JP2024001026A - Compound, resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound, a resin, a resist composition and the like which allow a resist pattern having good line edge roughness to be produced.

SOLUTION: There are provided a compound represented by formula (IA) or formula (IB), a resin, and a resist composition. [In the formula, X¹ and X² represent groups represented by formula (X¹-1); L¹ represents a group represented by formula (L¹B); R³ represents a hydrocarbon group having a group represented by formula (IC); and R⁴ and R⁵ each represent an H atom or a hydrocarbon group which may have a group represented by the formula (IC).]

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

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

特許文献２には、下記化合物に由来する構造単位を有する樹脂を含有するレジスト組成
物が記載されている。

特許文献３には、下記化合物が記載されている。

特許文献４には、下記化合物に由来する構造単位を有する樹脂を含有するレジスト組成
物が記載されている。

Patent Document 1 describes the following compounds.

Patent Document 2 describes a resist composition containing a resin having a structural unit derived from the following compound.

Patent Document 3 describes the following compounds.

Patent Document 4 describes a resist composition containing a resin having a structural unit derived from the following compound.

Japanese Unexamined Patent Publication No. 55-060941 Japanese Patent Application Publication No. 2007-155851 Japanese Patent Application Publication No. 09-258441 Japanese Patent Application Publication No. 2017-095444

The present invention provides a compound that can produce a resist pattern with better CD uniformity (CDU) than a resist pattern formed from a resist composition containing a resin having a structural unit derived from the above compound. .

［式（ＩＡ）及び式（ＩＢ）中、
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又はメチル基を表す。
Ｘ^１及びＸ^２は、それぞれ独立に、式（Ｘ^１－１）～式（Ｘ^１－７）のいずれかで表さ
れる基を表す。

（式（Ｘ^１－１）～式（Ｘ^１－７）中、
＊、＊＊は結合部位を表し、＊＊はＬ^１との結合部位を表す。）
Ｌ^１は、置換基を有していてもよい炭素数１～４８の炭化水素基を表し、該炭化水素基
に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていて
もよい。
Ｒ^３は、式（ＩＣ）で表される基を有する炭素数１～３６の炭化水素基（該炭化水素基
は置換基を有してもよく、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－Ｃ
Ｏ－又は－ＳＯ_２－に置き換わっていてもよい。）を表す。
Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又は式（ＩＣ）で表される基を有していて
もよい炭素数１～３６の炭化水素基（該炭化水素基は置換基を有してもよく、該炭化水素
基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わってい
てもよい。）を表す。］

［式（ＩＣ）中、
Ｒ^Aは、炭素数１～１２の飽和炭化水素基を表す。
ｕ１は、０～２のいずれかの整数を表し、ｕ１が２である場合、複数のＲ^Ａは同一であ
るか、相異なる。
ｓ１は、１又は２を表す。
ｔ１は、０又は１を表す。但し、ｓ１とｔ１との和は、１又は２である。
＊は、結合部位を表す。］
［２］Ｌ^１が、式（Ｌ^１Ａ）で表される基又は式（Ｌ^１Ｂ）で表される基である［１］
記載の化合物。

［式（Ｌ^１Ａ）及び式（Ｌ^１Ｂ）中、
Ｌ⁴及びＬ^4'は、それぞれ独立に、単結合又は置換基を有していてもよい炭素数１～２
４の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ
－又は－ＳＯ_２－に置き換わっていてもよい。
Ｌ²及びＬ³は、それぞれ独立に、単結合又は炭素数１～４のアルカンジイル基を表す。
Ｌ^3'は、炭素数１～４のアルカントリイル基を表す。
＊ａはＸ^１との結合部位を表し、＊ｂは－ＯＲ⁵における酸素原子又はＸ²との結合部位
を表し、＊ｃは－ＯＲ^３における酸素原子との結合部位を表し、＊ｄは－ＯＲ^４における
酸素原子との結合部位を表す。］
［３］Ｌ⁴及びＬ^4’が、それぞれ独立に、単結合、炭素数１～６のアルカンジイル基又
は炭素数１～６のアルカンジイル基と炭素数３～１８の脂環式炭化水素基とを組み合わせ
た基（前記アルカンジイル基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっ
ていてもよく、前記脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ
－又は－ＳＯ_２－に置き換わっていてもよい）であり、Ｌ²が単結合又は炭素数１～４の
アルカンジイル基であり、Ｌ³が炭素数１～４のアルカンジイル基であり、Ｌ^3'が炭素数
１～４のアルカントリイル基である［２］記載の化合物。
［４］Ｘ^１が、式（Ｘ^１－１）、式（Ｘ^１－３）又は式（Ｘ^１－４）のいずれかで表さ
れる基である［１］～［３］のいずれかに記載の化合物。
［５］［１］～［４］のいずれかに記載の化合物に由来する構造単位を含有する樹脂。
［６］さらに、酸不安定基を有する構造単位を含む［５］記載の樹脂。
［７］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の少なくとも１種を含む［６］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－（ＣＨ_２）_k1－ＣＯ－Ｏ－を表
し、ｋ１は１～７のいずれかの整数を表し、＊は－ＣＯ－との結合部位を表す。
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合せた基を表す。
ｍ１は、０～１４のいずれかの整数を表す。
ｎ１は、０～１０のいずれかの整数を表す。
ｎ１’は、０～３のいずれかの整数を表す。］
［８］［５］～［７］のいずれかに記載の樹脂と、酸発生剤とを含むレジスト組成物。
［９］酸発生剤が、式（Ｂ１）で表される塩を含む［８］記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ^b1及びＱ^b2は、それぞれ独立に、フッ素原子又は炭素数１～６のペルフルオロアルキ
ル基を表す。
Ｌ^b1は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含
まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化
水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１
８の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－ＣＨ_２－は、－Ｏ－、－
Ｓ（Ｏ）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。］
［１０］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
［８］又は［９］記載のレジスト組成物。
［１１］（１）［８］～［１０］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] Compound represented by formula (IA) or formula (IB).

[In formula (IA) and formula (IB),
R ¹ and R ² each independently represent a hydrogen atom or a methyl group.
X ¹ and X ² each independently represent a group represented by any one of formulas (X ¹ -1) to (X ¹ -7).

(In formulas (X ¹ -1) to (X ¹ -7),
*, ** represent the binding site, and ** represents the binding site with ^L1 . )
L ¹ represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group is -O-, -S-, -CO- or -SO ₂ - may be substituted.
R ³ is a hydrocarbon group having 1 to 36 carbon atoms having a group represented by formula (IC) (the hydrocarbon group may have a substituent, and -CH ₂ - contained in the hydrocarbon group) is -O-, -S-, -C
It may be replaced with O- or -SO ₂ -. ) represents.
R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms which may have a group represented by formula (IC) (the hydrocarbon group has a substituent); -CH ₂ - contained in the hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -. ]

[In formula (IC),
R ^A represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
u1 represents any integer from 0 to 2, and when u1 is 2, the plurality of R ^A are the same or different.
s1 represents 1 or 2.
t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2.
* represents a binding site. ]
[2] L ¹ is a group represented by formula (L ¹ A) or a group represented by formula (L ¹ B) [1]
Compounds described.

[In formula (L ¹ A) and formula (L ¹ B),
L ⁴ and L ^4' each independently have a single bond or a carbon number of 1 to 2 which may have a substituent.
-CH ₂ - contained in the hydrocarbon group represents -O-, -S-, -CO
- or -SO ₂ - may be substituted.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^3' represents an alkantriyl group having 1 to 4 carbon atoms.
*a represents the bonding site with X ¹ , *b represents the bonding site with the oxygen atom in -OR ⁵ or with X ² , *c represents the bonding site with the oxygen atom in -OR ³ , and *d represents the bonding site with the oxygen atom in -OR 3. -Represents the bonding site with the oxygen atom in OR ⁴ . ]
[3] L ⁴ and L ^4' are each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms, or an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (The -CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-, and the -CH ₂ - contained in the alicyclic hydrocarbon group is - O-, -S-, -CO
- or -SO ₂ -), L ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms, L ³ is an alkanediyl group having 1 to 4 carbon atoms, and L The compound according to [2], wherein ^3' is an alkantriyl group having 1 to 4 carbon atoms.
[4] Any one of [ ^{1] to [3], wherein X 1} is a group represented by formula (X ¹ -1), formula (X ¹ -3) or formula (X ¹ -4) Compounds described in.
[5] A resin containing a structural unit derived from the compound according to any one of [1] to [4].
[6] The resin according to [5], further comprising a structural unit having an acid-labile group.
[7] The structural unit having an acid-labile group is a structural unit represented by the formula (a1-1) and a structural unit having the formula (a
The resin according to [6], comprising at least one structural unit represented by 1-2).

[In formula (a1-1) and formula (a1-2),
L ^a1 and L ^a2 each independently represent -O- or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents any integer from 1 to 7, and * represents -CO- represents the binding site with.
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 any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1' represents any integer from 0 to 3. ]
[8] A resist composition comprising the resin according to any one of [5] to [7] and an acid generator.
[9] The resist composition according to [8], wherein the acid generator contains a salt represented by formula (B1).

[In formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y is a methyl group that may have a substituent or a carbon number of 3 to 1 that may have a substituent
-CH ₂ - contained in the alicyclic hydrocarbon group represents -O-, -
It may be replaced with S(O) ₂ - or -CO-.
Z ⁺ represents an organic cation. ]
[10] The resist composition according to [8] or [9], further containing a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator.
[11] (1) Applying the resist composition according to any one of [8] to [10] onto a substrate,
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer to light;
(4) a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

By using a resist composition containing a resin having a structural unit derived from the compound of the present invention, a resist pattern can be manufactured with good CD uniformity (CDU).

In this specification, unless otherwise specified, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate." Notations such as "(meth)acrylic acid" and "(meth)acryloyl" have similar meanings. “CH ₂ =C
(CH ₃ )--CO-" or "CH ₂ =CH--CO-", structural units having both groups are similarly exemplified. A "combined group" means a group in which two or more of the exemplified groups are bonded together, and the valency of these groups may be changed as appropriate depending on the bonding form. Moreover, when stereoisomers exist, all stereoisomers are included.
As used herein, "solid content of the resist composition" refers to the total amount of components excluding the solvent (E) described below from the total amount of the resist composition.

[Compounds represented by formula (IA) and formula (IB)]
The compound of the present invention is a compound represented by formula (IA) (hereinafter sometimes referred to as "compound (IA)") and a compound represented by formula (IB) (hereinafter sometimes referred to as "compound (IB)"). )
Regarding.
In formula (IA) and formula (IB), X ¹ and X ² are represented by formulas (X ¹ -1) to (X ¹ -7
) is a group represented by any of the following. Among them, X ¹ is the formula (X ¹ -1), the formula (X ¹ -3)
or a group represented by either formula (X ¹ -4), and more preferably a group represented by either formula (X ¹ -1) or formula (X ¹ -4). preferable.
The hydrocarbon group having 1 to 48 carbon atoms in L ¹ includes aliphatic hydrocarbon groups (chain hydrocarbon groups such as an alkantetrayl group, an alkenetetrayl group, an alkynetetrayl group, and a monocyclic or polycyclic group). alicyclic hydrocarbon groups), aromatic hydrocarbon groups, etc., and tetravalent hydrocarbon groups that are a combination of two or more of these groups (for example, a tetravalent aliphatic hydrocarbon group and a divalent hydrocarbon group). A tetravalent hydrocarbon group that is a combination of alicyclic hydrocarbon groups, a tetravalent alicyclic hydrocarbon group that is a combination of an aromatic hydrocarbon group, and one or more divalent aliphatic hydrocarbon groups , a trivalent or tetravalent alicyclic hydrocarbon group, and/or a tetravalent hydrocarbon group combining an aromatic hydrocarbon group and an alkanediyl group, etc.).

Examples of the alkanetetryl group include methanetetryl group, ethanetetryl group, propanetetryl group, butanetetryl group, pentanetetryyl group, hexanetetryl group, heptanetetryl group, octanetetryl group, nonanetetryl group. A linear or branched alkanetetrayl group such as a decanetetrayl group, an undecanetetrayl group, a dodecantetrayl group, and the like.
Examples of the alkenetetryl group include etenetetryl group, propentetrayl group, isopropentetryl group, butenetetryl group, isobutenetetryl group, tert-butenetetryyl group, pententetrayl group, hexenetetryl group, heptenetetryl group,
Examples include octynetetrayl group, isooctynetetrayl group, and nonenetetrayl group.
Examples of the alkynetetrayl group include propynetetrayl group, isopropinetetrayl group,
Examples include butynetetrayl group, isobutynetetrayl group, tert-butynetetrayl group, pentinetetrayl group, hexynetetrayl group, octynetetrayl group, noninetetrayl group, and the like.
Examples of the monocyclic alicyclic hydrocarbon group include monocyclic cycloalkanetetryyl groups such as a cyclobutanetetryl group, a cyclopentanetetrayl group, a cyclohexanetetrayl group, a cyclohexenetetrayl group, and a cyclooctanetetrayl group. Can be mentioned.
Examples of polycyclic alicyclic hydrocarbon groups include polycyclic cycloalkanetetrayl groups such as norbornanetetrayl group, norbornanetetrayl group, 5-norbornetetrayl group, adamantanetetrayl group, and adamantanetetrayl group. Can be mentioned.
Examples of the aromatic hydrocarbon group include a benzenetetryl group, a naphthalenetetryl group, an anthracetetryl group, and the like.
Examples of hydrocarbon groups that are a combination of two or more types include groups that combine a chain hydrocarbon group with an alicyclic hydrocarbon group and/or an aromatic hydrocarbon group, and specifically, alkanetetryl A group in which a group is combined with a monovalent alicyclic hydrocarbon group and/or an aromatic hydrocarbon group, or a group in which the methylene group contained in the alkanetetryl group is a divalent alicyclic hydrocarbon group and/or a divalent alicyclic hydrocarbon group. Examples include a group replacing an aromatic hydrocarbon group, a trivalent or tetravalent alicyclic hydrocarbon group, and/or a group combining an aromatic hydrocarbon group and an alkanediyl group.

Examples of the substituent that the hydrocarbon group of L ¹ may have include a halogen atom and a cyano group.
Hydroxy group (-CH ₂ - contained in the methyl group is replaced with -O-), carboxy group (-CH ₂ -CH ₂ - contained in the ethyl group is replaced with -O-CO-) basis)
, an alkoxy group having 1 to 12 carbon atoms (-CH ₂ - contained in an alkyl group having 2 to 13 carbon atoms)
is replaced with -O-), an alkoxycarbonyl group having 2 to 13 carbon atoms (a group having 4 to 13 carbon atoms),
-CH ₂ -CH ₂ - contained in the alkyl group of No. 15 is replaced with -O-CO-),
Alkylcarbonyl group having 2 to 13 carbon atoms (-C contained in the alkyl group having 3 to 14 carbon atoms)
a group in which H ₂ - is replaced with -CO-), an alkylcarbonyloxy group having 2 to 13 carbon atoms (a group in which -CH ₂ -CH ₂ - contained in an alkyl group having 4 to 15 carbon atoms is replaced by -CO-O The group substituted with - is a group in which -CH ₂ - contained in a hydrocarbon group is replaced with -O- or -CO-.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group group, dodecyloxy group, etc.
The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms are groups in which a carbonyl group or carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. represents.
Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, and examples of the alkylcarbonyl group having 2 to 13 carbon atoms include acetyl group, propionyl group, butyryl group, etc. carbon number 2-1
As the alkylcarbonyloxy group of 3, an acetyloxy group, a propionyloxy group,
Examples include butyryloxy group.
The tetravalent hydrocarbon group having 1 to 48 carbon atoms represented by L ¹ may have one substituent or a plurality of substituents.

-CH ₂ - contained in the hydrocarbon group having 1 to 48 carbon atoms in L ¹ is -O-, -S-, -CO
- or -SO ₂ - may be substituted.
When the hydrocarbon group having 1 to 48 carbon atoms in L ¹ has a substituent, or -CH ₂ - contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO ₂ -. If so, the number of carbon atoms before substitution is defined as the number of carbon atoms in the hydrocarbon group.

［式（ＩＩＡ）及び式（ＩＩＢ）中、
Ｌ^４及びＬ^4'は、それぞれ独立に、単結合又は置換基を有していてもよい炭素数１～２
４の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ
－又は－ＳＯ_２－に置き換わっていてもよい。
Ｌ^２及びＬ^３は、それぞれ独立に、単結合又は炭素数１～４のアルカンジイル基を表す
。
Ｌ^3'は、炭素数１～４のアルカントリイル基を表す。
＊ａはＸ^１との結合部位を表し、＊ｂは酸素原子又はＸ^２との結合部位を表し、＊ｃは
－ＯＲ^３における酸素原子との結合部位を表し、＊ｄは－ＯＲ^４における酸素原子との結
合部位を表す。］ L ¹ is preferably a group represented by formula (L ¹ A) or formula (L ¹ B).

[In formula (IIA) and formula (IIB),
L ⁴ and L ^4' each independently have a single bond or a carbon number of 1 to 2 which may have a substituent.
-CH ₂ - contained in the hydrocarbon group represents -O-, -S-, -CO
- or -SO ₂ - may be substituted.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^3' represents an alkantriyl group having 1 to 4 carbon atoms.
*a represents the binding site with X ¹ , *b represents the binding site with oxygen atom or X ² , *c represents the binding site with oxygen atom in -OR ³ , *d represents the binding site with oxygen atom in -OR ⁴ Represents a bonding site with an oxygen atom. ]

The hydrocarbon group having 1 to 24 carbon atoms for L ⁴ and L ^4' includes aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkanediyl group, alkenediyl group, alkynediyl group, and monocyclic or polycyclic (divalent alicyclic hydrocarbon group), aromatic hydrocarbon group, etc., and a divalent hydrocarbon group that is a combination of two or more of these groups may be used.

Examples of alkanediyl groups include 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-1,1
Straight chain alkanediyl group such as 2-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 are mentioned.
Examples of the alkenediyl group include ethenediyl group, propenediyl group, isopropendiyl group, butenediyl group, isobutenediyl group, tert-butenediyl group, pentenediyl group, hexenediyl group, heptenediyl group, octynediyl group, isooctynediyl group,
Examples include nonenediyl group.
Examples of the alkynediyl group include ethynediyl group, propynediyl group, isopropylenediyl group, butynediyl group, isobutynediyl group, tert-butynediyl group, pentyndiyl group, hexynediyl group, octyndiyl group, nonynediyl group, and the like.
Examples of the monocyclic divalent alicyclic hydrocarbon group include cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclohexene-3
, 6-diyl group, and monocyclic cycloalkanediyl group such as cyclooctane-1,5-diyl group.
Examples of polycyclic divalent alicyclic hydrocarbon groups include norbornane-1,4-diyl group, norbornane-2,5-diyl group, 5-norbornene-2,3-diyl group, adamantane-1,
Examples include polycyclic cycloalkanediyl groups such as 5-diyl group and adamantane-2,6-diyl group.
Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, and a phenanthrylene group.
Examples of hydrocarbon groups that are a combination of two or more types include groups that combine a chain hydrocarbon group with an alicyclic hydrocarbon group and/or an aromatic hydrocarbon group, and specifically, an alkanediyl group. and an alicyclic hydrocarbon group and/or an aromatic hydrocarbon group, etc., and -
Cycloalkanediyl group - alkanediyl group -, - alkanediyl group - cycloalkanediyl group -, - alkanediyl group - cycloalkanediyl group - alkanediyl group -, - alkanediyl group - aromatic hydrocarbon group -, - aromatic Group hydrocarbon groups - alkanediyl groups - and the like.

Examples of the substituents that the hydrocarbon groups of L ⁴ and L ^4' may have include the same substituents as the substituents that the hydrocarbon group of L ¹ has. Further, the group included by substitution of -CH ₂ - in the hydrocarbon group is also the same as the hydrocarbon group of L ¹ .
The divalent hydrocarbon group having 1 to 24 carbon atoms represented by L ⁴ and L ^4' may have one substituent or a plurality of substituents.

-CH ₂ - contained in the hydrocarbon group having 1 to 24 carbon atoms in L ⁴ and L ^4' is -O-, -S-
, -CO- or -SO ₂ -.
When the hydrocarbon group having 1 to 24 carbon atoms in L ⁴ and L ^4' has a substituent, or -CH ₂ - contained in the hydrocarbon group is -O-, -S-, -CO- or -SO ₂ When substituted with -, the number of carbon atoms before substitution is the number of carbon atoms in the hydrocarbon group.

L ⁴ and L ^4' each independently represent a single bond, an alkanediyl group having 1 to 6 carbon atoms, or a combination of an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms; The base (
-CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-, and -CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S- , -CO- or -SO ₂ -) is preferable,
Single bond, alkanediyl group having 1 to 6 carbon atoms or *-alicyclic hydrocarbon group having 3 to 18 carbon atoms-alkanediyl group having 1 to 6 carbon atoms (-CH ₂ - contained in the alkanediyl group) ,-O
- or -CO- may be replaced)- is more preferable,
Single bond, alkanediyl group having 1 to 4 carbon atoms or *-adamantanediyl group - having 1 to 4 carbon atoms
4 alkanediyl group (-CH ₂ - contained in the alkanediyl group is -O- or -CO
- may be substituted with) - is more preferable (* represents a binding site with X ¹ or X ² ). L ⁴ and LL ^4' may be different groups, but are preferably the same group.

