JP2022021312A - Carboxylate, carboxylic acid generator, resist composition and method for producing resist pattern - Google Patents

Abstract

To provide a carboxylate that makes it possible to produce a resist pattern having excellent line edge roughness, a carboxylic acid generator and a resist composition comprising the same.SOLUTION: The present invention discloses, for example, a carboxylate represented by formula (I-1).SELECTED DRAWING: None

Description

The present invention relates to a carboxylic acid salt, a carboxylic acid generator, a resist composition and a method for producing a resist pattern.

特許文献２には、下記式で表されるカルボン酸塩をカルボン酸発生剤として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、下記式で表される塩を酸発生剤として含有するレジスト組成物が記載されている。

特許文献４には、下記式で表される塩を酸発生剤として含有するレジスト組成物が記載されている。

Patent Document 1 describes a resist composition containing a carboxylic acid salt represented by the following formula as a carboxylic acid generator.

Patent Document 2 describes a resist composition containing a carboxylic acid salt represented by the following formula as a carboxylic acid generator.

Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator.

Patent Document 4 describes a resist composition containing a salt represented by the following formula as an acid generator.

Japanese Unexamined Patent Publication No. 2011-039502 Japanese Unexamined Patent Publication No. 2016-09547 Japanese Unexamined Patent Publication No. 2011-08587 Japanese Unexamined Patent Publication No. 2020-015713

The present invention provides a carboxylate that forms a resist pattern with better line edge roughness (LER) than the resist pattern formed by the resist composition containing the above salts.

［式（Ｉ）中、
Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、－Ｏ－Ｒ^１０、－Ｏ－ＣＯ－Ｒ^１０、－Ｏ－ＣＯ－Ｏ－Ｒ^１０、－Ｏ－Ｌ^１－ＣＯ－Ｏ－Ｒ^１０を表す。
Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に、ハロゲン原子、ヒドロキシ基、炭素数１～１２のフッ化アルキル基又は炭素数１～１８の炭化水素基を表し、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－で置き換わっていてもよい。
Ｌ^１は、炭素数１～６のアルカンジイル基を表す。
Ｒ^１０は、ラクトン構造を有する基を表す。
Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、酸素原子又は硫黄原子を表す。
ｍ１は、０～５のいずれかの整数を表し、ｍ１が２以上のとき、複数の括弧内の基は互いに同一であっても異なってもよい。
ｍ２は、０～４のいずれかの整数を表し、ｍ２が２以上のとき、複数の括弧内の基は互いに同一であっても異なってもよい。
ｍ３は、０～４のいずれかの整数を表し、ｍ３が２以上のとき、複数の括弧内の基は互いに同一であっても異なってもよい。
ｍ４は、０～４のいずれかの整数を表し、ｍ４が２以上のとき、複数のＲ^４は互いに同一であっても異なってもよい。
ｍ５は、０～４のいずれかの整数を表し、ｍ５が２以上のとき、複数のＲ^５は互いに同一であっても異なってもよい。
ｍ６は、０～４のいずれかの整数を表し、ｍ６が２以上のとき、複数のＲ^６は互いに同一であっても異なってもよい。
ｍ７は、０～５のいずれかの整数を表し、ｍ７が２以上のとき、複数のＲ^７は互いに同一であっても異なってもよい。
ｍ８は、０～４のいずれかの整数を表し、ｍ８が２以上のとき、複数のＲ^８は互いに同一であっても異なってもよい。
ｍ９は、０～４のいずれかの整数を表し、ｍ９が２以上のとき、複数のＲ^９は互いに同一であっても異なってもよい。
但し、０≦ｍ１＋ｍ７≦５、０≦ｍ２＋ｍ８≦４、０≦ｍ３＋ｍ９≦４であり、ｍ１、ｍ２、ｍ３の少なくとも一つは、１以上の整数を表す。
Ｘ^４は、単結合、－ＣＨ₂－、－Ｏ－、－Ｓ－、－ＣＯ－、－ＳＯ－又は－ＳＯ_２－を表す。
Ｘ^０は、置換基を有してもよい炭素数１～７２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。］
［２］Ｘ^１、Ｘ^２及びＸ^３が酸素原子である［１］記載のカルボン酸塩。
［３］Ｒ^１、Ｒ^２及びＲ^３が－Ｏ－ＣＯ－Ｏ－Ｒ^１０－又は－Ｏ－Ｌ^１－ＣＯ－Ｏ－Ｒ^１０である［１］又は［２］記載のカルボン酸塩。
［４］Ｒ^１０のラクトン構造を有する基が、式（Ｒ^１０－１）、式（Ｒ^１０－２）又は式（Ｒ^１０－３）で表されるラクトン環基を有する基である［１］～［３］のいずれかに記載のカルボン酸塩。

［式（Ｒ^１０－１）～式（Ｒ^１０－３）中、
＊は、結合手を表す。
Ｚ¹²は、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^１１、Ｒ^１２及びＲ^１３は、それぞれ独立に、ハロゲン原子、炭素数１～６のフッ化アルキル基又は炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい。
ｍ１１は、０～５のいずれかの整数を表し、ｍ１１が２以上のとき、複数のＲ^１１は互いに同一であっても異なってもよい。
ｍ１２は、０～５のいずれかの整数を表し、ｍ１２が２以上のとき、複数のＲ^１２は互いに同一であっても異なってもよい。
ｍ１３は、０～５のいずれかの整数を表し、ｍ１３が２以上のとき、複数のＲ^１３は互いに同一であっても異なってもよい。
ｎ１０は、１～３の整数を表す。］
［５］Ｘ^０が、置換基を有してもよい炭素数１～７２の脂肪族炭化水素基（但し、該脂肪族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。）又は置換基を有してもよい炭素数６～３６の芳香族炭化水素基である［１］～［４］のいずれかに記載のカルボン酸塩。
［６］Ｘ^０が、フッ素原子もしくはヒドロキシ基を有してもよい炭素数３～３６の脂環式炭化水素基（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。）又はハロゲン原子、ヒドロキシ基、もしくは炭素数１～４のペルフルオロアルキル基を有してもよい炭素数６～３６の芳香族炭化水素基である［１］～［５］のいずれかに記載のカルボン酸塩。
［７］［１］～［６］のいずれかに記載のカルボン酸塩を含有するカルボン酸発生剤。
［８］［７］記載のカルボン酸発生剤、該カルボン酸発生剤以外の酸発生剤及び酸不安定基を有する樹脂を含有するレジスト組成物。
［９］酸不安定基を有する樹脂が、式（ａ１－１）で表される構造単位及び式（ａ１－２）で表される構造単位からなる群より選ばれる少なくとも１種を含む［８］記載のレジスト組成物。

［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－との結合位を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、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。
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２～８のアルケニル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族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。］
［１０］さらに、フッ素原子を有する構造単位を含む樹脂を含有する［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] Carboxylate represented by the formula (I).

[In formula (I),
R ¹ , R ² and R ³ are independently of -OR ¹⁰ , -O-CO-R ¹⁰ , -O-CO-O-R ¹⁰ , -OL ¹ -CO-O-R ¹⁰ . Represents.
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently have a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms. Represented, the hydrocarbon group may have a substituent, and -CH _2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- . May be good.
L ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
R ¹⁰ represents a group having a lactone structure.
X ¹ , X ² and X ³ independently represent an oxygen atom or a sulfur atom, respectively.
m1 represents an integer of 0 to 5, and when m1 is 2 or more, the groups in the plurality of parentheses may be the same or different from each other.
m2 represents an integer of 0 to 4, and when m2 is 2 or more, the groups in the plurality of parentheses may be the same or different from each other.
m3 represents an integer of 0 to 4, and when m3 is 2 or more, the groups in the plurality of parentheses may be the same or different from each other.
m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of ^R4s may be the same or different from each other.
m5 represents an integer of 0 to 4, and when m5 is 2 or more, a plurality of ^R5s may be the same or different from each other.
m6 represents an integer of 0 to 4, and when m6 is 2 or more, a plurality of ^R6s may be the same or different from each other.
m7 represents an integer of 0 to 5, and when m7 is 2 or more, a plurality of ^R7s may be the same or different from each other.
m8 represents an integer of 0 to 4, and when m8 is 2 or more, a plurality of ^R8s may be the same or different from each other.
m9 represents an integer of 0 to 4, and when m9 is 2 or more, a plurality of ^R9s may be the same or different from each other.
However, 0 ≦ m1 + m7 ≦ 5, 0 ≦ m2 + m8 ≦ 4, 0 ≦ m3 + m9 ≦ 4, and at least one of m1, m2, and m3 represents an integer of 1 or more.
X ⁴ represents a single bond, -CH _2- , -O-, -S-, -CO-, -SO- or -SO _2- .
X ⁰ represents a hydrocarbon group having 1 to 72 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- . ]
[2] The carboxylic acid salt according to [1], wherein X ¹ , X ² and X ³ are oxygen atoms.
[3] The carboxylic acid salt according to [1] or [2], wherein R ¹ , R ² and R ³ are -O-CO-O-R ^10- or -OL ¹ -CO-O-R ¹⁰ .
[4] The group having a lactone structure of R ¹⁰ is a group having a lactone ring group represented by the formula (R ¹⁰ -1), the formula (R ^10-2 ) or the formula (R ¹⁰ -3) [1]. ] To the carboxylate according to any one of [3].

[In equation (R ¹⁰ -1) to equation (R ¹⁰ -3),
* Represents a bond.
Z ¹² represents an oxygen atom, a sulfur atom or a methylene group.
R ¹¹ , R ¹² and R ¹³ each independently represent a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, and are contained in the hydrocarbon group-CH ₂ . -May be replaced by -O- or -CO-.
m11 represents an integer of 0 to 5, and when m11 is 2 or more, a plurality of ^R11s may be the same or different from each other.
m12 represents an integer of 0 to 5, and when m12 is 2 or more, a plurality of R ^12s may be the same or different from each other.
m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of ^R13s may be the same or different from each other.
n10 represents an integer of 1 to 3. ]
[5] An aliphatic hydrocarbon group having 1 to 72 carbon atoms in which X ⁰ may have a substituent (provided that -CH _2- contained in the aliphatic hydrocarbon group is -O-, -S. -, -CO- or -SO _2- may be replaced with) or any of [1] to [4] which is an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. The carboxylate according to.
[6] An alicyclic hydrocarbon group having 3 to 36 carbon atoms in which ^X0 may have a fluorine atom or a hydroxy group (-CH _2- contained in the alicyclic hydrocarbon group is -O-. , -S-, -CO- or -SO _2- ) or may have a halogen atom, a hydroxy group, or a perfluoroalkyl group having 1 to 4 carbon atoms and having 6 to 36 carbon atoms. The carboxylate according to any one of [1] to [5], which is an aromatic hydrocarbon group.
[7] The carboxylic acid generator containing the carboxylic acid salt according to any one of [1] to [6].
[8] A resist composition containing the carboxylic acid generator according to [7], an acid generator other than the carboxylic acid generator, and a resin having an acid unstable group.
[9] The resin having an acid unstable group contains at least one selected from the group consisting of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) [8]. ] The resist composition described.

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent -O- or * -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents -CO-. Represents the binding site with.
R ^a4 and R ^a5 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a6 and R ^a7 are independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group or a group combining these groups.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]
[10] The resist composition according to [8] or [9], which further contains a resin containing a structural unit having a fluorine atom.
[11] (1) A step of applying the resist composition according to any one of [8] to [10] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
A method for producing a resist pattern, which comprises (4) a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

By using the resist composition using the carboxylate of the present invention, a resist pattern can be produced with good line edge roughness (LER).

As used herein, the term "(meth) acrylic monomer" means "at least one of an acrylic monomer and a methacrylic monomer". Notations such as "(meth) acrylate" and "(meth) acrylic acid" have the same meaning. Any of the groups described herein that can have both a linear structure and a branched structure may be used. When -CH _2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO _2- , the same example shall be applied to each group. The "combined group" means a group in which two or more kinds of exemplified groups are bonded, and the valence of these groups may be appropriately changed depending on the bonding form. "Derived" or "derived" means that the polymerizable C = C bond contained in the molecule becomes a —C—C— group by polymerization. If a steric isomer is present, it includes all steric isomers.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］ [Carboxylate represented by the formula (I)]
The present invention relates to a carboxylic acid salt represented by the formula (I) (hereinafter, may be referred to as "salt (I)").
Of the salt (I), the side having a negative charge may be referred to as "anion (I)", and the side having a positive charge may be referred to as "cation (I)".

[In the formula, all the symbols have the same meanings as described above. ]

In the formula (I), the alkanediyl group in L ¹ contained in ^R1 , ^R2 and R3 includes ^a methylene group, an ethylene group, a propane-1,3-diyl group and a butane-1,4-diyl group. Linear alkanediyl groups such as pentane-1,5-diyl group, hexane-1,6-diyl group; and 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-1,2-diyl group, pentan-1, Examples thereof include a branched alkanediyl group such as a 4-diyl group and a 2-methylbutane-1,4-diyl group.
L ¹ is preferably an alkanediyl group having 1 to 3 carbon atoms, and more preferably a methylene group.

R ¹⁰ contained in R ¹ , R ² and R ³ represents a group having a lactone structure. The lactone structure refers to a structure obtained by removing one or more hydrogen atoms bonded to an atomic group constituting a lactone ring. The lactone ring is a cyclic ester and is a ring containing —CO—O— as an atomic group constituting the ring. The lactone structure may contain one or more heteroatoms such as a nitrogen atom, an oxygen atom, and a sulfur atom in addition to —CO—O— as an atomic group constituting the ring, and the atom constituting the lactone ring may be contained. The hydrogen atom bonded to the group may be replaced with a substituent. The lactone ring may be a monocyclic ring such as β-propiolactone ring, γ-butyrolactone ring and δ-valerolactone ring, or may be a fused ring of a monocyclic lactone ring and another ring. Among these lactone rings, a γ-butyrolactone ring, an adamantanane lactone ring, and a fused ring of a γ-butyrolactone ring and another ring are preferable because the salt (I) described later can be easily produced.

上記ラクトン環としては、式（Ｒ－１）、式（Ｒ－２）、式（Ｒ－３）、式（Ｒ－６）で表されるラクトン環が好ましい。 Examples of the lactone ring corresponding to the structure before the hydrogen atom is removed in the lactone structure include a lactone ring having 3 to 18 carbon atoms, and more specifically, the formula (R-1) and the formula (R-). 2), formula (R-3), formula (R-4), formula (R-5), formula (R-6), formula (R-7) and formula (R-8), respectively. Can be mentioned. Further, as the compound represented by the formula (R-3) or the formula (R-8), a hetero atom may be contained in addition to —CO—O— as the atomic group constituting the ring. Further, the hydrogen atom contained in the lactone ring may be replaced with a substituent.

As the lactone ring, the lactone ring represented by the formula (R-1), the formula (R-2), the formula (R-3), and the formula (R-6) is preferable.

［式（Ｒ^１０－１）～式（Ｒ^１０－３）中、
＊は、結合手を表す。
Ｚ¹²は、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^１１、Ｒ^１２及びＲ^１３は、それぞれ独立に、ハロゲン原子、炭素数１～６のフッ化アルキル基又は炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい。
ｍ１１は、０～５のいずれかの整数を表し、ｍ１１が２以上のとき、複数のＲ^１１は互いに同一であっても異なってもよい。
ｍ１２は、０～５のいずれかの整数を表し、ｍ１２が２以上のとき、複数のＲ^１２は互いに同一であっても異なってもよい。
ｍ１３は、０～５のいずれかの整数を表し、ｍ１３が２以上のとき、複数のＲ^１３は互いに同一であっても異なってもよい。
ｎ１０は、１～３の整数を表す。］ The group having a lactone structure of R ¹⁰ is preferably a group having a lactone ring group represented by the formula (R ¹⁰ -1), the formula (R ¹⁰ -2-) or the formula (R ¹⁰ -3).

[In equation (R ¹⁰ -1) to equation (R ¹⁰ -3),
* Represents a bond.
Z ¹² represents an oxygen atom, a sulfur atom or a methylene group.
R ¹¹ , R ¹² and R ¹³ each independently represent a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, and are contained in the hydrocarbon group-CH ₂ . -May be replaced by -O- or -CO-.
m11 represents an integer of 0 to 5, and when m11 is 2 or more, a plurality of ^R11s may be the same or different from each other.
m12 represents an integer of 0 to 5, and when m12 is 2 or more, a plurality of R ^12s may be the same or different from each other.
m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of ^R13s may be the same or different from each other.
n10 represents an integer of 1 to 3. ]

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６～１８であり、より好ましくは６～１４であり、さらに好ましくは６～１０である。
組み合わせることにより形成される基としては、芳香族炭化水素基と鎖式炭化水素基とを組み合わせた基（例えば、芳香族炭化水素基－アルカンジイル基－＊、アルキル基－芳香族炭化水素基－＊）、脂環式炭化水素基と鎖式炭化水素基とを組み合わせた基（例えば、脂環式炭化水素基－アルカンジイル基－＊、アルキル基－脂環式炭化水素基－＊）、芳香族炭化水素基と脂環式炭化水素基とを組み合わせた基（例えば、芳香族炭化水素基－脂環式炭化水素基－＊、脂環式炭化水素基－芳香族炭化水素基－＊）が挙げられる。＊は結合部位を表す。
芳香族炭化水素基－アルカンジイル基－＊としては、ベンジル基、フェネチル基等のアラルキル基が挙げられる。
アルキル基－芳香族炭化水素基－＊としては、トリル基、キシリル基、クメニル基等が挙げられる。
脂環式炭化水素基－アルカンジイル基－＊としては、シクロヘキシルメチル基、シクロヘキシルエチル基、１－（アダマンタン－１－イル）メチル基、１－（アダマンタン－１－イル）－１－メチルエチル等のシクロアルキルアルキル基等が挙げられる。
アルキル基－脂環式炭化水素基－＊としては、メチルシクロヘキシル基、ジメチルシクロヘキシル基、２－アルキルアダマンタン－２－イル基等のアルキル基を有するシクロアルキル基等が挙げられる。
芳香族炭化水素基－脂環式炭化水素基－＊としては、フェニルシクロヘキシル基等が挙げられる。
脂環式炭化水素基－芳香族炭化水素基－＊としては、シクロヘキシルフェニル基等が挙げられる。
なお、組み合わせにおいて、脂環式炭化水素基、芳香族炭化水素基、鎖式炭化水素基は、それぞれ２種以上を組み合わせてもよい。また、環式炭化水素基、鎖式炭化水素基（アルカンジイル基、アルキル基）に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わってもよい。組み合わせた基は、いずれの基がベンゼン環に結合していてもよい。 Examples of the halogen atom of R ¹¹ , R ¹² and R ¹³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The fluorinated alkyl group having 1 to 6 carbon atoms of R ¹¹ , R ¹² and R ¹³ represents an alkyl group having 1 to 6 carbon atoms having a fluorine atom, and a perfluoroalkyl group having 1 to 6 carbon atoms (trifluoromethyl). Group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), and 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl Groups and 3,3,4,4,4-pentafluorobutyl groups and the like can be mentioned. The alkyl fluoride group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms.
The hydrocarbon groups having 1 to 18 carbon atoms of R ¹¹ , R ¹² and R ¹³ are formed by chain-type hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and combinations thereof. The groups to be used are mentioned.
The alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group and an octyl group. , Nonyl group, decyl group, undecyl group, dodecyl group and the like. The number of carbon atoms of the chain hydrocarbon group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, still more preferably 1 to 4, and even more preferably. It is 1 to 3.
The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group. Examples thereof include monocyclic cycloalkyl groups such as cyclooctyl groups and cyclodecyl groups. Examples of the polycyclic alicyclic hydrocarbon group include a polycyclic cycloalkyl group such as a decahydronaphthyl group, an adamantyl group and a norbornyl group. The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and further preferably 3 to 12 carbon atoms.
Specifically, examples of the alicyclic hydrocarbon group include the groups represented below. The binding site can be any position.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a binaphthyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.
The groups formed by the combination include a group in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined (for example, an aromatic hydrocarbon group-alkandyl group- *, an alkyl group-an aromatic hydrocarbon group-. *), A group that combines an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, an alicyclic hydrocarbon group-alkandyl group- *, an alkyl group-an alicyclic hydrocarbon group- *), aroma. A group that combines a group hydrocarbon group and an alicyclic hydrocarbon group (for example, an aromatic hydrocarbon group-an alicyclic hydrocarbon group- *, an alicyclic hydrocarbon group-an aromatic hydrocarbon group- *) Can be mentioned. * Represents the binding site.
Examples of the aromatic hydrocarbon group-alkandyl group-* include an aralkyl group such as a benzyl group and a phenethyl group.
Examples of the alkyl group-aromatic hydrocarbon group- * include a tolyl group, a xylyl group, a cumenyl group and the like.
As the alicyclic hydrocarbon group-alkandyl group- *, cyclohexylmethyl group, cyclohexylethyl group, 1- (adamantan-1-yl) methyl group, 1- (adamantan-1-yl) -1-methylethyl, etc. Cycloalkylalkyl groups and the like.
Examples of the alkyl group-alicyclic hydrocarbon group- * include a cycloalkyl group having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group.
Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group- * include a phenylcyclohexyl group and the like.
Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group- * include a cyclohexylphenyl group and the like.
In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Further, -CH _2- contained in the cyclic hydrocarbon group and the chain hydrocarbon group (alkanediyl group, alkyl group) may be replaced with -O-, -S-, -CO- or -SO _2- . good. As for the combined group, any group may be bonded to the benzene ring.

炭化水素基に含まれる－ＣＨ_２－が、－Ｏ－又は－ＣＯ－で置き換わっている場合、置き換わる前の炭素数を該炭化水素基の総炭素数とする。また、その数は、１つでもよいし、２以上でもよい。 As a group in which -CH _2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- , a hydroxy group (-CH ₂ -contained in the methyl group-" is used. -O-replaced group), carboxy group (-CH ₂ -CH ₂ -replaced in -O-CO- in the ethyl group), Thiol group (-CH ₂ contained in the methyl group) -Is a group replaced by -S-), an alkoxy group (a group in which -CH _2- at any position contained in the alkyl group is replaced by -O-), an alkylthio group (any contained in the alkyl group). -CH 2- at the position of -CH ₂ -is replaced with -S-), alkoxycarbonyl group (group in which -CH ₂ -CH _2- at any position contained in the alkyl group is replaced with -O-CO-). ), Alkoxysulfonyl group (group in which -CH _2- at any position contained in the alkyl group is replaced with -SO _2- ), alkylcarbonyl group (-CH ₂ -at any position contained in the alkyl group-) Is a group replaced with -CO-), an alkylcarbonyloxy group (a group in which -CH ₂ -CH _2- at any position contained in the alkyl group is replaced with -CO-O-), a cycloalkoxy group, Examples thereof include a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyloxy group, and a group in which two or more of these groups are combined.
Examples of the alkoxy group include an alkoxy group having 1 to 17 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group and a nonyloxy group. Groups, decyloxy groups, undecyloxy groups and the like can be mentioned. The alkoxy group has preferably 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms.
Examples of the alkylthio group include an alkylthio group having 1 to 17 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3.
The alkoxycarbonyl group, an alkylcarbonyl group and an alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group.
Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 17 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include an alkylcarbonyl group having 2 to 18 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a butyryl group. Examples of the alkylcarbonyloxy group include an alkylcarbonyloxy group having 2 to 17 carbon atoms, and examples thereof include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkoxycarbonyl group has preferably 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and even more preferably 2 or 3 carbon atoms. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The alkylcarbonyloxy group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and even more preferably 2 or 3 carbon atoms.
Examples of the alkylsulfonyl group include an alkylsulfonyl group having 1 to 17 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3.
Examples of the cycloalkoxy group include a cycloalkoxy group having 3 to 17 carbon atoms, and examples thereof include a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include a cycloalkylalkoxy group having 4 to 17 carbon atoms, and examples thereof include a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include an alkoxycarbonyloxy group having 2 to 16 carbon atoms, and examples thereof include a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyloxy group include an aromatic hydrocarbon group-carbonyloxy group having 7 to 17 carbon atoms, and examples thereof include a benzoyloxy group.
Examples of the group in which -CH _2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- include the groups represented below. .. Among the groups represented below, there are also groups in which -O- is replaced with -S- and -CO- is replaced with -SO _2- . The binding site can be any position.

