounds in which ring Z ² is a group represented by formula (6a) include 2-vinyloxynorbornane, 5-methoxycarbonyl-2-vinyloxynorbornane, 2- [1- (norbornan-2-yl) -1-vinyloxyethyl] norbornane, 2- (vinyloxymethyl) norbornane, 2- (1-methyl-1-vinyloxyethyl) norbornane, 2- (1-methyl-1-vinyloxypentyl) norbornane, 3- Hydroxy-4-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-hydroxy-8-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-methoxycarbonyl-8-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-methoxycarbonyl-9-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3- (vinyloxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-hydroxymethyl-8-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 3-hydroxymethyl-9-vinyloxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 8-hydroxy-3- (vinyloxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 9-hydroxy-3- (vinyloxymethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and the corresponding isopropenyl ethers.

Examples of the vinyl ether compound in which ring Z ² is a group represented by formula (6b) include vinyloxycyclopentane, vinyloxycyclohexane, cis-1,1,3-trimethyl-5-vinyloxycyclohexane, trans-1, 1,3-trimethyl-5-vinyloxycyclohexane, 1-isopropyl-4-methyl-2-vinyloxycyclohexane, 3-vinyloxytricyclo [6.2.1.0 ^2,7 ] undecane, 4-vinyloxy Tricyclo [6.2.1.0 ^2,7 ] undecane, 2-vinyloxy-7-oxabicyclo [3.2.1] octane-6-one, (2,2,2-trifluoro-1-tri Fluoromethyl-1-cyclohexylethyl) vinyl ether, [2,2,2-trifluoro-1-trifluoromethyl-1- (4-trifluoro) Olomethylcyclohexyl) ethyl] vinyl ether, (1-trifluoromethyl-1-cyclohexylethyl) vinyl ether, [1-trifluoromethyl-1- (4-trifluoromethylcyclohexyl) ethyl] vinyl ether, and the corresponding isopropenyls And ethers.

Examples of vinyl ether compounds in which ring Z ² is a group represented by formula (6c) include 1-vinyloxyadamantane, 2-vinyloxyadamantane, 2-methyl-2-vinyloxyadamantane, and 2-ethyl-2-vinyl. Oxyadamantane, 1,3-dimethyl-5-vinyloxyadamantane, 1-carboxy-3-vinyloxyadamantane, 1-amino-3-vinyloxyadamantane, 1-nitro-3-vinyloxyadamantane, 1-sulfo-3 -Vinyloxyadamantane, 1-t-butyloxycarbonyl-3-vinyloxyadamantane, 4-oxo-1-vinyloxyadamantane, 1- (vinyloxymethyl) adamantane, 1- (1-methyl-1-vinyloxyethyl) Adamantane, 1- (1-ethyl-1-vinyloxy) Ethyl) adamantane, 1- (1- (norbornan-2-yl) -1-vinyloxyethyl) adamantane, and corresponding isopropenyl ethers.

Examples of the vinyl ether compound in which ring Z ² is a group represented by the formula (6d) include 8-vinyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3,5-dione, 4-vinyloxy-11-oxapentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadecane-10,12-dione, an isopropenyl ether corresponding to them.

Examples of vinyl ether compounds in which ring Z ² is a group represented by the formula (6e) include α-vinyloxy-γ-butyrolactone, β-vinyloxy-γ-butyrolactone, γ-vinyloxy-γ-butyrolactone, α-vinyloxy-γ. , Γ-dimethyl-γ-butyrolactone, α, γ, γ-trimethyl-α-vinyloxy-γ-butyrolactone, γ, γ-dimethyl-β-methoxycarbonyl-α-vinyloxy-γ-butyrolactone, 8-vinyloxy-4- Oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one, 9-vinyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one, and these And isopropenyl ethers corresponding to the above.

Examples of the vinyl ether compound in which the ring Z ² is a group represented by the formula (6f) include 4-vinyloxy-2,7-dioxabicyclo [3.3.0] octane-3,6-dione, and And corresponding isopropenyl ethers.

Examples of vinyl ether compounds in which ring Z ² is a group represented by the formula (6 g) include 5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5- Methyl-5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 9-methyl-5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one and the corresponding isopropenyl ethers.

Examples of the vinyl ether compound in which ring Z ² is a group represented by formula (6h) include 6-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one, 6- Hydroxy-8-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one, 8-hydroxy-6-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one and the corresponding isopropenyl ethers.

In the formula (7b), the alkyl group which may have a substituent in R ¹² is the same as the alkyl group which may have a substituent in R ⁸ . Examples of the organic group for R ¹³ , R ^14, and R ¹⁵ include the same organic groups as those for R ⁹ , R ¹⁰ , and R ¹¹ . Preferred R ¹³ , R ¹⁴ and R ¹⁵ include a hydrogen atom and a hydrocarbon group (for example, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _3-15 cycloalkyl group, C _6-10 aromatic hydrocarbon group, C _3-12 cycloalkyl-C _1-4 alkyl group, C _7-14 aralkyl group, etc.). R ¹³ , R ¹⁴ and R ¹⁵ are particularly preferably a C _1-3 alkyl group such as a hydrogen atom or a methyl group. The ring that can be formed together with one or more adjacent atoms by bonding at least two of R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ includes a non-aromatic carbocycle or heterocycle. .