The alkanediyl groups for L ² and L ³ include methylene group, ethylene group, propane-1,
Straight chain alkanediyl groups such as 3-diyl group and butane-1,4-diyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples include branched alkanediyl groups such as methylpropane-1,2-diyl group.
Examples of the alkanetriyl group for L ^3' include a methine group, an ethyne group, a propanetriyl group, a butanetriyl group, and the like.
L ² and L ³ are each independently preferably a single bond or an alkanediyl group having 1 to 4 carbon atoms, and more preferably a single bond or a methylene group. Although L ² and L ³ may be different groups, they are preferably the same group.
L ^3' is preferably an alkantriyl group having 1 to 4 carbon atoms, more preferably a methine group or an ethyne group.

芳香族炭化水素基としては、フェニル基、ナフチル基、ビフェニル基、アントリル基、
フェナントリル基、ビナフチル基等のアリール基等が挙げられる。芳香族炭化水素基の炭
素数は、好ましくは６～１４であり、より好ましくは６～１０である。芳香族炭化水素基
は、後述の組み合わせた基のように、鎖式炭化水素基又は脂環式炭化水素基を有していて
もよく、鎖式炭化水素基を有する芳香族炭化水素基（トリル基、キシリル基、クメニル基
、メシチル基、ｐ－エチルフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、２，６－ジエ
チルフェニル基、２－メチル－６－エチルフェニル基等）、脂環式炭化水素基を有する芳
香族炭化水素基（ｐ－シクロへキシルフェニル基、ｐ－アダマンチルフェニル基等）等が
挙げられる。
組み合わせた基とは、
脂環式炭化水素基と鎖式炭化水素基（アルキル基、アルケニル基及び／又はアルキニル
基）とを組み合わせた基（該鎖式炭化水素基（アルキル基、アルケニル基、アルキニル基
）及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－Ｓ
Ｏ_２－に置き換わっていてもよい）、
鎖式炭化水素基（アルキル基、アルケニル基及び／又はアルキニル基）と芳香族炭化水
素基とを組み合わせた基（該鎖式炭化水素基（アルキル基、アルケニル基及び／又はアル
キニル基）に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換
わっていてもよい）、及び
脂環式炭化水素基と芳香族炭化水素基とを組み合わせた基（該脂環式炭化水素基に含ま
れる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい
）を表す。なお、組み合わせにおいて、脂環式炭化水素基、鎖式炭化水素基（アルキル基
、アルケニル基、アルキニル）基及び芳香族炭化水素基は、それぞれ２種以上を組み合わ
せてもよい。
具体的には、組み合わせた基としては、
アダマンチルメチル基、シクロヘキシルメチル基等の脂環式炭化水素基－鎖式炭化水素
基－＊（該鎖式炭化水素基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－
Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい）、
メチルアダマンチル基等の鎖式炭化水素基－脂環式炭化水素基－＊（該鎖式炭化水素基
及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ
_２－に置き換わっていてもよい）、
トリル基、キシリル基等の鎖式炭化水素基－芳香族炭化水素基－＊（該鎖式炭化水素基
に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていて
もよい）、
シクロヘキシルフェニル基等の脂環式炭化水素基－芳香族炭化水素基－＊（該脂環式炭
化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わ
っていてもよい）、
メチルシクロヘキシルメチル基等の鎖式炭化水素基－脂環式炭化水素基－鎖式炭化水素
基－＊（該鎖式炭化水素基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－
Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい）、
ベンジル基等の芳香族炭化水素基－鎖式炭化水素基－＊（該鎖式炭化水素基に含まれる
－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい）、
トリルメチル基等の鎖式炭化水素基－芳香族炭化水素基－鎖式炭化水素基－＊（該鎖式
炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換
わっていてもよい）
等が挙げられる。ここで、＊は酸素原子との結合部位を表す。 A hydrocarbon group having a group represented by formula (IC) in R ³ , R ⁴ and R ⁵ is a hydrocarbon group substituted with one or more groups represented by formula (IC) as a substituent. It means something that exists. The hydrocarbon group here is -CH ₂ - contained in the hydrocarbon group, -O-, -S-, -C
It may be replaced with O- or -SO ₂ -, or it may have one or more substituents other than the group represented by formula (IC).
Hydrocarbon groups for R ³ , R ⁴ and R ⁵ include aliphatic hydrocarbon groups (chain hydrocarbon groups and alicyclic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups), aromatic hydrocarbon groups and groups combining these.
Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group,
Examples include alkyl groups such as isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and nonyl group. The alkyl group preferably has 1 to 9 carbon atoms, more preferably 1 to 4 carbon atoms.
Examples of alkenyl groups include ethenyl group, propenyl group, isopropenyl group, butenyl group,
isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group,
Examples include octynyl group, isooctynyl group, and nonenyl group.
Alkynyl groups include ethynyl group, propynyl group, isopropynyl group, butynyl group,
Isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group,
Examples include nonynyl group.
The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Examples of alicyclic hydrocarbon groups include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and cyclododecyl group, norbornyl group, and adamantyl group. and polycyclic cycloalkyl groups such as groups.
The alicyclic hydrocarbon groups represented by R ³ , R ⁴ and R ⁵ are preferably groups represented by formulas (Y1) to (Y41) (* represents a bonding site), and formula (Y1) ~Equation (Y20), Equation (Y2
6), is more preferably a group represented by any one of formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y41), and formula (Y3), (Y4) , formula (Y9), formula (
Y11), formula (Y14), formula (Y15), formula (Y16), formula (Y20), and formula (Y30) are more preferable. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 3.
18, more preferably 3 to 16.

Aromatic hydrocarbon groups include phenyl group, naphthyl group, biphenyl group, anthryl group,
Examples include aryl groups such as phenanthryl group and binaphthyl group. The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, as in the combined groups described below, and an aromatic hydrocarbon group having a chain hydrocarbon group (tolyl, group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group), alicyclic hydrocarbon Examples include aromatic hydrocarbon groups having groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.).
The combined group is
A group that combines an alicyclic hydrocarbon group and a chain hydrocarbon group (alkyl group, alkenyl group, and/or alkynyl group) (the chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group) and the alicyclic group) -CH ₂ - contained in the formula hydrocarbon group is -O-, -S-, -CO- or -S
may be replaced by O ₂ -),
A group that combines a chain hydrocarbon group (alkyl group, alkenyl group and/or alkynyl group) and an aromatic hydrocarbon group (included in the chain hydrocarbon group (alkyl group, alkenyl group and/or alkynyl group) -CH ₂ - may be replaced with -O-, -S-, -CO- or -SO ₂ -), and a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (such as -CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -. In addition, in the combination, two or more types of alicyclic hydrocarbon groups, chain hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl) groups, and aromatic hydrocarbon groups may be combined.
Specifically, the combined groups are:
Alicyclic hydrocarbon group such as adamantylmethyl group or cyclohexylmethyl group - Chain hydrocarbon group -* (-CH ₂ - contained in the chain hydrocarbon group and the alicyclic hydrocarbon group is -O- ,-
may be replaced with S-, -CO- or -SO ₂ -),
Chain hydrocarbon group such as methyladamantyl group - alicyclic hydrocarbon group -* (-CH ₂ - contained in the chain hydrocarbon group and the alicyclic hydrocarbon group is -O-, -S- , -CO- or -SO
₂ - may be replaced),
Chain hydrocarbon groups such as tolyl group and xylyl group - aromatic hydrocarbon group -* (-CH ₂ - contained in the chain hydrocarbon group is -O-, -S-, -CO- or -SO ₂ - may be replaced),
Alicyclic hydrocarbon group such as cyclohexylphenyl group - aromatic hydrocarbon group -* (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO ₂ - may be replaced),
Chain hydrocarbon group such as methylcyclohexylmethyl group - Alicyclic hydrocarbon group - Chain hydrocarbon group -* (-CH ₂ - contained in the chain hydrocarbon group and the alicyclic hydrocarbon group is -O-,-
may be replaced with S-, -CO- or -SO ₂ -),
Aromatic hydrocarbon group such as benzyl group - chain hydrocarbon group -* (-CH ₂ - contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO ₂ -) may be replaced),
Chain hydrocarbon group such as tolylmethyl group - aromatic hydrocarbon group - chain hydrocarbon group -* (-CH ₂ - contained in the chain hydrocarbon group is -O-, -S-, -CO- or may be replaced with -SO ₂ -)
etc. Here, * represents a bonding site with an oxygen atom.

The hydrocarbon group represented by R ³ preferably has 1 to 3 carbon atoms and may have a substituent.
6 aliphatic hydrocarbon group (However, -CH ₂ - contained in the aliphatic hydrocarbon group is -O-, -
It may be substituted with S-, -CO- or -SO ₂ -, and at least one hydrogen atom contained in the aliphatic hydrocarbon group is substituted with a group represented by formula (IC). ) and
More preferably, an alkyl group (-CH ₂ - contained in the alkyl group is -O- or -C
At least one hydrogen atom contained in the alkyl group may be replaced with O-,
Substituted with a group represented by formula (IC). ) or a group that combines an alicyclic hydrocarbon group and an alkyl group (-CH ₂ - contained in the alkyl group may be replaced with -O- or -CO-, and hydrogen contained in the alkyl group At least one of the atoms is substituted with a group represented by formula (IC)),
More preferably, *-alkyl group (-CH ₂ - contained in the alkyl group may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group
One is substituted with a group represented by formula (IC). * represents a bonding site with an oxygen atom. )
or *-alkyl group-alicyclic hydrocarbon group-alkyl group (-CH ₂ contained in the alkyl group)
- may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). * represents a bonding site with an oxygen atom. ).

The hydrocarbon group represented by R ⁴ and R ⁵ is preferably an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a hydrogen atom or a substituent (however, the aliphatic hydrocarbon group Contains-C
H ₂ - may be replaced with -O-, -S-, -CO- or -SO ₂ -, and at least one hydrogen atom contained in the aliphatic hydrocarbon group is represented by formula (IC). It may be substituted with the represented group. ) and
More preferably, a hydrogen atom, an alkyl group (-CH ₂ - contained in the alkyl group, -O
- or -CO- may be substituted, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). ) or a group that combines an alicyclic hydrocarbon group and an alkyl group (-CH ₂ - contained in the alkyl group may be replaced with -O- or -CO-, and hydrogen contained in the alkyl group At least one of the atoms has the formula (I
It may be substituted with a group represented by C). ) and
More preferably, a hydrogen atom, a *-alkyl group (-CH ₂ - contained in the alkyl group may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC).* represents a bonding site with an oxygen atom) or *-alkyl group-alicyclic hydrocarbon group-alkyl group (contained in the alkyl group) -CH ₂ - may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group may be substituted with a group represented by formula (IC). Good. * represents the bonding site with the oxygen atom),
Even more preferably, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a substituent (provided that -CH ₂ - contained in the aliphatic hydrocarbon group is -O-, - It may be substituted with S-, -CO- or -SO ₂ -, and at least one hydrogen atom contained in the aliphatic hydrocarbon group is substituted with a group represented by formula (IC). ) and
Even more preferably, a hydrogen atom, an alkyl group (-CH ₂ - contained in the alkyl group may be replaced with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group , substituted with a group represented by formula (IC)) or a group combining an alicyclic hydrocarbon group and an alkyl group (-CH ₂ - contained in the alkyl group is substituted with -O- or - C
At least one hydrogen atom contained in the alkyl group may be replaced with O-,
Substituted with a group represented by formula (IC). ) and
Particularly preferably, a hydrogen atom, a *-alkyl group (-CH ₂ - contained in the alkyl group,
It may be substituted with -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is substituted with a group represented by formula (IC). * represents a bonding site with an oxygen atom. ) or *-alkyl group-alicyclic hydrocarbon group-alkyl group (-CH ₂ - contained in the alkyl group may be replaced with -O- or -CO-, and hydrogen contained in the alkyl group At least one of the atoms is substituted with a group represented by formula (IC) (* represents a bonding site with an oxygen atom).

［式（ＩＣ）中、
Ｒ^Aは、炭素数１～１２の飽和炭化水素基を表す。
ｕ１は、０～２のいずれかの整数を表し、ｕ１が２である場合、複数のＲ^Aは同一であ
るか、相異なる。
ｓ１は、１又は２を表す。
ｔ１は、０又は１を表す。但し、ｓ１とｔ１との和は、１又は２である。
＊は、結合部位を表す。］ The group represented by formula (IC) is as follows.

[In formula (IC),
R ^A represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
u1 represents any integer from 0 to 2, and when u1 is 2, the plurality of R ^A are the same or different.
s1 represents 1 or 2.
t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2.
* represents a binding site. ]

s1 is preferably 1, t1 is preferably 1, the sum of s1 and t1 is preferably 1 or 2, and it is more preferable that the sum of s1 and t1 is 2.
The group represented by formula (IC) is preferably a group represented by the following.

Ｒ^Ａの飽和炭化水素基としては、アルキル基、脂環式炭化水素基及びこれらの組み合わ
せが挙げられる。
Ｒ^Ａのアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチ
ル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニ
ル基等のアルキル基が挙げられる。アルキル基の炭素数は、好ましくは１～９であり、よ
り好ましくは１～４である。
脂環式炭化水素基は、単環式、多環式及びスピロ環のいずれでもよい。脂環式炭化水素
基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基
、シクロオクチル基、シクロノニル基、シクロデシル基、シクロドデシル基等の単環式シ
クロアルキル基、ノルボルニル基、アダマンチル基等の多環式シクロアルキル基が挙げら
れる。 In the group represented by the formula (IC), when u1 is 1, the group represented by the following formula also has the formula (I
Included in C).

The saturated hydrocarbon group of R ^A includes an alkyl group, an alicyclic hydrocarbon group, and a combination thereof.
Examples of the alkyl group of R ^A include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and nonyl group. The alkyl group preferably has 1 to 9 carbon atoms, more preferably 1 to 4 carbon atoms.
The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic. Examples of alicyclic hydrocarbon groups include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and cyclododecyl group, norbornyl group, and adamantyl group. and polycyclic cycloalkyl groups such as groups.

Examples of substituents other than the group represented by formula (IC) in the hydrocarbon groups represented by R ³ , R ⁴ and R ⁵ include a halogen atom, a cyano group, and the like.
Examples of the halogen atom include those similar to those exemplified for ^L1 .
Also, groups included by substitution of -CH ₂ - in a hydrocarbon group, that is, a hydroxy group, a carboxy group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and a group having 2 to 13 carbon atoms. The ^same applies to the alkylcarbonyl group and the alkylcarbonyloxy group having 2 to 13 carbon atoms.
-CH ₂ - contained in the hydrocarbon groups represented by R ³ , R ⁴ and R ⁵ is -O-, -S-, -
When substituted with CO- or -SO ₂ -, the number of carbon atoms before substitution is the total number of carbon atoms of the hydrocarbon group. Further, when a substituent such as formula (IC) is bonded to a hydrocarbon group represented by R ³ , R ⁴ and R ⁵ , the number of carbon atoms before substitution is the total number of carbon atoms of the hydrocarbon group.

Examples of the compound (IA) include the following compounds.

Formula (IA-1) to Formula (IA-10), Formula (IA-12), Formula (IA-14), Formula (IA
-16) - Compounds represented by formula (IA-32) in which the methyl group corresponding to R ¹ in formula (IA) is replaced with a hydrogen atom, as well as formula (IA-11) and formula (IA-13) , a compound represented by formula (IA-15) in which the hydrogen atom corresponding to R ¹ in formula (IA) is replaced with a methyl group can also be mentioned as a specific example of compound (IA). Among them, formula (IA-1) to formula (IA-12), formula (IA-17) to formula (IA-18), formula (
Compounds represented by formulas IA-23) to (IA-26) are preferred.

Examples of the compound (IB) include the following compounds.

Formula (IB-1) to Formula (IB-10), Formula (IB-12), Formula (IB-14), Formula (IB-10), Formula (IB-12), Formula (IB-14), Formula (IB-10)
-16) ~ Compounds represented by formula (IB-26) in which the methyl groups corresponding to R ¹ and R ² of formula (IB) are replaced with hydrogen atoms, as well as compounds represented by formula (IB-11) and formula (IB -1
3) Compounds represented by formula (IB-15) in which the hydrogen atoms corresponding to R ¹ and R ² of formula (IB) are replaced with methyl groups may also be cited as specific examples of compound (IB). I can do it. Among them, formula (IB-1) to formula (IB-12), formula (IB-17) to formula (I
B-18) and compounds represented by formulas (IB-23) to (IB-26) are preferred.

（式（ＩＣＩ）中、ｓ１、ｔ１、ｕ１及びＲ^Ａは、それぞれ前記と同じ意味を表す。Ｌ
^2Iは、置換基を有していてもよい炭素数１～３４の炭化水素基を表し、該炭化水素基に含
まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよ
い。ｎｎは０又は１を表す。＊は、酸素原子との結合部位を表す。）

<Method for producing compound (IA) or compound (IB)>
In compound (IA),
A compound in which R ³ , R ⁴ and R ⁵ are each independently a group represented by formula (ICI) (compound represented by formula (IA1)),
A compound in which R ⁵ is a hydrogen atom, and R ³ and R ⁴ are each independently a group represented by formula (ICI) (compound represented by formula (IA2)),
A compound in which R ⁴ and R ⁵ are hydrogen atoms and R ³ is a group represented by formula (ICI) (compound represented by formula (IA3)) is, for example, a compound represented by formula (IA3) It can be produced by reacting the compound and carbonyldiimidazole in a solvent, and then reacting the compound with a salt represented by formula (IA-a).
In compound (IB),
A compound in which R ³ and R ⁴ are each independently a group represented by formula (ICI) (formula (IB
1),
A compound in which R ⁴ is a hydrogen atom and R ³ is a group represented by the formula (ICI) (formula (IB2
) is prepared by, for example, reacting the compound represented by formula (I-b) with carbonyldiimidazole in a solvent, and then reacting the compound represented by formula (IB-a) with a salt represented by formula (IB-a). It can be produced by reaction.

(In formula (ICI), s1, t1, u1 and ^RA each have the same meaning as above.L
^2I represents a hydrocarbon group having 1 to 34 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group is -O-, -S-, -CO- or - It may be replaced with SO ₂ -. nn represents 0 or 1. * represents a bonding site with an oxygen atom. )

(In the formula, all symbols represent the same meanings as above.)
Examples of the solvent in this reaction include chloroform and acetonitrile.
2 mols of the compound represented by the formula (I-b) per 1 mol of the compound represented by the formula (IA-a)
．． When 6 mol or more (preferably 3.0 mol or more) is reacted, a compound represented by formula (IA1) is obtained as the main product. For 1 mole of the compound represented by formula (IA-a),
When 1.6 to 2.4 mol (preferably 1.8 to 2.2 mol) of the compound represented by -b) is reacted, a compound represented by formula (IA2) is obtained as the main product. 0.6 to 1.4 mol (preferably 0.8 to 1.1 mol) of the compound represented by formula (Ib) per 1 mol of the compound represented by formula (IA-a). Upon reaction, a compound represented by formula (IA3) is obtained as the main product.
1 mole of the compound represented by formula (IB-a), 1 mole of the compound represented by formula (I-b)
．． When 6 mol or more (preferably 2.0 mol or more) is reacted, a compound represented by formula (IB1) is obtained as the main product. For 1 mol of the compound represented by formula (IB-a),
-b) 0.6 mol to 1.4 mol (preferably 0.8 to 1.1 mol)
Upon reaction, a compound represented by formula (IB2) is obtained as the main product.
The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 to 24 hours.
Examples of the compound represented by formula (Ib) include compounds represented by the following formula, which are easily available on the market.

（式中、Ｒ¹、Ｌ¹、及びＲ^２は、それぞれ前記と同じ意味を表す。Ｘ^1A及びＸ^2Aは、単
結合１，４－フェニレン基、又は－ＣＯ－Ｏ－Ａｒ¹－＊を表し、Ａｒ¹は１，４－フェニ
レン基を表す。＊はカルボニル基の炭素原子との結合部位を表す。）
溶媒としては、テトラヒドロフラン、クロロホルム及びアセトニトリルなどが挙げられ
る。
酸としては、ｐ－トルエンスルホン酸、硫酸、塩酸等が挙げられる。
反応温度は通常０℃～８０℃であり、反応時間は通常０．５時間～２４時間である。
式（Ｉ１－ｃ１）及び式（Ｉ１－ｃ２）で表される化合物としては、下記式で表される
化合物等が挙げられ、市場より容易に入手することができる。

式（Ｉ－ｄ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場
より容易に入手でき、また、公知の合成方法により容易に製造できる。

In the compound represented by formula (IA-a), X ¹ is formula (X ¹ -1), formula (X ¹ -3)
or a compound represented by formula (X ^1-4 ) (compound represented by formula (I1A-a)), a compound represented by formula (I1-c1) and carbonyldiimidazole It can be produced by reacting in a solvent, further reacting with a compound represented by formula (Id), and treating with an acid.
In the compound represented by formula (IB-a), X ¹ and X ² each independently represent formula (X
^1-1 ), a group represented by formula (X ^1-3 ) or formula (X ^1-4 ) (a compound represented by formula (I1B-a)) is a group represented by formula (I1-1), The compound represented by c1) and the formula (I1-
It can be produced by reacting the compound represented by c2) with carbonyldiimidazole in a solvent, further reacting with the compound represented by formula (I-d), and treating with an acid.