When -CH _2- contained in the hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before the replacement is taken as the total number of carbon atoms of the hydrocarbon group. Further, the number may be one or two or more.

m11, m12, and m13 are preferably 0 to 2, and more preferably 0.

Ｒ^１、Ｒ^２及びＲ^３は、－Ｏ－ＣＯ－Ｒ^１０、－Ｏ－ＣＯ－Ｏ－Ｒ^１０、－Ｏ－Ｌ^１－ＣＯ－Ｏ－Ｒ^１０であることが好ましく、－Ｏ－ＣＯ－Ｏ－Ｒ^１０－又は－Ｏ－Ｌ^１－ＣＯ－Ｏ－Ｒ^１０であることがより好ましい。
Ｒ^１、Ｒ^２及びＲ^３の結合位置は、それぞれＸ^１、Ｘ^２及びＸ^３の結合位置に対してо位、ｍ位、ｐ位のいずれでもよい。なかでも、Ｘ^１、Ｘ^２及びＸ^３の結合位置に対してｐ位に結合していることが好ましい。 Examples of the group having a lactone ring group represented by the formula (R ¹⁰ -1), the formula (R ^10-2 ) or the formula (R ¹⁰ -3) include the following groups and the like.

R ¹ , R ² and R ³ are preferably -O-CO-R ¹⁰ , -O-CO-O-R ¹⁰ , -OL ¹ -CO-O-R ¹⁰ and -O-CO. -OR ¹⁰ -or -OL ¹ -CO-OR ¹⁰ is more preferable.
The bonding positions of R ¹ , R ² and R ³ may be о-positions, m-positions, or p-positions with respect to the bonding positions of X ¹ , X ² and X ³ , respectively. Above all, it is preferable that the bond is at the p-position with respect to the bond positions of X ¹ , X ² and X ³ .

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６～１８であり、より好ましくは６～１４であり、さらに好ましくは６～１０である。
組み合わせることにより形成される基としては、芳香族炭化水素基と鎖式炭化水素基とを組み合わせた基（例えば、芳香族炭化水素基－アルカンジイル基－＊、アルキル基－芳香族炭化水素基－＊）、脂環式炭化水素基と鎖式炭化水素基とを組み合わせた基（例えば、脂環式炭化水素基－アルカンジイル基－＊、アルキル基－脂環式炭化水素基－＊）、芳香族炭化水素基と脂環式炭化水素基とを組み合わせた基（例えば、芳香族炭化水素基－脂環式炭化水素基－＊、脂環式炭化水素基－芳香族炭化水素基－＊）が挙げられる。＊は結合部位を表す。
芳香族炭化水素基－アルカンジイル基－＊としては、ベンジル基、フェネチル基等のアラルキル基が挙げられる。
アルキル基－芳香族炭化水素基－＊としては、トリル基、キシリル基、クメニル基等が挙げられる。
脂環式炭化水素基－アルカンジイル基－＊としては、シクロヘキシルメチル基、シクロヘキシルエチル基、１－（アダマンタン－１－イル）メチル基、１－（アダマンタン－１－イル）－１－メチルエチル等のシクロアルキルアルキル基等が挙げられる。
アルキル基－脂環式炭化水素基－＊としては、メチルシクロヘキシル基、ジメチルシクロヘキシル基、２－アルキルアダマンタン－２－イル基等のアルキル基を有するシクロアルキル基等が挙げられる。
芳香族炭化水素基－脂環式炭化水素基－＊としては、フェニルシクロヘキシル基等が挙げられる。
脂環式炭化水素基－芳香族炭化水素基－＊としては、シクロヘキシルフェニル基等が挙げられる。
なお、組み合わせにおいて、脂環式炭化水素基、芳香族炭化水素基、鎖式炭化水素基は、それぞれ２種以上を組み合わせてもよい。また、環式炭化水素基、鎖式炭化水素基（アルカンジイル基、アルキル基）に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わってもよい。組み合わせた基は、いずれの基がベンゼン環に結合していてもよい。
炭化水素基に含まれる－ＣＨ₂－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わった基としては、ヒドロキシ基（メチル基中に含まれる－ＣＨ₂－が、－Ｏ－に置き換わった基）、カルボキシ基（エチル基中に含まれる－ＣＨ₂－ＣＨ₂－が、－Ｏ－ＣＯ－に置き換わった基）、チオール基（メチル基中に含まれる－ＣＨ₂－が、－Ｓ－に置き換わった基）、アルコキシ基（アルキル基中に含まれる任意の位置の－ＣＨ₂－が、－Ｏ－に置き換わった基）、アルキルチオ基（アルキル基中に含まれる任意の位置の－ＣＨ₂－が、－Ｓ－に置き換わった基）、アルコキシカルボニル基（アルキル基中に含まれる任意の位置の－ＣＨ₂－ＣＨ₂－が、－Ｏ－ＣＯ－に置き換わった基）、アルキルスルホニル基（アルキル基中に含まれる任意の位置の－ＣＨ₂－が、－ＳＯ_２－に置き換わった基）、アルキルカルボニル基（アルキル基中に含まれる任意の位置の－ＣＨ₂－が、－ＣＯ－に置き換わった基）、アルキルカルボニルオキシ基（アルキル基中に含まれる任意の位置の－ＣＨ₂－ＣＨ₂－が、－ＣＯ－Ｏ－に置き換わった基）、シクロアルコキシ基、シクロアルキルアルコキシ基、アルコキシカルボニルオキシ基、芳香族炭化水素基－カルボニルオキシ基、これらの基うち２種以上を組み合わせた基等が挙げられる。
アルコキシ基としては、炭素数１～１７のアルコキシ基が挙げられ、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、オクチルオキシ基、２－エチルヘキシルオキシ基、ノニルオキシ基、デシルオキシ基、ウンデシルオキシ基等が挙げられる。アルコキシ基の炭素数は、好ましくは１～１１であり、より好ましくは１～６であり、さらに好ましくは１～４であり、さらにより好ましくは１～３である。
アルキルチオ基としては、炭素数１～１７のアルキルチオ基が挙げられ、例えば、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基等が挙げられる。アルキルチオ基の炭素数は、好ましくは１～１１であり、より好ましくは１～６であり、さらに好ましくは１～４であり、さらにより好ましくは１～３である。
アルコキシカルボニル基、アルキルカルボニル基及びアルキルカルボニルオキシ基は、上述したアルキル基又はアルコキシ基にカルボニル基又はカルボニルオキシ基が結合した基を表す。
アルコキシカルボニル基としては、炭素数２～１７のアルコキシカルボニル基が挙げられ、例えば、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基等が挙げられる。アルキルカルボニル基としては、炭素数２～１８のアルキルカルボニル基が挙げられ、例えば、アセチル基、プロピオニル基及びブチリル基等が挙げられる。アルキルカルボニルオキシ基としては、炭素数２～１７のアルキルカルボニルオキシ基が挙げられ、例えば、アセチルオキシ基、プロピオニルオキシ基、ブチリルオキシ基等が挙げられる。アルコキシカルボニル基の炭素数は、好ましくは２～１１であり、より好ましくは２～６であり、さらに好ましくは２～４である。アルキルカルボニル基の炭素数は、好ましくは２～１２であり、より好ましくは２～６であり、さらに好ましくは２～４である。アルキルカルボニルオキシ基の炭素数は、好ましくは２～１１であり、より好ましくは２～６であり、さらに好ましくは２～４である。
アルキルスルホニル基としては、炭素数１～１７のアルキルスルホニル基が挙げられ、例えば、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基等が挙げられる。アルキルスルホニル基の炭素数は、好ましくは１～１１であり、より好ましくは１～６であり、さらに好ましくは１～４であり、さらにより好ましくは１～３である。
シクロアルコキシ基としては、炭素数３～１７のシクロアルコキシ基が挙げられ、例えば、シクロヘキシルオキシ基等が挙げられる。シクロアルキルアルコキシ基としては、炭素数４～１７のシクロアルキルアルコキシ基が挙げられ、例えば、シクロヘキシルメトキシ基等が挙げられる。アルコキシカルボニルオキシ基としては、炭素数２～１６のアルコキシカルボニルオキシ基が挙げられ、例えば、ブトキシカルボニルオキシ基等が挙げられる。芳香族炭化水素基－カルボニルオキシ基としては、炭素数７～１７の芳香族炭化水素基－カルボニルオキシ基が挙げられ、例えば、ベンゾイルオキシ基等が挙げられる。
また、脂環式炭化水素基に含まれる－ＣＨ_２－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わった基としては、以下に表される基等が挙げられる。以下に表される基のうち、－Ｏ－が－Ｓ－、－ＣＯ－が－ＳＯ_２－にそれぞれ置き換わった基等も挙げられる。結合部位は任意の位置とすることができる。

炭化水素基に含まれる－ＣＨ_２－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっている場合、置き換わる前の炭素数を該炭化水素基の総炭素数とする。また、その数は、１つでもよいし、２以上でもよい、
Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９の炭化水素基が有していてもよい置換基としては、ハロゲン原子、シアノ基、炭素数１～１２のアルキル基（該アルキル基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい）が挙げられる。
ハロゲン原子としては、上述した基と同様の基が挙げられる。
炭素数１～１２のアルキル基としては、上述した基と同様の基が挙げられる。
置換基として、アルキル基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっている場合、置き換わる前の炭素数を該アルキル基の総炭素数とする。置き換わった基としては、ヒドロキシ基、カルボキシ基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルカルボニルオキシ基等が挙げられる。
アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基及びアルキルカルボニルオキシ基としては、上述した基と同様の基が挙げられる。
炭化水素基は、１つの置換基又は複数の置換基を有していてもよい。 Examples of the halogen atom of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The fluorinated alkyl group having 1 to 12 carbon atoms of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ represents an alkyl group having 1 to 12 carbon atoms having a fluorine atom and having 1 to 12 carbon atoms. Twelve perfluoroalkyl groups (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), as well as 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, Examples thereof include a 4,4,4-trifluorobutyl group and a 3,3,4,4,4-pentafluorobutyl group. The alkyl fluoride group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms.
The hydrocarbon groups having 1 to 18 carbon atoms of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups and aromatic hydrocarbons. Examples thereof include a hydrogen group and a group formed by combining these groups.
The alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group and an octyl group. , Nonyl group, decyl group, undecyl group, dodecyl group and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group. , Cycloalkyl groups such as cyclooctyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the like. The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and further preferably 3 to 12 carbon atoms.
Specifically, examples of the alicyclic hydrocarbon group include the groups represented below. The binding site can be any position.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a binaphthyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.
The groups formed by the combination include a group in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined (for example, an aromatic hydrocarbon group-alkandyl group- *, an alkyl group-an aromatic hydrocarbon group-. *), A group that combines an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, an alicyclic hydrocarbon group-alkandyl group- *, an alkyl group-an alicyclic hydrocarbon group- *), aroma. A group that combines a group hydrocarbon group and an alicyclic hydrocarbon group (for example, an aromatic hydrocarbon group-an alicyclic hydrocarbon group- *, an alicyclic hydrocarbon group-an aromatic hydrocarbon group- *) Can be mentioned. * Represents the binding site.
Examples of the aromatic hydrocarbon group-alkandyl group- * include an aralkyl group such as a benzyl group and a phenethyl group.
Examples of the alkyl group-aromatic hydrocarbon group- * include a tolyl group, a xylyl group, a cumenyl group and the like.
As the alicyclic hydrocarbon group-alkandyl group- *, cyclohexylmethyl group, cyclohexylethyl group, 1- (adamantan-1-yl) methyl group, 1- (adamantan-1-yl) -1-methylethyl, etc. Cycloalkylalkyl groups and the like.
Examples of the alkyl group-alicyclic hydrocarbon group- * include a cycloalkyl group having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group.
Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group- * include a phenylcyclohexyl group and the like.
Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group- * include a cyclohexylphenyl group.
In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Further, -CH _2- contained in the cyclic hydrocarbon group and the chain hydrocarbon group (alkanediyl group, alkyl group) may be replaced with -O-, -S-, -CO- or -SO _2- . good. As for the combined group, any group may be bonded to the benzene ring.
As a group in which -CH _2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- , a hydroxy group (-CH ₂ -contained in the methyl group-" is used. -O-replaced group), carboxy group (-CH ₂ -CH ₂ -replaced in -O-CO- in the ethyl group), Thiol group (-CH ₂ contained in the methyl group) -Is a group replaced by -S-), an alkoxy group (a group in which -CH _2- at any position contained in the alkyl group is replaced by -O-), an alkylthio group (any contained in the alkyl group). -CH 2- at the position of -CH ₂ -is replaced with -S-), alkoxycarbonyl group (group in which -CH ₂ -CH _2- at any position contained in the alkyl group is replaced with -O-CO-). ), Alkoxysulfonyl group (group in which -CH _2- at any position contained in the alkyl group is replaced with -SO _2- ), alkylcarbonyl group (-CH ₂ -at any position contained in the alkyl group-) Is a group replaced with -CO-), an alkylcarbonyloxy group (a group in which -CH ₂ -CH _2- at any position contained in the alkyl group is replaced with -CO-O-), a cycloalkoxy group, Examples thereof include a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyloxy group, and a group in which two or more of these groups are combined.
Examples of the alkoxy group include an alkoxy group having 1 to 17 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group and a nonyloxy group. Groups, decyloxy groups, undecyloxy groups and the like can be mentioned. The alkoxy group has preferably 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms.
Examples of the alkylthio group include an alkylthio group having 1 to 17 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3.
The alkoxycarbonyl group, an alkylcarbonyl group and an alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group.
Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 17 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include an alkylcarbonyl group having 2 to 18 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a butyryl group. Examples of the alkylcarbonyloxy group include an alkylcarbonyloxy group having 2 to 17 carbon atoms, and examples thereof include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkoxycarbonyl group has preferably 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The alkylcarbonyloxy group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
Examples of the alkylsulfonyl group include an alkylsulfonyl group having 1 to 17 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3.
Examples of the cycloalkoxy group include a cycloalkoxy group having 3 to 17 carbon atoms, and examples thereof include a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include a cycloalkylalkoxy group having 4 to 17 carbon atoms, and examples thereof include a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include an alkoxycarbonyloxy group having 2 to 16 carbon atoms, and examples thereof include a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyloxy group include an aromatic hydrocarbon group-carbonyloxy group having 7 to 17 carbon atoms, and examples thereof include a benzoyloxy group.
Examples of the group in which -CH _2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- include the groups represented below. .. Among the groups represented below, there are also groups in which -O- is replaced with -S- and -CO- is replaced with -SO _2- . The binding site can be any position.

When -CH _2- contained in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO _2- , the number of carbon atoms before the replacement is taken as the total number of carbon atoms of the hydrocarbon group. .. Further, the number may be one or two or more.
The substituents that the hydrocarbon groups of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may have include halogen atoms, cyano groups, and alkyl groups having 1 to 12 carbon atoms (the alkyl). -CH ₂ -contained in the group may be replaced with -O- or -CO-).
Examples of the halogen atom include groups similar to those described above.
Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those described above.
When -CH _2- contained in the alkyl group as a substituent is replaced with -O- or -CO-, the carbon number before the replacement is taken as the total carbon number of the alkyl group. Examples of the replaced group include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group and the like.
Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group and the alkylcarbonyloxy group include the same groups as those described above.
The hydrocarbon group may have one substituent or a plurality of substituents.

X ¹ is preferably an oxygen atom.
X ² is preferably an oxygen atom.
X ³ is preferably an oxygen atom.
The bond position of X ¹ , X ² and X ³ may be any of the о position, the m position and the p position with respect to the S ⁺ bond position. Among them, it is preferable that the bond is at the p-position or the m-position with respect to the S ⁺ bond position, and it is more preferable that the bond is at the p-position.
m1 is preferably 0, 1 or 2, and more preferably 1.
It is preferred that m2 is 0 or 1.
It is preferred that m3 is 0 or 1.
When m1 is 0 or 1, it is preferable that both m2 and m3 are 1.
m4 is preferably 0, 1, 2 or 4. When m4 is 1 or 2, it is preferable that at least one ^R4 bond position is bonded to the o-position with respect to the X1 bond position, and when m4 is 2, ^{one R4} bond position is preferable. Is preferably bonded to the o-position with respect to the bond position of X ¹ , and the other bond position of R ⁴ is preferably bonded to the m-position with respect to the bond position of X ¹ .
m5 is preferably 0, 1 or 2. When m5 is 1 or 2, it is preferable that at ^least one R5 bond position is bonded to the o ^- position with respect to the X2 bond position, and when m5 is ² , one R5 bond position is preferable. Is preferably bonded to the o ^- position with respect to the bond position of X2, and the other bond position of R5 is preferably bonded to the ^{m -} position with respect to the bond position of X2.
m6 is preferably 0, 1 or 2. When m6 is 1 or 2, it is preferable that at least one R6 bond position is bonded to the o ^- position with respect to the X3 bond position, and when m6 is ² , one ^R6 bond position is preferable. Is preferably bonded to the o ^- position with respect to the bond position of X3 ^, and the other bond position of R6 is preferably bonded to the m ^- position with respect to the bond position of X3.
m7 is preferably 0, 1 or 2, and more preferably 0 or 1.
m8 is preferably 0 or 1.
m9 is preferably 0 or 1.
When m1 + m2 + m3 is 2 or more, the groups in the plurality of parentheses may be the same or different from each other, that is, when there are a plurality of X1 to X3 and when there ^{are a} plurality of ^R1 to R3 ^, respectively. When there are a plurality of ^R4 to R6, they may be the ^same as each other or may be different from each other.
R ⁴ , R ⁵ and R ⁶ are independently each of a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 6 carbon atoms (-CH _2- contained in the alkyl group is-. It may be replaced with O- or -CO-), and is preferably a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms (included in the alkyl group). CH ₂ − may be replaced with —O— or —CO—), and may be a fluorine atom, an iodine atom, a trifluoromethyl group, or an alkyl group having 1 to 4 carbon atoms. More preferred.
R ⁷ , R ⁸ and R ⁹ are independently each of a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 6 carbon atoms (-CH _2- contained in the alkyl group-is-. It may be replaced with O- or -CO-), and is preferably a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms (included in the alkyl group). CH ₂ − may be replaced with —O— or —CO—), more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or an alkyl having 1 to 4 carbon atoms. More preferably, it is a group (-CH _2- contained in the alkyl group may be replaced with -O- or -CO-), and a fluorine atom, an iodine atom, a trifluoromethyl group, a methyl group, and the like. It is even more preferably a t-butyl group, a hydroxy group or a methoxy group.
The bonding positions of R ⁷ , R ⁸ and R ⁹ are not particularly limited. When m2 is 0, the coupling position of R8 may be о ^- position, m-position, or p-position with respect to the coupling position of S ⁺ , and in particular, it is coupled to the p-position with respect to the coupling position of S ⁺ . Is more preferable. When m3 is 0, the coupling position of R ⁹ may be о-position, m-position, or p-position with respect to the coupling position of S ⁺ , and in particular, it is coupled to the p-position with respect to the coupling position of S ⁺ . Is more preferable.
For ^X4 , a single bond, —CH _2- , —O—, —CO— is preferable, a single bond, —CH ₂ -is more preferable, and a single bond is even more preferable.

Examples of the cation of the salt (I) include cations represented by the following formulas (I-c-1) to (I-c-53).

In the formula (I), the hydrocarbon group represented by ^X0 includes an aliphatic hydrocarbon group (chain hydrocarbon group such as alkyl group, alkenyl group and alkynyl group and alicyclic hydrocarbon group) and aromatic group. Examples thereof include a hydrocarbon group and a group combining these groups. -CH _2- contained in the aliphatic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- .
Examples of the alkyl group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a nonyl group. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. Is.
Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octynyl group, an isooctynyl group and a nonenyl group.
Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group and a nonynyl group.
As a group in which -CH _2- contained in the chain hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- , a hydroxy group (-CH ₂ -contained in the methyl group-" is used. Is a group replaced with -O-), a carboxy group (a group in which -CH ₂ -CH _2- is replaced with -O-CO- contained in an ethyl group), and a thiol group (a group contained in a methyl group-). CH ₂ -replaced with -S-), alkoxy group (group in which _-CH2- at any position contained in the alkyl group is replaced with -O-), alkoxycarbonyl group (in the alkyl group) -CH ₂ -CH _2- at any position contained is replaced with -O-CO-, and an alkylcarbonyl group (-CH _2- at any position contained in the alkyl group is replaced with -CO-). (Replaced group), alkylsulfonyl group (group in which -CH _2- at any position contained in the alkyl group is replaced with -SO _2- ), alkylcarbonyloxy group (group at any position contained in the alkyl group). -CH ₂ -CH _2- is a group in which -CO-O- is replaced), an alkylthio group (a group in which -CH _2- at an arbitrary position contained in the alkyl group is replaced with -S-), etc. are mentioned. Be done.
Examples of the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group, the alkylcarbonyloxy group and the alkylthio group include the same groups as described above. Examples of the alkylsulfonyl group include an alkylsulfonyl group having 1 to 17 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4.
The substitution in the alkenyl group and the alkynyl group may be any one containing a carbon-carbon double bond or a carbon-carbon triple bond at an arbitrary position in the above-mentioned example of substitution in the alkyl group.
The alicyclic hydrocarbon group may be a monocyclic, polycyclic or spiro ring, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group 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. Examples thereof include a polycyclic cycloalkyl group such as a group.
Specific examples of the groups in which -CH _2- contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group are replaced with -O-, -S-, -CO- or -SO _2- are as follows. The basis of. The binding site can be any position.

脂環式炭化水素基又は脂環式炭化水素基に含まれる－ＣＨ₂－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わった基としては、式（ｙ１）～（ｙ７１）で表される基が好ましく、式（ｙ１）～式（ｙ２０）、式（ｙ２６）、式（ｙ２７）、式（ｙ３０）、式（ｙ３１）、式（ｙ３９）～式（ｙ７１）のいずれかで表される基がより好ましく、式（ｙ３）、（ｙ４）、式（ｙ９）、式（ｙ１１）、式（ｙ１４）、式（ｙ１５）、式（ｙ１６）、式（ｙ２０）、式（ｙ２６）、式（ｙ２７）、式（ｙ３０）、式（ｙ３１）、式（ｙ３９）、式（ｙ４０）、式（ｙ４２）、式（ｙ４３）、式（ｙ４９）～式（ｙ５８）、式（ｙ６２）～式（ｙ７１）で表される基がさらに好ましい。脂環式炭化水素基の炭素数は、好ましくは３～３６であり、より好ましくは３～２４であり、さらに好ましくは３～１８であり、より一層好ましくは３～１６である。

Examples of the group in which -CH _2- contained in the alicyclic hydrocarbon group or the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- are given by the formulas (y1) to "y1". The group represented by (y71) is preferable, and formulas (y1) to (y20), formulas (y26), formulas (y27), formulas (y30), formulas (y31), formulas (y39) to formulas (y71). The group represented by any of the above is more preferable, and the formula (y3), (y4), the formula (y9), the formula (y11), the formula (y14), the formula (y15), the formula (y16), and the formula (y20) are more preferable. , Formula (y26), formula (y27), formula (y30), formula (y31), formula (y39), formula (y40), formula (y42), formula (y43), formula (y49) to formula (y58). , The groups represented by the formulas (y62) to (y71) are more preferable. The alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 24 carbon atoms, still more preferably 3 to 18 carbon atoms, and even more preferably 3 to 16 carbon atoms.

Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group and a binaphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, still more preferably 6 to 14, and even more preferably. It is 6 to 10.
In the case of a combined group, the above-mentioned groups include groups having different valences (alkanediyl group, alkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.). It may be.

The combined group is
A group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (-CH _2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group is -O-, -S-,- It may be replaced with CO- or -SO _2- ),
A group that combines a chain hydrocarbon group and an aromatic hydrocarbon group (-CH _2- contained in the chain hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- . (May be), and a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (-CH _2- contained in the alicyclic hydrocarbon group is -O-, -S-,- It may be replaced with CO- or -SO _2- ).
In the combination, two or more kinds of alicyclic hydrocarbon group, chain hydrocarbon group and aromatic hydrocarbon group may be combined.
Specifically, as a combined group,
Alicyclic hydrocarbon groups such as adamantyl methylene group and cyclohexyl methylene group-chain hydrocarbon group- *, (alicyclic hydrocarbon group) ₂ -chain hydrocarbon group- * (the chain hydrocarbon group and the above) -CH _2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- ),.
Chain hydrocarbon groups such as methyl adamantyl groups and dimethyl adamantyl groups-alicyclic hydrocarbon groups-*, (chain hydrocarbon groups) ₂ -Alicyclic hydrocarbon groups-* (the chain hydrocarbon groups and the same) -CH _2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- ),.
Chain hydrocarbon groups such as tolyl groups and xylyl groups-aromatic hydrocarbon groups-* (-CH _2- contained in the chain hydrocarbon groups are -O-, -S-, -CO- or -SO. It may be replaced with _2- ),
Chain Hydrocarbon Group such as Methylcyclohexylmethylene Group-Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group- *, (Chain Hydrocarbon Group) ₂ -Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group- * , (Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group) ₂ -Chain 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),
Aromatic hydrocarbon groups such as benzyl groups-chain hydrocarbon groups-* (-CH ₂ -contained in the chain hydrocarbon groups-is changed to -O-, -S-, -CO- or -SO _2- May be replaced),
Chain hydrocarbon groups such as trillmethyl groups-aromatic hydrocarbon groups-chain hydrocarbon groups-* (-CH ₂ -contained in the chain hydrocarbon groups-is -O-, -S-, -CO- Or it may be replaced with -SO _2- ),
Methyl adamantanmethylene adamantyl group, di (methyl adamantanmethylene) adamantyl group, etc. Chain hydrocarbon group-Alicyclic hydrocarbon group-Chain hydrocarbon group-Alicyclic hydrocarbon group- *, (Chain hydrocarbon group) -Ali ring hydrocarbon group-Chain hydrocarbon group) ₂ -Ali ring hydrocarbon group- *, (Chain hydrocarbon group-Ali ring hydrocarbon group) ₂ -Chain hydrocarbon group-Ali ring type Hydrocarbon groups-*, (chain hydrocarbon groups) ₂ -Alicyclic hydrocarbon groups-Chain hydrocarbon groups-Alicyclic hydrocarbon groups-* (Chain hydrocarbon groups and alicyclic hydrocarbons) -CH ₂ -contained in the group may be replaced with -O-, -S-, -CO- or -SO _2- ),
Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group-*, (Alicyclic Hydrocarbon Group) ₂ -Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group -Chain-type hydrocarbon group-*, (Ali-ring-type hydrocarbon group-Chain-type hydrocarbon group) ₂ -Ali-ring-type hydrocarbon group-Chain-type hydrocarbon group- *, (Ali-ring-type hydrocarbon group-Chain type) Hydrocarbon Group-Alicyclic Hydrocarbon Group) ₂ -Chain 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 Group-Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group-*, (Chain Hydrocarbon Group) ₂ -Alicyclic Hydrocarbon Group- Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group-*, (Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group) ₂ -Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group- Chain Hydrocarbon Group-*, (Chain Hydrocarbon Group-Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group) ₂ -Alicyclic Hydrocarbon Group-Chain Hydrocarbon Group-*, (Chain Hydrocarbon Group) Group-Alicyclic hydrocarbon group-Chain hydrocarbon group-Alicyclic hydrocarbon group) ₂ -Chain hydrocarbon group-* (included in the chain hydrocarbon group and the alicyclic hydrocarbon group- CH _2- may be replaced with -O-, -S-, -CO- or -SO _2- ),
And so on. Here, * represents the binding site of the carbonyl group with the carbon atom.

炭素数６～１０の芳香族炭化水素基としては、フェニル基、ナフチル基等のアリール基が挙げられる。
組み合わせた基としては、ヒドロキシ基と炭素数１～１２のアルキル基とを組み合わせた基、炭素数１～１２のアルキル基と炭素数６～１０の芳香族炭化水素基とを組み合わせた基、炭素数３～１２の脂環式炭化水素基と炭素数６～１０の芳香族炭化水素基とを組み合わせた基等が挙げられる。
ヒドロキシ基と炭素数１～１２のアルキル基とを組み合わせた基としては、ヒドロキシメチル基、ヒドロキシエチル基等の炭素数１～１２のヒドロキシアルキル基等が挙げられる。
炭素数１～１２のアルキル基と炭素数６～１０の芳香族炭化水素基とを組み合わせた基としては、ベンジル基等の炭素数７～２２のアラルキル基、トリル基、キシリル基等の炭素数７～２２のアルキルアリール基が挙げられる。
炭素数３～１２の脂環式炭化水素基と炭素数６～１０の芳香族炭化水素基とを組み合わせた基としては、シクロヘキシルフェニル基等が挙げられる。 When -CH _2- contained in the hydrocarbon group represented by X ⁰ is replaced with -O-, -S-, -CO- or -SO _2- , the number of carbon atoms before the replacement is the hydrocarbon group. The total number of carbon atoms in. When a substituent is bonded to the hydrocarbon group represented by ^X0 , the number of carbon atoms before the substitution is defined as the total number of carbon atoms of the hydrocarbon group.
The hydrocarbon group represented by X ⁰ may have one or more substituents.
The substituents include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and an alkylcarbonyl group having 2 to 13 carbon atoms. Examples thereof include a group, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a nonyl group.
The alkoxy group having 1 to 12 carbon atoms includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group and an undecyloxy group. Groups, dodecyloxy groups and the like can be mentioned.
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 a 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 a methoxycarbonyl group, an ethoxycarbonyl group and a butoxycarbonyl group, and examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** represents the binding site with X ⁰ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include an aryl group such as a phenyl group and a naphthyl group.
The combined group includes a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and carbon. Examples thereof include a group in which an alicyclic hydrocarbon group having a number of 3 to 12 and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined.
Examples of the group in which a hydroxy group and an alkyl group having 1 to 12 carbon atoms are combined include a hydroxyalkyl group having 1 to 12 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group.
As a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, the number of carbon atoms such as an aralkyl group having 7 to 22 carbon atoms such as a benzyl group, a trill group and a xylyl group Examples thereof include 7 to 22 alkylaryl groups.
Examples of the group in which an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined include a cyclohexylphenyl group and the like.

［式（ａａ）中、
Ｘ^a及びＸ^bは、それぞれ独立に、－Ｏ－又は－Ｓ－を表す。
Ｘ^１ａは、置換基を有してもよい炭素数１～２４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。
Ｘ^２ａは、置換基を有してもよい炭素数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。
＊は、－ＣＯＯ^－の炭素原子との結合位を表す。］
［式（ｂｂ）中、
Ｌ^Ａは、フッ素原子を有していてもよい炭素数１～６のアルカンジイル基又はハロゲン原子もしくは炭素数１～４のペルフルオロアルキル基を有していてもよい炭素数６の芳香族炭化水素基を表す。
Ｌ^Ｂは、単結合又は炭素数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－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい。
Ｒ^Ａは、置換基を有してもよい炭素数１～３６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。
＊は、－ＣＯＯ^－の炭素原子との結合位を表す。］ As the hydrocarbon group represented by X0, preferably, an aliphatic hydrocarbon group having ¹ to 72 carbon atoms which may have a substituent (-CH _2- contained in the aliphatic hydrocarbon group-is It is an aromatic hydrocarbon group having 6 to 36 carbon atoms and may be replaced with —O—, —S—, —CO— or _—SO2- ) or may have a substituent.
More preferably, an alicyclic hydrocarbon group which may have a hydroxy group or a fluorine atom (-CH _2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO ₂ -may be replaced), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (-CH _2- contained in the alicyclic hydrocarbon group is -O- , -S-, -CO- or -SO _2- may be replaced, and -CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-. The alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group), a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms. An aromatic hydrocarbon group, a group represented by the formula (aa) or a group represented by the formula (bb).
More preferably, * -an alicyclic hydrocarbon group (-CH _2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2-- . Often, the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * Represents the bond position of -COO- with a carbon atom.) ^, * -Alicyclic hydrocarbon group- A chain hydrocarbon group (-CH _2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- , and the chain hydrocarbon may be replaced. -CH _2- contained in the group may be replaced with -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. Good. * Represents the bond position of -COO ^- with a carbon atom.), *-Chain-type hydrocarbon group-Alicyclic hydrocarbon group (-CH ₂ -contained in the chain-type hydrocarbon group-is- It 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- . Often, the chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * Represents the bond position of —COO with a carbon atom) ^, a fluorine atom or An aromatic hydrocarbon group which may have a hydroxy group, a group represented by the formula (aa) or a group represented by the formula (bb).
Even more preferably, * -polycyclic alicyclic hydrocarbon group (-CH _2- contained in the polycyclic alicyclic hydrocarbon group is -O-, -S-, -CO- or It may be replaced with _−SO2- , and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * Represents the bond position of −COO ⁻ with a carbon atom. ), * -Polycyclic alicyclic hydrocarbon group-Chain hydrocarbon group (-CH _2- contained in the polycyclic alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO _2- may be replaced, and -CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the polycyclic fat may be replaced. The cyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * Represents the bond position with the carbon atom of −COO—), * ⁻ Chain hydrocarbon group. -The polycyclic alicyclic hydrocarbon group (-CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the polycyclic alicyclic hydrocarbon may be replaced. -CH _2- contained in the hydrogen group may be replaced with -O-, -S-, -CO- or -SO _2- , and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon may be replaced. The hydrogen group may have a fluorine atom or a hydroxy group. * Represents the bond position of —COO with a carbon atom) ^, an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, and the like. A group represented by the formula (aa) or a group represented by the formula (bb).
Particularly preferably, an adamantanone group, a hydroxyadamantyl group, or a group in which an adamantyl group and an alkyl group are combined (-CH _2- contained in the alkyl group may be replaced with -O- or -CO-). , A phenyl group having a group represented by the formula (Y30F) or a hydroxy group.
In the above group, the alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 24 carbon atoms, still more preferably 3 to 18 carbon atoms, and even more preferably 3 to 16 carbon atoms. Yes, and even more preferably 3-12. The number of carbon atoms of the chain hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, still more preferably 1 to 6, and even more preferably. It is 1 to 4. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, still more preferably 6 to 14, and even more preferably. It is 6 to 10.

[In the formula (aa),
X ^a and X ^b independently represent -O- or -S-, respectively.
X ^1a represents a hydrocarbon group having 1 to 24 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- .
X ^2a 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-. It may be replaced with SO _2- .
* Represents the binding ^site of -COO- with a carbon atom. ]
[In equation (bb),
^LA is an aromatic hydrocarbon having 6 carbon atoms which may have an alkanediyl group having 1 to 6 carbon atoms or a halogen atom or a perfluoroalkyl group having 1 to 4 carbon atoms which may have a fluorine atom. Represents a group.
^LB represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and -CH _2- contained in the alkanediyl group is replaced with -O-, -S-, -CO- or -SO _2- . May be.
^RA represents a hydrocarbon group having 1 to 36 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- .
* Represents the binding ^site of -COO- with a carbon atom. ]

X ^a and X ^b are preferably the same atom, and more preferably both oxygen atoms.

Examples of the hydrocarbon group represented by X ^1a and X ^2a include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which two or more of these are combined. In addition, these hydrocarbon groups may have a substituent. Further, -CH _2- contained in these hydrocarbon groups may be replaced with -O-, -S-, -CO- or -SO _2- . Here, the carbon number of the hydrocarbon group means the carbon number of the hydrocarbon group having no substituent and having no replacement.

Examples of the aliphatic hydrocarbon group of X ^1a include a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, or a group combining these.
Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, a butantryyl group, a pentantriyl group, a hexanetriyl group, a heptanthryyl group, an octantriyl group, a nonantriyl group and a decantryyl group. , Undecantryyl group, dodecantryyl group and the like.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic.
Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutanetriyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, a cyclooctanetriyl group and the like.
Examples of the polycyclic alicyclic hydrocarbon group include a norbornane triyl group and an adamantane triyl group.
Examples of the aromatic hydrocarbon group include a benzenetriyl group, a naphthalenetriyl group, an anthracene triyl group and the like.
In the case of a combined group, even if the above-mentioned groups contain groups having different valences (alkyl group, alkanediyl group, alkanetetrayl group, cycloalkyl group, cycloalkanediyl group, cycloalkanetetrayl group, etc.) good.

The hydrocarbon group represented by X ^1a has 1 to 24 carbon atoms and may further have one or a plurality of substituents. Examples of the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and an alkyl having 2 to 13 carbon atoms. Examples thereof include a carbonyl group, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these.
Examples of the halogen atom, the alkyl group, the alkoxy group, the alkoxycarbonyl group, the alkylcarbonyl group and the alkylcarbonyloxy group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group and the group combining them include the same groups as described above. ..

［式（ｗ１－１）～式（ｗ１－１１）中、
環は、ヒドロキシ基、ハロゲン原子、シアノ基、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、炭素数２～１３のアルコキシカルボニル基、炭素数２～１３のアルキルカルボニル基、炭素数２～１３のアルキルカルボニルオキシ基、炭素数３～１２の脂環式炭化水素基、炭素数６～１０の芳香族炭化水素基又はこれらを組み合わせた基を有していてもよい。
＊は結合位を表す。］ As the hydrocarbon group represented by X ^1a , an alcantryl group having 1 to 6 carbon atoms which may have a substituent or an alicyclic hydrocarbon having 3 to 18 carbon atoms which may have a substituent may be used. It is preferably a group, more preferably an hydrocarbon group having 1 to 6 carbon atoms, and more preferably a group represented by the formulas (w1-1) to (w1-11), and the hydrocarbon having 1 to 6 carbon atoms. A polycyclic hydrocarbon group such as a triyl group, a group represented by the formula (w1-1) or a group represented by the formula (w1-3), a group represented by the formula (w1-2) or a group represented by the formula (w1-2). It is more preferable that it is a monocyclic hydrocarbon group such as the group represented by w1-6).

[In equation (w1-1) to equation (w1-11),
The ring includes a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and an alkylcarbonyl group having 2 to 13 carbon atoms. It may have an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these.
* Represents the binding site. ]

The number of carbon atoms of the hydrocarbon group represented by X ^2a is preferably 2 to 48, more preferably 4 to 48, further preferably 6 to 44, and preferably 8 to 40. Even more preferably, it is even more preferably 10 to 38.

The substituents that the hydrocarbon group in X ^2a may have include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 2 to 13 carbon atoms. Alkoxycarbonyl group, alkylcarbonyl group with 2 to 13 carbon atoms, alkylcarbonyloxy group with 2 to 13 carbon atoms, alicyclic hydrocarbon group with 3 to 12 carbon atoms, aromatic hydrocarbon group with 6 to 10 carbon atoms. Alternatively, a group obtained by combining these can be mentioned.
Examples of the halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group and a group combining these groups include the same groups as described above. ..
The hydrocarbon group having 1 to 48 carbon atoms represented by X ^2a may have one substituent or a plurality of substituents.

The hydrocarbon group in X ^2a includes a linear or branched chain hydrocarbon group (for example, an alkanediyl group, etc.), a monocyclic or polycyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group. However, a combination of two or more of these groups may be used.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl group, Octane-1,8-Diyl group and other linear alkanediyl groups;
Etan-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
A monocyclic cycloalkandyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Alicyclic hydrocarbon group of the formula;
A polycyclic cycloalkanediyl group such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. Polycyclic hydrocarbon group;
Examples thereof include aromatic hydrocarbon groups such as a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group, a phenanthrylene group and a binaphthylene group.
In the case of a combined group, the above-mentioned groups include groups having different valences (alkyl group, alkanetriyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.). May be.
The combined groups include a group combining a chain hydrocarbon group and an alicyclic hydrocarbon group, a group combining a chain hydrocarbon group and an aromatic hydrocarbon group, and an alicyclic hydrocarbon group and an aromatic hydrocarbon. Examples thereof include groups in which groups are combined, and specifically, a group in which one or more alicyclic hydrocarbon groups are bonded to a chain hydrocarbon group (for example,-chain hydrocarbon group-alicyclic hydrocarbon group, etc., -Chain hydrocarbon group- (Alicyclic hydrocarbon group) ₂ etc.), Group in which one or more chain hydrocarbon groups are bonded to an alicyclic hydrocarbon group (for example, -Alicyclic hydrocarbon group-Chain Type hydrocarbon group, -Alicyclic hydrocarbon group- (chain hydrocarbon group) ₂ etc.), Group in which one or more alicyclic hydrocarbon groups and chain hydrocarbon group are bonded to a chain hydrocarbon group ( For example, -chain hydrocarbon group-aliphatic hydrocarbon group-chain hydrocarbon group, -chain hydrocarbon group- (alicyclic hydrocarbon group-chain hydrocarbon group) ₂ , etc.) and the like can be mentioned. ..

As the hydrocarbon group in X ^2a ,
A chain hydrocarbon group having 2 to 18 carbon atoms (-CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the chain hydrocarbon group is substituted. It may have a group.),
Even if the alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH _2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2-- Often, the alicyclic hydrocarbon group may have a substituent) or
A chain hydrocarbon group having 1 to 12 carbon atoms (-CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-) and a fat having 3 to 18 carbon atoms. A group in which a cyclic hydrocarbon group (-CH _2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- ) is combined. (The group may have a substituent.)
A chain hydrocarbon group having 4 to 18 carbon atoms (-CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the chain hydrocarbon group is substituted. It may have a group.) Or
A chain hydrocarbon group having 1 to 12 carbon atoms (-CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-) and a fat having 3 to 16 carbon atoms. A group in which a cyclic hydrocarbon group (-CH _2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- ) is combined. (The group may have a substituent.) It is more preferable that the group has a substituent.
A chain hydrocarbon group having 6 to 14 carbon atoms (-CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the chain hydrocarbon group is substituted. It may have a group.) Or
A chain hydrocarbon group having 1 to 12 carbon atoms (-CH _2- contained in the chain hydrocarbon group may be replaced with -O- or -CO-) and a fat having 5 to 14 carbon atoms. A group in which a cyclic hydrocarbon group (-CH _2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- ) is combined. (The group may have a substituent.) It is more preferable.

Specifically, as the hydrocarbon group in X ^2a ,
An alkanediyl group having 2 to 18 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-),.
An alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (-CH _2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or It may be replaced with -SO _2- ),
An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-) and a substituent. The alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH _2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO. A group consisting of (which may be replaced with _2- )) or an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group is-. It may be replaced with O- or -CO-) and may have an alicyclic hydrocarbon group having 3 to 18 carbon atoms and a substituent may have 1 to 1 carbon atoms. It is preferably a group consisting of 12 alkyl groups (-CH _2- contained in the alkyl group may be replaced with -O- or -CO-).
An alkanediyl group having 4 to 18 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-),.
An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-) and a substituent. The alicyclic hydrocarbon group having 3 to 16 carbon atoms (-CH _2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO. A group consisting of (which may be replaced with _2- ) or an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group is -O. -Or -CO- may be replaced with) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent and an alicyclic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. More preferably, it is a group consisting of an alkyl group (-CH _2- contained in the alkyl group may be replaced with -O- or -CO-).
An alkanediyl group having 6 to 14 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-),.
An alkanediyl group having 1 to 12 carbon atoms which may have a substituent (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-) and a substituent. It has a group or a substituent consisting of an adamantandiyl group (-CH _2- contained in the adamantandiyl group may be replaced with -O- or -CO-). It may have an alkanediyl group having 1 to 12 carbon atoms (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-) and a substituent. A good adamantandiyl group and an alkyl group having 1 to 12 carbon atoms which may have a substituent (-CH _2- contained in the alkyl group may be replaced with -O- or -CO-). It is more preferable that the group consists of.

［式中、
Ｒ^1ｘ、Ｒ^2ｘ、Ｒ^3ｘ、Ｒ^4ｘ、Ｒ^5ｘ及びＲ^6ｘは、それぞれ独立に、炭素数１～６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の２種以上の基を組み合わせた基を表し、該アルキル基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよく、該アルキル基及び該脂環式炭化水素基は、置換基を有していてもよい。
＊は、Ｘ^a及びＸ^bとの結合位を表す。］
組み合わせた基は、上述したアルキル基と脂環式炭化水素基とを１つずつ組み合わせたものでも、いずれかを２以上又は双方を２以上組み合わせた基でもよい。この場合、組み合わせた基の炭素数は３９以下であり、３７以下が好ましい。 Specifically, X ^2a is a group represented by the formula (X 2-1), a group represented by the formula (X ² -2-), a group represented by the formula (X ^{2-3), or a formula (X 2 -3} ). It is preferably a group represented by X ² -4).

[During the ceremony,
R ^1x , R ^2x , R ^3x , R ^4x , R ^5x and R ^6x are independently an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or two or more of them. Represents a group in which the groups of the above are combined, and even if -CH _2- contained in the alkyl group and the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- . Often, the alkyl group and the alicyclic hydrocarbon group may have a substituent.
* Represents the binding site with X ^a and X ^b . ]
The combined group may be a combination of the above-mentioned alkyl group and an alicyclic hydrocarbon group one by one, or a group in which either two or more or both are combined in two or more. In this case, the number of carbon atoms of the combined group is 39 or less, preferably 37 or less.

Among them, as R ^1x , R ^2x , R ^3x , R ^4x , R ^5x and R ^6x , an alkyl group having 1 to 6 carbon atoms (-CH _2- contained in the alkyl group is -O- or -CO. It may be replaced with —, and the alkyl group may have a substituent), an alicyclic hydrocarbon group having 5 to 12 carbon atoms (included in the alicyclic hydrocarbon group—CH). _2- may be replaced with -O-, -S-, -CO- or -SO _2- , and the alicyclic hydrocarbon group may have a substituent) or the number of carbon atoms. An alkyl group of 1 to 6 (-CH _2- contained in the alkyl group may be replaced with -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (the fat). -CH _2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- ) (the group is a substituent). It is preferable that the group has a methoxy group and an adamantyl group (-CH _2- contained in the adamantyl group may be replaced with -O- or -CO-, and the adamantyl group may be substituted. May have a substituent) or an alkyl group having 1 to 6 carbon atoms (-CH _2- contained in the alkyl group may be replaced with -O- or -CO-). It is more preferable that the group is a combination of the adamantyl group and the adamantyl group (the group may have a substituent).