  Representative examples of the vinyl ether compound represented by the formula (7b) include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, s-butyl vinyl ether, t-butyl vinyl ether, hexyl vinyl ether, ethylene glycol monovinyl ether, ethylene Glycol divinyl ether, trifluoromethyl vinyl ether, (2,2,2-trifluoroethyl) vinyl ether, (2,2,3,3,3-pentafluoropropyl) vinyl ether, (2,2,3,3-tetrafluoro Propyl) vinyl ether, (2,2,3,3,4,4,4-heptafluorobutyl) vinyl ether, (2,2,3,3,4,4-hexafluorobutyl) vinyl ether, (2,2,3 , 3, , 4,5,5,5-nonafluoropentyl) vinyl ether, (2,2,3,3,4,4,5,5-octafluoropentyl) vinyl ether, (2,2,3,3,4,4) , 5,5,6,6,7,7,7-tridecafluoroheptyl) vinyl ether, (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl) ) Vinyl ether, (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecyl) vinyl ether, (2, 2, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-icosafluoroundecyl) vinyl ether, (2,2,2 -Trifluoro-1-trifluoromethylethyl) vinyl ether, (1,2,2,2-tetraph (Luoro-1-trifluoromethylethyl) vinyl ether, [1,1-bis (trifluoromethyl) ethyl] vinyl ether, (1-trifluoromethyl-1-methylethyl) vinyl ether, (2,2,2-trifluoro- 1-trifluoromethyl-1-phenylethyl) vinyl ether, (1-trifluoromethyl-1-phenylethyl) vinyl ether, and corresponding isopropenyl ethers, dihydropyran and the like.

In the vinyl ether monomer, (1) among the compounds represented by the formula (7a), the ring Z ² is represented by the formula (6d), (6e), (6f), (6g) or (6h). ring, compound, (2) (7a) ring Z ² has the formula among the compounds represented by (6a), (6b) or a ring represented by (6c), and the the ring Z ² A compound in which a polar group or a group containing a polar group is bonded, or W ² , R ⁹ , R ¹⁰ or R ¹¹ is a group containing a polar group, and (3) a compound represented by the formula (7b) Among them, the compound in which R ¹² , R ¹³ , R ¹⁴ or R ¹⁵ is a group containing a polar group forms a repeating unit having substrate adhesion and / or hydrophilic function by being subjected to copolymerization as a comonomer.

  The vinyl ether monomer can be produced by a known method or by utilizing a known reaction. Moreover, it can also manufacture according to the method shown as a manufacturing method of the compound whose n is 0 among the compounds represented by the said Formula (4a) or (4b).

As another example of the polymerizable unsaturated monomer other than the polymerizable adamantane derivative represented by the above formula (4a) or (4b) used for imparting various functions as a resist to the polymer compound of the present invention And the cyclic unsaturated monomer represented by the formula (8a) or (8b). In formulas (8a) and (8b), Y ⁶ and Y ⁷ each represent an alkylene group, an oxygen atom, a sulfur atom or no bond. Y ⁸ represents an oxygen atom or a —NH— group. f shows the integer of 0-3. The atoms constituting the ring in the formula may have a substituent.

  Among such cyclic unsaturated monomers, the compound of the formula (8a) can improve the etching resistance of the polymer, and the compound of the formula (8b) can improve the substrate adhesion. . Further, in the above cyclic unsaturated monomer, when the ring has a fluorine atom or a fluorine atom-containing group, the transparency to light having a wavelength of 300 nm or less, particularly vacuum ultraviolet light can be increased, and the polar group is included in the ring. Or when the group containing a polar group has couple | bonded, board | substrate adhesiveness and / or hydrophilicity can be improved. Furthermore, when it has an ester group in which a tertiary carbon atom is bonded to an oxygen atom constituting the ester bond, the acid-eliminating function can be improved. These cyclic unsaturated monomers can be used alone or in combination.

In the formula, the alkylene group is the same as the alkylene group in Y ¹ and the like. Examples of the substituent that the ring may have include the same substituents that the ring Z ¹ [rings represented by formulas (6a) to (6h)] may have. When there are two or more ring substituents, they may be bonded to each other to form a 4-membered or more ring, for example, a cycloalkane ring or a lactone ring, together with the carbon atoms constituting the ring. These rings may have a substituent (eg, a fluorine atom, an alkyl group, a fluoroalkyl group, etc.) similar to the substituent that the atom constituting the ring Z ¹ may have. .

Representative examples of the cyclic unsaturated monomer represented by the formula (8a) include, for example, norbornene (= bicyclo [2.2.1] -2-heptene), 5-carboxy-5-trifluoromethylbicyclo [2.2.1] -2-heptene, 5-t-butoxycarbonyl-5-trifluoromethylbicyclo [2.2.1] -2-heptene, 7-oxa-bicyclo [2.2.1]- 2-heptene, tricyclo [4.3.0.1 ^2,5 ] -3-decene, tricyclo [4.4.0.1 ^2,5 ] -3-undecene, tetracyclo [4.4.0.1 ^{2 , 5} . 1 ^7,10 ] -3-dodecene, 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decene-3-one, 4-oxatricyclo [5.2.1.0 ^{2 , 6} ] -8-decene-3,5-dione.

  Representative examples of the cyclic unsaturated monomer represented by the formula (8b) include, for example, maleic anhydride, 2-fluoromaleic anhydride, 2-trifluoromethylmaleic anhydride, maleimide, N-carboxymaleimide, N-methylmaleimide etc. are mentioned.

