JP2022008650A - Resin, resist composition and production method of resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin and a resist composition that enable production of a resist pattern with excellent line edge roughness.

SOLUTION: A resin includes: a structural unit derived from a chemical compound expressed by a formula (I) and at least one kind of structural unit selected from a group composed of structural units expressed by formulas (a4-0) to (a4-4); or these structural units and a structural unit expressed by a formula (a5-1). Based on a sum total of all the structural units of the resin, a percentage content of the structural unit of the formula (I) is 1 to 10 mol%, a total percentage content of the structural unit expressed by the formulas (a4-0), etc. is 90 to 99 mol%. If the resin includes the structural unit expressed by the formula (a5-1), a total percentage content of the structural units expressed by the formulas (a4-0), etc. and the structural unit expressed by the formula (a5-1) is 90 to 99 mol%, and a percentage content of the structural unit expressed by the formula (a5-1) is 2 to 80 mol%. In the resin, a weight average molecular weight is 6000 to 80000.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a resin, a resist composition containing the resin, a method for producing a resist pattern using the resist composition, and the like.

Patent Document 1 describes a resin composed of the following structural units.

Japanese Unexamined Patent Publication No. 2004-91613

In the resist composition using the above resin, the line edge roughness (LER) may not always be satisfactory.

［式（Ｉ）中、
Ｒ^１及びＲ^２は、それぞれ独立に、ハロゲン原子を有してもよい炭素数１～６のアルキ
ル基、水素原子又はハロゲン原子を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１～４のアルキル基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、炭素数１～６のアルカンジイル基又は^＊－Ａ^３－Ｘ
¹－（Ａ^４－Ｘ²）_a－Ａ^５－を表す。＊は酸素原子との結合手を表す。但し、酸素原子と
の結合位の炭素原子は３級炭素原子ではない。
Ａ^３、Ａ^４及びＡ^５は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、酸素原子、カルボニルオキシ基又はオキシカルボニル
基を表す。
ａは、０又は１を表す。］
〔２〕Ａ¹及びＡ^２が、それぞれ独立に、炭素数１～６のアルカンジイル基である〔１
〕記載の樹脂。
〔３〕〔１〕又は〔２〕記載の樹脂、酸不安定基を有する構造単位を有する樹脂（Ａ）
及び酸発生剤を含有するレジスト組成物。
〔４〕酸発生剤が、式（Ｂ１）で表される塩である〔３〕記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１～６のペルフルオロアルキル
基を表す。
Ｌ^b1は、置換基を有していてもよい炭素数１～２４の２価の飽和炭化水素基を表し、該
２価の飽和炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていて
もよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で
置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１
８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる－ＣＨ₂－は
、－Ｏ－、－ＳＯ₂－又は－ＣＯ－に置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］
〔５〕酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する〔
３〕又は〔４〕記載のレジスト組成物。
〔６〕（１）〔３〕～〔５〕のいずれかに記載のレジスト組成物を基板上に塗布する工
程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resin having a structural unit derived from the compound represented by the formula (I) and a structural unit (a4) having a fluorine atom.

[In formula (I),
R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom which may have a halogen atom.
R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² are independently alkanediyl groups having 1 to 6 carbon atoms or ^* -A ³ -X.
^1- (A ⁴ -X ² ) _a -A ⁵ -represents. * Represents a bond with an oxygen atom. However, the carbon atom in the binding site with the oxygen atom is not a tertiary carbon atom.
A ³ , A ⁴ and A ⁵ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² independently represent an oxygen atom, a carbonyloxy group or an oxycarbonyl group, respectively.
a represents 0 or 1. ]
[2] A ¹ and A ² are independently alkanediyl groups having 1 to 6 carbon atoms [1].
] The resin described.
[3] The resin according to [1] or [2], a resin having a structural unit having an acid unstable group (A).
And a resist composition containing an acid generator.
[4] The resist composition according to [3], wherein the acid generator is a salt represented by the formula (B1).

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH _2- contained in the divalent saturated hydrocarbon group is -O- or. It may be replaced with —CO—, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced with a fluorine atom or a hydroxy group.
Y may have a methyl group or a substituent which may have a substituent, and may have 3 to 1 carbon atoms.
Represents a monovalent alicyclic hydrocarbon group of 8, even if -CH _2- contained in the monovalent alicyclic hydrocarbon group is replaced with -O-, -SO _2- or -CO-. good.
Z ⁺ represents an organic cation. ]
[5] Further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator [
3] or the resist composition according to [4].
[6] (1) A step of applying the resist composition according to any one of [3] to [5] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A method for producing a resist pattern, which comprises a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

By using a resist composition using the resin of the present invention, line edge roughness (
LER) can produce a good resist pattern.

As used herein, the term "(meth) acrylate" means "at least one of acrylate and methacrylate," respectively. Notations such as "(meth) acrylic acid" and "(meth) acryloyl" have the same meaning.
Further, unless otherwise specified, a group capable of taking a linear, branched and / or ring such as "aliphatic hydrocarbon group" includes any of them. The "aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bonded to an aromatic ring. If a steric isomer is present, it includes all steric isomers.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

<Resin>
The resin of the present invention has a structural unit derived from a compound represented by the formula (I) (hereinafter, may be referred to as “compound (I)”) (hereinafter, may be referred to as “structural unit (I)”) and fluorine. It is a resin (hereinafter, may be referred to as “resin (X)”) including a structural unit (a4) having an atom (hereinafter, may be referred to as “structural unit (a4)”).

［式（Ｉ）中、
Ｒ^１及びＲ^２は、それぞれ独立に、ハロゲン原子を有してもよい炭素数１～６のアルキ
ル基、水素原子又はハロゲン原子を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１～４のアルキル基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、炭素数１～６のアルカンジイル基又は^＊－Ａ^３－Ｘ
¹－（Ａ^４－Ｘ²）_a－Ａ^５－を表す。＊は酸素原子との結合手を表す。但し、酸素原子と
の結合位の炭素原子は３級炭素原子ではない。
Ａ^３、Ａ^４及びＡ^５は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、酸素原子、カルボニルオキシ基又はオキシカルボニル
基を表す。
ａは、０又は１を表す。］ <Structural unit (I)>
The structural unit (I) is a structural unit derived from the compound (I).

[In formula (I),
R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom which may have a halogen atom.
R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² are independently alkanediyl groups having 1 to 6 carbon atoms or ^* -A ³ -X.
^1- (A ⁴ -X ² ) _a -A ⁵ -represents. * Represents a bond with an oxygen atom. However, the carbon atom in the binding site with the oxygen atom is not a tertiary carbon atom.
A ³ , A ⁴ and A ⁵ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² independently represent an oxygen atom, a carbonyloxy group or an oxycarbonyl group, respectively.
a represents 0 or 1. ]

Alkyl groups of R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n.
-Hexyl groups and the like are mentioned, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group and an ethyl group.
Examples of the halogen atom of R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Alkyl groups having halogen atoms of R ¹ and R ² include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group and perfluoropentyl. Examples thereof include a group, a perfluorohexyl group, a perchloromethyl group, a perbromomethyl group and a periodomethyl group.
R ¹ and R ² are preferably hydrogen atoms or methyl groups.

Examples of the alkyl group of R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a sec-butyl group, and an alkyl group having 1 to 3 carbon atoms is preferable. , More preferably a methyl group and an ethyl group, and even more preferably.
It is a methyl group.

The alkanediyl groups having ¹ to ⁶ carbon atoms of A1, ^A2 , A3 ^{, A4} and A5 include methylene group, ethylene group, propane-1,3-diyl group and butane-1,4-diyl group. , Pentan-1,5-diyl group, hexane-1,6-diyl group and other linear alkanediyl groups, linear alkanediyl groups, and alkyl groups (particularly, alkyl groups having 1 to 4 carbon atoms). Methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, etc.) with side chains, ethane-1,1-diyl group, propane-1,2-diyl Moto,
Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4- Examples thereof include a branched alkanediyl group such as a diyl group.

^* -A ³ -X ^1- (A ⁴ -X ² ) _a -A ^5- , ^* -A ³ -CO-O-A ^5- , ^*
-A ³ -O-CO-A ^5- , ^* -A ³ -CO-O-A ⁴ -CO-O-A ^5- , etc. may be mentioned. Of these, ^* -A ³ -CO-O-A ^5-- is preferable. * Represents a bond with an oxygen atom.

A ¹ , A ² , A ³ , A ⁴ and A ⁵ are independent, preferably alkanediyl groups having 1 to 6 carbon atoms.
A ¹ and A ² are each independently preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, and an alkane having 1 to 2 carbon atoms. It is more preferably a diyl group.

Examples of the compound (I) include compounds represented by the following formulas.

Among the compounds represented by the formulas (I-1) to (I-6), compounds in which both or one of the methyl groups corresponding to R ¹ and R ² are replaced with hydrogen atoms are also specific compounds of the compound (I). It can be given as an example.

［式中、Ｒ¹、Ｒ²、Ｒ^３、Ｒ^４、Ａ^１及びＡ^２は、上記と同義である。］ <Method for producing compound (I)>
(1) The compound (I) can be obtained by reacting a compound represented by the formula (Ia) with a compound represented by the formula (Ib) in the presence of a base catalyst in a solvent. Can be done.

[In the formula, R ¹ , R ² , R ³ , R ⁴ , A ¹ and A ² are synonymous with the above. ]

Examples of the solvent include chloroform, tetrahydrofuran, toluene and the like.
Examples of the base catalyst include pyridine, dimethylaminopyridine and the like.
Examples of the compound represented by the formula (Ib) include compounds represented by the following formula, which can be easily obtained from the market.

溶媒としては、クロロホルム、テトラヒドロフラン及びトルエンなどが挙げられる。
塩基触媒としては、ピリジン、ジメチルアミノピリジンなどが挙げられる。
式（Ｉ－ｃ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場
より容易に入手することができる。

式（Ｉ－ｄ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場
より容易に入手することができる。

The compound represented by the formula (Ia) is a reaction between the compound represented by the formula (Ic) and the compound represented by the formula (Id) in the presence of a base catalyst in a solvent. It can also be obtained by letting it.

Examples of the solvent include chloroform, tetrahydrofuran, toluene and the like.
Examples of the base catalyst include pyridine, dimethylaminopyridine and the like.
Examples of the compound represented by the formula (Ic) include compounds represented by the following formula, which can be easily obtained from the market.

Examples of the compound represented by the formula (Id) include compounds represented by the following formula, which can be easily obtained from the market.

溶媒としては、クロロホルム、テトラヒドロフラン及びトルエンなどが挙げられる。
塩基触媒としては、ピリジン、ジメチルアミノピリジンなどが挙げられる。 (2) The compound (II) in which R ¹ and R ² have the same group is a compound represented by the formula (Ic) and a compound represented by the formula (Id) in the presence of a base catalyst. , Can be obtained by reacting in a solvent.

Examples of the solvent include chloroform, tetrahydrofuran, toluene and the like.
Examples of the base catalyst include pyridine, dimethylaminopyridine and the like.

［式（ａ４－０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^５は、単結合又は炭素数１～４の脂肪族飽和炭化水素基を表す。
Ｌ^３は、炭素数１～８のペルフルオロアルカンジイル基又は炭素数３～１２のペルフル
オロシクロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ <Structural unit (a4)>
The structural unit (a4) having a fluorine atom is preferably a structural unit having a fluorine atom and no acid unstable group.
Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0).

[In equation (a4-0),
^R5 represents a hydrogen atom or a methyl group.
L ⁵ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

Examples of the aliphatic saturated hydrocarbon group of L ⁵ include a methylene group, an ethylene group, and a propane-1,3-.
Linear alkanediyl group such as diyl group, butane-1,4-diyl group, ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methyl Examples thereof include branched alkanediyl groups such as a propane-1,3-diyl group and a 2-methylpropane-1,2-diyl group.

Examples of the perfluoroalkanediyl group of L ³ include a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, and a perfluoropropane-1,3-.
Diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2,2-
Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2- Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7- Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctanoic-1,8-diyl group, perfluorooctano-2,2- Examples thereof include a diyl group, a perfluorooctane-3,3-diyl group, and a perfluorooctano-4,4-diyl group.
Examples of the perfluorocycloalkanediyl group of L ³ include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, and a perfluorocycloheptanediyl group.
Examples thereof include a perfluoroadamantandiyl group.

^L5 is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
L ³ is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms, and further preferably 1 to 3 carbon atoms.
It is a perfluoroalkanediyl group of 2, and particularly preferably a difluoromethylene group.

Examples of the structural unit (a4-0) include the following structural units.

In the compounds represented by the formulas (a4-0-1) to (a4-0-16), R ⁵
A compound in which the methyl group corresponding to the above is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit represented by the formula (a4-0).

［式（ａ４－１）中、
Ｒ^ａ４１は、水素原子又はメチル基を表す。
Ｒ^ａ４２は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水
素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ａ^ａ４１は、置換基を有していてもよい炭素数１～６のアルカンジイル基又は式（ａ－
ｇ１）で表される基を表す。］

［式（ａ－ｇ１）中、
ｓは、０又は１を表す。
Ａ^ａ４２及びＡ^ａ４４は、互いに独立に、置換基を有していてもよい炭素数１～５の脂
肪族炭化水素基を表す。
Ａ^ａ４３は、単結合又は置換基を有していてもよい炭素数１～５の脂肪族炭化水素基を
表す。
Ｘ^ａ４１及びＸ^ａ４２は、互いに独立に、酸素原子、カルボニル基、カルボニルオキシ
基又はオキシカルボニル基を表す。
ただし、Ａ^ａ４２、Ａ^ａ４３、Ａ^ａ４４、Ｘ^ａ４１及びＸ^ａ４２の炭素数の合計は７以
下である。
＊及び＊＊は結合手を表し、＊＊が－Ｏ－ＣＯ－Ｒ^ａ４２との結合手である。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-1).

[In equation (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-. good.
^Aa41 is an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a formula (a-).
Represents a group represented by g1). ]

[In the formula (ag1),
s represents 0 or 1.
^Aa42 and ^Aa44 represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent independently of each other.
^Aa43 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 independently represent an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less.
** and ** represent a bond, and ** is a bond with -O-CO-R ^a42 . ]

Examples of the hydrocarbon group of R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups.
Chain and cyclic aliphatic hydrocarbon groups may have carbon-carbon unsaturated bonds, but are formed by chain and cyclic aliphatic saturated hydrocarbon groups and their combination. Groups are preferred. The aliphatic saturated hydrocarbon group is a fat formed by combining a linear or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group. Examples include group hydrocarbon groups.

Chain-type aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-decyl. Examples thereof include an alkyl group such as a group, an n-dodecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group and an n-octadecyl group. The cyclic aliphatic hydrocarbon group includes a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* is a bond). A polycyclic group such as (representing a hand) can be mentioned.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthryl group and a fluorenyl group.