In the formula (bb), examples of the alkanediyl group having 1 to 6 carbon atoms in LA and LB include a methylene group, an ethylene group, a propane ^- 1,3-diyl group, and a butane ^- 1,4-diyl group. Linear alkanediyl groups such as pentane-1,5-diyl group, hexane-1,6-diyl group; propane-1,2-diyl group, 1-methylpropane-1,3-diyl group, 2-methyl Branched alkanediyl groups such as propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Can be mentioned. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3.
Examples of the alkanediyl group which may have a fluorine atom include a perfluoroalkanediyl group such as a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group and a perfluoropentanediyl group.
When -CH _2- contained in the alkanediyl group is replaced with -O- or -CO-, the carbon number before the replacement is taken as the total carbon number of the alkanediyl group. The alkandyl group includes a hydroxy group (a group in which -CH _2- contained in the methyl group is replaced with -O-) and a carboxy group (-CH ₂ -CH _2- contained in the ethyl group is -O-. CO-replaced group), alkoxy group (group in which -CH _2- at any position contained in the alkyl group is replaced with -O-), alkoxycarbonyl group (group at any position contained in the alkyl group). -CH ₂ -CH ₂ -replaced with -O-CO-), alkylcarbonyl group (group in which _-CH2- at any position contained in the alkyl group is replaced with -CO-), alkyl A carbonyloxy group (a group in which -CH ₂ -CH _2- at any position contained in an alkyl group is replaced with -CO-O-), an alkandyloxy group (a group at any position contained in an alkandyl group). -CH ₂ -replaced with -O-), alcandiyloxycarbonyl group (group in which _{-CH2 -} CH2- at any position contained in the alcandiyl group is replaced with -O-CO- ), Alcandiylcarbonyl group (a group in which -CH _2- at any position contained in the alcandiyl group is replaced with -CO-), alcandiylcarbonyloxy group (at any position contained in the alcandiyl group). -CH ₂ -CH _2- may have a group in which -CO-O- is replaced.
Examples of the alkanediyloxy group include a methyleneoxy group, an ethyleneoxy group, a propandiyloxy group, a butanediyloxy group, a pentanediyloxy group and the like.
Examples of the alkanediyloxycarbonyl group include a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propandiyloxycarbonyl group, a butanediyloxycarbonyl group and the like.
Examples of the alkanediylcarbonyl group include a methylenecarbonyl group, an ethylenecarbonyl group, a propandiylcarbonyl group, a butanjiylcarbonyl group, a pentandiylcarbonyl group and the like.
Examples of the alkanediylcarbonyloxy group include a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propandiylcarbonyloxy group, a butanediylcarbonyloxy group and the like.
^LA is preferably an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom, and more preferably an alkanediyl group having 1 to 3 carbon atoms having a fluorine atom.
^LB is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms (-CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-). It is more preferably a single bond, a methylene group or an ethylene group.

As the hydrocarbon group in ^RA , an aliphatic hydrocarbon group (chain hydrocarbon group such as alkyl group, alkenyl group, alkynyl group and alicyclic hydrocarbon group), aromatic hydrocarbon group and a combination thereof can be used. Examples include the groups formed.
As the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and 2 -Ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like can be mentioned. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 9, even more preferably 1 to 6, and even more preferably 1 to 4. Is.
Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octynyl group, an isooctynyl group and a nonenyl group.
Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group and a nonynyl group.
As the group in which -CH _2- contained in the chain hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- , a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, etc. Examples thereof include an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylthio group and an alkylsulfonyl group.
Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylsulfonyl group and alkylthio group include an alkoxy group having 1 to 17 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms and 2 to 2 carbon atoms. Examples thereof include an alkylcarbonyl group having 18 carbon atoms, an alkylcarbonyloxy group having 2 to 17 carbon atoms, an alkylsulfonyl group having 1 to 17 carbon atoms and an alkylthio group having 1 to 17 carbon atoms, and the same groups as those described above can be mentioned.
The alicyclic hydrocarbon group may be a monocyclic, polycyclic or spiro ring, and may be saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include a monocyclic group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group and a cyclododecyl group. Cycloalkyl groups can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a polycyclic cycloalkyl group such as a decahydronaphthyl group, an adamantyl group and a norbornyl group.
Specific examples of the group in which -CH _2- contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- are as described above. Examples thereof include groups represented by the formulas (y1) to (y71) of. The alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 24 carbon atoms, still more preferably 3 to 18 carbon atoms, still more preferably 3 to 16 carbon atoms, and even more preferably. Is 3-12.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group and a binaphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 18, still more preferably 6 to 14, and even more preferably. It is 6 to 10.

In the case of a combined group, the above-mentioned groups may contain groups having different valences (alkanediyl group, alkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.).
The groups formed by the combination include a group in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined (for example, an aromatic hydrocarbon group-alkandyl group- *, an alkyl group-an aromatic hydrocarbon group-. *), A group that combines an alicyclic hydrocarbon group and a chain hydrocarbon group (for example, an alicyclic hydrocarbon group-alkandyl group- *, an alkyl group-an alicyclic hydrocarbon group- *), aroma. A group that combines a group hydrocarbon group and an alicyclic hydrocarbon group (for example, an aromatic hydrocarbon group-an alicyclic hydrocarbon group- *, an alicyclic hydrocarbon group-an aromatic hydrocarbon group- *) Can be mentioned. * Represents the binding site.
Examples of the aromatic hydrocarbon group-alkandyl group- * include an aralkyl group such as a benzyl group and a phenethyl group.
Examples of the alkyl group-aromatic hydrocarbon group- * include a tolyl group, a xylyl group, a cumenyl group and the like.
As the alicyclic hydrocarbon group-alkandyl group- *, cyclohexylmethyl group, cyclohexylethyl group, 1- (adamantan-1-yl) methyl group, 1- (adamantan-1-yl) -1-methylethyl, etc. Cycloalkylalkyl groups and the like.
Examples of the alkyl group-alicyclic hydrocarbon group- * include a cycloalkyl group having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group.
Examples of the aromatic hydrocarbon group-alicyclic hydrocarbon group- * include a phenyladamantyl group and the like.
Examples of the alicyclic hydrocarbon group-aromatic hydrocarbon group- * include an adamantylphenyl group and the like.
In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Moreover, any group may be bonded to ^LB.
As the group in which -CH _2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- , in addition to the above-mentioned group, a cycloalkoxy group or a cycloalkylalkoxy group is used. , An alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyloxy group, a group in which two or more of these groups are combined, and the like can also be mentioned.
Examples of the cycloalkoxy group include a cycloalkoxy group having 3 to 17 carbon atoms, and examples thereof include a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include a cycloalkylalkoxy group having 4 to 17 carbon atoms, and examples thereof include a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include an alkoxycarbonyloxy group having 2 to 16 carbon atoms, and examples thereof include a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyloxy group include an aromatic hydrocarbon group-carbonyloxy group having 7 to 17 carbon atoms, and examples thereof include a benzoyloxy group.
When -CH _2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO _2- or -CO-, the number of carbon atoms before the replacement is taken as the total number of carbon atoms of the hydrocarbon group. .. Further, the number may be one or two or more.

The substituents that the hydrocarbon group of ^RA may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (-CH _2- contained in the alkyl group is -O-,-. It may be replaced with S-, -CO- or -SO _2- ).
Examples of the halogen atom include groups similar to those described above.
Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those described above.
Examples of the group in which -CH _2- contained in the alkyl group is replaced with -O- or -CO- include a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group and the like. ..
Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group include an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms and 2 carbon atoms. Examples thereof include the alkylcarbonyloxy groups to 11 to 11, and examples thereof include groups similar to those described above.
The hydrocarbon group in ^RA may have one substituent or a plurality of substituents.

As the hydrocarbon group in ^RA , an alkyl group having 1 to 12 carbon atoms which may have a substituent (however, -CH _2- contained in the alkyl group is -O-, -S-, -CO. -Or -SO ₂ -may be replaced with-) or a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (provided that -CH _2- contained in the cyclic hydrocarbon group-is It may be replaced with —O—, —S—, —CO— or _—SO2- ), and may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms. A cyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH _2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO _2- . ) Is more preferable.

The cyclic hydrocarbon group includes a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. Group etc. can be mentioned.
Examples of the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the combined group include the same groups as described above.
In the combination, two or more alicyclic hydrocarbon groups and aromatic hydrocarbon groups may be combined. Moreover, any group may be bonded to ^LB.

A cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms, and is included in the alicyclic hydrocarbon group-. CH _2- may be replaced with -O-, -S-, -CO- or -SO _2- ).
An alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms (-CH _2- contained in the alicyclic hydrocarbon group-is-. It may be replaced with O-, -S-, -CO- or -SO _2- ), or
It is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms.
An alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms (-CH _2- contained in the alicyclic hydrocarbon group-is-. It may be replaced with O- or -CO-).
As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the following groups (bonding sites are arbitrary positions) are preferable, and aromatic hydrocarbons are used. As the group, a phenyl group and a naphthyl group are preferable.

Examples of the carboxylic acid anion in the carboxylic acid salt represented by the formula (I) include the carboxylic acid anions described below.

Specific examples of the carboxylate (I) include salts in which the above-mentioned cations and anions are arbitrarily combined. Specific examples of the salt (I) are shown in the table below.
In the table below, each reference numeral represents a reference numeral attached to the above-mentioned structure representing an anion or cation, and "to" indicates that the carboxylate (I) and the anion (I) correspond to each other. For example, the carboxylate (I-1) is a salt composed of an anion represented by the formula (I-a-1) and a cation represented by the formula (I-c-1), the carboxylate (I-2). Is a salt composed of an anion represented by the formula (I-a-2) and a cation represented by the formula (I-c-1), and the carboxylate (I-96) is the formula (I-a-1). The salt composed of the anion represented by the above and the cation represented by the formula (Ic-2) is shown.

Among them, the carboxylates (I) include formulas (I-a-1) to (I-a-5), formulas (I-a-10) to formulas (I-a-21) and formulas (I-a-21). Anions represented by any of the formulas (I-a-57) to (I-a-66) and cations represented by any of the formulas (I-c-1) to (I-c-53). A salt that combines the above is preferable, and specifically,
Carboxylate (I-1) to Carboxylate (I-5), Carboxylate (I-10) to Carboxylate (I-21), Carboxylate (I-57) to Carboxylate (I) -66), Carboxylate (I-96) to Carboxylate (I-100), Carboxylate (I-105) to Carboxylate (I-116), Carboxylate (I-152) to Carboxylate Hydrochloride (I-161), Carboxylate (I-191) -Carboxylate (I-195), Carboxylate (I-200) -Carboxylate (I-411) Carboxylate (I-247) )-Carboxylate (I-256), Carboxylate (I-286) -Carboxylate (I-290), Carboxylate (I-295) -Carboxylate (I-306), Carboxylate (I-342) -carboxylate (I-351), carboxylate (I-381) -carboxylate (I-385), carboxylate (I-390) -carboxylate (I-401) , Carboxylates (I-437) to Carboxylates (I-446), Carboxylates (I-476) to Carboxylates (I-480) Carboxylates (I-485) to Carboxylates (I) -496), Carboxylate (I-532) -Carboxylate (I-541), Carboxylate (I-571) -Carboxylate (I-575), Carboxylate (I-580) -Carboxylate Hydrochloride (I-591), Carboxylate (I-627) -Carboxylate (I-636), Carboxylate (I-666) -Carboxylate (I-670), Carboxylate (I- 675) to Carboxylic Acids (I-686), Carboxylic Acids (I-722) to Carboxylic Acids (I-731), Carboxylic Acids (I-761) to Carboxylic Acids (I-765), Carboxylic Acids Salt (I-770) -carboxylate (I-781), carboxylate (I-817) -carboxylate (I-826), carboxylate (I-856) -carboxylate (I-860) ), Carboxylate (I-865) to Carboxylate (I-876), Carboxylate (I-912) to Carboxylate (I-921), Carboxylate (I-951) to Carboxylate (I-955), Carboxylate (I-960) to Carboxylate (I-971), Carboxylate (I-1007) to Carboxylate (I-1016), Carboxylate (I-1046) ~ Carboxylate (I-1050), Carboxylate (I-1055) ~ Carboxylate (I-1066), Carboxylate (I-1102) ~ Carboxylate (I-1) 111), Carboxylic Acids (I-1141) to Carboxylic Acids (I-1145), Carboxylic Acids (I-1150) to Carboxylic Acids (I-1161), Carboxylic Acids (I-1197) to Carboxylic Acids Salt (I-1206), Carboxylate (I-1236) to Carboxylate (I-1240), Carboxylate (I-1245) to Carboxylate (I-1256), Carboxylate (I-1292) )-Carboxylate (I-1301), Carboxylate (I-1331) -Carboxylate (I-1335), Carboxylate (I-1340) -Carboxylate (I-1351), Carboxylate (I-1387) to carboxylate (I-1396), carboxylate (I-1426) to carboxylate (I-1430), carboxylate (I-1435) to carboxylate (I-1446). , Carboxylates (I-1482) to Carboxylates (I-1491), Carboxylates (I-1521) to Carboxylates (I-1525), Carboxylates (I-1530) to Carboxylates ( I-1541), carboxylate (I-1577) to carboxylate (I-1586), carboxylate (I-1616) to carboxylate (I-1620), carboxylate (I-1625) to Carboxylates (I-1636), Carboxylates (I-1672) to Carboxylates (I-1681), Carboxylates (I-1711) to Carboxylates (I-1715), Carboxylates (I) -1720) to carboxylate (I-1731), carboxylate (I-1767) to carboxylate (I-1776), carboxylate (I-1806) to carboxylate (I-1810), carboxylic acid Hydrochloride (I-1815) to Carboxylate (I-1826), Carboxylate (I-1862) to Carboxylate (I-1871), Carboxylate (I-1901) to Carboxylate (I- 1905), Carboxylic Acids (I-1910) to Carboxylic Acids (I-1921), Carboxylic Acids (I-1957) to Carboxylic Acids (I-1966), Carboxylic Acids (I-1996) to Carboxylic Acids Salt (I-2000), Carboxylate (I-2005) -Carboxylate (I-2016), Carboxylate (I-2052) -Carboxylate (I-2061), Carboxylate (I-2091) )-Carboxylic acid (I-2095), Carboxylic acid (I-2100) -Carboxylic acid (I-2111), Carboxylic acid (I-2147) -Carboxylic acid (I-2156), Carboxylic acid Salt (I-2186) to carboxylate (I-2190), carboxylate (I-2195) to carboxylate (I-2206), carboxylate (I-2242) to carboxylate (I-2251) ), carboxylate (I-2281) to carboxylate (I-2285), carboxylate (I-2290) to carboxylate (I-2301), carboxylate (I-2337) to carboxylate. (I-2346), carboxylate (I-2376) to carboxylate (I-2380), carboxylate (I-2385) to carboxylate (I-2396), carboxylate (I-2432) -Carboxylate (I-2441), carboxylate (I-2471) -carboxylate (I-2475), carboxylate (I-2480) -carboxylate (I-2491), carboxylate ( I-2527) to carboxylate (I-2536), carboxylate (I-2566) to carboxylate (I-2570), carboxylate (I-2575) to carboxylate (I-2586), Carboxylate (I-2622) to carboxylate (I-2631), carboxylate (I-2661) to carboxylate (I-2665), carboxylate (I-2670) to carboxylate (I) -2681), carboxylate (I-2717) to carboxylate (I-2726), carboxylate (I-2756) to carboxylate (I-2760), carboxylate (I-2765) to carboxylic Acid (I-2767), carboxylate (I-2812) to carboxylate (I-2821), carboxylate (I-2851) to carboxylate (I-2855), carboxylate (I- 2860) to carboxylate (I-2871), carboxylate (I-2907) to carboxylate (I-2916), carboxylate (I-2946) to carboxylate (I-2950), carboxylic acid Salt (I-2955) to carboxylate (I-2966), carboxylate (I-3002) to carboxylate (I-3011), carboxylate (I-3041) to carboxylate (I-3045) ), carboxylate (I-3050) to carboxylate (I-3061), carboxylate (I-3097) to carboxylate (I-3106), carboxylate (I-3136) to carboxylate. (I-3140), carboxylate (I-3145) to carboxylate (I-3156), carboxylate (I-3192) to carboxylate (I-3201), carboxylate (I-3231). ~ Carboxylate (I-3235), carboxylate (I-3240) to carboxylate (I-3251), carboxylate (I-3287) to carboxylate (I-3296), carboxylate (I) -3326) to carboxylate (I-3330), carboxylate (I-3335) to carboxylate (I-3346), carboxylate (I-3382) to carboxylate (I-3391), carboxylic Acid (I-3421) to carboxylate (I-3425), carboxylate (I-3430) to carboxylate (I-3441), carboxylate (I-3477) to carboxylate (I-) 3486), carboxylate (I-3516) to carboxylate (I-3520), carboxylate (I-3525) to carboxylate (I-3536), carboxylate (I-3572) to carboxylic acid. Salt (I-3581), carboxylate (I-3611) to carboxylate (I-3615), carboxylate (I-3620) to carboxylate (I-3331), carboxylate (I-3667) )-Carboxylate (I-3676), carboxylate (I-3706) -carboxylate (I-3710), carboxylate (I-3715) -carboxylate (I-3726), carboxylate (I-3762) to carboxylate (I-3771), carboxylate (I-3801) to carboxylate (I-3805), carboxylate (I-3810) to carboxylate (I-3821). , Carboxylate (I-3857) to carboxylate (I-3866), carboxylate (I-3896) to carboxylate (I-3900), carboxylate (I-3905) to carboxylate (I-3905) to carboxylate (I-3905) I-3916), carboxylate (I-3952) to carboxylate (I-3961),
Carboxylate (I-3991) to carboxylate (I-3995), carboxylate (I-4000) to carboxylate (I-4011), carboxylate (I-4047) to carboxylate (I) -4056), carboxylate (I-4086) to carboxylate (I-4090), carboxylate (I-4095) to carboxylate (I-4106), carboxylate (I-4142) to carboxylic Acid (I-4151), carboxylate (I-4181) to carboxylate (I-4185), carboxylate (I-4190) to carboxylate (I-4201), carboxylate (I-) 4237) to carboxylate (I-4246), carboxylate (I-4276) to carboxylate (I-4280), carboxylate (I-4285) to carboxylate (I-4296), carboxylic acid Salt (I-4332) to carboxylate (I-4341), carboxylate (I-4371) to carboxylate (I-4375), carboxylate (I-4380) to carboxylate (I-4391) ), carboxylate (I-4427) to carboxylate (I-4436), carboxylate (I-4466) to carboxylate (I-4470), carboxylate (I-4475) to carboxylate. (I-4486), carboxylate (I-4522) to carboxylate (I-4531), carboxylate (I-4561) to carboxylate (I-4565), carboxylate (I-4570). -Carboxylate (I-4581), carboxylate (I-4617) -carboxylate (I-4626), carboxylate (I-4656) -carboxylate (I-4660), carboxylate ( I-4665) to carboxylate (I-4676), carboxylate (I-4712) to carboxylate (I-4721), carboxylate (I-4751) to carboxylate (I-4755), Carboxylate (I-4760) to carboxylate (I-4771), carboxylate (I-4807) to carboxylate (I-4816), carboxylate (I-4846) to carboxylate (I) -4850), carboxylate (I-4855) to carboxylate (I-4866), carboxylate (I-4902) to carboxylate (I-4911), carboxylate (I-4941) to carboxylic Preference is given to the acid salt (I-4945), the carboxylate (I-4950) to the carboxylate (I-4961), and the carboxylate (I-4997) to the carboxylate (I-5006).

［式中、全ての符号は、それぞれ前記と同じ意味を表す。
Ｒ^A、Ｒ^B及びＲ^Cは、それぞれ独立に、炭素数１～１２の炭化水素基を表すが、又は、Ｒ^A、Ｒ^B及びＲ^Cが一緒になって芳香環を形成してもよい。Ｒ^Dは、水素原子又は炭素数１～１２の炭化水素基を表す。］
この反応における溶媒としては、クロロホルム、アセトニトリル、イオン交換水等が挙げられる。
反応温度は、通常１５℃～８０℃であり、反応時間は、通常０．５～２４時間である。 <Manufacturing method of salt (I)>
The salt (I) can be produced by reacting a salt represented by the formula (Ia) with a salt represented by the formula (Ib) in a solvent.

[In the formula, all the symbols have the same meanings as described above.
^RA , ^RB and ^RC each independently represent a hydrocarbon group having 1 to 12 carbon atoms, or ^RA , ^RB and ^RC may be combined to form an aromatic ring. .. ^RD represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ]
Examples of the solvent in this reaction include chloroform, acetonitrile, ion-exchanged water and the like.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.

The salt represented by the formula (Ib) can be synthesized with reference to the methods described in JP-A-2011-393502 and JP-A-2014-88367, and the salt represented by the following can be synthesized. Can be mentioned.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
塩基としては、炭酸カリウム、ヨウ化カリウム、ピリジン、トリエチルアミンなどが挙げられる。
溶剤としては、クロロホルム、モノクロロベンゼン、ジメチルホルムアミド、アセトニトリル、酢酸エチル、水などが挙げられる。
反応温度は、通常１５℃～８０℃であり、反応時間は、通常０．５～２４時間である。 In the salt (Ia), the salt in which ^R1 , ^R2 and R3 ^are —OL ¹ −CO—O—R ¹⁰ (the salt represented by the formula (Ia1)) is the formula (the salt represented by the formula (Ia1)). It can be produced by reacting the salt represented by Ic) with the compound represented by the formula (Id) in a solvent in the presence of a base catalyst.

[In the formula, all the symbols have the same meanings as described above. ]
Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine and the like.
Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.

Examples of the compound represented by the formula (Id) include compounds represented by the following, which can be easily obtained from the market, and can also be easily produced by a known production method.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
触媒としては、炭酸カリウム、水素化ナトリウムなどが挙げられる。
溶剤としては、クロロホルム、モノクロロベンゼン、アセトニトリル、水などが挙げられる。
反応温度は、通常１５℃～１００℃であり、反応時間は、通常０．５～２４時間である。 The salt represented by the formula (Ic) is a salt represented by the formula (I-e), a compound represented by the formula (I-f1), and a compound represented by the formula (I-f2). And the compound represented by the formula (I-f3) can be produced by reacting in a solvent in the presence of a catalyst.

[In the formula, all the symbols have the same meanings as described above. ]
Examples of the catalyst include potassium carbonate and sodium hydride.
Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water and the like.
The reaction temperature is usually 15 ° C to 100 ° C, and the reaction time is usually 0.5 to 24 hours.

Examples of the salt represented by the formula (Ie) include salts represented by the following formula, which can be easily obtained from the market.

Examples of the compound represented by the formula (I-f1), the compound represented by the formula (I-f2) and the compound represented by the formula (I-f3) include the compounds represented by the following, which are marketed. It can be obtained more easily.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。
Ｒ^acは、酸不安定基を表す。］
溶剤としては、クロロホルム、モノクロロベンゼン、アセトニトリル、水などが挙げられる。
反応温度は、通常１５℃～１００℃であり、反応時間は、通常０．５～２４時間である。
酸としては、ｐ－トルエンスルホン酸、塩酸などが挙げられる。 The salt represented by the formula (Ic) is a salt represented by the formula (I-e), a compound represented by the formula (I-f4), and a compound represented by the formula (I-f5). And the compound represented by the formula (I-f6) can also be produced by reacting with the compound represented by the formula (I-f6) in a solvent in the presence of potassium carbonate and then treating with an acid.

[In the formula, all the symbols have the same meanings as described above.
R ^ac represents an acid unstable group. ]
Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water and the like.
The reaction temperature is usually 15 ° C to 100 ° C, and the reaction time is usually 0.5 to 24 hours.
Examples of the acid include p-toluenesulfonic acid and hydrochloric acid.

Examples of the compound represented by the formula (I-f4), the compound represented by the formula (I-f5) and the compound represented by the formula (I-f6) include the compounds represented by the following, and the market. It can be obtained more easily.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
塩基としては、炭酸カリウム、ヨウ化カリウム、ピリジン、トリエチルアミンなどが挙げられる。
溶剤としては、クロロホルム、モノクロロベンゼン、ジメチルホルムアミド、アセトニトリル、酢酸エチル、水などが挙げられる。
反応温度は、通常１５℃～８０℃であり、反応時間は、通常０．５～２４時間である。 In the salt (Ia), the salt in which ^R1 , ^R2 and R3 ^are —O—CO ^— R10 (the salt represented by the formula (Ia2)) is represented by the formula (Ic). It can be produced by reacting the salt represented by the formula (Id2) with the compound represented by the formula (Id2) in a solvent in the presence of a base catalyst.