  In the cyclic unsaturated monomer, among the compounds represented by (1) formula (8a), a compound in which the ring or a group containing a polar group is bonded to the ring, and (2) formula (8b) Is subjected to copolymerization as a comonomer to form a repeating unit having substrate adhesion and / or hydrophilic function. The cyclic unsaturated monomer can be produced by a known method or using a known reaction.

  In the polymer compound of the present invention, the ratio of the repeating unit corresponding to the polymerizable adamantane derivative represented by the formula (4a) or (4b) is not particularly limited, but generally, with respect to all monomer units constituting the polymer. 1 to 99 mol%, preferably 5 to 95 mol%, more preferably 10 to 80 mol%, and particularly preferably about 10 to 70 mol%. The ratio of the repeating unit having an acid-eliminating function is, for example, about 5 to 80 mol%, preferably about 10 to 60 mol%, based on all monomer units constituting the polymer. Further, a repeating unit corresponding to the acrylate monomer represented by the formula (5a) or (5b) [excluding the compound represented by the formula (4a) or (4b)], the formula (7a) or ( 7b) is a repeating unit corresponding to the vinyl ether monomer represented by [excluding the compounds represented by formulas (4a) and (4b)], the cyclic unsaturated unit represented by formula (8a) or (8b) The ratio of the repeating unit corresponding to the monomer can be appropriately selected according to the function of each monomer unit. The total proportion of these repeating units is from 1 to 99 mol%, preferably from 5 to 95 mol%, more preferably from 20 to 90 mol%, particularly preferably from 30 to 90 mol%, based on all monomer units constituting the polymer. %.

  In obtaining the polymer compound by subjecting the polymerizable adamantane derivative of the present invention to (co) polymerization, the polymerization may be solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, acrylic polymer, etc. The polymerization can be carried out by a conventional method used in the production of solution, and solution polymerization is particularly preferred. In solution polymerization, a drop polymerization method may be used to obtain a homogeneous polymer.

  As the polymerization solvent, a known solvent can be used. For example, ether (chain ether such as diethyl ether, propylene glycol monomethyl ether, etc., chain ether such as tetrahydrofuran, dioxane, etc.), ester (methyl acetate, ethyl acetate, Glycol ether esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.) ), Sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, etc.), hydrocarbon (aromatic hydrocarbons such as benzene, toluene, xylene, etc.) Aliphatic hydrocarbons such as hexane, and alicyclic hydrocarbons such as cyclohexane), and mixtures of these solvents. Moreover, a well-known polymerization initiator can be used as a polymerization initiator. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.

  The polymer obtained by polymerization can be purified by precipitation or reprecipitation. The precipitation or reprecipitation solvent may be either an organic solvent or water, or a mixed solvent. Examples of the organic solvent used as the precipitation or reprecipitation solvent include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatics such as benzene, toluene, and xylene. Aromatic hydrocarbons), halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.) , Nitrile (acetonitrile, benzonitrile, etc.), ether (chain ether such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ether such as tetrahydrofuran, dioxane), ketone (acetone, methyl ethyl ketone) Diisobutyl ketone, etc.), ester (ethyl acetate, butyl acetate, etc.), carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohol (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (acetic acid, etc.) Etc.), and mixed solvents containing these solvents.

  The weight average molecular weight (Mw) of the polymer compound is, for example, about 1000 to 500000, preferably about 3000 to 50000, and the molecular weight distribution (Mw / Mn) is, for example, about 1.5 to 2.5. In addition, said Mn shows a number average molecular weight, and both Mn and Mw are values of polystyrene conversion.

[Production of Resin Composition for Photoresist and Semiconductor]
The resin composition for photoresists of the present invention contains at least the polymer compound of the present invention and a photoacid generator. In addition, a polymer other than the polymer compound may be included as long as the resist performance is not impaired.

  Examples of the photoacid generator include conventional or known compounds that efficiently generate acid upon exposure, such as diazonium salts, iodonium salts (for example, diphenyliodohexafluorophosphate), sulfonium salts (for example, triphenylsulfonium hexafluoroantimony). Nates, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonate esters [eg 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, 1,2,3-tri Sulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) -1-hydroxy-1-benzo Rumetan etc.], oxathiazole derivatives, s- triazine derivatives, disulfone derivatives (diphenyl sulfone) imide compound, an oxime sulfonate, a diazonaphthoquinone, and benzoin tosylate. These photoacid generators can be used alone or in combination of two or more.

  The amount of the photoacid generator used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each repeating unit in the polymer, and the like. Parts, preferably 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight.

  The resin composition for a photoresist, if necessary, an alkali-soluble component such as an alkali-soluble resin (for example, a novolak resin, a phenol resin, an imide resin, a carboxyl group-containing resin), a colorant (for example, a dye), Organic solvents (for example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof), bases May contain a functional compound (such as a hindered amine compound), a surfactant, a dissolution inhibitor, a sensitizer, and a stabilizer.

  The photoresist resin composition thus obtained is applied onto a substrate or a substrate, dried, and then exposed to light on a coating film (resist film) through a predetermined mask (or further subjected to post-exposure baking. Perform) By forming a latent image pattern and then developing it, a fine pattern can be formed with high accuracy.

  Examples of the base material or the substrate include a silicon wafer, metal, plastic, glass, and ceramic. The application of the photoresist resin composition can be performed using a conventional application means such as a spin coater, a dip coater, or a roller coater. The thickness of the coating film is, for example, about 0.01 to 20 μm, preferably about 0.05 to 1 μm.

