JP2023052755A - Resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin and a resist composition which allow a resist pattern to be produced with good CD uniformity.

SOLUTION: The resin contains: a structural unit represented by formula (I); at least one structural unit selected from structural units represented by formula (a1-1) and formula (a1-2); and at least one structural unit selected from the group consisting of structural units represented by formula (a1-0), formula (a1-3), formula (a1-4), formula (a1-5), formula (a4-0), formula (a4-1), formula (a4-4) and formula (a5-1). The total content of all the structural units constituting the resin is 100 mol%. The content of the structural unit of the formula (I) is 1-60 mol% and the total content of the structural units of the formula (a1-1) and the formula (a1-2) is 10-95 mol% based on the total of all the structural units constituting the resin.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

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

特許文献２には、下記構造単位の組合せからなる樹脂が記載されている。

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

Patent Literature 2 describes a resin composed of a combination of the following structural units.

WO2009/078078 JP 2012-168497 A

The CD uniformity (CDU) of the resist pattern formed from the resist composition containing the resin described above may not always be satisfactory.

［式（Ｉ）中、
Ｒ^１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。
Ｘは、－Ｏ－、－Ｓ－又は－ＮＲ^１１－を表す。
Ｒ^１１は水素原子又は炭素数１～６のアルキル基を表す。
ｓ及びｖは、それぞれ独立に、１～４の整数を表す。
Ｒ^２は、炭素数１～６の脂肪族炭化水素基を表す。
ｕは、０～３の整数を表し、ｕが２以上のとき、複数のＲ^２は互いに同一又は相異なる
。
Ａ¹は、単結合、炭素数１～６のアルカンジイル基又は＊－Ａ²－Ｘ¹－（Ａ³－Ｘ²）_a－
（Ａ⁴）_b－を表す。＊は基Ｘとの結合手を表す。
Ａ²、Ａ³及びＡ⁴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、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ
－Ｏ－を表す。
ａは、０又は１を表す。
ｂは、０又は１を表す。］
〔２〕Ａ¹が、単結合である〔１〕記載の樹脂。
〔３〕酸不安定基を有する構造単位が、式（ａ１－１）で表される構造単位及び式（ａ
１－２）で表される構造単位から選ばれる少なくとも１つである〔１〕又は〔２〕に記載
の樹脂。

［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た基を表す。
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。］
〔４〕さらに、式（ａ３－４）で表される構造単位を含む〔１〕～〔３〕のいずれかに
記載の樹脂。

［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。］
〔５〕〔１〕～〔４〕のいずれかに記載の樹脂及び酸発生剤を含有するレジスト組成物
。
〔６〕酸発生剤が、式（Ｂ１）で表される塩である〔５〕記載のレジスト組成物。

［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、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－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、水素原子又は置換基を有していてもよい炭素数３～１８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。］
〔７〕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〔
５〕又は〔６〕記載のレジスト組成物。
〔８〕さらに、フッ素原子を有する構造単位を含む樹脂を含有する〔５〕～〔７〕のい
ずれかに記載のレジスト組成物。
〔９〕（１）〔５〕～〔８〕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 containing a structural unit represented by formula (I) and a structural unit having an acid-labile group.

[in the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
X represents -O-, -S- or -NR ¹¹ -.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4;
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer of 0 to 3, and when u is 2 or more, a plurality of R ² are the same or different.
A ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms, or *-A ² -X ¹ -(A ³ -X ² ) _a -
(A ⁴ ) represents _b- . * represents a bond with the group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² are each independently -O-, -CO-O-, -O-CO- or -O-CO
represents -O-.
a represents 0 or 1;
b represents 0 or 1; ]
[2] The resin of [ ¹ ], wherein A 1 is a single bond.
[3] A structural unit having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a
The resin according to [1] or [2], which is at least one structural unit selected from structural units represented by 1-2).

[In the formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 each independently represent —O— or ^* —O—(CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, * is 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 combination thereof.
m1 represents an integer from 0 to 14;
n1 represents an integer from 0 to 10;
n1' represents an integer of 0 to 3; ]
[4] The resin according to any one of [1] to [3], further comprising a structural unit represented by formula (a3-4).

[In the formula (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
L ^a7 is -O-, ^* -OL ^a8 -O-, ^* -OL ^a8 -CO-O-, ^* -OL ^a8 -C
OO-L ^a9 -CO-O- or ^* -O-L ^a8 -O-CO-L ^a9 -O-.
* represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]
[5] A resist composition containing the resin according to any one of [1] to [4] and an acid generator.
[6] The resist composition of [5], wherein the acid generator is a salt represented by formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents an optionally substituted divalent saturated hydrocarbon group having 1 to 24 carbon atoms,
—CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO—, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be a fluorine atom or a hydroxyl may be substituted with a group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the monovalent alicyclic hydrocarbon group; may be replaced by -O-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ]
[7] Further containing a salt that generates an acid with a weaker acidity than the acid generated from the acid generator [
5] or the resist composition described in [6].
[8] The resist composition according to any one of [5] to [7], further comprising a resin containing a structural unit having a fluorine atom.
[9] (1) a step of applying the resist composition according to any one of [5] to [8] onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) A method for producing a resist pattern, comprising the steps of: (4) heating the exposed composition layer; and (5) developing the heated composition layer.

By using the resin or resist composition of the present invention, a resist pattern with good CD uniformity (CDU) can be produced.

As used herein, "(meth)acrylate" means "at least one of acrylate and methacrylate". Notations such as "(meth)acrylic acid" and "(meth)acryloyl" have the same meaning.
In addition, unless otherwise specified, a group that can be linear, branched and/or cyclic such as an "aliphatic hydrocarbon group" includes any of them. An "aromatic hydrocarbon group" also includes a hydrocarbon group containing an aromatic ring. Where stereoisomers exist, all stereoisomers are included.
As used herein, "the solid content of the resist composition" means the total amount of components excluding the solvent (E) described below from the total amount of the resist composition.

<Resin>
The resin of the present invention includes a structural unit represented by formula (I) (hereinafter sometimes referred to as "structural unit (I)") and a structural unit having an acid labile group (hereinafter referred to as "resin (A )”).

［式（Ｉ）中、
Ｒ^１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。
Ｘは、－Ｏ－、－Ｓ－又は－ＮＲ^１１－を表す。
Ｒ^１１は水素原子又は炭素数１～６のアルキル基を表す。
ｓ及びｖは、それぞれ独立に、１～４の整数を表す。
Ｒ^２は、炭素数１～６の脂肪族炭化水素基を表す。
ｕは、０～３の整数を表し、ｕが２以上のとき、複数のＲ^２は互いに同一又は相異なる
。
Ａ¹は、単結合、炭素数１～６のアルカンジイル基又は＊－Ａ²－Ｘ¹－（Ａ³－Ｘ²）_a－
（Ａ⁴）_b－を表す。＊は基Ｘとの結合手を表す。
Ａ²、Ａ³及びＡ⁴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、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ
－Ｏ－を表す。
ａは、０又は１を表す。
ｂは、０又は１を表す。］ <Structural unit (I)>

[in the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
X represents -O-, -S- or -NR ¹¹ -.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4;
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer of 0 to 3, and when u is 2 or more, a plurality of R ² are the same or different.
A ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms, or *-A ² -X ¹ -(A ³ -X ² ) _a -
(A ⁴ ) represents _b- . * represents a bond with the group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² are each independently -O-, -CO-O-, -O-CO- or -O-CO
represents -O-.
a represents 0 or 1;
b represents 0 or 1; ]

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- unsubstituted alkyl groups having 1 to 6 carbon atoms such as pentyl group and n-hexyl group, and trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro-sec-butyl group, Haloalkyl groups having 1 to 6 carbon atoms such as perfluoro-tert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group and triiodomethyl group can be mentioned.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms for R ¹¹ include methyl group, ethyl group, n-propyl group,
Examples include isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group.
One of s and v is preferably 1.

Aliphatic hydrocarbon groups having 1 to 6 carbon atoms for R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-pentyl group. and alkyl groups such as n-hexyl groups.
R ² is preferably a methyl group or an ethyl group.
u is preferably 0 or 1;

The alkanediyl group having 1 to 6 carbon atoms for A ¹ , A ² , A ³ and A ⁴ includes methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-
Linear alkanediyl groups such as diyl groups and hexane-1,6-diyl groups, linear alkanediyl groups, alkyl groups (especially alkyl groups having 1 to 4 carbon atoms, methyl groups, ethyl groups, propyl groups , isopropyl group, butyl group, sec-butyl group, tert-butyl group, etc.), ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,
3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-
branched alkanediyl groups such as a diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group;

*-A ² -X ¹ -(A ³ -X ² ) _a -(A ⁴ ) _b - are *-A ² -O-, *-A ² -CO
-O-, *-A ² -O-CO-O-, *-A ² -CO-O-A ⁴ -, *-A ² -O-CO-,
* ^-A2 -CO- ^OA3 -CO-O-, * ^-A2 -CO- ^OA3 -CO- ^OA4- , *
-A ² -O-CO-A ³ -O-, *-A ² -OA ³ -CO-O-, *-A ² -CO-OA ³
-O-CO-, *-A ² -O-CO-A ³ -O-CO-. Above all, *-A ²
-O-, *-A ² -CO-O- or *-A ² -O-CO-O- is preferred, and *-A ² -CO
-O- or *-A ² -O-CO-O- is more preferred. * represents a bond with the group X.

A ¹ , A ² , A ³ and A ⁴ are each independently preferably an alkanediyl group having 1 to 6 carbon atoms.
A ¹ is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, and even more preferably an alkanediyl group having 1 to 3 carbon atoms. .

The cyclic sulfoxide structure in formula (I) is preferably a structure represented by any one of formulas (S-1) to (S-9), and any one of formulas (S-1) to (S-3). The structure represented by the structure represented by is more preferable. * is a bond with ^A1 .

Structural unit (I) includes structural units represented by formulas (I-1) to (I-28) below, which correspond to R ¹ of structural units represented by formulas (I-1) to (I-28) below. and a structural unit in which the methyl group is replaced with a hydrogen atom or a trifluoromethyl group.

なかでも、式（Ｉ－１）～式（Ｉ－３）で表される構造単位が好ましい。

Among them, structural units represented by formulas (I-1) to (I-3) are preferable.

［式（Ｉ）中、Ａ^１、Ｒ^１、Ｒ^３、Ｘ、ｓ、ｖ及びｕは、上記と同じ意味を表す。］ Structural unit (I) is derived from a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)").

[In formula (I), A ¹ , R ¹ , R ³ , X, s, v and u have the same meanings as above. ]

As the compound (I), compounds represented by formulas (I'-1) to (I'-28), formula (I
Examples thereof include compounds represented by '-1) to (I'-28) in which the methyl group corresponding to R ¹ is replaced with a hydrogen atom or a trifluoromethyl group.

なかでも、式（Ｉ’－１）～式（Ｉ’－３）で表される構造単位が好ましい。

Among them, structural units represented by formulas (I'-1) to (I'-3) are preferable.

［式中、Ａ^１、Ｒ^１、Ｒ^３、Ｘ、ｓ、ｖ及びｕは、上記と同じ意味を表す。］
溶媒としては、酢酸及びアセトンなどが挙げられる。
酸化剤としては、過酸化水素などが挙げられる。 <Method for producing compound (I)>
Compound (I) can be obtained by subjecting the compound represented by formula (I0-a) to an oxidation reaction in a solvent.

[In the formula, A ¹ , R ¹ , R ³ , X, s, v and u represent the same meanings as above. ]
Solvents include acetic acid and acetone.
Hydrogen peroxide etc. are mentioned as an oxidizing agent.

［式中、Ａ^１、Ｒ^１、Ｒ^３、ｓ、ｖ及びｕは、上記と同じ意味を表す。］
溶媒としては、ジメチルホルムアミド、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、炭酸カリウム、ヨウ化カリウム、ピリジン、ジメチルアミノピリジ
ンなどが挙げられる。 Compound (I0-a) wherein X is -O- is a compound represented by formula (Ia') and formula (I-
It can be obtained by reacting the compound represented by b) in the presence of a base catalyst in a solvent.