[In the formula, all the symbols have the same meanings as described above. ]
Examples of the base include potassium carbonate, potassium iodide, pyridine, triethylamine and the like.
Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.

Examples of the compound represented by the formula (Id2) include compounds represented by the following, which can be easily obtained from the market, and can also be easily produced by a known production method.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
塩基としては、水酸化ナトリウム、水酸化カリウムなどが挙げられる。
溶剤としては、クロロホルム、モノクロロベンゼン、ジメチルホルムアミド、アセトニトリル、酢酸エチル、水などが挙げられる。
反応温度は、通常１５℃～８０℃であり、反応時間は、通常０．５～２４時間である。 In the salt (Ia), the salt in which ^R1 , ^R2 and R3 ^are —OR ¹⁰ (salt represented by the formula (Ia3)) is represented by the formula (Ic). It can be produced by reacting the salt with the compound represented by the formula (Id3) in a solvent in the presence of a base catalyst.

[In the formula, all the symbols have the same meanings as described above. ]
Examples of the base include sodium hydroxide and potassium hydroxide.
Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.

Examples of the compound represented by the formula (Id3) include compounds represented by the following, which can be easily obtained from the market, and can also be easily produced by a known production method.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
溶剤としては、クロロホルム、モノクロロベンゼン、ジメチルホルムアミド、アセトニトリル、酢酸エチル、水などが挙げられる。
反応温度は、通常１５℃～８０℃であり、反応時間は、通常０．５～２４時間である。 In the salt (Ia), the salt in which ^R1 , ^R2 and R3 ^are —O—CO—O—R10 (the salt represented by the formula ( ^Ia4 )) is the formula (Ic). ) And the compound represented by the formula (Id3) can be produced by reacting in a solvent in the presence of carbonyldiimidazole.

[In the formula, all the symbols have the same meanings as described above. ]
Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, water and the like.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.

[Carboxylic acid generator]
The carboxylic acid generator of the present invention is an acid generator containing a carboxylic acid salt (I). The carboxylate (I) of the present invention can act as an acid generator in the resist composition. When the carboxylate (I) is used as an acid generator in the resist composition, the acid generator may contain only one type or two or more types of the carboxylate (I).
Further, as described later, the acid generator of the present invention is an acid generator known in the resist field other than the carboxylate (I) (hereinafter, may be referred to as “acid generator (B)”) and / or. A carboxylic acid generator known in the resist field other than the carboxylate (I) may be further contained. The acid generator (B) may be used alone or in combination of two or more.
When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the ratio of the contents of the carboxylic acid salt (I) to the acid generator (B) or the like (mass ratio; carboxylic acid salt (I)). ): The acid generator (B)) and the like are usually 1:99 to 100: 0, preferably 1:99 to 99: 1, more preferably 2:98 to 98: 2, still more preferably 5:95 to. It is 95: 5.

[Resist composition]
The resist composition comprises a carboxylic acid generator containing the carboxylic acid salt (I) of the present invention, an acid generator (B) other than the carboxylic acid salt (I), and a resin having an acid unstable group (hereinafter, "resin"). (A) ”) and. The term "acid-unstable group" as used herein means a group having a leaving group, which is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). ..
The resist composition may further contain a quencher (hereinafter sometimes referred to as "quencher (C)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)").
In the resist composition of the present invention, the content of the carboxylate (I) is preferably 0.1% by mass or more and 35% by mass or less, and 0.5% by mass or more and 30% by mass, based on the solid content of the resist composition. It is more preferably 1% by mass or less, and further preferably 1% by mass or more and 25% by mass or less.

<Acid generator (B)>
As the acid generator (B), either a nonionic type or an ionic type may be used. Examples of the nonionic acid generator include sulfonate esters (eg 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg disulfone, etc.). Ketosulfone, sulfonyldiazomethane) and the like. As the ionic acid generator, an onium salt containing an onium cation (for example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt) is typical. Examples of the onium salt anion include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.

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

［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３～２４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－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter, may be 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 represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH _2- may be replaced with -O-, -SO _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 thereof include a perfluorohexyl group.
It is preferable that Q ^b1 and Q ^b2 are independently fluorine atoms or trifluoromethyl groups, and it is more preferable that 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 be a group formed by combining two or more kinds of groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl group, Octane-1,8-Diyl group, Nonan-1,9-Diyl group, Decan-1,10-Diyl group, Undecan-1,11-Diyl group, Dodecan-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-diyl group. Alcandiyl group;
Etan-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. The group etc. can be mentioned.

Examples of the group in which -CH _2- replaced by -O- or -CO- contained in the divalent saturated hydrocarbon group represented by L ^b1 are represented by the formulas (b1-1) to (b1-3). The group represented by any of the above is mentioned. In addition, in the group represented by the formulas (b1-1) to (b1-3) and the groups represented by the formulas (b1-4) to (b1-11) which are specific examples thereof, * and *. * Represents the binding site, and * represents the 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 equation (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single 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 hydrocarbon group may be substituted. -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In equation (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single 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 hydrocarbon group may be substituted. -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of L ^b4 and L ^b5 is 22 or less.
In equation (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single 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 hydrocarbon group may be substituted. -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. ]

In the groups represented by the formulas (b1-1) to (b1-3), when _-CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the carbon before the replacement is performed. Let the number be the number of carbon atoms of 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 _-CH2- in the divalent saturated hydrocarbon group represented by L ^b1 is replaced with -O- or -CO- is represented by the formula (b1-1) or the formula (b1-3). Is preferred.

［式（ｂ１－４）中、
Ｌ^b8は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
式（ｂ１－５）中、
Ｌ^b9は、炭素数１～２０の２価の飽和炭化水素基を表し、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。］ Examples of the group represented by the formula (b1-1) include groups represented by the formulas (b1-4) to (b1-8).

[In equation (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In equation (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, 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 equation (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In equation (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group is replaced with -O- or -CO-. May be good.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total number of carbon atoms of L ^b13 to L ^b15 is 19 or less.
In equation (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, 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 number of carbon atoms of L ^b16 to L ^b18 is 19 or less. ]

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

［式（ｂ１－９）中、
Ｌ^b19は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該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 the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11).

[In equation (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the 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. May be good. -CH _2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In equation (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the 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. May be good. -CH _2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and L ^b23 is 21 or less.
In equation (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the 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. May be good. -CH _2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced 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 the formula (b1-11) from the group represented by the formula (b1-9), when the hydrogen atom contained in the saturated hydrocarbon group is replaced with the alkylcarbonyloxy group, it is replaced. The previous carbon number is taken as the carbon number of the saturated hydrocarbon group.

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

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

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

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

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

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

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

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

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

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

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11) and the formulas (Y36) to (Y38).
When -CH _2- contained in the alicyclic hydrocarbon group represented by Y is replaced with -O-, -SO _2- or -CO-, the number may be one or two or more. Examples of such a group include groups represented by the formulas (Y12) to the formula (Y35) and the formulas (Y39) to the formula (Y43). * Represents the binding site with L ^b1 .

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（Ｙ４３）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（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）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（Ｙ４０）、式（Ｙ４２）、式（Ｙ４３）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。

As the alicyclic hydrocarbon group represented by Y, the formula (Y1) to the formula (Y20), the formula (Y26), the formula (Y27), the formula (Y30), the formula (Y31), and the formula (Y39) are preferable. It is a group represented by any of the formula (Y43), and more preferably the formula (Y11), the formula (Y15), the formula (Y16), the formula (Y20), the formula (Y26), the formula (Y27), and the formula. (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), more preferably formula (Y11), formula (Y15), formula. (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43). ..
When the alicyclic hydrocarbon group represented by Y is a spiro ring of the formulas (Y28) to (Y35), formula (Y39), formula (Y40), formula (Y42), formula (Y43) and the like. The alkylandyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

As the substituent of the methyl group represented by Y, a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, and-( 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 and 3 to 16 carbon atoms. Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group in which they are combined. Ja represents an integer of 0 to 4. The alkyl group and the alicyclic carbonization. -CH _2- contained in the hydrogen group may be replaced with -O-, -S (O) _2- or -CO-, and the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon may be replaced. The hydrogen atom contained in the group may be replaced with a hydroxy group or a fluorine atom.) And the like.
As the substituent of the alicyclic hydrocarbon group represented by Y, an alkyl group having 1 to 16 carbon atoms which may be substituted with a halogen atom, a hydroxy group or a hydroxy group (-CH ₂ contained in the alkyl group). -May be replaced with -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and 7 to 21 carbon atoms. Aralkyl group, glycidyloxy group,-(CH ₂ ) _ja -CO-O-R ^b1 group or-(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula, R ^b1 has 1 to 16 carbon atoms. It represents an alkyl group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. Ja represents an integer of 0 to 4. -CH _2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O-, -SO _2- or -CO-, and the alkyl group and the alicyclic hydrocarbon group may be replaced. The hydrogen atom contained in the aromatic hydrocarbon group may be replaced with a hydroxy group or a fluorine atom.) And the like.

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, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group and a dimethylcyclohexyl group. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and may have an aromatic hydrocarbon group having 1 to 18 carbon atoms (trill group, xylyl group). Group, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and carbon Examples thereof include aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.) having alicyclic hydrocarbon groups of number 3 to 18. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group and a nonyl group. Examples include a group, a decyl group, an undecyl group, a dodecyl group and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4.
Examples of the alkyl group substituted with the hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the group in which -CH _2- is replaced with -O-, -SO _2- or -CO- contained in the alkyl group include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group or Examples include a group that combines these.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group. The alkoxy group has preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.
Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like. The alkoxycarbonyl group has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group and the like. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The alkylcarbonyloxy group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
Examples of the combined group include a group combining an alkoxy group and an alkyl group, a group combining an alkoxy group and an alkoxy group, a group combining an alkoxy group and an alkylcarbonyl group, and an alkoxy group and an alkylcarbonyloxy group. Examples include a group that combines the above.
Examples of the group in which the alkoxy group and the alkyl group are combined include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group and an ethoxymethyl group. The alkoxyalkyl group has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms.
Examples of the group in which the alkoxy group and the alkoxy group are combined include an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group. The alkoxyalkoxy group has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms.
Examples of the group in which the alkoxy group and the alkylcarbonyl group are combined include an alkoxyalkylcarbonyl group such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group and an ethoxypropionyl group. The alkoxyalkylcarbonyl group preferably has 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5.
Examples of the group in which the alkoxy group and the alkylcarbonyloxy group are combined include an alkoxyalkylcarbonyloxy group such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group and an ethoxypropionyloxy group. The alkoxyalkylcarbonyloxy group preferably has 3 to 13 carbon atoms, more preferably 3 to 7 carbon atoms, and even more preferably 3 to 5 carbon atoms.
Examples of the group in which -CH _2- contained in the alicyclic hydrocarbon group is replaced with -O-, -SO _2- or -CO- are the formulas (Y12) to (Y35) and the formula (Y39) to. Examples thereof include a group represented by (Y43).

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group, more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and even more preferably an alicyclic hydrocarbon group substituted with a hydroxy group. Further, more preferably, it is an adamantyl group which may have a substituent, and -CH _2- which constitutes the alicyclic hydrocarbon group or the adamantyl group becomes -CO-, -SO _2- or -CO-. It may be replaced. Y is specifically preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the formulas (Y42) and the formulas (Y100) to (Y114), and particularly preferably the hydroxyadamantyl group and the oxo. An adamantyl group, a group containing these or a group represented by the formula (Y42), the formula (Y100) to the formula (Y114).

Examples of the anion in the salt represented by the formula (B1) include anions represented by the formulas (B1-A-1) to (B1-A-59) [hereinafter, "anion (B1-A)" according to the formula number. -1) ”and so on. ] Are preferable, and the formulas (B1-A-1) to (B1-A-4), formulas (B1-A-9), formulas (B1-A-10), and formulas (B1-A-24) to formulas (B1-A-24) to formulas are preferable. (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-59). Anions are more preferred.

Here, R ⁱ² to R ⁱ⁷ are independently, 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 a chain 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. Group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. ^LA41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q ^b1 and Q ^b2 have the same meanings as described above.
Specific examples of the anion in the salt represented by the formula (B1) include the anion described in JP-A-2010-204646.

Examples of the anion in the salt represented by the preferred formula (B1) include anions represented by the formulas (B1a-1) to (B1a-38).

Among them, it is represented by any of the formulas (B1a-1) to (B1a-3), the formulas (B1a-7) to (B1a-19), and the formulas (B1a-22) to (B1a-38). Anions are preferred.

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、炭素数１～１８の脂肪族炭化水素基、炭素数１～１２のフッ化アルキル基又は炭素数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、ハロゲン原子、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、該鎖式炭化水素基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、ハロゲン原子、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のフッ化アルキル基又は炭素数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。
水素原子が脂肪族炭化水素基で置換された脂環式炭化水素基としては、メチルシクロヘキシル基、ジメチルシクロへキシル基、２－メチルアダマンタン－２－イル基、２－エチルアダマンタン－２－イル基、２－イソプロピルアダマンタン－２－イル基、メチルノルボルニル基、イソボルニル基等が挙げられる。水素原子が脂肪族炭化水素基で置換された脂環式炭化水素基においては、脂環式炭化水素基と脂肪族炭化水素基との合計炭素数が好ましくは２０以下である。
フッ化アルキル基とは、フッ素原子を有する炭素数１～１２のアルキル基を表し、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ペルフルオロブチル等が挙げられる。フッ化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１～６であり、さらに好ましくは１～４である。
芳香族炭化水素基としては、フェニル基、ビフェニル基、ナフチル基、フェナントリル基等のアリール基が挙げられる。芳香族炭化水素基は、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、炭素数１～１８の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）、及び炭素数３～１８の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。
なお、芳香族炭化水素基が、鎖式炭化水素基又は脂環式炭化水素基を有する場合は、炭素数１～１８の鎖式炭化水素基及び炭素数３～１８の脂環式炭化水素基が好ましい。
水素原子がアルコキシ基で置換された芳香族炭化水素基としては、ｐ－メトキシフェニル基等が挙げられる。
水素原子が芳香族炭化水素基で置換された鎖式炭化水素基としては、ベンジル基、フェネチル基、フェニルプロピル基、トリチル基、ナフチルメチル基、ナフチルエチル基等のアラルキル基が挙げられる。
アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、デシルオキシ基及びドデシルオキシ基等が挙げられる。
アルキルカルボニル基としては、アセチル基、プロピオニル基及びブチリル基等が挙げられる。
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。
アルキルカルボニルオキシ基としては、メチルカルボニルオキシ基、エチルカルボニルオキシ基、プロピルカルボニルオキシ基、イソプロピルカルボニルオキシ基、ブチルカルボニルオキシ基、ｓｅｃ－ブチルカルボニルオキシ基、ｔｅｒｔ－ブチルカルボニルオキシ基、ペンチルカルボニルオキシ基、ヘキシルカルボニルオキシ基、オクチルカルボニルオキシ基及び２－エチルヘキシルカルボニルオキシ基等が挙げられる。
Ｒ^b4とＲ^b5とが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形成する環は、単環式、多環式、芳香族性、非芳香族性、飽和及び不飽和のいずれの環であってもよい。この環は、炭素数３～１８の環が挙げられ、好ましくは炭素数４～１８の環である。また、硫黄原子を含む環は、３員環～１２員環が挙げられ、好ましくは３員環～７員環であり、例えば下記の環が挙げられる。＊は結合位を表す。

Ｒ^b9とＲ^b10とが一緒になって形成する環は、単環式、多環式、芳香族性、非芳香族性、飽和及び不飽和のいずれの環であってもよい。この環は、３員環～１２員環が挙げられ、好ましくは３員環～７員環である。例えば、チオラン－１－イウム環（テトラヒドロチオフェニウム環）、チアン－１－イウム環、１，４－オキサチアン－４－イウム環等が挙げられる。
Ｒ^b11とＲ^b12とが一緒になって形成する環は、単環式、多環式、芳香族性、非芳香族性、飽和及び不飽和のいずれの環であってもよい。この環は、３員環～１２員環が挙げられ、好ましくは３員環～７員環である。オキソシクロヘプタン環、オキソシクロヘキサン環、オキソノルボルナン環、オキソアダマンタン環等が挙げられる。 Examples of the organic cation of Z1 ⁺ include an organic onium cation, an organic sulfonium cation, an organic iodinenium cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation and the like. Among these, organic sulfonium cations and organic iodonium cations are preferable, and aryl sulfonium cations are more preferable. Specifically, the cation represented by any of the formulas (b2-1) to (b2-4) (hereinafter, may be referred to as "cation (b2-1)" or the like depending on the formula number). Can be mentioned.

In equations (b2-1) to (b2-4),
R ^b4 to R ^b6 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. It may be substituted, and the hydrogen atom contained in the alicyclic hydrocarbon group is 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 aromatic hydrocarbon group may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms, or carbon. It may be substituted with the number 1 to 12 alkoxy groups.
R ^b4 and R ^b5 may be bonded to each other to 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. It may be replaced with -CO-.
R ^b7 and R ^b8 independently represent a halogen atom, 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 an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 independently represent a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may be bonded to each other to 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. It may be replaced with -CO-.
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 contained hydrogen atom 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 an alkoxy group having 1 to 12 carbon atoms or 1 carbon atom. 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 replaced.
R ^b13 to R ^b18 independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkyl fluoride 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 an integer of 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, and when q2 is 2 or more, multiple R ^b15s are the same or different. , When r2 is 2 or more, the plurality of R ^b16s are the same or different, when s2 is 2 or more, the plurality of R ^b17s are the same or different, and when t2 is 2 or more, the plurality of R ^b18s are the same or different. different.
The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
The chain hydrocarbon group includes an alkyl group of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group. Can be mentioned.
In particular, the chain hydrocarbon group of R ^b9 to R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclo. Cycloalkyl groups such as a heptyl group, a cyclooctyl group and a cyclodecyl group can be mentioned. 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 group of R ^b9 to R ^b12 preferably has 3 to 18 carbon atoms, and more preferably 4 to 12 carbon atoms.
Examples of the alicyclic hydrocarbon group in which the hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group and a 2-ethyladamantan-2-yl group. , 2-Isopropyl adamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which the hydrogen atom is substituted with an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.
The fluoride alkyl group represents an alkyl group having 1 to 12 carbon atoms having a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and perfluorobutyl. The alkyl fluoride group preferably has 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a biphenyl group, a naphthyl group and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and may have an aromatic hydrocarbon group having 1 to 18 carbon atoms (trill group, xylyl group). Group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and fats with 3 to 18 carbon atoms Examples thereof include aromatic hydrocarbon groups having a cyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.).
When the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are used. Is preferable.
Examples of the aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Examples of the chain hydrocarbon group in which the hydrogen atom is substituted with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, and a pentylcarbonyloxy group. , Hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group and the like.
Rings formed by the bonds of R ^b4 and R ^b5 together with the sulfur atoms they bond to can be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. It may be a ring of. Examples of this ring include a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Further, the ring containing a sulfur atom may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include the following rings. * Represents the binding site.

The ring formed by R ^b9 and R ^b10 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. This ring may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring and the like can be mentioned.
The ring formed by R ^b11 and R ^b12 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. This ring may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among the cations (b2-1) to cations (b2-4), the cation (b2-1) is preferable.
Examples of the cation (b2-1) include the following cations.

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

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

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

The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), the formulas (B1a-1) to (B1a-3), the formulas (B1a-7) to the formulas (B1a-16), the formulas (B1a-18), and the formulas (B1a-) are preferable. 19), the combination of the anion represented by any of the formulas (B1a-22) to (B1a-38) and the cation (b2-1), the cation (b2-3) or the cation (b2-4) is Can be mentioned.

Examples of the acid generator (B) preferably include those represented by the formulas (B1-1) to (B1-56), and among them, those containing an arylsulfonium cation are preferable, and the acid generator (B1-1) contains an arylsulfonium cation. -Formula (B1-3), Formula (B1-5) -Formula (B1-7), Formula (B1-11) -Formula (B1-14), Formula (B1-20) -Formula (B1-26), Those represented by the formulas (B1-29) and the formulas (B1-31) to (B1-56) are particularly preferable.

In the resist composition of the present invention, the content of the acid generator (B) is preferably 1 part by mass or more and 45 parts by mass or less, and more preferably 1 part by mass or more and 40 parts by mass with respect to 100 parts by mass of the resin (A). It is not less than parts by mass, more preferably 3 parts by mass or more and 35 parts by mass or less. The resist composition of the present invention may contain one kind of the acid generator (B) alone or may contain a plurality of kinds.

<Resin (A)>
The resin (A) has a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”). The resin (A) preferably further contains a structural unit other than the structural unit (a1). The structural unit other than the structural unit (a1) includes a structural unit having no acid unstable group (hereinafter, may be referred to as “structural unit (s)”), a structural unit (a1), and a structural unit other than the structural unit (s). Structural unit (for example, a structural unit having a halogen atom described later (hereinafter, may be referred to as “structural unit (a4)”), and a structural unit having a non-desorbed hydrocarbon group described later (hereinafter referred to as “structural unit (a5)”). In some cases) and other structural units derived from monomers known in the art.

［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２～８のアルケニル基、炭素数３～２０の脂環式炭化水素基、炭素数６～１８の芳香族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の複素環基を形成し、該炭化水素基及び該複素環基に含まれる－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。
＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid unstable group (hereinafter, may be referred to as “monomer (a1)”).
The acid unstable group contained in the resin (A) is a group represented by the formula (1) (hereinafter, also referred to as a group (1)) and / or a group represented by the formula (2) (hereinafter, a group (2). ) Is also preferable.

[In the formula (1), R ^a1 , R ^a2 , and R ^a3 are independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alicyclic hydrocarbon having 3 to 20 carbon atoms. Represents a group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, or R ^a1 and R ^a2 are alicyclic hydrocarbons having 3 to 20 carbon atoms together with carbon atoms to which they are bonded to each other. Form a hydrocarbon group.
ma and na independently represent 0 or 1, and at least one of ma and na represents 1.
* Represents the binding site. ]

[In the formula (2), R ^a1'and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Represented, R ^a2'and R ^a3' are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and are contained in the hydrocarbon group and the heterocyclic group-. CH _2- may be replaced by —O— or —S—.
X represents an oxygen atom or a sulfur atom.
na'represents 0 or 1.
* Represents a bond. ]

Ｒ^ａ１、Ｒ^ａ２及びＲ^ａ３における芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニル基、フェナントリル基等のアリール基が挙げられる。
組み合わせた基としては、上述したアルキル基と脂環式炭化水素基とを組み合わせた基（例えばアルキルシクロアルキル基又はシクロアルキルアルキル基）、ベンジル基等のアラルキル基、アルキル基を有する芳香族炭化水素基（ｐ－メチルフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、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－シクロヘキシルフェニル基、ｐ－アダマンチルフェニル基等）、フェニルシクロヘキシル基等のアリール－シクロアルキ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－との結合位を表す。

Examples of the alkyl group in R ^a1 , R ^a2 and R ^a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
The alkenyl groups in R ^a1 , R ^a2 and R ^a3 include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group and isooctenyl group. Nonenyl group is mentioned.
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 cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a bond). The alicyclic hydrocarbon group of R ^a1 , R ^a2 and R ^a3 has preferably 3 to 16 carbon atoms.