For exposure, various wavelengths of light such as ultraviolet rays and X-rays can be used. For semiconductor resists, g-line, i-line, and excimer lasers (eg, XeCl, KrF, KrCl, ArF, ArCl, F) are generally used. ₂ , Kr ₂ , KrAr, Ar ₂ etc.). The exposure energy is, for example, about 0.1 to 1000 mJ / cm ² .

  By irradiation with light, an acid is generated from the photoacid generator. By this acid, for example, the elimination site of the acid-leaving group of the polymer compound is rapidly eliminated, and a carboxyl group that contributes to solubilization is generated. . Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developer.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the number on the lower right of the parentheses in the structural formula of the polymer indicates the charged mol% of the monomer corresponding to the repeating unit (monomer unit). The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined in terms of standard polystyrene by GPC measurement using a refractometer (RI) as a detector and tetrahydrofuran (THF) as an eluent. GPC uses three columns KF-806L (trade name) manufactured by Showa Denko Co., Ltd. connected in series, column temperature 40 ° C., RI temperature 40 ° C., eluent flow rate 0.8 ml / min. Performed under conditions.

Production Example 1
To a mixed liquid of 10.2 g of α-hydroxy-γ-butyrolactone, 11.1 g of triethylamine and 100 ml of tetrahydrofuran, 17.4 g of 2-trifluoromethylacrylic acid chloride was added and stirred at room temperature for 3 hours. Ethyl acetate and water are added to the reaction solution to perform extraction, and the concentrate obtained by concentrating the organic layer is subjected to silica gel column chromatography, whereby α- (2- 13.7 g of trifluoromethyl-2-propenoyloxy) -γ-butyrolactone was obtained.

Production Example 2
A three-necked flask equipped with a thermometer was charged with 7.41 g (0.10 mol) of tert-butyl alcohol, 12.1 g (0.12 mol) of triethylamine, and 200 ml of tetrahydrofuran, and stirred while cooling with ice in a nitrogen stream. In this mixed solution, 19.0 g (0.12 mol) of 2- (trifluoromethyl) acrylic acid chloride was added and stirred at room temperature for 2 hours. After the reaction, the mixture was concentrated under reduced pressure, 300 ml of pure water was added to the concentrated residue, and the mixture was extracted twice with 300 ml of ethyl acetate. The organic layers were combined, washed with 300 ml of 5 wt% aqueous sodium hydrogen carbonate solution and 300 ml of 10 wt% brine, dried over magnesium sulfate and concentrated under reduced pressure. By purifying the concentrated residue by silica gel column chromatography, tert-butyl 2-trifluoromethyl acrylate represented by the following formula (12) [= 2-methyl-2- (2-trifluoromethyl-2-propenoyl) 10.2 g (0.052 mol) of oxy) propane] was obtained.

In addition, γ, γ-dimethyl-α-vinyloxy-γ-butyrolactone used as a monomer in the following examples is obtained from α-hydroxy-γ, γ-dimethyl-γ-butyrolactone and vinyl acetate. A compound synthesized according to the method described in JP 73321 and purified by distillation under reduced pressure was used. Further, 1-vinyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one [= 6-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8]. ] Undecan-2-one] is 1-hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-5-one [= 6-hydroxy-3-oxatricyclo [4.3. and a .1.1 ^4,8] undecane-2-one] and vinyl acetate was synthesized according to the method described in JP 2003-73321, a product which was purified by alumina column chromatography Using.

Example 1
In a three-necked flask equipped with a Dean Stark apparatus and a thermometer, 129 g (0.7 mol) of 1,3,5-adamantanetriol, 434 g (3.10 mol) of 2-trifluoromethylacrylic acid, 1.24 g (0.01 mol) of p-methoxyphenol and 745 ml of toluene were added. While the mixture was heated to reflux, a mixture of 6.86 g (0.07 mol) of sulfuric acid and 100 ml of toluene was added dropwise over 5 minutes, and the mixture was further heated to reflux for 3 hours for dehydration reaction. After the reaction, the mixture was neutralized by adding 1580 g of a 10 wt% aqueous sodium carbonate solution. This mixture was extracted once with 2 L and 1 L of n-hexane to remove diesters and triesters as impurities. After the aqueous layer was extracted four times with 1 L of ethyl acetate, the ethyl acetate layer was concentrated until the liquid volume became 1.2 L, washed successively with 250 g of 10 wt% aqueous sodium hydrogencarbonate and 250 g of 20 wt% brine, and then anhydrous. After drying with magnesium sulfate, the solution was concentrated until the liquid volume became 500 g. While cooling the concentrated solution with ice, 1 L of n-hexane was added dropwise over 30 minutes, followed by stirring for 30 minutes. The precipitated crystals are collected by filtration, washed with 200 ml of n-hexane, and dried to give 1- (2-trifluoromethyl-2-propenoyloxy) -3,5- represented by the following formula (13). 137 g of dihydroxyadamantane was obtained. The raw material 1,3,5-adamantanetriol used was synthesized by the method described in JP-A-9-327626.
[Spectral data of 1- (2-trifluoromethyl-2-propenoyloxy) -3,5-dihydroxyadamantane]
¹ H-NMR (DMSO-d ₆ ) δ: 1.40-1.50 (m, 5H), 1.54-1.58 (m, 1H), 1.87 (d, 2H), 1.89-1.95 (m, 4H), 2.24 (m, 1H), 4.80 (s, 2H), 6.60 (s, 1H), 6.70 (s, 1H)