［式（ａ－ｇ３）中、
Ｘ^ａ４３は、酸素原子、カルボニル基、カルボニルオキシ基又はオキシカルボニル基を
表す。
Ａ^ａ４５は、少なくとも１つのハロゲン原子を有する炭素数１～１７の脂肪族炭化水素
基を表す。
＊は、結合手を表す。］ Examples of the substituent of R ^a42 include a halogen atom or a group represented by the formula (ag3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

[In the formula (ag3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
^Aa45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and having at least one halogen atom.
* Represents a bond. ]

Examples of the aliphatic hydrocarbon group of A ^a45 include the same groups as those exemplified in Ra ⁴² .
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and is an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (ag3). Is more preferable.
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably having a carbon number of carbon atoms. It is a perfluoroalkyl group of 1 to 6, and more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.

When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (ag3), the formula (
The total number of carbon atoms of the aliphatic hydrocarbon group is 1 including the number of carbon atoms contained in the group represented by ag3).
5 or less is preferable, and 12 or less is more preferable. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.

［式（ａ－ｇ２）中、
Ａ^ａ４６は、ハロゲン原子を有していてもよい炭素数１～１７の脂肪族炭化水素基を表
す。
Ｘ^ａ４４は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^ａ４７は、ハロゲン原子を有していてもよい炭素数１～１７の脂肪族炭化水素基を表
す。
ただし、Ａ^ａ４６、Ａ^ａ４７及びＸ^ａ４４の炭素数の合計は１８以下であり、Ａ^ａ４６
及びＡ^ａ４７のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊は結合手を表す。］ The aliphatic hydrocarbon group having a group represented by the formula (ag3) is more preferably the formula (a-).
It is a group represented by g2).

[In the formula (ag2),
^Aa46 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents a carbonyloxy group or an oxycarbonyl group.
^Aa47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47 and X ^a44 is 18 or less, and A ^a46.
And A ^a47 , at least one has at least one halogen atom.
* Represents a bond. ]

The number of carbon atoms in the aliphatic hydrocarbon group of ^Aa46 is preferably 1 to 6, and more preferably 1 to 3.
The aliphatic hydrocarbon group of A ^a47 preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and even more preferably a cyclohexyl group or an adamantyl group.

The preferred structure represented by * -A ^a46- X ^a44 -A ^a47 is the following structure.

The alkanediyl group of ^Aa41 includes a methylene group, an ethylene group, and a propane-1,3-.
Diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6
-Linear alkanediyl group such as diyl group; propane-1,2-diyl group, butane-1,3
Examples thereof include a branched alkanediyl group such as a diyl group, a 2-methylpropane-1,2-diyl group, a 1-methylbutane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.
As the substituent in the alkanediyl group of ^Aa41 , a hydroxy group and 1 to 6 carbon atoms are used.
Alkoxy group and the like can be mentioned.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and further preferably an ethylene group.

The aliphatic hydrocarbon groups ^Aa42 to ^Aa44 in the group (a-g1) may have a carbon-carbon unsaturated bond, but chain-type and ring-type aliphatic saturated hydrocarbon groups and these are used. Groups formed by combination are preferred. Examples of the aliphatic saturated hydrocarbon group include linear and branched alkyl groups, alicyclic hydrocarbon groups, and aliphatic hydrocarbon groups formed by combining an alkyl group and an alicyclic hydrocarbon group. Can be mentioned. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-
Examples thereof include a diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group and the like.
As the substituent of the aliphatic hydrocarbon group of ^Aa42 to ^Aa44 , a hydroxy group and 1 carbon number are used.
Examples thereof include up to 6 alkoxy groups.
s is preferably 0.

Examples of the group (ag1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group include the following groups. In the following examples, * and **
Represents a bond, and ** is a bond with -O-CO-R ^a42 .

［式（ａ４－２）中、
Ｒ^ｆ１は、水素原子又はメチル基を表す。
Ａ^ｆ１は、炭素数１～６のアルカンジイル基を表す。
Ｒ^ｆ２は、フッ素原子を有する炭素数１～１０の炭化水素基を表す。］ As the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2) and the formula (a4-3) is preferable.

[In equation (a4-2),
R ^f1 represents a hydrogen atom or a methyl group.
A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms.
R ^f2 represents a hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom. ]

The alkanediyl group of A ^f1 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-.
Linear alkanediyl groups such as diyl group, hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-
1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-
Examples thereof include a branched alkanediyl group such as a diyl group.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic type and a group formed by a combination thereof. As the aliphatic hydrocarbon group, an alkyl group (straight or branched) and an alicyclic hydrocarbon group are preferable.
Alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n.
-Includes octyl group and 2-ethylhexyl group.
The alicyclic hydrocarbon group may be a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and a cycloheptyl group.
Cycloalkyl groups such as a cyclooctyl group, a cycloheptyl group and a cyclodecyl group can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, and 2-.
Examples thereof include an alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, a norbornyl group, a methylnorbornyl group and an isobornyl group.

Examples of the hydrocarbon group having a fluorine atom of R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
As the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,
1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1-(
Trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,
2-Tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,
1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1
-Bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group,
Perfluoropentyl group, 1,1,2,2,3,3,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3-3 Pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2,3,3,4,4,5
, 5-Decafluorohexyl group, 1,1,2,2,3,4,4,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group and other fluorinated alkyl The group is mentioned.
Examples of the alicyclic hydrocarbon group having a fluorine atom include a fluorocycloalkyl group such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

As ^Af1 in the formula (a4-2), an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.
As R ^f1 , an alkyl fluoride group having 1 to 6 carbon atoms is preferable.

［式（ａ４－３）中、
Ｒ^ｆ１１は、水素原子又はメチル基を表す。
Ａ^ｆ１１は、炭素数１～６のアルカンジイル基を表す。
Ａ^ｆ１３は、フッ素原子を有していてもよい炭素数１～１８の脂肪族炭化水素基を表す
。
Ｘ^ｆ１２は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^ｆ１４は、フッ素原子を有していてもよい炭素数１～１７の脂肪族炭化水素基を表す
。
ただし、Ａ^ｆ１３及びＡ^ｆ１４の少なくとも１つは、フッ素原子を有する脂肪族炭化水
素基を表す。］

[In equation (a4-3),
R ^f11 represents a hydrogen atom or a methyl group.
A ^f11 represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 represents an aliphatic hydrocarbon group having a fluorine atom. ]

Examples of the alkanediyl group of A ^f11 include the same groups as the alkanediyl group of A ^f1 .
The aliphatic hydrocarbon group of A ^f13 includes a chain type and a cyclic type aliphatic hydrocarbon group, and a divalent aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group which may have a fluorine atom of A ^f13 include an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Be done.
Examples of the divalent chain-type aliphatic hydrocarbon group which may have a fluorine atom include a methylene group.
Alcandiyl groups such as ethylene group, propanediyl group, butandyl group and pentandiyl group; perfluoroalkandyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutandyl group and perfluoropentanediyl group can be mentioned. ..
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a group containing either a monocyclic or polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantandiyl group, a norbornanediyl group, and a perfluoroadamantandiyl group.

The aliphatic hydrocarbon group of A ^f14 includes a chain type and a cyclic type aliphatic hydrocarbon group, and an aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f14 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Chain-type aliphatic hydrocarbon groups that may have a fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, and 1,1. , 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, Examples thereof include a heptyl group, a perfluoroheptyl group, an octyl group and a perfluorooctyl group.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl group and the like.

In the formula ( ^a4-3 ), A f11 is preferably an ethylene group.
The aliphatic hydrocarbon group of A ^f13 is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably an aliphatic hydrocarbon group having 2 to 3 carbon atoms.
As the aliphatic hydrocarbon group of A ^f14 , an aliphatic hydrocarbon group having 3 to 12 carbon atoms is preferable, and an aliphatic hydrocarbon group having 3 to 10 carbon atoms is more preferable. Among them, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The structural units represented by the formula (a4-2) include formulas (a4-1-1) to formulas (a4-1-2).
The structural unit represented by 2) can be mentioned.

As the structural unit represented by the formula (a4-3), the formulas (a4-1'-1) to the formula (a4-1') are used.
The structural units represented by -22) are listed.

［式（ａ４－４）中、
Ｒ^ｆ２１は、水素原子又はメチル基を表す。
Ａ^ｆ２１は、－（ＣＨ_２）_ｊ１－、－（ＣＨ_２）_ｊ２－Ｏ－（ＣＨ_２）_ｊ３－又は－（
ＣＨ_２）_ｊ４－ＣＯ－Ｏ－（ＣＨ_２）_ｊ５－を表す。
ｊ１～ｊ５は、互いに独立に、１～６の整数を表す。
Ｒ^ｆ２２は、フッ素原子を有する炭素数１～１０の炭化水素基を表す。］ The structural unit (a4) may be a structural unit represented by the formula (a4-4).

[In equation (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^{f21 is-} (CH ₂ ) _j1 -,-(CH ₂ ) _j2 -O- (CH ₂ ) _j3 -or-(
CH ₂ ) Represents _j4 -CO-O- (CH ₂ ) _j5- .
j1 to j5 represent integers of 1 to 6 independently of each other.
R ^f22 represents a hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom. ]

Examples of the hydrocarbon group having a fluorine atom of R ^f22 include the same hydrocarbon group of R ^f2 in the formula (a4-2). R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and an alkyl having 1 to 10 carbon atoms having a fluorine atom. It is more preferably a group, and further preferably an alkyl group having 1 to 6 carbon atoms having a fluorine atom.

In the formula (a4-4), as A ^f21 , − (CH ₂ ) _j1 − is preferable, an ethylene group or a methylene group is more preferable, and a methylene group is further preferable.

Examples of the structural unit represented by the formula (a4-4) include the following structural units.

In the resin (X), the content of the structural unit (I) is higher than that of all the structural units of the resin (X).
1 to 10 mol% is preferable, 2 to 8 mol% is more preferable, and 3 to 6 mol% is further preferable.
In the resin (X), the content of the structural unit (a4) is preferably 90 to 99 mol%, more preferably 92 to 98 mol%, and 94 to 97 mol% with respect to all the structural units of the resin (X). Is even more preferable.

The resin (X) further has a structural unit having an acid unstable group described later (hereinafter, “structural unit (a1)”.
) ”), A structural unit having no acid unstable group (hereinafter sometimes referred to as“ structural unit (s) ”), a structural unit having a non-eliminating hydrocarbon group (a5), and other known structural units. It may contain a structural unit derived from the monomer of. Above all, it is preferable to include the structural unit (a5).

［式（ａ５－１）中、
Ｒ^５１は、水素原子又はメチル基を表す。
Ｒ^５２は、炭素数３～１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる
水素原子は炭素数１～８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。
ただし、Ｌ^５１との結合位置にある炭素原子に結合する水素原子は、炭素数１～８の脂肪
族炭化水素基で置換されない。
Ｌ^５１は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group of the structural unit (a5) include a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably contains an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).

[In equation (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or a hydroxy group having 1 to 8 carbon atoms. May be.
However, the hydrogen atom bonded to the carbon atom at the bonding position with L ⁵¹ is not substituted with the aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

The alicyclic hydrocarbon group of R ⁵² may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, and the like.
Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group,
Alkyl groups such as a hexyl group, an octyl group and a 2-ethylhexyl group can be mentioned.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-hydroxyadamantyl group and a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group of L ⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. Be done.
Examples of the divalent aliphatic saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl group and a norbornanediyl group.

［式（Ｌ１－１）中、
Ｘ^ｘ１は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ｌ^ｘ１は、炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
Ｌ^ｘ２は、単結合又は炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^ｘ１及びＬ^ｘ２の合計炭素数は、１６以下である。
式（Ｌ１－２）中、
Ｌ^ｘ３は、炭素数１～１７の２価の脂肪族飽和炭化水素基を表す。
Ｌ^ｘ４は、単結合又は炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^ｘ３及びＬ^ｘ４の合計炭素数は、１７以下である。
式（Ｌ１－３）中、
Ｌ^ｘ５は、炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^ｘ６及びＬ^ｘ７は、互いに独立に、単結合又は炭素数１～１４の２価の脂肪族飽和炭
化水素基を表す。
ただし、Ｌ^ｘ５～Ｌ^ｘ７の合計炭素数は、１５以下である。
式（Ｌ１－４）中、
Ｌ^ｘ８及びＬ^ｘ９は、互いに独立に、単結合又は炭素数１～１２の２価の脂肪族飽和炭
化水素基を表す。
Ｗ^ｘ１は、炭素数３～１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^ｘ８、Ｌ^ｘ９及びＷ^ｘ１の合計炭素数は、１５以下である。］ Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by the formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

[In the formula (L1-1),
X ^x1 represents a carbonyloxy group or an oxycarbonyl group.
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total number of carbon atoms of L ^x1 and L ^x2 is 16 or less.
In equation (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total number of carbon atoms of L ^x3 and L ^x4 is 17 or less.
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms independently of each other.
However, the total number of carbon atoms of L ^x5 to L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms independently of each other.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total number of carbon atoms of L ^x8 , L ^x9 and W ^x1 is 15 or less. ]

L ^x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
More preferably, it is a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
More preferably, it is a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
More preferably, it is a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
More preferably, it is a single bond or a methylene group.
W ^x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a cyclohexanediyl group or an adamantanediyl group.

Examples of the group represented by the formula (L1-1) include the divalent group shown below.

Examples of the group represented by the formula (L1-2) include the divalent group shown below.

Examples of the group represented by the formula (L1-3) include the divalent group shown below.

Examples of the group represented by the formula (L1-4) include the divalent group shown below.

L ⁵¹ is preferably a single bond or a group represented by the formula (L1-1).

Examples of the structural unit (a5-1) include the following.

In the formulas (a5-1-1) to (a5-1-18), the structural unit in which the methyl group corresponding to R ⁵¹ is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a5-1). can.

When the resin (X) has the structural unit (a5), the content thereof is preferably 1 to 90 mol% with respect to the total of all the structural units of the resin (X), and 2 to 80 mol%. Is more preferable, and 3 to 70 mol% is further preferable.
When the resin (X) has a structural unit (a5), the structural unit (a4) and the structural unit (a5)
) Is preferably 90 to 99 mol% with respect to all the structural units of the resin (X), 9
2 to 98 mol% is more preferable, and 94 to 97 mol% is even more preferable.

The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7.0).
00 or more), 80,000 or less (more preferably 60,000 or less). The weight average molecular weight is determined by gel permeation chromatography analysis as a conversion value based on standard polystyrene, and detailed analysis conditions for analysis will be described in detail in Examples of the present application.