Examples of the aromatic hydrocarbon group in R ^a1 , Ra ² and Ra ³ include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
Examples of the combined group include a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aromatic hydrocarbon having an alkyl group. Group (p-methylphenyl group, p-tert-butylphenyl group, trill group, hydroxyyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic Examples thereof include aromatic hydrocarbon groups having a formula hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, and the like. Preferably, ma is 0 and na is 1.
Examples of -C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R a ² are bonded to each other to form an alicyclic hydrocarbon group include the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents the binding 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 in 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 the alicyclic hydrocarbon group include the same groups as those mentioned in R ^a1 , R a ² and R a ³ .
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
The combined group includes a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group (benzyl group, etc.), and an aromatic hydrocarbon having an alkyl group. Hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), fat Examples thereof include an aromatic hydrocarbon group having a cyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an alicyclic hydrocarbon group having an aromatic hydrocarbon group (phenylcyclohexyl group, etc.), and the like. ..
When R ^a2'and R ^a3' are bonded to each other to form a heterocyclic group together with the carbon atom and X to which they are bonded, -C (R ^a1' ) (R ^a2' )-X-R ^a3' The following groups can be mentioned. * Represents the binding site.

Of R ^a1'and R ^a2' , at least one is preferably 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 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, and R ^a3 is an alkyl group, ma = 0, and na = 1. ..
In formula (1), R ^a1 and R ^a2 are independently alkyl groups, R ^a3 is an adamantyl group, ma = 0, and na = 1.
Specific examples of the group (1) include the following groups. * Represents a bond.

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

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

Among the (meth) acrylic monomers having an acid unstable group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. 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－との結合手を表す。
Ｒ^a01、Ｒ^a4及びＲ^a5は、それぞれ独立に、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。
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、炭素数６～１８の芳香族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２～８のアルケニル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族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。］ As the structural unit derived from the (meth) acrylic monomer having the group (1), the structural unit represented by the formula (a1-0) (hereinafter, may be referred to as the structural unit (a1-0)), the formula (. The structural unit represented by a1-1) (hereinafter, may be referred to as a structural unit (a1-1)) or the structural unit represented by the formula (a1-2) (hereinafter, referred to as a structural unit (a1-2)). In some cases). Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more.

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
L ^a01 , L ^a1 and L ^a2 independently represent -O- or ^* -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents an integer of 1 to 7. -Represents a bond with CO-.
R ^a01 , R ^a4 and R ^a5 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a02 , R ^a03 and R ^a04 independently contain an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or these. Represents a combined group.
R ^a6 and R ^a7 are independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group or a group formed by combining them.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]

R ^a01 , R ^a4 and R ^a5 are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or * -O- (CH ₂ ) _k01 -CO-O- (where k01 is preferably an integer of 1 to 4, more preferably. Is 1), more preferably an oxygen atom.
The alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups in R ^a02 , R ^a03 and R ^a04 and the groups in which these are combined are the same as the groups listed in R ^a1 to R ^a3 of the formula (1). The group is mentioned.
The alkyl group, ^alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group in R ^a6 and Ra 7 and the group obtained by combining these are the groups listed in R ^a1 , R a ² and R a ³ of the formula (1). The same group as.
The alkyl group in R ^a02 , R ^a03 , and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
The alkyl group in R ^a6 and R ^a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, and further preferably an ethyl group or an isopropyl group. Or it is a t-butyl group.
The ^alkenyl group in R ^a6 and Ra 7 is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an ethenyl group, a propenyl group, an isopropenyl group or a butenyl group.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 and R ^a04 have preferably 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms.
The aromatic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 have preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group.
The group in which an alkyl group and an aromatic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination with these alkyl groups and an aromatic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
R ^a6 and R ^a7 are preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. It is an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, and more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group.
m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1'is preferably 0 or 1.

The structural unit (a1-0) is, for example, a structural unit represented by any one of the formulas (a1-0-1) to (a1-0-18) and R ^a01 in the structural unit (a1-0). Examples thereof include structural units in which the corresponding methyl group is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group, and the formulas (a1-0-1) to (a1-0-10) and (a1-0) are mentioned. -13), the structural unit represented by any of the formulas (a1-0-14) is preferable.

Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, the methyl group corresponding to R ^a4 in the structural unit represented by any of the formulas (a1-1-1) to (a1-1-7) and the structural unit (a1-1) was replaced with a hydrogen atom. Structural units are preferable, and structural units represented by any of the formulas (a1-1-1) to (a1-1-4) are more preferable.

The structural unit (a1-2) corresponds to the structural unit represented by any of the formulas (a1-2-1) to (a1-2-14) and R ^a5 in the structural unit (a1-2). Structural units in which a methyl group is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group include formulas (a1-2-2), formulas (a1-2-5), and formulas (a1-2-6). ) And the structural unit represented by any of the formulas (a1-2-10) to (a1-2-14) are preferable.

When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 60 mol%, preferably 5 to 50 mol%, based on all the structural units of the resin (A). Yes, more preferably 10-40 mol%.
When the resin (A) contains a structural unit (a1-1) and / or a structural unit (a1-2), the total content of these is usually 10 to 95 mol with respect to all the structural units of the resin (A). %, Preferably 15 to 85 mol%, more preferably 15 to 80 mol%, still more preferably 20 to 80 mol%, still more preferably 20 to 75 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２～１２のアルコキシアルキル基、炭素数２～１２のアルコキシアルコキシ基、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^a30は、単結合又は^＊－Ｘ^a31－（Ａ^a32－Ｘ^a32）_nc－を表し、＊は－Ｒ^a32が結合する炭素原子との結合部位を表す。
Ａ^a32は、炭素数１～６のアルカンジイル基を表す。
Ｘ^a31及びＸ^a32は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ｎｃは、０又は１を表す。
ｌａは０～４のいずれかの整数を表す。ｌａが２以上のいずれかの整数である場合、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 the group (2) in the structural unit (a1) include structural units represented by the formula (a1-4) (hereinafter, may be referred to as “structural unit (a1-4)”). ..

[In equation (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 has a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, and a carbon number of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a30 represents a single bond or ^* -X ^a31- (A ^a32 -X ^a32 ) _nc- , and * represents the binding site with the carbon atom to which -R ^a32 is bonded.
A ^a32 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a31 and X ^a32 independently represent -O-, -CO-O- or -O-CO-, respectively.
nc represents 0 or 1.
la represents an integer of 0 to 4. When la is any integer of 2 or more, the plurality of Ra ^33s may be the same as or different from each other.
R ^a34 and R ^a35 independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^a35 and R ^a36 are bonded to each other. Then, together with -CO- to which they are bonded, a divalent hydrocarbon group having 2 to 20 carbon atoms is formed, and the hydrocarbon group and -CH _2- contained in the divalent hydrocarbon group are-. It may be replaced by O- or -S-. ]

Examples of the halogen atom in 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 in ^Ra32 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, and a 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-nonafluoropentyl group, pentyl group, hexyl group and perfluoro Hexyl group is mentioned.
R ^a32 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 in R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group.
Examples of the alkoxy group in R ^a33 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a hexyloxy group. The alkoxy group 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.
Examples of the alkoxyalkyl group in R ^a33 include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.
Examples of the alkoxyalkoxy group in R ^a33 include methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, and tert-butoxymethoxy group. Can be mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethyl group or an ethoxyethyl group.
Examples of the alkylcarbonyl group in R ^a33 include an acetyl group, a propionyl group, a butyryl group and the like. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.
Examples of the alkylcarbonyloxy group in R ^a33 include an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.
R ^a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, and is preferably a fluorine atom, an iodine atom, a hydroxy group or a methyl. A group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group is more preferable, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group is further preferable.

* -X ^a31- (A ^a32 -X ^a32 ) _nc- includes * -O-, * -CO-O-, * -O-CO-, * -CO-O-A ^a32 -CO-O-, * -O-CO-A ^a32 -O-, * -O-A a32-CO-O-, * -CO-O-A ^a32 -O- ^CO- , * -O-CO-A ^a32 -O-CO -, Can be mentioned. Of these, * -CO-O-, * -CO-O-A ^a32 -CO-O- or * -O-A ^a32 -CO-O- are preferable.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -Methylbutane-1,4-diyl group and the like can be mentioned.
A ^a32 is preferably a methylene group or an ethylene group.

A ^a30 is preferably single bond, * -CO-O- or * -CO-O-A ^a32 -CO-O-, and is preferably single bond, * -CO-O- or * -CO-O-CH. ₂ -CO-O- is more preferred, and single bond or * -CO-O- is even more preferred.

芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニル基、フェナントリル基等のアリール基が挙げられる。
組み合わせた基としては、上述したアルキル基と脂環式炭化水素基とを組み合わせた基（例えばシクロアルキルアルキル基）、ベンジル基等のアラルキル基、アルキル基を有する芳香族炭化水素基（ｐ－メチルフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、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－シクロヘキシルフェニル基、ｐ－アダマンチルフェニル基等）、フェニルシクロヘキシル基等のアリール－シクロアルキル基等が挙げられる。特に、Ｒ^a36としては、炭素数１～１８のアルキル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基又はこれらを組み合わせることにより形成される基が挙げられる。 The la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.
Examples of the hydrocarbon group in R ^a34 , R ^a35 and R ^a36 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group combining these.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
The alicyclic hydrocarbon group may be either a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a binding site) and the like.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
Examples of the combined group include a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methyl). Phenyl group, p-tert-butylphenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon group Examples thereof include an aromatic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, and the like. In particular, ^Ra36 includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining them. Can be mentioned.

R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. It is a group to be formed, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms 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 in R ^a36 is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

-OC (R ^a34 ) (R ^a35 ) -OR ^a36 in the structural unit (a1-4) is contacted with an acid (for example, p-toluenesulfonic acid) and desorbed to form a hydroxy group.
-OC (R ^a34 ) (R ^a35 ) -OR ^a36 is preferably bonded to the o-position or p-position of the benzene ring, and more preferably to the p-position.

樹脂（Ａ）が、構造単位（ａ１－４）を有する場合、その含有率は、樹脂（Ａ）の全構造単位の合計に対して、５～６０モル％であることが好ましく、５～５０モル％であることがより好ましく、１０～４０モル％であることがさらに好ましい。 Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the hydrogen atom corresponding to R ^a32 in the structural unit represented by the formulas (a1-4-1) to (a1-4-18) and the structural unit (a1-4) is a halogen atom or a haloalkyl group. Alternatively, a structural unit replaced with an alkyl group can be mentioned, and more preferably, formulas (a1-4-1) to (a1-4-5), formulas (a1-4-10), and formulas (a1-4-13) are used. ) And the structural unit represented by the formula (a1-4-14), respectively.

When the resin (A) has a structural unit (a1-4), the content thereof is preferably 5 to 60 mol% with respect to the total of all the structural units of the resin (A), 5 to 50. It is more preferably mol%, and even more preferably 10-40 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。 Examples of the structural unit derived from the (meth) acrylic monomer having the group (2) include the structural unit represented by the formula (a1-5) (hereinafter, may be referred to as “structural unit (a1-5)”). Be done.

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

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

樹脂（Ａ）が、構造単位（ａ１－５）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、１～５０モル％が好ましく、３～４５モル％がより好ましく、５～４０モル％がさらに好ましく、５～３０モル％がさらにより好ましい。 Examples of the structural unit (a1-5) include the structural unit derived from the monomer described in JP-A-2010-61117. Among them, the structural units represented by the formulas (a1-5-1) to (a1-5-4) are preferable, and they are represented by the formula (a1-5-1) or the formula (a1-5-2). Structural units are more preferred.

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

樹脂（Ａ）が上記構造単位を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、５～６０モル％が好ましく、５～５０モル％がより好ましく、１０～４０モル％がさらに好ましい。 Moreover, the following structural unit is also mentioned as a structural unit (a1).

When the resin (A) contains the above structural units, the content thereof is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and 10 to 40 mol% with respect to all the structural units of the resin (A). % Is more preferable.

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

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

［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２～１２のアルコキシアルキル基、炭素数２～１２のアルコキシアルコキシ基、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位を表す。
Ａ^a52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。
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。］ Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include structural units represented by the formula (a2-A) (hereinafter, may be referred to as “structural unit (a2-A)”).

[In formula (a2-A),
R ^a50 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a51 has a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, and a carbon number of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or * -X ^a51- (A ^a52- X ^a52 ) _nb- , and * represents the binding site with the carbon atom to which -R ^a50 is bonded.
A ^a52 independently represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 independently represent —O—, —CO—O— or —O—CO—, respectively.
nb represents 0 or 1.
mb represents any integer from 0 to 4. When mb is any integer of 2 or more, the plurality of Ra ^51s may be the same as or different from each other. ]

Examples of the halogen atom in R ^a50 and R ^a51 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 in ^Ra50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group and 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, 2,2,3,3,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluorohexyl The group is mentioned.
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 in ^Ra51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-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 alkoxy group in ^Ra51 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group 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.
Examples of the alkoxyalkyl group in ^Ra51 include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.
Examples of the alkoxyalkoxy group in ^Ra51 include methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, and tert-butoxymethoxy group. Can be mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group.
Examples of the alkylcarbonyl group in ^Ra51 include an acetyl group, a propionyl group, a butyryl group and the like. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.
Examples of the alkylcarbonyloxy group in ^Ra51 include an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.
R ^a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, and is preferably a fluorine atom, an iodine atom, a hydroxy group or a methyl. A group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group is more preferable, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group is further preferable.

* -X ^a51- (A ^a52- X ^a52 ) _nb- includes * -O-, * -CO-O-, * -O-CO-, * -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. Of these, * -CO-O-, * -CO-O-A ^a52 -CO-O- or * -O-A ^a52 -CO-O- are preferable.
The alkanediyl group includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -Methylbutane-1,4-diyl group and the like can be mentioned.
A ^a52 is preferably a methylene group or an ethylene group.
A ^a50 is preferably single bond, * -CO-O- or * -CO-O-A ^a52 -CO-O-, and is preferably single bond, * -CO-O- or * -CO-O-CH. ₂ -CO-O- is more preferred, and single bond or * -CO-O- is even more preferred.
The mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
The hydroxy group is preferably bonded to the ortho-position or the para-position of the benzene ring, and more preferably to the para-position.

樹脂（Ａ）中に構造単位（ａ２－Ａ）が含まれる場合の構造単位（ａ２－Ａ）の含有率は、全構造単位に対して、好ましくは５～８０モル％であり、より好ましくは１０～７０モル％であり、さらに好ましくは１５～６５モル％であり、さらにより好ましくは２０～６５モル％である。
構造単位（ａ２－Ａ）は、例えば構造単位（ａ１－４）を用いて重合した後、ｐ－トルエンスルホン酸等の酸で処理することにより、樹脂（Ａ）に含ませることができる。また、アセトキシスチレン等を用いて重合した後、テトラメチルアンモニウムヒドロキシド等のアルカリで処理することにより、構造単位（ａ２－Ａ）を樹脂（Ａ）に含ませることができる。 Examples of the structural unit (a2-A) include structural units derived from the monomers described in JP-A-2010-204634 and JP-A-2012-12577.
The structural unit (a2-A) includes a structural unit represented by the formulas (a2-2-1) to the formula (a2-2-16) and the formulas (a2-2-1) to the formula (a2-2-2). In the structural unit represented by 16), a structural unit in which the methyl group corresponding to ^Ra50 in the structural unit (a2-A) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group can be mentioned. The structural unit (a2-A) is represented by a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), and a formula (a2-2-6). Structural unit, structural unit represented by the formula (a2-2-8), structural unit represented by the formula (a2-2-12) to the formula (a2-2-14), and the formula (a2-2-1). ), The structural unit represented by the formula (a2-2-3), the structural unit represented by the formula (a2-2-6), and the structural unit represented by the formula (a2-2-8). Structural unit, a structure in which the methyl group corresponding to ^Ra50 in the structural unit (a2-A) is replaced with a hydrogen atom in the structural units represented by the formulas (a2-2-12) to (a2-2-14). It is preferably a unit, a structural unit represented by the formula (a2-2-3), a structural unit represented by the formula (a2-2-8), and formulas (a2-2-12) to (a2-). The structural unit represented by 2-14) and the structural unit represented by the formula (a2-2-3) or the structural unit represented by the formula (a2-2-8), the formulas (a2-2-12) to In the structural unit represented by the formula (a2-2-14), it is more preferable that the methyl group corresponding to ^Ra50 in the structural unit (a2-A) is replaced with a hydrogen atom, and it is more preferable that the structural unit is a structural unit represented by the formula (a2-A2-A). In the structural unit represented by 2-8) and the structural unit represented by the formula (a2-2-8), the methyl group corresponding to ^Ra50 in the structural unit (a2-A) is replaced with a hydrogen atom. Is more preferable.

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% with respect to all the structural units. It is 10 to 70 mol%, more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol%.
The structural unit (a2-A) can be contained in the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Further, the structural unit (a2-A) can be contained 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。 Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include structural units represented by the formula (a2-1) (hereinafter, may be referred to as “structural unit (a2-1)”).

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

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

樹脂（Ａ）が構造単位（ａ２－１）を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、通常１～４５モル％であり、好ましくは１～４０モル％であり、より好ましくは１～３５モル％であり、さらに好ましくは２～２０モル％であり、さらにより好ましくは２～１０モル％である。 Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. The structural unit represented by any of the formulas (a2-1-1) to (a2-1-6) is preferable, and any of the formulas (a2-1-1) to (a2-1-4) is preferable. The structural unit represented is more preferable, and the structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is further preferable.

When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on all the structural units of the resin (A). It is more preferably 1 to 35 mol%, further preferably 2 to 20 mol%, and even more preferably 2 to 10 mol%.

［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－ＣＯ－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は互いに同一でも異なっていてもよい。］ <Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocyclic ring such as β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a fused ring of a monocyclic lactone ring and another ring. But it may be. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) can be mentioned.
The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). One of these may be contained alone, or two or more thereof may be contained.

[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4),
L ^a4 , ^La 5 and ^{La 6} are independently represented by -O- or * -O- (CH ₂ ) _k3 -CO-O- (k3 represents an integer of 1 to 7). Represents a group.
L ^a7 is -O-, * -OL ^{a8-O-, * -O-L a8 -} CO-O-, * ^{-OL a8} -CO-O-L ^a9 -CO-O- or * -O-L ^a8 -O-CO-L ^a9 -O-represented.
L ^a8 and ^{La 9} each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents the binding site with the 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, a hydrogen atom or a halogen atom which may have a halogen atom.
X ^a3 represents _−CH2- 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 an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 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 is 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same or different from each other. ]

Examples of the aliphatic hydrocarbon group in R ^a21 , Ra ²² , Ra ²³ and Ra ²⁵ include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group. Be done.
Examples of the halogen atom in ^Ra24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group in ^Ra24 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like, and preferably have 1 to 4 carbon atoms. Alkyl group of, more preferably a methyl group or an ethyl group.
Alkyl groups having a halogen atom in ^Ra24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. Examples thereof include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

The alkanediyl group in ^La8 and ^La9 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples thereof include a 4-diyl group and a 2-methylbutane-1,4-diyl group.

In the formulas (a3-1) to (a3-3), ^La4 to ^La6 are independently, preferably k3 in -O- or * -O- (CH ₂ ) _k3 -CO-O-, respectively. Is an integer of 1 to 4, more preferably —O— and * —O— _CH2 -CO—O—, and 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 independently, preferably an integer of 0 to 2, and more preferably 0 or 1.

（式中、Ｒ^ａ２４、Ｌ^ａ７は、上記と同じ意味を表す。） In the formula (a3-4), ^Ra24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group. Is.
^Ra25 is preferably a carboxy group, a cyano group or a methyl group.
L ^a7 is preferably -O- or * -O-L ^a8 -CO-O-, and more preferably -O-, -O-CH ₂ -CO-O- or -O-C ₂ H _4- . It is CO-O-.
w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
In particular, the formula (a3-4) is preferably the formula (a3-4)'.

(In the formula, ^Ra24 and ^La7 have the same meanings as above.)

樹脂（Ａ）が構造単位（ａ３）を含む場合、その合計含有率は、樹脂（Ａ）の全構造単位に対して、通常１～７０モル％であり、好ましくは１～６５モル％であり、より好ましくは１～６０モル％である。
また、構造単位（ａ３－１）、構造単位（ａ３－２）、構造単位（ａ３－３）又は構造単位（ａ３－４）の含有率は、それぞれ、樹脂（Ａ）の全構造単位に対して、１～６０モル％が好ましく、１～５０モル％がより好ましく、１～５０モル％がさらに好ましい。 The structural unit (a3) is a structure derived from the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and the monomer described in JP-A-2012-41274. The unit is mentioned. The structural unit (a3) includes the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula (a3--2-2), and the formula (a3-3-3). 1), the structural unit represented by any of the equations (a3-3-2) and the equations (a3-4-1) to (a3-4-12), and in the structural unit, the equation (a3-1). )-The structural unit in which the methyl group corresponding to Ra 18, Ra ¹⁹ , Ra ²⁰ and Ra 24 in the formula ( ^a3-4 ) ^is replaced with a hydrogen atom is preferable.

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

［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 equation (a4),
R ⁴¹ represents a hydrogen atom or a methyl group.
R ⁴² represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, 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 the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. Can be mentioned.
Examples of the monocyclic or polycyclic alicyclic hydrocarbon group 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 thereof include a polycyclic alicyclic hydrocarbon group such as (* represents a bond position).

Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alcandiyl groups and one or more alicyclic hydrocarbon groups, and examples thereof include-alcandiyl group-. Examples thereof include an alicyclic hydrocarbon group, an alicyclic hydrocarbon group, an alkyl group, an alcandyl group, an alicyclic hydrocarbon group, and an alkyl group.

［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。］ The structural unit (a4) is at least selected from the group consisting of the formula (a4-0), the formula (a4-1), the formula (a4-2), the formula (a4-3) and the formula (a4-4). A structural unit represented by one can be mentioned.

[In equation (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. ]

The alkanediyl group in L ^4a includes a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and an ethane-1,1-diyl group. Examples include branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group. Be done.

The perfluoroalkanediyl group in L ^3a includes a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a 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 Examples thereof include -2,2-diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like.
Examples of the perfluorocycloalkandyl group in L ^3a include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantandiyl group and the like.

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

Examples of the structural unit (a4-0) include the structural unit shown below and the structural unit in which the methyl group corresponding to ^R5a in the structural unit (a4-0) in the following structural unit is replaced with a hydrogen atom.

［式（ａ４－１）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ｒ^a42は、置換基を有していてもよい炭素数１～２０の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。
Ａ^a41は、置換基を有していてもよい炭素数１～６のアルカンジイル基又は式（ａ－ｇ１）で表される基を表す。ただし、Ａ^ａ４１及びＲ^ａ４２のうち少なくとも１つは、置換基としてハロゲン原子（好ましくはフッ素原子）を有する。

〔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。〕
＊は結合位であり、右側の＊が－Ｏ－ＣＯ－Ｒ^a42との結合位である。］

[In equation (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 may.
A ^a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (ag1). However, at least one of ^Aa41 and ^Ra42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In the formula (ag1),
s represents 0 or 1.
A a ⁴² and A a ⁴⁴ 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 independently represent -O-, -CO-, -CO-O- or -O-CO-, respectively.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* Is the binding site, and * on the right is the binding site with -O-CO-R ^a42 . ]

Examples of the saturated hydrocarbon group in R ^a42 include a chain-type 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。 The chain saturated hydrocarbon group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. Can be mentioned.
Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group and the following. Examples thereof include a polycyclic alicyclic saturated hydrocarbon group such as a group (* represents a bond position).

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 saturated hydrocarbon groups, and examples thereof include-alkanediyl groups. -Alicyclic saturated hydrocarbon group, -Alicyclic saturated hydrocarbon group-Alkyl group, -Alkanediyl group-Alicyclic saturated hydrocarbon group-Alkyl group and the like can be mentioned.