[In the formula, A ¹ , R ¹ , R ³ , s, v and u have the same meanings as above. ]
Solvents include dimethylformamide, chloroform, tetrahydrofuran and toluene.
Basic catalysts include potassium carbonate, potassium iodide, pyridine, dimethylaminopyridine and the like.

Examples of the compound represented by the formula (Ia') include compounds represented by the following formula, etc., which are readily available on the market.

Examples of the compound represented by formula (Ib) include compounds represented by the following formula, etc., which are readily available on the market.

The compound represented by the formula (I0-a) wherein X is -S- is a compound represented by the formula (Ia'') instead of the compound represented by the formula (Ia'). It can be obtained by carrying out the above method using
Compound (I) wherein X is -NR ¹¹ - can be prepared by the above method using a compound represented by formula (Ia''') instead of the compound represented by formula (Ia'). can be obtained by implementing

Examples of the compound represented by the formula (Ia'') include compounds represented by the following formula.

Examples of the compound represented by the formula (Ia''') include compounds represented by the following formula.

Two or more types of structural units (I) may be contained in the resin (A).
The content of structural unit (I) contained in resin (A) is, with respect to all structural units of resin (A),
Usually 1 to 60 mol%, preferably 3 to 40 mol%, more preferably 4 to 35 mol%
, more preferably 5 to 30 mol %, particularly preferably 5 to 25 mol %.

The resin (A) of the present invention has, in addition to the structural unit (I), a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). An "acid-labile group" has a leaving group, and upon contact with an acid, the leaving group is eliminated, and the structural unit is converted into a structural unit having a hydrophilic group (e.g., hydroxy group or carboxy group). means a group that

［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-labile group (hereinafter sometimes referred to as "monomer (a1)").
As the acid-labile group contained in the structural unit (a1), the following group (1) and/or group (2)
is preferred.

[In the formula (1), R ^a1 to R ^a3 are each independently an alkyl group having 1 to 8 carbon atoms,
represents an alicyclic hydrocarbon group of up to 20 or a combination thereof, or R ^a1 and R ^a2 are bonded to each other and together with the carbon atom to which they are bonded, a divalent alicyclic hydrocarbon having 3 to 20 carbon atoms; form a base.
na represents 0 or 1;
* represents a bond. ]

[In 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. or R ^a2′ and R ^a3′
are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and —CH ₂ — contained in the hydrocarbon group and the divalent heterocyclic group is , —O— or —S—.
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等
のアルキル－シクロアルキル基、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のシクロアルキル－アルキル基、メチルシクロヘキシルメチル基等の
アルキル－シクロアルキル－アルキ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 methyl group, ethyl group, propyl group, n-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like.
The alicyclic hydrocarbon groups of R ^a1 to R ^a3 may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bond). The alicyclic hydrocarbon groups of R ^a1 to R ^a3 preferably have 3 to 16 carbon atoms.

Groups in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, alkyl-cycloalkyl groups such as a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group and a methyladamantyl group, a cyclohexylmethyl group, Examples include cycloalkyl-alkyl groups such as adamantylmethyl group and norbornylmethyl group, and alkyl-cycloalkyl-alkyl groups such as methylcyclohexylmethyl group.
na is preferably zero.

—C(R ^a1 ) when R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group;
(R ^a2 ) and (R ^a3 ) include, for example, 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 hydrocarbon groups represented by R ^a1′ to R ^a3′ include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, groups formed by combining these groups, and the like.
Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl and biphenyl groups. group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl, and the like.

Ｒ^a1'及びＲ^a2'のうち、少なくとも１つは水素原子であることが好ましい。 Groups formed by combining these include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, alkyl-cycloalkyl-alkyl groups, aralkyl groups (e.g., phenylmethyl group, 1-phenylethyl group, 2-phenyl ethyl group, 1-phenyl-1-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.), aryl-cycloalkyl groups (phenyladamantyl group, phenylcyclohexyl group, etc.) and the like.
R ^a2′ and R ^a3′ are bonded together to form 2 with the carbon atom to which they are bonded and X
The following groups are mentioned as a valent heterocyclic group. * represents a bond.

At least one of R ^a1′ and R ^a2′ is preferably a hydrogen atom.

Examples of groups represented by formula (1) include 1,1-dialkylalkoxycarbonyl groups (groups in which R ^a1 to R ^a3 are alkyl groups in formula (1), preferably tert-butoxycarbonyl groups), 2-alkyladamantan-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-( and adamantan-1-yl)-1-alkylalkoxycarbonyl group (in formula (1), R ^a1 and R ^a2 are alkyl groups and R ^a3 is an adamantyl group).

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

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

Of the (meth)acrylic monomers having an acid labile group, preferably having 5 to 20 carbon atoms
having an alicyclic hydrocarbon group. When 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 20 to 90 mol%, more preferably 25 to 85 mol%, based on the total structural units of the resin (A). It is preferably 30 to 80 mol %.

As a structural unit derived from a (meth)acrylic monomer having a group represented by formula (1), preferably a structural unit represented by formula (a1-0), represented by formula (a1-1) structural units or structural units represented by formula (a1-2). They may be used alone,
You may use 2 or more types together. In this specification, structural units represented by formula (a1-0), formula (a
1-1) and the structural unit represented by formula (a1-2) are referred to as structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2), respectively. , the structural unit (a1-
0), the monomer that induces the structural unit (a1-1) and the structural unit (a1
-2) are sometimes referred to as monomer (a1-0), monomer (a1-1) and 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 the formula (a1-0),
L ^a01 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 each independently represent an alkyl group having 1 to 8 carbon atoms,
represents 18 alicyclic hydrocarbon groups or a combination thereof. ]

L ^a01 is preferably an oxygen atom or *—O—(CH ₂ ) _k01 —CO—O— (provided that k01 is preferably an integer of 1 to 4, more preferably 1), more preferably is an oxygen atom.
Examples of the alkyl groups, alicyclic hydrocarbon groups, and groups in which these are combined for R ^a02 , R ^a03 and R ^a04 include the same groups as those listed for R ^a1 to R ^a3 in formula (1).
The alkyl groups of R ^a02 , R ^a03 and R ^a04 are preferably C 1-6 alkyl groups.
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.
It is preferable that the combined group of an alkyl group and an alicyclic hydrocarbon group has a total carbon number of 18 or less. Examples of such groups include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group and a norbornylmethyl group. be done.
R ^a02 and R ^a03 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl or ethyl groups.

［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 formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 each independently represent -O- or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, * is 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 these.
m1 represents an integer from 0 to 14;
n1 represents an integer from 0 to 10;
n1' represents an integer of 0 to 3; ]

R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, 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; is), more preferably -O-
is.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl groups, alicyclic hydrocarbon groups, and groups formed by combining these groups for R ^a6 and R ^a7 include the same groups as those listed for R ^a1 to R ^a3 in formula (1).
The alkyl groups of R ^a6 and R ^a7 are preferably C 1-6 alkyl groups.
The alicyclic hydrocarbon groups of R ^a6 and R ^a7 preferably have 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
is less than or equal to an alicyclic hydrocarbon group of
m1 is preferably an integer from 0 to 3, more preferably 0 or 1.
n1 is preferably an integer from 0 to 3, more preferably 0 or 1.
n1' is preferably 0 or 1.

Examples of structural units (a1-0) include formulas (a1-0-1) to formulas (a1-0-12)
Structural units represented by any of the formulas (a1-0-1) to (a1-0-10) are preferred.
Structural units represented by either are more preferable.

In the above structural unit, a structural unit in which the methyl group corresponding to R ^a01 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 monomers described in JP-A-2010-204646. Among them, a monomer represented by any one of formulas (a1-1-1) to (a1-1-8) is preferable, and any one of formulas (a1-1-1) to (a1-1-4) A monomer represented by is more preferred.

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

When the resin (A) contains the structural unit (a1-0) and/or the structural unit (a1-1) and/or the structural unit (a1-2), the total content of these is the total structure of the resin (A) for the unit
Usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20
~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し、該アルキル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、該アルキル基及び該脂環式
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。 Furthermore, structural units (a1) having group (1) also include structural units represented by formula (a1-3). The structural unit represented by formula (a1-3) may be referred to as structural unit (a1-3). Further, a monomer that induces the structural unit (a1-3) is a monomer (a1-3)
There is a case.

In formula (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxy group, a carboxy group, a cyano group, a hydrogen atom or —COOR ^a13 .
R ^a13 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these, and the alkyl group and the alicyclic hydrocarbon group A hydrogen atom contained may be substituted with a hydroxy group, and -CH ₂ - contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O-- or -CO- .
R ^a10 , R ^a11 and R ^a12 each independently represent an alkyl group having 1 to 8 carbon atoms,
20 alicyclic hydrocarbon groups or groups formed by combining them, or R
^a10 and R ^a11 are bonded to each other and together with the carbon atom to which they are bonded, 2 having 3 to 20 carbon atoms
form a divalent alicyclic hydrocarbon group.

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

The aliphatic hydrocarbon group optionally having a hydroxy group for R ^a9 includes methyl group, ethyl group, propyl group, cyclohexyl group, hydroxymethyl group and 2-hydroxyethyl group.
Examples of alkyl groups having 1 to 8 carbon atoms represented by R ^a10 to R ^a12 and R ^a13 include methyl group, ethyl group,
propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group and the like.
The alicyclic hydrocarbon group having 3 to 20 carbon atoms for R ^a13 includes cyclopentyl group, cyclopropyl group, adamantyl group, adamantylmethyl group, 1-adamantyl-1-methylethyl group, 2-oxo-oxolane-3- yl group, 2-oxo-oxolan-4-yl group and the like.
The alicyclic hydrocarbon groups of R ^a10 to R ^a12 may be either monocyclic or polycyclic, and examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl and cyclopentyl. cycloalkyl groups such as a group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1-(adamantan-1-yl)alkane-
1-yl group, norbornyl group, methylnorbornyl group, isobornyl group and the like.
—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 atoms to which they are bonded, groups are preferred.

Monomer (a1-3) is specifically 5-norbornene-2-carboxylic acid-tert
-butyl, 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylate,
1-methylcyclohexyl 5-norbornene-2-carboxylic acid, 5-norbornene-2-
2-methyl-2-adamantyl carboxylate, 2-ethyl-2-adamantyl 5-norbornene-2-carboxylate, 1-(4-methylcyclohexyl)-1-methylethyl 5-norbornene-2-carboxylate, 5- Norbornene-2-carboxylic acid 1-(4-hydroxycyclohexyl)-1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1
-(4-oxocyclohexyl)ethyl and 5-norbornene-2-carboxylic acid 1-(1
-adamantyl)-1-methylethyl and the like.

Since the resin (A) containing the structural unit (a1-3) contains a sterically bulky structural unit, the resist composition of the present invention containing such a resin (A) has a higher A resist pattern can be obtained with high resolution. Moreover, since a rigid norbornane ring is introduced into the main chain, the resulting resist pattern tends to be excellent in dry etching resistance.

When the resin (A) contains the structural unit (a1-3), its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on the total 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 group (2), a structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)") is mentioned.

[In the formula (a1-4),
R ^a32 is a hydrogen atom, a halogen atom, or 1 to 6 carbon atoms which may have a halogen atom
represents an 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 of 0 to 4; When la is 2 or more, a plurality of R ^a33 may be the same or different.
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 form a divalent heterocyclic group having 3 to 20 carbon atoms together with the C—O to which it is bonded, --CH ₂ -- contained in the hydrocarbon group and the divalent heterocyclic group may be replaced with --O-- or --S--. ]

Examples of alkyl groups for R ^a32 and R ^a33 include methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl groups. The alkyl group has 1 carbon atom
An alkyl group of ∼4 is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.
The halogen atoms of R ^a32 and R ^a33 include fluorine, chlorine and bromine atoms.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 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.
Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy groups. Among them, 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.
Acyl groups include acetyl, propionyl and butyryl groups.
The acyloxy group includes acetyloxy group, propionyloxy group, butyryloxy group and the like.
The hydrocarbon groups of R ^a34 and R ^a35 include the same groups as R ^a1′ and R ^a2′ in formula (2).
R ^a36 is 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 group formed by combining these groups may be mentioned.

In 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 or an ethoxy group, even more preferably a methoxy group.
la is preferably 0 or 1, more preferably 0.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, 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 of these A group formed, more preferably an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 1 carbon atoms
8 alicyclic aliphatic hydrocarbon group 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 for R ^a36 has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.