Example 2
A three-necked flask equipped with a Dean Stark apparatus and a thermometer was charged with 150 g of 1,3-adamantanediol, 125 g of 2-trifluoromethylacrylic acid, 18.2 g of p-methoxyphenol, and 1500 g of toluene. The mixture was heated to a temperature of 80 ° C., a mixed solution of 8.7 g of sulfuric acid and 100 g of toluene was added dropwise over 15 minutes, and the mixture was further heated to reflux for 2.5 hours for dehydration reaction. The reaction solution was allowed to cool to room temperature, and 1500 g of 5 wt% saline was added for extraction. The aqueous layer was extracted twice with 1.5 L each of ethyl acetate, all the organic layers were combined, and the solvent was distilled off under reduced pressure. The concentrated residue was subjected to silica gel chromatography to obtain 37 g of 1- (2-trifluoromethyl-2-propenoyloxy) -3-hydroxyadamantane represented by the following formula (14). The raw material 1,3-adamantanediol was synthesized by the method described in JP-A-9-327626.
[Spectral data of 1- (2-trifluoromethyl-2-propenoyloxy) -3-hydroxyadamantane]
¹ H-NMR (CDCl ₃ ) δ: 1.53-1.72 (m, 8H), 2.05-2.16 (m, 6H), 2.37 (s, 2H), 6.35 (s, 1H), 6.62 (s, 1H)

還流管、撹拌子、３方コックを備えた１００ｍｌ丸底フラスコに、２−メチル−２−（２−トリフルオロメチル−２−プロペノイルオキシ）プロパン３．８８ｇ（１９．８ｍｍｏｌ）、γ，γ−ジメチル−α−ビニルオキシ−γ−ブチロラクトン３．０９ｇ（１９．８ｍｍｏｌ）、１−（２−トリフルオロメチル−２−プロペノイルオキシ）−３，５−ジヒドロキシアダマンタン３．０３ｇ（９．９ｍｍｏｌ）、及び開始剤［和光純薬工業（株）製、商品名「Ｖ−６５」］０．１０ｇを入れ、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）４．０ｇとメタノール２．０ｇの混合液に溶解させた。続いて、フラスコ内を乾燥窒素置換した後、反応系の温度を６０℃に保ち、窒素雰囲気下、３時間撹拌した。反応液をテトラヒドロフラン３０．０ｇで希釈し、続いてヘキサン４５０ｇと酢酸エチル５０ｇの混合液５００ｇに滴下して、生じた沈殿物を濾過することで精製を行った。回収した沈殿物を減圧乾燥後、テトラヒドロフラン３５ｇに溶解し、続いて水３８０ｇとメタノール１２０ｇの混合液５００ｇに滴下して、生じた沈殿物を濾別することで精製を繰り返した。減圧乾燥後に得られたポリマーは７．６ｇであった。このポリマーをＧＰＣ分析したところ、標準ポリスチレン換算の重量平均分子量が８３００、分子量分布が２．１３であった。また、¹³Ｃ−ＮＭＲ（ＣＤＣｌ₃中）分析の結果、ポリマーの組成は４１：４４：１５（モル比）（構造式の左から順）であった。 Example 3
Synthesis of polymer compounds with the following structure

To a 100 ml round bottom flask equipped with a reflux tube, a stirring bar, and a three-way cock, 3.88 g (19.8 mmol) of 2-methyl-2- (2-trifluoromethyl-2-propenoyloxy) propane, γ, γ -3.09 g (19.8 mmol) of dimethyl-α-vinyloxy-γ-butyrolactone, 3.03 g (9.9 mmol) of 1- (2-trifluoromethyl-2-propenoyloxy) -3,5-dihydroxyadamantane, And 0.10 g of an initiator [trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.] were added and dissolved in a mixture of 4.0 g of propylene glycol monomethyl ether acetate (PGMEA) and 2.0 g of methanol. . Subsequently, after replacing the inside of the flask with dry nitrogen, the temperature of the reaction system was kept at 60 ° C., and the mixture was stirred for 3 hours in a nitrogen atmosphere. The reaction solution was diluted with 30.0 g of tetrahydrofuran, subsequently added dropwise to 500 g of a mixture of 450 g of hexane and 50 g of ethyl acetate, and purification was performed by filtering the resulting precipitate. The recovered precipitate was dried under reduced pressure, dissolved in 35 g of tetrahydrofuran, subsequently dropped into 500 g of a mixture of 380 g of water and 120 g of methanol, and purification was repeated by separating the resulting precipitate by filtration. The polymer obtained after drying under reduced pressure was 7.6 g. When the GPC analysis of this polymer was carried out, the weight average molecular weight of standard polystyrene conversion was 8300, and molecular weight distribution was 2.13. As a result of ¹³ C-NMR (in CDCl ₃ ) analysis, the polymer composition was 41:44:15 (molar ratio) (in order from the left of the structural formula).