［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。
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Ｒ^a42との結合位を表す。］
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^a45は、少なくとも１つのハロゲン原子を有する炭素数１～１７の脂肪族炭化水素基を表す。 Examples of the substituent contained in R ^a42 include at least one selected from the group consisting of a halogen atom and a group represented by the formula (ag3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

[In the formula (ag3),
X ^a43 represents an oxygen atom, a carbonyl group, * -O-CO- or * -CO-O-.
A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* Represents the binding site with R ^a42 . ]
However, in R ^a42- X ^a43 -A ^a45 , when R ^a42 does not have a halogen atom, A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.

The aliphatic hydrocarbon group in A ^a45 includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and a heptadecyl group. Alkyl groups such as octadecyl groups;
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 (* represents a bond position). ) Etc., a polycyclic alicyclic hydrocarbon group can be mentioned.

R ^a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (ag3).
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 further preferably having 1 to 1 to carbon atoms. It is a perfluoroalkyl group of 6, and 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 (ag3), the total carbon of R ^a42 including the number of carbon atoms contained in the group represented by the formula (ag3). The number is preferably 15 or less, more preferably 12 or less. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.

［式（ａ－ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数１～１７の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位を表す。］ When R ^a42 is a saturated hydrocarbon group having a group represented by the formula (ag3), R ^a42 is more preferably a group represented by the formula (ag2).

[In the formula (ag2),
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 the binding site with the carbonyl group. ]

The saturated hydrocarbon group of A ^a46 preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.
The aliphatic hydrocarbon group of A ^a47 preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and further preferably A ^a47 having a cyclohexyl group or an adamantyl group.

The preferred structure of the group represented by the formula (ag2) is the following structure (* is the binding site with the carbonyl group).

The alkanediyl group in A ^a41 is a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. Linear alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, etc. Examples thereof include a branched alkanediyl group such as 2-methylbutane-1,4-diyl group.
Examples of the substituent in the alkanediyl group represented by A ^a41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and further preferably an ethylene group.

The divalent saturated hydrocarbon group represented by A ^a42 , A ^a43 and A ^a44 in the group represented by the formula (ag1) includes a linear or branched alkanediyl group and a monocyclic or polycyclic divalent group. Examples thereof include an alicyclic hydrocarbon group and a group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, Examples thereof include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
Examples of the substituent of 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.
s is preferably 0.

In the group represented by the formula (ag1), examples of the group in which X ^a42 is —O—, —CO—, —CO—O— or —O—CO— include the following groups. In the following examples, * and ** represent the binding sites, respectively, and ** is the binding site with -O-CO-R ^a42 .

As the structural unit represented by the formula (a4-1), the methyl group corresponding to R ^a41 in the structural unit shown below and the structural unit represented by the formula (a4-1) in the following structural unit is a hydrogen atom. Examples include replaced 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－ＣＨ₂－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。］ As the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2) is preferable.

[In equation (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 -CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-.
R ^f6 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴⁴ and R ^f6 is 21. ]

Examples of the ^arcandyl group of L ⁴⁴ include the same groups as those exemplified in A a 41.
Examples of the saturated hydrocarbon group of R ^f6 include the same groups as those exemplified in R ^a42 .
As the alkanediyl group in L ⁴⁴ , an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

Examples of the structural unit represented by the formula (a4-2) include structural units represented by the formulas (a4-1-1) to (a4-1-11). A structural unit in which the methyl group corresponding to R ^f5 in the structural unit (a4-2) is replaced with a hydrogen atom is also mentioned as a structural unit represented by the 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－（＊はＡ^f13との結合位を表す。）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 equation (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 the upper limit of the total carbon number of L ⁵ , A ^f13 and A ^f14 is 20. ]

Examples of the alkanediyl group in L ⁵ include the same groups as those exemplified in the alkanediyl group of A ^a41 .
The divalent saturated hydrocarbon group which may have a fluorine atom in A ^f13 preferably has a divalent chain saturated hydrocarbon group which may have a fluorine atom and a fluorine atom. It is also a good divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkandyl group.
Examples of the divalent chain hydrocarbon group which may have a fluorine atom include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group; a difluoromethylene group, a perfluoroethylene group and a perfluoro. Examples thereof include a perfluoroarcandyl group 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 a monocyclic type or a polycyclic type. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantandiyl group, a norbornanediyl group, a perfluoroadamantandiyl group and the like.

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 in 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-Nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group and the like fluoride Alkyl 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 , Perfluoroadamantylmethyl group and the like are preferable.

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

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

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

The saturated hydrocarbon group of R ^{f22 may be the same 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, and 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 having a fluorine atom is more preferable.
In the formula (a4-4), as A ^f21 , − (CH ₂ ) _j1 − is preferable, an ethylene group or a methylene group is more preferable, and a methylene group is further preferable.

樹脂（Ａ）が、構造単位（ａ４）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、１～２０モル％が好ましく、２～１５モル％がより好ましく、３～１０モル％がさらに好ましい。 As the structural unit represented by the formula (a4-4), for example, in the following structural unit and the structural unit represented by the following formula, the methyl group corresponding to R ^f21 in the structural unit (a4-4) is hydrogen. A structural unit that has been replaced by an atom can be mentioned.

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

［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 of the structural unit (a5) include a group having a linear, branched or cyclic hydrocarbon group. Among them, 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 the formula (a5-1).

[In equation (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group 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 in R ⁵² may be either a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and 2 -Alkyl groups such as ethylhexyl groups can be mentioned.
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, and more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group in L ⁵⁵ include a divalent chain-type saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent chain-type saturated hydrocarbon group is preferable. ..
Examples of the divalent chain saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl group and a norbornanediyl group.

式（Ｌ１－１）中、
Ｘ^x1は、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＬ^x１との結合位を表す。）。
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 the group in which _-CH2- contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ is replaced with -O- or -CO- are represented by the formulas (L1-1) to (L1-4). The groups represented are mentioned. In the following formula, * and ** represent the binding site, and * represents the binding site with the oxygen atom.

In equation (L1-1),
X ^x1 represents * -O-CO- or * -CO-O- (* represents the 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 number of carbon atoms of L ^x 1 and L ^{x 2} is 16 or less.
In equation (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total number of carbon atoms of L ^x3 and L ^x4 is 17 or less.
In formula (L1-3),
L ^{x 5} 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 ^x 1 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, and more preferably a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and 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 ^{x 5} is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and 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, and 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, and 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, and more preferably a cyclohexanediyl group or an adamantanediyl group.

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

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

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

Ｌ⁵⁵は、好ましくは、単結合又は式（Ｌ１－１）で表される基である。 Examples of the group represented by the formula (L1-4) include the following divalent groups.

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

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

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

<Structural unit (a6)>
The structural unit (a6) is a structural unit having an —SO ₂ -group, and preferably has a —SO ₂ -group in the side chain.
The structural unit having -SO ₂ -group may have a linear structure having _-SO2 -group, or may have a branched structure having _-SO2 -group. It may have a cyclic structure (single ring and polycyclic structure) having a —SO ₂ − group. A structural unit having a cyclic structure having an —SO ₂ -group is preferable, and a structural unit having a cyclic structure (sultone ring) containing —SO ₂ -O— is more preferable.

Examples of the sultone ring include rings represented by the following equations (T ^1-1 ), (T ^1-2 ), (T ^1-3 ) and (T ^1-4 ). The binding site can be any position. The sultone ring may be a monocyclic type, but is preferably a polycyclic type. The polycyclic sultone ring means a bridged ring containing _−SO2 -O— as an atomic group constituting the ring, and is represented by the formulas (T ^1-1 ) and (T ^1-2 ). Ring is mentioned. Like the ring represented by the formula (T ^1-2 ), the sultone ring may further contain a heteroatom in addition to _−SO2 -O— as an atomic group constituting the ring. Examples of the hetero atom include an oxygen atom, a sulfur atom or a nitrogen atom, and an oxygen atom is preferable.

The sulton ring may have a substituent, and as the substituent, an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxy group, a cyano group, or a hydroxy group may have a halogen atom or a hydroxy group. Examples thereof include an alkoxy group having 12 to 12, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms and an alkylcarbonyl group having 2 to 4 carbon atoms. Be done.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and a decyl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Is.
Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Examples thereof include a trichloromethyl group, a tribromomethyl group and a triiodomethyl group, preferably a trifluoromethyl group.
Examples of the alkyl group having a hydroxy group include a hydroxyalkyl group of a hydroxymethyl group and a 2-hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a trill group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group and a phenanthryl group. Groups include 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the alkoxycarbonyl group include a group in which an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or less carbon atoms, and more preferably a methoxycarbonyl group. Can be mentioned.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group.

［式（Ｔ１’）中、
Ｘ^１１は、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^４１は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１～１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１～１２のアルコキシ基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基、グリシジルオキシ基、炭素数２～１２のアルコキシカルボニル基又は炭素数２～４のアルキルカルボニル基を表す。
ｍａは、０～９のいずれかの整数を表す。ｍａが２以上のとき、複数のＲ^４１は同一であっても異なってもよい。
結合部位は任意の位置である。］
Ｘ^１１は、好ましくは酸素原子又はメチレン基であり、より好ましくはメチレン基である。
Ｒ^４１としては、スルトン環の置換基と同様のものが挙げられ、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１～１２のアルキル基が好ましい。 A sultone ring having no substituent is preferable from the viewpoint that the monomer for deriving the structural unit (a6) can be easily produced.
As the sultone ring, a ring represented by the following formula (T1') is preferable.

[In the formula (T1'),
X ¹¹ represents an oxygen atom, a sulfur atom or a methylene group.
R ⁴¹ has an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, and an aryl having 6 to 12 carbon atoms, which may have a halogen atom or a hydroxy group. It represents a group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms.
ma represents an integer of 0 to 9. When ma is 2 or more, the plurality of R ^41s may be the same or different.
The binding site is at any position. ]
X ¹¹ is preferably an oxygen atom or a methylene group, and more preferably a methylene group.
Examples of R ⁴¹ include the same as the substituent of the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferable.

［式（Ｔ１）中、
Ｒ^８は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１～１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１～１２のアルコキシ基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基、グリシジルオキシ基、炭素数２～１２のアルコキシカルボニル基あるいは炭素数２～４のアルキルカルボニル基を表す。
ｍは、０～９のいずれかの整数を表す。ｍが２以上のとき、複数のＲ^８は同一であっても異なってもよい。
結合部位は任意の位置である。］ As the sultone ring, the ring represented by the formula (T1) is more preferable.

[In formula (T1),
R ⁸ has an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, and an aryl having 6 to 12 carbon atoms, which may have a halogen atom or a hydroxy group. It represents a group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms.
m represents any integer from 0 to 9. When m is 2 or more, the plurality of R ^8s may be the same or different.
The binding site is at any position. ]

Examples of R ⁸ are the same as those of R ⁴¹ .
The ma in the formula (T1') and m in the formula (T1) are preferably 0 or 1, and more preferably 0.

Examples of the ring represented by the formula (T1') and the ring represented by the formula (T1) include the following rings. The binding site is at any position.

The structural unit having a sultone ring preferably has the following groups. * In the following groups represents a binding site.

The structural unit having a —SO ₂ − group further preferably has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group and the like.
Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth) acrylic monomer.

［式（Ｉｘ）中、Ｒ^ｘ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。
Ａ^ｘｘは、酸素原子、－Ｎ（Ｒ^ｃ）－又は硫黄原子を表す。
Ａ^ｘ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－、－ＣＯ－又は－Ｎ（Ｒ^ｄ）－に置き換わっていてもよい。
Ｘ^１１は、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^４１は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１～１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１～１２のアルコキシ基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基、グリシジルオキシ基、炭素数２～１２のアルコキシカルボニル基又は炭素数２～４のアルキルカルボニル基を表す。
ｍａは、０～９のいずれかの整数を表す。ｍａが２以上のとき、複数のＲ^４１は同一であっても異なってもよい。
Ｒ^ｃ及びＲ^ｄは、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。］ The structural unit (a6) is preferably a structural unit represented by the formula (Ix).

[In the formula (Ix), R ^x represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
A ^xx represents an oxygen atom, -N (R ^c )-or a sulfur atom.
A ^x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group becomes -O-, -CO- or -N (R ^d )-. It may be replaced.
X ¹¹ represents an oxygen atom, a sulfur atom or a methylene group.
R ⁴¹ has an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, and an aryl having 6 to 12 carbon atoms, which may have a halogen atom or a hydroxy group. It represents a group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms.
ma represents an integer of 0 to 9. When ma is 2 or more, the plurality of R ^41s may be the same or different.
R ^c and R ^d represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms independently of each other. ]

Examples of the halogen atom of ^Rx include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group of ^Rx include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of ^Rx include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. , Perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like.
^Rx is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.

^Examples of the divalent saturated hydrocarbon group of Ax include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. A combination of two or more of the groups may be used.
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, nonan-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, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4- Branched alkanediyl groups such as diyl groups;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. The group etc. can be mentioned.

Examples of R ⁴¹ , X ¹¹ and ma are the same as those in the equation (T1').
Examples of the sultone ring include the above-mentioned ones, and among them, the above-mentioned ones in which the bond position is specified are preferable.

Examples of the structural unit (a6) include the following structural units.

Among them, the structural units represented by the formula (a6-1), the formula (a6-2), the formula (a6-6), the formula (a6-7), the formula (a6-8) and the formula (a6-12). Is preferable, and structural units represented by the formulas (a6-1), formulas (a6-2), formulas (a6-7) and (a6-8) are more preferable.
When the resin (A) has the structural unit (a6), the content thereof is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and 3) with respect to all the structural units of the resin (A). ~ 30 mol% is more preferable.

<Structural unit (II)>
The resin (A) may further contain a structural unit (hereinafter, may be referred to as “structural unit (II)”) that decomposes by exposure to generate an acid. Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and the structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or sulfonio in the side chain. It is preferably a structural unit having a group and an organic anion.

［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 a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by the formula (II-2-A').

[In the 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 may be replaced with a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, 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 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
ZA ⁺ represents an organic cation. ]

Examples of the halogen atom represented by R ^III3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3 includes an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 . The same can be mentioned.
The alkanediyl group having 1 to 8 carbon atoms represented by A ^x1 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a 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-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Can be mentioned.
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms that may be substituted with A ^x1 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, and a perfluorotert. -Butyl group, perfluoropentyl group, perfluorohexyl group and the like can be mentioned.
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. And may be a combination of these.
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, nonan-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group and other linear alkanediyl groups; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , Pentan-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 , 4-Diyl group, cyclooctane-1,5-Diyl group and other cycloalkandyl groups; norbornan-1,4-diyl group, norbornan-2,5-diyl group, adamantan-1,5-diyl group, adamantan Examples thereof include a divalent polycyclic alicyclic saturated hydrocarbon group such as -2,6-diyl group.
When -CH _2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-, for example, a divalent group represented by the formulas (X1) to (X53) is used. Can be mentioned. However, the number of carbon atoms before that -CH _2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following equation, * and ** represent a bond, and * represents a bond 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 saturated hydrocarbon group having 1 to 13 divalent carbon atoms.
X ⁶ represents a saturated hydrocarbon group having 1 to 14 divalent carbon atoms.
X ⁷ represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms.
X ⁸ represents a saturated hydrocarbon group having 1 to 13 divalent carbon atoms.

Examples of ZA ⁺ in the formula (II-2-A') include those similar to the cation Z1 ⁺ in the acid generator (B1).

［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、ｚ２Ａ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、前述の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 the formula (II-2-A') is preferably the structural unit represented by the formula (II-2-A).

[In formula (II-2-A),
R ^III3 , X ^III3 and ZA ⁺ have the same meanings as above.
z2A represents an integer of 0 to 6.
R III 2 and R ^III 4 independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms, and when ^z2A is 2 or more, a plurality of R ^{III 2} and R ^III 4 are identical to each other. It may or may not 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 above. ..

［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 the formula (II-2-A) is preferably the structural unit represented by the formula (II-2-A-1).

[In the formula (II-2-A-1),
R ^III2 , R ^III3 , R ^III4 , ^Qa , ^Qb and ZA ⁺ have 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.
^XI2 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 atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group. ]
Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ^III5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Examples thereof include a linear or branched alkyl group such as a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
Examples of the divalent saturated hydrocarbon group represented by X ^I 2 include those similar to the divalent saturated hydrocarbon group represented by X ^{III 3} .

［式（ＩＩ－２－Ａ－２）中、
Ｒ^III3、Ｒ^III5及びＺＡ^＋は、上記と同じ意味を表す。
ｍＡ及びｎＡは、それぞれ独立に、１又は２を表す。］ As the structural unit represented by the formula (II-2-A-1), the structural unit represented by the formula (II-2-A-2) is more preferable.

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

As the structural unit represented by the formula (II-2-A'), for example, the following structural unit, the group corresponding to the methyl group of R ^III3 is a hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen atom. Examples thereof include structural units replaced with alkyl groups having 1 to 6 carbon atoms (for example, trifluoromethyl groups, etc.) which may be possessed, and 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。
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 sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1).

[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 together with the sulfur atom to which they are bonded.
R ^II4 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or 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.
Examples of the halogen atom represented by R ^II4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 includes an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 . The same 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 by -O-, -S- or -CO-. Specifically, the same divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X ^III3 can be mentioned.

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

Examples of the organic anion represented by A ⁻ include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, a carboxylic acid anion and the like. The organic anion represented by A ⁻ is preferably a sulfonic acid anion, and the sulfonic acid anion is more preferably an anion contained in the salt represented by the above formula (B1).

スルホニルメチドアニオンとしては、以下のものが挙げられる。

カルボン酸アニオンとしては、以下のものが挙げられる。

Examples of the sulfonylimide anion represented by A ⁻ include the following.

Examples of the sulfonylmethide anion include the following.

Examples of the carboxylic acid anion include the following.

樹脂（Ａ）中に、構造単位（ＩＩ）を含有する場合の構造単位（ＩＩ）の含有率は、樹脂（Ａ）の全構造単位に対して、好ましくは１～２０モル％であり、より好ましくは２～１５モル％であり、さらに好ましくは３～１０モル％である。 Examples of the structural unit represented by the formula (II-1-1) include structural units represented by the following.

When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol% with respect to all the structural units of the resin (A), and more. It is preferably 2 to 15 mol%, more preferably 3 to 10 mol%.

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

The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s).
The structural unit (a1) is preferably a group consisting of a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group). It is at least one selected from, more preferably at least two, and even more preferably a structural unit (a1-1) and / or a structural unit (a1-2).
The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-A) or a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably a group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4). It is at least one selected from.

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, a radical polymerization method) using a monomer that leads to these structural units. be able to. The content of each structural unit of the resin (A) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, still more preferable). Is 15,000 or less). In the present specification, the weight average molecular weight is a value obtained by gel permeation chromatography under the conditions described in Examples.

<Resin other than resin (A)>
The resist composition of the present invention may be used in combination with a resin other than the resin (A).
Examples of the resin other than the resin (A) include a resin containing a structural unit (a4) or a structural unit (a5) (hereinafter, may be referred to as a resin (X)) and the like.
As the resin (X), a resin containing the structural unit (a4) is particularly preferable.
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 the structural units of the resin (X). , 45 mol% or more is more preferable.
Examples of the structural unit that the resin (X) may further include include a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers. Among them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), and more preferably a resin composed of only the structural unit (a4).
Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that of the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). It is more preferably 1 to 40 parts by mass, still more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass.

The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. When a resin other than the resin (A) is contained, 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 with respect to the solid content of the resist composition. It is preferably 90% by mass or more and 99% by mass or less, more preferably 90% by mass or less. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Solvent (E)>
The content of the solvent (E) 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 in the resist composition. % Or less. The content of the solvent (E) can be measured by a known analytical means such as liquid chromatography or gas chromatography.
Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate. Esters; ketones such as acetone, methylisobutylketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of solvent (E) may be used alone, or two or more kinds may be used.

<Quencher (C)>
The quencher (C) is a salt that generates an acid having a weaker acidity than the acid generated from the basic nitrogen-containing organic compound or the acid generator (B) (however, the carboxylate represented by the formula (I)). Except for.). When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15% by mass based on the solid content of the resist composition, and 0. It is more preferably about 01 to 10% by mass, further preferably about 0.1 to 8% by mass, and even more preferably about 0.1 to 7% by mass.
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.
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, trypentylamine, trihexylamine, tri Heptylamine, 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, tri Isopropanolamine, 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-di) Pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethen, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ) Etan, di (2-pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicorylamine, bipyridine and the like. Aromatic amines such as diisopropylaniline are preferred, and 2,6-diisopropylaniline is more preferred.
Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, and 3- (trifluoromethyl) phenyltrimethyl. Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

The acidity of a salt that produces an acid that is weaker than the acid generated by the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B) is usually a salt having an acid dissociation constant of -3 <pKa, preferably -1 <. It is a salt of pKa <7, more preferably a salt of 0 <pKa <5.
Examples of the salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B) include a salt represented by the following formula and a salt represented by the formula (D) described in JP-A-2015-147926. (Hereinafter, it may be referred to as "weak acid intramolecular salt (D)"), and JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502. Examples thereof include the salts described in JP-A-2011-191745. A salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B) is preferably a salt that generates a carboxylic acid having a weaker acidity than the acid generated from the acid generator (B) (carboxylic). A salt having an acid anion), more preferably a weak acid intramolecular salt (D).

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

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

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

<Manufacturing method of resist pattern>
The method for producing a resist pattern of the present invention is
(1) A step of applying the resist composition of the present invention onto a substrate,
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
It includes (4) a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.
The resist composition can be applied onto the substrate by a commonly used device such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer and an organic substrate having a resist film already formed. The substrate may be washed before the resist composition is applied, or an antireflection film or the like may be formed on the substrate.
By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a depressurizing device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure for drying under reduced pressure is preferably about ¹ to 1.0 × 105 Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. The exposure light source includes a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excima laser (wavelength 157 nm) that emits laser light in the ultraviolet region, and a solid-state laser light source (YAG or semiconductor laser). Etc.), and various ones such as those that radiate harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by radiating the laser light from, electron beam, and those that irradiate super-ultraviolet light (EUV) are used. Can be done. In addition, in this specification, irradiation of these radiations may be generically referred to as "exposure". At the time of exposure, the exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, it may be exposed by direct drawing without using a mask.
The composition layer after exposure is heat-treated (so-called post-exposure bake) in order to promote the deprotection reaction at the acid unstable group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C. Chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating. Further, before the development, the steps of applying, drying, exposing and heating the resist composition may be repeated on the composition layer after exposure.
The heated composition layer is usually developed using a developer and a developer. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense method. The development temperature is preferably, for example, 5 to 60 ° C., and the development time is preferably, for example, 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any alkaline aqueous solution used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) can be mentioned. The alkaline developer may contain a surfactant.
After development, it is preferable to wash the resist pattern with ultrapure water and then remove the substrate and the water remaining on the pattern.
When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter, may be referred to as "organic developer") is used as the developer.
Examples of the organic solvent contained in the organic developer include a ketone solvent such as 2-hexanone and 2-heptanone; a glycol ether ester solvent such as propylene glycol monomethyl ether acetate; an ester solvent such as butyl acetate; and a glycol such as propylene glycol monomethyl ether. Examples include an ether solvent; an amide solvent such as N, N-dimethylacetamide; an aromatic hydrocarbon solvent such as anisole, and the like.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and further preferably substantially only the organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and substantially butyl acetate and / or 2 -It is more preferable that it is only heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a small amount of water.
At the time of development, the development may be stopped by substituting with a solvent of a type different from that of the organic developer.
It is preferable to wash the resist pattern after development with a rinsing solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

<Use>
The resist composition of the present invention includes 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 EUV exposure, particularly ArF. It is suitable as a resist composition for excimer laser exposure and is useful for fine processing of semiconductors.