Examples of the monomer leading to the structural unit (a1-4) include, for example, JP-A-2010-204646
Examples thereof include monomers described in JP-A-2003-201213. Among them, formula (a1-4-1) to formula (a1-4
-8) are preferred, respectively represented by formulas (a1-4-1) to formulas (a1-4-5
and (a1-4-8)) are more preferable.

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

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。 As the structural unit derived from a (meth)acrylic monomer having a group represented by formula (2), a structural unit represented by formula (a1-5) (hereinafter referred to as "structural unit (a1-5)" There is) is also mentioned.

In formula (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or 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 each independently represent -O- or -S-.
s1 represents an integer of 1-3.
s1' represents an integer of 0 to 3;

Halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl group, ethyl group,
Examples include propyl, butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl and trifluoromethyl groups.
In formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
One of L ⁵² and L ⁵³ is preferably -O- and the other is -S-.
As for s1, 1 is preferable.
s1' is preferably an integer of 0-2.
Z ^a1 is preferably a single bond or *—CH ₂ —CO—O—. * represents a bond with ^L51 .

Examples of the monomer leading to the structural unit (a1-5) include monomers described in JP-A-2010-61117. Among them, formula (a1-5-1) ~ formula (a1-5-
4) is preferably a monomer represented by formula (a1-5-1) or formula (a1-5-2
) is more preferred.

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

The structural unit (a) having an acid labile group in the resin (A) includes a structural unit (a1-0),
At least one selected from the group consisting of the structural unit (a1-1), the structural unit (a1-2) and the structural unit (a1-5) is preferred, and at least two or more are more preferred, and the structural unit (a1-1) and a combination of the structural unit (a1-2), a combination of the structural unit (a1-1) and the structural unit (a1-5), a combination of the structural unit (a1-1) and the structural unit (a1-0), a structural unit ( a1-2) and a combination of the structural unit (a1-0), the structural unit (a1-
5) and a combination of the structural unit (a1-0), the structural unit (a1-0), the structural unit (a1-
1) and a combination of the structural unit (a1-2), the structural unit (a1-0), the structural unit (a1-
1) and the structural unit (a1-5) are more preferred, 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)
is even more preferred.

<Structural unit (s)>
The resin (A) further contains a structural unit having no acid-labile group (hereinafter referred to as “structural unit (s
)”), a structural unit having a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”), a structural unit having a non-eliminating hydrocarbon group (a5), and other known monomers It may contain a structural unit derived from. Among them, it is preferable that the structural unit (s) is included. Structural unit (s) is a monomer having no acid labile group (hereinafter referred to as "monomer (s)
”). As the monomer (s), a monomer having no acid-labile group known in the field of resists can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and not having an acid labile group is preferred. A structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and/or a structure having a lactone ring and no acid-labile group When 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 adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group possessed by 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 using a high-energy beam such as an excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light), the structural unit (a2) is a structural unit having a phenolic hydroxy group (
It is preferred to use a2). When using an ArF excimer laser (193 nm) or the like, the structural unit (a2) having an alcoholic hydroxy group (a2
) 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 hydroxy group, the total content is preferably 5 to 95 mol%, more preferably 10 to 80 mol%, based on the total structural units of the resin (A). More preferably, 15 to 80 mol % is even more 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。］ The structural unit (a2) having a phenolic hydroxy group includes a structural unit represented by formula (a2-0) (hereinafter sometimes referred to as "structural unit (a2-0)").

[In formula (a2-0),
R ^a30 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have 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 of 0-4. When ma is an integer of 2 or more, multiple R ^a31 may be the same or different. ]

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, n
-pentyl group, n-hexyl group and the like.
A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 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. 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, even more preferably a hydrogen atom or a methyl group.
The alkoxy group for R ^a31 includes methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy groups. Among them, 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.
Acyl groups include acetyl, propionyl and butyryl groups.
The acyloxy group includes acetyloxy group, propionyloxy group, butyryloxy group and the like.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

As a monomer that induces the structural unit (a2-0), for example, JP-A-2010-2046
The monomers described in JP-A-34 may be mentioned.
Among them, as the structural unit (a2-0), formula (a2-0-1), formula (a2-0-2),
Those represented by formulas (a2-0-3) and (a2-0-4) are preferable, and formula (a
2-0-1) or those represented by formula (a2-0-2) are more preferred.

The resin (A) containing the structural unit (a2-0) is polymerized using a monomer in which the phenolic hydroxy group of the monomer deriving the structural unit (a2-0) is protected with a protecting group, and then deprotected. It can be produced by processing. However, when the deprotection treatment is carried out, it is necessary to carry out in such a manner as not to significantly impair the acid-labile group of the structural unit (a1). An acetyl group etc. are mentioned as such a protecting group.

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

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。 The structural unit (a2) having an alcoholic hydroxy group includes a structural unit represented by formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)").

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

In formula (a2-1), L ^a3 is preferably —O—, —O—(CH ₂ ) _f1 —CO—O—
(f1 is an integer of 1 to 4), 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 from 0 to 3, more preferably 0 or 1.

As a monomer that induces the structural unit (a2-1), for example, JP 2010-2046
Monomers described in JP-A-46 can be mentioned. Formula (a2-1-1) ~ Formula (a2-1-6
) are preferred, and the monomers represented by formulas (a2-1-1) to (a2-1-4)
More preferably, the monomer represented by either formula (a2-1-1) or formula (a2-1-
More preferred are the monomers represented by 3).

When the resin (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on the total 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 a β-propiolactone ring, γ-butyrolactone ring, δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. It's okay. The lactone ring preferably includes a γ-butyrolactone ring, an adamantanelactone ring or a bridged ring containing a γ-butyrolactone ring structure.

Structural unit (a3) is preferably represented by formula (a3-1), formula (a3-2), formula (a3-3)
or a structural unit represented by formula (a3-4). It may contain one of these alone,
You may contain 2 or more types.

［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。］

[In the formula (a3-1),
L ^a4 is —O— or *—O—(CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7;
) represents a group represented by * 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 of 0 to 5; When p1 is 2 or more, a plurality of R ^a21 are the same or different.
In formula (a3-2),
L ^a5 is —O— or *—O—(CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7;
) represents a group represented by * 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 R ^a22 are the same or different.
In formula (a3-3),
L ^a6 is —O— or *—O—(CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7;
) represents a group represented by * 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 R ^a23 are the same or different.
In formula (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
L ^a7 is -O-, ^* -OL ^a8 -O-, ^* -OL ^a8 -CO-O-, ^* -OL ^a8 -C
OO-L ^a9 -CO-O- or ^* -O-L ^a8 -O-CO-L ^a9 -O-.
* represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]

The aliphatic hydrocarbon groups represented by R ^a21 , R ^a22 and R ^a23 include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl groups. mentioned.
Halogen atoms of R ^a24 include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkyl group for R ^a24 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 group. , preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
The alkyl group having a halogen atom for R ^a24 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluoro A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group and the like are included.

The alkanediyl groups of L ^a8 and L ^a9 include methylene group, ethylene group, 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,
4-diyl group, 2-methylbutane-1,4-diyl group and the like.

In formulas (a3-1) to (a3-3), L ^a4 to L ^a6 are each independently preferably -O- or *-O-(CH ₂ where k3 is an integer of 1 to 4 ) a group represented by _k3 --CO--O--, more preferably --O-- and *--O--CH ₂ --CO--O--, 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 each independently preferably an integer of 0 to 2, more preferably 0 or 1.

In formula (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, still more preferably a hydrogen atom or a methyl group.
L ^a7 is preferably -O- or ^* -O-L ^a8 -CO-O-, more preferably
-O-, -O-CH ₂ -CO-O- or -O-C ₂ H ₄ -CO-O-.

As the monomer leading to the structural unit (a3), monomers described in JP-A-2010-204646, monomers described in JP-A-2000-122294, JP-A-201
Examples thereof include monomers described in JP-A-2-41274. As the structural unit (a3),
formula (a3-1-1) ~ formula (a3-1-4), formula (a3-2-1) ~ formula (a3-2-4),
Formula (a3-3-1) ~ formula (a3-3-4) and formula (a3-4-1) ~ formula (a3-4-12
) is preferably a structural unit represented by either formula (a3-1-1), formula (a3-1-2)
, formula (a3-2-3) ~ formula (a3-2-4) and formula (a3-4-1) ~ formula (a3-4-1
2) is more preferably a structural unit represented by any one of formulas (a3-4-1) to (a3-4
-12) is more preferably a structural unit represented by any one of formulas (a3-4-1) to (a
Structural units represented by any one of 3-4-6) are even more preferred.

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

When the resin (A) contains the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on the total structural units of the resin (A). , more preferably 10 to 60 mol %.
Further, the content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) and structural unit (a3-4) is , 5 to 60
mol % is preferred, 5 to 50 mol % is more preferred, and 10 to 50 mol % is even more preferred.

<Other structural units (t)>
The resin (A) may contain another structural unit (t) as a structural unit other than the structural unit (I), the structural unit (a1) and the structural unit (s). The structural unit (t) includes a structural unit (hereinafter sometimes referred to as “structural unit (a4)”) that may have a halogen atom other than the structural unit (a2) and the structural unit (a3). Structural units containing hydrocarbon radicals (
s) (hereinafter sometimes referred to as “structural unit (a5)”) and the like. The resin (A) is
It may have structural units other than the structural units described above, and examples of such structural units include structural units well known in the art.

［式（ａ４－０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^４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 units (a4) include structural units represented by formula (a4-0).

[In the formula (a4-0),
^R5 represents a hydrogen atom or a methyl group.
L ⁴ represents a single bond or a C 1-4 saturated aliphatic hydrocarbon group.
L ³ represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
^R6 represents a hydrogen atom or a fluorine atom. ]

The aliphatic saturated hydrocarbon group for ^L4 includes methylene group, ethylene group, propane-1,3-
diyl group, linear alkanediyl group such as butane-1,4-diyl group, ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methyl Branched alkanediyl groups such as propane-1,3-diyl group and 2-methylpropane-1,2-diyl group can be mentioned.

The perfluoroalkanediyl group for L ³ includes a difluoromethylene group, perfluoroethylene group, perfluoroethylfluoromethylene group, 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, perfluorooctane-1,8-diyl group, perfluorooctane-2,2- diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like.
The perfluorocycloalkanediyl group for ^L3 includes a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group,
A perfluoroadamantanediyl group and the like can be mentioned.

^L4 is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group.
L ³ is preferably a C 1-6 perfluoroalkanediyl group, more preferably a C 1-3 perfluoroalkanediyl group.

Examples of the structural unit (a4-0) include structural units shown below. The following formula (a1-
0-1) to formula (a4-0-16), compounds in which the methyl group corresponding to R ⁵ is replaced with a hydrogen atom are also given as specific examples of the structural unit (a4-0). be able to.

［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、－Ｏ－、－ＣＯ－、－ＣＯ－Ｏ－又は－Ｏ－
ＣＯ－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。
＊、＊＊は結合手であり、＊＊が－Ｏ－ＣＯ－Ｒ^ａ４２との結合手である。］ Structural units (a4) include structural units represented by formula (a4-1).

[In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO— good.
A ^a41 is an optionally substituted alkanediyl group having 1 to 6 carbon atoms or the formula (a-
It represents a group represented by g1). ]

[In the formula (a-g1),
s represents 0 or 1;
A ^a42 and A ^a44 each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ^a43 represents a single bond or an optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms.
X ^a41 and X ^a42 are independently of each other -O-, -CO-, -CO-O- or -O-
represents CO-.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less.
* and ** are bonds, and ** is a bond with —O—CO—R ^a42 . ]

The hydrocarbon group for R ^a42 includes chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combinations thereof.
Chain and cyclic aliphatic hydrocarbon groups may have a carbon-carbon unsaturated bond, but chain and cyclic saturated aliphatic hydrocarbon groups are preferred. The aliphatic saturated hydrocarbon group includes a linear or branched alkyl group, a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic hydrocarbon group formed by combining an alkyl group and an alicyclic hydrocarbon group. group hydrocarbon groups and the like.
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. n-dodecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl groups. Cyclic aliphatic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; decahydronaphthyl, adamantyl, norbornyl and the following groups (* indicates a bond represent a hand.
) and other polycyclic alicyclic hydrocarbon groups.

Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenylyl, phenanthryl and fluorenyl groups.

［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。］ Substituents for R ^a42 include halogen atoms and groups represented by formula (a-g3). A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom.

[In the formula (a-g3),
^Xa43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents a C 1-17 aliphatic hydrocarbon group having at least one halogen atom.
* represents a bond. ]

Examples of the aliphatic hydrocarbon group for A ^a45 include the same groups as those exemplified for R ^a42 .
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, an alkyl group having a halogen atom and/or an aliphatic hydrocarbon group having a group represented by formula (a-g3) 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, still more preferably having It is a perfluoroalkyl group having 1 to 6 carbon atoms, particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl and perfluorooctyl groups. A perfluorocyclohexyl group etc. are mentioned as a perfluorocycloalkyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by formula (a-g3), the formula (
The total number of carbon atoms in the aliphatic hydrocarbon group, including the number of carbon atoms contained in the groups represented by a-g3), is 1
5 or less is preferable, and 12 or less is more preferable. When it has a group represented by formula (a-g3) 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。
＊はカルボニル基との結合手を表す。］ An aliphatic hydrocarbon group having a group represented by formula (a-g3) is more preferably represented by formula (a-
It is a group represented by g2).

[In the formula (a-g2),
A ^a46 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
^Xa44 represents a carbonyloxy group or an oxycarbonyl group.
A ^a47 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 with a carbonyl group. ]

The number of carbon atoms in the aliphatic hydrocarbon group of A ^a46 is preferably 1-6, more preferably 1-3.
The number of carbon atoms in the aliphatic hydrocarbon group of A ^a47 is preferably 4 to 15, more preferably 5 to 12, and A ^a47 is further preferably a cyclohexyl group or an adamantyl group.

The structure represented by *-A ^a46 -X ^a44 -A ^a47 includes the following structures.

A ^methylene group, ethylene group, 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
-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups.
The substituents in the alkanediyl group of A ^a41 include a hydroxy group and 1 to 6 carbon atoms
and the like.
^Aa41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

The aliphatic hydrocarbon groups of A ^a42 , A ^a43 and A ^a44 in group (a-g1) may have carbon-carbon unsaturated bonds, but chain and cyclic saturated aliphatic hydrocarbon groups and groups formed by combining these are preferred. As the aliphatic saturated hydrocarbon group,
Linear or branched alkyl groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and aliphatic hydrocarbon groups formed by combining alkyl groups and alicyclic hydrocarbon groups are included.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2
-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-
Examples include methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
Substituents of the aliphatic hydrocarbon groups of A ^a42 , A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably zero.

Examples of the group (a-g1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group include the following groups. In the examples below, * and **
each 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。］ Structural units represented by formula (a4-1) are preferably structural units represented by formulas (a4-2) and (a4-3).

[In formula (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 and having a fluorine atom. ]

The alkanediyl group of A ^f1 includes methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-
Linear alkanediyl groups such as diyl group and 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-
A branched alkanediyl group such as a diyl group can be mentioned.

Hydrocarbon groups for R ^f2 include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and aliphatic hydrocarbon groups include groups formed by chain, cyclic and combinations thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferred.
Examples of the alkyl group 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, n
-octyl and 2-ethylhexyl groups.
Alicyclic hydrocarbon groups may be monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl,
A cycloalkyl group such as a cyclooctyl group and a cyclodecyl group can be mentioned. Polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1-(adamantan-1-yl)alkane-1-yl group, norbornyl group, Methylnorbornyl and isobornyl groups are included.

Examples of the hydrocarbon group having a fluorine atom for R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Alkyl groups having a fluorine atom include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 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, 1,1,2,2,3,3,4,4,5,5-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, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group and perfluorohexyl group. groups.
The alicyclic hydrocarbon group having a fluorine atom includes fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

A ^f1 in formula (a4-2) is preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an ethylene group.
R ^f2 is preferably a fluorinated alkyl group having 1 to 6 carbon atoms.

［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 formula (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. ]

The alkanediyl group for A ^f11 includes the same alkanediyl groups for A ^f1 .
Aliphatic hydrocarbon groups of A ^f13 include chain and cyclic aliphatic hydrocarbon groups, and divalent aliphatic hydrocarbon groups formed by combining these. 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 for A ^f13 is preferably a saturated aliphatic hydrocarbon group which may have a fluorine atom, more preferably a perfluoroalkanediyl group.
The divalent chain aliphatic hydrocarbon group which may have a fluorine atom includes a methylene group,
alkanediyl groups such as ethylene group, propanediyl group, butanediyl group and pentanediyl group; perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group; .
The bivalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a group containing both monocyclic and polycyclic groups. The monocyclic aliphatic hydrocarbon group includes a cyclohexanediyl group, a perfluorocyclohexanediyl group, and the like. The polycyclic divalent aliphatic hydrocarbon group includes an adamantanediyl group, a norbornanediyl group, a perfluoroadamantanediyl group, and the like.

Aliphatic hydrocarbon groups for A ^f14 include chain and cyclic aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups formed by combining these. This aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group optionally having a fluorine atom for A ^f14 is preferably an aliphatic saturated hydrocarbon group optionally having a fluorine atom.
Chain type aliphatic hydrocarbon groups which may have a fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 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 include heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Groups containing monocyclic aliphatic hydrocarbon groups include cyclopropylmethyl, cyclopropyl, cyclobutylmethyl, cyclopentyl, cyclohexyl, and perfluorocyclohexyl groups. Groups containing polycyclic aliphatic hydrocarbon groups include adamantyl groups, adamantylmethyl groups, norbornyl groups, norbornylmethyl groups, perfluoroadamantyl groups, and perfluoroadamantylmethyl groups.

In 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, more preferably an aliphatic hydrocarbon group having 2 to 3 carbon atoms.
The aliphatic hydrocarbon group of A ^f14 is preferably an aliphatic hydrocarbon group having 3 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms. Above all, A ^f1
4 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

The structural unit represented by formula (a4-2) includes formulas (a4-1-1) to (a4-1-2
2) includes structural units.

The structural unit represented by formula (a4-3) includes formulas (a4-1'-1) to (a4-1'
-22), respectively.

［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。］ Structural units (a4) also include structural units represented by formula (a4-4).

[In formula (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 -(
represents CH ₂ ) _j4 -CO-O-(CH ₂ ) _j5 -.
j1 to j5 each independently represent an integer of 1 to 6;
R ^f22 represents a hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom. ]

The hydrocarbon group having a fluorine atom for R ^f22 includes the same hydrocarbon groups as those for R ^f2 in 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 preferably has 1 to 10 carbon atoms having a fluorine atom.
An alkyl group of 10 is more preferred, and an alkyl group of 1 to 6 carbon atoms having a fluorine atom is even more preferred.

In formula (a4-4), A ^f21 is preferably —(CH ₂ ) _j1 —, more preferably an ethylene group or a methylene group, and still more preferably a methylene group.

Examples of structural units represented by formula (a4-4) include the following structural units.
In the structural unit represented by the formula below, a compound in which the methyl group corresponding to R ^f21 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a4-4).

When the resin (A) has the structural unit (a4), the content thereof is preferably 1 to 20 mol%, preferably 2 to 15 mol%, based on the total of all structural units of the resin (A). and more preferably 3 to 10 mol %.

［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。
但し、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 non-leaving hydrocarbon groups possessed by the structural unit (a5) include linear, branched and cyclic hydrocarbon groups. Among them, the structural unit (a5) is preferably an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include structural units represented by formula (a5-1).

[In the formula (a5-1),
^R51 represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydroxy group. may
However, the hydrogen atom bonded to the carbon atom at the bonding position with L ⁵¹ is not substituted with an 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 for R ⁵² may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl groups and norbornyl groups.
Aliphatic hydrocarbon groups having 1 to 8 carbon atoms include, for example, methyl group, ethyl group, n-propyl group,
isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group,
Examples include alkyl groups such as hexyl group, octyl group and 2-ethylhexyl group.
The substituted alicyclic hydrocarbon group includes a 3-hydroxyadamantyl group and a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

The divalent saturated hydrocarbon group for L ⁵¹ includes a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. be done.
Examples of divalent aliphatic saturated hydrocarbon groups include alkanediyl groups such as methylene, ethylene, propanediyl, butanediyl and pentanediyl groups.
The bivalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. The monocyclic alicyclic saturated hydrocarbon group includes cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

Examples of the saturated hydrocarbon group in which the methylene group is replaced with an oxygen atom or a carbonyl group include groups represented by formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

［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^ｘ３Ｌ^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^ｘ６及び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、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。］

[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 carbon number of L ^x1 and L ^x2 is 16 or less.
In formula (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 carbon number of L ^x3 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 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6 and L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 each represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent saturated alicyclic hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number 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, 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,
A single bond is more preferred.
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, 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,
A methylene group or an ethylene group is more preferable.
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,
A single bond or a methylene group is more preferable.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms,
A single bond or a methylene group is more preferable.
W ^x1 is preferably a divalent saturated alicyclic hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

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

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

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

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

L ⁵¹ is preferably a single bond or a group represented by formula (L1-1).
Examples of the structural unit (a5-1) include the following.

In formulas (a5-1-1) to (a5-1-18), a structural unit in which a 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 (A) has the structural unit (a5), the content thereof is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, based on the total structural units of the resin (A), and 3 ~15 mol% is more preferred.

Resin (A) preferably does not contain a structural unit having a fluorine atom. Moreover, the structural unit having an acid labile group is preferably a structural unit having no fluorine atom. That is, the resin (A) is preferably a resin composed of the structural unit (I), the structural unit (a1) and the structural unit (s), that is, the compound (I), the monomer (a1) and the monomer (s) is a copolymer of
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 of (a1-5), more preferably structural unit (a1-1)
or structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
Structural unit (s) is preferably at least one of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably a structural unit represented by formula (a2-1).
Structural unit (a3) is preferably at least one structural unit represented by a γ-butyrolactone ring, a bridged ring containing a γ-butyrolactone ring structure, or an adamantanelactone ring, more preferably represented by formula (a3-1) is at least one selected from structural units represented by formula (a3-2), and structural units represented by formula (a3-4), more preferably represented by formula (a3-4) is the structural unit represented.

The resin (A) may contain a structural unit derived from a monomer having an adamantyl group (in particular, the structural unit (a1-1)) in an amount of 15 mol% or more relative to the content of the structural unit (a1). preferable. When the content of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

Each structural unit that constitutes the resin (A) may be used alone or in combination of two or more. Using a monomer that induces these structural units, it is produced by a known polymerization method (e.g., radical polymerization method). can do. The content of each structural unit in the resin (A) can be adjusted by adjusting the amount of monomer used for polymerization.
The weight average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,5
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). In addition, the weight average molecular weight is
It is a value determined by gel permeation chromatography.

<Resist composition>
The resist composition of the present invention contains a resin (A) and an acid generator (hereinafter sometimes referred to as "acid generator (B)").
In addition, the resist composition contains a resin other than the resin (A), a quencher (hereinafter sometimes referred to as "quencher (C)") and/or a solvent (hereinafter sometimes referred to as "solvent (E)"). preferably.

<Resins other than resin (A)>
The resist composition of the present invention may contain a resin other than resin (A). Examples of such a resin include a resin consisting only of the structural unit (s), a resin containing the structural unit (a4) (hereinafter referred to as "resin (
X)” in some cases) and the like.

<Resin (X)>
Resin (X) is preferable as the resin other than resin (A). In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more with respect to the total structural units of the resin (X),
45 mol % or more is more preferable, and 50 mol % or more is even more preferable.
Structural units that the resin (X) may further have include structural units (a1), structural units (a2), structural units (a3), structural units (a5), and other structures derived from known monomers. units, and among them, the structural unit (a5) is preferred.
The weight average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000
00 or more) and 80,000 or less (more preferably 60,000 or less). Resin (X)
is the same as for the resin (A).
When the resist composition contains resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of resin (A). It is preferably 1 to 40 parts by mass, particularly preferably 2 to 30 parts by mass.