原料モノマーとして、２−メチル−２−（２−トリフルオロメチル−２−プロペノイルオキシ）プロパン３．１４ｇ（１６．０ｍｍｏｌ）、１−ビニルオキシ−４−オキサトリシクロ［４．３．１．１^3,8］ウンデカン−５−オン４．７６ｇ（２２．９ｍｍｏｌ）、１−（２−トリフルオロメチル−２−プロペノイルオキシ）−３，５−ジヒドロキシアダマンタン２．１０ｇ（６．９ｍｍｏｌ）を用いた以外は実施例３と同様の手順で高分子化合物を合成した。減圧乾燥後に得られたポリマーは８．２ｇであった。このポリマーをＧＰＣ分析したところ、標準ポリスチレン換算の重量平均分子量が８１００、分子量分布が２．０９であった。また、¹³Ｃ−ＮＭＲ（ＣＤＣｌ₃中）分析の結果、ポリマーの組成は３７：４５：１８（モル比）（構造式の左から順）であった。 Example 4
Synthesis of polymer compounds with the following structure

As a raw material monomer, 2-methyl-2- (2-trifluoromethyl-2-propenoyloxy) propane 3.14 g (16.0 mmol), 1-vinyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] 4.76 g (22.9 mmol) of undecan-5-one and 2.10 g (6.9 mmol) of 1- (2-trifluoromethyl-2-propenoyloxy) -3,5-dihydroxyadamantane were used. A polymer compound was synthesized by the same procedure as in Example 3 except that. The polymer obtained after drying under reduced pressure was 8.2 g. When this polymer was analyzed by GPC, the weight average molecular weight in terms of standard polystyrene was 8100, and the molecular weight distribution was 2.09. As a result of ¹³ C-NMR (in CDCl ₃ ) analysis, the polymer composition was 37:45:18 (molar ratio) (in order from the left of the structural formula).

還流管、撹拌子、３方コックを備えた１００ｍｌ丸底フラスコに、２−メチル−２−（２−トリフルオロメチル−２−プロペノイルオキシ）プロパン３．９４ｇ（２０．１ｍｍｏｌ）、γ，γ−ジメチル−α−ビニルオキシ−γ−ブチロラクトン３．１４ｇ（２０．１ｍｍｏｌ）、１−（２−トリフルオロメチル−２−プロペノイルオキシ）−３−ヒドロキシアダマンタン２．９２ｇ（１０．１ｍｍｏｌ）、及び開始剤［和光純薬工業（株）製、商品名「Ｖ−６５」］０．１０ｇを入れ、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）４．０ｇとメタノール２．０ｇの混合液に溶解させた。続いて、フラスコ内を乾燥窒素置換した後、反応系の温度を６０℃に保ち、窒素雰囲気下、３時間撹拌した。反応液をテトラヒドロフラン３０．０ｇで希釈し、続いてヘキサン４５０ｇと酢酸エチル５０ｇの混合液５００ｇに滴下して、生じた沈殿物を濾過することで精製を行った。回収した沈殿物を減圧乾燥後、テトラヒドロフラン３５ｇに溶解し、続いてヘキサン４５０ｇと酢酸エチル５０ｇの混合液５００ｇに滴下して、生じた沈殿物を濾別することで精製を繰り返した。減圧乾燥後に得られたポリマーは７．３ｇであった。このポリマーをＧＰＣ分析したところ、標準ポリスチレン換算の重量平均分子量が８１００、分子量分布が２．１４であった。また、¹³Ｃ−ＮＭＲ（ＣＤＣｌ₃中）分析の結果、ポリマーの組成は３９：４２：１９（モル比）（構造式の左から順）であった。 Example 5
Synthesis of polymer compounds with the following structure

To a 100 ml round bottom flask equipped with a reflux tube, a stirring bar, and a three-way cock, 3.94 g (20.1 mmol) of 2-methyl-2- (2-trifluoromethyl-2-propenoyloxy) propane, γ, γ -Dimethyl-α-vinyloxy-γ-butyrolactone 3.14 g (20.1 mmol), 1- (2-trifluoromethyl-2-propenoyloxy) -3-hydroxyadamantane 2.92 g (10.1 mmol), and initiation 0.10 g of an agent [trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.] was added and dissolved in a mixed solution of 4.0 g of propylene glycol monomethyl ether acetate (PGMEA) and 2.0 g of methanol. Subsequently, after replacing the inside of the flask with dry nitrogen, the temperature of the reaction system was kept at 60 ° C., and the mixture was stirred for 3 hours in a nitrogen atmosphere. The reaction solution was diluted with 30.0 g of tetrahydrofuran, subsequently added dropwise to 500 g of a mixture of 450 g of hexane and 50 g of ethyl acetate, and purification was performed by filtering the resulting precipitate. The collected precipitate was dried under reduced pressure, dissolved in 35 g of tetrahydrofuran, subsequently dropped into 500 g of a mixture of 450 g of hexane and 50 g of ethyl acetate, and purification was repeated by separating the resulting precipitate by filtration. The polymer obtained after drying under reduced pressure was 7.3 g. When this polymer was analyzed by GPC, it had a weight average molecular weight of 8100 in terms of standard polystyrene and a molecular weight distribution of 2.14. As a result of ¹³ C-NMR (in CDCl ₃ ) analysis, the polymer composition was 39:42:19 (molar ratio) (in order from the left of the structural formula).