<Resist composition>
The resist composition of the present invention is a resin (X), a resin having a structural unit having an acid unstable group (
A) and an acid generator (hereinafter sometimes referred to as "acid generator (B)") are contained.
Further, the resist composition preferably contains a quencher (hereinafter, may be referred to as “quencher (C)”) and / or a solvent (hereinafter, may be referred to as “solvent (E)”).

<Resin (A)>
The resin (A) has a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”). The "acid-unstable group" means a group having a leaving group, which is removed by contact with an acid to form a hydrophilic group (eg, a hydroxy group or a carboxy group).
It is preferable that the resin (A) further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include the structural unit (s), other structural units (hereinafter sometimes referred to as “structural unit (t)”), and structural units derived from other known monomers. Be done.

［式（１）中、Ｒ^a1～Ｒ^a3は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３
～２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに
結合してそれらが結合する炭素原子とともに炭素数３～２０の２価の脂環式炭化水素基を
形成する。
ｎａは、０又は１を表す。
＊は結合手を表す。］

［式（２）中、Ｒ^a1’及びＲ^a2’は、それぞれ独立に、水素原子又は炭素数１～１２の
炭化水素基を表し、Ｒ^a3’は、炭素数１～２０の炭化水素基を表すか、Ｒ^a2’及びＲ^a3’
は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３～２０の２価の複素
環基を形成し、該炭化水素基及び該２価の複素環基に含まれる－ＣＨ₂－は、－Ｏ－又は
－Ｓ－で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid unstable group (hereinafter, may be referred to as “monomer (a1)”).
The term "acid-unstable group" as used herein means a group having a leaving group, which is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). .. In the resin (A), the following groups (1) and / or groups (2) are preferable as the acid unstable group contained in the structural unit (a1).

[In the formula (1), R ^a1 to R ^a3 are independently alkyl groups having 1 to 8 carbon atoms and 3 carbon atoms.
Represents an alicyclic hydrocarbon group of ~ 20 or a group combining these, or R ^a1 and R ^a2 are divalent alicyclic hydrocarbons having 3 to 20 carbon atoms together with carbon atoms to which they are bonded to each other. Form a group.
na represents 0 or 1.
* Represents a bond. ]

[In the formula (2), R ^a1'and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Represent or R ^a2'and R ^a3'
Form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and the hydrocarbon group and the divalent heterocyclic group contained-CH _2- , -O- or -S- may be replaced.
X represents an oxygen atom or a sulfur atom.
* Represents a bond. ]

アルキル基と脂環式炭化水素基とを組み合わせた基としては、例えば、メチルシクロヘ
キシル基、ジメチルシクロへキシル基、メチルノルボルニル基、メチルアダマンチル基、
シクロヘキシルメチル基、メチルシクロヘキシルメチル基、アダマンチルメチル基、ノル
ボルニルメチル基等が挙げられる。
ｎａは、好ましくは０である。 The alkyl groups of R ^a1 to R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, and the like.
Examples thereof include an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group.
The alicyclic hydrocarbon group of R ^a1 to R ^a3 may be either a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a bond). The alicyclic hydrocarbon group of R ^a1 to R ^a3 preferably has 3 to 16 carbon atoms.

Examples of the group in which the alkyl group and the alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and a methyladamantyl group.
Examples thereof include a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, a norbornylmethyl group and the like.
na is preferably 0.

-C (R ^a1 ) when R ^a1 and R a ² are bonded to each other to form a divalent alicyclic hydrocarbon group.
Examples of (R ^a2 ) and (R ^a3 ) include the following groups. The divalent alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the hydrocarbon group of R a1'to R ^{a3' include} an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group formed by combining these.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, trill group, xylyl group, cumenyl group, mesityl group and biphenyl. Examples thereof include an aryl group such as a group, a phenanthryl group, a 2,6-diethylphenyl group and a 2-methyl-6-ethylphenyl group.
R ^a2'and R ^a3'bond to each other and form with the carbon atoms and X to which they bond 2
Examples of the valence heterocyclic group include the following groups. * Represents a bond.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^a1 to R ^a3 are alkyl groups in the formula (1), preferably a tert-butoxycarbonyl group). 2-Alkyl adamantan-2-yloxycarbonyl group (in formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- (group) and 1- (in the formula (1)). Examples thereof include adamantan-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups and R ^a3 is an adamantyl group).
Of R ^a1'and R ^a2' , at least one is preferably a hydrogen atom.

Specific examples of the group represented by the formula (2) include the following groups. * Represents a bond.

The monomer (a1) is preferably a monomer having an acid unstable group and an ethylenically unsaturated bond, and more preferably a (meth) acrylic monomer having an acid unstable group.

Of the (meth) acrylic monomers having an acid unstable group, preferably 5 to 20 carbon atoms.
Examples thereof include those having an alicyclic hydrocarbon group of. If the resin (A) having a structural unit derived from the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

In the resin (A), the content of the structural unit (a1) is preferably 30 to 90 mol%, more preferably 35 to 85 mol%, and further, with respect to all the structural units of the resin (A). It is preferably 40 to 80 mol%.

As the structural unit derived from the (meth) acrylic monomer having a group represented by the formula (1), the structural unit represented by the formula (a1-0) is preferably represented by the formula (a1-1). Examples thereof include a structural unit or a structural unit represented by the formula (a1-2). These may be used alone
Two or more kinds may be used together. In the present specification, the structural unit represented by the formula (a1-0), the formula (a).
The structural unit represented by 1-1) and the structural unit represented by the formula (a1-2) are referred to as a structural unit (a1-0), a structural unit (a1-1), and a structural unit (a1-2), respectively. , Structural unit (a1-
Monomer for inducing 0), monomer for inducing structural unit (a1-1) and structural unit (a1)
The monomer that induces -2) may be referred to as a monomer (a1-0), a monomer (a1-1), and a monomer (a1-2), respectively.

［式（ａ１－０）中、
Ｌ^a01は、酸素原子又は^＊－Ｏ－（ＣＨ₂）_k01－ＣＯ－Ｏ－を表し、ｋ０１は１～７の
整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～
１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。］

[In equation (a1-0),
^La01 represents an oxygen atom or ^* -O- (CH ₂ ) _k01 -CO-O-, k01 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 are independently alkyl groups having 1 to 8 carbon atoms and 3 to 3 carbon atoms, respectively.
Represents 18 alicyclic hydrocarbon groups or a combination thereof. ]

［式（ａ１－１）及び式（ａ１－２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k1－ＣＯ－Ｏ－を表
し、ｋ１は１～７の整数を表し、＊は－ＣＯ－との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１８の脂環
式炭化水素基又はこれらを組み合わせることにより形成される基を表す。
ｍ１は０～１４の整数を表す。
ｎ１は０～１０の整数を表す。
ｎ１’は０～３の整数を表す。］

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent -O- or ^* -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents a bond with -CO-. Represent a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.
m1 represents an integer from 0 to 14.
n1 represents an integer from 0 to 10.
n1'represents an integer from 0 to 3. ]

^La01 is preferably an oxygen atom or ^* -O- (CH ₂ ) _k01 -CO-O- (where k01 is preferably an integer of 1 to 4, more preferably 1), more preferably. Is an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03 and R ^a04 , the alicyclic hydrocarbon group and the group combining these groups include the same groups as those mentioned in R ^a1 to R ^a3 of the formula (1).
The alkyl group of R ^a02 , R ^a03 and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 and R ^a04 are preferably aliphatic hydrocarbon groups having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, a norbornylmethyl group and the like. Be done.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

L ^a1 and L ^a2 are preferably -O- or ^* -O- (CH ₂ ) _k1' -CO-O- (where k1'is an integer of 1 to 4, preferably 1). Yes), more preferably -O-
Is.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group and the group formed by combining them include the same groups as those mentioned in R ^a1 to R ^a3 of the formula (1).
The alkyl groups of R ^a6 and R ^a7 are preferably alkyl groups having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a6 and R ^a7 preferably have 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms.
It is less than or equal to the alicyclic hydrocarbon group of.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1'is preferably 0 or 1.

Examples of the structural unit (a1-0) include equations (a1-0-1) to equations (a1-0-12).
The structural unit represented by any of the above is preferable, and the formulas (a1-0-1) to (a1-0-10) are preferable.
The structural unit represented by any of the above is more preferable.

In the above structural unit, a structural unit in which a methyl group corresponding to ^Ra01 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a1-0).

Examples of the monomer (a1-1) include the monomers described in JP-A-2010-204646. Among them, the monomers represented by any of the formulas (a1-1-1) to (a1-1-8) are preferable, and any of the formulas (a1-1-1) to (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include monomers represented by any of the formulas (a1-2-1) to (a1-2-12), and the formulas (a1-2-3) and (a1). -2-4), equation (a1)
The monomer represented by -2-9) or the formula (a1-2-10) is preferable, and the monomer represented by the formula (a1-2-3) is preferable.
) Or the monomer represented by the formula (a1-2-9) is more preferable.

When the resin (A) contains a structural unit (a1-0) and / or a structural unit (a1-1) and / or a structural unit (a1-2), the total content of these is the total structure of the resin (A). For the unit
It is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20.
It is ~ 85 mol%.

［式（ａ１－３）中、
Ｒ^a9は、ヒドロキシ基を有していてもよい炭素数１～３の脂肪族炭化水素基、カルボキ
シ基、シアノ基、水素原子又は－ＣＯＯＲ^a13を表す。
Ｒ^a13は、炭素数１～８の脂肪族炭化水素基、炭素数３～２０の脂環式炭化水素基、又
はこれらを組み合わせることにより形成される基を表し、該脂肪族炭化水素基及び該脂環
式炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよく、該脂肪族炭
化水素基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－－又は－ＣＯ－に置き
換わっていてもよい。
Ｒ^a10、Ｒ^a11及びＲ^a12は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～
２０の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表すか、Ｒ
^a10及びＲ^a11は互いに結合して、それらが結合する炭素原子とともに炭素数３～２０の２
価の脂環式炭化水素基を形成する。］ Further, as the structural unit (a1) having the group (1), a structural unit represented by the formula (a1-3) can also be mentioned. The structural unit represented by the formula (a1-3) may be referred to as a structural unit (a1-3). Further, the monomer for inducing the structural unit (a1-3) is referred to as the monomer (a1-3).
In some cases.

[In equation (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a carboxy group, a cyano group, a hydrogen atom or -COOR ^a13 , which may have a hydroxy group.
R ^a13 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these groups, the aliphatic hydrocarbon group and the said group. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group, and the aliphatic hydrocarbon group and -CH _2- contained in the alicyclic hydrocarbon group are -O--. Alternatively, it may be replaced with -CO-.
R ^a10 , R ^a11 and R ^a12 are independently alkyl groups having 1 to 8 carbon atoms and 3 to 3 carbon atoms, respectively.
Represents 20 alicyclic hydrocarbon groups or groups formed by combining them, or R
^a10 and R ^a11 are bonded to each other, and 2 with 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
It forms a valent alicyclic hydrocarbon group. ]

Here, -COOR ^a13 includes, for example, a group in which a carbonyl group is bonded to an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the aliphatic hydrocarbon group which may have a hydroxy group of R ^a9 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a 2-hydroxyethyl group.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^a13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and n. -Hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group and the like can be mentioned.
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ^a13 include cyclopentyl group, cyclopropyl group, adamantyl group, adamantylmethyl group, 1-adamantyl-1-methylethyl group and 2-oxo-oxolan-3-. Examples thereof include an yl group and a 2-oxo-oxolan-4-yl group.
Alkyl groups of R ^a10 to R ^a12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-.
Examples thereof include a hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group and the like.
The alicyclic hydrocarbon group of R ^a10 to R ^a12 may be either a monocyclic or polycyclic group, and the monocyclic alicyclic hydrocarbon group may be, for example, a cyclopropyl group, a cyclobutyl group or a cyclopentyl. Examples thereof include a cycloalkyl group such as a group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cycloheptyl group and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, and 1- (adamantan-1).
-Il) Alkane-1-yl group, norbornyl group, methylnorbornyl group, isobornyl group and the like can be mentioned.
The -C (R ^a10 ) (R ^a11 ) (R ^a12 ) when R ^a10 and R ^a11 are bonded to each other to form a divalent hydrocarbon group together with the carbon atom to which they are bonded is as follows. Groups are preferred.

Specifically, the monomer (a1-3) is 5-norbornene-2-carboxylic acid-tert.
-Butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl,
5-Norbornene-2-carboxylic acid 1-methylcyclohexyl, 5-norbornene-2-
2-Methyl-2-adamantyl Carboxylic Acid, 5-Norbornen-2-Carboxylic Acid 2-ethyl-2-adamantyl, 5-Norbornen-2-Carboxylic Acid 1- (4-Methylcyclohexyl) -1-methylethyl, 5- Norbornen-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornen-2-carboxylic acid 1-methyl-1
-(4-Oxocyclohexyl) ethyl and 5-norbornene-2-carboxylic acid 1- (1)
-Adamantyl) -1-methylethyl and the like can be mentioned.

Since the resin (A) containing the structural unit (a1-3) contains a three-dimensionally bulky structural unit, it is higher than the resist composition of the present invention containing such a resin (A). A resist pattern can be obtained at a resolution. Further, since a rigid norbornane ring is introduced into the main chain, the obtained resist pattern tends to have excellent dry etching resistance.

When the resin (A) contains structural units (a1-3), the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). 20-8
5 mol% is more preferred.

［式（ａ１－４）中、
Ｒ^a32は、水素原子、ハロゲン原子、又は、ハロゲン原子を有してもよい炭素数１～６
のアルキル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６の
アルコキシ基、炭素数２～４のアシル基、炭素数２～４のアシルオキシ基、アクリロイル
オキシ基又はメタクリロイルオキシ基を表す。
ｌａは０～４の整数を表す。ｌａが２以上である場合、複数のＲ^a33は互いに同一であ
っても異なってもよい。
Ｒ^a34及びＲ^a35はそれぞれ独立に、水素原子又は炭素数１～１２の炭化水素基を表し、
Ｒ^a36は、炭素数１～２０の炭化水素基を表すか、Ｒ^a35及びＲ^a36は互いに結合してこれ
が結合するＣ－Ｏとともに炭素数３～２０の２価の複素環基を形成し、該炭化水素基及び
該２価の複素環基に含まれる－ＣＨ₂－は、－Ｏ－又は－Ｓ－で置き換わってもよい。］ As the structural unit (a1) having a group represented by the group (2), the structural unit represented by the formula (a1-4) (hereinafter, may be referred to as “structural unit (a1-4)”). Can be mentioned.