The total content of the resin (A) and the resin other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, relative to the solid content of the resist composition. preferable. The solid content and resin content of the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Acid Generator (B)>
Acid generators are classified into nonionic and ionic acid generators, and any of them may be used as the acid generator (B) of the resist composition of the present invention. Nonionic acid generators include organic halides, sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate,
oximesulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical ionic acid generators are onium salts containing onium cations (eg, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). The anions of the onium salts include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, and the like.

As the acid generator (B), JP-A-63-26653, JP-A-55-164824,
JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,
778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., which generate acid upon radiation. Moreover, you may use the compound manufactured by the well-known method. 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、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－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、水素原子又は置換基を有していてもよい炭素数３～１８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。］ Acid generator (B) is preferably a fluorine-containing acid generator, more preferably of formula (B1)
is a salt represented by (hereinafter sometimes referred to as "acid generator (B1)").

[In the formula (B1),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents an optionally substituted divalent saturated hydrocarbon group having 1 to 24 carbon atoms,
—CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO—, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be a fluorine atom or a hydroxyl may be substituted with a group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the monovalent alicyclic hydrocarbon group; may be replaced by -O-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl groups for Q ¹ and Q ² include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl and perfluoro A hexyl group and the like can be mentioned.
Q ¹ and Q ² are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both a fluorine atom.

The divalent saturated hydrocarbon group for L ^b1 includes a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic bivalent alicyclic saturated hydrocarbon group. A group formed by combining two or more of the groups may also be used.
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-
a linear alkanediyl group such as a diyl group;
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, and 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; alicyclic saturated hydrocarbon group;
norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-
Examples thereof include polycyclic divalent alicyclic saturated hydrocarbon groups such as 1,5-diyl group and 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。］ The group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced with —O— or —CO— is, for example, any one of formulas (b1-1) to (b1-3). The group represented by is mentioned. In the formulas (b1-1) to (b1-3) and the specific examples below, * is -Y
represents a bond with

[In formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated A methylene group contained in the hydrocarbon group may be substituted 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 formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated A methylene group contained in the hydrocarbon group may be substituted 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 formula (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated A methylene group contained in the hydrocarbon group may be substituted 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 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 replacement is the carbon of the saturated hydrocarbon group. number.
As the divalent saturated hydrocarbon group, the same divalent saturated hydrocarbon group as L ^b1 can be mentioned.

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 a 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 a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; A methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

The group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced with —O— or —CO— is a group represented by formula (b1-1) or formula (b1-3) is preferred.

［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 formula (b1-1) include groups represented by formulas (b1-4) to (b1-8).

[In formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (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 a 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 formula (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 a 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 formula (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 a 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 ^b13 to L ^b15 is 19 or less.
In formula (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 a 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 ^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 C 1-19 divalent saturated hydrocarbon group, more preferably a single bond or a C 1-8 divalent saturated hydrocarbon group.
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 C 1-18 divalent saturated hydrocarbon group, more preferably a single bond or a C 1-8 divalent saturated hydrocarbon group.
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 C 1-17 divalent saturated hydrocarbon group, more preferably a single bond or a C 1-4 divalent saturated hydrocarbon group.

［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 formula (b1-3) include groups represented by formulas (b1-9) to (b1-11).

[In formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a 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, a hydrogen atom contained in the divalent saturated hydrocarbon group being substituted with a fluorine atom, a hydroxy group or an acyloxy group; good too. A methylene group contained in the acyloxy group may be substituted with an oxygen atom or a carbonyl group, and a hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and a 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 a hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. may A methylene group contained in the acyloxy group may be substituted with an oxygen atom or a carbonyl group, and a hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b21 to L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a 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 a hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. may A methylene group contained in the acyloxy group may be substituted with an oxygen atom or a carbonyl group, and a hydrogen atom contained in the acyloxy group may be substituted 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 a hydrogen atom contained in a divalent saturated hydrocarbon group is substituted with an acyloxy group, the number of carbon atoms in the acyloxy group, CO in the ester bond and The number of carbon atoms in the divalent saturated hydrocarbon group includes the number of O atoms.

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

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

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

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

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

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

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

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

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

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

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y11).
When —CH ₂ — contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced with —O—, —SO ₂ — or —CO—, the number thereof may be 1, or 2 or more. It can be multiple. Such groups include groups represented by formulas (Y12) to (Y38).

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

Among them, preferably a group represented by any one of formulas (Y1) to (Y20), formula (Y30), and formula (Y31), more preferably formula (Y11), formula (Y15), formula ( Y16)
, a group represented by formula (Y19), formula (Y20), formula (Y30) or formula (Y31), more preferably represented by formula (Y11), formula (Y15) or formula (Y30) groups.

Substituents for 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 and having 1 to 12 carbon atoms, and 3 carbon atoms. -16 monovalent alicyclic hydrocarbon groups, C1-12 alkoxy groups, C6-18 monovalent aromatic hydrocarbon groups, C7-21 aralkyl groups, C2- 4 acyl group, glycidyloxy group or —(CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is a C 1-16 alkyl group, a C 3-16 monovalent lipid represents a cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4).

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

Examples of Y include the following.

Y is preferably an optionally substituted monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an optionally substituted adamantyl group, A 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, an oxoadamantyl group, or a group represented below.

The sulfonate anion in the salt represented by formula (B1) includes formulas (B1-A-1) to
The anion represented by the formula (B1-A-46) [hereinafter referred to as “anion (B1-A
-1)”, etc. ] is preferable, formula (B1-A-1) ~ formula (B1-A-4)
, Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24) ~ Formula (B1-A-
33) and anions represented by any one of formulas (B1-A-36) to (B1-A-40) are more preferred.

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
an alkyl group of 4, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. .
L ⁴⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and Q ² are the same as above.
Specifically, as the sulfonate anion in the salt represented by formula (B1),
Examples thereof include anions described in JP-A-10-204646.

A preferred sulfonate anion in the salt represented by formula (B1) is represented by formula (B1a-
1) to the anions represented by formulas (B1a-22).

Among them, formula (B1a-1) ~ formula (B1a-3) and formula (B1a-7) ~ formula (B1a-
16), formula (B1a-18), formula (B1a-19), or formula (B1a-22).
The organic cations of Z ⁺ include organic onium cations such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, organic phosphonium cations, etc., preferably organic sulfonium cations or organic iodonium cations. and more preferably an arylsulfonium cation.
Z ⁺ in formula (B1) is preferably a cation represented by any one of formulas (b2-1) to (b2-4) [hereinafter, "cation (b2-1)" etc. depending on the formula number There is a case. ]
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のアルキル基、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、該アルキル
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３～１
２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のアルキル基、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のアルキル基又は炭素数３～３
６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のアルキル基、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のアルキル基、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、該アルキル基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 formulas (b2-1) to (b2-4),
R ^b4 to R ^b6 each independently represent an alkyl group having 1 to 30 carbon atoms, 1 having 3 to 36 carbon atoms,
represents a monovalent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or a 3 to 1
may be substituted with a monovalent alicyclic hydrocarbon group of 2 or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the monovalent alicyclic hydrocarbon group are , halogen atom, carbon number 1
It may be substituted with an alkyl group having 18 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atoms contained in the monovalent aromatic hydrocarbon group are halogen atoms, hydroxy groups or carbon atoms It may be substituted with 1 to 12 alkoxy groups.
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 each 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 each independently represent an integer of 0 to 5;
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 are each independently an alkyl group having 1 to 36 carbon atoms or an alkyl group having 3 to 3 carbon atoms
represents a monovalent alicyclic hydrocarbon group of 6;
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 represents a hydrogen atom, an alkyl 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.
R ^b12 represents an alkyl 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, and the alkyl group The hydrogen atoms contained may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the monovalent aromatic hydrocarbon groups are those having 1 to 12 carbon atoms. It may be substituted with an alkoxy group or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may together form a ring containing —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring is —O—, —SO— Alternatively, it may be replaced with -CO-.
R ^b13 to R ^b18 each 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 independently represent integers from 0 to 5;
q2 and r2 each independently represent an integer of 0 to 4;
u2 represents 0 or 1;
When o2 is 2 or more, the plurality of R ^b13 may be the same or different, when p2 is 2 or more, the plurality of R ^b14 may be the same or different, and when q2 is 2 or more , the plurality of R ^b15 may be the same or different, when r2 is 2 or more, the plurality of R ^b16 may be the same or different, and when s2 is 2 or more, the plurality of R ^b17 may be They may be the same or different, and when t2 is 2 or more, a plurality of R ^b18 may be the same or different. ]

中でも、Ｒ^ｂ９～Ｒ^ｂ１２のアルキル基の炭素数は、好ましくは３～１８であり、より
好ましくは４～１２である。 Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. be done. Among them, the alkyl groups of R ^b9 to R ^b12 are
It preferably has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of monovalent monovalent alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclo Cycloalkyl groups such as a hexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group can be mentioned. The polycyclic monovalent alicyclic hydrocarbon group includes decahydronaphthyl group, adamantyl group, norbornyl group and the following groups.

Among them, the number of carbon atoms in the alkyl groups of R ^b9 to R ^b12 is preferably 3-18, more preferably 4-12.

Examples of the monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group and an isobornyl group. and the like. In the monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with any group, the total carbon number of the monovalent alicyclic hydrocarbon group and the alkyl group is preferably 20 or less.
Aliphatic hydrocarbon groups for R ^b7 and R ^b8 and R ^b13 to R ^b18 include the same alkyl groups, alicyclic hydrocarbon groups, and combinations thereof.

Examples of monovalent aromatic hydrocarbon groups include a phenyl group, a tolyl group, a xylyl group, 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 an alkyl group or a monovalent alicyclic hydrocarbon group, an alkyl group having 1 to 18 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms A hydrogen group is preferred.
Examples of monovalent aromatic hydrocarbon groups in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Alkyl groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl, and naphthylethyl groups.

Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups.
Acyl groups include acetyl, propionyl and butyryl groups.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group and the like.

The ring that R ^b4 and R ^b5 may form together with the sulfur atom to which they are bonded is a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. There may be. The ring includes a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Further, the ring containing a sulfur atom includes a 3- to 12-membered ring, preferably a 3- to 7-membered ring, and specific examples 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 polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring includes a 3- to 12-membered ring, preferably a 3- to 7-membered ring, such as
thiolan-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1
, 4-oxathian-4-ium ring and the like.
The ring formed by R ^b11 and R ^b12 together may be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. The ring includes a 3- to 12-membered ring, preferably a 3- to 7-membered ring, such as an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, an oxoadamantane ring, and the like. be done.

Among the cations (b2-1) to (b2-4), preferably the cation (b2-1
).

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 sulfonate anion and the above organic cation, and these can be combined arbitrarily. As the acid generator (B1), the formula (
B1a-1) to formula (B1a-3) and combinations of anions and cations (b2-1) represented by any of formulas (B1a-7) to (B1a-16).

The acid generator (B1) preferably includes those represented by the formulas (B1-1) to (B1-40), preferably the formula (B1-1
), formula (B1-2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7
), formula (B1-11), formula (B1-12), formula (B1-13), formula (B1-14), formula (
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 ), formula (B1-35), formula (B1-
36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40)
Those represented by are respectively mentioned.

The acid generator (B) may contain an acid generator other than the acid generator (B1).
In the resist composition of the present invention, the acid generator (B1) may be contained singly or in combination. Among them, the acid generator (B1) preferably contains two or more acid generators. The content of the acid generator (B1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, relative to the total amount of the acid generator (B). Especially preferred is the agent (B1) only.
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 35 parts by mass), relative to 100 parts by mass of the resin (A). part and below).

<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 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; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; It may contain one kind of solvent (E) alone,
You may contain 2 or more types.

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

<Basic nitrogen-containing organic compound>
Basic nitrogen-containing organic compounds include amines and ammonium salts. Amines include aliphatic amines and aromatic amines. Aliphatic amines include primary, secondary 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, tripentylamine, 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)ethene, 1,2-di(4-pyridyl)ethene, 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'-dipicolylamine, bipyridine and the like, preferably diisopropylaniline. and particularly preferably 2,6-diisopropylaniline.

Ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethyl ammonium hydroxide, tetra-n-butylammonium salicylate and choline;

<Salts that generate weakly acidic acids>
The acidity of a salt that generates an acid that is weaker than the acid generated from the acid generator is indicated by the acid dissociation constant (pKa). The salt that generates an acid weaker in 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.
A salt with a<7, more preferably a salt with 0<pKa<5. Salts that generate an acid weaker than the acid generated by the acid generator include salts represented by the following formula, weak acid inner salts represented by formula (D), and JP-A-2012-229206 and JP-A-2012-229206. 2012-6908, JP 2012-72109, JP 2011-39502 and JP 2011-19
The salts described in JP-A-1745 can be mentioned.

［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 the formula (D),
R ^D1 and R ^D2 are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms and 1 to 6 carbon atoms;
alkoxy group, acyl group having 2 to 7 carbon atoms, acyloxy group having 2 to 7 carbon atoms, 2 to
represents an alkoxycarbonyl group of 7, a nitro group or a halogen atom;
m' and n' each independently represents an integer of 0 to 4, when m' is 2 or more, the plurality of R ^D1 are the same or different, and when n' is 2 or more, the plurality of R ^D2 Same or different. ]

The hydrocarbon groups for R ^D1 and R ^D2 in the compound represented by formula (D) include an alkyl group,
A monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, a group formed by combining these groups, and the like are included.
Alkyl groups include methyl, ethyl, propyl, isopropyl, butyl,
isobutyl group, tert-butyl group, pentyl group, hexyl group, nonyl group and the like.
The monovalent alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be saturated or unsaturated. cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group and cyclododecyl group; norbornyl group; adamantyl group;
The monovalent aromatic hydrocarbon group includes a phenyl group, 1-naphthyl group, 2-naphthyl group, 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-
and aryl groups such as 6-ethylphenyl.

Groups formed by combining these groups include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, aralkyl groups (e.g., phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1 -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.) , an alkyl-aryl group (e.g., 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, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aryl-
Cycloalkyl groups, cycloalkyl-aryl groups (eg, p-adamantylphenyl groups) can be mentioned.

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

In formula (D), R ^D1 and R ^D2 are each independently an alkyl group having 1 to 8 carbon atoms,
a cycloalkyl group having 3 to 10 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 alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or Halogen atoms are preferred.
Each of m' and n' is preferably an integer of 0 to 2, more preferably 0. m'
is 2 or more, the plurality of R ^D1 may be the same or different, and when n' is 2 or more, the plurality of R ^D2 may be the same or different.

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

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

The content of the quencher (C) in the solid content of the resist composition is preferably from 0.01 to
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 components other than the components described above (hereinafter sometimes referred to as "other components (F)"). Other components (F) are not particularly limited, and additives known in the field of resists, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc., can be used.

<Preparation of resist composition>
The resist composition of the present invention comprises the resin (A) and acid generator (B) of the present invention, and optionally resin (X), quencher (C), solvent (E) and other components. (F)
can be prepared by mixing The mixing order is arbitrary and not particularly limited. The temperature during mixing is from 10 to 40 ° C., depending on the type of resin and the solvent (E) such as resin
An appropriate temperature can be selected according to the solubility of An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is also not particularly limited, and stirring and mixing 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.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(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) exposing the composition layer;
(4) heating the exposed composition layer; and (5) developing the heated composition layer.

The coating of the resist composition on the substrate can be carried out using a commonly used device such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

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

The resulting composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an _F2 excimer laser (wavelength: 157 nm) that emits a laser beam in the ultraviolet region, a solid-state laser source (YAG or semiconductor laser etc.) and emits harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, electron beam, and extreme ultraviolet light (EUV). can be done. In this specification, these irradiations with radiation may be collectively referred to as "exposure". During exposure, exposure is usually performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.

The exposed composition layer is subjected to a heat treatment (so-called post-exposure bake) in order to promote the deprotection reaction at the acid-labile groups. The heating temperature is usually about 50 to 200°C, preferably about 70 to 150°C.

The composition layer after heating is usually developed using a developer using a developing device. The developing method includes a dipping method, a paddle method, a spraying method, a dynamic dispensing method, and the like. The developing temperature is preferably 5 to 60° C., and the developing 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 of various alkaline aqueous solutions used in this field. Examples thereof include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).
The alkaline developer may contain a surfactant.
After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and pattern is removed.

When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer.
Examples of organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. ether solvents; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole;
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 more preferably 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
100% by mass or less is preferable, 90% by mass or more and 100% by mass or less is more preferable, and substantially only butyl acetate and/or 2-heptanone is further preferable.
The organic developer may contain a surfactant. In addition, the organic developer may contain a trace amount of water.
During development, the development may be stopped by replacing the organic developer with a solvent of a different type.

It is preferable to wash the resist pattern after development with a rinsing liquid. As a rinse,
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, preferably an alcohol solvent or an ester solvent.
After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and pattern.

<Application>
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 an EU
It is suitable as a resist composition for V exposure, particularly as a resist composition for ArF excimer laser liquid immersion exposure, and is useful for microfabrication of semiconductors.

EXAMPLES The present invention will be described more specifically with reference to examples. In the examples, "%" and "parts" representing the content or 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.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
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 Corporation)

In addition, the structure of the compound is determined by mass spectrometry (LC is Agilent 1100 type, MASS is A
It was confirmed by measuring the molecular peak using LC/MSD type manufactured by gilent). In the examples below, the value of this molecular peak is indicated by "MASS".

式（Ｉ－１－ａ）で表される化合物９．００部、テトラヒドロフラン４５部、ピリジン
８．２０部及びジメチルアミノピリジン０．５３部を添加し、式（Ｉ－１－ｂ）で表され
る化合物１３．３２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合
物に、酢酸エチル２５０部を加え、５％塩酸９１部を仕込み、２３℃で３０分間攪拌した
。静置、分液することにより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。このような水洗操作を３
回繰り返した。回収された有機層を濃縮した。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（Ｉ－１－ｃ）で表される化合物９．４６部を得た。

式（Ｉ－１－ｃ）で表される化合物９．４３部及び酢酸４４．４０部を添加した後、２
３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％
）６．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した
後、濃縮残に、酢酸エチル１００部及びイオン交換水１００部を加え、２３℃で３０分間
攪拌、静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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（Ｉ－１）で表される
化合物６．４２部を得た。
ＭＳ（質量分析）：１８８．１（分子イオンピーク） Synthesis Example 1: Synthesis of Compound Represented by Formula (I-1)

9.00 parts of the compound represented by the formula (I-1-a), 45 parts of tetrahydrofuran, 8.20 parts of pyridine and 0.53 parts of dimethylaminopyridine were added, and the mixture represented by the formula (I-1-b) was added. was added 13.32 parts of the compound. After that, the mixture was stirred at 23° C. for 5 hours. 250 parts of ethyl acetate was added to the resulting reaction mixture, 91 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23° C. for 30 minutes. 50 parts of ion-exchanged water was added to the organic layer recovered by standing and liquid separation, and the mixture was stirred at 23° C. for 30 minutes, and the organic layer was washed with water by standing and liquid separation. 3
repeated times. The collected organic layer was concentrated. Column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane/ethyl acetate = 1/
1) By fractionating, 9.46 parts of the compound represented by the formula (I-1-c) was obtained.

After adding 9.43 parts of the compound represented by formula (I-1-c) and 44.40 parts of acetic acid, 2
Stir at 3°C for 30 minutes and cool to 5°C. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
) 6.00 parts was added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. After concentrating the obtained reaction product, 100 parts of ethyl acetate and 100 parts of ion-exchanged water were added to the concentration residue, and the mixture was stirred at 23° C. for 30 minutes, allowed to stand, and separated to recover an organic layer. The collected organic layer was concentrated. Compound 6 represented by formula (I-1) is separated by column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane/ethyl acetate=1/1). .42 copies were obtained.
MS (mass spectroscopy): 188.1 (molecular ion peak)

式（Ｉ－２－ａ）で表される化合物６．７５部、テトラヒドロフラン５０部、トリエチ
ルアミン６．７２部及びジメチルアミノピリジン０．７０部を添加し、式（Ｉ－２－ｂ）
で表される化合物９．２４部を添加した。その後、２３℃で５時間攪拌した。得られた反
応混合物に、酢酸エチル１００部を加え、５％塩酸５０部を仕込み、２３℃で３０分間攪
拌した。静置、分液することにより回収された有機層に、イオン交換水５０部を仕込み２
３℃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３回繰り返した。回収された有機層を濃縮した。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（Ｉ－２－ｃ）で表される化合物６．２４部を得た。

式（Ｉ－１－ｃ）で表される化合物５．１０部及び酢酸２２．２０部を添加した後、２
３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％
）３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した
。濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、
静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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（Ｉ－２）で表される化合物
３．６８部を得た。
ＭＳ（質量分析）：２０２．１（分子イオンピーク） Synthesis Example 2: Synthesis of Compound Represented by Formula (I-2)

6.75 parts of the compound represented by the formula (I-2-a), 50 parts of tetrahydrofuran, 6.72 parts of triethylamine and 0.70 parts of dimethylaminopyridine are added to obtain the formula (I-2-b)
9.24 parts of the compound represented by are added. After that, the mixture was stirred at 23° C. for 5 hours. 100 parts of ethyl acetate was added to the resulting reaction mixture, 50 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23° C. for 30 minutes. 50 parts of ion-exchanged water is added to the organic layer recovered by standing still and liquid separation 2
The mixture was stirred at 3° C. for 30 minutes, allowed to stand still, and separated to wash the organic layer with water. Such washing with water was repeated three times. The collected organic layer was concentrated. By fractionating the concentrated mass with a column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane/ethyl acetate = 1/1), it is represented by formula (I-2-c) 6.24 parts of compound are obtained.

After adding 5.10 parts of the compound represented by formula (I-1-c) and 22.20 parts of acetic acid, 2
Stir at 3°C for 30 minutes and cool to 5°C. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
) 3.00 parts was added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. The resulting reaction was concentrated. 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes.
The organic layer was collected by standing still and liquid separation. The collected organic layer was concentrated. Column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n
-heptane/ethyl acetate=1/1) to obtain 3.68 parts of the compound represented by the formula (I-2).
MS (mass spectroscopy): 202.1 (molecular ion peak)

式（Ｉ－２５－ａ）で表される化合物５．９部、テトラヒドロフラン５０部、トリエチ
ルアミン６．７部及びジメチルアミノピリジン０．７部を添加し、式（Ｉ－１－ｂ）で表
される化合物９．２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合
物に、酢酸エチル１００部を加え、さらに５％塩酸５０部を加え、２３℃で３０分間攪拌
した。得られた混合物を静置、分液することにより回収された有機層に、イオン交換水５
０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３回繰り返した。回収された有機層を濃縮した。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（Ｉ－２５－ｃ）で表される化合物６
．２２部を得た。

式（Ｉ－２５－ｃ）で表される化合物４．７部及び酢酸２２．２部を添加した後、２３
℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）
３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後
、濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、
静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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（Ｉ－２５）で表される化合
物３．１１部を得た。
ＭＳ（質量分析）：１８７．１（分子イオンピーク） Synthesis Example 3: Synthesis of Compound Represented by Formula (I-25)

5.9 parts of the compound represented by the formula (I-25-a), 50 parts of tetrahydrofuran, 6.7 parts of triethylamine and 0.7 parts of dimethylaminopyridine were added, and the mixture represented by the formula (I-1-b) was added 9.2 parts of the compound. After that, the mixture was stirred at 23° C. for 5 hours. 100 parts of ethyl acetate and 50 parts of 5% hydrochloric acid were added to the obtained reaction mixture, and the mixture was stirred at 23° C. for 30 minutes. The obtained mixture was allowed to stand still, and the organic layer recovered by liquid separation was added with ion-exchanged water 5.
0 part was charged, stirred at 23° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing with water was repeated three times. The collected organic layer was concentrated. Column (
Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm Developing solvent: n-heptane/ethyl acetate = 1/1) Compound 6 represented by formula (I-25-c)
. 22 copies were obtained.