(In the formula, R ¹ , ^{L 1 , and} R ² each represent the same meaning as above. (Ar ¹ represents a 1,4-phenylene group. * represents the bonding site with the carbon atom of the carbonyl group.)
Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
Examples of acids include p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid.
The reaction temperature is usually 0°C to 80°C, and the reaction time is usually 0.5 to 24 hours.
Examples of the compounds represented by formula (I1-c1) and formula (I1-c2) include compounds represented by the following formulas, which can be easily obtained from the market.

Examples of the compound represented by formula (I-d) include compounds represented by the following formula, etc., which are easily available on the market and can be easily produced by known synthesis methods.

（式中、Ｒ¹、Ｌ¹及びＲ^２は、それぞれ前記と同じ意味を表す。Ｘ^1B及びＸ^2Bは、－Ａ
ｒ¹－＊又は－ＣＯ－Ｏ－Ａｒ¹－＊を表す。Ａｒは１，４－フェニレン基を表す。＊は酸
素原子との結合部位を表す。）
溶媒としては、テトラヒドロフラン、クロロホルム及びアセトニトリルなどが挙げられ
る。
塩基としては、水酸化カリウムなどが挙げられる。
酸としては、ｐ－トルエンスルホン酸、硫酸、塩酸等が挙げられる。
反応温度は通常０℃～８０℃であり、反応時間は通常０．５時間～２４時間である。
式（Ｉ２－ｃ１）及び式（Ｉ２－ｃ２）で表される化合物としては、下記式で表される
化合物等が挙げられ、市場より容易に入手することができる。

In the compound represented by formula (IA-a), X ¹ is formula (X ¹ -2) or formula (X ¹ -5
) (compound represented by formula (I2A-a)) is a group represented by formula (I2-c1
) and the compound represented by formula (I-d) are reacted in a solvent in the presence of a base, followed by treatment with an acid.
In the compound represented by formula (IB-a), X ¹ and X ² each independently represent formula (X
^1-2 ) or a group represented by formula (X ^1-5 ) (compound represented by formula (I2B-a)), a compound represented by formula (I2-c1) and a group represented by formula (I2 It can be produced by reacting a compound represented by -c2) with a compound represented by formula (I-d) in a solvent in the presence of a base, and then treating with an acid.

(In the formula, R ¹ , L ¹ and R ² each have the same meaning as above. ^{X 1B} and X ^2B are -A
Represents r ¹ -* or -CO-O-Ar ¹ -*. Ar represents a 1,4-phenylene group. * represents a bonding site with an oxygen atom. )
Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
Examples of the base include potassium hydroxide.
Examples of acids include p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid.
The reaction temperature is usually 0°C to 80°C, and the reaction time is usually 0.5 to 24 hours.
Examples of the compounds represented by formula (I2-c1) and formula (I2-c2) include compounds represented by the following formulas, which can be easily obtained from the market.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
溶媒としては、テトラヒドロフラン、クロロホルム及びアセトニトリルなどが挙げられ
る。
酸としては、ｐ－トルエンスルホン酸、硫酸、塩酸等が挙げられる。
反応温度は通常０℃～８０℃であり、反応時間は通常０．５時間～２４時間である。 A compound represented by formula (I3A-a) in which X ¹ is a group represented by formula (X ¹ -6) or formula (X ¹ -7) is a compound represented by formula (I2-c1) It can be produced by reacting and carbonyldiimidazole in a solvent, further reacting with a compound represented by formula (Id), and then treating with an acid.
A compound represented by formula (I3B-a) in which X ¹ and X ² are each independently a group represented by formula (X ^1-6 ) or formula (X ^1-7 ) is a compound represented by formula (I3B-a), The compound represented by c1) and the formula (I
Produced by reacting the compound represented by 2-c2) with carbonyldiimidazole in a solvent, further reacting with the compound represented by formula (I-d), and then treating with an acid. be able to.

(In the formula, all symbols represent the same meanings as above.)
Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
Examples of acids include p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid.
The reaction temperature is usually 0°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

〔resin〕
The resin of the present invention is a resin (hereinafter sometimes referred to as "resin (A)") containing a structural unit (hereinafter sometimes referred to as "structural unit (I)") derived from compound (IA) or compound (IB). .
). The resin (A) may be a homopolymer of the structural unit (I), or may be a homopolymer of the structural unit (I).
It may be a copolymer consisting only of I) or a polymer containing one or more structural units other than structural unit (I).
Structural units other than structural unit (I) include structural units having acid-labile groups (hereinafter sometimes referred to as "structural units (a1)"), structural units other than structural units having acid-labile groups; Structural units with halogen atoms (hereinafter sometimes referred to as "structural units (a4)"), structural units without acid-labile groups (hereinafter sometimes referred to as "structural units (s)"), non-eliminating carbonization Examples include a structural unit having a hydrogen group (hereinafter sometimes referred to as "structural unit (a5)"). Here, the acid-labile group is a hydrophilic group (
For example, it means a group forming a hydroxy group or a carboxy group.

［式（１）中、Ｒ^a1、Ｒ^a２及び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の脂環式炭化水素
基を形成する。
ｍａ及びｎａは、それぞれ独立して、０又は１を表し、ｍａ及びｎａの少なくとも一方
は１を表す。
＊は結合部位を表す。］

［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の複素環を形成し
、該炭化水素基及び該複素環に含まれる－ＣＨ_２－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。
ｎａ’は、０又は１を表す。
＊は結合部位を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)").
The acid labile group contained in the resin (A) is a group represented by formula (1) (hereinafter also referred to as group (1)) and/or a group represented by formula (2) (hereinafter referred to as group (2)). ) is preferred.

[In formula (1), R ^a1 , R ^a2 and R ^a3 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof. Watermelon, R ^a1 and R
^a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.
ma and na each independently represent 0 or 1, and at least one of ma and na represents 1.
* represents a binding site. ]

[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. Alternatively, R ^a2' and R ^a3' combine with each other to form a heterocycle 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 heterocycle - may be replaced with -O- or -S-.
X represents an oxygen atom or a sulfur atom.
na' represents 0 or 1.
* represents a binding site. ]

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、シクロヘキシルメチル基
、アダマンチルメチル基、アダマンチルジメチル基、ノルボルニルエチル基等が挙げられ
る。
好ましくは、ｍａは０であり、ｎａは１である。
Ｒ^a1及びＲ^a2が互いに結合して脂環式炭化水素基を形成する場合の－Ｃ（Ｒ^a1）（Ｒ^a2
）（Ｒ^a3）としては、下記の基が挙げられる。脂環式炭化水素基は、好ましくは炭素数３
～１２である。＊は－Ｏ－との結合部位を表す。

The alkyl groups in R ^a1 , R ^a2 and R ^a3 include methyl group, ethyl group, propyl group,
Examples include butyl group, pentyl group, hexyl group, heptyl group, octyl group, and the like.
The alicyclic hydrocarbon group in R ^a1 , R ^a2 and R ^a3 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (
* represents a binding site. ) etc. The number of carbon atoms in the alicyclic hydrocarbon groups of R ^a1 , R ^a2 and R ^a3 is preferably 3 to 16.

Examples of groups combining an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, and a norbornyl group. Examples include ethyl group.
Preferably ma is 0 and na is 1.
-C(R ^a1 )(R ^a2 when R ^a1 and R ^a2 combine with each other to form an alicyclic hydrocarbon group
)(R ^a3 ) include the following groups. The alicyclic hydrocarbon group preferably has 3 carbon atoms.
~12. * represents a bonding site with -O-.

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。
ｎａ’は、好ましくは０である。 Examples of the hydrocarbon group for R ^a1' , R ^a2' and R ^a3' include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group include the same groups as those listed for R ^a1 , R ^a2 and R ^a3 .
Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group,
Examples include aryl groups such as phenanthryl groups.
Examples of combined groups include groups combining the above-mentioned alkyl groups and alicyclic hydrocarbon groups (for example, cycloalkylalkyl groups), aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl groups (p-methyl Phenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-
(6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups (phenylcyclohexyl group, etc.), etc. It will be done.
When R ^a2' and R ^a3' combine with each other to form a heterocycle with the carbon atom to which they are bonded and X, -C(R ^a1' ) (R ^a3' ) -X-R ^a2' is , the following groups are mentioned. * represents a binding site.

It is preferable that at least one of R ^a1' and R ^a2' is a hydrogen atom.
na' is preferably 0.

Examples of the group (1) include the following groups.
In formula (1), R ^a1 , R ^a2 and R ^a3 are alkyl groups, ma=0, and na=1
The group that is. The group is preferably a tert-butoxycarbonyl group.
In formula (1), R ^a1 and R ^a2 form an adamantyl group together with the carbon atom to which they are bonded, R ^a3 is an alkyl group, ma = 0, and na = 1. .
In formula (1), R ^a1 and R ^a2 are each independently an alkyl group, R ^a3 is an adamantyl group, ma=0, and na=1.
Specific examples of the group (1) include the following groups. * represents a binding site.

Specific examples of group (2) include the following groups. * represents a binding site.

The 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.

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

［式（ａ１－０）、式（ａ１－１）及び式（ａ１－２）中、
Ｌ^a01、Ｌ^a1及びＬ^a2は、それぞれ独立に、－Ｏ－又は^＊－Ｏ－（ＣＨ_２）_k1－ＣＯ－
Ｏ－を表し、ｋ１は１～７のいずれかの整数を表し、＊は－ＣＯ－との結合部位を表す。
Ｒ^a01、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^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。
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合せることにより形成される基を表す。
ｍ１は０～１４のいずれかの整数を表す。
ｎ１は０～１０のいずれかの整数を表す。
ｎ１’は０～３のいずれかの整数を表す。］ The structural unit derived from a (meth)acrylic monomer having group (1) is preferably a structural unit represented by formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)).
), the structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)), or the structural unit represented by formula (a1-2) (hereinafter referred to as structural unit (a1-1)) -2) may be mentioned. These may be used alone or in combination of two or more.

[In formula (a1-0), formula (a1-1) and formula (a1-2),
L ^a01 , L ^a1 and L ^a2 are each independently -O- or ^* -O-(CH ₂ ) _k1 -CO-
represents O-, k1 represents any integer from 1 to 7, and * represents a binding site with -CO-.
R ^a01 , R ^a4 and R ^a5 each independently represent 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, or an alkyl group having 3 to 8 carbon atoms;
18 alicyclic hydrocarbon groups or a combination thereof.
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 a combination thereof.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1' represents any integer from 0 to 3. ]

R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
L ^a01 , L ^a1 and L ^a2 are preferably oxygen atoms or *-O-(CH ₂ ) _k01 -CO-O-
(However, k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom.
Examples of the alkyl group, alicyclic hydrocarbon group, and a combination thereof in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 include the groups listed for R ^a1 , R ^a2 and R ^a3 in formula (1); Examples include groups similar to .
The number of carbon atoms in the alkyl group in R ^a02 , R ^a03 , and R ^a04 is preferably 1 to 6,
More preferably a methyl group or an ethyl group, still more preferably a methyl group.
The number of carbon atoms in the alkyl group in R ^a6 and R ^a7 is preferably 1 to 6, more preferably a methyl group, an ethyl group, or an isopropyl group, and even more preferably an ethyl group or an isopropyl group.
The number of carbon atoms in the alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 is preferably 5 to 12,
More preferably it is 5-10.
In the group that is a combination of an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total carbon number of the alkyl group and alicyclic hydrocarbon group is 18 or less.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, ethyl group, cyclohexyl group or adamantyl group.
R ^a6 and R ^a7 are preferably 1 to 6 alkyl groups, more preferably methyl, ethyl or isopropyl, even more preferably ethyl or isopropyl.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1' is preferably 0 or 1.

As the structural unit (a1-0), for example, formulas (a1-0-1) to (a1-0-12)
Structural units represented by any of formula (a1-0-1) to formula ( ^a1- 0
A structural unit represented by any one of -10) is preferred.

Examples of the structural unit (a1-1) include structural units derived from monomers described in JP-A No. 2010-204646. Among them, formula (a1-1-1) to formula (a1
-1-4) and structural units in which the methyl group corresponding to R ^a4 in the structural unit (a1-1) is replaced with a hydrogen atom are preferred, and the structural units represented by formulas (a1-1-1) to formula(
A structural unit represented by any one of a1-1-4) is more preferred.

The structural unit (a1-2) corresponds to a structural unit represented by any of formulas (a1-2-1) to (a1-2-6) and R ^a5 in the structural unit (a1-2). Examples include structural units in which a methyl group is replaced with a hydrogen atom, and structural units represented by formula (a1-2-2), formula (a1-2-5), and formula (a1-2-6) are preferred.

When the resin (A) contains a structural unit (a1-0), its content is usually 1 to 50 mol%, preferably 3 to 40 mol%, based on the total structural units of the resin (A). The content is more preferably 5 to 30 mol%.
When the resin (A) contains a structural unit (a1-1) and/or a structural unit (a1-2), the total content of these units is based on the total structural units of the resin (A).
Usually 10 to 95 mol%, preferably 15 to 80 mol%, more preferably 15 to 80 mol%.
75 mol%, more preferably 20 to 70 mol%, even more preferably 20 to 65 mol%.

［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のアルキルカルボニル基、炭素数２～４のアルキルカルボニ
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のいずれかの整数を表す。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は互いに結合してそれ
らが結合する－Ｃ－Ｏ－とともに炭素数２～２０の２価の炭化水素基を形成し、該炭化水
素基及び該２価の炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－Ｓ－で置き換わって
もよい。］ Examples of the structural unit having a group (2) in the structural unit (a1) include a structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). .

[In formula (a1-4),
R ^a32 is a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 that may contain a halogen atom
represents an alkyl group.
R ^a33 is a halogen atom, hydroxy group, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl Represents an oxy group or a methacryloyloxy group.
la represents any integer from 0 to 4. When la is 2 or more, a plurality of R ^a33 's 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 combine with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -C-O- to which they are bonded. -CH ₂ - formed and contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced with -O- or -S-. ]

Examples of the alkyl group for R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
Examples of the halogen atom for R ^a32 and R ^a33 include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1, 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3, 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, etc. Can be mentioned.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group and hexyloxy group. Among these, an alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like.
Examples of the hydrocarbon groups in R ^a34 , R ^a35 and R ^a36 include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining these. Examples include the same groups as the alkyl group and alicyclic hydrocarbon group in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 .
Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group,
Examples include aryl groups such as phenanthryl groups.
Examples of the combined group include a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert- butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having alicyclic hydrocarbon group ( p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group (phenylcyclohexyl group, etc.), and the like. In particular, 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 a combination thereof. can 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, and even more preferably a methoxy group.
la is preferably 0 or 1, and more preferably 0.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably an alkyl group or an alicyclic 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 thereof. It is a group formed, more preferably an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 1 carbon atoms.
8 alicyclic hydrocarbon group or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. The aromatic hydrocarbon group for R ^a36 is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.
--OC(R ^a34 )(R ^a35 )-O-R ^a36 in structural unit (a1-4) comes into contact with an acid (for example, p-toluenesulfonic acid) and is eliminated to form a hydroxy group.

Examples of the structural unit (a1-4) include structural units derived from monomers described in JP-A No. 2010-204646. Preferably, formulas (a1-4-1) to (a1
-4-12) and a structural unit in which the hydrogen atom corresponding to R ^a32 in the structural unit (a1-4) is replaced with a methyl group, more preferably, the structural unit represented by the formula (a
Examples include structural units represented by formulas (a1-4-1) to (a1-4-5) and (a1-4-10), respectively.

When the resin (A) has a structural unit (a1-4), its content is preferably 5 to 60 mol%, and 5 to 50 mol%, based on the total of all structural units of the resin (A). It is more preferably mol%, and even more preferably 10 to 40 mol%.

式（ａ１－５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロゲ
ン原子を表す。
Ｚ^a1は、単結合又は＊－（ＣＨ₂）_h3－ＣＯ－Ｌ⁵⁴－を表し、ｈ３は１～４のいずれか
の整数を表し、＊は、Ｌ⁵¹との結合部位を表す。
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のいずれかの整数を表す。
ｓ１’は、０～３のいずれかの整数を表す。 As a structural unit derived from a (meth)acrylic monomer having group (2), formula (a1
-5) (hereinafter sometimes referred to as "structural unit (a1-5)") is also included.

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 binding site with L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent -O- or -S-.
s1 represents an integer of 1 to 3.
s1' represents any integer from 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, with a fluorine atom being preferred.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group and trifluoromethyl group. Examples include 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.
It is preferable that one of L ⁵² and L ⁵³ is -O- and the other is -S-.
s1 is preferably 1.
s1' is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or *-CH ₂ -CO-O-.

Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A No. 2010-61117. Among them, formula (a1-5-1) to formula (a1-5-
Structural units represented by formula (a1-5-1) or formula (a1-5-2) are preferable.
) is more preferable.

When the resin (A) has a structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, based on the total structural units of the resin (A). , 5-40
More preferably mol %, and even more preferably 5 to 30 mol %.

［式（ａ１－０Ｘ）中、
Ｒ^X1は、水素原子又はメチル基を表す。
Ｒ^x2及びＲ^x3は、それぞれ独立に、炭素数１～６の飽和炭化水素基を表す。
Ａｒ^X1は、炭素数６～３６の芳香族炭化水素基を表す。］ Examples of the structural unit (a1) include a structural unit represented by the formula (a1-0X) (hereinafter sometimes referred to as the structural unit (a1-0X)).

[In formula (a1-0X),
R ^X1 represents a hydrogen atom or a methyl group.
R ^x2 and R ^x3 each independently represent a saturated hydrocarbon group having 1 to 6 carbon atoms.
Ar ^X1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms. ]

Examples of the saturated hydrocarbon group for R ^x2 and R ^x3 include an alkyl group, an alicyclic hydrocarbon group, and a group formed by a combination thereof.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the aromatic hydrocarbon group for Ar ^X1 include aryl groups having 6 to 36 carbon atoms such as phenyl group, naphthyl group, and anthryl group.
The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 1 carbon atoms.
8, more preferably a phenyl group.
Ar ^X1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group.
R ^x1 , R ^x2 and R ^x3 are each independently preferably a methyl group or an ethyl group, more preferably a methyl group.

The structural unit (a1-0X) is the structural unit and structural unit (a1-0X) described below.
Examples include compounds in which the methyl group corresponding to R ^X1 in R X1 is replaced with a hydrogen atom. The structural unit (a1-0X) is preferably one of the structural units (a1-0X-1) to (a1-0X-3).

When the resin (A) has a structural unit (a1-0X), its content is preferably 5 to 60 mol%, and 5 to 50 mol%, based on the total monomers in the resin (A). It is more preferable that the amount is 10 to 40 mol%.
The resin (A) may contain two or more types of structural units (a1-0X).

Moreover, as the structural unit (a1), the following structural units can also be mentioned.

When the resin (A) contains the above structural unit, the content thereof is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and 10 to 40 mol%, based on the total structural units of the resin (A). % is more preferable.

<Structural unit (s)>
As the monomer leading to the structural unit (s), monomers having no acid-labile groups known in the field of resists can be used.
The structural unit (s) preferably has a hydroxy group or a lactone ring. A structural unit having a hydroxy group and not having an acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and/or a structure having a lactone ring and not having an acid-labile group By using a resin having the unit (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group that the structural unit (a2) has may be an alcoholic hydroxy group or a phenolic hydroxy group.
When manufacturing 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 (ultra-ultraviolet light), the structural unit (a2) is a structural unit having a phenolic hydroxy group (
It is preferable to use a2). In addition, when using ArF excimer laser (193 nm) etc., the structural unit (a2) is a structural unit having an alcoholic hydroxyl group (a2
) is preferable, and it is more preferable to use the structural unit (a2-1) described below. Structural unit (
As a2), one type may be included alone, or two or more types may be included.

［式（ａ２－Ａ）中、
Ｒ^a50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^a51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のアルキルカルボニル基、炭素数２～４のアルキルカルボニ
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。
Ａ^a50は、単結合又は^＊－Ｘ^a51－（Ａ^a52－Ｘ^a52）_nｂ－を表し、＊は－Ｒ^a50が結合す
る炭素原子との結合部位を表す。
Ａ^a52は、炭素数１～６のアルカンジイル基を表す。
Ｘ^a51及びＸ^a52は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ｎｂは、０又は１を表す。
ｍｂは０～４のいずれかの整数を表す。ｍｂが２以上のいずれかの整数である場合、複
数のＲ^a51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 is represented by the formula (a2).
-A) (hereinafter sometimes referred to as "structural unit (a2-A)") can be mentioned.