[In equation (a1-4),
R ^a32 may have a hydrogen atom, a halogen atom, or a halogen atom and has 1 to 6 carbon atoms.
Represents the alkyl group of.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or Represents a methacryloyloxy group.
la represents an integer from 0 to 4. When la is 2 or more, a plurality of Ra ^33s may be the same or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
R ^a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^a35 and R ^a36 are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with CO to which the group is bonded. -CH _2- contained in the hydrocarbon group and the divalent heterocyclic group may be replaced with -O- or -S-. ]

Examples of the alkyl group of R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group and the like. The alkyl group has 1 carbon atom.
Alkyl groups of -4 are preferred, methyl or ethyl groups are more preferred, and methyl groups are even more preferred.
Examples of the halogen atom of R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, and 1,1,. 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -Perfluorohexyl group and the like can be mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
Examples of the hydrocarbon groups of R ^a34 and R ^a35 include groups similar to R a1'and R ^{a2' of} the formula (2).
R ^a36 includes an alkyl group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
Examples thereof include aromatic hydrocarbon groups having 6 to 18 carbon atoms or groups formed by combining them.

In the formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and even more preferably a methoxy group.
For la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. A group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms and 3 to 1 carbon atoms.
It is an alicyclic aliphatic hydrocarbon group of 8 or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. When the aromatic hydrocarbon group in R ^a36 has a substituent, the aryloxy group having 6 to 10 carbon atoms is preferable as the substituent.

As the monomer for deriving the structural unit (a1-4), for example, Japanese Patent Application Laid-Open No. 2010-204646
Examples thereof include the monomers described in the publication. Above all, equations (a1-4-1) to equations (a1-4)
The monomers represented by -8) are preferable, and the formulas (a1-4-1) to (a1-4-5) are preferable.
And the monomers represented by the formula (a1-4-8)) are more preferable.

When the resin (A) has a structural unit (a1-4), the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). , 20
It is more preferably ~ 85 mol%.

式（ａ１－５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロゲ
ン原子を表す。
Ｚ^a1は、単結合又は＊－（ＣＨ₂）_h3－ＣＯ－Ｌ⁵⁴－を表し、ｈ３は１～４の整数を表
し、＊は、Ｌ⁵¹との結合手を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、－Ｏ－又は－Ｓ－を表す。
ｓ１は、１～３の整数を表す。
ｓ１’は、０～３の整数を表す。 The structural unit derived from the (meth) acrylic monomer having a group represented by the formula (2) is a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”). There is).

In equation (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
Z ^a1 represents a single bond or *-(CH ₂ ) _h3 -CO-L ^54- , h3 represents an integer of 1 to 4, and * represents a bond with L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ independently represent -O- or -S-, respectively.
s1 represents an integer of 1 to 3.
s1'represents an integer from 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Alkyl groups having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. The group is mentioned.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
It is preferable that one of L ⁵² and L ⁵³ is -O- and the other is -S-.
1 is preferable for s1.
s1'is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * -CH ₂ -CO-O-. * Represents a bond with L ⁵¹ .

Examples of the monomer for deriving the structural unit (a1-5) include the monomers described in JP-A-2010-61117. Among them, the formulas (a1-5-1) to the formulas (a1-5-)
The monomers represented by 4) are preferable, and the formula (a1-5-1) or the formula (a1-5-2) is preferable.
) Is more preferable.

When the resin (A) has a structural unit (a1-5), the content thereof is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, based on all the structural units of the resin (A). 5-40
Mol% is more preferred.

Examples of the structural unit (a) having an acid unstable group in the resin (A) include the structural unit (a1-0).
At least one selected from the group consisting of structural units (a1-1), structural units (a1-2) and structural units (a1-5) is preferable, at least two or more are more preferable, and structural units (a1-1). And a combination of structural units (a1-2), a combination of structural units (a1-1) and structural units (a1-5), a combination of structural units (a1-1) and structural units (a1-0), structural units ( A combination of a1-2) and structural unit (a1-0), structural unit (a1-
5) Combination of structural unit (a1-0), structural unit (a1-0), structural unit (a1-0)
1) and combination of structural unit (a1-2), structural unit (a1-0), structural unit (a1-
The combination of 1) and the structural unit (a1-5) is more preferable, and the combination of the structural unit (a1-1) and the structural unit (a1-2), the structural unit (a1-1) and the structural unit (a1-5).
The combination of is even more preferable.

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid unstable group (hereinafter, may be referred to as “monomer (s)”). As the monomer (s), a monomer having no acid unstable group known in the resist field can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid unstable group is preferable. A structure having a hydroxy group and no acid unstable group (hereinafter sometimes referred to as "structural unit (a2)") and / or having a lactone ring and no acid unstable group. If a resin having a unit (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When producing a resist pattern from the resist composition of the present invention, KrF is used as an exposure light source.
When a high-energy beam such as an excimer laser (248 nm), electron beam or EUV (ultraviolet light) is used, the structural unit (a2) is a structural unit having a phenolic hydroxy group (the structural unit (a2)).
It is preferable to use a2). When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) is a structural unit (a2) having an alcoholic hydroxy group.
) Is preferable, and it is more preferable to use the structural unit (a2-1). As the structural unit (a2), one type may be contained alone, or two or more types may be contained.

When the resin (A) has a structural unit (a2) having a phenolic hydroxy group, the content thereof is preferably 5 to 95 mol%, preferably 10 to 80 mol%, based on all the structural units of the resin (A). Is more preferable, and 15 to 80 mol% is further preferable.

［式（ａ２－０）中、
Ｒ^a30は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１～６のア
ルキル基を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６の
アルコキシ基、炭素数２～４のアシル基、炭素数２～４のアシルオキシ基、アクリロイル
オキシ基又はメタクリロイルオキシ基を表す。
ｍａは０～４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は互いに同
一であっても異なってもよい。］ Examples of the structural unit (a2) having a phenolic hydroxy group include structural units represented by the formula (a2-0) (hereinafter, may be referred to as “structural unit (a2-0)”).

[In equation (a2-0),
R ^a30 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or Represents a methacryloyloxy group.
ma represents an integer from 0 to 4. When ma is an integer of 2 or more, a plurality of Ra ^31s may be the same or different from each other. ]

Alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and n.
-Pentyl group, n-hexyl group and the like can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, and 1,1,. 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -Perfluorohexyl group and the like can be mentioned. R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
Examples of the alkoxy group of R ^a31 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
The ma is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.

Examples of the monomer for inducing the structural unit (a2-0) include JP-A-2010-2046.
Examples thereof include the monomers described in Japanese Patent Publication No. 34.
Among them, the structural unit (a2-0) includes the formula (a2-0-1), the formula (a2-0-2), and the like.
Those represented by the formula (a2-0-3) and the formula (a2-0-4) are preferable, and the formula (a) is preferable.
Those represented by 2-0-1) or the formula (a2-0-2) are more preferable.

The resin (A) containing the structural unit (a2-0) undergoes a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer inducing the structural unit (a2-0) is protected with a protecting group, and then deprotected. It can be manufactured by processing. However, when performing the deprotection treatment, it is necessary to carry out the deprotection treatment so as not to significantly impair the acid unstable group of the structural unit (a1). Examples of such a protecting group include an acetyl group and the like.

When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, the content thereof is preferably 5 to 95 mol% with respect to all the structural units of the resin (A), and 10 to 10 to
80 mol% is more preferable, and 15-80 mol% is even more preferable.

式（ａ２－１）中、
Ｌ^a3は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k2－ＣＯ－Ｏ－を表す。
ｋ２は１～７の整数を表す。＊は－ＣＯ－との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０～１０の整数を表す。 Examples of the structural unit (a2) having an alcoholic hydroxy group include structural units represented by the formula (a2-1) (hereinafter, may be referred to as “structural unit (a2-1)”).

In equation (a2-1),
L ^a3 represents -O- or ^* -O- (CH ₂ ) _k2 -CO-O-.
k2 represents an integer from 1 to 7. * Represents a bond with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 independently represent a hydrogen atom, a methyl group or a hydroxy group, respectively.
o1 represents an integer from 0 to 10.

In the formula (a2-1), ^La3 is preferably −O−, —O− (CH ₂ ) _f1 -CO—O−.
(The f1 is an integer of 1 to 4), and more preferably —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

Examples of the monomer for inducing the structural unit (a2-1) include JP-A-2010-2046.
Examples thereof include the monomers described in Japanese Patent Publication No. 46. Equation (a2-1-1) to Equation (a2-1-6)
) Is preferable, and formulas (a2-1-1) to (a2-1-4) are preferable.
The monomer represented by any of the above is more preferable, and the formula (a2-1-1) or the formula (a2-1-1) is preferable.
The monomer represented by 3) is more preferable.

When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on all the structural units of the resin (A). Yes, more preferably 1 to 35 mol%, still more preferably 2 to 20 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocyclic ring such as β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a fused ring of a monocyclic lactone ring and another ring. But it may be. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure.

The structural unit (a3) is preferably the formula (a3-1), the formula (a3-2), and the formula (a3-3).
Alternatively, it is a structural unit represented by the formula (a3-4). One of these may be contained alone.
It may contain two or more kinds.

［式（ａ３－１）中、
Ｌ^a4は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k3－ＣＯ－Ｏ－（ｋ３は１～７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
Ｒ^a21は、炭素数１～４の脂肪族炭化水素基を表す。
ｐ１は０～５の整数を表す。ｐ１が２以上のとき、複数のＲ^a21は互いに同一又は相異
なる。
式（ａ３－２）中、
Ｌ^a5は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k3－ＣＯ－Ｏ－（ｋ３は１～７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。
ｑ１は、０～３の整数を表す。ｑ１が２以上のとき、複数のＲ^a22は互いに同一又は相
異なる。
式（ａ３－３）中、
Ｌ^a6は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k3－ＣＯ－Ｏ－（ｋ３は１～７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。
ｒ１は、０～３の整数を表す。ｒ１が２以上のとき、複数のＲ^a23は互いに同一又は相
異なる。
式（ａ３－４）中、
Ｒ^a24は、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロ
ゲン原子を表す。
Ｌ^a7は、－Ｏ－、^＊－Ｏ－Ｌ^a8－Ｏ－、^＊－Ｏ－Ｌ^a8－ＣＯ－Ｏ－、^＊－Ｏ－Ｌ^a8－Ｃ
Ｏ－Ｏ－Ｌ^a9－ＣＯ－Ｏ－又は^＊－Ｏ－Ｌ^a8－Ｏ－ＣＯ－Ｌ^a9－Ｏ－を表す。
＊はカルボニル基との結合手を表す。
Ｌ^a8及びＬ^a9は、互いに独立に、炭素数１～６のアルカンジイル基を表す。
ｗ１は、０～８の整数を表す。
Ｒ^a25は、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。］

[In equation (a3-1),
L ^a4 represents -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 is an integer of 1 to 7).
) Represents a group. * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer from 0 to 5. When p1 is 2 or more, a plurality of ^Ra21s are the same or different from each other.
In equation (a3-2),
L ^a5 represents -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 is an integer of 1 to 7).
) Represents a group. * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, a plurality of ^Ra22s are the same or different from each other.
In equation (a3-3),
L ^a6 represents -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 is an integer of 1 to 7).
) Represents a group. * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, a plurality of ^Ra23s are the same or different from each other.
In equation (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
L ^a7 is -O-, ^* -OL ^a8 -O-, ^{* -OL a8} -CO-O-, ^* -OL ^a8 -C
Represents O- ^{OL a9} -CO-O- or ^* -OL ^a8 -O-CO-L ^a9 -O-.
* Represents a bond with a carbonyl group.
^La8 and ^La9 represent an alkanediyl group having 1 to 6 carbon atoms independently of each other.
w1 represents an integer of 0 to 8.
R ^a25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. ]

The aliphatic hydrocarbon groups of R ^a21 , R ^a22 , R ^a23 and R ^a25 include a methyl group, an ethyl group and n.
-Alkyl groups such as propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group can be mentioned.
Examples of the halogen atom of R ^a24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group of R ^a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Alkyl groups having a halogen atom of R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. Examples thereof include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

The alkanediyl groups of ^La8 and ^La9 include a methylene group, an ethylene group, and a propane-1,
3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1
, 5-Diyl group, Hexane-1,6-Diyl group, Butane-1,3-Diyl group, 2-Methylpropane-1,3-Diyl group, 2-Methylpropane-1,2-Diyl group, Pentane- 1,
Examples thereof include a 4-diyl group and a 2-methylbutane-1,4-diyl group.

In the formulas (a3-1) to (a3-3), ^La4 to ^La6 are independently, preferably -O- or k3 is an integer of 1 to 4 * -O- (CH ₂ ). ) A group represented by _k3 -CO-O-, more preferably -O- and * -O-CH ₂ -CO-O-, still more preferably an oxygen atom.
R ^a18 to R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently, preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are independently, preferably integers of 0 to 2, and more preferably 0 or 1.

In equation (a3-4)
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
R ^a25 is preferably a carboxy group, a cyano group or a methyl group.
L ^a7 is preferably —O— or ^* —OL ^a8 −CO—O—, and more preferably.
-O-, -O-CH ₂ -CO-O- or -OC ₂ H ₄ -CO-O-.
w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.

Examples of the monomer for deriving the structural unit (a3) include the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and JP-A-201.
Examples thereof include the monomers described in Japanese Patent Publication No. 2-41274. As a structural unit (a3),
Equations (a3-1-1) to (a3-1-4), equations (a3-2-1) to equations (a3-2-4),
Formulas (a3-3-1) to formulas (a3-3-4) and formulas (a3-4-1) to formulas (a3-4-6)
The structural unit represented by any of the above is preferable, and any one of the formula (a3-1-1), the formula (a3-1-2) and the formula (a3-2-3) to the formula (a3-2-4). The structural unit represented by is more preferable, and the structural unit represented by the formula (a3-1-1) or the formula (a3-2-3) is further preferable.

In the structural units represented by the following equations (a3-4-1) to (a3-4-12), R
A compound in which a methyl group corresponding to ^a24 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a3-4).

When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). , More preferably 10-60 mol%.
Further, the contents of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) and the structural unit (a3-4) are the respective contents with respect to all the structural units of the resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is further preferable.

<Other structural units (t)>
The resin (A) may contain other structural units (t) as structural units other than the structural unit (a1) and the structural unit (s). Examples of the structural unit (t) include the above-mentioned structural unit (a4) and structural unit (a5) in addition to the structural unit (a2) and the structural unit (a3). The resin (A) may have a structural unit other than the above-mentioned structural unit, and examples of such a structural unit include structural units well known in the art.

When the resin (A) has a structural unit (a4), the content thereof is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and 3) with respect to all the structural units of the resin (A). -10 mol% is more preferred.

When the resin (A) has a structural unit (a5), the content thereof is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 3) with respect to all the structural units of the resin (A). It is more preferably ~ 15 mol%.