原料モノマーとして、２−メチル−２−（２−トリフルオロメチル−２−プロペノイルオキシ）プロパン３．１７ｇ（１６．２ｍｍｏｌ）、１−ビニルオキシ−４−オキサトリシクロ［４．３．１．１^3,8］ウンデカン−５−オン４．８１ｇ（２３．１ｍｍｏｌ）、１−（２−トリフルオロメチル−２−プロペノイルオキシ）−３−ヒドロキシアダマンタン２．０１ｇ（６．９ｍｍｏｌ）を用いた以外は実施例５と同様の手順で高分子化合物を合成した。減圧乾燥後に得られたポリマーは７．３ｇであった。このポリマーをＧＰＣ分析したところ、標準ポリスチレン換算の重量平均分子量が７９００、分子量分布が２．０８であった。また、¹³Ｃ−ＮＭＲ（ＣＤＣｌ₃中）分析の結果、ポリマーの組成は３８：４６：１６（モル比）（構造式の左から順）であった。 Example 6
Synthesis of polymer compounds with the following structure

As raw material monomers, 3.17 g (16.2 mmol) of 2-methyl-2- (2-trifluoromethyl-2-propenoyloxy) propane, 1-vinyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] Other than using 4.81 g (23.1 mmol) of undecan-5-one and 2.01 g (6.9 mmol) of 1- (2-trifluoromethyl-2-propenoyloxy) -3-hydroxyadamantane Synthesized a polymer compound by the same procedure as in Example 5. The polymer obtained after drying under reduced pressure was 7.3 g. When this polymer was analyzed by GPC, the weight average molecular weight in terms of standard polystyrene was 7900, and the molecular weight distribution was 2.08. As a result of ¹³ C-NMR (in CDCl ₃ ) analysis, the polymer composition was 38:46:16 (molar ratio) (in order from the left of the structural formula).

原料モノマーとして、２−メチル−２−（２−トリフルオロメチル−２−プロペノイルオキシ）プロパン３．８０ｇ（１９．３ｍｍｏｌ）、α−（２−トリフルオロメチル−２−プロペノイルオキシ）−γ−ブチロラクトン２．１６ｇ（９．７ｍｍｏｌ）、１，３−ジヒドロキシ−５−ビニルオキシアダマンタン４．０５ｇ（１９．３ｍｍｏｌ）を用いた以外は実施例３と同様の手順で高分子化合物を合成した。減圧乾燥後に得られたポリマーは７．５ｇであった。このポリマーをＧＰＣ分析したところ、標準ポリスチレン換算の重量平均分子量が８３００、分子量分布が２．１２であった。また、¹³Ｃ−ＮＭＲ（ＣＤＣｌ₃中）分析の結果、ポリマーの組成は３８：１８：４４（モル比）（構造式の左から順）であった。 Example 7
Synthesis of polymer compounds with the following structure

As raw material monomers, 2-methyl-2- (2-trifluoromethyl-2-propenoyloxy) propane 3.80 g (19.3 mmol), α- (2-trifluoromethyl-2-propenoyloxy) -γ A polymer compound was synthesized in the same procedure as in Example 3 except that 2.16 g (9.7 mmol) of butyrolactone and 4.05 g (19.3 mmol) of 1,3-dihydroxy-5-vinyloxyadamantane were used. The polymer obtained after drying under reduced pressure was 7.5 g. When the GPC analysis of this polymer was carried out, the weight average molecular weight of standard polystyrene conversion was 8300, and molecular weight distribution was 2.12. As a result of ¹³ C-NMR (in CDCl ₃ ) analysis, the composition of the polymer was 38:18:44 (molar ratio) (in order from the left of the structural formula).

原料モノマーとして、２−メチル−２−（２−トリフルオロメチル−２−プロペノイルオキシ）プロパン３．９０ｇ（１９．９ｍｍｏｌ）、α−（２−トリフルオロメチル−２−プロペノイルオキシ）−γ−ブチロラクトン２．２３ｇ（１０．０ｍｍｏｌ）、１−ヒドロキシ−３−ビニルオキシアダマンタン３．８６ｇ（１９．９ｍｍｏｌ）を用いた以外は実施例５と同様の手順で高分子化合物を合成した。減圧乾燥後に得られたポリマーは８．５ｇであった。このポリマーをＧＰＣ分析したところ、標準ポリスチレン換算の重量平均分子量が８８００、分子量分布が２．２１であった。また、¹³Ｃ−ＮＭＲ（ＣＤＣｌ₃中）分析の結果、ポリマーの組成は３９：２１：４０（モル比）（構造式の左から順）であった。 Example 8
Synthesis of polymer compounds with the following structure

As raw material monomers, 2-methyl-2- (2-trifluoromethyl-2-propenoyloxy) propane 3.90 g (19.9 mmol), α- (2-trifluoromethyl-2-propenoyloxy) -γ -A polymer compound was synthesized in the same procedure as in Example 5 except that 2.23 g (10.0 mmol) of butyrolactone and 3.86 g (19.9 mmol) of 1-hydroxy-3-vinyloxyadamantane were used. The polymer obtained after drying under reduced pressure was 8.5 g. When the GPC analysis of this polymer was carried out, the weight average molecular weight of standard polystyrene conversion was 8800, and molecular weight distribution was 2.21. As a result of ¹³ C-NMR (in CDCl ₃ ) analysis, the composition of the polymer was 39:21:40 (molar ratio) (in order from the left of the structural formula).

Evaluation test (polymer permeability)
About each polymer obtained in the said Examples 3-8, 1 g of this polymer was dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA), and it filtered with a 0.2 micrometer filter, and prepared the polymer solution. These polymer solutions were applied onto an MgF ₂ substrate by spin coating, and then baked at 100 ° C. for 120 seconds using a hot plate to prepare a polymer film having a thickness of 100 nm. When the transmittance of light at a wavelength of 157 nm of this polymer film was measured using a vacuum ultraviolet photometer [manufactured by JASCO Corporation, VUV-200S], it was 45% or more in any case.