[In formula (a2-A),
R ^a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a51 is a halogen atom, hydroxy group, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl Represents an oxy group or a methacryloyloxy group.
A ^a50 represents a single bond or ^* -X ^a51 -(A ^a52 -X ^a52 ) _nb -, and * represents a bonding site with the carbon atom to which -R ^a50 is bonded.
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent -O-, -CO-O- or -O-CO-.
nb represents 0 or 1.
mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of R ^a51 's may be the same or different. ]

Examples of the halogen atom for R ^a50 include 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 in R ^a50 include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2
-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1, 1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluorohexyl group.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
Examples of the alkyl group for R ^a51 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group.
Examples of the alkoxy group for R ^a51 include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, and tert-butoxy group.
An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred.
Examples of the alkylcarbonyl group for R ^a51 include an acetyl group, a propionyl group, a butyryl group, and the like.
Examples of the alkylcarbonyloxy group for R ^a51 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
R ^a51 is preferably a methyl group.

^* -X ^a51 - (A ^a52 -X ^a52 ) _nb - includes ^* -O-, ^* -CO-O-, ^* -O-C
O-, ^* -CO-O-A ^a52 -CO-O-, ^* -O-CO-A ^a52 -O-, ^* -O-A ^a52
-CO-O-, ^* -CO-O-A ^a52 -O-CO-, ^* -O-CO-A ^a52 -O-CO-,
can be mentioned. Among them, ^* -CO-O-, ^* -CO-O-A ^a52 -CO-O- or ^* -
O-A ^a52 -CO-O- is preferred.

Examples of alkanediyl groups 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,
Examples include 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group.
A ^a52 is preferably a methylene group or an ethylene group.

A ^a50 is preferably a single bond, ^* -CO-O- or ^* -CO-O-A ^a52 -CO-O-, and is preferably a single bond, ^* -CO-O- or ^* -CO-O-CH ₂ -CO-O- is more preferred, and a single bond or ^* -CO-O- is even more preferred.

mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
The hydroxy group is preferably bonded to the o-position or p-position of the benzene ring, more preferably to the p-position.

As the structural unit (a2-A), JP-A No. 2010-204634, JP-A No. 2012-
Examples include structural units derived from monomers described in Japanese Patent No. 12577.

Structural units (a2-A) include structural units represented by formulas (a2-2-1) to (a2-2-6) and formulas (a2-2-1) to (a2-2- Examples of the structural unit represented by 6) include a structural unit in which the methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom. Structural unit (a2-A) is a structural unit represented by formula (a2-2-1),
Structural unit represented by formula (a2-2-3), structural unit represented by formula (a2-2-6) and structural unit represented by formula (a2-2-1), formula (a2-2) -3) Structural unit or formula represented by (
The structural unit represented by a2-2-6) is preferably a structural unit in which the methyl group corresponding to R ^a50 in structural unit (a2-A) is replaced with a hydrogen atom.

When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 5 to 80 mol% based on the total structural units. 10-70
mol%, more preferably 15 to 65 mol%, even more preferably 20 to 65 mol%
It is 65 mol%.
The structural unit (a2-A) can be incorporated into the resin (A) by, for example, treating the resin containing the structural unit (a1-4) with an acid such as p-toluenesulfonic acid. Further, the structural unit (a2-A) can be included in the resin (A) by polymerizing with acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide.

式（ａ２－１）中、
Ｌ^a3は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k2－ＣＯ－Ｏ－を表し、
ｋ２は１～７のいずれかの整数を表す。＊は－ＣＯ－との結合部位を表す。
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のいずれかの整数を表す。 The structural unit (a2) having an alcoholic hydroxy group is represented by the 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 any integer from 1 to 7. * represents a binding site 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 any integer from 0 to 10.

In formula (a2-1), L ^a3 is preferably -O-, -O-(CH ₂ ) _f1 -CO-O-
(the above f1 represents an integer of 1 to 4), and more preferably -O-.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

Examples of the structural unit (a2-1) include structural units derived from monomers described in JP-A-2010-204646. Formula (a2-1-1) to formula (a2-1-6
) are preferably structural units represented by any of formulas (a2-1-1) to (a2-1-4)
A structural unit represented by either of formula (a2-1-1) or formula (a2-1-
The structural unit represented by 3) is more preferred.

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). It is more preferably 1 to 35 mol%, still more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol%.

<Structural unit (a3)>
The lactone ring possessed by the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a fused ring of a monocyclic lactone ring and another ring. But that's fine. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or a γ-butyrolactone ring.
-Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2))
can be mentioned.

［式（ａ３－１）、式（ａ３－２）、式（ａ３－３）及び式（ａ３－４）中、
Ｌ^a4、Ｌ^a5及びＬ^a6は、それぞれ独立に、－Ｏ－又は^＊－Ｏ－（ＣＨ_２）_k3－ＣＯ－Ｏ
－（ｋ３は１～７のいずれかの整数を表す。）で表される基を表す。
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。
Ｌ^a8及びＬ^a9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。
＊はカルボニル基との結合部位を表す。
Ｒ^a18、Ｒ^a19及びＲ^a20は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a24は、ハロゲン原子を有していてもよい炭素数１～６のアルキル基、水素原子又は
ハロゲン原子を表す。
Ｘ^a3は、－ＣＨ_２－又は酸素原子を表す。
Ｒ^a21は炭素数１～４の脂肪族炭化水素基を表す。
Ｒ^a22、Ｒ^a23及びＲ^a25は、それぞれ独立に、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。
ｐ１は０～５のいずれかの整数を表す。
ｑ１は、０～３のいずれかの整数を表す。
ｒ１は、０～３のいずれかの整数を表す。
ｗ１は、０～８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^a21、Ｒ^a22、Ｒ^a23及び／
又はＲ^a25は互いに同一であってもよく、異なっていてもよい。］ The structural unit (a3) is preferably a formula (a3-1), a formula (a3-2), or a formula (a3-3).
Or a structural unit represented by formula (a3-4). One of these may be contained alone,
Two or more types may be contained.

[In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4),
L ^a4 , L ^a5 and L ^a6 are each independently -O- or ^* -O-(CH ₂ ) _k3 -CO-O
-(k3 represents any integer from 1 to 7).
L ^a7 is -O-, ^* -O-L ^a8 -O-, ^* -O-L ^a8 -CO-O-, ^* -O-L ^a8 -C
Represents O-O-L ^a9 -CO-O- or ^* -O-L ^a8 -O-CO-L ^a9 -O-.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* represents a bonding site with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
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.
X ^a3 represents -CH ₂ - or an oxygen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group, or a group having 1 to 1 carbon atoms;
4 represents an aliphatic hydrocarbon group.
p1 represents any integer from 0 to 5.
q1 represents any integer from 0 to 3.
r1 represents any integer from 0 to 3.
w1 represents any integer from 0 to 8.
When p1, q1, r1 and/or w1 are 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and/
Alternatively, R ^a25 may be the same or different. ]

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

Examples of alkanediyl groups in 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-
Examples include methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

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

（式中、Ｒ^a24、Ｌ^a7は、上記と同じ意味を表す。） 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, and even more preferably a hydrogen atom or a methyl group. It is.
R ^a25 is preferably a carboxy group, a cyano group 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-.
w1 is preferably an integer of 0 to 2, more preferably 0 or 1.
In particular, formula (a3-4) is preferably formula (a3-4)'.

(In the formula, R ^a24 and L ^a7 represent the same meanings as above.)

As the structural unit (a3), monomers described in JP-A No. 2010-204646, monomers described in JP-A No. 2000-122294, and JP-A No. 2012-41274 can be used.
Examples include structural units derived from the monomers described in the above publication. As the structural unit (a3), formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2)
, formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-1)
2) and the structural unit represented by formula (a3-1) to formula (
Structural units in which the methyl groups corresponding to R ^a18 , R ^a19 , R ^a20 and R ^a24 in a3-4) are replaced with hydrogen atoms are preferred.

When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on the total structural units of the resin (A). , more preferably 10 to 60 mol%.
In addition, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), or the structural unit (a3-4) is relative to the total structural units of the resin (A), respectively. The amount is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, even more preferably 10 to 50 mol%.

［式（ａ４）中、
Ｒ⁴¹は、水素原子又はメチル基を表す。
Ｒ⁴²は、炭素数１～２４のフッ素原子を有する飽和炭化水素基を表し、該飽和炭化水素
基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯに置き換わっていてもよい。］
Ｒ⁴²で表される飽和炭化水素基は、鎖式炭化水素基及び単環又は多環の脂環式炭化水素
基、並びに、これらを組み合わせることにより形成される基等が挙げられる。 <Structural unit (a4)>
Examples of the structural unit (a4) include the following structural units.

[In formula (a4),
R ⁴¹ represents a hydrogen atom or a methyl group.
R ⁴² represents a saturated hydrocarbon group having 1 to 24 carbon atoms and having a fluorine atom, and -CH ₂ - contained in the saturated hydrocarbon group may be replaced with -O- or -CO. ]
Examples of the saturated hydrocarbon group represented by R ⁴² include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

組み合わせにより形成される基としては、１以上のアルキル基又は１以上のアルカンジ
イル基と、１以上の脂環式炭化水素基とを組み合わせることにより形成される基が挙げら
れ、－アルカンジイル基－脂環式炭化水素基、－脂環式炭化水素基－アルキル基、－アル
カンジイル基－脂環式炭化水素基－アルキル基等が挙げられる。 Examples of chain hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group,
Examples include hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group.
Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups. Examples include polycyclic alicyclic hydrocarbon groups such as (* represents a bonding site).

Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups and one or more alicyclic hydrocarbon groups, such as -alkanediyl group- Examples include alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, and the like.

［式（ａ４－０）中、
Ｒ^5aは、水素原子又はメチル基を表す。
Ｌ^4aは、単結合又は炭素数１～４のアルカンジイル基を表す。
Ｌ^3a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^6aは、水素原子又はフッ素原子を表す。］ As the structural unit (a4), formula (a4-0), formula (a4-1), formula (a4-2), formula (
a4-3) and a structural unit represented by at least one selected from the group consisting of formula (a4-4).

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

As the alkanediyl group in L ^4a , methylene group, ethylene group, propane-1,3
-diyl group, linear alkanediyl group such as butane-1,4-diyl group, ethane-1,1-
Branched alkanediyl groups such as diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group Examples include groups.

Examples of the perfluoroalkanediyl group in L ^3a include a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, and a perfluoropropane-1,1-diyl group.
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.
Examples of the perfluorocycloalkanediyl group for L ^3a include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

L ^4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group.
L ^3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

As the structural unit (a4-0), the structural units shown below and the structural units (
Examples include structural units in which the methyl group corresponding to R ^5a in a4-0) is replaced with a hydrogen atom.

〔式（ａ－ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１～５の２価の
飽和炭化水素基を表す。
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２価の脂肪族炭化水素
基を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、－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。〕
＊は結合部位を表し、右側の＊が－Ｏ－ＣＯ－Ｒ^a42との結合部位を表す。］ [In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group is replaced with -O- or -CO-. You can.
A ^a41 is an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or the formula (a-g
Represents a group represented by 1). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 are each independently -O-, -CO-, -CO-O- or -O-CO
- represents.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* represents a binding site, and the * on the right side represents a binding site with -O-CO-R ^a42 . ]

Examples of the saturated hydrocarbon group for R ^a42 include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

組み合わせにより形成される基としては、１以上のアルキル基又は１以上のアルカンジ
イル基と、１以上の脂環式飽和炭化水素基とを組み合わせることにより形成される基が挙
げられ、－アルカンジイル基－脂環式飽和炭化水素基、－脂環式飽和炭化水素基－アルキ
ル基、－アルカンジイル基－脂環式飽和炭化水素基－アルキル基等が挙げられる。 Examples of chain saturated hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. can be mentioned. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group, and the following. Examples include polycyclic alicyclic saturated hydrocarbon groups such as groups (* represents a bonding site).

Examples of groups formed by a combination include groups formed by combining one or more alkyl groups or one or more alkanediyl groups and one or more alicyclic saturated hydrocarbon groups, and -alkanediyl groups -Alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group, and the like.

［式（ａ－ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊は
Ｒ^a42との結合部位を表す。）。
Ａ^a45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
。
＊は結合部位を表す。］
ただし、Ｒ^a42－Ｘ^a43－Ａ^a45において、Ｒ^a42がハロゲン原子を有しない場合は、Ａ^a4
5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
。 Examples of the substituent that R ^a42 may have include at least one selected from the group consisting of a halogen atom and a group represented by formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[In formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O- (* represents a bonding site with R ^a42 ).
A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* represents a binding site. ]
However, in R ^a42 -X ^a43 -A ^a45 , if R ^a42 does not have a halogen atom, A ^a4
5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and having at least one halogen atom.

組み合わせにより形成される基としては、１以上のアルキル基又は１以上のアルカンジ
イル基と、１以上の脂環式炭化水素基とを組み合わせることにより形成される基が挙げら
れ、－アルカンジイル基－脂環式炭化水素基、－脂環式炭化水素基－アルキル基、－アル
カンジイル基－脂環式炭化水素基－アルキル基等が挙げられる。 The aliphatic hydrocarbon groups in A ^a45 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and Alkyl groups such as octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; and decahydronaphthyl group, adamantyl group, norbornyl group and the following groups Examples include polycyclic alicyclic hydrocarbon groups such as (* represents a bonding site).

Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups and one or more alicyclic hydrocarbon groups, such as -alkanediyl group- Examples thereof include alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

R ^a42 is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably a saturated hydrocarbon group having an alkyl group having a halogen atom and/or a group represented by formula (a-g3).
When R ^a42 is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and even more preferably a group having 1 to 1 carbon atoms. 6 perfluoroalkyl group, particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), the formula (a-
The total number of carbon atoms in R ^a42 including the number of carbon atoms contained in the group represented by g3) is preferably 15 or less, more preferably 12 or less. When having a group represented by formula (a-g3) as a substituent,
The number 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２価の飽和炭化水素基を
表す。
Ｘ^a44は、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＡ^a46との結合部位を表す。
）。
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部位を表す。］ When R ^a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R ^a42 is more preferably a group represented by formula (a-g2).

[In formula (a-g2),
A ^a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents *-O-CO- or *-CO-O- (* represents the binding site with A ^a46 .
).
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 at least one of A ^a46 and A ^a47 has at least one halogen atom.
* represents a bonding site with a carbonyl group. ]

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

A preferable structure of the group represented by formula (a-g2) is the following structure (* represents a bonding site with a carbonyl group).

The alkanediyl group in A ^a41 includes methylene group, ethylene group, propane-1,
3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1
,6-diyl group; linear alkanediyl group such as propane-1,2-diyl group, butane-1
,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-
Branched alkanediyl groups such as diyl group and 2-methylbutane-1,4-diyl group can be mentioned.
Substituents in the alkanediyl group represented by A ^a41 include a hydroxy group and a group having 1 to 1 carbon atoms.
6 alkoxy groups and the like.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

The divalent saturated hydrocarbon groups represented by A ^a42 , A ^a43 and A ^a44 in the group represented by formula (a-g1) include linear or branched alkanediyl groups and monocyclic or polycyclic divalent hydrocarbon groups. Examples thereof include an alicyclic hydrocarbon group and a group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. 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-methylpropane-1,3-diyl group, 2-methylpropane-1
, 2-diyl group, etc.
Examples of the substituent for the divalent saturated hydrocarbon group represented by A ^a42 , A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
Preferably, s is 0.

Examples of the group represented by formula (a-g1) in which X ^a42 is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a binding site, and ** represents a binding site with -O-CO-R ^a42 .

As the structural unit represented by formula (a4-1), the methyl group corresponding to R ^a41 in the structural unit shown below and the structural unit represented by formula (a4-1) in the following structural unit is a hydrogen atom. Examples include substituted structural units.

［式（ａ４－２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ⁴⁴は、炭素数１～６のアルカンジイル基を表し、該アルカンジイル基に含まれる－Ｃ
Ｈ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ｒ^f6は、炭素数１～２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ⁴⁴及びＲ^f6の合計炭素数の上限は２１である。］ The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2).

[In formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴⁴ represents an alkanediyl group having 1 to 6 carbon atoms, and -C contained in the alkanediyl group
H ₂ - may be replaced with -O- or -CO-.
R ^f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom.
However, the upper limit of the total number of carbon atoms in L ⁴⁴ and R ^f6 is 21. ]

Examples of the alkanediyl group for L ⁴⁴ include the same groups as exemplified for L ^4a .
Examples of the saturated hydrocarbon group for R ^f6 include the same groups as exemplified for R ^a42 .
The alkanediyl group in L ⁴⁴ is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

Examples of the structural unit represented by formula (a4-2) include formulas (a4-1-1) to (a4
-1-11), respectively. A structural unit in which the methyl group corresponding to R ^f5 in structural unit (a4-2) is replaced with a hydrogen atom is also included as the structural unit represented by formula (a4-2).

［式（ａ４－３）中、
Ｒ^f7は、水素原子又はメチル基を表す。
Ｌ⁵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２価の飽和炭化水素基を表
す。
Ｘ^f12は、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＡ^f13との結合部位を表す。
）。
Ａ^f14は、フッ素原子を有していてもよい炭素数１～１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14
の合計炭素数の上限は２０である。］

[In formula (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
X ^f12 represents *-O-CO- or *-CO-O- (* represents the binding site with A ^f13 .
).
A ^f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 has a fluorine atom, and L ⁵ , A ^f13 and A ^f14
The upper limit of the total number of carbon atoms is 20. ]

Examples of the alkanediyl group for L ⁵ include the same groups as exemplified for the alkanediyl group for L ^4a .

The divalent saturated hydrocarbon group which may have a fluorine atom in A ^f13 is preferably a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent saturated hydrocarbon group which may have a fluorine atom. A divalent alicyclic saturated hydrocarbon group is preferable, and a perfluoroalkanediyl group is more preferable.
Examples of the divalent chain hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; difluoromethylene group, perfluoroethylene group, perfluoroethylene group, etc. Examples include perfluoroalkanediyl groups such as a propanediyl group, a perfluorobutanediyl group, and a perfluoropentanediyl group.
The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

Examples of the saturated hydrocarbon group of A ^f14 and the saturated hydrocarbon group which may have a fluorine atom include the same groups as those exemplified for R ^a42 . Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1
,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,
3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,
2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2
, 2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, and perfluorooctyl group. group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, A perfluoroadamantylmethyl group is preferred.

In formula (a4-3), L ⁵ is preferably an ethylene group.
The divalent saturated hydrocarbon group of A ^f13 is a divalent chain hydrocarbon group having 1 to 6 carbon atoms, and a divalent chain hydrocarbon group having 3 carbon atoms.
A group containing a divalent alicyclic hydrocarbon group having ~12 carbon atoms is preferred, and a divalent chain hydrocarbon group having 2 to 3 carbon atoms is more preferred.
The saturated hydrocarbon group of A ^f14 is preferably a group containing a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a chain hydrocarbon group having 3 to 10 carbon atoms. and carbon number 3-1
More preferred is a group containing 0 alicyclic hydrocarbon groups. Among these, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

Examples of the structural unit represented by formula (a4-3) include formulas (a4-1'-1) to (a
Examples include structural units represented by 4-1'-11). A structural unit in which the methyl group corresponding to R ^f7 in structural unit (a4-3) is replaced with a hydrogen atom is also included as the structural unit represented by formula (a4-3).

［式（ａ４－４）中、
Ｒ^f21は、水素原子又はメチル基を表す。
Ａ^f21は、－（ＣＨ₂）_j1－、－（ＣＨ₂）_j2－Ｏ－（ＣＨ₂）_j3－又は－（ＣＨ₂）_j4－
ＣＯ－Ｏ－（ＣＨ₂）_j5－を表す。
ｊ１～ｊ５は、それぞれ独立に、１～６のいずれかの整数を表す。
Ｒ^f22は、フッ素原子を有する炭素数１～１０の飽和炭化水素基を表す。］ The structural unit (a4) also includes a structural unit 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 -(CH ₂ ) _j4 -
Represents CO-O-(CH ₂ ) _j5 -.
j1 to j5 each independently represent an integer of 1 to 6.
R ^f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom. ]

Examples of the saturated hydrocarbon group for R ^f22 include the same saturated hydrocarbon group as the saturated hydrocarbon group represented by R ^a42 .
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, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom. Preferably, an alkyl group having 1 to 6 carbon atoms and having a fluorine atom is more preferable.

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

As the structural unit represented by formula (a4-4), for example, in the following structural units and the structural unit represented by the following formula, the methyl group corresponding to R ^f21 in structural unit (a4-4) is hydrogen. Examples include structural units that replace atoms.

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

［式（ａ５－１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²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で置換されていてもよい。
Ｌ⁵⁵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－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group possessed by the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Among these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by formula (a5-1).

[In formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. .
L ⁵⁵ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. . ]

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

Examples of the divalent saturated hydrocarbon group in L ⁵⁵ include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent chain saturated hydrocarbon group. .
Examples of the divalent chain saturated hydrocarbon group include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group, and pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include 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.

式（Ｌ１－１）中、
Ｘ^x1は、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＬ^x１との結合部位を表す。
）。
Ｌ^x1は、炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x2は、単結合又は炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x1及びＬ^x2の合計炭素数は、１６以下である。
式（Ｌ１－２）中、
Ｌ^x3は、炭素数１～１７の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x4は、単結合又は炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x3及びＬ^x4の合計炭素数は、１７以下である。
式（Ｌ１－３）中、
Ｌ^x5は、炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x6及びＬ^x7は、それぞれ独立に、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。 Examples of groups in which -CH ₂ - contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ are replaced with -O- or -CO- include formulas (L1-1) to (L1-4). The groups represented are exemplified. In the following formula, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom.