The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s), that is, a copolymer of a monomer (a1) and a monomer (s).
The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group) and a structural unit. At least one selected from (a1-5), more preferably a structural unit (
At least two kinds selected from a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1).
The structural unit (a3) is preferably selected from the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-4). At least one kind.

The resin (A) may contain a structural unit (particularly, a structural unit (a1-1)) derived from a monomer having an adamantane group in an amount of 15 mol% or more based on the content of the structural unit (a1). preferable. As the content of the structural unit having an adamantyl group increases, the dry etching resistance of the resist pattern is improved.

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (A) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500).
00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30)
000 or less, more preferably 15,000 or less). The weight average molecular weight is
It is a value obtained by gel permeation chromatography.

The content of the resin (X) in the resist composition is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 1 to 40 parts by mass with respect to 100 parts by mass of the resin (A). It is a mass portion, and particularly preferably 2 to 30 parts by mass.

The total content of the resin (A) and the resin (X) is preferably 80% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator is classified into a nonionic type and an ionic type, and any of them may be used in the acid generator (B) of the resist composition of the present invention. Examples of the nonionic acid generator include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), and sulfones. (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like can be mentioned. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salt, phosphonium salt, sulfonium salt, etc.).
Iodonium salt) is typical. Examples of the onium salt anion include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.

Examples of the acid generator (B) include JP-A-63-26653, JP-A-55-164824, and JP-A-55-164824.
Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Application Laid-Open No. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 63-146029, US Pat. No. 3,779,
Compounds that generate acid by radiation as described in 778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Further, a compound produced by a known method may be used. The acid generator (B) may be used alone or in combination of two or more.

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又は炭素数１～６のペルフルオロアルキル
基を表す。
Ｌ^ｂ１は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に
含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭
化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１
８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる－ＣＨ_２－は
、－Ｏ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably the formula (B1).
It is a salt represented by (hereinafter, may be referred to as "acid generator (B1)").

[In formula (B1),
^Q1 and ^Q2 independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y may have a methyl group or a substituent which may have a substituent, and may have 3 to 1 carbon atoms.
Represents a monovalent alicyclic hydrocarbon group of 8, even if -CH _2- contained in the monovalent alicyclic hydrocarbon group is replaced with -O-, -SO _2- or -CO-. good.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl groups of ^Q1 and ^Q2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. A hexyl group and the like can be mentioned.
^Q1 and ^Q2 are preferably fluorine atoms or trifluoromethyl groups independently of each other, and more preferably both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group of L ^b1 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a group formed by combining two or more kinds of groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4
-Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1
, 7-Diyl group, Octane-1,8-Diyl group, Nonane-1,9-Diyl group, Decane-1
, 10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group,
Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-
1,15-Diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-
Linear alkanediyl groups such as diyl groups;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-
Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-
Examples thereof include a polycyclic divalent alicyclic saturated hydrocarbon group such as a 1,5-diyl group and an adamantane-2,6-diyl group.

［式（ｂ１－１）中、
Ｌ^ｂ２は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ３は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和
炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよ
い。
ただし、Ｌ^ｂ２とＬ^ｂ３との炭素数合計は、２２以下である。
式（ｂ１－２）中、
Ｌ^ｂ４は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ５は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和
炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよ
い。
ただし、Ｌ^ｂ４とＬ^ｂ５との炭素数合計は、２２以下である。
式（ｂ１－３）中、
Ｌ^ｂ６は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
Ｌ^ｂ７は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和
炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよ
い。
ただし、Ｌ^ｂ６とＬ^ｂ７との炭素数合計は、２３以下である。］ Examples of the group in which -CH _2- in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO- are any of the formulas (b1-1) to (b1-3). The group represented by is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * is -Y.
Represents a bond with.

[In equation (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single-bonded or divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In equation (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single-bonded or divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b4 and L ^b5 is 22 or less.
In equation (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single-bonded or divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. ]

In the formulas (b1-1) to (b1-3), when the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group, the number of carbon atoms before the replacement is the carbon of the saturated hydrocarbon group. Let it be a number.
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L ^b1 .

L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single-bonded or divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. The methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

The group in which _-CH2- in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO- is a group represented by the formula (b1-1) or the formula (b1-3). Is preferable.

［式（ｂ１－４）中、
Ｌ^ｂ８は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
式（ｂ１－５）中、
Ｌ^ｂ９は、炭素数１～２０の２価の飽和炭化水素基を表す。
Ｌ^ｂ１０は、単結合又は炭素数１～１９の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい
。
ただし、Ｌ^ｂ９及びＬ^ｂ１０の合計炭素数は２０以下である。
式（ｂ１－６）中、
Ｌ^ｂ１１は、炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^ｂ１２は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい
。
ただし、Ｌ^ｂ１１及びＬ^ｂ１２の合計炭素数は２１以下である。
式（ｂ１－７）中、
Ｌ^ｂ１３は、炭素数１～１９の２価の飽和炭化水素基を表す。
Ｌ^ｂ１４は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表す。
Ｌ^ｂ１５は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい
。
ただし、Ｌ^ｂ１３～Ｌ^ｂ１５の合計炭素数は１９以下である。
式（ｂ１－８）中、
Ｌ^ｂ１６は、炭素数１～１８の２価の飽和炭化水素基を表す。
Ｌ^ｂ１７は、炭素数１～１８の２価の飽和炭化水素基を表す。
Ｌ^ｂ１８は、単結合又は炭素数１～１７の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい
。
ただし、Ｌ^ｂ１６～Ｌ^ｂ１８の合計炭素数は１９以下である。］ Examples of the formula (b1-1) include groups represented by the formulas (b1-4) to (b1-8).

[In equation (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In equation (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In equation (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In equation (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total number of carbon atoms of L ^b13 to L ^b15 is 19 or less.
In equation (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total number of carbon atoms of L ^b16 to L ^b18 is 19 or less. ]

L ^b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

［式（ｂ１－９）中、
Ｌ^ｂ１９は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ２０は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子はフッ素原子、ヒドロキシ基又はアシルオキシ基に置換さ
れていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル基
に置き換わっていてもよく、該アシルオキシ基に含まれる水素原子は、ヒドロキシ基に置
換されていてもよい。
ただし、Ｌ^ｂ１９及びＬ^ｂ２０の合計炭素数は２３以下である。
式（ｂ１－１０）中、
Ｌ^ｂ２１は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ２２は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^ｂ２３は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアシルオキシ基に置換
されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル
基に置き換わっていてもよく、該アシルオキシ基に含まれる水素原子は、ヒドロキシ基に
置換されていてもよい。
ただし、Ｌ^ｂ２１～Ｌ^ｂ２３の合計炭素数は２１以下である。
式（ｂ１－１１）中、
Ｌ^ｂ２４は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ２５は、炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^ｂ２６は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該２価の飽和
炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアシルオキシ基に置換
されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル
基に置き換わっていてもよく、該アシルオキシ基に含まれる水素原子は、ヒドロキシ基に
置換されていてもよい。
ただし、Ｌ^ｂ２４～Ｌ^ｂ２６の合計炭素数は２１以下である。］ Examples of the formula (b1-3) include groups represented by the formulas (b1-9) to (b1-11).

[In equation (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be good. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In equation (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b21 to L ^b23 is 21 or less.
In equation (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b24 to L ^b26 is 21 or less. ]

In formulas (b1-9) to (b1-11), when the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with an acyloxy group, the number of carbon atoms of the acyloxy group, CO in the ester bond and The number of carbon atoms of the divalent saturated hydrocarbon group including the number of O is used.

Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.
Examples of the acyloxy group having a substituent include an oxoadamantylcarbonyloxy group, a hydroxyadamantylcarbonyloxy group, and an oxocyclohexylcarbonyloxy group.
Hydroxycyclohexylcarbonyloxy group and the like can be mentioned.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-4) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-5) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-6) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-7) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-8) include the following.

Examples of the group represented by the formula (b1-2) include the following.

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-9) include the following.

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-10) include the following.

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-11) include the following.

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11).
When -CH _2- contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO _2- or -CO-, the number may be one or two or more. There may be more than one. Examples of such a group include groups represented by the formulas (Y12) to (Y38).

That is, in Y, two hydrogen atoms contained in the alicyclic hydrocarbon group are each replaced with an oxygen atom, and the two oxygen atoms are combined with an arcandyl group having 1 to 8 carbon atoms to form a ketal ring. Alternatively, it may contain a structure in which an oxygen atom is bonded to different carbon atoms. However, when forming a spiro ring of the formulas (Y28) to (Y33), it is preferable that the alkanediyl group between the two oxygens has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, those in which the fluorine atom is not substituted in the methylene group adjacent to the oxygen atom are preferable.

Among them, a group represented by any one of the formula (Y1) to the formula (Y20), the formula (Y30), and the formula (Y31) is preferable, and the formula (Y11), the formula (Y15), and the formula (Y31) are more preferable. Y16)
, A group represented by the formula (Y19), the formula (Y20), the formula (Y30) or the formula (Y31), and more preferably represented by the formula (Y11), the formula (Y15) or the formula (Y30). The group is mentioned.

The substituent of the methyl group represented by Y includes a halogen atom, a hydroxy group, and 3 to 1 carbon atoms.
A monovalent alicyclic hydrocarbon group of 6, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group or-(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula, R). ^b1 represents an alkyl group having 1 to 16 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents 0 to 0 to 1. (Representing an integer of 4) and the like.
Substituents of the monovalent alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkyl group containing a hydroxy group having 1 to 12 carbon atoms, and 3 carbon atoms. ~ 16 monovalent alicyclic hydrocarbon groups, 1-12 carbons alkoxy groups, 6-18 carbons monovalent aromatic hydrocarbon groups, 7-21 carbon aralkyl groups, 2 ~ carbons Acylic group of 4, glycidyloxy group or-(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms and a monovalent fat having 3 to 16 carbon atoms. A cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms is represented. Ja represents an integer of 0 to 4) and the like.

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
The monovalent aromatic hydrocarbon group includes a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group; a trill group, a xylyl group, a cumenyl group and a mesityl. Group, biphenyl group, phenanthryl group, 2,6-
Examples thereof include an aryl group such as a diethylphenyl group and 2-methyl-6-ethylphenyl.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of Y include the following.

When Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon at the bond position with Y is used. It is preferable that the -CH _2- of the group is replaced with -O- or -CO-.

Y is a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may preferably have a substituent, and more preferably an adamantyl group, which may have a substituent. The methylene group constituting the group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is more preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group or a group represented by the following.

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include the formulas (B1-A-1) to
Anion represented by the formula (B1-A-46) [hereinafter, "anion (B1-A)" according to the formula number.
-1) ”and so on. ] Is preferable, and the formulas (B1-A-1) to (B1-A-4)
, Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24) to Formula (B1-A-)
33), anions represented by any of the formulas (B1-A-36) to (B1-A-40) are more preferable.

Here, R ⁱ² to R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 12 carbon atoms.
It is an alkyl group of 4, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining them, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. ..
L4 is a single bond or an alkanediyl group having 1 to ⁴ carbon atoms.
^Q1 and ^Q2 are the same as above.
Specifically, the sulfonic acid anion in the salt represented by the formula (B1) is JP-A-20.
Examples thereof include the anions described in JP-A-10-204646.

The sulfonic acid anion in the salt represented by the preferred formula (B1) is the formula (B1a-).
Examples thereof include anions represented by the formulas (1) to (B1a-22).

Among them, formulas (B1a-1) to formulas (B1a-3) and formulas (B1a-7) to formulas (B1a-).
16), the anion represented by the formula (B1a-18), the formula (B1a-19), or the formula (B1a-22) is preferable.
Examples of the Z ⁺ organic cation include an organic onium cation, for example, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation, and the like, preferably an organic sulfonium cation or an organic iodine cation. These include, more preferably aryl sulfonium cations.
Z ⁺ in the formula (B1) is preferably a cation represented by any of the formulas (b2-1) to (b2-4) [hereinafter, "cation (b2-1)" or the like according to the formula number. In some cases. ]
Is.

［式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^ｂ４～Ｒ^ｂ６は、互いに独立に、炭素数１～３０の１価の脂肪族炭化水素基、炭素数
３～３６の１価の脂環式炭化水素基又は炭素数６～３６の１価の芳香族炭化水素基を表し
、該１価の脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１～１２のア
ルコキシ基、炭素数３～１２の１価の脂環式炭化水素基又は炭素数６～１８の１価の芳香
族炭化水素基で置換されていてもよく、該１価の脂環式炭化水素基に含まれる水素原子は
、ハロゲン原子、炭素数１～１８の１価の脂肪族炭化水素基、炭素数２～４のアシル基又
はグリシジルオキシ基で置換されていてもよく、該１価の芳香族炭化水素基に含まれる水
素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１～１２のアルコキシ基で置換されて
いてもよい。
Ｒ^ｂ４とＲ^ｂ５とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に
含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ７及びＲ^ｂ８は、互いに独立に、ヒドロキシ基、炭素数１～１２の１価の脂肪族炭
化水素基又は炭素数１～１２のアルコキシ基を表す。
ｍ２及びｎ２は、互いに独立に、０～５の整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一であっても異なってもよく、ｎ２が２以上の
とき、複数のＲ^ｂ８は同一であっても異なってもよい。
Ｒ^ｂ９及びＲ^ｂ１０は、互いに独立に、炭素数１～３６の１価の脂肪族炭化水素基又は
炭素数３～３６の１価の脂環式炭化水素基を表す。
Ｒ^ｂ９とＲ^ｂ１０とは、それらが結合する硫黄原子とともに環を形成してもよく、該環
に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ１１は、水素原子、炭素数１～３６の１価の脂肪族炭化水素基、炭素数３～３６の
１価の脂環式炭化水素基又は炭素数６～１８の１価の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１～１２の１価の脂肪族炭化水素基、炭素数３～１８の１価の脂環
式炭化水素基又は炭素数６～１８の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化
水素に含まれる水素原子は、炭素数６～１８の１価の芳香族炭化水素基で置換されていて
もよく、該１価の芳香族炭化水素基に含まれる水素原子は、炭素数１～１２のアルコキシ
基又は炭素数１～１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^ｂ１１とＲ^ｂ１２とは、一緒になってそれらが結合する－ＣＨ－ＣＯ－を含む環を形
成していてもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き
換わってもよい。
Ｒ^ｂ１３～Ｒ^ｂ１８は、互いに独立に、ヒドロキシ基、炭素数１～１２の１価の脂肪族
炭化水素基又は炭素数１～１２のアルコキシ基を表す。
Ｌ^ｂ３１は、－Ｓ－又は－Ｏ－を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、互いに独立に、０～５の整数を表す。
ｑ２及びｒ２は、互いに独立に、０～４の整数を表す。
ｕ２は、０又は１を表す。
ｏ２が２以上のとき、複数のＲ^ｂ１３は同一であっても異なってもよく、ｐ２が２以上
のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数の
Ｒ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一
であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異な
ってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］