After adding 4.7 parts of the compound of formula (I-25-c) and 22.2 parts of acetic acid, 23
C. for 30 minutes and cooled to 5.degree. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
3.00 parts was added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. After concentrating the obtained reaction product, 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentration residue, and the mixture was stirred at 23°C for 30 minutes.
The organic layer was collected by standing still and liquid separation. The collected organic layer was concentrated. Column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n
-heptane/ethyl acetate=1/1) to obtain 3.11 parts of the compound represented by the formula (I-25).
MS (mass spectroscopy): 187.1 (molecular ion peak)

式（Ｉ－２６－ａ）で表される化合物６．７部、テトラヒドロフラン５０部、トリエチ
ルアミン６．７部及びジメチルアミノピリジン０．７部を添加し、式（Ｉ－１－ｂ）で表
される化合物９．２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合
物に、酢酸エチル１００部を加え、さらに５％塩酸５０部を加え、２３℃で３０分間攪拌
した。静置、分液することにより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。このような水洗操作
を３回繰り返した。回収された有機層を濃縮した。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（Ｉ－２６―ｃ）で表される化合物５．９８部を得た。

式（Ｉ－２６－ｃ）で表される化合物５．１部及び酢酸２２．２部を添加した後、２３
℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）
３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後
、濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、
静置、分液することにより有機層を回収した。回収された有機層を濃縮した。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（Ｉ－２６）で表される化合
物３．２部を得た。
ＭＳ（質量分析）：２０１．１（分子イオンピーク） Synthesis Example 4: Synthesis of Compound Represented by Formula (I-26)

6.7 parts of the compound represented by the formula (I-26-a), 50 parts of tetrahydrofuran, 6.7 parts of triethylamine and 0.7 parts of dimethylaminopyridine were added, and the mixture represented by the formula (I-1-b) was added. was added 9.2 parts of the compound. After that, the mixture was stirred at 23° C. for 5 hours. 100 parts of ethyl acetate and 50 parts of 5% hydrochloric acid were added to the obtained reaction mixture, and the mixture was stirred at 23° C. for 30 minutes. 50 parts of ion-exchanged water is added to the organic layer recovered by standing still and liquid separation 23
The mixture was stirred at ℃ for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing with water was repeated three times. The collected organic layer was concentrated. Column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane/ethyl acetate =
1/1) By fractionating, 5.98 parts of the compound represented by the formula (I-26-c) was obtained.

After adding 5.1 parts of the compound represented by the formula (I-26-c) and 22.2 parts of acetic acid, 23
C. for 30 minutes and cooled to 5.degree. Hydrogen peroxide (purity 31%) was added to the resulting mixture.
3.00 parts was added dropwise over 5 minutes, and the mixture was stirred at 23°C for 3 hours. After concentrating the obtained reaction product, 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentration residue, and the mixture was stirred at 23°C for 30 minutes.
The organic layer was collected by standing still and liquid separation. The collected organic layer was concentrated. Column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n
-heptane/ethyl acetate=1/1) to obtain 3.2 parts of the compound represented by the formula (I-26).
MS (mass spectroscopy): 201.1 (molecular ion peak)

Synthesis Example 5: Synthesis of Compound Represented by Formula (I-5)

式（Ｉ－５－ｃ）で表される化合物１９．３部、式（Ｉ－１－ａ）で表される化合物１
０．４部及びアセトニトリル２００部を仕込み、２３℃で５時間攪拌した。得られた反応
物を濃縮し、クロロホルム３００部及びイオン交換水１５０部を加え、２３℃で３０分間
攪拌した。静置、分液することにより回収された有機層に、イオン交換水１５０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３回繰り返した。回収された有機層を濃縮した。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：酢酸エチル）分取する
ことにより、式（Ｉ－５―ｄ）で表される化合物２２．２８部を得た。

式（Ｉ－５－ｄ）で表される化合物６．３部及び酢酸２２．２部を添加した後、２３℃
で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）３
．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後、
濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、静
置、分液することにより有機層を回収した。回収された有機層を濃縮した。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（Ｉ－５）で表される化合物２
．８９部を得た。
ＭＳ（質量分析）：２４６．１（分子イオンピーク） 33.5 parts of the compound represented by the formula (I-5-a), dicyclohexylcarbodiimide 23
. 9 parts and 40 parts of methylene chloride were added and stirred at 23° C. for 30 minutes. To the resulting mixture, 18.83 parts of the compound represented by formula (I-5-b) was added at 0°C and stirred at 0°C for 1 hour. The mixture was heated to 23°C, stirred for 30 minutes, and then filtered. The resulting filtrate was concentrated to obtain 42.2 parts of the compound represented by formula (I-5-c).

19.3 parts of the compound represented by the formula (I-5-c), the compound 1 represented by the formula (I-1-a)
0.4 part and 200 parts of acetonitrile were added and stirred at 23° C. for 5 hours. The resulting reaction product was concentrated, 300 parts of chloroform and 150 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes. 150 parts of ion-exchanged water was added to the organic layer recovered by standing still and liquid separation, and the mixture was stirred at 23° C. for 30 minutes, and the organic layer was washed with water by standing still and liquid separation. Such washing with water was repeated three times. The collected organic layer was concentrated. Column (Kanto Kagaku
Silica gel 60N (spherical, neutral) 100-210 μm, developing solvent: ethyl acetate) was fractionated to obtain 22.28 parts of the compound represented by formula (I-5-d).

After adding 6.3 parts of the compound represented by formula (I-5-d) and 22.2 parts of acetic acid,
for 30 minutes and cooled to 5°C. Hydrogen peroxide (purity 31%) 3
. 00 parts over 5 minutes and stirred at 23° C. for 3 hours. After concentrating the resulting reactant,
50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentration residue, and the mixture was stirred at 23° C. for 30 minutes, allowed to stand, and separated to recover an organic layer. The collected organic layer was concentrated. Column (Kanto Kagaku silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-
Compound 2 represented by formula (I-5) is obtained by fractionating heptane/ethyl acetate = 1/1)
. 89 parts were obtained.
MS (mass spectroscopy): 246.1 (molecular ion peak)

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
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 resulting reaction solution was separated into two layers, the chloroform layer was separated and taken out.
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 was concentrated, and the resulting residue was treated with tert-butyl methyl ether 100
and the mixture was stirred at 23° C. for 30 minutes and filtered to obtain 48.57 parts of the 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
を、アセトニトリル５３．５１部に溶解し、濃縮した。得られた濃縮物にｔｅｒｔ－ブチ
ルメチルエーテル１１３．０５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. .
0.21 part of copper (II) dibenzoate was added to the resulting mixture, and the mixture was further stirred at 100° C. for 1 hour. The resulting reaction solution was concentrated. 200 parts of chloroform and 50 parts of ion-exchanged water were added to the obtained residue, and the mixture was stirred at 23° C. for 30 minutes, and separated to obtain an organic layer. 50 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23° C. for 30 minutes, and separated to obtain the organic layer. This washing operation was repeated 5 times. The organic layer obtained was concentrated. The resulting residue was dissolved in 53.51 parts of acetonitrile and concentrated. 113.05 parts of tert-butyl methyl ether was added to the resulting concentrate, stirred, and filtered to obtain the formula (B1-21
) to give 10.47 parts of the salt.
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 and heated to 23°C. 15 in
Stirred for hours. Since the resulting reaction solution was separated into two layers, the chloroform layer was separated and taken out, and 15 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. Concentrate the chloroform layer, add 50 parts of tert-butyl methyl ether to the resulting residue, stir at 23 ° C. for 30 minutes, and filter to obtain the formula (B1-22
11.75 parts of the salt represented by -c) were 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 heated at 23°C for 30 minutes. Stirred. 0.12 part of copper (II) dibenzoate was added to the resulting mixed solution, and further heated at 100° C. for 3
Stir for 0 minutes. The resulting reaction solution was concentrated. 50 parts of chloroform and 12.50 parts of ion-exchanged water were added to the obtained residue, and the mixture was stirred at 23° C. for 30 minutes, and separated to obtain an 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,
After liquid separation, the organic layer was taken out. This washing operation was repeated eight times. The organic layer obtained was concentrated. 50 parts of tert-butyl methyl ether was added to the obtained residue, and the mixture was stirred and filtered to obtain 6.84 parts of the 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。 Synthesis of Resin The compounds (monomers) used in synthesizing the resin are shown below.

Hereinafter, these monomers are referred to as "monomer (a1-1-3)" and the like according to their formula numbers.

Example 1 [Synthesis of Resin A1]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-1), monomer (a2-1-1) and monomer (a3-4-2), the molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I -1): Monomer (a2-1-1): Monomer (a3-4-2)] is 40:9:10:2.5:38.5
and propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers was added to form a solution. To this solution were added azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators,
1 mol % and 3 mol % were added and these were heated at 75° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered.
The resulting resin was again poured into a methanol/water mixed solvent for repulping, and the resin was filtered to obtain Resin A1 having a weight average molecular weight of 8.2×10 ³ with a yield of 62%. This resin A
1 has the following structural units.

Example 2 [Synthesis of resin A2]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-2), the monomer (a2-1-1) and the monomer (a3-4-2), the molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I -2): Monomer (a2-1-1): Monomer (a3-4-2)] is 40:9:10:2.5:38.5
and propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers was added to form a solution. To this solution were added azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators,
1 mol % and 3 mol % were added and these were heated at 75° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered.
The resulting resin was again poured into a methanol/water mixed solvent for repulping, and the resin was filtered to obtain Resin A2 having a weight average molecular weight of 8.3×10 ³ with a yield of 63%. This resin A
2 has the following structural units.

Example 3 [Synthesis of Resin A3]
Monomer (a1-1-1) and monomer (I-2) are used as monomers, and mixed so that the molar ratio [monomer (a1-1-1):monomer (I-2)] is 48:52. Then, propylene glycol monomethyl ether acetate was added in an amount 1.5 times the mass of the total amount of monomers to form a solution. 0.6 mol % and 1.8 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added to this solution as initiators, respectively, based on the total amount of monomers. Heated for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The resulting resin was again poured into a methanol/water mixed solvent for repulping, and the resin was filtered to obtain Resin A3 having a weight average molecular weight of 1.6×10 ⁴ with a yield of 87%. This resin A3 has the following structural units.

Example 4 [Synthesis of resin A4]
As monomers, monomer (a1-1-2), monomer (a2-1-1), monomer (
a3-1-1) and the monomer (I-1), the molar ratio (monomer (a1-1-2)
: Monomer (a2-1-1): Monomer (a3-1-1): Monomer (I-1)) is 30
: 20:40:10, and propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers was added to obtain a solution. To this solution, 0.8 mol % and 2.4 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the total amount of monomers, respectively. Heated for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The resulting resin was again poured into a mixed solvent of methanol/water for repulping, and the resin was filtered to obtain Resin A4 (copolymer) having a weight average molecular weight of 1.0×10 ⁴ with a yield of 72%. rice field. This resin A4 has the following structural units.

Example 5 [Synthesis of Resin A5]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-5), using the monomer (a2-1-1) and the monomer (a3-4-2), the molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I -5): Monomer (a2-1-1): Monomer (a3-4-2)] is 40:9:10:2.5:38.5
and propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers was added to form a solution. To this solution were added azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators,
1 mol % and 3 mol % were added and these were heated at 75° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered.
The resulting resin was again poured into a methanol/water mixed solvent for repulping, and the resin was filtered to obtain Resin A5 having a weight average molecular weight of 7.9×10 ³ with a yield of 58%. This resin A
5 has the following structural units.

Example 6 [Synthesis of Resin A6]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-25), monomer (a2-1-1) and monomer (a3-4-2), the molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I -25): Monomer (a2-1-1): Monomer (a3-4-2)] is 40:9:10:2.5:38
. 5, and propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers was added to obtain a solution. To this solution, 1 mol % and 3 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the total amount of monomers, respectively, and these were heated at 75° C. for about 5 hours. bottom. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The obtained resin was again poured into a mixed solvent of methanol/water for repulping, and the resin was filtered to obtain resin A6 having a weight average molecular weight of 8.8×10 ³ with a yield of 60%. This resin A6 has the following structural units.