In formula (L1-1),
X ^x1 represents *-O-CO- or *-CO-O- (* represents a binding site with L ^x1 .
).
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 and L ^x4 is 17 or less.
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 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 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated 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,
It is a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably,
It is a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.
W ^x1 is preferably a divalent alicyclic saturated 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 following divalent groups.

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 ⁵⁵ is preferably a single bond or a group represented by formula (L1-1).

As the structural unit (a5-1), the structural units shown below and the structural units (
Examples include structural units in which the methyl group corresponding to R ⁵¹ in a5-1) is replaced with a hydrogen atom.

樹脂（Ａ）が、構造単位（ａ５）を有する場合、その含有率は、樹脂（Ａ）の全構造単
位に対して、１～３０モル％が好ましく、２～２０モル％がより好ましく、３～１５モル
％がさらに好ましい。

When the resin (A) has a structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 3 to 30 mol%, based on the total structural units of the resin (A). More preferably 15 mol%.

<Structural unit (II)>
The resin (A) may further contain a structural unit (hereinafter sometimes referred to as "structural unit (II)") that decomposes and generates an acid upon exposure to light. Examples include the structural unit described in JP-A-2016-79235, which is a structural unit having a sulfonate group or carboxylate group and an organic cation in the side chain, or a structural unit having a sulfonio group and an organic anion in the side chain. It is preferable that there be.

［式（ＩＩ－２－Ａ’）中、
Ｘ^III3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－ＣＨ_２－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよく、該飽和炭化水
素基に含まれる水素原子は、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１～
６のアルキル基又はヒドロキシ基で置き換わっていてもよい。
Ａ^x1は、炭素数１～８のアルカンジイル基を表し、該アルカンジイル基に含まれる水素
原子は、フッ素原子又は炭素数１～６のペルフルオロアルキル基で置換されていてもよい
。
ＲＡ^－は、スルホナート基又はカルボキシレート基を表す。
Ｒ^III3は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６
のアルキル基を表す。
ＺＡ^＋は、有機カチオンを表す。］ The structural unit having a sulfonate group or carboxylate group and an organic cation in its side chain is preferably a structural unit represented by formula (II-2-A').

[In formula (II-2-A'),
X ^III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group may be replaced with -O-, -S- or -CO-. Often, the hydrogen atom contained in the saturated hydrocarbon group is a halogen atom, or a hydrogen atom having 1 to 1 carbon atoms that may contain a halogen atom.
6 may be substituted with an alkyl group or a hydroxy group.
A ^x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
RA ⁻ represents a sulfonate group or a carboxylate group.
R ^III3 is a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 which may contain a halogen atom;
represents an alkyl group.
ZA ⁺ represents an organic cation. ]

Examples of the halogen atom represented by R ^III3 include fluorine atom, chlorine atom, bromine atom, and iodine atom.
The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom represented by R ^III3 includes the alkyl group having 1 to 6 carbon atoms optionally having a halogen atom represented by R ^a8 ; The same things can be mentioned.
The alkanediyl group having 1 to 8 carbon atoms represented by A ^x1 includes a methylene group, an ethylene group,
Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-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-1,3-diyl group, 2-methylpropane-1, Examples thereof include 2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted with A ^x1 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert group. -butyl group, perfluoropentyl group, perfluorohexyl group, etc.
Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X ^III3 include a linear or branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. or a combination thereof.
Specifically, 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, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-
Linear alkanediyl groups such as 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group; butane-1,3-diyl group ,
Branched alkanediyl groups such as 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group ; Cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; norbornane-1,4 Examples include divalent polycyclic alicyclic saturated hydrocarbon groups such as -diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.
Examples of saturated hydrocarbon groups in which -CH ₂ - is replaced with -O-, -S- or -CO- include divalent groups represented by formulas (X1) to (X53). Can be mentioned. However, the number of carbon atoms in each of the saturated hydrocarbon groups before --CH ₂ -- is replaced with --O-, --S-, or --CO- is 17 or less. In the formula below, * and ** represent the binding site,
* represents the binding site with A ^X1 .

X ³ represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.
X ⁴ represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
X ⁵ represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
X ⁶ represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
X ⁷ represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms.
X ⁸ represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

Examples of the organic cation represented by ZA ⁺ include organic onium cations, such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, organic benzothiazolium cations, and organic phosphonium cations, and organic sulfonium cations and organic iodonium cations. are preferred, and arylsulfonium cations are more preferred.
ZA ⁺ in formula (II-2-A') represents the organic cation Z in the acid generator (B1) described below.
Examples include those similar to ⁺ .

［式（ＩＩ－２－Ａ）中、Ｒ^III3、Ｘ^III3及びＺＡ^＋は、上記と同じ意味を表す。
ｚ２Ａは、０～６のいずれかの整数を表す。
Ｒ^III2及びＲ^III4は、それぞれ独立して、水素原子、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し、ｚが２以上のとき、複数のＲ^III2及びＲ^III4は互いに同一
であってもよいし、異なっていてもよい。
Ｑ^ａ及びＱ^ｂは、それぞれ独立して、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。］
Ｒ^III2、Ｒ^III４、Ｑ^ａ及びＱ^ｂで表される炭素数１～６のペルフルオロアルキル基と
しては、後述のＱ^b1で表される炭素数１～６のペルフルオロアルキル基と同じものが挙げ
られる。 The structural unit represented by formula (II-2-A') is preferably a structural unit represented by formula (II-2-A).

[In formula (II-2-A), R ^III3 , X ^III3 and ZA ⁺ represent the same meanings as above.
z2A represents any integer from 0 to 6.
R ^III2 and R ^III4 each independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms, and when z is 2 or more, a plurality of R ^III2 and R ^III4 are the same as each other; It may be different or it may be different.
Q ^a and Q ^b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. ]
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R ^III2 , R ^III4 , Q ^a and Q ^b include the same perfluoroalkyl group having 1 to 6 carbon atoms represented by Q ^b1 described below. .

［式（ＩＩ－２－Ａ－１）中、
Ｒ^III2、Ｒ^III3、Ｒ^III4、Ｑ^a、Ｑ^b及びＺＡ^＋は、上記と同じ意味を表す。
Ｒ^III5は、炭素数１～１２の飽和炭化水素基を表す。
ｚ２Ａ１は、０～６のいずれかの整数を表す。
Ｘ^I2は、炭素数１～１１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
－ＣＨ_２－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよく、該飽和炭化水素
基に含まれる水素原子は、ハロゲン原子又はヒドロキシ基で置換されていてもよい。］
Ｒ^III5で表される炭素数１～１２の飽和炭化水素基としては、メチル基、エチル基、プ
ロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチ
ル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基及びド
デシル基等の直鎖又は分岐のアルキル基が挙げられる。
Ｘ^I2で表される２価の飽和炭化水素基としては、Ｘ^III3で表される２価の飽和炭化水素
基と同様のものが挙げられる。 The structural unit represented by formula (II-2-A) is preferably a structural unit represented by formula (II-2-A-1).

[In formula (II-2-A-1),
R ^III2 , R ^III3 , R ^III4 , Q ^a , Q ^b and ZA ⁺ represent the same meanings as above.
R ^III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
z2A1 represents any integer from 0 to 6.
X ^I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group may be replaced with -O-, -S- or -CO-. Often, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group. ]
The saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ^III5 includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Straight chain or branched alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group are mentioned.
Examples of the divalent saturated hydrocarbon group represented by X ^I2 include those similar to the divalent saturated hydrocarbon group represented by X ^III3 .

［式（ＩＩ－２－Ａ－２）中、Ｒ^III3、Ｒ^III5及びＺＡ^＋は、上記と同じ意味を表す。
ｍ及びｎは、互いに独立に、１又は２を表す。］ As the structural unit represented by formula (II-2-A-1), a structural unit represented by formula (II-2-A-2) is more preferable.

[In formula (II-2-A-2), R ^III3 , R ^III5 and ZA ⁺ represent the same meanings as above.
m and n each independently represent 1 or 2. ]

Examples of the structural unit represented by formula (II-2-A') include the following structural units and the structural units described in International Publication No. 2012/050015. ZA ⁺ represents an organic cation.

［式（ＩＩ－１－１）中、
Ａ^II1は、単結合又は２価の連結基を表す。
Ｒ^II1は、炭素数６～１８の２価の芳香族炭化水素基を表す。
Ｒ^II2及びＲ^II3は、それぞれ独立して、炭素数１～１８の炭化水素基を表し、Ｒ^II2及
びＲ^II3は互いに結合してそれらが結合する硫黄原子とともに環を形成していてもよい。
Ｒ^II4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。
Ａ^－は、有機アニオンを表す。］
Ｒ^II1で表される炭素数６～１８の２価の芳香族炭化水素基としては、フェニレン基及
びナフチレン基等が挙げられる。
Ｒ^II2及びＲ^II3で表される炭化水素基としては、アルキル基、脂環式炭化水素基、芳香
族炭化水素基及びこれらを組み合わせることにより形成される基等が挙げられる。具体的
には、Ｒ^a1’、Ｒ^a2’及びＲ^a3’における炭化水素基と同じものが挙げられる。
Ｒ^II4で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素
原子等が挙げられる。
Ｒ^II4で表されるハロゲン原子を有していてもよい炭素数１～６のアルキル基としては
、Ｒ^a8で表されるハロゲン原子を有していてもよい炭素数１～６のアルキル基と同じもの
が挙げられる。
Ａ^II1で表される２価の連結基としては、例えば、炭素数１～１８の２価の飽和炭化水
素基が挙げられ、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－又は
－ＣＯ－で置き換わっていてもよい。具体的には、Ｘ^III3で表される炭素数１～１８の２
価の飽和炭化水素基と同じものが挙げられる。 The structural unit having a cation having a sulfonio group in the side chain and an organic anion has the formula (II
A structural unit represented by -1-1) is preferable.

[In formula (II-1-1),
A ^II1 represents a single bond or a divalent linking group.
R ^II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^II2 and R ^II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R ^II2 and R ^II3 may be bonded to each other to form a ring with the sulfur atom to which they are bonded.
R ^II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
A ⁻ represents an organic anion. ]
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^II1 include a phenylene group and a naphthylene group.
Examples of the hydrocarbon group represented by R ^II2 and R ^II3 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. Specifically, the same hydrocarbon groups as R ^a1' , R ^a2' and R ^a3' can be mentioned.
Examples of the halogen atom represented by R ^II4 include fluorine atom, chlorine atom, bromine atom, and iodine atom.
The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom represented by R ^II4 includes the alkyl group having 1 to 6 carbon atoms optionally having a halogen atom represented by R ^a8 ; The same things can be mentioned.
Examples of the divalent linking group represented by A ^II1 include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH ₂ - contained in the divalent saturated hydrocarbon group is It may be replaced with -O-, -S- or -CO-. Specifically, 2 having 1 to 18 carbon atoms represented by X ^III3
The same groups as the saturated hydrocarbon groups can be mentioned.

As the structural unit containing a cation in formula (II-1-1), the structural unit represented below and the group corresponding to the methyl group of R ^II4 are replaced with a hydrogen atom, a fluorine atom, trifluoromethyl, etc. Examples include structural units.

Examples of the organic anion represented by A ^- include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, and carboxylic acid anions. The organic anion represented by A ^- is preferably a sulfonate anion, and the sulfonate anion is more preferably an anion contained in a salt represented by formula (B1) described below.

Examples of the sulfonylimide anion represented by A ^- include the following.

Examples of sulfonyl methide anions include the following.

Examples of carboxylic acid anions include the following.

Examples of the structural unit represented by formula (II-1-1) include the structural units shown below.

When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol%, and more preferably 1 to 20 mol% based on the total structural units of the resin (A). Preferably 2~
The content is 15 mol%, more preferably 3 to 10 mol%.

The resin (A) may have structural units other than the above-mentioned structural units, and examples of such structural units include structural units well known in the art.

The resin (A) is preferably a resin consisting of a structural unit (I) and an acid labile group, a resin consisting of a structural unit (I) and a structural unit (a1), a resin consisting of a structural unit (I) and a structural unit (s ), a resin consisting of a structural unit (I), a structural unit (a1) and a structural unit (s), a resin consisting of a structural unit (I), a structural unit (a1), a structural unit (s) and a structural unit (a4). ) and/or structural unit (a
5), a resin consisting only of the structural unit (I), or a resin consisting only of the structural unit (I) and the structural unit (a4), more preferably a resin consisting of the structural unit (I) and the structural unit (
A resin consisting of a1) and a structural unit (s), a resin consisting of a structural unit (I) and a structural unit (s), or only a structural unit (I), a structural unit (a4), and a structural unit (a5) A resin consisting only of the structural unit (I) and the structural unit (a4), and a resin consisting only of the structural unit (I), the structural unit (a4), and the structural unit (a1).
The content of the structural unit (I) is usually 1 to 20 mol%, preferably 2 to 10 mol%, more preferably 2 to 6 mol%, based on the total monomers in the resin (A). .
When the resin (A) contains a structural unit represented by formula (a4) and/or (a5) (hereinafter sometimes referred to as "resin (AX)"), the structural unit ( The content of I) is preferably 2 to 10 mol% based on the total of all structural units of the resin (AX) of the present invention.
and more preferably 2 to 6 mol%.

Structural unit (a1) preferably contains structural unit (a1-0), structural unit (a1-0X), structural unit (a1-1) and structural unit (a1-2) (preferably a cyclohexyl group and a cyclopentyl group). Structural unit (a1-0), structural unit (a1-0X), structural unit (a1-1), and structural unit (a1-2). (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
The structural unit (s) is preferably at least one type selected from the group consisting of the structural unit (a2) and the structural unit (a3). Structural unit (a2) is preferably a structural unit represented by formula (a2-A). Structural unit (a3) is preferably a group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2), and a structural unit represented by formula (a3-4). At least one type selected from

Each structural unit constituting the resin (A) may be used alone or in combination of two or more,
It can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that leads to these structural units. 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 the resin (A) is preferably 2,000 or more (more preferably 2,50
0 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 this specification, the weight average molecular weight is a value determined by gel permeation chromatography. Gel permeation chromatography can be measured using the analysis conditions described in Examples.

[Resist composition]
The resist composition of the present invention preferably contains a resin (A) and an acid generator known in the resist field (hereinafter sometimes referred to as "acid generator (B)").
It is preferable that the resist composition of the present invention further contains a resin other than the resin (A).
The resist composition of the present invention preferably contains a quencher (hereinafter sometimes referred to as "quencher (C)") such as a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator. , a solvent (hereinafter sometimes referred to as "solvent (E)") is preferably contained.

<Resin other than resin (A)>
The resist composition of the present invention may contain resins other than resin (A). Resins other than resin (A) are resins that do not contain the structural unit (I), and examples of such resins include, for example, resins that have a structural unit that has an acid-labile group and that do not contain the structural unit (I). Resin that does not contain (hereinafter referred to as “resin (A)
2)"), a resin consisting only of the structural unit (a4), and a structural unit (a4)
and structural unit (a5) (hereinafter, a resin consisting only of structural unit (a4) and a resin consisting of structural unit (a4) and structural unit (a5) may be collectively referred to as resin (X). ) etc.

In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total of all structural units of the resin (X). , more preferably 45 mol% or more.

Each structural unit constituting the resin (X) may be used alone or in combination of two or more,
It can be produced by a known polymerization method (eg, radical polymerization method) using a monomer that induces these structural units. The content of each structural unit in the resin (X) can be adjusted by adjusting the amount of monomer used for polymerization.
The weight average molecular weights of resin (A2) and resin (X) are each independently preferably 6,
000 or more (more preferably 7,000 or more), 80,000 or less (more preferably 60
,000 or less). The means for measuring the weight average molecular weight of resin (A2) and resin (X) is the same as that for resin (A).
When the resist composition of the present invention contains resin (A2), the content is 10
Usually 1 to 2,500 parts by mass (more preferably 10 to 1,000 parts by mass) relative to 0 parts by mass
It is.
Further, when the resist composition contains resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of resin (A). ,
The amount is more preferably 1 to 40 parts by weight, particularly preferably 1 to 30 parts by weight, and particularly preferably 1 to 8 parts by weight.

The content of the resin (A) in the resist composition is 8% based on the solid content of the resist composition.
It is preferably from 0% by mass to 99% by mass, more preferably from 90 to 99% by mass.
In addition, when a resin other than the resin (A) is included, the total content of the resin (A) and the resin other than the resin (A) is 80% by mass or more and 99% by mass based on the solid content of the resist composition. It is preferably below, more preferably 90 to 99% by mass. The solid content of the resist composition and the resin content relative to the solid content can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator (B) may be either nonionic or ionic. Examples of nonionic acid generators include sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane), etc. Typical ionic acid generators include onium salts containing onium cations (eg, diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts). Examples of the anion of the onium salt include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, and the like.

As the acid generator (B), JP-A-63-26653, JP-A-55-164824,
JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP 63-146029, US Patent No. 3,779,
Compounds that generate acids by radiation as described in No. 778, US Pat. No. 3,849,137, German Patent No. 3,914,407, European Patent No. 126,712, etc. can be used. Moreover, you may use the compound manufactured by the well-known method. The acid generator (B) may be used in combination of two or more types.

［式（Ｂ１）中、
Ｑ^b1及びＱ^b2は、それぞれ独立に、フッ素原子又は炭素数１～６のペルフルオロアルキ
ル基を表す。
Ｌ^b1は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含
まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化
水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１
８の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－ＣＨ_２－は、－Ｏ－、－
Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, more preferably represented by formula (B1)
(hereinafter sometimes referred to as "acid generator (B1)").

[In formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y is a methyl group that may have a substituent or a carbon number of 3 to 1 that may have a substituent
-CH ₂ - contained in the alicyclic hydrocarbon group represents -O-, -
It may be replaced with S(O) ₂ - or -CO-.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl groups represented by Q ^b1 and Q ^b2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, and Examples include perfluorohexyl group.
Q ^b1 and Q ^b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group in L ^b1 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may also be a group formed by combining two or more of the groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4
-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1
,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1
, 10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group,
tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-
1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-
Straight-chain alkanediyl groups such as diyl groups;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-
Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group;
A monocyclic cycloalkanediyl group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, or a cyclooctane-1,5-diyl group. alicyclic saturated hydrocarbon group;
norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-
Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as 1,5-diyl group and adamantane-2,6-diyl group.

Examples of groups in which -CH ₂ - contained in the divalent saturated hydrocarbon group represented by L ^b1 are replaced with -O- or -CO- include formulas (b1-1) to (b1-3) Examples include groups represented by any of the following. In addition, in the groups represented by formulas (b1-1) to (b1-3) and the groups represented by formulas (b1-4) to (b1-11), which are specific examples thereof, * and * * represents a binding site; * represents a binding site with -Y.

［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－ＣＨ_２－は、－Ｏ－又は－ＣＯ－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－ＣＨ_２－は、－Ｏ－又は－ＣＯ－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－ＣＨ_２－は、－Ｏ－又は－ＣＯ－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。］

[In formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated -CH ₂ - contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total carbon number 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 the 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, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated -CH ₂ - contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total carbon number 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated -CH ₂ - contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total carbon number of L ^b6 and L ^b7 is 23 or less. ]

In the groups represented by formulas (b1-1) to (b1-3), when -CH ₂ - contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the carbon before being replaced The number is the number of carbon atoms in the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L ^b1 .
L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group,
-CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.
The group in which -CH ₂ - contained in the divalent saturated hydrocarbon group represented by L ¹ is replaced with -O- or -CO- is represented by formula (b1-1) or formula (b1-3). Preferred groups are

［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い。
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い。
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い。
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。］
Ｌ^b8は、好ましくは炭素数１～４の２価の飽和炭化水素基である。
Ｌ^b9は、好ましくは炭素数１～８の２価の飽和炭化水素基である。
Ｌ^b10は、好ましくは単結合又は炭素数１～１９の２価の飽和炭化水素基であり、より
好ましくは単結合又は炭素数１～８の２価の飽和炭化水素基である。
Ｌ^b11は、好ましくは炭素数１～８の２価の飽和炭化水素基である。
Ｌ^b12は、好ましくは単結合又は炭素数１～８の２価の飽和炭化水素基である。
Ｌ^b13は、好ましくは炭素数１～１２の２価の飽和炭化水素基である。
Ｌ^b14は、好ましくは単結合又は炭素数１～６の２価の飽和炭化水素基である。
Ｌ^b15は、好ましくは単結合又は炭素数１～１８の２価の飽和炭化水素基であり、より
好ましくは単結合又は炭素数１～８の２価の飽和炭化水素基である。
Ｌ^b16は、好ましくは炭素数１～１２の２価の飽和炭化水素基である。
Ｌ^b17は、好ましくは炭素数１～６の２価の飽和炭化水素基である。
Ｌ^b18は、好ましくは単結合又は炭素数１～１７の２価の飽和炭化水素基であり、より
好ましくは単結合又は炭素数１～４の２価の飽和炭化水素基である。 Examples of the group represented by formula (b1-1) include groups represented by formulas (b1-4) to (b1-8), respectively.