[In equations (b2-1) to (b2-4),
R ^b4 to R ^b6 are independent of each other, a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group represents a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, and a monovalent alicyclic hydrocarbon having 3 to 12 carbon atoms. It may be substituted with a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the monovalent alicyclic hydrocarbon group is a halogen atom and has 1 to 18 carbon atoms. It may be substituted with a monovalent aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is a halogen atom or hydroxy. It may be substituted with a group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b7 and R ^b8 independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 represent integers from 0 to 5 independently of each other.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 independently represent a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b11 is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Represents a hydrogen group.
R ^b12 contains a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the monovalent aromatic hydrocarbon group. The hydrogen atom may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may be used together to form a ring containing -CH-CO- to which they are bound, and -CH _2- contained in the ring is -O-, -SO-. Alternatively, it may be replaced with -CO-.
R ^b13 to R ^b18 independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents —S— or —O—.
o2, p2, s2, and t2 represent integers from 0 to 5 independently of each other.
q2 and r2 represent integers from 0 to 4 independently of each other.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13s may be the same or different, when p2 is 2 or more, the plurality of R ^b14s may be the same or different, and when q2 is 2 or more. , The plurality of R ^b15s may be the same or different, and when r2 is 2 or more, the plurality of R ^b16s may be the same or different, and when s2 is 2 or more, the plurality of R ^b17s are. It may be the same or different, and when t2 is 2 or more, the plurality of R ^b18s may be the same or different. ]

中でも、Ｒ^ｂ９～Ｒ^ｂ１２の１価の脂環式炭化水素基の炭素数は、好ましくは３～１８
であり、より好ましくは４～１２である。 The monovalent aliphatic hydrocarbon group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and 2 -Alkyl groups of ethylhexyl groups can be mentioned. Above all, R ^b9 ~ R
The monovalent aliphatic hydrocarbon group of ^b12 preferably has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic monovalent alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclo. Examples thereof include cycloalkyl groups such as a hexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

Above all, the carbon number of the monovalent alicyclic hydrocarbon group of R ^b9 to R ^b12 is preferably 3 to 18.
It is more preferably 4 to 12.

As a monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, for example,
Methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantane-2-
Examples thereof include an yl group, a methylnorbornyl group and an isobornyl group. In a monovalent alicyclic hydrocarbon group in which a hydrogen atom is replaced with a monovalent aliphatic hydrocarbon group, the total number of carbon atoms of the monovalent alicyclic hydrocarbon group and the monovalent aliphatic hydrocarbon group Is preferably 20 or less.

Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, and a cumenyl group.
Mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantylphenyl group, biphenylyl group, naphthyl group, phenanthryl group, 2,6-diethylphenyl group, 2- Aryl groups such as a methyl-6-ethylphenyl group can be mentioned.
When the monovalent aromatic hydrocarbon group contains a monovalent aliphatic hydrocarbon group or a monovalent alicyclic hydrocarbon group, the monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms and carbon A monovalent alicyclic hydrocarbon group having a number of 3 to 18 is preferable.
Examples of the monovalent aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Examples of the monovalent aliphatic hydrocarbon group in which the hydrogen atom is replaced with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group. ..

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, and a tert-butylcarbonyloxy group. Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group and a 2-ethylhexylcarbonyloxy group.

The rings that R ^b4 and R ^b5 may form with the sulfur atoms to which they are attached are monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. There may be. Examples of this ring include a ring having 3 to 18 carbon atoms, and preferably a ring having 4 to 18 carbon atoms. Examples of the ring containing a sulfur atom include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and specific examples thereof include the following rings.

The ring formed by R ^b9 and R ^b10 together with the sulfur atom to which they are bonded is monocyclic,
It may be a polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include a 3-membered ring to a 7-membered ring.
Thioran-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1
, 4-oxatian-4-ium ring and the like.
The ring formed by R ^b11 and R ^b12 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring. Be done.

Among the cations (b2-1) to cations (b2-4), the cation (b2-) is preferable.
1) can be mentioned.

Examples of the cation (b2-1) include the following cations.

Examples of the cation (b2-2) include the following cations.

Examples of the cation (b2-3) include the following cations.

Examples of the cation (b2-4) include the following cations.

The acid generator (B1) is a combination of the above-mentioned sulfonic acid anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B1) is preferably of the formula (
A combination of an anion represented by any of B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-16) and a cation (b2-1) or a cation (b2-3). Can be mentioned.

Examples of the acid generator (B1) preferably include those represented by the formulas (B1-1) to (B1-40), and preferably the formula (B1-1) containing an aryl sulfonium cation.
), Equation (B1-2), Equation (B1-3), Equation (B1-5), Equation (B1-6), Equation (B1-7)
), Equation (B1-11), Equation (B1-12), Equation (B1-13), Equation (B1-14), Equation (
B1-17), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-2)
4), formula (B1-25), formula (B1-26), formula (B1-29), formula (B1-31), formula (B1-32), formula (B1-33), formula (B1-34). ), Equation (B1-35), Equation (B1-
36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40)
The ones represented by are listed below.

The content of the acid generator (B1) is 30% by mass or more and 100 with respect to the total amount of the acid generator (B).
It is preferably 5% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and further preferably substantially only the acid generator (B1).
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). (Below). The resist composition of the present invention may contain one kind of acid generator (B) or a plurality of kinds.

<Solvent (E)>
The content of the solvent (E) is usually 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more, and 99.9% by mass or less, preferably 99% by mass or less in the resist composition. Is. The content of the solvent (E) can be measured by a known analytical means such as liquid chromatography or gas chromatography.

Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate. Esters; ketones such as acetone, methylisobutylketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One of the solvent (E) may be contained alone, and the solvent (E) may be contained alone.
It may contain two or more kinds.

<Quencher (C)>
The resist composition of the present invention may contain a quencher (hereinafter, may be referred to as "quencher (C)"). Examples of the quencher (C) include a basic nitrogen-containing organic compound or a salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B).

<Basic nitrogen-containing organic compounds>
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine. , Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, Triheptylamine, Trioctylamine, Trinonylamine, Tridecylamine, Methyldibutylamine, Methyldipentylamine, Methyldihexylamine, Methyldicyclohexylamine, Methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine , Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, Triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino- 3,3'-diethyldiphenylmethane,
2,2'-Methylenebisaniline, imidazole, 4-methylimidazole, pyridine,
4-Methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl)
Ethane, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,
3-Di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-)
Pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicorylamine, bipyridine and the like, preferably diisopropylaniline. , Particularly preferably 2,6-diisopropylaniline.

Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, and 3- (trifluoromethyl) phenyltrimethyl. Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

<Salt that produces acid with weak acidity>
The acidity of a salt that produces an acid that is weaker than the acid generated by the acid generator is indicated by the acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator is a salt in which the pKa of the acid generated from the salt is usually -3 <pKa, preferably -1 <pK.
It is a salt of a <7, more preferably a salt of 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid intramolecular salt represented by the formula (D), and JP-A-2012-229206, JP-A. 2012-6908, 2012-72109, 2011-39502 and 2011-19
Examples thereof include the salt described in Japanese Patent Publication No. 1745.

［式（Ｄ）中、
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１～１２の１価の炭化水素基、炭素数１～６
のアルコキシ基、炭素数２～７のアシル基、炭素数２～７のアシルオキシ基、炭素数２～
７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０～４の整数を表し、ｍ’が２以上の場合、複数の
Ｒ^D1は同一又は相異なり、ｎ’が２以上の場合、複数のＲ^D2は同一又は相異なる。］

[In formula (D),
R ^D1 and R ^D2 are independently monovalent hydrocarbon groups having 1 to 12 carbon atoms and 1 to 6 carbon atoms.
Alkoxy group, acyl group with 2 to 7 carbon atoms, acyloxy group with 2 to 7 carbon atoms, 2 to 7 carbon atoms
Represents an alkoxycarbonyl group, a nitro group or a halogen atom of 7.
m'and n'independently represent integers from 0 to 4, and when m'is 2 or more, multiple R ^D1s are the same or different, and when n'is 2 or more, multiple R ^D2s are. Same or different. ]

The hydrocarbon groups of R ^D1 and R ^D2 in the compound represented by the formula (D) include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Examples thereof include groups formed by combining these.
Examples of the monovalent aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group and a nonyl group.
The monovalent alicyclic hydrocarbon group may be either a monocyclic or polycyclic group, and may be saturated or unsaturated. Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbonyl group, adamantyl group and the like can be mentioned.
The monovalent aromatic hydrocarbon group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and 2
-Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group,
4-t-Butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group,
Anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-
Examples thereof include an aryl group such as a 6-ethylphenyl group.
Examples of the group formed by combining these groups include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, and an aralkyl group (for example, a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, and a 1-phenyl-1 group. -Propyl group, 1-phenyl-2
-Propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc.) And so on.

Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the acyl group include an acetyl group, a propanoyl group, a benzoyl group, a cyclohexanecarbonyl group and the like.
Examples of the acyloxy group include a group in which an oxy group (—O—) is bonded to the above acyl group.
Examples of the alkoxycarbonyl group include a group in which a carbonyl group (-CO-) is bonded to the above alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.

In the formula (D), R ^D1 and R ^D2 are independently alkyl groups having 1 to 8 carbon atoms.
Cycloalkyl group with 3 to 10 carbon atoms, alkoxy group with 1 to 6 carbon atoms, acyl group with 2 to 4 carbon atoms, acyloxy group with 2 to 4 carbon atoms, alkoxycarbonyl group with 2 to 4 carbon atoms, nitro group or Halogen atoms are preferred.
For m'and n', an integer of 0 to 2 is preferable, and 0 is more preferable, respectively. m'
When is 2 or more, the plurality of R ^D1s are the same or different, and when n'is 2 or more, the plurality of R ^D2s are the same or different.

Examples of the weak acid intramolecular salt (D) include the following compounds.

The weak acid intramolecular salt (D) can be produced by the method described in "Tetrahedron Vol. 45, No. 19, p6281-6296". Further, as the weak acid intramolecular salt (D), a commercially available compound can be used.

The content of the quencher (C) is preferably 0.01 to the solid content of the resist composition.
It is 5% by mass, more preferably 0.01 to 4% by mass, and particularly preferably 0.01 to 3% by mass.

<Other ingredients>
If necessary, the resist composition of the present invention may contain a component other than the above-mentioned components (hereinafter, may be referred to as "other component (F)"). The other component (F) is not particularly limited, and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes and the like, can be used.

<Preparation of resist composition>
The resist composition of the present invention comprises the resin (X), the resin (A) and the acid generator (B) of the present invention, and a citric acid (C), a solvent (E) and other components used as necessary. (F)
Can be prepared by mixing. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing is from 10 to 40 ° C., types of resin and the like, and solvent (E) such as resin.
An appropriate temperature can be selected according to the solubility of the substance. As the mixing time, an appropriate time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing or the like can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Manufacturing method of resist pattern>
The method for producing a resist pattern of the present invention is
(1) A step of applying the resist composition of the present invention onto a substrate,
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
It includes (4) a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

The resist composition can be applied onto the substrate by a commonly used device such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. The substrate may be washed before the resist composition is applied, or an antireflection film or the like may be formed on the substrate.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying
For example, it is carried out by evaporating the solvent using a heating device such as a hot plate (so-called prebaking), or by using a depressurizing device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure for drying under reduced pressure is 1 to 1.
About 0 × 10 ⁵ Pa is preferable.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. The exposure light source includes a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excima laser (wavelength 157 nm) that emits laser light in the ultraviolet region, and a solid-state laser light source (YAG or semiconductor laser). Etc.), and various ones such as those that radiate harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, those that irradiate electron beams, super-ultraviolet light (EUV), etc. are used. Can be done. In addition, in this specification, irradiation of these radiations may be generically referred to as "exposure". At the time of exposure, the exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, it may be exposed by direct drawing without using a mask.

The composition layer after exposure is heat-treated (so-called post-exposure bake) in order to promote the deprotection reaction at the acid unstable group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.

The heated composition layer is usually developed using a developer and a developer. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense method. The development temperature is preferably 5 to 60 ° C., and the development time is preferably 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any alkaline aqueous solution used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) can be mentioned.
The alkaline developer may contain a surfactant.
After development, it is preferable to wash the resist pattern with ultrapure water and then remove the substrate and the water remaining on the pattern.

When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter, may be referred to as "organic developer") is used as the developer.
Examples of the organic solvent contained in the organic developer include a ketone solvent such as 2-hexanone and 2-heptanone; a glycol ether ester solvent such as propylene glycol monomethyl ether acetate; an ester solvent such as butyl acetate; and a glycol such as propylene glycol monomethyl ether. Examples include an ether solvent; an amide solvent such as N, N-dimethylacetamide; an aromatic hydrocarbon solvent such as anisole, and the like.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less.
It is more preferably 95% by mass or more and 100% by mass or less, and it is further preferable that it is substantially only an organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass.
It is preferably 100% by mass or more, more preferably 90% by mass or more and 100% by mass or less, and further preferably substantially only butyl acetate and / or 2-heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a small amount of water.
At the time of development, the development may be stopped by substituting with a solvent of a type different from that of the organic developer.

It is preferable to wash the resist pattern after development with a rinsing solution. As a rinse liquid,
There is no particular limitation as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

<Use>
The resist composition of the present invention is a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or EU.
It is suitable as a resist composition for V-exposure, particularly as a resist composition for ArF excimer laser immersion exposure, and is useful for microfabrication of semiconductors.

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part" indicating the content or the amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value obtained by gel permeation chromatography under the following conditions.
Equipment: HLC-8120GPC type (manufactured by Tosoh)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh)

The structure of the compound is mass spectrometry (LC is Agilent 1100 type, MASS is A.
It was confirmed by measuring the molecular peak using a gelent LC / MSD type). In the following examples, the value of this molecular peak is indicated by "MASS".