Example 7 [Synthesis of Resin A7]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (
I-26), monomer (a2-1-1) and monomer (a3-4-2), the molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I -26): Monomer (a2-1-1): Monomer (a3-4-2)] is 40:9:10:2.5:38
. 5, and propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers was added to obtain a solution. To this solution, 1 mol % and 3 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the total amount of monomers, respectively, and these were heated at 75° C. for about 5 hours. bottom. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The resulting resin was again poured into a methanol/water mixed solvent for repulping, and the resin was filtered to obtain Resin A7 having a weight average molecular weight of 9.1×10 ³ with a yield of 63%. This resin A7 has the following structural units.

Synthesis Example 8 [Synthesis of Resin AX1]
Monomer (a1-1-1) and monomer (IX-1) are used as monomers, and mixed so that the molar ratio [monomer (a1-1-1):monomer (IX-1)] is 48:52. Then, propylene glycol monomethyl ether acetate was added in an amount 1.5 times the mass of the total amount of monomers to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 0.6 mol % each based on the total amount of monomers.
and 1.8 mol % were added and these were heated at 75° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The resulting resin was again poured into a methanol/water mixed solvent for repulping, and the resin was filtered to obtain resin AX1 having a weight average molecular weight of 1.7×10 ⁴ with a yield of 87%. This resin AX1
has the following structural units.

Synthesis Example 9 [Synthesis of Resin AX2]
As monomers, monomer (a1-1-2), monomer (a2-1-1), monomer (
a3-1-1) and the monomer (IX-2), the molar ratio (monomer (a1-1-2
) : Monomer (a2-1-1) : Monomer (a3-1-1) : Monomer (IX-2)) was mixed so that the ratio was 30:20:40:10, and 1.5 mass of the total monomer amount 100% of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, 0.8 mol % and 2.4 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the total amount of monomers, respectively. Heated for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The resulting resin was again poured into a mixed solvent of methanol/water for repulping, and filtered to give a resin AX having a weight average molecular weight of 1.1×10 ⁴ .
2 (copolymer) was obtained with a yield of 66%. This resin AX2 has the following structural units.

Synthesis Example 10 [Synthesis of Resin X1]
Using the monomer (a5-1-1) and the monomer (a4-0-12) as the monomer,
The molar ratio (monomer (a5-1-1):monomer (a4-0-12)) was mixed to be 50:50, and methyl isobutyl ketone was added in an amount 0.6 times the mass of the total amount of monomers to obtain a solution. and To this solution, 3 mol % of azobis(2,4-dimethylvaleronitrile) was added as an initiator with respect to the total amount of monomers, and the mixture was heated at 70° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered to obtain Resin X1 having a weight average molecular weight of 1.5×10 ⁴ with a yield of 88%. This resin X1 has the following structural units.

Synthesis Example 11 [Synthesis of Resin X2]
Monomer (a4-1-7) was used as a monomer, and methyl isobutyl ketone was added in an amount of 1.2 times the total amount of monomer to prepare a solution. To this solution, 1 mol % and 3 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the total amount of monomers, respectively, and these were heated at 75° C. for about 5 hours. bottom. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The resulting resin was repulped in a methanol/water mixed solvent and filtered to obtain resin X2 having a weight average molecular weight of 7.8×10 ³ with a yield of 86%. This resin X2 has the following structural units.

<Preparation of resist composition>
As shown in Table 1, a resist composition was prepared by mixing the following components and filtering the resulting mixture through a fluororesin filter having a pore size of 0.2 μm.

＜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>
A1 to A7, X1, X2: Resin A1 to Resin A7, Resin X1, Resin X2
<Acid Generator>
B1-21: a salt represented by the formula (B1-21) B1-22: a salt represented by the formula (B1-22) <Compound (D)>
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

<CD uniformity (CDU) evaluation (negative development)>
An organic antireflection film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205° C. for 60 seconds to form an organic reflective film having a film thickness of 78 nm on the wafer. A protective film was formed. Then, the above resist composition was applied (spin-coated) onto the organic antireflection film so that the film thickness after drying was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature indicated in the "PB" column of Table 1 for 60 seconds to form a composition layer. An ArF excimer stepper for immersion exposure (XT: 1900Gi; manufactured by ASML, NA = 1.35, 3
/4Annular XY polarization), contact hole pattern (hole pitch 90n
Using a mask for forming (m/hole diameter 55 nm), exposure was performed by changing the exposure dose stepwise. Ultrapure water was used as the liquid immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on a hot plate at the temperature listed in the "PEB" column of Table 1. Next, the composition layer on the silicon wafer is developed using butyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a developer by a dynamic dispensing method at 23° C. for 20 seconds to form a negative resist pattern. manufactured.

In the resist pattern obtained after development, the effective sensitivity was defined as the amount of exposure at which the hole diameter formed using the mask was 50 nm.

In the effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 55 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. In the same wafer, the average hole diameter of the pattern formed by the mask with a hole diameter of 70 nm was measured at 400 points, and the standard deviation was obtained as a population,
"○" when the standard deviation is 2.00 nm or less,
A case where the standard deviation was larger than 2.00 nm was judged as "x".
Table 2 shows the results. Numerical values in parentheses indicate standard deviations (nm).

<CD uniformity (CDU) evaluation (positive development)>
An organic antireflection film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205° C. for 60 seconds to form an organic reflective film having a film thickness of 78 nm on the wafer. A protective film was formed. Then, the above resist composition was applied (spin-coated) onto the organic antireflection film so that the film thickness after drying (prebaking) was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature indicated in the "PB" column of Table 1 for 60 seconds to form a composition layer. An ArF excimer stepper for immersion exposure (XT: 1900Gi; manufactured by ASML, NA
= 1.35, 3/4 Annular XY polarized light), using a mask for forming a contact hole pattern (hole pitch: 100 nm/hole diameter: 70 nm), the exposure amount was changed stepwise. Ultrapure water was used as the liquid immersion medium.
After the exposure, the silicon wafer was heated (post-exposure bake treatment) on a hot plate at the temperature indicated in the "PEB" column of Table 1 for 60 seconds. Next, this silicon wafer was subjected to puddle development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

In the resist pattern obtained after development, the effective sensitivity was defined as the exposure dose at which the hole diameter formed using the mask was 55 nm.

In the effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 70 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. In the same wafer, the average hole diameter of the pattern formed by the mask with a hole diameter of 70 nm was measured at 400 points, and the standard deviation was obtained as a population,
"○" when the standard deviation is 1.80 nm or less,
A case where the standard deviation was larger than 1.80 nm was judged as "x".
Table 3 shows the results. Numerical values in parentheses indicate standard deviations (nm).

From the above results, according to the resin of the present invention and the resist composition using the same, good CD
It can be seen that a resist pattern can be manufactured with uniformity.

INDUSTRIAL APPLICABILITY The resin and the resist composition using the resin of the present invention are suitable for microfabrication of semiconductors because the resulting resist pattern has excellent CD uniformity.

Claims (7)

a structural unit represented by formula (I);
at least one structural unit selected from structural units represented by formula (a1-1) and structural units represented by formula (a1-2);
Structural Unit Represented by Formula (a1-0), Structural Unit Represented by Formula (a1-3), Structural Unit Represented by Formula (a1-4), Structure Represented by Formula (a1-5) unit, a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), a structural unit represented by formula (a4-4) and a structural unit represented by formula (a5-1) a resin containing at least one structural unit selected from the group consisting of a structural unit represented by the formula (I);
at least one structural unit selected from structural units represented by formula (a1-1) and structural units represented by formula (a1-2);
Structural Unit Represented by Formula (a2-0), Structural Unit Represented by Formula (a2-1), Structural Unit Represented by Formula (a3-1), Structure Represented by Formula (a3-2) at least one structural unit selected from the group consisting of units, structural units represented by formula (a3-3), and structural units represented by formula (a3-4);
Structural Unit Represented by Formula (a1-0), Structural Unit Represented by Formula (a1-3), Structural Unit Represented by Formula (a1-4), Structure Represented by Formula (a1-5) unit, a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), a structural unit represented by formula (a4-4) and a structural unit represented by formula (a5-1) A resin comprising at least one structural unit selected from the group consisting of structural units comprising
For the sum of all structural units that make up the resin,
The content of the structural unit represented by formula (I) is 1 to 60 mol%,
The total content of the structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2) is 10 to 95 mol%,
When the structural unit represented by formula (a2-0) is included, the content is 10 to 80 mol%,
When the structural unit represented by formula (a2-1) is contained, the content is 1 to 40 mol%, and the structural unit represented by formula (a3-1) and the structural unit represented by formula (a3-2) The total content of the structural unit, the structural unit represented by formula (a3-3) and the structural unit represented by formula (a3-4) is 5 to 70 mol%,
A resin in which the total content of all structural units constituting the resin is 100 mol %.

[in the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
X represents -O-, -S- or -NR ¹¹ -.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4;
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer of 0 to 3, and when u is 2 or more, a plurality of R ² are the same or different.
A ¹ represents a single bond, an alkanediyl group having 1 to 6 carbon atoms or *-A ² -X ¹ -(A ³ -X ² ) _a -(A ⁴ ) _b -. * represents a bond with the group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² each independently represent -O-, -CO-O-, -O-CO- or -O-CO-O-.
a represents 0 or 1;
b represents 0 or 1; ]

[In the formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 each independently represent -O- or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, * is 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 combination thereof.
m1 represents an integer from 0 to 14;
n1 represents an integer from 0 to 10;
n1' represents an integer of 0 to 3; ]

[In formula (a2-0),
R ^a30 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have 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 of 0-4. When ma is an integer of 2 or more, multiple R ^a31 may be the same or different. ]

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

[In the formula (a3-1),
L ^a4 represents a group represented by —O— or *—O—(CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). * 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 of 0 to 5; When p1 is 2 or more, a plurality of R ^a21 are the same or different.
In formula (a3-2),
L ^a5 represents a group represented by —O— or *—O—(CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). * 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 R ^a22 are the same or different.
In formula (a3-3),
L ^a6 represents a group represented by —O— or *—O—(CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). * 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 R ^a23 are the same or different.
In formula (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
L ^a7 is -O-, ^* -OL ^a8 -O-, ^* -OL ^a8 -CO-O-, ^* -OL ^a8 -CO-O-L ^a9 -CO-O- or ^* -O-L ^a8 -O-CO-L ^a9 -O-.
* represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]

[In the formula (a1-0),
L ^a01 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 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. ]

[In formula (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxy group, a carboxy group, a cyano group, a hydrogen atom or —COOR ^a13 .
R ^a13 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these, and the alkyl group and the alicyclic hydrocarbon group A hydrogen atom contained may be substituted with a hydroxy group, and -CH ₂ - contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O- or -CO-.
R ^a10 , R ^a11 and R ^a12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these; ^a10 and R ^a11 are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. ]

[In the formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
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 of 0 to 4; When la is 2 or more, a plurality of R ^a33 may be the same or different.
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 together with C--O to which this is bonded, a divalent heterocyclic group having 3 to 20 carbon atoms is formed, and -CH ₂ - contained in the hydrocarbon group and the divalent heterocyclic group is -O- or -S- may be substituted. ]

[In the formula (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or 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 each independently represent -O- or -S-.
s1 represents an integer of 1-3.
s1' represents an integer of 0 to 3; ]

[In the formula (a4-0),
^R5 represents a hydrogen atom or a methyl group.
L ⁴ represents a single bond or a C 1-4 saturated aliphatic hydrocarbon group.
L ³ represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
^R6 represents a hydrogen atom or a fluorine atom. ]

[In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO— good.
A ^a41 represents an optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by formula (a-g1). ]

[In the formula (a-g1),
s represents 0 or 1;
A ^a42 and A ^a44 each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ^a43 represents a single bond or an optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms.
X ^a41 and X ^a42 each independently represent -O-, -CO-, -CO-O- or -O-CO-.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less.
* and ** are bonds, and ** is a bond with —O—CO—R ^a42 . ]

[In the formula (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 each independently represent an integer of 1 to 6;
R ^f22 represents a hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom. ]

[In formula (a5-1),
^R51 represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydroxy group. may However, the hydrogen atom bonded to the carbon atom at the bonding position with L ⁵¹ is not substituted with an 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 of Claim ¹ , wherein A1 is a single bond. A resist composition comprising the resin according to claim 1 or 2 and an acid generator. 4. The resist composition according to claim 3, wherein the acid generator is a salt represented by formula (B1).

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