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part" indicating the content or the amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value obtained by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows.
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ℃
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh)
The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent 1100 type, MASS: Agilent LC / MSD type). 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－ｃ）で表される化合物２．２８部、酢酸エチル１００部及びテトラヒドロフラン１５部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｂ）で表される化合物６．５５部を添加し、２３℃で１８時間攪拌した。得られた反応マスに、ｎ－ヘプタン２０部及びイオン交換水７０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。回収された有機層にイオン交換水６０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４回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（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）分取することにより、式（Ｉ－１－ｄ）で表される化合物７．４８部を得た。

式（Ｉ－１－ｄ）で表される化合物０．９５部及びテトラヒドロフラン１０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却し、水素化ナトリウム０．１４部を添加した。得られた混合物に、式（Ｉ－１－ｅ）で表される塩１．８１部を添加し、５℃で３時間撹拌した。得られた混合物に、１Ｎ塩酸６．３０部を加えた後、２３℃まで昇温し、２３℃で６時間攪拌した。得られた混合物に、クロロホルム３０部及びイオン交換水１５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。得られた有機層を濃縮した後、濃縮残渣に、アセトニトリル１部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１－ｆ）で表される塩１．５２部を得た。

式（Ｉ－１－ｆ）で表される塩０．９５部及びジメチルホルムアミド３０部を混合し、２３℃で３０分間攪拌した後、炭酸カリウム０．１６部及びヨウ化カリウム０．０５部を添加し、７５℃まで昇温した。得られた混合物に、式（Ｉ－１－ｇ）で表される化合物０．５４部を添加し、７５℃で５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することにより、式（Ｉ－１－ｈ）で表される塩１．１２部を得た。

式（Ｉ－１－ｈ）で表される塩０．７５部、式（Ｉ－１－ｉ）で表される塩０．３７部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－１）で表される塩０．８３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５６３．２
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ １９５．１ Example 1: Synthesis of salt represented by formula (I-1)

20 parts of the compound represented by the formula (I-1-a), 2.28 parts of the compound represented by the formula (I-1-c), 100 parts of ethyl acetate and 15 parts of tetrahydrofuran are mixed and 30 at 23 ° C. Stir for minutes. 6.55 parts of the compound represented by the formula (I-1-b) was added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 18 hours. To the obtained reaction mass, 20 parts of n-heptane and 70 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 60 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 4 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 7.48 parts of the compound represented by the formula (I-1-d) was obtained.

0.95 part of the compound represented by the formula (I-1-d) and 10 parts of tetrahydrofuran were mixed, stirred at 23 ° C. for 30 minutes, cooled to 5 ° C., and 0.14 part of sodium hydride was added. .. To the obtained mixture, 1.81 parts of a salt represented by the formula (I-1-e) was added, and the mixture was stirred at 5 ° C. for 3 hours. After adding 6.30 parts of 1N hydrochloric acid to the obtained mixture, the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 6 hours. To the obtained mixture, 30 parts of chloroform and 15 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After concentrating the obtained organic layer, 1 part of acetonitrile and 30 parts of tert-butylmethyl ether were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated. 1.52 parts of the salt represented by (I-1-f) was obtained.

0.95 parts of the salt represented by the formula (I-1-f) and 30 parts of dimethylformamide were mixed, and after stirring at 23 ° C. for 30 minutes, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added. It was added and the temperature was raised to 75 ° C. To the obtained mixture, 0.54 part of the compound represented by the formula (I-1-g) was added, the mixture was stirred at 75 ° C. for 5 hours, and then cooled to 23 ° C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.12 parts of a salt represented by the formula (I-1-h) was obtained.

0.75 parts of the salt represented by the formula (I-1-h), 0.37 parts of the salt represented by the formula (I-1-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.83 part of a salt represented by the formula (I-1) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 563.2
MASS (ESI (-) Spectrum): M ^- 195.1

式（Ｉ－１－ｈ）で表される塩０．７５部、式（Ｉ－２－ｉ）で表される塩０．３７部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－２）で表される塩０．８２部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５６３．２
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ １９３．１ Example 2: Synthesis of salt represented by formula (I-2)

0.75 parts of the salt represented by the formula (I-1-h), 0.37 parts of the salt represented by the formula (I-2-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.82 parts of a salt represented by the formula (I-2) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 563.2
MASS (ESI (-) Spectrum): M ^- 193.1

式（Ｉ－１－ｈ）で表される塩０．７５部、式（Ｉ－４－ｉ）で表される塩０．５５部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－４）で表される塩１．０２部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５６３．２
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３７．１ Example 3: Synthesis of salt represented by formula (I-4)

0.75 parts of the salt represented by the formula (I-1-h), 0.55 parts of the salt represented by the formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.02 parts of a salt represented by the formula (I-4) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 563.2
MASS (ESI (-) Spectrum): M ^- 337.1

式（Ｉ－１－ｆ）で表される塩０．９５部及びジメチルホルムアミド３０部を混合し、２３℃で３０分間攪拌した後、炭酸カリウム０．１６部及びヨウ化カリウム０．０５部を添加し、７５℃まで昇温した。得られた混合物に、式（Ｉ－７４８－ｇ）で表される化合物０．５４部を添加し、７５℃で５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することにより、式（Ｉ－７４８－ｈ）で表される塩１．０９部を得た。

式（Ｉ－７４８－ｈ）で表される塩０．７６部、式（Ｉ－４－ｉ）で表される塩０．５５部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－７４８）で表される塩０．９９部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５６５．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３７．１ Example 4: Synthesis of salt represented by formula (I-748)

0.95 parts of the salt represented by the formula (I-1-f) and 30 parts of dimethylformamide were mixed, and after stirring at 23 ° C. for 30 minutes, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added. It was added and the temperature was raised to 75 ° C. To the obtained mixture, 0.54 part of the compound represented by the formula (I-748-g) was added, the mixture was stirred at 75 ° C. for 5 hours, and then cooled to 23 ° C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.09 parts of a salt represented by the formula (I-748-h) was obtained.

0.76 parts of the salt represented by the formula (I-748-h), 0.55 parts of the salt represented by the formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.99 parts of a salt represented by the formula (I-748) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 565.1
MASS (ESI (-) Spectrum): M ^- 337.1

式（Ｉ－７４８－ｈ）で表される塩０．７６部、式（Ｉ－２－ｉ）で表される塩０．３７部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－７４６）で表される塩０．８４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５６５．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ １９３．１ Example 5: Synthesis of salt represented by the formula (I-746)

0.76 parts of the salt represented by the formula (I-748-h), 0.37 parts of the salt represented by the formula (I-2-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.84 parts of a salt represented by the formula (I-746) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 565.1
MASS (ESI (-) Spectrum): M ^- 193.1

式（Ｉ－７４８－ｈ）で表される塩０．７６部、式（Ｉ－１－ｉ）で表される塩０．３７部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－７４５）で表される塩０．８０部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５６５．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ １９５．１ Example 6: Synthesis of salt represented by the formula (I-745)

0.76 parts of the salt represented by the formula (I-748-h), 0.37 parts of the salt represented by the formula (I-1-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.80 part of a salt represented by the formula (I-745) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 565.1
MASS (ESI (-) Spectrum): M ^- 195.1

式（Ｉ－１－ｆ）で表される塩０．９５部及びジメチルホルムアミド３０部を混合し、２３℃で３０分間攪拌した後、炭酸カリウム０．１６部及びヨウ化カリウム０．０５部を添加し、７５℃まで昇温した。得られた混合物に、式（Ｉ－１１４４－ｇ）で表される化合物０．６１部を添加し、７５℃で５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することにより、式（Ｉ－１１４４－ｈ）で表される塩１．２３部を得た。

式（Ｉ－１１４４－ｈ）で表される塩０．７９部、式（Ｉ－４－ｉ）で表される塩０．５５部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－１１４４）で表される塩１．０９部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５９１．２
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３７．１ Example 7: Synthesis of salt represented by the formula (I-1144)

0.95 parts of the salt represented by the formula (I-1-f) and 30 parts of dimethylformamide were mixed, and after stirring at 23 ° C. for 30 minutes, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added. It was added and the temperature was raised to 75 ° C. To the obtained mixture, 0.61 part of the compound represented by the formula (I-1144-g) was added, the mixture was stirred at 75 ° C. for 5 hours, and then cooled to 23 ° C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.23 parts of a salt represented by the formula (I-1144-h) was obtained.

0.79 parts of the salt represented by the formula (I-1144-h), 0.55 parts of the salt represented by the formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.09 parts of a salt represented by the formula (I-1144) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 591.2
MASS (ESI (-) Spectrum): M ^- 337.1

式（Ｉ－１－ｄ）で表される化合物２．１０部及びテトラヒドロフラン２０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却し、水素化ナトリウム０．２８部を添加した。得られた混合物に、式（Ｉ－３２３４－ｅ）で表される塩１．９１部を添加し、５℃で３時間撹拌した。得られた混合物に、１Ｎ塩酸１２．６０部を加えた後、２３℃まで昇温し、２３℃で６時間攪拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２５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。得られた有機層を濃縮した後、濃縮残渣に、アセトニトリル３部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－３２３４－ｆ）で表される塩２．４２部を得た。

式（Ｉ－３２３４－ｆ）で表される塩１．２０部及びジメチルホルムアミド３０部を混合し、２３℃で３０分間攪拌した後、炭酸カリウム０．３２部及びヨウ化カリウム０．１０部を添加し、７５℃まで昇温した。得られた混合物に、式（Ｉ－１１４４－ｇ）で表される化合物１．４５部を添加し、７５℃で５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することにより、式（Ｉ－３２３４－ｈ）で表される塩１．５５部を得た。

式（Ｉ－３２３４－ｈ）で表される塩０．７９部、式（Ｉ－４－ｉ）で表される塩０．５５部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－３２３４）で表される塩１．２７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ９２１．３
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３７．１ Example 8: Synthesis of salt represented by the formula (I-3234)

2.10 parts of the compound represented by the formula (I-1-d) and 20 parts of tetrahydrofuran were mixed, stirred at 23 ° C. for 30 minutes, cooled to 5 ° C., and 0.28 part of sodium hydride was added. .. To the obtained mixture, 1.91 parts of a salt represented by the formula (I-3234-e) was added, and the mixture was stirred at 5 ° C. for 3 hours. After adding 12.60 parts of 1N hydrochloric acid to the obtained mixture, the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 6 hours. To the obtained mixture, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After concentrating the obtained organic layer, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated. 2.42 parts of the salt represented by (I-3234-f) was obtained.

1.20 parts of the salt represented by the formula (I-3234-f) and 30 parts of dimethylformamide were mixed, and after stirring at 23 ° C. for 30 minutes, 0.32 parts of potassium carbonate and 0.10 parts of potassium iodide were added. It was added and the temperature was raised to 75 ° C. To the obtained mixture, 1.45 parts of the compound represented by the formula (I-1144-g) was added, the mixture was stirred at 75 ° C. for 5 hours, and then cooled to 23 ° C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.55 parts of a salt represented by the formula (I-3234-h) was obtained.

0.79 parts of the salt represented by the formula (I-3234-h), 0.55 parts of the salt represented by the formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.27 parts of a salt represented by the formula (I-3234) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 921.3
MASS (ESI (-) Spectrum): M ^- 337.1

式（Ｉ－１－ｄ）で表される化合物３．１５部及びテトラヒドロフラン３０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却し、水素化ナトリウム０．４２部を添加した。得られた混合物に、式（Ｉ－３７０９－ｅ）で表される塩２．０１部を添加し、５℃で３時間撹拌した。得られた混合物に、１Ｎ塩酸１８．９０部を加えた後、２３℃まで昇温し、２３℃で６時間攪拌した。得られた混合物に、クロロホルム１００部及びイオン交換水５０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。得られた有機層を濃縮した後、濃縮残渣に、アセトニトリル５部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－３７０９－ｆ）で表される塩３．１１部を得た。

式（Ｉ－３７０９－ｆ）で表される塩１．４５部及びジメチルホルムアミド３０部を混合し、２３℃で３０分間攪拌した後、炭酸カリウム０．４８部及びヨウ化カリウム０．１５部を添加し、７５℃まで昇温した。得られた混合物に、式（Ｉ－１１４４－ｇ）で表される化合物２．１７部を添加し、７５℃で５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することにより、式（Ｉ－３７０９－ｈ）で表される塩２．１２部を得た。

式（Ｉ－３７０９－ｈ）で表される塩１．６１部、式（Ｉ－４－ｉ）で表される塩０．５５部及びクロロホルム２０部を混合し、２３℃で１２時間攪拌した。得られた混合物に、５％シュウ酸水溶液１０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１０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することにより、式（Ｉ－３７０９）で表される塩１．８１部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋１２５１．４
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３７．１ Example 9: Synthesis of salt represented by the formula (I-3709)

3.15 parts of the compound represented by the formula (I-1-d) and 30 parts of tetrahydrofuran were mixed, stirred at 23 ° C. for 30 minutes, cooled to 5 ° C., and 0.42 parts of sodium hydride was added. .. To the obtained mixture, 2.01 part of a salt represented by the formula (I-3709-e) was added, and the mixture was stirred at 5 ° C. for 3 hours. After adding 18.90 parts of 1N hydrochloric acid to the obtained mixture, the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 6 hours. To the obtained mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After concentrating the obtained organic layer, 5 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated. 3.11 parts of salt represented by (I-3709-f) was obtained.

1.45 parts of the salt represented by the formula (I-3709-f) and 30 parts of dimethylformamide were mixed, and after stirring at 23 ° C. for 30 minutes, 0.48 parts of potassium carbonate and 0.15 parts of potassium iodide were added. It was added and the temperature was raised to 75 ° C. 2.17 parts of the compound represented by the formula (I-1144-g) was added to the obtained mixture, the mixture was stirred at 75 ° C. for 5 hours, and then cooled to 23 ° C. To the obtained mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 2.12 parts of a salt represented by the formula (I-3709-h) was obtained.

1.61 parts of the salt represented by the formula (I-3709-h), 0.55 parts of the salt represented by the formula (I-4-i) and 20 parts of chloroform were mixed and stirred at 23 ° C. for 12 hours. .. To the obtained mixture, 10 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.81 parts of a salt represented by the formula (I-3709) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 1251.4
MASS (ESI (-) Spectrum): M ^- 337.1

Synthesis of Resin The compounds (monomers) used for the synthesis of the resin (A) are shown below. Hereinafter, these compounds will be referred to as "monomer (a1-1-3)" or the like according to the formula number.

Synthesis Example 1: Synthesis of Resin A1 As the monomer, a monomer (a1-1-3), a monomer (a1-2-6), a monomer (a2-1-1) and a monomer (a3-4-2) are used. The molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-1): monomer (a3-4-2)] is 45: 14: 2.5: 38. The mixture was mixed so as to have a value of 5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is dissolved again in propylene glycol monomethyl ether acetate, and the obtained solution is poured into a methanol / water mixed solvent to precipitate the resin, and the resin is filtered. The reprecipitation operation is performed twice, and the weight average is obtained. A resin A1 having a molecular weight of 7.8 × 10 ³ was obtained in a yield of 69%. This resin A1 has the following structural units.

Synthesis Example 2: Synthesis of resin X1 A monomer (a5-1-1) and a monomer (a4-0-12) are used as the monomer, and the molar ratio thereof [monomer (a5-1-1): monomer (a4-0-). 12)] was mixed so that the ratio was 50:50, and methyl isobutyl ketone 1.2% by mass of the total amount of the monomers was added to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution 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 a mixed methanol / water solvent to precipitate a resin, and the resin was filtered to obtain a resin X having a weight ^average molecular weight of 1.0 × 104 in a yield of 91%. This resin X1 has the following structural units.

<Preparation of resist composition>
As shown in Table 2, each of the following components was mixed, and the obtained mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

＜カルボン酸塩（Ｉ）＞
Ｉ－１：式（Ｉ－１）で表される塩
Ｉ－２：式（Ｉ－２）で表される塩
Ｉ－４：式（Ｉ－４）で表される塩
Ｉ－７４５：式（Ｉ－７４５）で表される塩
Ｉ－７４６：式（Ｉ－７４６）で表される塩
Ｉ－７４８：式（Ｉ－７４８）で表される塩
Ｉ－１１４４：式（Ｉ－１１４４）で表される塩
Ｉ－３２３４：式（Ｉ－３２３４）で表される塩
Ｉ－３７０９：式（Ｉ－３７０９）で表される塩
＜クエンチャー（Ｃ）＞
ＩＸ－１
ＩＸ－２
ＩＸ－３
ＩＸ－４

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２－ヘプタノン ２０部
γ－ブチロラクトン ３．５部 <Resin>
A1, X1: Resin A1, Resin X1
<Acid generator (B)>
B1-21: Salt represented by the formula (B1-21) B1-22: Salt represented by the formula (B1-22)

<Carboxylate (I)>
I-1: Salt represented by formula (I-1) I-2: Salt represented by formula (I-2) I-4: Salt represented by formula (I-4) I-745: Salt represented by formula (I-4) Salt represented by (I-745) I-746: Salt represented by formula (I-746) I-748: Salt represented by formula (I-748) I-1144: Salt represented by formula (I-1144) Salt represented by I-3234: Salt represented by formula (I-3234) I-3709: Salt represented by formula (I-3709) <Quencher (C)>
IX-1
IX-2
IX-3
IX-4

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

<Manufacturing of resist pattern and its evaluation>
An organic antireflection film composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] is applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to make it organic with a thickness of 78 nm. An antireflection film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (prebaking) was 100 nm. After coating, the silicon wafer was prebaked on a direct hot plate at the temperature shown in the “PB” column of Table 2 for 60 seconds to form a composition layer on the silicon wafer.
ArF excimer laser stepper for immersion exposure [XT: 1900Gi; ASML, NA = 1.35, Anal σ _out = 0.85 σ _in = 0.65 XY- pol. In [Illumination], a mask for forming a trench pattern (pitch 120 nm / trench width 40 nm) was used, and the exposure amount was changed stepwise for exposure. Ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed on a hot plate at the temperature listed in the “PEB” column of Table 2 for 60 seconds. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution at 23 ° C. for 20 seconds by the dynamic dispensing method to obtain a negative resist pattern. Manufactured.

In the obtained resist pattern, the exposure amount at which the width of the trench pattern was 40 nm was taken as the effective sensitivity.

比較組成物１～４と比較して、組成物１～９は、ラインエッジラフネス（ＬＥＲ）が良好であった。 <Line edge roughness evaluation (LER)>
With respect to the obtained resist pattern, the fluctuation width of the unevenness of the wall surface was observed and measured with a scanning electron microscope. The results are shown in Table 3. The numerical values in the table indicate the runout width (nm).

Compared with the comparative compositions 1 to 4, the compositions 1 to 9 had better line edge roughness (LER).

The carboxylic acid salt of the present invention and the resist composition containing the carboxylic acid salt are suitable for fine processing of semiconductors because a resist pattern having good line edge roughness (LER) can be obtained, and are extremely useful in industry. ..

Claims (11)

Carboxylate represented by the formula (I).

[In formula (I),
R ¹ , R ² and R ³ are independently of -OR ¹⁰ , -O-CO-R ¹⁰ , -O-CO-O-R ¹⁰ , -OL ¹ -CO-O-R ¹⁰ . Represents.
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently have a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms. Represented, the hydrocarbon group may have a substituent, and -CH _2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO- or -SO _2- . May be good.
L ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
R ¹⁰ represents a group having a lactone structure.
X ¹ , X ² and X ³ independently represent an oxygen atom or a sulfur atom, respectively.
m1 represents an integer of 0 to 5, and when m1 is 2 or more, the groups in the plurality of parentheses may be the same or different from each other.
m2 represents an integer of 0 to 4, and when m2 is 2 or more, the groups in the plurality of parentheses may be the same or different from each other.
m3 represents an integer of 0 to 4, and when m3 is 2 or more, the groups in the plurality of parentheses may be the same or different from each other.
m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of ^R4s may be the same or different from each other.
m5 represents an integer of 0 to 4, and when m5 is 2 or more, a plurality of ^R5s may be the same or different from each other.
m6 represents an integer of 0 to 4, and when m6 is 2 or more, a plurality of ^R6s may be the same or different from each other.
m7 represents an integer of 0 to 5, and when m7 is 2 or more, a plurality of ^R7s may be the same or different from each other.
m8 represents an integer of 0 to 4, and when m8 is 2 or more, a plurality of ^R8s may be the same or different from each other.
m9 represents an integer of 0 to 4, and when m9 is 2 or more, a plurality of ^R9s may be the same or different from each other.
However, 0 ≦ m1 + m7 ≦ 5, 0 ≦ m2 + m8 ≦ 4, 0 ≦ m3 + m9 ≦ 4, and at least one of m1, m2, and m3 represents an integer of 1 or more.
X ⁴ represents a single bond, -CH _2- , -O-, -S-, -CO-, -SO- or -SO _2- .
X ⁰ represents a hydrocarbon group having 1 to 72 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- . ] The carboxylate according to claim 1, wherein X ¹ , X ² and X ³ are oxygen atoms. The carboxylate according to claim 1 or 2, wherein R ¹ , R ² and R ³ are —O—CO—O—R ¹⁰ − or —OL ¹ −CO—OR ¹⁰ . Claims 1 to 3 in which the group having a lactone structure of R ¹⁰ is a group having a lactone ring group represented by the formula (R ¹⁰ -1), the formula (R ¹⁰ -2-) or the formula (R ¹⁰ -3). The carboxylate according to any of the above.

[In equation (R ¹⁰ -1) to equation (R ¹⁰ -3),
* Represents a bond.
Z ¹² represents an oxygen atom, a sulfur atom or a methylene group.
R ¹¹ , R ¹² and R ¹³ each independently represent a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, and are contained in the hydrocarbon group-CH ₂ . -May be replaced by -O- or -CO-.
m11 represents an integer of 0 to 5, and when m11 is 2 or more, a plurality of ^R11s may be the same or different from each other.
m12 represents an integer of 0 to 5, and when m12 is 2 or more, a plurality of R ^12s may be the same or different from each other.
m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of ^R13s may be the same or different from each other.
n10 represents an integer of 1 to 3. ] X ⁰ is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (however, -CH _2- contained in the aliphatic hydrocarbon group is -O-, -S-,-. The carboxylic acid according to any one of claims 1 to 4, which is an aromatic hydrocarbon group having 6 to 36 carbon atoms which may be replaced with CO- or -SO _2- ) or may have a substituent. salt. An alicyclic hydrocarbon group having 3 to 36 carbon atoms in which ^X0 may have a fluorine atom or a hydroxy group (-CH _2- contained in the alicyclic hydrocarbon group is -O-, -S. -, -CO- or -SO _2- may be replaced.) Or an aromatic hydrocarbon having 6 to 36 carbon atoms which may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms. The carboxylate according to any one of claims 1 to 5, which is a group. A carboxylic acid generator containing the carboxylic acid salt according to any one of claims 1 to 6. A resist composition containing the carboxylic acid generator according to claim 7, an acid generator other than the carboxylic acid generator, and a resin having an acid unstable group. The eighth aspect of the present invention, wherein the resin having an acid unstable group contains at least one selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2). Resist composition.

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent -O- or * -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents -CO-. Represents a bond with.
R ^a4 and R ^a5 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a6 and R ^a7 are independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group or a group combining these groups.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ] The resist composition according to claim 8 or 9, further comprising a resin containing a structural unit having a fluorine atom. (1) A step of applying the resist composition according to any one of claims 8 to 10 onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) Step of heating the composition layer after exposure, and (5) Step of developing the composition layer after heating,
A method for manufacturing a resist pattern including.