式（Ｉ－１－ａ）で表される化合物１０部、テトラヒドロフラン５０部、ピリジン８．
１２部及びジメチルアミノピリジン１．０４部を添加し、２３℃で３０分間攪拌した。得
られた混合溶液を５℃まで冷却し、式（Ｉ－１－ｂ）で表される化合物３２．５７部を３
０分かけて添加し、さらに、２３℃で１２時間攪拌した。得られた反応物に、酢酸エチル
３００部及び５％塩酸１８０部を仕込み、２３℃で３０分間攪拌し、静置、分液すること
により有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で
３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１
０％炭酸カリウム水溶液３５部を仕込み、２３℃で３０分間攪拌し、静置、分液すること
により有機層を水洗した。回収された有機層に、イオン交換水７５部を仕込み、２３℃で
３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４
回繰り返した。回収された有機層を濃縮した後、濃縮マスをカラム（関東化学 シリカゲ
ル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：ｎ－ヘプタン／酢酸エチル＝１
／１）分取することにより、式（Ｉ－１）で表される化合物８．８４部を得た。
ＭＳ（質量分析）：２４０．１（分子イオンピーク） Synthesis Example 1 [Synthesis of compound represented by formula (I-1)]

10. 10 parts of the compound represented by the formula (I-1-a), 50 parts of tetrahydrofuran, pyridine 8.
12 parts and 1.04 parts of dimethylaminopyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., and 32.57 parts of the compound represented by the formula (I-1-b) was added to 3 parts.
The mixture was added over 0 minutes and further stirred at 23 ° C. for 12 hours. The obtained reaction product was charged with 300 parts of ethyl acetate and 180 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 1 for the recovered organic layer
35 parts of a 0% potassium carbonate aqueous solution was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 75 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 4 such washing operations
Repeated times. After concentrating the recovered organic layer, concentrate the concentrated mass on a column (Kanto Chemical Silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1
/ 1) By fractionation, 8.84 parts of the compound represented by the formula (I-1) was obtained.
MS (Mass Spectrometry): 240.1 (Molecular Ion Peak)

式（Ｉ－２－ａ）で表される化合物１１．４部、テトラヒドロフラン５０部、ピリジン
８．１部及びジメチルアミノピリジン１部を添加し、２３℃で３０分間攪拌した。得られ
た混合溶液を５℃まで冷却し、式（Ｉ－１－ｂ）で表される化合物３２．６部を３０分か
けて添加し、さらに、２３℃で１２時間攪拌した。得られた反応物に、酢酸エチル３００
部及び５％塩酸１８０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより
有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分
間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭
酸カリウム水溶液３５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより
有機層を水洗した。回収された有機層に、イオン交換水７５部を仕込み、２３℃で３０分
間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り
返した。回収された有機層を濃縮した後、濃縮マスをカラム（関東化学 シリカゲル６０
Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／１）
分取することにより、式（Ｉ－２）で表される化合物９．１１部を得た。
ＭＳ（質量分析）：２５４．２（分子イオンピーク） Synthesis Example 2 [Synthesis of compound represented by formula (I-2)]

11.4 parts of the compound represented by the formula (I-2-a), 50 parts of tetrahydrofuran, 8.1 parts of pyridine and 1 part of dimethylaminopyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 32.6 parts of the compound represented by the formula (I-1-b) was added over 30 minutes, and the mixture was further stirred at 23 ° C. for 12 hours. Ethyl acetate 300 was added to the obtained reaction product.
The organic layer was washed by charging parts and 180 parts of 5% hydrochloric acid, stirring at 23 ° C. for 30 minutes, allowing to stand, and separating the liquids. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 35 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 75 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 4 times. After concentrating the recovered organic layer, concentrate the concentrated mass on a column (Kanto Chemical Silica Gel 60).
N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 1/1)
By fractionation, 9/11 parts of the compound represented by the formula (I-2) was obtained.
MS (Mass Spectrometry): 254.2 (Molecular Ion Peak)

式（Ｉ－２－ａ）で表される化合物１１．４部、テトラヒドロフラン５０部、ピリジン
８．１部及びジメチルアミノピリジン１部を添加し、２３℃で３０分間攪拌した。得られ
た混合溶液を５℃まで冷却し、式（Ｉ－１－ｂ）で表される化合物３２．６部を３０分か
けて添加し、さらに、２３℃で１２時間攪拌した。得られた反応物に、酢酸エチル３００
部及び５％塩酸１８０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより
有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分
間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭
酸カリウム水溶液３５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより
有機層を水洗した。回収された有機層に、イオン交換水７５部を仕込み、２３℃で３０分
間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り
返した。回収された有機層を濃縮した後、濃縮マスをカラム（関東化学 シリカゲル６０
Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／１）
分取することにより、式（Ｉ－４）で表される化合物８．７９部を得た。
ＭＳ（質量分析）：２６８．２（分子イオンピーク） Synthesis Example 3 [Synthesis of compound represented by formula (I-4)]

11.4 parts of the compound represented by the formula (I-2-a), 50 parts of tetrahydrofuran, 8.1 parts of pyridine and 1 part of dimethylaminopyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 32.6 parts of the compound represented by the formula (I-1-b) was added over 30 minutes, and the mixture was further stirred at 23 ° C. for 12 hours. Ethyl acetate 300 was added to the obtained reaction product.
The organic layer was washed by charging parts and 180 parts of 5% hydrochloric acid, stirring at 23 ° C. for 30 minutes, allowing to stand, and separating the liquids. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 35 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 75 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 4 times. After concentrating the recovered organic layer, concentrate the concentrated mass on a column (Kanto Chemical Silica Gel 60).
N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 1/1)
By fractionation, 8.79 parts of the compound represented by the formula (I-4) was obtained.
MS (Mass Spectrometry): 268.2 (Molecular Ion Peak)

式（ａ４－１－ｘ－ａ）で表される化合物６７．５６部、テトラヒドロフラン１３５部
、ピリジン１５．３９部及びジメチルアミノピリジン０．７９部を添加し、２３℃で３０
分間攪拌した。得られた混合溶液を５℃まで冷却し、式（ａ４－１－ｘ－ｂ）で表される
化合物２０．００部を３０分かけて添加した。その後、さらに、２３℃で１時間攪拌した
。得られた反応物に、酢酸エチル３８０部及び５％塩酸１７１部を仕込み、２３℃で３０
分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン
交換水７７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水
洗した。回収された有機層に、１０％炭酸カリウム水溶液５４部を仕込み、２３℃で３０
分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン
交換水１１５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を
水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮することによ
り、式（ａ４－１－ｘ－ｃ）で表される化合物１５．２６部を得た。

式（ａ４－１－ｘ－ｃ）で表される化合物１５．２５部、テトラヒドロフラン１０５部
及びピリジン８．４１部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃
まで冷却し、式（ａ４－１－ｘ－ｄ）で表される化合物３２．９５部を３０分かけて添加
した。その後、さらに、２３℃で１時間攪拌した。得られた反応物に、酢酸エチル５３０
部及び５％塩酸９３部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有
機層を洗浄した。回収された有機層に、イオン交換水１０５部を仕込み、２３℃で３０分
間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭
酸カリウム水溶液４４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより
有機層を水洗した。回収された有機層に、イオン交換水１６０部を仕込み、２３℃で３０
分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰
り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカ
ゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：ｎ－ヘプタン／酢酸エチル＝
１／１）分取することにより、式（ａ４－１－ｘ）で表される化合物２２．５６部を得た
。
ＭＳ（質量分析）：３１８．１（分子イオンピーク） Synthesis Example 4 [Synthesis of compound represented by formula (a4-1-x)]

67.56 parts of the compound represented by the formula (a4-1-x-a), 135 parts of tetrahydrofuran, 15.39 parts of pyridine and 0.79 parts of dimethylaminopyridine were added, and 30 parts were added at 23 ° C.
Stir for minutes. The obtained mixed solution was cooled to 5 ° C., and 20.00 parts of the compound represented by the formula (a4-1-x-b) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. 380 parts of ethyl acetate and 171 parts of 5% hydrochloric acid were added to the obtained reaction product, and 30 at 23 ° C.
The organic layer was washed by stirring for 1 minute, allowing it to stand, and separating the liquid. 77 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 54 parts of a 10% potassium carbonate aqueous solution was added to the recovered organic layer, and 30 at 23 ° C.
The organic layer was washed with water by stirring for 1 minute, allowing it to stand, and separating the liquid. 115 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 4 times. By concentrating the recovered organic layer, 15.26 parts of the compound represented by the formula (a4-1-x-c) was obtained.

15.25 parts of the compound represented by the formula (a4-1-x-c), 105 parts of tetrahydrofuran and 8.41 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was heated to 5 ° C.
After cooling to, 32.95 parts of the compound represented by the formula (a4-1-x-d) was added over 30 minutes. Then, the mixture was further stirred at 23 ° C. for 1 hour. Ethyl acetate 530 was added to the obtained reaction product.
The organic layer was washed by charging parts and 93 parts of 5% hydrochloric acid, stirring at 23 ° C. for 30 minutes, allowing to stand, and separating the liquids. 105 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 44 parts of a 10% potassium carbonate aqueous solution was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. 160 parts of ion-exchanged water was added to the recovered organic layer, and 30 at 23 ° C.
The organic layer was washed with water by stirring for 1 minute, allowing it to stand, and separating the liquid. Such a washing operation was repeated 4 times. The recovered organic layer was concentrated. The obtained concentrated mass was used as a column (Kanto Chemical Co., Ltd. silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate =
By 1/1) fractionation, 22.56 parts of the compound represented by the formula (a4-1-x) was obtained.
MS (Mass Spectrometry): 318.1 (Molecular Ion Peak)

式（Ｂ１－５－ａ）で表される塩５０．４９部及びクロロホルム２５２．４４部を反応
器に仕込み、２３℃で３０分間攪拌し、式（Ｂ１－５－ｂ）で表される化合物１６．２７
部を滴下し、２３℃で１時間攪拌することにより、式（Ｂ１－５－ｃ）で表される塩を含
む溶液を得た。得られた式（Ｂ１－５－ｃ）で表される塩を含む溶液に、式（Ｂ１－５－
ｄ）で表される塩４８．８０部及びイオン交換水８４．１５部を添加し、２３℃で１２時
間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取り
出し、さらに、このクロロホルム層にイオン交換水８４．１５部を添加し、水洗した。こ
の操作を５回繰り返した。得られたクロロホルム層に、活性炭３．８８部を添加攪拌し、
ろ過した。回収されたろ液を濃縮し、得られた残渣に、アセトニトリル１２５．８７部を
添加攪拌し、濃縮した。得られた残渣に、アセトニトリル２０．６２部及びｔｅｒｔ－ブ
チルメチルエーテル３０９．３０部を加えて２３℃で３０分間攪拌し、上澄み液を除去し
、濃縮した。得られた残渣に、ｎ－ヘプタン２００部を添加、２３℃で３０分間攪拌し、
ろ過することにより、式（Ｂ１－５）で表される塩６１．５４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ３７５．２
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３９．１ Synthesis Example 5 [Synthesis of salt represented by formula (B1-5)]

50.49 parts of the salt represented by the formula (B1-5-a) and 252.44 parts of chloroform were charged into the reactor, stirred at 23 ° C. for 30 minutes, and the compound represented by the formula (B1-5-b). 16.27
The parts were added dropwise and stirred at 23 ° C. for 1 hour to obtain a solution containing a salt represented by the formula (B1-5-c). In the obtained solution containing the salt represented by the formula (B1-5-c), the formula (B1-5-c) is added.
48.80 parts of the salt represented by d) and 84.15 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 12 hours. Since the obtained reaction solution was separated into two layers, the chloroform layer was separated and taken out, and 84.15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. 3.88 parts of activated carbon was added to the obtained chloroform layer and stirred.
Filtered. The recovered filtrate was concentrated, 125.87 parts of acetonitrile was added to the obtained residue, and the mixture was stirred and concentrated. To the obtained residue, 20.62 parts of acetonitrile and 309.30 parts of tert-butyl methyl ether were added, and the mixture was stirred at 23 ° C. for 30 minutes to remove the supernatant and concentrated. To the obtained residue, 200 parts of n-heptane was added, and the mixture was stirred at 23 ° C. for 30 minutes.
By filtration, 61.54 parts of a salt represented by the formula (B1-5) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (-) Spectrum): M ^- 339.1

特開２００８－２０９９１７号公報に記載された方法によって得られた式（Ｂ１－２１
－ｂ）で表される化合物３０．００部、式（Ｂ１－２１－ａ）で表される塩３５．５０部
、クロロホルム１００部及びイオン交換水５０部を仕込み、２３℃で１５時間攪拌した。
得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、
このクロロホルム層にイオン交換水３０部を添加し、水洗した。この操作を５回繰り返し
た。クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ－ブチルメチルエーテル１００
部を加えて２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１－２１－ｃ）で表さ
れる塩４８．５７部を得た。 Synthesis Example 6 [Synthesis of salt represented by formula (B1-21)]

Formula (B1-21) obtained by the method described in Japanese Patent Application Laid-Open No. 2008-209917.
30.00 parts of the compound represented by −b), 35.50 parts of the salt represented by the formula (B1-21-a), 100 parts of chloroform and 50 parts of ion-exchanged water were charged and stirred at 23 ° C. for 15 hours. ..
Since the obtained reaction solution was separated into two layers, the chloroform layer was separated and taken out, and further.
30 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer is concentrated, and tert-butylmethyl ether 100 is added to the obtained residue.
Parts were added, and the mixture was stirred at 23 ° C. for 30 minutes and filtered to obtain 48.57 parts of a salt represented by the formula (B1-21-c).

式（Ｂ１－２１－ｃ）で表される塩２０．００部、式（Ｂ１－２１－ｄ）で表される化
合物２．８４部及びモノクロロベンゼン２５０部を仕込み、２３℃で３０分間攪拌した。
得られた混合液に、二安息香酸銅（ＩＩ）０．２１部を添加し、更に、１００℃で１時間
攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム２００部及びイ
オン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収
された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を
取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮した。得られた残渣
に、アセトニトリル５３．５１部に溶解し、濃縮し、ｔｅｒｔ－ブチルメチルエーテル１
１３．０５部を加えて攪拌し、ろ過することにより、式（Ｂ１－２１）で表される塩１０
．４７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２３７．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３９．１

20.00 parts of the salt represented by the formula (B1-21-c), 2.84 parts of the compound represented by the formula (B1-21-d) and 250 parts of monochlorobenzene were charged and stirred at 23 ° C. for 30 minutes. ..
To the obtained mixed solution, 0.21 part of copper (II) dibenzoate was added, and the mixture was further stirred at 100 ° C. for 1 hour. The obtained reaction solution was concentrated. To the obtained residue, 200 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. 50 parts of ion-exchanged water was added to the recovered organic layer, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated. The obtained residue was dissolved in 53.51 parts of acetonitrile, concentrated, and tert-butylmethyl ether 1
The salt 10 represented by the formula (B1-21) is obtained by adding 13.05 parts, stirring, and filtering.
.. I got 47 copies.
MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 339.1

式（Ｂ１－２２－ａ）で表される塩１１．２６部、式（Ｂ１－２２－ｂ）で表される化
合物１０．００部、クロロホルム５０部及びイオン交換水２５部を仕込み、２３℃で１５
時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取
り出し、更に、このクロロホルム層にイオン交換水１５部を添加し、水洗した。この操作
を５回繰り返した。クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ－ブチルメチル
エーテル５０部を加えて２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１－２２
－ｃ）で表される塩１１．７５部を得た。 Synthesis Example 7 [Synthesis of salt represented by formula (B1-22)]

11.26 parts of the salt represented by the formula (B1-22-a), 10.00 parts of the compound represented by the formula (B1-22-b), 50 parts of chloroform and 25 parts of ion-exchanged water were charged at 23 ° C. At 15
Stir for hours. Since the obtained reaction solution was separated into two layers, the chloroform layer was separated and taken out, and 15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer is concentrated, 50 parts of tert-butylmethyl ether is added to the obtained residue, the mixture is stirred at 23 ° C. for 30 minutes, and filtered to obtain the formula (B1-22).
11.75 parts of salt represented by −c) was obtained.