[In formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In 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 the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In 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, and -CH ₂ - contained in the divalent saturated hydrocarbon group is replaced with -O- or -CO-. Good too.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total 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, and -CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total 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 divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

式（ｂ１－９）中、
Ｌ^b19は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素
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ルキルカルボニルオキシ基に
置換されていてもよい。該アルキルカルボニルオキシ基に含まれる－ＣＨ₂－は、－Ｏ－
又は－ＣＯ－に置き換わっていてもよく、該アルキルカルボニ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ルキルカルボニルオキシ基に
置換されていてもよい。該アルキルカルボニルオキシ基に含まれる－ＣＨ₂－は、－Ｏ－
又は－ＣＯ－に置き換わっていてもよく、該アルキルカルボニ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^b22及び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ルキルカルボニルオキシ基に
置換されていてもよい。該アルキルカルボニルオキシ基に含まれる－ＣＨ₂－は、－Ｏ－
又は－ＣＯ－に置き換わっていてもよく、該アルキルカルボニ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^b25及びＬ^b26の合計炭素数は２１以下である。 Examples of the group represented by formula (b1-3) include groups represented by formulas (b1-9) to (b1-11), respectively.

In formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. Good too. -CH ₂ - contained in the alkylcarbonyloxy group is -O-
Alternatively, it may be substituted with -CO-, and the hydrogen atom contained in the alkylcarbonyloxy 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. Good too. -CH ₂ - contained in the alkylcarbonyloxy group is -O-
Alternatively, it may be substituted with -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. Good too. -CH ₂ - contained in the alkylcarbonyloxy group is -O-
Alternatively, it may be substituted with -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b24 , L ^b25 and L ^b26 is 21 or less.

In addition, in the group represented by formula (b1-9) to the group represented by formula (b1-11), when the hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group,
The number of carbon atoms before substitution is defined as the number of carbon atoms of the saturated hydrocarbon group.

Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.

Examples of the group represented by formula (b1-4) include the following.

Examples of the group represented by formula (b1-5) include the following.

Examples of the group represented by formula (b1-6) include the following.

Examples of the group represented by formula (b1-7) include the following.

Examples of the group represented by formula (b1-8) include the following.

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

Examples of the group represented by formula (b1-9) include the following.

Examples of the group represented by formula (b1-10) include the following.

Examples of the group represented by formula (b1-11) include the following.

The alicyclic hydrocarbon group represented by Y includes formulas (Y1) to (Y11), and formulas (Y36) to
Examples include a group represented by formula (Y38).
-CH ₂ - contained in the alicyclic hydrocarbon group represented by Y is -O-, -S(O) ₂ - or -
When replaced with CO-, the number may be one or two or more. Examples of such groups include groups represented by formulas (Y12) to (Y35) and formulas (Y39) to (Y41).

Ｙで表される脂環式炭化水素基としては、好ましくは式（Ｙ１）～式（Ｙ２０）、式（
Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）～式（Ｙ４１）の
いずれかで表される基であり、より好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ１６
）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ
３９）又は式（Ｙ４０）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１
５）、式（Ｙ２０）、式（Ｙ３０）、式（Ｙ３９）又は式（Ｙ４０）で表される基である
。
Ｙで表される脂環式炭化水素基が式（Ｙ２８）～式（Ｙ３５）、式（Ｙ３９）～式（Ｙ
４０）等のスピロ環である場合には、２つの酸素原子間のアルカンジイル基は、１以上の
フッ素原子を有することが好ましい。また、ケタール構造に含まれるアルカンジイル基の
うち、酸素原子に隣接するメチレン基には、フッ素原子が置換されていないのが好ましい
。

The alicyclic hydrocarbon group represented by Y is preferably one of formulas (Y1) to (Y20), formula (
Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y41), more preferably formula (Y11) or formula (Y15) , formula (Y16
), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y
39) or a group represented by the formula (Y40), more preferably a group represented by the formula (Y11) or the formula (Y1
5), a group represented by formula (Y20), formula (Y30), formula (Y39) or formula (Y40).
The alicyclic hydrocarbon group represented by Y is represented by formula (Y28) to formula (Y35), formula (Y39) to formula (Y
In the case of a spiro ring such as 40), the alkanediyl group between two oxygen atoms preferably has one or more fluorine atoms. Moreover, among the alkanediyl groups included in the ketal structure, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

Substituents for the methyl group represented by Y include a halogen atom, a hydroxy group, and a carbon number of 3 to 1.
6 alicyclic hydrocarbon group, aromatic hydrocarbon group having 6 to 18 carbon atoms, glycidyloxy group, -(
CH ₂ ) _ja -CO-O-R ^b1 group or -(CH ₂ ) _ja -O-CO-R ^b1 group (wherein R ^b1 is
It represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. ja represents any integer from 0 to 4. -CH ₂ - contained in the alkyl group having 1 to 16 carbon atoms and the alicyclic hydrocarbon group having 3 to 16 carbon atoms is replaced with -O-, -S(O) ₂ - or -CO-. Good too. ) etc.
Substituents for the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, and an alicyclic group having 3 to 16 carbon atoms. Hydrocarbon group, alkoxy group having 1 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, aralkyl group having 7 to 21 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms, glycidyloxy group, -( CH ₂ ) _ja -CO-O-R ^b1 group or -(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula,
R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an alicyclic hydrocarbon group having 6 carbon atoms;
~18 aromatic hydrocarbon groups or a combination thereof. ja represents any integer from 0 to 4. -CH ₂ - contained in the alkyl group having 1 to 16 carbon atoms and the alicyclic hydrocarbon group having 3 to 16 carbon atoms is replaced with -O-, -S(O) ₂ - or -CO-. Good too. ) etc.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an adamantyl group.
Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group (tolyl group, xylyl group, cumenyl group, mesityl group) group, p-ethylphenyl group, pt
ert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p- adamantylphenyl group, etc.).
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, and nonyl group. group, decyl group, undecyl group, dodecyl group, etc.
Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent; -CH ₂ - constituting the hydrogen group or adamantyl group may be replaced with -CO-, -S(O) ₂ - or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented below.

Anions in the salt represented by formula (B1) include formulas (B1-A-1) to (B1-
Anion represented by A-55) [Hereinafter, it may be referred to as "anion (B1-A-1)" etc. depending on the formula number. ] are preferred, and formulas (B1-A-1) to (B1-A-4), formula (B1
-A-9), Formula (B1-A-10), Formula (B1-A-24) to Formula (B1-A-33), Formula (B1-A-36) to Formula (B1-A-40) , formula (B1-A-47) to formula (B1-A-5
Anions represented by any of 5) are more preferred.

ここでＲⁱ²～Ｒⁱ⁷は、互いに独立に、例えば、炭素数１～４のアルキル基、好ましくは
メチル基又はエチル基である。Ｒⁱ⁸は、例えば、炭素数１～１２の脂肪族炭化水素基、好
ましくは炭素数１～４のアルキル基、炭素数５～１２の脂環式炭化水素基又はこれらを組
合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基
又はアダマンチル基である。Ｌ^A41は、単結合又は炭素数１～４のアルカンジイル基であ
る。
Ｑ^b1及びＱ^b2は、上記と同じ意味を表す。
式（Ｂ１）で表される塩におけるスルホン酸アニオンとしては、具体的には、特開２０
１０－２０４６４６号公報に記載されたアニオンが挙げられる。

Here, R ⁱ² to R ⁱ⁷ each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is formed, for example, by an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. and more preferably a methyl group, ethyl group, cyclohexyl group or adamantyl group. L ^A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ^b1 and Q ^b2 represent the same meanings as above.
Specifically, as the sulfonic acid anion in the salt represented by formula (B1),
Examples include anions described in Japanese Patent No. 10-204646.

Preferred anions in the salt represented by formula (B1) include formulas (B1a-1) to (
Examples include anions represented by B1a-34).

Among them, formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-
16), formula (B1a-18), formula (B1a-19), formula (B1a-22) to formula (B1a-
Anion represented by any one of 34) is preferable.

Examples of the organic cation of Z ⁺ include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" etc. depending on the formula number) is Can be mentioned.

式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^b4～Ｒ^b6は、それぞれ独立に、炭素数１～３０の鎖式炭化水素基、炭素数３～３６の
脂環式炭化水素基又は炭素数６～３６の芳香族炭化水素基を表し、該鎖式炭化水素基に含
まれる水素原子は、ヒドロキシ基、炭素数１～１２のアルコキシ基、炭素数３～１２の脂
環式炭化水素基又は炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該脂環
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の脂肪族炭化水素基
、炭素数２～４のアルキルカルボニ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、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成し
てもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっても
よい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ヒドロキシ基、炭素数１～１２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、それぞれ独立に０～５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^b7は同一でも異なってもよく、ｎ２が２以上のとき、複
数のＲ^b8は同一でも異なってもよい。
Ｒ^b9及びＲ^b10は、それぞれ独立に、炭素数１～３６の鎖式炭化水素基又は炭素数３～
３６の脂環式炭化水素基を表す。
Ｒ^b9とＲ^b10とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成
してもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－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の鎖式炭化水素基、炭素数３～３６の脂環式炭化
水素基又は炭素数６～１８の芳香族炭化水素基を表す。
Ｒ^b12は、炭素数１～１２の鎖式炭化水素基、炭素数３～１８の脂環式炭化水素基又は
炭素数６～１８の芳香族炭化水素基を表し、該鎖式炭化水素に含まれる水素原子は、炭素
数６～１８の芳香族炭化水素基で置換されていてもよく、該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、互いに結合してそれらが結合する－ＣＨ－ＣＯ－を含めて環を形成
していてもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わ
ってもよい。
Ｒ^b13～Ｒ^b18は、それぞれ独立に、ヒドロキシ基、炭素数１～１２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、硫黄原子又は酸素原子を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０～５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０～４のいずれかの整数を表す。
ｕ２は０又は１を表す。
ｏ２が２以上のとき、複数のＲ^b13は同一又は相異なり、ｐ２が２以上のとき、複数の
Ｒ^b14は同一又は相異なり、ｑ２が２以上のとき、複数のＲ^b15は同一又は相異なり、ｒ２
が２以上のとき、複数のＲ^b16は同一又は相異なり、ｓ２が２以上のとき、複数のＲ^b17は
同一又は相異なり、ｔ２が２以上のとき、複数のＲ^b18は同一又は相異なる。
脂肪族炭化水素基とは、鎖式炭化水素基及び脂環式炭化水素基を表す。
鎖式炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル
基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基及び
２－エチルヘキシル基のアルキル基が挙げられる。
特に、Ｒ^b9～Ｒ^b12の鎖式炭化水素基は、好ましくは炭素数１～１２である。
脂環式炭化水素基としては、単環式又は多環式のいずれでもよく、単環式の脂環式炭化
水素基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシ
ル基、シクロヘプチル基、シクロオクチル基、シクロデシル基等のシクロアルキル基が挙
げられる。多環式の脂環式炭化水素基としては、デカヒドロナフチル基、アダマンチル基
、ノルボルニル基及び下記の基等が挙げられる。

特に、Ｒ^b9～Ｒ^b12の脂環式炭化水素基は、好ましくは炭素数３～１８、より好ましく
は炭素数４～１２である。

In formulas (b2-1) to (b2-4),
R ^b4 to R ^b6 each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the chain hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, a hydroxy group, or a hydrogen atom having a carbon number of 1.
It may be substituted with ~12 alkoxy groups.
R ^b4 and R ^b5 may bond to each other and form a ring together with the sulfur atom to which they are bonded, and -CH ₂ - contained in the ring may be -O-, -S- or -CO- may be substituted.
R ^b7 and R ^b8 each independently represent a hydroxy group, an 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 any integer from 0 to 5.
When m2 is 2 or more, multiple R ^b7s may be the same or different; when n2 is 2 or more, multiple R ^b8s may be the same or different.
R ^b9 and R ^b10 are each independently a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 36 carbon atoms;
36 alicyclic hydrocarbon group.
R ^b9 and R ^b10 may bond to each other and form a ring together with the sulfur atom to which they are bonded, and -CH ₂ - contained in the ring may be -O-, -S- or -CO- may be substituted.
R ^b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms; The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and -CH ₂ - contained in the ring is -O-, -S - or -CO- may be substituted.
R ^b13 to R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represent any integer 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, multiple R ^b13s are the same or different; when p2 is 2 or more, multiple R ^b14s are the same or different; when q2 is 2 or more, multiple R ^b15s are the same or different. , r2
When t2 is 2 or more, multiple R ^b16s are the same or different; when s2 is 2 or more, multiple R ^b17s are the same or different; when t2 is 2 or more, multiple R ^b18s are the same or different.
The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group.
Examples of chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. Can be mentioned.
In particular, the chain hydrocarbon groups R ^b9 to R ^b12 preferably have 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclo Examples include cycloalkyl groups such as heptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

In particular, the alicyclic hydrocarbon groups R ^b9 to R ^b12 preferably have 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

Examples of alicyclic hydrocarbon groups in which hydrogen atoms are substituted with aliphatic hydrocarbon groups include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, and 2-ethyladamantan-2-yl group. , 2-isopropyladamantane-2-yl group, methylnorbornyl group, isobornyl group, and the like. In an alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenylyl group, naphthyl group, and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms (tolyl group, xylyl group, group, cumenyl group, mesityl group, p-ethylphenyl group, p-ter
t-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and an aromatic hydrocarbon group having an alicyclic hydrocarbon group having 3 to 18 carbon atoms (p-adamantylphenyl group, etc.) group, p-cyclohexylphenyl group, etc.) are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl group.
Examples of the chain hydrocarbon group in which the hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group.

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

The ring formed by R ^b4 and R ^b5 combined with each other and the sulfur atom to which they are bonded may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. It may be a ring. Examples of this ring include a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Further, examples of the ring containing a sulfur atom include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, such as the following rings. * represents a binding site.

The ring formed by R ^b9 and R ^b10 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of this ring include a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples include thiolane-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 monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of this ring include a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among cations (b2-1) to cations (b2-4), cations (b2-4) are preferably
-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 (B) is a combination of the above-mentioned sulfonic acid anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), preferably formula (B1
a-1) ~Formula (B1a-3) and Formula (B1a-7) ~Formula (B1a-16), Formula (B1a-
18), a combination of an anion represented by formula (B1a-19), formula (B1a-22) to formula (B1a-34), and cation (b2-1) or cation (b2-3) Can be mentioned.

The acid generator (B) preferably includes those represented by formulas (B1-1) to (B1-48), among which those containing an arylsulfonium cation are preferred,
Formula (B1-1) to Formula (B1-3), Formula (B1-5) to Formula (B1-7), Formula (B1-11)
~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B
Particularly preferred are those represented by formulas 1-31) to (B1-48).

In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of the resin (A). , more preferably 10 parts by mass or more and 35 parts by mass or less. The resist composition of the present invention may contain one type of acid generator (B) alone, or may contain multiple types of acid generators (B).

<Salt that generates an acid with weaker acidity than the acid generated from the acid generator>
The acidity of the salt that generates an acid that is weaker than the acid generated from the acid generator (B) is:
It is expressed as acid dissociation constant (pKa). The salt that generates an acid with weaker acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3<pKa, preferably -1<pKa. A salt with a pKa<7, more preferably a salt with a pKa<5.
Examples of the salt that generates an acid with weaker acidity than the acid generated from the acid generator (B) include a salt represented by the following formula, a salt represented by the formula (D) described in JP-A-2015-147926; (below,"
Sometimes referred to as "weak acid inner salt (D)". ), as well as JP 2012-229206, JP 2012-6908, JP 2012-72109, JP 2011-3
Examples include salts described in JP-A No. 9502 and JP-A No. 2011-191745. A weak acid inner salt (D) is preferable as a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator (B).

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

The content of the salt that generates an acid weaker than the acid generated from the acid generator contained in the resist composition is usually 0.01 to 5% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resist composition. is 0.01 to 3% by mass.

<Solvent (E)>
The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass. % or less. 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, ethyl pyruvate, etc. Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; Cyclic esters such as γ-butyrolactone; and the like. One type of solvent (E) may be used alone,
Two or more types may be used.

<Quencher (C)>
Examples of the quencher (C) include basic nitrogen-containing organic compounds in addition to the above-mentioned salts that generate an acid that is weaker in acidity than the acid generated from the acid generator (B). Quencher (C
) is preferably about 0.01 to 5% by mass based on the solid content of the resist composition.
Basic nitrogen-containing organic compounds include amines and ammonium salts. Amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.
Examples of amines include 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, etc., preferably diisopropylaniline, etc. aromatic amines, more preferably 2,6-diisopropylaniline.
Examples of ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethyl Examples include ammonium hydroxide, tetra-n-butylammonium salicylate, and choline.

<Other ingredients>
The resist composition of the present invention may contain components other than the above-mentioned components (hereinafter sometimes referred to as "other components (F)"), if necessary. Other components (F) are not particularly limited, and additives known in the resist field, 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) of the present invention, an acid generator (B), a salt that generates an acid weaker in acidity than the acid generated from the acid generator, and, if necessary, a resin. It can be prepared by mixing (A2), resin (X), quencher (C), solvent (E), and other components (F). The mixing order is arbitrary and is not particularly limited. An appropriate temperature for mixing can be selected from 10 to 40° C. depending on the type of resin and the solubility of the resin in the solvent (E). An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. Note that the mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter it using a filter with a pore size of about 0.003 to 0.2 μm.

<Resist pattern manufacturing method>
The method for manufacturing a resist pattern of the present invention includes:
(1) Applying the resist composition of the present invention onto a substrate,
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer to light;
(4) a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.
The resist composition can be applied onto the substrate using a commonly used device such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be cleaned, 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, the solvent may be evaporated using a heating device such as a hot plate (so-called pre-baking), or a pressure reducing device may be used. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 10 to 180 seconds. Further, the pressure during reduced pressure drying is preferably about 1 to 1.0×10 ⁵ Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid state laser light source (YAG or semiconductor laser). etc.) that converts the wavelength of laser light and emits harmonic laser light in the far ultraviolet or vacuum ultraviolet range, and uses various methods such as those that emit electron beams and ultraviolet light (EUV). I can do it. Note that in this specification, irradiation with these radiations may be collectively referred to as "exposure." During exposure, the 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 writing 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 in acid-labile groups. The heating temperature is usually about 50 to 200°C, preferably about 70 to 150°C.
The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60°C, and the development time is, for example, 5 to 60°C.
The time period is preferably 300 seconds. By selecting the type of developer as described below, a positive resist pattern or a negative resist pattern can be manufactured.
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 the various alkaline aqueous solutions used in this field. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline).
The alkaline developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove water remaining on the substrate and pattern.
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 organic developers 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. Examples include ether solvents; amide solvents such as N,N-dimethylacetamide; and 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 even more preferably substantially only an organic solvent.
Among these, as the organic developer, a developer containing butyl acetate and/or 2-heptanone is preferred. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass.
It is preferably 100% by mass or more, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and/or 2-heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a trace amount of water.
During development, development may be stopped by replacing the organic developer with a different type of solvent.
It is preferable to wash the resist pattern after development with a rinsing liquid. As a rinse liquid,
There is no particular restriction as long as it does not dissolve the resist pattern, and any 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 rinsing 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 a resist composition for EU
It is suitable as a resist composition for V exposure, more suitable as a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, and Useful for processing.

The present invention will be explained in more detail with reference to Examples. In the examples, "%" and "part" representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Equipment: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh)
Eluent: Tetrahydrofuran Flow rate: 1.0mL/min
Detector: RI detector Column temperature: 40°C
Injection volume: 100μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)
The structure of the compound was determined by mass spectrometry (LC: Agilent Model 1100, MASS: A
This was confirmed by measuring the molecular ion peak using an LC/MSD model manufactured by Gilent.
In the following examples, the value of this molecular ion peak is indicated by "MASS".

式（Ｉ－１－ａ）で表される化合物２０部、式（Ｉ－１－ｂ）で表される化合物１４０
部及び硫酸０．７４部を混合し、７０℃で１０時間撹拌した後、２３℃まで冷却した。得
られた混合物に、クロロホルム３００部及び５％炭酸水素ナトリウム水溶液１３０部を混
合し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、
イオン交換水１００部を加えて２３℃で３０分間攪拌した後、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、濃縮残渣をカラム（シリ
カゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エ
チル）を用いて分取することにより、式（Ｉ－１－ｃ）で表される化合物１０．２２部を
得た。

式（Ｉ－１－ｄ）で表される化合物０．６５部及びアセトニトリル２０部を混合し、２
３℃で３０分間攪拌した後、式（Ｉ－１－ｅ）で表される化合物１．３４部を添加し、５
０℃に昇温後、５０℃で２時間撹拌した。得られた混合物に、式（Ｉ－１－ｃ）で表され
る化合物０．６６部を添加し、５０℃で２時間撹拌した。得られた混合物を２３℃まで冷
却した後、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌し
た後、分液して有機層を取り出した。得られた有機層に、イオン交換水２０部を添加し、
２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（シリカゲル６０Ｎ（球状、中性）
１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／１
）を用いて分取することにより、式（ＩＢ－１－ｆ）で表される化合物０．５２部を得た
。得られた式（ＩＢ－１－ｆ）で表される化合物０．５２部、硫酸０．０１部及びアセト
ニトリル２０部を混合し、２３℃で６時間攪拌した。得られた混合物を濃縮することによ
り、式（ＩＢ－１－ｇ）で表される化合物０．４１部を得た。

式（Ｉ－１－ｈ）で表される化合物０．２９部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．３
９部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＢ－１
－ｇ）で表される化合物０．３３部を添加し、さらに、５０℃で４時間攪拌した後、２３
℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液３
０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機
層にイオン交換水３０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（
シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ
－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＢ－１）で表さ
れる化合物０．３５部を得た。
ＭＡＳＳ：５５７．３［Ｍ＋Ｈ］^＋ Example 1: Synthesis of compound represented by formula (IB-1)

20 parts of the compound represented by formula (I-1-a), 140 parts of the compound represented by formula (I-1-b)
1 part and 0.74 part of sulfuric acid were mixed, stirred at 70°C for 10 hours, and then cooled to 23°C. The resulting mixture was mixed with 300 parts of chloroform and 130 parts of a 5% aqueous sodium bicarbonate solution, stirred at 23°C for 30 minutes, and then separated to take out the organic layer. In the obtained organic layer,
After adding 100 parts of ion-exchanged water and stirring at 23°C for 30 minutes, the mixture was separated and the organic layer was taken out. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was fractionated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: ethyl acetate) to obtain the formula ( 10.22 parts of a compound represented by I-1-c) was obtained.