(Preparation of resist and formation of pattern)
For the polymers obtained in Examples 3 to 8, 100 parts by weight of the polymer and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were mixed with propylene glycol monomethyl ether acetate (PGMEA) as a solvent to obtain a polymer concentration of 17 A resin composition for weight% photoresist was prepared. This composition was applied to a silicon wafer by a spin coating method to form a photosensitive layer having a thickness of 1.0 μm. After pre-baking at a temperature of 100 ° C. for 150 seconds using a hot plate, exposure was performed at a dose of 30 mJ / cm ² through a mask using a KrF excimer laser with a wavelength of 247 nm, and then post-baking was performed at a temperature of 100 ° C. for 60 seconds. Subsequently, development was performed with a 0.3 M aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water. In each case, a 0.20 μm line and space pattern was obtained.

Claims (9)

Following formula (1a) or (1b)

(In the formula, R ¹ and R ² each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and R ³ represents a fluorine atom or a fluoroalkyl group. The ring in the formula has a substituent. May be)
A polymerizable adamantane derivative represented by: Following formula (2a) or (2b)

(The ring in the formula may have a substituent)
An adamantanol represented by the following formula (3)

(Wherein R ¹ and R ² each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and R ³ represents a fluorine atom or a fluoroalkyl group)
Is reacted with an unsaturated carboxylic acid represented by the following formula (1a) or (1b)

(In the formula, R ¹ , R ² and R ³ are the same as above. The ring in the formula may have a substituent)
A process for producing a polymerizable adamantane derivative, characterized in that a compound represented by the formula: Following formula (4a) or (4b)

(Wherein R ¹ , R ² and R ⁴ each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group, and n represents 0 or 1, provided that when n = 1, R ⁴ Is a fluorine atom or a fluoroalkyl group, and the ring in the formula may have a substituent)
The high molecular compound containing the repeating unit corresponding to the polymerizable adamantane derivative represented by these. Furthermore, the high molecular compound of Claim 3 containing the repeating unit which has an acid-elimination function. Furthermore, the following formula (5a) or (5b)

[In the formula (5a), the ring Z ¹ is represented by the following formula (6a), (6b), (6c), (6d), (6e), (6f), (6g) or (6h)

(Wherein Y ¹ represents an alkylene group, an oxygen atom or a sulfur atom, and Y ² , Y ³ , Y ⁴ and Y ⁵ represent an alkylene group, an oxygen atom, a sulfur atom or no bond, respectively. A, c , D and e each represent an integer of 0 to 3, and b represents 1 or 2. The ring in the formula may have a substituent.
And W ¹ represents a divalent hydrocarbon group. R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group. p represents 0 or 1, and q represents an integer of 1 to 8. When q is 2 or more, the groups in q parentheses may be the same or different. In formula (5b), R ⁸ represents an alkyl group which may have a substituent. R ⁵ , R ⁶ and R ⁷ are the same as above. r shows the integer of 1-8. when r is 2 or more, the groups in r parentheses may be the same or different.]
The high molecular compound of Claim 3 containing the repeating unit corresponding to the acrylate-type monomer represented by [However, the compound represented by Formula (4a), (4b) is remove | excluded]. Furthermore, the following formula (7a) or (7b)

[In the formula (7a), ring Z ² represents the following formula (6a), (6b), (6c), (6d), (6e), (6f), (6g) or (6h)

(Wherein Y ¹ represents an alkylene group, an oxygen atom or a sulfur atom, and Y ² , Y ³ , Y ⁴ and Y ⁵ represent an alkylene group, an oxygen atom, a sulfur atom or no bond, respectively. A, c , D and e each represent an integer of 0 to 3, and b represents 1 or 2. The ring in the formula may have a substituent.
And W ² represents a divalent hydrocarbon group. R ⁹ , R ¹⁰ and R ¹¹ are the same or different and each represents a hydrogen atom or an organic group. At least two of the rings Z ² , W ² , R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring together with one or more adjacent atoms. s represents 0 or 1, and t represents an integer of 1 to 8. When t is 2 or more, the groups in t parentheses may be the same or different. In formula (7b), R ¹² represents an alkyl group which may have a substituent, and R ¹³ , R ¹⁴ and R ¹⁵ are the same or different and represent a hydrogen atom or an organic group. At least two of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring together with one or more adjacent atoms. u represents an integer of 1 to 8. When u is 2 or more, the groups in u parentheses may be the same or different.]
The polymer compound according to claim 3 or 5, comprising a repeating unit corresponding to a vinyl ether monomer represented by the formula (except for the compounds represented by formulas (4a) and (4b)). Furthermore, the following formula (8a) or (8b)

[In formulas (8a) and (8b), Y ⁶ and Y ⁷ each represent an alkylene group, an oxygen atom, a sulfur atom, or no bond. Y ⁸ represents an oxygen atom or a —NH— group. f shows the integer of 0-3. (The atoms constituting the ring in the formula may have a substituent)
The polymer compound according to claim 3, comprising a repeating unit corresponding to the cyclic unsaturated monomer represented by the formula: A resin composition for a photoresist, comprising at least the polymer compound according to claim 3 and a photoacid generator. A method for producing a semiconductor, comprising: applying a resin composition for a photoresist according to claim 8 to a substrate or a substrate to form a resist coating film; and exposing and developing to form a pattern.