式（Ｂ１－２２－ｃ）で表される塩１１．７１部、式（Ｂ１－２２－ｄ）で表される化
合物１．７０部及びモノクロロベンゼン４６．８４部を仕込み、２３℃で３０分間攪拌し
た。得られた混合液に、二安息香酸銅（ＩＩ）０．１２部を添加し、更に、１００℃で３
０分間攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム５０部及
びイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出
した。回収された有機層にイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、
分液して有機層を取り出した。この水洗操作を８回繰り返した。得られた有機層を濃縮し
た。得られた残渣に、ｔｅｒｔ－ブチルメチルエーテル５０部を加えて攪拌し、ろ過する
ことにより、式（Ｂ１－２２）で表される塩６．８４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２３７．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３２３．０

11.71 parts of the salt represented by the formula (B1-22-c), 1.70 parts of the compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged and charged at 23 ° C. for 30 minutes. Stirred. To the obtained mixed solution, 0.12 part of copper (II) dibenzoate was added, and further, 3 at 100 ° C.
The mixture was stirred for 0 minutes. The obtained reaction solution was concentrated. To the obtained residue, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and separated to remove the organic layer. 12.50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes.
The liquid was separated and the organic layer was taken out. This washing operation was repeated 8 times. The obtained organic layer was concentrated. To the obtained residue, 50 parts of tert-butylmethyl ether was added, stirred, and filtered to obtain 6.84 parts of a salt represented by the formula (B1-22).
MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 323.0

以下、これらのモノマーを式番号に応じて「モノマー（ａ１－１－３）」等という。 Resin synthesis The compounds (monomers) used in the resin synthesis are shown below.

Hereinafter, these monomers will be referred to as "monomer (a1-1-3)" or the like according to the formula number.

Synthesis Example 8 [Synthesis of resin A1]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (
Using a2-1-3) and a monomer (a3-4-2), their molar ratio [monomer (a1-1-1)
-3): Monomer (a1-2-9): Monomer (a2-1-3): Monomer (a3-4-)
2)] was mixed so as to be 45: 14: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of the monomers, and these were added 73.
It was heated at ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is dissolved again in propylene glycol monomethyl ether acetate, and the obtained solution is poured into a methanol / water mixed solvent to precipitate the resin, and the resin is filtered. Molecular weight 7
.. A 6 × 10 ³ resin A1 (copolymer) was obtained in a yield of 68%. This resin A1 has the following structural units.

Synthesis Example 9 [Synthesis of resin X1]
As the monomer, the monomer (I-1) and the monomer (a4-1-x) are used and mixed so that the molar ratio [monomer (I-1): monomer (a4-1-x)] is 3:97. death,
Propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, 12 mol% of azobisisobutyronitrile was added as an initiator with respect to the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was poured into methanol again and repulped, and the resin was filtered to obtain a resin X1 having a weight average molecular weight of 9.8 × 10 ³ in a yield of 75%. This resin X1 has the following structural units.

Synthesis Example 10 [Synthesis of resin X2]
As the monomers, the monomer (I-1), the monomer (a4-0-12) and the monomer (a)
5-1-1) is used, and its molar ratio [monomer (I-1): monomer (a4-0-12) :.
Monomer (a5-1-1)] was mixed so as to be 2:49:49, and the total amount of monomer was 1.
Propylene glycol monomethyl ether acetate of 5% by mass was added to prepare a solution. Azobisisobutyronitrile as an initiator in this solution is 12 mo with respect to the total amount of monomers.
l% was added and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is used again.
By pouring it into methanol, repulping it, and filtering this resin, the weight average molecular weight is 9.1.
A resin X2 (copolymer) of × 10 ³ was obtained in a yield of 75%. This resin X2 has the following structural units.

Synthesis Example 11 [Synthesis of resin X3]
As the monomer, the monomer (I-1) and the monomer (a4-0-12) are used and mixed so that the molar ratio (monomer (I-1): monomer (a4-0-12)) is 2:98. Then, 1.5% by mass of methyl isobutyl ketone was added to prepare a solution. To this solution, 8 mol% of azobisisobutyronitrile was added as an initiator with respect to the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. The resulting reaction mixture was mixed with a large amount of methanol /
Pour into a water-mixed solvent to precipitate the resin, filter the resin, and weigh average molecular weight 9.6 × 10 ³
Resin X3 (copolymer) was obtained in a yield of 78%. This resin X3 has the following structural units.

Synthesis Example 12 [Synthesis of resin X4]
As the monomer, the monomer (I-1) and the monomer (a4-1-7) are used and mixed so that the molar ratio (monomer (I-1): monomer (a4-1-7)) is 3:97. death,
Methyl isobutyl ketone 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, 12 mol% of azobisisobutyronitrile was added as an initiator with respect to the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture is poured into a large amount of a mixed methanol / water solvent to precipitate a resin, and the resin is filtered to obtain a resin X4 (copolymer) having a weight average molecular weight of 8.5 × 10 ³ in a yield of 70%. I got it in. This resin X4 has the following structural units.

合成例１４〔樹脂Ｘ６の合成〕
モノマーとして、モノマー（Ｉ－４）及びモノマー（ａ４－１－ｘ）を用い、そのモル
比〔モノマー（Ｉ－４）：モノマー（ａ４－１－ｘ）〕が３：９７となるように混合し、
全モノマー量の１．５質量倍のプロピレングリコールモノメチルエーテルアセテートを加
えて溶液とした。この溶液に、開始剤としてアゾビスイソブチロニトリルを全モノマー量
に対して、１２ｍｏｌ％添加し、これらを７５℃で約５時間加熱した。得られた反応混合
物を、大量のメタノール／水混合溶媒に注いで樹脂を沈殿させ、この樹脂をろ過した。得
られた樹脂を再び、メタノールに注いでリパルプし、この樹脂をろ過することにより、重
量平均分子量９．２×１０^３の樹脂Ｘ６を収率６８％で得た。この樹脂Ｘ６は、以下の構
造単位を有するものである。

Synthesis Example 13 [Synthesis of resin X5]
As the monomer, the monomer (I-2) and the monomer (a4-1-x) are used and mixed so that the molar ratio [monomer (I-2): monomer (a4-1-x)] is 3:97. death,
Propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, 12 mol% of azobisisobutyronitrile was added as an initiator with respect to the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was poured into methanol again and repulped, and the resin was filtered to obtain a resin X5 having a weight average molecular weight of 9.9 × 10 ³ in a yield of 71%. This resin X5 has the following structural units.

Synthesis Example 14 [Synthesis of resin X6]
Monomers (I-4) and monomers (a4-1-x) are used as the monomers, and mixed so that the molar ratio [monomer (I-4): monomer (a4-1-x)] is 3:97. death,
Propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, 12 mol% of azobisisobutyronitrile was added as an initiator with respect to the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was poured into methanol again and repulped, and the resin was filtered to obtain a resin X6 having a weight average molecular weight of 9.2 × 10 ³ in a yield of 68%. This resin X6 has the following structural units.

Synthesis Example 15 [Synthesis of resin XX1]
As the monomers, the monomer (I-1), the monomer (a5-x1) and the monomer (a5-)
Using x2), its molar ratio [monomer (I-1): monomer (a5-x1): monomer (
a5-x2)] was mixed so as to be 19:52:19, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. In this solution,
Azobisisobutyronitrile was added as an initiator in an amount of 8 mol% based on the total amount of the monomers.
These were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was poured into methanol again and repulped, and the resin was filtered to obtain a resin XX1 (copolymer) having a weight average molecular weight of 1.4 × 10 ⁴ in a yield of 55%. This resin XX1 has the following structural units.

<Preparation of resist composition>
Each of the components shown below was mixed in parts by mass shown in Table 1, dissolved in a solvent, and filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

＜クエンチャー（Ｃ）＞
Ｄ１：（東京化成工業（株）製）

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２－ヘプタノン ２０部
γ－ブチロラクトン ３．５部 <Resin (A)>
A1, X1 to X6, XX1: Resin A1, Resin X1 to Resin X6, Resin XX1
<Acid generator (B)>
B1-5: Salt represented by the formula (B1-5) B1-21: Salt represented by the formula (B1-21) B1-22: Salt represented by the formula (B1-22) B1-3: Special Synthesized according to the examples of Japanese Patent Publication No. 2010-152341

<Quencher (C)>
D1: (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene Glycol Monomethyl Ether Acetate 265 Parts Propylene Glycol Monomethyl Ether 20 Parts 2-Heptanone 20 Parts γ-Butyrolactone 3.5 Parts

<Manufacturing of resist pattern and its evaluation>
A composition for an organic antireflection film [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 78.
An organic antireflection film of nm was formed. Next, the above resist composition was spin-coated on the organic antireflection film so that the film thickness after drying (prebaking) was 85 nm.
The obtained silicon wafer was prebaked (PB) on a direct hot plate at the temperature listed in the "PB" column of Table 1 for 60 seconds. ArF excimer stepper for immersion exposure [XT: 1900Gi; ASML, N.] on the wafer on which the resist composition film was formed in this way.
Using A = 1.35, 3/4 Anal XY polarization], the line-and-space pattern was immersed and exposed by changing the exposure amount stepwise. Ultrapure water was used as the immersion medium.
After exposure, post-exposure baking (PEB) is performed on a hot plate at the temperature listed in the “PEB” column of Table 1 for 60 seconds, and then with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Paddle development was performed to obtain a resist pattern.

In each of the obtained resist pattern films, the exposure amount at which the line-and-space pattern of 50 nm was 1: 1 was defined as the effective sensitivity.

<Line edge roughness evaluation (LER)>
The wall surface of the resist pattern after the lithography process was observed with a scanning electron microscope, and the deflection width (nm) of the unevenness of the side wall of the resist pattern was determined. The results of this swing width are shown in Table 2.

From the above results, it can be seen that the resist composition containing the resin of the present invention has good line edge roughness (LER).

The resin and resist composition of the present invention have good line edge roughness and are useful for microfabrication of semiconductors.

Claims (6)

A structural unit derived from the compound represented by the formula (I) and
The structural unit represented by the formula (a4-0), the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2), and the structure represented by the formula (a4-3). A structural unit having at least one structural unit selected from the group consisting of a unit and a structural unit represented by the formula (a4-4), or a structural unit derived from a compound represented by the formula (I).
The structural unit represented by the formula (a4-0), the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2), and the structure represented by the formula (a4-3). At least one structural unit selected from the group consisting of units and structural units represented by the formula (a4-4), and
A resin having a structural unit represented by the formula (a5-1).
For the total of all structural units of resin
The content of the structural unit (I) is 1 to 10 mol%,
The structural unit represented by the formula (a4-0), the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2), and the structural unit represented by the formula (a4-3). The total content of the structural units and the structural units represented by the formula (a4-4) is 90 to 99 mol%.
When it has a structural unit represented by the above formula (a5-1),
The structural unit represented by the formula (a4-0), the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2), and the structural unit represented by the formula (a4-3). The total content of the structural unit and the structural unit represented by the formula (a4-4) and the structural unit represented by the formula (a5-1) is 90 to 99 mol%, and the formula (a5-1). The content of the structural unit represented by is 2 to 80 mol%, and is
A resin having a weight average molecular weight of 6000 or more and 80,000 or less.

[In formula (I),
R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom which may have a halogen atom.
R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² independently represent an alkanediyl group having 1 to 6 carbon atoms or ^* -A ³ -X ^1- (A ⁴ -X ² ) _a -A ^5- . * Represents a bond with an oxygen atom. However, the carbon atom in the binding site with the oxygen atom is not a tertiary carbon atom.
A ³ , A ⁴ and A ⁵ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² independently represent an oxygen atom, a carbonyloxy group or an oxycarbonyl group, respectively.
a represents 0 or 1. ]

[In equation (a4-0),
^R5 represents a hydrogen atom or a methyl group.
L ⁵ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

[In equation (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having a fluorine atom or a group represented by the formula (a-g3) and having 1 to 20 carbon atoms, and -CH _2- contained in the hydrocarbon group is -O- or-. It may be replaced with CO-.
^Aa41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (ag1). ]

[In the formula (ag3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
^Aa45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and having at least one fluorine atom.
* Represents a bond. ]

[In the formula (ag1),
s represents 0 or 1.
^Aa42 and ^Aa44 represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent independently of each other.
^Aa43 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 independently represent an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less.
** and ** represent a bond, and ** is a bond with -O-CO-R ^a42 . ]

[In equation (a4-2),
R ^f1 represents a hydrogen atom or a methyl group.
A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms.
R ^f2 represents a hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom. ]

[In equation (a4-3),
R ^f11 represents a hydrogen atom or a methyl group.
A ^f11 represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 represents an aliphatic hydrocarbon group having a fluorine atom. ]

[In equation (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents-(CH ₂ ) _j1 -,-(CH ₂ ) _j2 -O- (CH ₂ ) _{j3- or-} (CH ₂ ) _j4 -CO-O- (CH ₂ ) _j5- .
j1 to j5 represent integers of 1 to 6 independently of each other.
R ^f22 represents a hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom. ]

[In equation (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or a hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the bonding position with L ⁵¹ is not substituted with the aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ] The resin according to claim 1, wherein A ¹ and A ² are independently alkanediyl groups having 1 to 6 carbon atoms. A resist composition containing the resin according to claim 1 or 2, the resin (A) having a structural unit having an acid unstable group, and an acid generator. The resist composition according to claim 3, wherein the acid generator is a salt represented by the formula (B1).

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH _2- contained in the divalent saturated hydrocarbon group is -O- or. It may be replaced with —CO—, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon. -CH _2- contained in the hydrogen group may be replaced with -O-, -SO _2- or -CO-.
Z ⁺ represents an organic cation. ] The resist composition according to claim 3 or 4, further comprising a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. (1) A step of applying the resist composition according to any one of claims 3 to 5 onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) Step of heating the composition layer after exposure, and (5) Step of developing the composition layer after heating,
A method for manufacturing a resist pattern including.