Mix 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile,
After stirring at 3°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and 5
After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. To the resulting mixture, 0.66 parts of the compound represented by formula (I-1-c) was added, and the mixture was stirred at 50°C for 2 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. 20 parts of ion-exchanged water was added to the obtained organic layer,
After stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral).
100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/1
) to obtain 0.52 part of a compound represented by formula (IB-1-f). 0.52 part of the obtained compound represented by formula (IB-1-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. By concentrating the obtained mixture, 0.41 part of a compound represented by formula (IB-1-g) was obtained.

Mix 0.29 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.3 of the compound represented by formula (I-1-e) was added to the resulting mixture.
9 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IB-1
After adding 0.33 parts of the compound represented by -g) and further stirring at 50°C for 4 hours,
Cooled to ℃. To the obtained reaction mixture, 50 parts of chloroform and 3 parts of a 5% aqueous oxalic acid solution were added.
After adding 0 part of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (
Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 0.35 part of a compound represented by formula (IB-1).
MASS:557.3 [M+H] ⁺

式（Ｉ－１－ｄ）で表される化合物０．６５部及びアセトニトリル２０部を混合し、２
３℃で３０分間攪拌した後、式（Ｉ－１－ｅ）で表される化合物１．３４部を添加し、５
０℃に昇温後、５０℃で２時間撹拌した。得られた混合物に、式（Ｉ－１－ｃ）で表され
る化合物１．３２部を添加し、５０℃で２時間撹拌した。得られた混合物を２３℃まで冷
却した後、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌し
た後、分液して有機層を取り出した。得られた有機層に、イオン交換水２０部を添加し、
２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（シリカゲル６０Ｎ（球状、中性）
１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／２
）を用いて分取することにより、式（ＩＡ－１－ｆ）で表される化合物０．６８部を得た
。得られた式（ＩＡ－１－ｆ）で表される化合物０．６８部、硫酸０．０１部及びアセト
ニトリル２０部を混合し、２３℃で６時間攪拌した。得られた混合物を濃縮することによ
り、式（ＩＡ－１－ｇ）で表される化合物０．５２部を得た。

式（Ｉ－１－ｈ）で表される化合物０．４４部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．５
９部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＡ－１
－ｇ）で表される化合物０．２５部を添加し、さらに、５０℃で４時間攪拌した後、２３
℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液３
０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機
層にイオン交換水３０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（
シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ
－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＡ－１）で表さ
れる化合物０．４２部を得た。
ＭＡＳＳ：６３１．３［Ｍ＋Ｈ］^＋ Example 2: Synthesis of compound represented by formula (IA-1)

Mix 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile,
After stirring at 3°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and 5
After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. 1.32 parts of the compound represented by formula (I-1-c) was added to the resulting mixture, and the mixture was stirred at 50°C for 2 hours. After cooling the obtained mixture to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, and then separated to take out the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer,
After stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral).
100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/2
) to obtain 0.68 part of a compound represented by formula (IA-1-f). 0.68 part of the obtained compound represented by formula (IA-1-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. By concentrating the obtained mixture, 0.52 part of a compound represented by formula (IA-1-g) was obtained.

Mix 0.44 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.5 of the compound represented by formula (I-1-e) was added to the resulting mixture.
9 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IA-1
After adding 0.25 parts of the compound represented by -g) and further stirring at 50°C for 4 hours,
Cooled to ℃. To the obtained reaction mixture, 50 parts of chloroform and 3 parts of a 5% aqueous oxalic acid solution were added.
After adding 0 part of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (
Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 0.42 part of a compound represented by formula (IA-1).
MASS:631.3 [M+H] ⁺

式（Ｉ－６－ｄ）で表される化合物１．７９部及びアセトニトリル２０部を混合し、２
３℃で３０分間攪拌した後、式（Ｉ－１－ｅ）で表される化合物１．３４部を添加し、５
０℃に昇温後、５０℃で２時間撹拌した。得られた混合物に、式（Ｉ－１－ｃ）で表され
る化合物１．２４部を添加し、５０℃で２時間撹拌した。得られた混合物を２３℃まで冷
却した後、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌し
た後、分液して有機層を取り出した。得られた有機層に、イオン交換水２０部を添加し、
２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（シリカゲル６０Ｎ（球状、中性）
１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／１
）を用いて分取することにより、式（ＩＢ－６－ｆ）で表される化合物１．０９部を得た
。得られた式（ＩＢ－６－ｆ）で表される化合物１．０５部、硫酸０．０１部及びアセト
ニトリル２０部を混合し、２３℃で６時間攪拌した。得られた混合物を濃縮することによ
り、式（ＩＢ－６－ｇ）で表される化合物０．９２部を得た。
式（Ｉ－１－ｈ）で表される化合物０．２９部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．３
９部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＢ－６
－ｇ）で表される化合物０．８０部を添加し、さらに、５０℃で４時間攪拌した後、２３
℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液３
０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機
層にイオン交換水３０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（
シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ
－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＢ－６）で表さ
れる化合物０．６５部を得た。
ＭＡＳＳ：９４５．４［Ｍ＋Ｈ］^＋ Example 3: Synthesis of compound represented by formula (IB-6)

1.79 parts of the compound represented by formula (I-6-d) and 20 parts of acetonitrile were mixed,
After stirring at 3°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and 5
After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. 1.24 parts of the compound represented by formula (I-1-c) was added to the resulting mixture, and the mixture was stirred at 50°C for 2 hours. After cooling the obtained mixture to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, and then separated to take out the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer,
After stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral).
100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/1
) to obtain 1.09 parts of a compound represented by formula (IB-6-f). 1.05 parts of the obtained compound represented by formula (IB-6-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. By concentrating the obtained mixture, 0.92 parts of a compound represented by formula (IB-6-g) was obtained.
Mix 0.29 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.3 of the compound represented by formula (I-1-e) was added to the resulting mixture.
9 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IB-6
-g) was added, and after further stirring at 50°C for 4 hours, 23
Cooled to ℃. To the obtained reaction mixture, 50 parts of chloroform and 3 parts of a 5% aqueous oxalic acid solution were added.
After adding 0 part of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (
Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 0.65 part of a compound represented by formula (IB-6).
MASS:945.4 [M+H] ⁺

式（Ｉ－６－ｄ）で表される化合物１．７９部及びアセトニトリル２０部を混合し、２
３℃で３０分間攪拌した後、式（Ｉ－１－ｅ）で表される化合物１．３４部を添加し、５
０℃に昇温後、５０℃で２時間撹拌した。得られた混合物に、式（Ｉ－１－ｃ）で表され
る化合物２．４８部を添加し、５０℃で２時間撹拌した。得られた混合物を２３℃まで冷
却した後、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌し
た後、分液して有機層を取り出した。得られた有機層に、イオン交換水２０部を添加し、
２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（シリカゲル６０Ｎ（球状、中性）
１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／２
）を用いて分取することにより、式（ＩＡ－６－ｆ）で表される化合物２．２１部を得た
。得られた式（ＩＡ－６－ｆ）で表される化合物１．５０部、硫酸０．０１部及びアセト
ニトリル２０部を混合し、２３℃で６時間攪拌した。得られた混合物を濃縮することによ
り、式（ＩＡ－６－ｇ）で表される化合物１．２２部を得た。

式（Ｉ－１－ｈ）で表される化合物０．４４部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．５
９部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＡ－６
－ｇ）で表される化合物０．４９部を添加し、さらに、５０℃で４時間攪拌した後、２３
℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液３
０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機
層にイオン交換水３０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（
シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ
－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＡ－６）で表さ
れる化合物０．６２部を得た。
ＭＡＳＳ：８２５．４［Ｍ＋Ｈ］^＋ Example 4: Synthesis of compound represented by formula (IA-6)

1.79 parts of the compound represented by formula (I-6-d) and 20 parts of acetonitrile were mixed,
After stirring at 3°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and 5
After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. 2.48 parts of the compound represented by formula (I-1-c) was added to the resulting mixture, and the mixture was stirred at 50° C. for 2 hours. After cooling the obtained mixture to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, and then separated to take out the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer,
After stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral).
100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/2
) to obtain 2.21 parts of a compound represented by formula (IA-6-f). 1.50 parts of the obtained compound represented by formula (IA-6-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. By concentrating the obtained mixture, 1.22 parts of a compound represented by formula (IA-6-g) was obtained.

Mix 0.44 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.5 of the compound represented by formula (I-1-e) was added to the resulting mixture.
9 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with formula (IA-6
After adding 0.49 parts of the compound represented by -g) and further stirring at 50°C for 4 hours,
Cooled to ℃. To the obtained reaction mixture, 50 parts of chloroform and 3 parts of a 5% aqueous oxalic acid solution were added.
After adding 0 part of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (
Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 0.62 part of a compound represented by formula (IA-6).
MASS:825.4 [M+H] ⁺

式（Ｉ－１２－ｄ）で表される化合物１．５６部及びアセトニトリル２０部を混合し、
２３℃で３０分間攪拌した後、式（Ｉ－１－ｅ）で表される化合物１．３４部を添加し、
５０℃に昇温後、５０℃で２時間撹拌した。得られた混合物に、式（Ｉ－１－ｃ）で表さ
れる化合物０．３５部を添加し、５０℃で２時間撹拌した。得られた混合物を２３℃まで
冷却した後、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌
した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２０部を添加し
、２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（シリカゲル６０Ｎ（球状、中性
）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／
１）を用いて分取することにより、式（ＩＢ－１２－ｆ）で表される化合物０．２８部を
得た。得られた式（ＩＢ－１２－ｆ）で表される化合物０．２７部、硫酸０．０１部及び
アセトニトリル２０部を混合し、２３℃で６時間攪拌した。得られた混合物を濃縮するこ
とにより、式（ＩＢ－１２－ｇ）で表される化合物０．２４部を得た。

式（Ｉ－１－ｈ）で表される化合物０．１０部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．１
３部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＢ－１
２－ｇ）で表される化合物０．２１部を添加し、さらに、５０℃で４時間攪拌した後、２
３℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液
２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有
機層にイオン交換水２０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム
（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：
ｎ－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＢ－１２）で
表される化合物０．２４部を得た。
ＭＡＳＳ：７９７．３［Ｍ＋Ｈ］^＋ Example 5: Synthesis of compound represented by formula (IB-12)

Mixing 1.56 parts of the compound represented by formula (I-12-d) and 20 parts of acetonitrile,
After stirring at 23°C for 30 minutes, 1.34 parts of a compound represented by formula (I-1-e) was added,
After raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting mixture, 0.35 parts of the compound represented by formula (I-1-c) was added, and the mixture was stirred at 50°C for 2 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/
By fractionating using 1), 0.28 part of a compound represented by formula (IB-12-f) was obtained. 0.27 part of the obtained compound represented by formula (IB-12-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. By concentrating the obtained mixture, 0.24 part of a compound represented by formula (IB-12-g) was obtained.

Mix 0.10 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.1 of the compound represented by formula (I-1-e) was added to the resulting mixture.
3 parts were added and further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IB-1
After adding 0.21 part of the compound represented by 2-g) and further stirring at 50°C for 4 hours,
Cooled to 3°C. After adding 50 parts of chloroform and 20 parts of 5% oxalic acid aqueous solution to the obtained reaction mixture and stirring at 23°C for 30 minutes, the mixture was separated and the organic layer was taken out. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent:
By fractionating using n-heptane/ethyl acetate=1/1), 0.24 part of the compound represented by formula (IB-12) was obtained.
MASS:797.3 [M+H] ⁺

式（Ｉ－１２－ｄ）で表される化合物１．５６部及びアセトニトリル２０部を混合し、
２３℃で３０分間攪拌した後、式（Ｉ－１－ｅ）で表される化合物１．３４部を添加し、
５０℃に昇温後、５０℃で２時間撹拌した。得られた混合物に、式（Ｉ－１－ｃ）で表さ
れる化合物０．７０部を添加し、５０℃で２時間撹拌した。得られた混合物を２３℃まで
冷却した後、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌
した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２０部を添加し
、２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（シリカゲル６０Ｎ（球状、中性
）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／
２）を用いて分取することにより、式（ＩＡ－１２－ｆ）で表される化合物０．３９部を
得た。得られた式（ＩＡ－１２－ｆ）で表される化合物０．２７部、硫酸０．０１部及び
アセトニトリル２０部を混合し、２３℃で６時間攪拌した。得られた混合物を濃縮するこ
とにより、式（ＩＡ－１２－ｇ）で表される化合物０．２８部を得た。
式（Ｉ－１－ｈ）で表される化合物０．２２部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．３
０部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＡ－１
２－ｇ）で表される化合物０．２０部を添加し、さらに、５０℃で４時間攪拌した後、２
３℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液
２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有
機層にイオン交換水２０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム
（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：
ｎ－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＡ－１２）で
表される化合物０．２２部を得た。
ＭＡＳＳ：７５１．３［Ｍ＋Ｈ］^＋ Example 6: Synthesis of compound represented by formula (IA-12)

Mixing 1.56 parts of the compound represented by formula (I-12-d) and 20 parts of acetonitrile,
After stirring at 23°C for 30 minutes, 1.34 parts of a compound represented by formula (I-1-e) was added,
After raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting mixture, 0.70 parts of the compound represented by formula (I-1-c) was added, and the mixture was stirred at 50°C for 2 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/
By fractionating using 2), 0.39 parts of a compound represented by formula (IA-12-f) was obtained. 0.27 part of the obtained compound represented by formula (IA-12-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. By concentrating the obtained mixture, 0.28 part of a compound represented by formula (IA-12-g) was obtained.
Mix 0.22 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.3 of the compound represented by formula (I-1-e) was added to the resulting mixture.
0 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IA-1
After adding 0.20 parts of the compound represented by 2-g) and further stirring at 50°C for 4 hours,
Cooled to 3°C. After adding 50 parts of chloroform and 20 parts of 5% oxalic acid aqueous solution to the obtained reaction mixture and stirring at 23°C for 30 minutes, the mixture was separated and the organic layer was taken out. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent:
By fractionating using n-heptane/ethyl acetate=1/1), 0.22 part of the compound represented by formula (IA-12) was obtained.
MASS:751.3 [M+H] ⁺

式（Ｉ－１－ｈ）で表される化合物０．２９部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．３
９部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＢ－１
７－ｇ）で表される化合物０．３１部を添加し、さらに、５０℃で４時間攪拌した後、２
３℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液
３０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有
機層にイオン交換水３０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム
（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：
ｎ－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＢ－１７）で
表される化合物０．２９部を得た。
ＭＡＳＳ：５４３．２［Ｍ＋Ｈ］^＋ Example 7: Synthesis of compound represented by formula (IB-17)
Mix 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile,
After stirring at 3°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and 5
After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. To the resulting mixture, 0.61 part of the compound represented by formula (I-17-c) was added, and the mixture was stirred at 50°C for 2 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/
By fractionating using 1), 0.48 part of a compound represented by formula (IB-17-f) was obtained. 0.48 part of the obtained compound represented by formula (IB-17-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23°C for 6 hours. By concentrating the obtained mixture, 0.39 parts of a compound represented by formula (IB-17-g) was obtained.

Mix 0.29 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.3 of the compound represented by formula (I-1-e) was added to the resulting mixture.
9 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IB-1
After adding 0.31 part of the compound represented by 7-g) and further stirring at 50°C for 4 hours,
Cooled to 3°C. To the resulting reaction mixture were added 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution, and the mixture was stirred at 23° C. for 30 minutes, then separated and the organic layer was taken out. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent:
By fractionating using n-heptane/ethyl acetate=1/1), 0.29 part of the compound represented by formula (IB-17) was obtained.
MASS:543.2 [M+H] ⁺

式（Ｉ－１－ｄ）で表される化合物０．６５部及びアセトニトリル２０部を混合し、２
３℃で３０分間攪拌した後、式（Ｉ－１－ｅ）で表される化合物１．３４部を添加し、５
０℃に昇温後、５０℃で２時間撹拌した。得られた混合物に、式（Ｉ－１７－ｃ）で表さ
れる化合物１．２２部を添加し、５０℃で２時間撹拌した。得られた混合物を２３℃まで
冷却した後、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌
した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２０部を添加し
、２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（シリカゲル６０Ｎ（球状、中性
）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／
２）を用いて分取することにより、式（ＩＡ－１７―ｆ）で表される化合物０．５７部を
得た。得られた式（ＩＡ－１７―ｆ）で表される化合物０．５７部、硫酸０．０１部及び
アセトニトリル２０部を混合し、２３℃で６時間攪拌した。得られた混合物を濃縮するこ
とにより、式（ＩＡ－１７－ｇ）で表される化合物０．４６部を得た。

式（Ｉ－１－ｈ）で表される化合物０．４４部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．５
９部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＡ－１
７－ｇ）で表される化合物０．２３部を添加し、さらに、５０℃で４時間攪拌した後、２
３℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液
３０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有
機層にイオン交換水３０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム
（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：
ｎ－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＡ－１７）で
表される化合物０．３４部を得た。
ＭＡＳＳ：６１７．３［Ｍ＋Ｈ］^＋ Example 8: Synthesis of compound represented by formula (IA-17)

Mix 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile,
After stirring at 3°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and 5
After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. 1.22 parts of the compound represented by formula (I-17-c) was added to the resulting mixture, and the mixture was stirred at 50°C for 2 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n-heptane/ethyl acetate = 1/
By fractionating using 2), 0.57 parts of a compound represented by formula (IA-17-f) was obtained. 0.57 parts of the obtained compound represented by formula (IA-17-f), 0.01 parts of sulfuric acid, and 20 parts of acetonitrile were mixed and stirred at 23° C. for 6 hours. By concentrating the obtained mixture, 0.46 part of a compound represented by formula (IA-17-g) was obtained.

Mix 0.44 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.5 of the compound represented by formula (I-1-e) was added to the resulting mixture.
9 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IA-1
After adding 0.23 parts of the compound represented by 7-g) and further stirring at 50°C for 4 hours,
Cooled to 3°C. To the resulting reaction mixture were added 50 parts of chloroform and 30 parts of a 5% aqueous oxalic acid solution, and the mixture was stirred at 23° C. for 30 minutes, then separated and the organic layer was taken out. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the layers were separated and the organic layer was taken out. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent:
By fractionating using n-heptane/ethyl acetate=1/1), 0.34 part of a compound represented by formula (IA-17) was obtained.
MASS:617.3 [M+H] ⁺

式（Ｉ－１－ｈ）で表される化合物０．２９部及びアセトニトリル３０部を混合し、２
３℃で３０分間攪拌した。得られた混合物に、式（Ｉ－１－ｅ）で表される化合物０．５
９部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物に、式（ＩＡ－１
－ｇ）で表される化合物０．２５部を添加し、さらに、５０℃で４時間攪拌した後、２３
℃まで冷却した。得られた反応混合物に、クロロホルム５０部及び５％シュウ酸水溶液３
０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機
層にイオン交換水３０部を加えて２３℃で３０分間攪拌した後、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、濃縮混合物をカラム（
シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ
－ヘプタン／酢酸エチル＝１／１）を用いて分取することにより、式（ＩＡ－２）で表さ
れる化合物０．２１部を得た。
ＭＡＳＳ：４８９．２［Ｍ＋Ｈ］^＋ Example 9: Synthesis of compound represented by formula (IA-2)

Mix 0.29 parts of the compound represented by formula (I-1-h) and 30 parts of acetonitrile,
The mixture was stirred at 3°C for 30 minutes. 0.5 of the compound represented by formula (I-1-e) was added to the resulting mixture.
9 parts were added thereto, and the mixture was further stirred at 50°C for 2 hours. The resulting reaction mixture was added with the formula (IA-1
After adding 0.25 parts of the compound represented by -g) and further stirring at 50°C for 4 hours,
Cooled to ℃. To the obtained reaction mixture, 50 parts of chloroform and 3 parts of a 5% aqueous oxalic acid solution were added.
After adding 0 part of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was separated. This water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (
Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Kagaku Co., Ltd., developing solvent: n
-heptane/ethyl acetate = 1/1) to obtain 0.21 part of the compound represented by formula (IA-2).
MASS:489.2 [M+H] ⁺

Synthesis of resin The compounds (monomers) used in the synthesis of the resin are shown below.

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。

Hereinafter, these monomers will be referred to as "monomers (a1-1-3)" etc. according to their formula numbers.

Example 10 [Synthesis of resin A1]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IB-1), and the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IB-1)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.0% each based on the total monomer amount.
5 mol% and 4.5 mol% were added, and these were heated at 73°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin A1 with a molecular weight of 7.7×10 ³ in a yield of 60
Obtained in %. This resin A1 has the following structural units.

Example 11 [Synthesis of resin A2]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IA-1), and the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IA-1)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 ml each based on the total monomer amount.
ol% and 3 mol% were added, and these were heated at 73° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The resulting resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin A2 with a molecular weight of 7.9×10 ³ was obtained in a yield of 58%. This resin A2 has the following structural units.

Example 12 [Synthesis of resin A3]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IB-6), and the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IB-6)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, 1.0% each of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators based on the total monomer amount.
5 mol% and 4.5 mol% were added, and these were heated at 73°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The resulting resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin A3 with a molecular weight of 8.0×10 ³ in a yield of 62
Obtained in %. This resin A3 has the following structural units.

Example 13 [Synthesis of resin A4]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IA-6), and their molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IA-6)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 ml each based on the total monomer amount.
ol% and 3 mol% were added, and these were heated at 73° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The resulting resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin A4 with a molecular weight of 7.9×10 ³ was obtained in a yield of 62%. This resin A4 has the following structural units.

Example 14 [Synthesis of resin A5]
As monomers, monomer (a1-1-1), monomer (a1-0-1), monomer (
a3-2-1) and monomer (IB-1), the molar ratio [monomer (a1-1-1
): Monomer (a1-0-1): Monomer (a3-2-1): Monomer (IB-1)] were mixed so that the ratio was 46:11:34:9, and 1.5 mass of the total monomer amount was mixed. Two times the amount of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were heated at 73°C. Approximately 5
heated for an hour. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Molecular weight 7.8×1
Resin A5 of ^0.03 was obtained with a yield of 85%. This resin A5 has the following structural units.

Example 15 [Synthesis of resin A9]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IB-17), and the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3
):monomer (a3-4-2):monomer (IB-17)] is 45:14:4:34:3
1.5 times the total amount of monomers by mass of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators, respectively, based on the total monomer amount.
1.5 mol% and 4.5 mol% were added, and these were heated at 73°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin A9 with a molecular weight of 7.4×10 ³ was obtained in a yield of 62%. This resin A9 has the following structural units.

Example 16 [Synthesis of resin A10]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IA-17), the molar ratio [monomer (a1-1-3):monomer (a1-2-5):monomer (a2 -1-3
):monomer (a3-4-2):monomer (IA-17)] is 45:14:4:34:3
1.5 times the total amount of monomers by mass of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators, respectively, based on the total monomer amount.
1 mol% and 3 mol% were added, and these were heated at 73°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered.
The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin A10 with molecular weight 7.7×10 ³ yield 61%
I got it from This resin A10 has the following structural units.

Example 17 [Synthesis of resin A11]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IA-2), and the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IA-2)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 ml each based on the total monomer amount.
ol% and 3 mol% were added, and these were heated at 73° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The resulting resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin A11 with a molecular weight of 7.8×10 ³ was obtained in a yield of 60%. This resin A11 has the following structural units.

Synthesis Example 1 [Synthesis of resin AX1]
As monomers, monomer (a1-1-1), monomer (a1-0-1), monomer (
a3-2-1) and monomer (IX-1), the molar ratio [monomer (a1-1-1)
): Monomer (a1-0-1): Monomer (a3-2-1): Monomer (IX-1)] were mixed so that the ratio was 46:11:34:9, and 1.5 mass of the total monomer amount was mixed. Two times the amount of propylene glycol monomethyl ether acetate was added to form a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were heated at 73°C. Approximately 5
heated for an hour. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Molecular weight 7.8×1
⁰³ resin AX1 was obtained with a yield of 85%. This resin AX1 has the following structural units.

Synthesis Example 2 [Synthesis of resin AX2]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IX-1), the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IX-1)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.0% each based on the total monomer amount.
5 mol% and 4.5 mol% were added, and these were heated at 73°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin AX2 with molecular weight 7.9×10 ³ in yield 6
Obtained at 0%. This resin AX2 has the following structural units.

Synthesis Example 3 [Synthesis of resin AX3]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IX-2), the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IX-2)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.0% each based on the total monomer amount.
5 mol% and 4.5 mol% were added, and these were heated at 73°C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin AX3 with molecular weight 7.8×10 ³ in yield 6
Obtained at 4%. This resin AX3 has the following structural units.

Synthesis Example 4 [Synthesis of resin AX4]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IX-3), and their molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IX-3)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 ml each based on the total monomer amount.
ol% and 3 mol% were added, and these were heated at 73° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin AX4 with a molecular weight of 8.0×10 ³ was obtained in a yield of 60%. This resin AX4 has the following structural units.

Synthesis Example 5 [Synthesis of resin AX5]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (
a2-1-1), monomer (a3-4-2) and monomer (IX-4), and the molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2 -1-3)
: Monomer (a3-4-2): Monomer (IX-4)] were mixed so that the ratio was 45:14:4:34:3, and 1.5 times the mass of the total monomer amount of propylene glycol monomethyl ether acetate was added. In addition, it was made into a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 ml each based on the total monomer amount.
ol% and 3 mol% were added, and these were heated at 73° C. for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and the resin was filtered. The resulting resin was again dissolved in propylene glycol monomethyl ether acetate, the resulting solution was poured into a methanol/water mixed solvent to precipitate the resin, and this resin was filtered. Resin AX5 with a molecular weight of 7.6×10 ³ was obtained in a yield of 55%. This resin AX5 has the following structural units.

Example 18 [Synthesis of resin A6]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IB-12), the molar ratio [monomer (a1-4-
2): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IB-12)
] were mixed in a ratio of 38:29:30:3, and further, methyl isobutyl ketone was mixed in an amount of 1.5 times the total mass of all monomers to this monomer mixture.
To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and collected to obtain resin A6 with a weight average molecular weight of approximately 5.6×10 ³ in a yield of 55%.
I got it from This resin A6 has the following structural units.

Example 19 [Synthesis of resin A7]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IA-12), the molar ratio [monomer (a1-4-
2): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IA-12)
] were mixed in a ratio of 38:29:30:3, and methyl isobutyl ketone was added to this monomer mixture in an amount of 1.5 times the total weight of all monomers.
To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and filtered and
By recovering, resin A7 having a weight average molecular weight of approximately 5.9×10 ³ was obtained in a yield of 59%. This resin A7 has the following structural units.

Example 20 [Synthesis of resin A8]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IB-1), the molar ratio [monomer (a1-4-2
):monomer (a1-1-3):monomer (a1-2-6):monomer (IB-1)] are mixed in a ratio of 38:29:30:3, and further, this monomer mixture 1.5 times the mass of methyl isobutyl ketone was mixed with the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain resin A8 with a weight average molecular weight of approximately 5.9×10 ³ in a yield of 48%. This resin A8 has the following structural units.

Example 21 [Synthesis of resin A12]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IA-1), the molar ratio [monomer (a1-4-2
):monomer (a1-1-3):monomer (a1-2-6):monomer (IA-1)] are mixed in a ratio of 38:29:30:3, and further, this monomer mixture 1.5 times the mass of methyl isobutyl ketone was mixed with the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain resin A12 with a weight average molecular weight of approximately 5.6×10 ³ in a yield of 64%. This resin A12 has the following structural units.

Example 22 [Synthesis of resin A13]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IB-17), the molar ratio [monomer (a1-4-
2): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IB-17)
] were mixed in a ratio of 38:29:30:3, and methyl isobutyl ketone was added to this monomer mixture in an amount of 1.5 times the total weight of all monomers.
To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and collected to obtain resin A13 with a weight average molecular weight of approximately 5.5×10 ³ in a yield of 54.
Obtained in %. This resin A13 has the following structural units.

Example 23 [Synthesis of resin A14]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IA-17), the molar ratio [monomer (a1-4-
2): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IA-17)
] were mixed in a ratio of 38:29:30:3, and methyl isobutyl ketone was added to this monomer mixture in an amount of 1.5 times the total weight of all monomers.
To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and filtered and
By recovering resin A14 with a weight average molecular weight of approximately 5.4 x ¹⁰³ , the yield was 62%.
I got it from This resin A14 has the following structural units.

Example 24 [Synthesis of resin A15]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IA-2), the molar ratio [monomer (a1-4-2)
):monomer (a1-1-3):monomer (a1-2-6):monomer (IA-2)] are mixed in a ratio of 38:29:30:3, and further, this monomer mixture 1.5 times the mass of methyl isobutyl ketone was mixed with the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain resin A15 with a weight average molecular weight of approximately 5.5×10 ³ in a yield of 65%. This resin A15 has the following structural units.

Synthesis Example 6 [Synthesis of resin AX6]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IX-1), the molar ratio [monomer (a1-4-2
):monomer (a1-1-3):monomer (a1-2-6):monomer (IX-1)] are mixed in a ratio of 38:29:30:3, and further, this monomer mixture 1.5 times the mass of methyl isobutyl ketone was mixed with the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain resin AX6 with a weight average molecular weight of approximately 5.7×10 ³ in a yield of 50%. This resin AX6 has the following structural units.

Synthesis Example 7 [Synthesis of resin AX7]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IX-2), the molar ratio [monomer (a1-4-2)
):monomer (a1-1-3):monomer (a1-2-6):monomer (IX-2)] are mixed in a ratio of 38:29:30:3, and further, this monomer mixture 1.5 times the mass of methyl isobutyl ketone was mixed with the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain resin AX7 with a weight average molecular weight of approximately 5.8×10 ³ in a yield of 53%. This resin AX7 has the following structural units.

Synthesis Example 8 [Synthesis of resin AX8]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IX-3), the molar ratio [monomer (a1-4-2
):monomer (a1-1-3):monomer (a1-2-6):monomer (IX-3)] are mixed in a ratio of 38:29:30:3, and further, this monomer mixture 1.5 times the mass of methyl isobutyl ketone was mixed with the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain resin AX8 with a weight average molecular weight of approximately 5.7×10 ³ in a yield of 50%. This resin AX8 has the following structural units.

Synthesis Example 9 [Synthesis of resin AX9]
As monomers, monomer (a1-4-2), monomer (a1-1-3), monomer (
a1-2-6) and monomer (IX-4), the molar ratio [monomer (a1-4-2
): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IX-4)] are mixed in a ratio of 38:29:30:3, and further, this monomer mixture 1.5 times the mass of methyl isobutyl ketone was mixed with the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was added as an initiator in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85° C. for about 5 hours to perform polymerization. Ta. Thereafter, an aqueous p-toluenesulfonic acid solution was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain resin AX9 with a weight average molecular weight of approximately 5.9×10 ³ in a yield of 55%. This resin AX9 has the following structural units.

Synthesis Example 10: Synthesis of Resin X1 Using monomer (a5-1-1) and monomer (a4-0-12) as monomers,
Mix them so that the molar ratio [monomer (a5-1-1):monomer (a4-0-12)] is 50:50, add 1.2 times the mass of the total monomer amount of methyl isobutyl ketone, and make a solution. And so. To this solution, azobis(2,4-dimethylvaleronitrile) was added as an initiator in an amount of 3 mol % based on the total amount of monomers, and the mixture was heated at 70° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, and this resin was filtered to obtain resin X1 with a weight average molecular weight of 1.0×10 ⁴ in a yield of 91%. This resin X1 has the following structural units.

<Preparation of resist composition>
A mixture obtained by mixing and dissolving the components shown in Table 1 was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Ｂ１－４３：式（Ｂ１－４３）で表される塩（特開２０１６－４７８１５号公報の実施
例に従って合成）

＜クエンチャー（Ｃ）＞
（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）
Ｄ１：特開２０１１－３９５０２号公報記載の方法で合成

Ｄ２：（東京化成工業（株）製）

＜溶剤：組成物１～５、９～１１、比較組成物１～５＞
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
＜溶剤：組成物６～８、１２～１５、比較組成物６～９＞
プロピレングリコールモノメチルエーテルアセテート ４００部
プロピレングリコールモノメチルエーテル １５０部
γ－ブチロラクトン ５部 <Resin>
A1 to A15, AX1 to AX9, X1: Resin A1 to Resin A15, Resin AX1 to Resin AX
9. Resin X1
<Acid generator (B)>
B1-21: Salt represented by formula (B1-21) (synthesized according to the examples of JP-A-2012-224611)
B1-22: Salt represented by formula (B1-22) (synthesized according to the examples of JP-A No. 2012-224611)

B1-43: Salt represented by formula (B1-43) (synthesized according to the examples of JP-A No. 2016-47815)

<Quencher (C)>
(Salt that generates an acid with weaker acidity than the acid generated from the acid generator)
D1: Synthesized by the method described in JP-A-2011-39502

D2: (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent: Compositions 1 to 5, 9 to 11, Comparative compositions 1 to 5>
Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts <Solvent: Compositions 6-8, 12-15, Comparative compositions 6-9>
Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 150 parts γ-butyrolactone 5 parts

(ArF exposure evaluation of resist composition)
A silicon wafer is coated with an organic anti-reflective film composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) and baked at 205°C for 60 seconds to form an organic reflective film with a thickness of 78 nm on the wafer. A preventive film was formed. Next, the resist composition described above was applied (spin coated) onto this organic antireflection film so that the film thickness after drying was 85 nm. After coating, the silicon wafer was prebaked for 60 seconds on a direct hot plate at the temperature listed in the "PB" column of Table 1 to form a composition layer. An ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3
/4Annular XY polarization), contact hole pattern (hole pitch 90n)
Using a mask for forming a hole diameter of 55 nm (hole diameter: 55 nm), exposure was performed while changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium.
After exposure, post-exposure baking was performed on a hot plate for 60 seconds at the temperature listed in the "PEB" column of Table 1. Next, the composition layer on the silicon wafer was developed by a dynamic dispensing method at 23° C. for 20 seconds using butyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a developer to form a negative resist pattern. Manufactured.
In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 45 nm was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In terms of 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. The average hole diameter of a pattern formed using a mask with a hole diameter of 55 nm was measured at 400 locations on the same wafer, and the standard deviation was determined using the population as a population.
The results are shown in Table 2. Values in parentheses indicate standard deviation (nm).

比較組成物１～５と比較して、組成物１～５、９～１１での標準偏差が小さく、ＣＤ均
一性（ＣＤＵ）評価が良好であった。

Compared to comparative compositions 1 to 5, compositions 1 to 5 and 9 to 11 had smaller standard deviations and better CD uniformity (CDU) evaluation.

(Electron beam exposure evaluation of resist composition)
A 6-inch silicon wafer was treated with hexamethyldisilazane at 90° C. for 60 seconds on a direct hot plate. A resist composition was spin-coated onto this silicon wafer so that the thickness of the composition layer was 0.04 μm. Thereafter, it was prebaked for 60 seconds on a direct hot plate at the temperature shown in the "PB" column of Table 1 to form a composition layer. The composition layer formed on the wafer was coated with an electron beam lithography machine [ELS-F1 manufactured by Elionix Co., Ltd.].
25 to 125 keV], a contact hole pattern (hole pitch 40 nm/hole diameter 17 nm) was directly drawn by changing the exposure dose stepwise.
After exposure, post-exposure baking was performed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 1, and further paddle development was performed for 60 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution. , a resist pattern was obtained.
In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 17 nm was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In terms of effective sensitivity, the hole diameter of a pattern formed using a mask with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The average hole diameter of a pattern formed using a mask with a hole diameter of 55 nm was measured at 400 locations on the same wafer, and the standard deviation was determined using the population as a population.
The results are shown in Table 3. Values in parentheses indicate standard deviation (nm).

比較組成物６～９と比較して、組成物６～８、１２～１５での標準偏差が小さく、ＣＤ
均一性（ＣＤＵ）評価が良好であった。

Compared to comparative compositions 6 to 9, the standard deviations of compositions 6 to 8 and 12 to 15 were smaller, and the CD
Uniformity (CDU) evaluation was good.

The resist composition of the present invention provides a resist pattern with good CD uniformity (CDU), and is therefore suitable for microfabrication of semiconductors and is extremely useful industrially.

Claims (11)

A compound represented by formula (IA) or formula (IB).

[In formula (IA) and formula (IB),
R ¹ and R ² each independently represent a hydrogen atom or a methyl group.
X ¹ and X ² represent a group represented by formula (X ¹ -1).

(In formula (X ¹ -1),
*, ** represent the binding site, and ** represents the binding site with ^L1 . )
L ¹ represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and represents a group represented by the formula (L ¹ B).

(In formula (L ¹ B),
L ⁴ and L ^4' each independently represent a single bond or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group is - It may be replaced with O-, -S-, -CO- or -SO ₂ -.
L ² represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^3' represents an alkantriyl group having 1 to 4 carbon atoms.
*a represents the bonding site with X ¹ , *b represents the bonding site with the oxygen atom in -OR ⁵ or with X ² , *c represents the bonding site with the oxygen atom in -OR ³ , and *d represents the bonding site with the oxygen atom in -OR 3. -Represents the bonding site with the oxygen atom in OR ⁴ . )
R ³ is a hydrocarbon group having 1 to 36 carbon atoms having a group represented by formula (IC) (the hydrocarbon group may have a substituent, and -CH ₂ - contained in the hydrocarbon group) may be replaced with -O-, -S-, -CO- or -SO ₂ -).
R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms which may have a group represented by formula (IC) (the hydrocarbon group has a substituent); -CH ₂ - contained in the hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -. ]

[In formula (IC),
R ^A represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
u1 represents any integer from 0 to 2, and when u1 is 2, the plurality of R ^A are the same or different.
s1 represents 1 or 2.
t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2.
* represents a binding site. ] A compound represented by formula (IA') or formula (IB').
[In formula (IA') and formula (IB'),
R ¹ and R ² each independently represent a hydrogen atom or a methyl group.
X ^1' and X ^2' each independently represent a group represented by any one of formulas (X ^1-2 ) to (X ^1-7 ).

(In formulas (X ¹ -2) to (X ¹ -7),
*, ** represent the binding site, and ** represents the binding site with ^L1 . )
L ^1' represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and represents a group represented by formula (L ¹ A) or a group represented by formula (L ¹ B). represent.

(In formula (L ¹ A) and formula (L ¹ B),
L ⁴ and L ^4' each independently represent a single bond or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group is - It may be replaced with O-, -S-, -CO- or -SO ₂ -.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^3' represents an alkantriyl group having 1 to 4 carbon atoms.
*a represents the bonding site with X ¹ , *b represents the bonding site with the oxygen atom in -OR ⁵ or with X ² , *c represents the bonding site with the oxygen atom in -OR ³ , and *d represents the bonding site with the oxygen atom in -OR 3. -Represents the bonding site with the oxygen atom in OR ⁴ . )
R ³ is a hydrocarbon group having 1 to 36 carbon atoms having a group represented by formula (IC) (the hydrocarbon group may have a substituent, and -CH ₂ - contained in the hydrocarbon group) may be replaced with -O-, -S-, -CO- or -SO ₂ -).
R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms which may have a group represented by formula (IC) (the hydrocarbon group has a substituent); -CH ₂ - contained in the hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -. ]

[In formula (IC),
R ^A represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
u1 represents any integer from 0 to 2, and when u1 is 2, the plurality of R ^A 's are the same or different.
s1 represents 1 or 2.
t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2.
* represents a binding site. ] 3. The compound according to claim 2, wherein X ¹ is a group represented by formula (X ¹ -3) or formula (X ¹ -4). L ⁴ and L ^4' are each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms, or a combination of an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms; group (-CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-, -CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -), L ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and L ³ is an alkane having 1 to 4 carbon atoms. 4. The compound according to claim 1, wherein the compound is a diyl group, and L ^3' is an alkantriyl group having 1 to 4 carbon atoms. A resin containing a structural unit derived from the compound according to any one of claims 1 to 4. The resin according to claim 5, further comprising a structural unit having an acid-labile group. The resin according to claim 6, wherein the structural unit having an acid-labile group includes at least one of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2).

[In formula (a1-1) and formula (a1-2),
L ^a1 and L ^a2 each independently represent -O- or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents any integer from 1 to 7, and * represents -CO- represents the binding site with.
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 any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1' represents any integer from 0 to 3. ] A resist composition comprising the resin according to any one of claims 5 to 7 and an acid generator. 9. The resist composition according to claim 8, wherein the acid generator contains a salt represented by formula (B1).

[In formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group that may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms that may have a substituent, and is included in the alicyclic hydrocarbon group. CH ₂ - may be replaced with -O-, -S(O) ₂ - or -CO-.
Z ⁺ represents an organic cation. ] 10. The resist composition according to claim 8, further comprising a salt that generates an acid less acidic than the acid generated from the acid generator. (1) applying the resist composition according to any one of claims 8 to 10 onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer to light;
(4) a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.
A method for manufacturing a resist pattern including: