JP2019003173A - Resist composition and method for producing resist pattern - Google Patents

Abstract

To provide a resist composition that makes it possible to produce a resist pattern with excellent line edge roughness (LER).SOLUTION: A resist composition contains a resin containing a structural unit derived from a compound represented by formula (I), an acid generator, and a salt that generates an acid with a weaker acidity than that of an acid generated from an acid generator. Ris a hydrogen atom or a methyl group. Ris a C1-6 saturated hydrocarbon group. Ris a hydrogen atom or a C1-6 saturated hydrocarbon group. Ar is an optionally substituted C6-36 divalent aromatic hydrocarbon group. Xis a divalent group having -CO-O-, -O-CO-, -O-CO-O- or -O-. Ris an optionally substituted C3-24 alicyclic hydrocarbon group or the like.SELECTED DRAWING: None

Description

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

特許文献１には、下記構造単位を有する樹脂と下記式で表される酸発生剤を含有するレジスト組成物も記載されている。

Patent Document 1 describes a resist composition containing a resin having the following structural unit, an acid generator, and an ammonium salt having the following structure.

Patent Document 1 also describes a resist composition containing a resin having the following structural unit and an acid generator represented by the following formula.

Patent Document 2 describes a resist composition containing a resin having the following structural units, an acid generator, and an ammonium salt having the following structure.

Patent Document 3 describes a resist composition containing a resin having the following structural unit, an acid generator, and an ammonium salt having the following structure.

Patent Document 4 describes a resist composition containing a resin having the following structural units, an acid generator, and an ammonium salt having the following structure.

JP 2013-122041 A JP 2013-116886 A JP2013-121942A JP2013-127051A

  An object of the present invention is to provide a resist composition for obtaining a resist pattern having better line edge roughness (LER) than a resist pattern formed from the above resist composition.

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ｒ^２は、炭素数１〜６の飽和炭化水素基を表す。
Ｒ^３は、水素原子又は炭素数１〜６の飽和炭化水素基を表す。
Ａｒは、置換基を有していてもよい炭素数６〜３６の２価の芳香族炭化水素基を表す。
Ｘ^１は、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−又は−Ｏ−を有する２価の基を表す。
Ｒ^４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（該脂環式炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−Ｓ（Ｏ）_２−に置き換わっていてもよい。）、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有する炭素数１〜１８の脂肪族炭化水素基（該脂環式炭化水素基及び該脂肪族炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−Ｓ（Ｏ）_２−に置き換わっていてもよい。）を表す。］
［２］ Ｒ^２が炭素数１〜６のアルキル基であり、Ｒ^３が水素原子である［１］記載のレジスト組成物。
［３］ Ｘ^１が、＊−ＣＯ−Ｏ−又は＊−Ｏ−Ａ^１１−ＣＯ−Ｏ−（＊は、Ａｒとの結合手を表し、Ａ^１１は炭素数１〜６のアルカンジイル基を表す。）である［１］又は［２］記載のレジスト組成物。
［４］ Ｒ^４が、炭素数１〜６のアルキル基、ヒドロキシ基又はハロゲン原子を有してもよい炭素数３〜１２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−Ｓ（Ｏ）_２−に置き換わっていてもよい。）である［１］〜［３］のいずれかに記載のレジスト組成物。
［５］ 酸発生剤から発生する酸よりも酸性度の弱い酸が、式（Ｃ１）で表される塩又は式（Ｄ）で表される塩である［１］〜［４］のいずれかに記載のレジスト組成物。

［式（Ｃ１）中、
Ｒ^Ａは、置換基を有していてもよい炭素数１〜３６の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−ＳＯ_２−に置き換わっていてもよい。
Ｚ^６＋は、有機カチオンを表す。］

［式（Ｄ）中、
Ｒ^Ｄ１及びＲ^Ｄ２は、それぞれ独立に、炭素数１〜１２の炭化水素基、炭素数１〜６のアルコキシ基、炭素数２〜７のアルキルカルボニル基、炭素数２〜７のアルキルカルボニルオキシ基、炭素数２〜７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０〜４のいずれかの整数を表し、ｍ’が２以上の場合、複数のＲ^Ｄ１は同一又は相異なり、ｎ’が２以上の場合、複数のＲ^Ｄ２は同一又は相異なる。］
［６］ 樹脂が、さらに、酸不安定基を有する構造単位を含む［１］〜［５］のいずれかに記載のレジスト組成物。
［７］ 酸発生剤が、式（Ｂ１）で表される塩を含む［１］〜［６］のいずれかに記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ^ｂ１及びＱ^ｂ２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８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−ＣＨ_２−は、−Ｏ−、−Ｓ（Ｏ）_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］
［８］（１）［１］〜［７］のいずれかに記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程、
を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resist composition comprising a resin containing a structural unit derived from the compound represented by formula (I), an acid generator, and a salt that generates an acid having a lower acidity than an acid generated from the acid generator.

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms.
Ar represents a C6-C36 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents a divalent group having —CO—O—, —O—CO—, —O—CO—O— or —O—.
R ⁴ represents an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (—CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—, -CO- or -S (O) _2- may be substituted.), Or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms and having 1 to 18 carbon atoms. An aliphatic hydrocarbon group (-CH ₂ — contained in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is replaced by —O—, —S—, —CO— or —S (O) ₂ —; May be present). ]
[2] The resist composition according to [1], wherein R ² is an alkyl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom.
[3] X ¹ represents * —CO—O— or * —O—A ¹¹ —CO—O— (* represents a bond to Ar, and A ¹¹ represents an alkanediyl group having 1 to 6 carbon atoms. The resist composition according to [1] or [2].
[4] R ⁴ is an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms, a hydroxy group or a halogen atom (included in the alicyclic hydrocarbon group). —CH ₂ — may be replaced by —O—, —S—, —CO— or —S (O) ₂ —.) The resist composition according to any one of [1] to [3] object.
[5] Any of [1] to [4], wherein the acid having a lower acidity than the acid generated from the acid generator is a salt represented by the formula (C1) or a salt represented by the formula (D). The resist composition described in 1.

[In the formula (C1),
R ^A represents an optionally substituted hydrocarbon group having 1 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or It may be replaced by —SO ₂ —.
Z ⁶⁺ represents an organic cation. ]

[In the formula (D),
R ^D1 and R ^D2 are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 7 carbon atoms, or an alkylcarbonyloxy group having 2 to 7 carbon atoms. Represents an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group, or a halogen atom.
m ′ and n ′ each independently represents an integer of 0 to 4, and when m ′ is 2 or more, a plurality of R ^D1 are the same or different, and when n ′ is 2 or more, a plurality of R ^D2 is the same or different. ]
[6] The resist composition according to any one of [1] to [5], wherein the resin further includes a structural unit having an acid labile group.
[7] The resist composition according to any one of [1] to [6], wherein the acid generator includes a salt represented by the formula (B1).

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
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 by —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 an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —S (O) ₂ —, or —CO—.
Z ⁺ represents an organic cation. ]
[8] (1) A step of applying the resist composition according to any one of [1] to [7] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including:

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

In the present specification, unless otherwise specified, “(meth) acrylate” means “at least one selected from the group consisting of acrylate and methacrylate”. The notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning. When structural units having “CH ₂ ═C (CH ₃ ) —CO—” or “CH ₂ ═CH—CO—” are exemplified, the structural units having both groups are also exemplified. Shall. Moreover, when a stereoisomer exists, all the stereoisomers are included.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition.

[Resist composition]
The resist composition of the present invention comprises a resin (A) containing a structural unit derived from the compound represented by formula (I), an acid generator (hereinafter sometimes referred to as “acid generator (B)”) and an acid. Contains a salt that generates an acid that is less acidic than the acid generated from the generator.
The resist composition preferably contains a solvent (hereinafter sometimes referred to as “solvent (E)”).

<Resin (A)>
The resin (A) includes a structural unit derived from a compound represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”).

Examples of the saturated hydrocarbon group having 1 to 6 carbon atoms of R ² and R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; and a group formed by combining these.
R ² is preferably a methyl group or an ethyl group, and more preferably a methyl group.
R ³ is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen 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、トリル基、キシリル基、シクロヘキシルフェニル基等が挙げられる。
芳香族炭化水素基の置換基におけ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のアルコキシ基と炭素数１〜１２のアルコキシ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のアルコキシ基と炭素数１〜１２のアルコキシ基とを組み合わせた基としては、エトキシエトキシ基等の炭素数２〜２４のアルコキシアルコキシ基等が挙げられる。
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のアラルキル基等が挙げられる。 Examples of the divalent aromatic hydrocarbon group for Ar include arylene groups having 6 to 36 carbon atoms such as a phenylene group, a naphthylene group, and an anthrylene group.
The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, and more preferably 6 to 18 carbon atoms.
Examples of the substituent of the aromatic hydrocarbon group 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 a carbon number. 2 to 13 alkylcarbonyl groups, C2 to C13 alkylcarbonyloxy groups, C3 to C12 alicyclic hydrocarbon groups, C6 to C10 aromatic hydrocarbon groups, or combinations thereof Is mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and iodine.
Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. .
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group Group, dodecyloxy group and the like.
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-described 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. 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.
The alicyclic hydrocarbon group having 3 to 12 carbon atoms may be monocyclic or polycyclic, and examples thereof include the following groups. ** is a bond with an aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a cyclohexylphenyl group.
Examples of the combined group in the substituent of the aromatic hydrocarbon group include a group in which a hydroxy group and an alkyl group having 1 to 12 carbon atoms are combined, an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. And a group in which an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined.
Examples of the group in which the hydroxy group and the 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.
Examples of the group in which the alkoxy group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms are combined include an alkoxyalkoxy group having 2 to 24 carbon atoms such as ethoxyethoxy group.
Examples of the group in which an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined include an aralkyl group having 7 to 22 carbon atoms such as a benzyl group.

X ¹ of -CO-O -, - O- CO -, - As the divalent group having a O-CO-O-or ^{-O-, * - X 11 -A 11} -X 12 -, * - X ^{13 -A 12 -X 14 -A 13 -} , * - X 15 -A 14 -X 16 -A 15 -X 17 - or * ^{-X 18} - (. * represents a bond to Ar) or the like Can be mentioned.
A ^{11 to} A ¹⁵ each independently represents an alkanediyl group having 1 to 6 carbon atoms.
X ^{11 to} X ¹⁸ each independently represent —CO—O—, —O—CO—, —O—CO—O— or —O—.
* ^-X 11 ^-A 11 ^{-X 12} - as, for _{example, * - O-CH 2 -CO} -O -, * - O-CO-CH 2 -O -, * - CO-O-CH 2 -O _{-, * - CO-O-} CH 2 -O-CO -, * - CO-O-CH 2 -O-CO-O -, * - CO-O-CH 2 -CO-O -, * - O- _{CO-O-CH 2 -CO-} O- , and the like.
* —X ¹³ —A ¹² —X ¹⁴ —A ¹³ — includes, for example, * —O—CH ₂ —CO—O—CH ₂ —, * —O—CH ₂ —O—CO—CH ₂ —, * _{-CO-O-CH 2 -O-} CH 2 -, * - O-CO-O-CH 2 -O-CH 2 -, * - CO-O-CH 2 -O-CO-CH 2 -, * - _{CO-O-CH 2 -CO-} O-CH 2 - , and the like.
* —X ¹⁵ —A ¹⁴ —X ¹⁶ —A ¹⁵ —X ¹⁷ — includes, for example, * —O—CH ₂ —CO—O—CH ₂ —CO—O—, * —O—CO—O—CH. _2— CO—O—CH ₂ —CO—O—, * —O—CH ₂ —O—CO—CH ₂ —CO—O—, * —CO—O—CH ₂ —O—CH ₂ —CO—O _{-, * - CO-O-} CH 2 -OCO-CH 2 -CO-O -, * - CO-O-CH 2 -CO-O-CH 2 -CO-O- , and the like.
Examples of * -X ¹⁸ -include * -CO-O-, * -O-CO-, * -O-CO-O-, * -O-, and the like.
The ^{X 1, * - X 11 -A} 11 -X 12 - or * ^{-X 18} - are ^{preferred, * - X 11 -A 11 -X} 12 - , or * is more preferably -CO-O-, * —O—CH ₂ —CO—O—, * —O—CO—CH ₂ —O—, * —O—CO—O—CH ₂ —O—, * —CO—O—CH ₂ —O—, * more preferably _{-CO-O-CH 2 -O-} CO- or * -CO-O-a _{is, * - O-CH 2 -CO} -O -, * - O-CO-CH 2 -O- , * —CO—O—, * —O—CO— or * —O—CO—O— is even more preferred, * —O—CH ₂ —CO—O—, * —CO—O—. (* Represents a bond with Ar).

An aliphatic hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent represented by R ^{4 (} the alicyclic hydrocarbon group and the —CH ₂ — contained in the aliphatic hydrocarbon group may be replaced by —O—, —S—, —CO— or —S (O) ₂ —). Examples include a group in combination with a hydrocarbon group.
The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be either saturated or unsaturated. The alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, and the like, a monocyclic cycloalkyl group, a norbornyl group, an adamantyl group And a polycyclic cycloalkyl group such as a group. Carbon number of an alicyclic hydrocarbon group becomes like this. Preferably it is 3-18, More preferably, it is 3-12.
Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and nonyl group. Carbon number of an alkyl group becomes like this. Preferably it is 1-9, More preferably, it is 1-4.
In the case where —CH ₂ — contained in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is replaced by —O—, —S—, —CO— or —S (O) ₂ —, the number of carbons before the replacement Is the total carbon number of the hydrocarbon group.

The alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent represented by R ⁴ (—CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S -, -CO- or -S (O) _2- may be substituted.) As the alicyclic hydrocarbon group in C 3-24, which may have a substituent, A C1-C18 aliphatic hydrocarbon group having a hydrogen group (-CH _2- contained in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is -O-, -S-, -CO- Or, it may be replaced by -S (O) _2- ), and represents the same group as the alicyclic hydrocarbon group.

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、トリル基、キシリル基、シクロヘキシルフェニル基等が挙げられる。
Ｒ^４の置換基におけ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のアラルキル基等が挙げられる。 The group represented by R ⁴ may have one or more substituents.
An aliphatic hydrocarbon group having 1 to 18 carbon atoms having an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (into the alicyclic hydrocarbon group and the aliphatic hydrocarbon group, -CH ₂ included - is -O -, - S -, - CO- or -S _{(O) 2} -. which may be substituted with) has an alicyclic hydrocarbon group moiety as a substituent It may have a substituent in the aliphatic hydrocarbon group portion, or may have in both of them.
Examples of the substituent include a hydroxy group, a carboxy 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 2 to 2 carbon atoms. 13 alkylcarbonyl group, C2-C13 alkylcarbonyloxy group, C3-C12 alicyclic hydrocarbon group, C6-C10 aromatic hydrocarbon group, or a combination thereof. It is done.
Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. .
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group Group, dodecyloxy group and the like.
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-described 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. 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 following groups. ** is a bond with a hydrocarbon group.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a cyclohexylphenyl group.
Examples of the combined group in the substituent of R ⁴ include a group in which a hydroxy group and an alkyl group having 1 to 12 carbon atoms are combined, an alkyl group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. And the like.
Examples of the group in which the hydroxy group and the 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.
Examples of the group in which an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined include an aralkyl group having 7 to 22 carbon atoms such as a benzyl group.

The alicyclic hydrocarbon group is preferably a group represented by the formulas (Y1) to (Y40). The formula (Y1) to the formula (Y20), the formula (Y30), the formula (Y31), the formula ( Y39) or a group represented by formula (Y40) is more preferable. Formula (Y11), Formula (Y15), Formula (Y18), Formula (Y20), Formula (Y30), Formula (Y39 Or a group represented by formula (Y40).

The substituent of R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms, a group having a hydroxy group or a halogen atom, and more preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a fluorine atom. A hydroxy group or a fluorine atom is more preferable.

The alicyclic hydrocarbon group having 3 to 24 carbon atoms represented by R ⁴ is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (the alicyclic hydrocarbon group). —CH ₂ — constituting the hydrocarbon group may be replaced by —O—, —S—, —CO— or —S (O) ₂ —, and more preferably has a substituent. An optionally substituted polycyclic hydrocarbon group having 7 to 12 carbon atoms (—CH ₂ — constituting the polycyclic hydrocarbon group is —O—, —S—, —CO— or —S (O)). _2- , which may be substituted with 2-, and more preferably a bicyclic hydrocarbon group or a tricyclic hydrocarbon group having 7 to 12 carbon atoms which may have a substituent (the polybicyclic ring). —CH ₂ — constituting the hydrocarbon group or tricyclic hydrocarbon group is replaced by —O—, —S—, —CO— or —S (O) ₂ —. It may be.)

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

In the monomers represented by the formulas (I-1) to (I-15), monomers in which the methyl group corresponding to R ¹ in the formula (I) is replaced with a hydrogen atom are also exemplified as specific examples of the monomer (I). be able to. Especially, the monomer represented by Formula (I-1)-Formula (I-5) and Formula (I-7)-Formula (I-11) is preferable, and Formula (I-1) and Formula (I) are preferable. −5), the formula (I-7), the formula (I-8), the formula (I-10), and the monomer represented by the formula (I-11) are more preferable, and the formula (I-1) and the formula (I -5) and monomers represented by the formula (I-7) are more preferable.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。） <Method for Producing Compound (I)>
Compound (I) can be obtained by reacting a compound represented by formula (Ia) and a compound represented by formula (Ib) in a solvent under a base catalyst.

(In the formula, all symbols have the same meaning as described above.)

Examples of the base catalyst include pyridine.
Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
The reaction temperature is usually from 0 ° C to 80 ° C, and the reaction time is usually from 0.5 hours to 24 hours.
Examples of the compound represented by the formula (Ia) include compounds represented by the following formula, which can be easily obtained from the market.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。） In the compound represented by the formula (Ib), R ³ is a hydrogen atom, and X ¹ is * —CO—O— (* represents a bond to Ar) (formula (I1 The compound represented by -b) can be obtained by reducing the compound represented by the formula (I1-c) in a solvent.

(In the formula, all symbols have the same meaning as described above.)

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
Examples of the reducing agent include lithium aluminum hydride and sodium borohydride.
The reaction temperature is usually from 0 ° C to 80 ° C, and the reaction time is usually from 0.5 hours to 24 hours.

溶媒としては、テトラヒドロフラン、クロロホルム及びアセトニトリルなどが挙げられる。
反応温度は通常１５℃〜８０℃であり、反応時間は通常０．５時間〜２４時間である。 The compound represented by the formula (I1-c) is further represented by the formula (I1-e) after reacting the compound represented by the formula (I1-d) with carbonyldiimidazole in a solvent. It can be obtained by reacting with a compound.

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

Examples of the compound represented by the formula (I1-d) include a compound represented by the following formula, and can be easily obtained from the market.

Examples of the compound represented by the formula (I1-e) include compounds represented by the following formula, and can be easily obtained from the market.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。） In the compound represented by the formula (Ib), a compound in which R ³ is a hydrogen atom and X ¹ is * —O—CO— (* represents a bond to Ar) (formula (I2 The compound represented by -b) can be obtained by reducing the compound represented by the formula (I2-c) in a solvent.

(In the formula, all symbols have the same meaning as described above.)

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
Examples of the reducing agent include lithium aluminum hydride and sodium borohydride.
The reaction temperature is usually from 0 ° C to 80 ° C, and the reaction time is usually from 0.5 hours to 24 hours.

溶媒としては、テトラヒドロフラン、クロロホルム及びアセトニトリルなどが挙げられる。
反応温度は通常１５℃〜８０℃であり、反応時間は通常０．５時間〜２４時間である。 The compound represented by formula (I2-c) is further represented by formula (I2-d) after reacting the compound represented by formula (I2-e) with carbonyldiimidazole in a solvent. It can be obtained by reacting with a compound.

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

Examples of the compound represented by the formula (I2-d) include compounds represented by the following formula, and can be easily obtained from the market.

Examples of the compound represented by the formula (I2-e) include compounds represented by the following formula, and can be easily obtained from the market.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。） In the compound represented by formula (Ib), R ³ is a hydrogen atom, and X ¹ is * —O—CO—O— (* represents a bond to Ar) (formula (Compound represented by (I3-b)) can be obtained by reducing the compound represented by formula (I3-c) in a solvent.

(In the formula, all symbols have the same meaning as described above.)

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
Examples of the reducing agent include lithium aluminum hydride and sodium borohydride.
The reaction temperature is usually from 0 ° C to 80 ° C, and the reaction time is usually from 0.5 hours to 24 hours.

溶媒としては、テトラヒドロフラン、クロロホルム及びアセトニトリルなどが挙げられる。
反応温度は通常１５℃〜８０℃であり、反応時間は通常０．５時間〜２４時間である。 The compound represented by the formula (I3-c) is further represented by the formula (I2-d) after reacting the compound represented by the formula (I1-e) with carbonyldiimidazole in a solvent. It can be obtained by reacting with a compound.

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。） In the compound represented by formula (I-b), R ³ is a hydrogen atom, and X ¹ is * —O— (* represents a bond to Ar) (formula (I4-b ) Can be obtained by reducing the compound represented by formula (I4-c) in a solvent.

(In the formula, all symbols have the same meaning as described above.)

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
Examples of the reducing agent include lithium aluminum hydride and sodium borohydride.
The reaction temperature is usually from 0 ° C to 80 ° C, and the reaction time is usually from 0.5 hours to 24 hours.

この反応における塩基としては、水酸化カリウム等が挙げられる。
この反応における溶媒としては、アセトニトリル等が挙げられる。
反応温度は通常５℃〜８０℃であり、反応時間は通常０．５時間〜２４時間である。 The compound represented by the formula (I4-c) is obtained by reacting the compound represented by the formula (I1-e) with the compound represented by the formula (I2-d) in a solvent under a base catalyst. be able to.

Examples of the base in this reaction include potassium hydroxide.
Examples of the solvent in this reaction include acetonitrile.
The reaction temperature is usually 5 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

In the compound represented by the formula (Ib), a compound wherein X ¹ is * —CO—O— (* represents a bond to Ar) (a compound represented by the formula (I5-b)) ) Can be obtained by reacting a compound represented by the formula (I5-d) with carbonyldiimidazole in a solvent and further reacting with a compound represented by the formula (I1-e). .

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

Examples of the compound represented by the formula (I5-d) include compounds represented by the following formula, and can be easily obtained from the market.

In the compound represented by the formula (Ib), a compound in which X ¹ is * —O—CO— (* represents a bond to Ar) (a compound represented by the formula (I6-b)) ) Can be obtained by reacting a compound represented by the formula (I2-e) with carbonyldiimidazole in a solvent and further reacting with a compound represented by the formula (I6-d). .

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

Examples of the compound represented by the formula (I6-d) include compounds represented by the following formula, and can be easily obtained from the market.

In the compound represented by the formula (Ib), a compound represented by the formula (I7-b), wherein X ¹ is * —O—CO—O— (* represents a bond to Ar). Is obtained by reacting the compound represented by the formula (I1-e) with carbonyldiimidazole in a solvent and further reacting with the compound represented by the formula (I6-d). Can do.

Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

この反応における塩基としては、水酸化カリウム等が挙げられる。
この反応における溶媒としては、アセトニトリル等が挙げられる。
反応温度は通常５℃〜８０℃であり、反応時間は通常０．５時間〜２４時間である。 In the compound represented by the formula (Ib), a compound (a compound represented by the formula (I8-b)) in which X ¹ is * —O— (* represents a bond to Ar). The compound represented by the formula (I1-e) and the compound represented by the formula (I6-d) can be obtained by reacting in a solvent under a base catalyst.

Examples of the base in this reaction include potassium hydroxide.
Examples of the solvent in this reaction include acetonitrile.
The reaction temperature is usually 5 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

〔resin〕
The resin of the present invention is a resin containing a structural unit derived from compound (I) (hereinafter sometimes referred to as “structural unit (I)”) (hereinafter sometimes referred to as “resin (A)”). Resin (A) may be a homopolymer of monomer (I), a copolymer consisting only of monomer (I), or a polymer containing one or more structural units other than structural unit (I). There may be. The structural unit other than the structural unit (I) includes a structural unit having an acid labile group other than the structural unit (I) (hereinafter sometimes referred to as “structural unit (a1)”), and a structural unit having an acid labile group. Other structural units having a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”), and having no acid labile group (hereinafter referred to as “structural unit (s)”). And a structural unit having a non-leaving hydrocarbon group (hereinafter sometimes referred to as “structural unit (a5)”). Here, the acid labile group means a group having a leaving group and forming a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid. Especially, it is preferable that resin (A) contains an acid labile group other than structural unit (I), and it is more preferable to have structural unit (a1).
The content of the structural unit (I) is usually from 5 to 90 mol%, preferably from 10 to 80 mol%, more preferably from 15 to 70 mol%, based on all monomers in the resin (A). .

［式（１）中、Ｒ^a1、Ｒ^a２及びＲ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の脂環式炭化水素基を形成する。
ｍａ及びｎａは、それぞれ独立して、０又は１を表し、ｍａ及びｎａの少なくとも一方は１を表す。
＊は結合手を表す。］

［式（２）中、Ｒ^ａ１’及びＲ^ａ２’は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３〜２０の複素環基を形成し、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 labile group (hereinafter sometimes referred to as “monomer (a1)”).
The acid labile group contained in the resin (A) is a group represented by formula (1) (hereinafter also referred to as group (1)) and / or a group represented by formula (2) (hereinafter referred to as group (2). )) Is preferred.

[In formula (1), R ^a1 , R ^a2 and R ^a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group obtained by combining these. R ^a1 and R ^a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
ma and na each independently represents 0 or 1, and at least one of ma and na represents 1.
* Represents a bond. ]

[In formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. 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 to which they are bonded and X, and are included 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. ]

アルキル基と脂環式炭化水素基とを組み合わせた基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基、シクロヘキシルメチル基、アダマンチルメチル基、アダマンチルジメチル基、ノルボルニルエチル基等が挙げられる。
好ましくは、ｍａは０であり、ｎａは１である。
Ｒ^a1及びＲ^a2が互いに結合して脂環式炭化水素基を形成する場合の−Ｃ（Ｒ^a1）（Ｒ^a2）（Ｒ^a3）としては、下記の基が挙げられる。脂環式炭化水素基は、好ましくは炭素数３〜１２である。＊は−Ｏ−との結合手を表す。

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

Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl An ethyl group etc. are mentioned.
Preferably, ma is 0 and na is 1.
Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) when R ^a1 and R ^a2 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 a bond 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 ″ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same groups as those described for R ^{a1 to} R ^a3 .
The aromatic hydrocarbon group includes phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl. Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
Examples of the combined group include a group in which the above-described alkyl group and alicyclic hydrocarbon group are combined (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aryl-cyclohexyl group such as a phenylcyclohexyl group. .
^{Examples of} the heterocyclic group formed together with the carbon atom to which R ^{a2 ′} and R ^{a3 ′} are bonded to each other and X, and X, include the following groups. * Represents a bond.

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 the formula (1), R ^{a1 to} R ^a3 are alkyl groups, ma = 0, and na = 1. As the group, a tert-butoxycarbonyl group is preferable.
In formula (1), R ^a1 and R ^a2 together with the carbon atom to which they are bonded form an adamantyl group, R ^a3 is an alkyl group, ma = 0 and na = 1 .
In the formula (1), R ^a1 and R ^a2 are each independently an alkyl group, R ^a3 is an adamantyl group, ma = 0, and na = 1.
Specific examples of the group (1) include the following groups. * Represents a bond.

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

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

  Among the (meth) acrylic monomers having an acid labile 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、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合せることにより形成される基を表す。
ｍ１は０〜１４のいずれかの整数を表す。
ｎ１は０〜１０のいずれかの整数を表す。
ｎ１’は０〜３のいずれかの整数を表す。］ The structural unit derived from the (meth) acrylic monomer having the group (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)). , A structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter structural unit (a1- 2) in some cases). These may be used alone or in combination of two or more.

[In Formula (a1-0), Formula (a1-1) and Formula (a1-2),
L ^a01 , L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents any integer of 1 to 7, and * represents It represents a bond with —CO—.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 each independently ^represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining these.
m1 represents an integer of 0 to 14.
n1 represents any integer of 0 to 10.
n1 ′ represents any integer of 0 to 3. ]

R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
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.
Examples of the alkyl group, alicyclic hydrocarbon group, and a combination thereof in R ^a02 , R ^a03 , R ^a04 , R ^a6, and R ^a7 are the same as those ^exemplified for R ^{a1 to} R ^a3 in formula (1). Groups.
The carbon number of the alkyl group in R ^a02 , R ^a03 and R ^a04 is preferably 1 to 6, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
The carbon number of the alkyl group in R ^a6 and R ^a7 is preferably 1 to 6, more preferably a methyl group, an ethyl group, or an isopropyl group, and still more preferably an ethyl group or an isopropyl group.
Carbon number of the alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 is preferably 5 to 12, more preferably 5 to 10.
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 the alkyl group and the alicyclic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As the structural unit (a1-0), for example, R ^a01 in the structural unit represented by any of the formulas (a1-0-1) to (a1-0-12) and the structural unit (a1-0) Examples include a structural unit in which a corresponding methyl group is replaced with a hydrogen atom, and a structural unit represented by any one of formulas (a1-0-1) to (a1-0-10) is preferable.

As a structural unit (a1-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Especially, the methyl group corresponding to R ^a4 in the structural unit represented by any one of the formulas (a1-1-1) to (a1-1-4) and the structural unit (a1-1) was replaced with a hydrogen atom. A structural unit is preferable, and a structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) is more preferable.

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

When the resin (A) includes the structural unit (a1-0) and / or the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is the total structure of the resin (A). For units
Usually, it is 10-95 mol%, Preferably it is 15-70 mol%, More preferably, it is 15-65 mol%, More preferably, it is 20-60 mol%, More preferably, it is 20-55 mol% It is.

［式（ａ１−４）中、
Ｒ^a32は、水素原子、ハロゲン原子、又は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアルキルカルボニル基、炭素数２〜４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｌａは０〜４のいずれかの整数を表す。ｌａが２以上である場合、複数のＲ^a33は互いに同一であっても異なってもよい。
Ｒ^a34及びＲ^a35はそれぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a36は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a35及びＲ^a36は互いに結合してそれらが結合する−Ｃ−Ｏ−とともに炭素数２〜２０の２価の炭化水素基を形成し、該炭化水素基及び該２価の炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−Ｓ−で置き換わってもよい。］ Examples of the structural unit having the group (2) in the structural unit (a1) include a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4)”). .

[In the formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl An oxy group or a methacryloyloxy group is represented.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ^a33 may be the same as or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are bonded to each other Together with —C—O— to which they are bonded to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent hydrocarbon group is — O- or -S- may be substituted. ]

^Examples of the alkyl group in R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
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 include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1, 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, etc. Can be mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group, aromatic hydrocarbon group and a group formed by combining these are exemplified, as the alkyl group and alicyclic hydrocarbon groups ^Includes the same groups as the alkyl group and alicyclic hydrocarbon group in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 .
The aromatic hydrocarbon group includes phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl. Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
Examples of the combined group include a group in which the above-described alkyl group and alicyclic hydrocarbon group are combined (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aryl-cyclohexyl group such as a phenylcyclohexyl group. . In particular, as R ^a36 , an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these Is mentioned.

In formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
As la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group.
The hydrocarbon group for R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. A group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, 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 for R ^a36 is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

As a structural unit (a1-4), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Preferably, hydrogen atom corresponding to ^{R a32} in equation (a1-4-1) represented respectively to Formula (a1-4-8) structural units and structural units (a1-4) is replaced by a methyl group structure And more preferably, structural units represented by formula (a1-4-1) to formula (a1-4-5), respectively.

  When resin (A) has a structural unit (a1-4), it is preferable that the content rate is 5-60 mol% with respect to the sum total of all the structural units of resin (A), and 5-50 It is more preferable that it is mol%, and it is further more preferable that it is 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との結合手を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の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 a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”). It is done.

In formula (a1-5),
R ^a8 represents a C 1-6 alkyl group optionally having a halogen atom, a hydrogen atom, or a halogen atom.
Z ^a1 represents a single bond or * — (CH ₂ ) _h3 —CO—L ⁵⁴ —, h3 represents an integer of 1 to 4, and * represents a bond to L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents any integer of 1 to 3.
s1 ′ represents any integer of 0 to 3.

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

As a structural unit (a1-5), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-611117 is mentioned, for example. Among these, structural units each represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and are represented by formula (a1-5-1) or formula (a1-5-2). A structural unit is more preferable.

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

［式（ａ１−０Ｘ）中、
Ｒ^ｘ１は、水素原子又はメチル基を表す。
Ｒ^ｘ２及びＲ^ｘ３は、互いに独立に、炭素数１〜６の飽和炭化水素基を表す。
Ａｒ^ｘ１は、炭素数６〜３６の芳香族炭化水素基を表す。］ As the structural unit (a1), for example, a structural unit represented by the formula (a1-0X) (hereinafter sometimes referred to as structural unit (a1-0X)) may also be mentioned.

[In the formula (a1-0X),
R ^x1 represents a hydrogen atom or a methyl group.
R ^x2 and R ^x3 each independently represent a C 1-6 saturated hydrocarbon group.
Ar ^x1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms. ]

Examples of the saturated hydrocarbon group for R ^x2 and R ^x3 include an alkyl group, an alicyclic hydrocarbon group, and a group formed by a combination thereof.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and the like.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the aromatic hydrocarbon group represented by Ar ^x1 include aryl groups having 6 to 36 carbon atoms such as a phenyl group, a naphthyl group, and an anthryl group.
The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably a phenyl group.

Ar ^x1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group.
R ^x1 , R ^x2 and R ^x3 are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group.

Examples of the structural unit (a1-0X) include compounds in which the methyl group corresponding to R ^x1 in the structural unit and structural unit (a1-0X) described below is replaced with a hydrogen atom. The structural unit (a1-0X) is preferably a structural unit (a1-0X-1) to a structural unit (a1-0X-3).

When resin (A) has a structural unit (a1-0X), it is preferable that the content rate is 5-60 mol% with respect to all the monomers in resin (A), and is 5-50 mol%. More preferably, it is more preferably 10 to 40 mol%.
The resin (A) may contain two or more structural units (a1-0X).

In addition, examples of the structural unit (a1) include the following structural units.

  When resin (A) contains the said structural unit, the content rate is preferable with respect to all the structural units of resin (A), 5-60 mol% is more preferable, 5-50 mol% is more preferable, 10-40 mol % Is more preferable.

<Structural unit (s)>
As the monomer for deriving the structural unit (s), a monomer having no acid labile 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 having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or a lactone ring and having no acid labile 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 contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When a resist pattern is produced from the resist composition of the present invention, when a high energy beam such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, the structural unit (a2) It is preferable to use the structural unit (a2) having a phenolic hydroxy group. In the case of using an ArF excimer laser (193 nm) or the like, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2), and the structural unit (a2-1) described later is more used. preferable. As a structural unit (a2), 1 type may be included independently and 2 or more types may be included.

［式（ａ２−Ａ）中、
Ｒ^a50は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^a51は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアルキルカルボニル基、炭素数２〜４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a50は、単結合又は^＊−Ｘ^a51−（Ａ^a52−Ｘ^a52）_nｂ−を表し、＊は−Ｒ^a50が結合する炭素原子との結合手を表す。
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 a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as “structural unit (a2-A)”).

[In the formula (a2-A),
R ^a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a51 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl An oxy group or a methacryloyloxy group is represented.
A ^a50 represents a single bond or ^* —X ^a51 — (A ^a52 —X ^a52 ) _nb —, and * represents a bond to the carbon atom to which —R ^a50 is bonded.
A ^a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent —O—, ^—CO —O— or —O—CO—.
nb represents 0 or 1.
mb represents an integer of 0 to 4. When mb is any integer of 2 or more, the plurality of ^Ra51s may be the same as or different from each other. ]

^Examples of the halogen atom for R ^a50 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 R ^a50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, 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, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluorohexyl Groups.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group for R ^a51 include 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 for R ^a51 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. A C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is more preferable.
^Examples of the alkylcarbonyl group for R ^a51 include an acetyl group, a propionyl group, and a butyryl group.
^Examples of the alkylcarbonyloxy group for R ^a51 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
R ^a51 is preferably a methyl group.

^* -X ^a51- (A ^a52 -X ^a52 ) _nb- includes ^* -O-, ^* -CO-O-, ^* -O-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 -. Of these, ^* —CO—O—, ^* —CO—O—A ^a52 —CO—O— or ^* —O—A ^a52 —CO—O— is preferable.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -Methylbutane-1,4-diyl group etc. are mentioned.
A ^a52 is preferably a methylene group or an ethylene group.

A ^a50 is preferably a single bond, ^* —CO—O— or ^* —CO—O—A ^a52 —CO—O—, and is preferably a single bond, ^* —CO—O— or ^* —CO—O—CH. _2- CO-O- is more preferable, and a single bond or ^* -CO-O- is more preferable.

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

  Examples of the structural unit (a2-A) include structural units derived from monomers described in JP2010-204634A and JP2012-12577A.

As the structural unit (a2-A), structural units represented by formula (a2-2-1) to formula (a2-2-4) and formula (a2-2-1) to formula (a2-2-2) In the structural unit represented by 4), a structural unit in which a methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom can be mentioned. The structural unit (a2-A) is represented by the structural unit represented by the formula (a2-2-1), the structural unit represented by the formula (a2-2-3), and the formula (a2-2-1). In the structural unit represented by formula (a2-2-3), the methyl group corresponding to R ^a50 in the structural unit (a2-A) is preferably a structural unit in which a hydrogen atom is replaced.

  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 based on all structural units. It is 10-70 mol%, More preferably, it is 15-65 mol%, More preferably, it is 20-65 mol%.

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−との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の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 a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).

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

In the formula (a2-1), L ^a3 is preferably —O—, —O— (CH ₂ ) _f1 —CO—O— (wherein f1 represents an integer of 1 to 4). More preferably, it is —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.

As a structural unit (a2-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A structural unit represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferred, and any one of formula (a2-1-1) to formula (a2-1-4) 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 more preferable.

  When resin (A) contains a structural unit (a2-1), the content rate is 1-45 mol% normally with respect to all the structural units of resin (A), Preferably it is 1-40 mol%. Yes, more preferably 1 to 35 mol%, still more preferably 2 to 20 mol%, and even more preferably 2 to 10 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. But you can. Preferably, a γ-butyrolactone ring, an adamantanelactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) is used.

［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手を表す。
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もよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^ａ２１は炭素数１〜４の脂肪族炭化水素基を表す。
Ｒ^ａ２２、Ｒ^ａ２３及びＲ^ａ２５は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５のいずれかの整数を表す。
ｑ１は、０〜３のいずれかの整数を表す。
ｒ１は、０〜３のいずれかの整数を表す。
ｗ１は、０〜８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^ａ２１、Ｒ^ａ２２、Ｒ^ａ２３及び／又はＲ^ａ２５は互いに同一であってもよく、異なっていてもよい。］ The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These 1 type may be contained independently and 2 or more types may be contained.

[In Formula (a3-1), Formula (a3-2), Formula (a3-3) and Formula (a3-4),
L ^a4 , L ^a5 and L ^a6 are each independently represented by —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents any integer of 1 to 7). Represents a group.
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom.
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 any integer of 0 to 5.
q1 represents any integer of 0 to 3.
r1 represents any integer of 0 to 3.
w1 represents an integer of 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 as or different from each other. ]

Examples of the aliphatic hydrocarbon group in R ^a21 , R ^a22 , R ^a23 and R ^a25 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group. It is done.
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group in R ^a24 include 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, and preferably have 1 to 4 carbon atoms. And more preferably a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom in R ^a24 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 perfluoro group. A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

^Examples of the alkanediyl group in ^La8 and ^La9 include 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, 4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

In the formula (a3-1) to the formula (a3-3), L ^{a4 to} L ^a6 are each independently, preferably —O— or * —O— (CH ₂ ) _k3 —CO—O—, Is a group of any one of 1 to 4, more preferably —O— and * —O—CH ₂ —CO—O—, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

（式中、Ｒ^ａ２４、Ｌ^ａ７は、上記と同じ意味を表す。） In formula (a3-4), R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group. It is.
R ^a25 is preferably a carboxy group, a cyano group, or a methyl group.
L ^a7 is preferably —O— or ^* —O—L ^a8 —CO—O—, more preferably —O—, —O—CH ₂ —CO—O— or —O—C ₂ H ₄ —. CO-O-.
w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
In particular, the formula (a3-4) is preferably the formula (a3-4) ′.

(Wherein R ^a24 and L ^a7 represent the same meaning as described above.)

As the structural unit (a3), a monomer derived from JP2010-204646, a monomer described in JP2000-122294A, a structure derived from a monomer described in JP2012-41274A Units are listed. As the structural unit (a3), the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula (a3-2-2), the formula (a3-3) 1), a structural unit represented by any one of formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and the structural unit represented by formula (a3-1) ) To a structural unit in which a methyl group corresponding to R ^a18 , R ^a19 , R ^a20 and R ^a24 in formula (a3-4) is replaced with a hydrogen atom.

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Moreover, the content rate of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), or a structural unit (a3-4) is respectively with respect to all the structural units of resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more 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 the formula (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. ]
Saturated hydrocarbon groups represented by R ⁴² is a chain hydrocarbon group and monocyclic or polycyclic alicyclic hydrocarbon group, and, 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。 The chain hydrocarbon group includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Can be mentioned.
Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups: And polycyclic alicyclic hydrocarbon groups such as (* represents a bond).

Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups and one or more alicyclic hydrocarbon groups, -alkanediyl group- An alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like can be mentioned.

［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 formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3), and formula (a4-4). A structural unit represented by one is mentioned.

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

As the alkanediyl group in L ^4a, a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, 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. It is done.

As the perfluoroalkanediyl group in L ^3a , a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, 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, perfluorohe Tan-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluoro Examples include an octane-3,3-diyl group and a perfluorooctane-4,4-diyl group.
^Examples of the perfluorocycloalkanediyl group in L ^3a include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

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 C 1-6 perfluoroalkanediyl group, more preferably a C 1-3 perfluoroalkanediyl group.

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

［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。〕
＊は結合手であり、右側の＊が−Ｏ−ＣＯ−Ｒ^a42との結合手である。］

[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a C1-C20 saturated hydrocarbon group which may have a substituent, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—. May be.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a ^C 1-5 divalent saturated hydrocarbon group which may have a substituent.
A ^a43 represents a ^C1-C5 divalent aliphatic hydrocarbon group which may have a single bond or a substituent.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* Is a bond, and * on the right side is a bond with —O—CO—R ^a42 . ]

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

Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups and one or more alicyclic hydrocarbon groups, -alkanediyl group- An alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic 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（＊はＲ^a42との結合手を表す。）を表す。
Ａ^a45は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
＊は結合手を表す。］
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 that R ^a42 may have include a halogen atom and a group represented by the formula (a-g3). As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom.

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, * ^—O —CO— or * —CO—O— (* represents a bond to R ^a42 ).
A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* Represents a bond. ]
However, in R ^a42 —X ^a43 —A ^a45 , when R ^a42 does not have a halogen atom, A ^a45 represents a C ^1-17 aliphatic hydrocarbon group having at least one halogen atom.

^Examples of the aliphatic hydrocarbon group for A ^a45 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and Alkyl groups such as octadecyl group;
Monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; and decahydronaphthyl, adamantyl, norbornyl, and the following groups (* represents a bond) And polycyclic alicyclic hydrocarbon groups.

R ^a42 is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3).
When R ^a42 is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably 1 to 1 carbon atoms. 6 perfluoroalkyl group, particularly preferably a C 1-3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the number of carbons contained in the group represented by the formula (a-g3), the total carbon of R ^a42 The number is preferably 15 or less, and more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

［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との結合手を表す。）を表す。
Ａ^a47は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合手を表す。］ When R ^a42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), R ^a42 is more preferably a group represented by the formula (a-g2).

[In the formula (a-g2),
A ^a46 represents a C ^1-17 divalent saturated hydrocarbon group which may have a halogen atom.
X ^a44 represents * ^—O —CO— or * —CO—O— (* represents a bond to A ^a46 ).
A ^a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47, and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* Represents a bond with a carbonyl group. ]

1-6 are preferable and, as for carbon number of the saturated hydrocarbon group of ^Aa46 , 1-3 are more preferable.
4-15 are preferable, as for carbon number of the aliphatic hydrocarbon group of A ^<a47> , 5-12 are more preferable, and A ^<a47> has a more preferable cyclohexyl group or an adamantyl group.

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

As the alkanediyl group in ^Aa41 , a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group Linear alkanediyl group such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, Examples include branched alkanediyl groups 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 still more 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 (a-g1) includes a linear or branched alkanediyl group and a monocyclic or polycyclic divalent divalent hydrocarbon group. Examples include an alicyclic hydrocarbon group, and a group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, Examples 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 (a-g1), ^{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 ** each represent a bond, and ** is a bond with —O—CO—R ^a42 .

As the structural unit represented by the formula (a4-1), a 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 structural units that have been replaced.

［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), a structural unit represented by the formula (a4-2) is preferable.

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

Alkanediyl group of L ⁴⁴ include the same groups as those exemplified with L ^4a.
Examples of the saturated hydrocarbon group for R ^f6 include the same groups as those exemplified for R ^a42 .
As the alkanediyl group for 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 formula (a4-2) include structural units represented by formula (a4-1-1) to formula (a4-1-11), respectively. A structural unit in which a methyl group corresponding to R ^f5 in the structural unit (a4-2) is replaced with a hydrogen atom is also exemplified as the 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−を表す（＊はＡ^f13との結合手を表す。）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 the formula (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a C 1-18 divalent saturated hydrocarbon group which may have a fluorine atom.
X ^f12 represents * —O—CO— or * —CO—O— (* represents a bond to 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 for the alkanediyl group of L ^4a .

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

As the saturated hydrocarbon group for A ^{f14 and} the saturated hydrocarbon group which may have a fluorine atom, the same groups as those exemplified for R ^a42 can be mentioned. 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, Fluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, Fluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyl dimethyl group, norbornyl group, norbornylmethyl group, perfluoro adamantyl group, a perfluoroalkyl adamantylmethyl group and the like are preferable.

In formula (a4-3), L ⁵ is preferably an ethylene group.
The divalent saturated hydrocarbon group for 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 for A ^f14 is preferably a group containing a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a chain hydrocarbon group having 3 to 10 carbon atoms. And 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 formula (a4-3) include structural units represented by formula (a4-1′-1) to formula (a4-1′-11), respectively. A structural unit in which a methyl group corresponding to R ^f7 in the structural unit (a4-3) is replaced with a hydrogen atom is also exemplified as the 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。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-4).

[In the formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents — (CH ₂ ) _j1 —, — (CH ₂ ) _j2 —O— (CH ₂ ) _j3 — or — (CH ₂ ) _j4 —CO—O— (CH ₂ ) _j5 —.
j1 to j5 each independently represents an integer of 1 to 6.
R ^f22 represents a C 1-10 saturated hydrocarbon group having a fluorine atom. ]

^Examples of the saturated hydrocarbon group for R ^f22 include the same saturated hydrocarbon groups represented by R ^a42 . R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, more preferably a C 1-10 alkyl group having a fluorine atom. Preferably, the C1-C6 alkyl group which has a fluorine atom is further more preferable.

In formula (A4-4), as the _{^{A f21, - (CH 2)}} j1 - , more preferably an ethylene group or a methylene group, more preferably a methylene group.

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, a methyl group corresponding to R ^f21 in the structural unit (a4-4) is hydrogen. Examples include structural units replaced by atoms.

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

［式（ａ５−１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基で置換されていてもよい。
Ｌ⁵⁵は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-elimination hydrocarbon group included in the structural unit (a5) include groups having a linear, branched, or cyclic hydrocarbon group. Among these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.

[In the formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a 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 by —O— or —CO—. . ]

The alicyclic hydrocarbon group for R ⁵² may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2 -Alkyl groups, such as an ethylhexyl group, are 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 for L ⁵⁵ include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent chain saturated hydrocarbon group. .
Examples of the divalent chain saturated hydrocarbon group include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ is replaced by —O— or —CO— include those represented by formulas (L1-1) to (L1-4): And the group represented. In the following formula, * represents a bond with an oxygen atom.

In formula (L1-1),
X ^x1 represents * —O—CO— or * —CO—O— (* represents a bond to L ^x1 ).
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total carbon number of L ^x1 and L ^x2 is 16 or less.

In formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total carbon number of L ^x3 and L ^x4 is 17 or less.

In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6 and L ^x7 is 15 or less.

In formula (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9 and W ^x1 is 15 or less.

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

As group represented by a formula (L1-1), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-2), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-3), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-4), the bivalent group shown below is mentioned, for example.

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

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

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

When the resin (A) has the structural unit (a5), the content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, based on all structural units of the resin (A). More preferred is ˜15 mol%.

<Structural unit (II)>
The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter sometimes referred to as “structural unit (II)”). Is a structural unit described in JP-A-2016-79235, which is a structural unit having a sulfonate group or carboxylate group and an organic cation in the side chain, or a structural unit having a sulfonio group and an organic anion in the side chain. Preferably there is.

［式（ＩＩ−２−Ａ’）中、
Ｘ^ＩＩＩ３は、炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−ＣＯ−に置き換わっていてもよく、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基又はヒドロキシ基で置き換わっていてもよい。
Ａ^ｘ１は、炭素数１〜８のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、フッ素原子又は炭素数１〜６のペルフルオロアルキル基で置換されていてもよい。
ＲＡ⁻は、スルホナート基又はカルボキシレート基を表す。
Ｒ^ＩＩＩ３は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１〜６のアルキル基を表す。
ＺＡ^＋は、有機カチオンを表す。］ The structural unit having a sulfonate group or carboxylate group and an organic cation in 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 by —O—, —S— or —CO—. 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 a 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 or carboxylate groups.
R ^III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have 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.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3 , an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 and The same can be mentioned.
Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A ^x1 include 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 divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by ^XIII3 include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. These may be combined.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Linear alkanediyl groups such as dodecane-1,12-diyl group; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Branched alkanediyl groups such as pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 , 4-diyl group, Cycloalkanediyl group such as looctane-1,5-diyl group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group Bivalent polycyclic alicyclic saturated hydrocarbon groups and the like.

Examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —S—, or —CO— include divalent groups represented by formula (X1) to formula (X53), for example. Can be mentioned. However, the number of carbon atoms before —CH ₂ — contained in the saturated hydrocarbon group is replaced with —O—, —S—, or —CO— is 17 or less. In the following formulas, * represents a bond to ^{A x1.}

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

Examples of organic cations represented by ZA ⁺ include organic onium cations such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, organic benzothiazolium cations, and organic phosphonium cations, and organic sulfonium cations and organic iodonium cations. Are preferred, and arylsulfonium cations are more preferred.
Examples of ZA ^{+ in} formula (II-2-A ′) are the same as those of the organic cation Z ⁺ in the acid generator (B1) described later.

［式（ＩＩ−２−Ａ）中、Ｒ^ＩＩＩ３、Ｘ^ＩＩＩ３及びＺＡ^＋は、上記と同じ意味を表す。
Ｚは、０〜６のいずれかの整数を表す。
Ｒ^ＩＩＩ２及びＲ^ＩＩＩ４は、それぞれ独立して、水素原子、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表し、ｚが２以上のとき、複数のＲ^ＩＩＩ２及びＲ^ＩＩＩ４は互いに同一であってもよいし、異なっていてもよい。
Ｑ^ａ及びＱ^ｂは、それぞれ独立して、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。］ The structural unit represented by the formula (II-2-A ′) is preferably a structural unit represented by the formula (II-2-A).

[In formula (II-2-A), R ^III3 , X ^III3 and ZA ⁺ represent the same meaning as described above.
Z represents an integer of 0 to 6.
R ^III2 and R ^III4 each independently represent a hydrogen atom, a fluorine atom or a C 1-6 perfluoroalkyl group, and when z is 2 or more, the plurality of R ^III2 and R ^III4 are the same as each other It may be different or different.
Q ^a and Q ^b each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. ]

^{Examples of} the C 1-6 perfluoroalkyl group represented by R ^III2 , R ^III4 , Q ^a and Q ^b include the same as the C 1-6 perfluoroalkyl group represented by Q ^b1 described later. .

［式（ＩＩ−２−Ａ−１）中、
Ｒ^ＩＩＩ２、Ｒ^ＩＩＩ３、Ｒ^ＩＩＩ４、Ｑ^a、Ｑ^b、ｚ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。
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。］ The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1).

[In the formula (II-2-A-1)
R ^III2 , R ^III3 , R ^III4 , Q ^a , Q ^b , z and ZA ⁺ represent the same meaning as described above.
R ^III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
X ^I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —S— or —CO—. 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include linear or branched alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group.
Examples of the divalent saturated hydrocarbon group represented by X ^I2, are the same as those of the divalent saturated hydrocarbon group represented by X ^III3.

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

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

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

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

[In the 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 a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
A ⁻ represents an organic anion. ]
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^II1 include a phenylene group and a naphthylene group.
Examples of the hydrocarbon group represented by R ^II2 and R ^II3 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the halogen atom represented by R ^II4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 , 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: -O-, -S- or -CO- may be substituted. Specifically, the same thing as a C1-C18 bivalent saturated hydrocarbon group represented by ^XIII3 is mentioned.

Examples of the structural unit containing a cation in formula (II-1-1) include the structural units represented below.

A ^- The organic anion represented by a sulfonic acid anion, sulfonyl imide anion, methide anion and a carboxylate anion, and the like. A ^- organic anion represented by the sulfonate anion are preferable, and as a sulfonate anion, more preferably an anion contained in the salt represented by the formula (B1) to be described later.

A ^- The sulfonyl imide anions represented by, the following may be mentioned.

Examples of the sulfonylmethide anion include the following.

Examples of the carboxylate anion include the following.

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

  When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol% with respect to the total structural units of the resin (A). Preferably it is 2-15 mol%, More preferably, it is 3-10 mol%.

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

  The resin (A) is preferably a resin comprising a structural unit (I) and an acid labile group, a resin comprising a structural unit (I) and a structural unit (a1), a structural unit (I) and a structural unit (s ), A resin comprising the structural unit (I), the structural unit (a1) and the structural unit (s), the structural unit (I), the structural unit (a1), the structural unit (s) and the structural unit (a4). ) And / or a structural unit (a5), a resin consisting only of the structural unit (I), or a resin consisting only of the structural unit (I) and the structural unit (a4), more preferably a structural unit. A resin comprising (I), structural unit (a1) and structural unit (s), a resin comprising structural unit (I) and structural unit (s), or structural unit (I) and structural unit (a4) Resin consisting only of structural unit (a5), structural unit (I) and structural unit Resin comprising a4) and only a resin comprising structural units (I) and the structural unit (a4) and the structural unit (a1) alone.

The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-0X), a structural unit (a1-1) and a structural unit (a1-2) (preferably a cyclohexyl group and a cyclopentyl group. At least one selected from the group consisting of structural units), more preferably structural units (a1-0), structural units (a1-0X), structural units (a1-1), and structural units (a1-2). It is at least two selected from the group consisting of (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
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 (a2-1). 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). 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, radical polymerization method) using a monomer that derives these structural units. be able to. The content rate of each structural unit which resin (A) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, more preferably 15,000 or less).
In this specification, the weight average molecular weight is a value determined by gel permeation chromatography. Gel permeation chromatography can be measured by the analytical conditions described in the examples.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). The resin other than the resin (A) is a resin that does not contain the structural unit (I). Examples of such a resin include a structural unit having an acid labile group and the structural unit (I). Resin not containing (hereinafter sometimes referred to as “resin (A2)”), resin consisting only of the structural unit (a4), and resin consisting of the structural unit (a4) and the structural unit (a5) (hereinafter referred to as the structural unit (a4)) ) And a resin composed of the structural unit (a4) and the structural unit (a5) may be referred to as a resin (X)).

  In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more with respect to the total of all the structural units of the resin (X). More preferably, it is 45 mol% or more.

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 that derives these structural units. can do. The content rate of each structural unit which resin (X) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weights of the resin (A2) and the resin (X) are preferably independently 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). is there. The measurement means of the weight average molecular weight of resin (A2) and resin (X) is the same as that of resin (A).
When the resist composition of the present invention contains a resin (A2), the content is usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) with respect to 100 parts by mass of the resin (A). is there.
Moreover, when a resist composition contains resin (X), the content becomes like this. Preferably it is 1-60 mass parts with respect to 100 mass parts of resin (A), More preferably, it is 1-50 mass parts. More preferably, it is 1-40 mass parts, Most preferably, it is 1-30 mass parts, Most preferably, it is 1-8 mass parts.

  The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90-99% by mass with respect to the solid content of the resist composition. Moreover, when resin other than resin (A) is included, the total content rate of resin other than resin (A) and resin (A) is 80 mass% or more and 99 mass% with respect to solid content of a resist composition. The following is preferable, and 90 to 99% by mass is more preferable. The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

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

  As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712, etc. The compound which generate | occur | produces an acid by the radiation as described in 1 can be used. Moreover, you may use the compound manufactured by the well-known method. Two or more acid generators (B) may be used in combination.

［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３〜１８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−ＣＨ_２−は、−Ｏ−、−Ｓ（Ｏ）_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
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 by —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 an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —S (O) ₂ —, or —CO—.
Z ⁺ represents an organic cation. ]

^Examples of the perfluoroalkyl group represented by Q ^b1 and Q ^b2 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 etc. are mentioned.
Q ^b1 and Q ^b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and these It may be a group formed by combining two or more of the groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group Alkanediyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 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 Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

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

In the groups represented by formula (b1-1) to formula (b1-3), when —CH ₂ — contained in the saturated hydrocarbon group is replaced with —O— or —CO—, the carbon before the replacement The number is the carbon number of the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include the same 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 by —O— or —CO—.

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

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

[In the formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
^Lb9 represents a C1-C20 bivalent saturated hydrocarbon group.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In formula (b1-6),
L ^b11 represents a C1-C21 divalent saturated hydrocarbon group.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b13 to} L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a C1-C18 divalent saturated hydrocarbon group.
L ^b17 represents a C1- ^C18 divalent saturated hydrocarbon group.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b16 to} L ^b18 is 19 or less. ]

L ^b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b9 is preferably a C 1-8 divalent saturated hydrocarbon group.
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 ^C 1-6 divalent saturated hydrocarbon group.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

式（ｂ１−９）中、
Ｌ^b19は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b20は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b19及びＬ^b20の合計炭素数は２３以下である。
式（ｂ１−１０）中、
Ｌ^b21は、単結合又は炭素数１〜２１の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b22は、単結合又は炭素数１〜２１の２価の飽和炭化水素基を表す。
Ｌ^b23は、単結合又は炭素数１〜２１の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b21、Ｌ^b22及びＬ^b23の合計炭素数は２１以下である。
式（ｂ１−１１）中、
Ｌ^b24は、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b25は、炭素数１〜２１の２価の飽和炭化水素基を表す。
Ｌ^b26は、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b24、Ｌ^b25及びＬ^b26の合計炭素数は２１以下である。 Examples of the group represented by formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11), respectively.

In formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, L ^b24, the total number of carbon atoms of L ^b25 and L ^b26 is 21 or less.

  In addition, in the group represented by the formula (b1-11) to the group represented by the formula (b1-9), when the hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the group is replaced. The previous carbon number is defined 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, and an adamantylcarbonyloxy group.

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 formulas (Y1) to (Y11) and formulas (Y36) to (Y38).
When —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced by —O—, —S (O) ₂ — or —CO—, the number may be one, or two or more. Good. Examples of such a group include groups represented by formula (Y12) to formula (Y35), formula (Y39), and formula (Y40).

Ｙとしては、好ましくは式（Ｙ１）〜式（Ｙ２０）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）又は式（Ｙ４０）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（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）又は式（Ｙ４０）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ３０）、式（Ｙ３９）又は式（Ｙ４０）で表される基である。
Ｙが式（Ｙ２８）〜式（Ｙ３５）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。

Y is preferably a group represented by any one of formulas (Y1) to (Y20), formula (Y30), formula (Y31), formula (Y39) or formula (Y40), more preferably formula (Y11), Formula (Y15), Formula (Y16), Formula (Y20), Formula (Y30), Formula (Y31), Formula (Y39), or Group represented by Formula (Y40), and more preferably Formula It is a group represented by (Y11), formula (Y15), formula (Y30), formula (Y39) or formula (Y40).
When Y is a spiro ring such as formula (Y28) to formula (Y35), the alkanediyl group between two oxygen atoms preferably has one or more fluorine atoms. Of the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

Examples of the substituent for the methyl group represented by Y include 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, or-( CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic group having 6 to 18 carbon atoms). Represents a hydrocarbon group, and ja represents an integer of 0 to 4).
Examples of the substituent for the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, and an alicyclic group having 3 to 16 carbon atoms. A hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, a glycidyloxy group or-( CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic group having 6 to 18 carbon atoms). Represents a hydrocarbon group, and ja represents an integer of 0 to 4).

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.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group, mesityl group. , Aryl groups such as biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, and nonyl. Group, decyl group, undecyl group, dodecyl group and the like.
Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

Examples of Y include the following.

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

  As the anion in the salt represented by the formula (B1), an anion represented by the formula (B1-A-1) to the formula (B1-A-55) [hereinafter referred to as an anion (B1-A -1) ". ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula (B1-A-33), Formula (B1-A-36) to Formula (B1-A-40), Formula (B1-A-47) to Formula (B1-A-55) An anion is more preferable.

ここでＲ^ｉ２〜Ｒ^ｉ７は、互いに独立に、例えば、炭素数１〜４のアルキル基、好ましくはメチル基又はエチル基である。Ｒ^ｉ８は、例えば、炭素数１〜１２の脂肪族炭化水素基、好ましくは炭素数１〜４のアルキル基、炭素数５〜１２の脂環式炭化水素基又はこれらを組合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基又はアダマンチル基である。Ｌ^Ａ４は、単結合又は炭素数１〜４のアルカンジイル基である。
Ｑ^ｂ１及びＱ^ｂ２は、上記と同じ意味を表す。
式（Ｂ１）で表される塩におけるアニオンとしては、具体的には、特開２０１０−２０４６４６号公報に記載されたアニオンが挙げられる。

Here, R ^{i2 to} R ⁱ⁷ are independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is formed by, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. More preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ^A4 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ^b1 and Q ^b2 represent the same meaning as described above.
Specific examples of the anion in the salt represented by the formula (B1) include anions described in JP 2010-204646 A.

Examples of the anion in the salt represented by the preferred formula (B1) include anions represented by formulas (B1a-1) to (B1a-34), respectively.

  Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) To (B1a-34) are preferable.

Examples of the organic cation of Z ⁺ include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable. Specifically, a cation represented by any one of 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.

式（ｂ２−１）〜式（ｂ２−４）において、
Ｒ^b4〜Ｒ^b6は、それぞれ独立に、炭素数１〜３０の鎖式炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜３６の芳香族炭化水素基を表し、該鎖式炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数３〜１２の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜１８の脂肪族炭化水素基、炭素数２〜４のアルキルカルボニル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。
Ｒ^b4とＲ^b5とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−又は−ＣＯ−に置き換わってもよい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０〜５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^b7は同一でも異なってもよく、ｎ２が２以上のとき、複数のＲ^b8は同一でも異なってもよい。
Ｒ^b9及びＲ^b10は、それぞれ独立に、炭素数１〜３６の鎖式炭化水素基又は炭素数３〜３６の脂環式炭化水素基を表す。
Ｒ^b9とＲ^b10とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−又は−ＣＯ−に置き換わってもよい。
Ｒ^b11は、水素原子、炭素数１〜３６の鎖式炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^b12は、炭素数１〜１２の鎖式炭化水素基、炭素数３〜１８の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表し、該鎖式炭化水素に含まれる水素原子は、炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜１２のアルコキシ基又は炭素数１〜１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^b11とＲ^b12とは、互いに結合してそれらが結合する−ＣＨ−ＣＯ−を含めて環を形成していてもよく、該環に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−又は−ＣＯ−に置き換わってもよい。
Ｒ^b13〜Ｒ^b18は、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
Ｌ^b31は、硫黄原子又は酸素原子を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０〜５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０〜４のいずれかの整数を表す。
ｕ２は０又は１を表す。
ｏ２が２以上のとき、複数のＲ^b13は同一又は相異なり、ｐ２が２以上のとき、複数のＲ^b14は同一又は相異なり、ｑ２が２以上のとき、複数のＲ^b15は同一又は相異なり、ｒ２が２以上のとき、複数のＲ^b16は同一又は相異なり、ｓ２が２以上のとき、複数のＲ^b17は同一又は相異なり、ｔ２が２以上のとき、複数のＲ^b18は同一又は相異なる。

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the chain hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group which may be substituted 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 hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may combine with each other to form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring is —O—, —S— or -CO- may be substituted.
R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represents an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each 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 together to form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring is —O—, —S— or -CO- may be substituted.
R ^b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the chain hydrocarbon. The 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 is an alkoxy group having 1 to 12 carbon atoms or 1 to 1 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may be bonded to each other to form a ring including —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring is —O—, —S -Or -CO- may be substituted.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, multiple R ^b13 are the same or different, when p2 is 2 or more, multiple R ^b14 are the same or different, and when q2 is 2 or more, multiple R ^b15 are the same or different , When r2 is 2 or more, a plurality of R ^b16 are the same or different, when s2 is 2 or more, a plurality of R ^b17 are the same or different, and when t2 is 2 or more, a plurality of R ^b18 are the same or different Different.

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。 An aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl alkyl groups. 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 monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo group. Examples thereof include cycloalkyl groups such as heptyl group, cyclooctyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 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, more preferably 4 to 12 carbon atoms.

  Examples of the alicyclic hydrocarbon group in which a 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-isopropyladamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

As aromatic hydrocarbon group, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantylphenyl group , Aryl groups such as a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
In addition, when the aromatic hydrocarbon group includes a chain hydrocarbon group or an alicyclic hydrocarbon group, the chain hydrocarbon group having 1 to 18 carbon atoms and the alicyclic hydrocarbon having 3 to 18 carbon atoms. Groups are preferred.
Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups 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 methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkylcarbonyloxy group, methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group Hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group and the like.

The ring formed by combining R ^b4 and R ^b5 together with the sulfur atom to which they are bonded is monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring may be Examples of the ring include a ring having 3 to 18 carbon atoms, and a ring having 4 to 18 carbon atoms is preferable. Moreover, the ring containing a sulfur atom includes 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.

The ring formed by combining R ^b9 and R ^b10 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Examples thereof include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
The ring formed by ^combining R ^b11 and R ^b12 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes 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 cation (b2-1) to cation (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.

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

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

  The acid generator (B) is a combination of the above-described sulfonate anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B) is preferably a formula (B1a-1) to a formula (B1a-3), a formula (B1a-7) to a formula (B1a-16), a formula (B1a-18), a formula (B1a- 19), a combination of an anion represented by any one of formulas (B1a-22) to (B1a-34) and a cation (b2-1) or a cation (b2-3).

As the acid generator (B), those represented by formulas (B1-1) to (B1-48) are preferably exemplified. Among them, those containing an arylsulfonium cation are preferable. Formula (B1-1) to Formula (B1-3), Formula (B1-5) to Formula (B1-7), Formula (B1-11) to Formula (B1-14) ), Formula (B1-20) to formula (B1-26), formula (B1-29), and formula (B1-31) to formula (B1-48) are particularly preferable.

  In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A). It is. The resist composition of the present invention may contain one kind of acid generator (B) alone, or may contain plural kinds.

<Quencher (C)>
Examples of the quencher (C) include a salt that generates an acid having a lower acidity than an acid generated from the acid generator (B) and a basic nitrogen-containing organic compound.

<Salt that generates an acid with a lower acidity than the acid generated from the acid generator>
The acidity in a salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is indicated by an acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 <pKa, preferably -1 < A salt having a pKa <7, more preferably a salt having a 0 <pKa <5.
Examples of the salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) include compounds represented by the formula (C1) described in JP-A-2011-39502 (hereinafter referred to as “carboxylate ( C1) "), a salt represented by the formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as" weak acid inner salt (D) "), and the following formula: And salts described in JP 2012-229206 A, JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A, and JP 2011-191745 A. It is done. The salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B) is preferably a carboxylate (C1) or a weak acid inner salt (D).

［式（Ｃ１）中、
Ｒ^Ａは、置換基を有していてもよい炭素数１〜３６の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−ＳＯ_２−に置き換わっていてもよい。
Ｚ^６＋は、有機カチオンを表す。］ <Carboxylate (C1)>
The carboxylate (C1) is a salt represented by the formula (C1).

[In the formula (C1),
R ^A represents an optionally substituted hydrocarbon group having 1 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or It may be replaced by —SO ₂ —.
Z ⁶⁺ represents an organic cation. ]

Examples of the hydrocarbon group represented by R ^A include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and nonyl group. Carbon number of an alkyl group becomes like this. Preferably it is 1-9, More preferably, it is 1-4.
The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be either saturated or unsaturated. The alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, and the like, a monocyclic cycloalkyl group, a norbornyl group, an adamantyl group And a polycyclic cycloalkyl group such as a group. Carbon number of an alicyclic hydrocarbon group becomes like this. Preferably it is 3-18, More preferably, it is 3-12.
Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl group, anthryl group, phenanthryl group, and binaphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10.
When —CH ₂ — contained in the hydrocarbon group represented by R ^A is replaced by —O—, —S—, —CO— or —SO ₂ —, the number of carbons before the replacement is The total number of carbons.

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、トリル基、キシリル基、シクロヘキシルフェニル基等が挙げられる。
Ｒ^３の置換基におけ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のアラルキル基等が挙げられる。 The hydrocarbon group represented by R ^A has a total carbon number of 1 to 36 and may further have one or more substituents. Examples of the substituent include a hydroxy group, a carboxy 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 2 to 2 carbon atoms. 13 alkylcarbonyl group, C2-C13 alkylcarbonyloxy group, C3-C12 alicyclic hydrocarbon group, C6-C10 aromatic hydrocarbon group, or a combination thereof. It is done.
Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group. .
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group Group, dodecyloxy group and the like.
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-described 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. 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 following groups. ** is a bond with a hydrocarbon group.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a cyclohexylphenyl group.
Examples of the combined group in the substituent of R ³ include a group in which a hydroxy group and an alkyl group having 1 to 12 carbon atoms are combined, an alkyl group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. And the like.
Examples of the group in which the hydroxy group and the 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.
Examples of the group in which an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined include an aralkyl group having 7 to 22 carbon atoms such as a benzyl group.

The alicyclic hydrocarbon group is preferably a group represented by the formulas (Y1) to (Y40). The formula (Y1) to the formula (Y20), the formula (Y30), the formula (Y31), the formula ( Y39) or a group represented by formula (Y40) is more preferable. Formula (Y4), formula (Y11), formula (Y15), formula (Y30), formula (Y39) or formula (Y40 More preferably, it is a group represented by

As the substituent in R ^A , a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, Examples thereof include a glycidyloxy group and an alkylcarbonyl group having 2 to 4 carbon atoms. Among these, a halogen atom, particularly a fluorine atom is preferable.

［式（Ｒ^Ａ−１）中、
環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１〜１２のアルキル基、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又は炭素数２〜４のアルキルカルボニル基で置換されていてもよく、環に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−又は−ＳＯ_２−で置換されていてもよい。
＊は、炭素原子との結合手を表す。］ As R ^A , an optionally substituted alicyclic hydrocarbon group having 3 to 36 carbon atoms (—CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—). , -CO- or -SO _2- may be substituted), and a polycyclic alicyclic hydrocarbon group having 7 to 18 carbon atoms which may have a substituent (the alicyclic group). —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO ₂ —), and is more preferably represented by the formula (R ^A -1). More preferably, it is a group.

[In the formula ( ^RA- 1),
The hydrogen atom contained in the ring is a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, It may be substituted with a glycidyloxy group or an alkylcarbonyl group having 2 to 4 carbon atoms, and —CH ₂ — contained in the ring is substituted with —O—, —S—, —CO— or —SO ₂ —. It may be.
* Represents a bond with a carbon atom. ]

For example, examples of the anion include anions represented by formula (C1-1) to formula (C1-18).

^Examples of the organic cation Z ⁶⁺ in the carboxylate (C1) include the same organic cation as Z ⁺ in the acid generator (B).

Examples of the carboxylate (C1) include salts represented below and salts described in JP2011-39502A.

［式（Ｄ）中、
Ｒ^Ｄ１及びＲ^Ｄ２は、それぞれ独立に、炭素数１〜１２の炭化水素基、炭素数１〜６のアルコキシ基、炭素数２〜７のアルキルカルボニル基、炭素数２〜７のアルキルカルボニルオキシ基、炭素数２〜７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０〜４のいずれかの整数を表し、ｍ’が２以上の場合、複数のＲ^Ｄ１は同一又は相異なり、ｎ’が２以上の場合、複数のＲ^Ｄ２は同一又は相異なる。］ <Weak acid inner salt (D)>
The weak acid intramolecular salt (D) is a salt represented by the formula (D).

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

In the weak acid inner salt (D), the hydrocarbon group of R ^D1 and R ^D2 includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by a combination thereof. Etc.
Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, and nonyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be either saturated or unsaturated. Examples thereof include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, and cyclododecyl group, norbornyl group, adamantyl group, and the like.
As aromatic hydrocarbon group, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group , Aryl groups such as mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
Examples of the group formed by combining these include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, an aralkyl group (for example, phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1 -Propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6 -Phenyl-1-hexyl group, etc.).

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

In the weak acid inner salt (D), R ^D1 and R ^D2 are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon An alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom is preferable.
m ′ and n ′ are each independently preferably an integer of 0 to 2, and more preferably 0. When m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n ′ is 2 or more, the plurality of R ^D2 are the same or different.

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

  The content of the salt that generates an acid having a lower acidity than the acid generated from the acid generator contained in the resist composition is usually 0.01 to 5% by mass in the solid content of the resist composition, preferably It is 0.01-3 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 the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tri Heptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, Rudicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyl Didecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 2,2′-methylenebisaniline, imidazole, 4- Tyrimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2- Di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4 , 4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine, bipyridine and the like, preferably aromatic amines such as diisopropylaniline, more preferably 2,6- Diisopropylaniline is mentioned.

As ammonium salts, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.
The content of the quencher (C) is preferably about 0.01 to 5% by mass based on the solid content of the resist composition.

<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, more preferably 94% by mass or more and 99% by mass in the resist composition. % Or less. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

  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 such as acetone, methyl isobutyl ketone, ketones such as 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

<Other ingredients>
The resist composition of the present invention may contain components other than the above components (hereinafter sometimes referred to as “other components (F)”) as necessary. 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 includes a resin (A) of the present invention, an acid generator (B), a salt that generates an acid having a lower acidity than an acid generated from the acid generator, and, if necessary, a resin. It can be prepared by mixing (A2), resin (X), quencher (C), solvent (E) and other components (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (E), such as resin. An appropriate mixing 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 can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(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 apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

By drying the 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 using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. Moreover, it is preferable that the pressure at the time of drying under reduced pressure is about 1-1.0 * 10 < ⁵ > Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do. In this specification, the irradiation of these radiations may be collectively referred to as “exposure”. At the time of exposure, exposure is usually performed through a mask corresponding to a required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.

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

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., for example, and the development time is preferably 5 to 300 seconds, for example. 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 various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline). The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent 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 still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid 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 the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention is suitable as 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. Yes, it is more suitable as a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure, and is useful for fine processing of semiconductors.

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

  Moreover, the structure of the compound was confirmed by measuring molecular ion peaks using mass spectrometry (LC: Model 1100 manufactured by Agilent, MASS: LC / MSD manufactured by Agilent). 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９．１１部及びアセトニトリル５０部を混合し、４０℃で３０分間攪拌した。得られた混合物に、式（Ｉ−１−ｂ）で表される化合物１０．７９部を加え、６０℃で１時間攪拌することにより、式（Ｉ−１−ｃ）で表される化合物を含む溶液を得た。

得られた式（Ｉ−１−ｃ）で表される化合物を含む溶液に、式（Ｉ−１−ｄ）で表される化合物８．６３部を混合し、２３℃で１時間攪拌した後、さらに、７０℃で１８時間攪拌した。得られた反応混合物に、酢酸エチル２００部及びイオン交換水１００部を加えた後、攪拌し、分液を行った。この水洗を５回行った。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−１−ｅ）で表される化合物１１．８９部を得た。

テトラヒドロフラン６０部を５℃にした後、リチウムアルミニウムハイドライド１．５９部を加え、その後、式（Ｉ−１−ｅ）で表される化合物１１．４３部及びテトラヒドロフラン４０部の混合溶液を、５℃で１時間かけて滴下した後、２３℃で１２時間攪拌した。さらに、５０℃で２時間攪拌した後、５℃まで冷却した。得られた混合物に、１０％硫酸２４．５４部を滴下した後、クロロホルム２００部及び５％炭酸水素ナトリウム水溶液１００部を加えて攪拌し、分液した。得られた有機層にイオン交換水１００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−１−ｆ）で表される化合物９．１２部を得た。

式（Ｉ−１−ｆ）で表される化合物１．８６部、Ｎ−メチルピロリジン１．８３部、及びメチルイソブチルケトン２０部を混合し、攪拌しながら、式（Ｉ−１−ｇ）で表される化合物０．７７部を添加し、６０℃で５時間攪拌した。その後、反応混合物にイオン交換水１０部を添加し、攪拌後、分液した。この水洗操作を５回行った。得られた有機層を濃縮後、カラムクロマトグラフィー（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）により分取することで、式（Ｉ−１）で表される化合物１．１４部を得た。 Synthesis Example 1: Synthesis of compound represented by formula (I-1)

9.11 parts of the compound represented by the formula (I-1-a) and 50 parts of acetonitrile were mixed and stirred at 40 ° C. for 30 minutes. The compound represented by the formula (I-1-c) is added to the obtained mixture by adding 10.79 parts of the compound represented by the formula (I-1-b) and stirring at 60 ° C. for 1 hour. A solution containing was obtained.

After mixing 8.63 parts of the compound represented by the formula (I-1-d) with the obtained solution containing the compound represented by the formula (I-1-c) and stirring at 23 ° C. for 1 hour, Further, the mixture was stirred at 70 ° C. for 18 hours. To the obtained reaction mixture, 200 parts of ethyl acetate and 100 parts of ion-exchanged water were added, followed by stirring and liquid separation. This water washing was performed 5 times. The obtained organic layer was concentrated, and fractionated by column chromatography (silica gel 60-200 mesh; developed solvent: ethyl acetate by Merck & Co., Inc.), whereby compound 11 represented by formula (I-1-e) was obtained. .89 parts were obtained.

After 60 parts of tetrahydrofuran was brought to 5 ° C., 1.59 parts of lithium aluminum hydride was added, and then a mixed solution of 11.43 parts of the compound represented by the formula (I-1-e) and 40 parts of tetrahydrofuran was added at 5 ° C. Was added dropwise over 1 hour, followed by stirring at 23 ° C. for 12 hours. Furthermore, after stirring at 50 degreeC for 2 hours, it cooled to 5 degreeC. After dropping 24.54 parts of 10% sulfuric acid into the obtained mixture, 200 parts of chloroform and 100 parts of 5% aqueous sodium hydrogen carbonate solution were added and stirred for separation. 100 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, then allowed to stand and liquid-separated to wash the organic layer with water. This washing operation was repeated 5 times. After concentrating the obtained organic layer, the compound 9 represented by the formula (I-1-f) is separated by column chromatography (silica gel 60-200 mesh; developing solvent: ethyl acetate manufactured by Merck & Co., Inc.). .12 parts were obtained.

1.86 parts of the compound represented by the formula (I-1-f), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone are mixed and stirred while the formula (I-1-g) 0.77 part of the compound represented was added and stirred at 60 ° C. for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mixture, followed by liquid separation after stirring. This washing operation was performed 5 times. The obtained organic layer was concentrated and fractionated by column chromatography (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.14 parts of the compound represented by the formula (I-1). It was.

MASS: 371.1 [M + H] ⁺

式（Ｉ−３−ａ）で表される化合物９．１１部及びアセトニトリル５０部を混合し、４０℃で３０分間攪拌した。得られた混合物に、式（Ｉ−３−ｂ）で表される化合物１０．７９部を加え、６０℃で１時間攪拌することにより、式（Ｉ−３−ｃ）で表される化合物を含む溶液を得た。

得られた式（Ｉ−３−ｃ）で表される化合物を含む溶液に、式（Ｉ−３−ｄ）で表される化合物９．３１部を加え、２３℃で１時間攪拌した後、さらに、７０℃で１８時間攪拌した。得られた反応混合物に、酢酸エチル２００部及びイオン交換水１００部を加えた後、攪拌し、分液を行った。この水洗を５回行った。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−３−ｅ）で表される化合物１２．２２部を得た。

テトラヒドロフラン６０部を５℃にした後、リチウムアルミニウムハイドライド１．５９部を混合し、その後、式（Ｉ−３−ｅ）で表される化合物１１．８９部及びテトラヒドロフラン４０部の混合溶液を、５℃で１時間かけて滴下した後、２３℃で１２時間攪拌した。さらに、５０℃で２時間攪拌した後、５℃まで冷却した。得られた混合物に、１０％硫酸２４．５４部を滴下した後、クロロホルム２００部及び５％炭酸水素ナトリウム水溶液１００部を加えて攪拌し、分液した。得られた有機層にイオン交換水１００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−３−ｆ）で表される化合物１０．４９部を得た。

式（Ｉ−３−ｆ）で表される化合物１．９３部、Ｎ−メチルピロリジン１．８３部、及びメチルイソブチルケトン２０部を混合し、攪拌しながら、式（Ｉ−３−ｇ）で表される化合物０．７７部を添加し、６０℃で５時間攪拌した。その後、反応混合物にイオン交換水１０部を添加し、攪拌後、分液を行った。この水洗の操作を５回行った。得られた有機層を濃縮後、カラムクロマトグラフィー（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）により分取することで、式（Ｉ−３）で表される化合物１．０１部を得た。 Synthesis Example 2: Synthesis of compound represented by formula (I-3)

9.11 parts of the compound represented by the formula (I-3-a) and 50 parts of acetonitrile were mixed and stirred at 40 ° C. for 30 minutes. To the obtained mixture is added 10.79 parts of the compound represented by the formula (I-3-b), and the mixture is stirred at 60 ° C. for 1 hour, whereby the compound represented by the formula (I-3-c) is obtained. A solution containing was obtained.

To the obtained solution containing the compound represented by formula (I-3-c), 9.31 parts of the compound represented by formula (I-3-d) was added and stirred at 23 ° C. for 1 hour. Furthermore, it stirred at 70 degreeC for 18 hours. To the obtained reaction mixture, 200 parts of ethyl acetate and 100 parts of ion-exchanged water were added, followed by stirring and liquid separation. This water washing was performed 5 times. After concentrating the obtained organic layer, the compound 12 represented by the formula (I-3-e) is fractionated by column chromatography (silica gel 60-200 mesh; developed solvent: ethyl acetate by Merck). .22 parts were obtained.

After 60 parts of tetrahydrofuran was brought to 5 ° C., 1.59 parts of lithium aluminum hydride was mixed, and then a mixed solution of 11.89 parts of the compound represented by the formula (I-3-e) and 40 parts of tetrahydrofuran was added to 5 parts. After dropwise addition at 1 ° C over 1 hour, the mixture was stirred at 23 ° C for 12 hours. Furthermore, after stirring at 50 degreeC for 2 hours, it cooled to 5 degreeC. After dropping 24.54 parts of 10% sulfuric acid into the obtained mixture, 200 parts of chloroform and 100 parts of 5% aqueous sodium hydrogen carbonate solution were added and stirred for separation. 100 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, then allowed to stand and liquid-separated to wash the organic layer with water. This washing operation was repeated 5 times. The obtained organic layer was concentrated and then fractionated by column chromatography (silica gel 60-200 mesh; developed solvent: ethyl acetate by Merck) to give compound 10 represented by formula (I-3-f). .49 parts were obtained.

1.93 parts of the compound represented by the formula (I-3-f), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone are mixed and stirred while the formula (I-3-g) 0.77 part of the compound represented was added and stirred at 60 ° C. for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mixture, followed by liquid separation after stirring. This washing operation was performed 5 times. The obtained organic layer was concentrated and fractionated by column chromatography (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.01 part of a compound represented by the formula (I-3). It was.

MASS: 383.2 [M + H] ⁺

式（Ｉ−４−ａ）で表される化合物９．１１部及びアセトニトリル５０部を混合し、４０℃で３０分間攪拌した。得られた混合物に、式（Ｉ−４−ｂ）で表される化合物１０．７９部を加え、６０℃で１時間攪拌することにより、式（Ｉ−４−ｃ）で表される化合物を含む溶液を得た。

得られた式（Ｉ−４−ｃ）で表される化合物を含む溶液に、式（Ｉ−４−ｄ）で表される化合物９．４２部を混合し、２３℃で１時間攪拌した後、さらに、７０℃で１８時間攪拌した。得られた反応混合物に、酢酸エチル２００部及びイオン交換水１００部を加えた後、攪拌し、分液を行った。この水洗を５回行った。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−４−ｅ）で表される化合物９．１８部を得た。

テトラヒドロフラン３０部を５℃にした後、リチウムアルミニウムハイドライド０．８０部を加え、その後、式（Ｉ−４−ｅ）で表される化合物５．９８部及びテトラヒドロフラン２０部の混合溶液を、５℃で１時間かけて滴下した後、２３℃で１２時間攪拌した。さらに、５０℃で２時間攪拌した後、５℃まで冷却した。得られた混合物に、１０％硫酸１２．２７部を滴下した後、クロロホルム１００部及び５％炭酸水素ナトリウム水溶液５０部を加えて攪拌し、分液した。得られた有機層にイオン交換水５０部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−４−ｆ）で表される化合物４．６６部を得た。

式（Ｉ−４−ｆ）で表される化合物１．９４部、Ｎ−メチルピロリジン１．８３部、及びメチルイソブチルケトン２０部を混合し、攪拌しながら、式（Ｉ−４−ｇ）で表される化合物０．７７部を添加し、６０℃で５時間攪拌した。その後、反応混合物にイオン交換水１０部を添加、攪拌後、分液を行った。この水洗の操作を５回行った。得られた有機層を濃縮後、カラムクロマトグラフィー（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）により分取することで、式（Ｉ−４）で表される化合物０．９４部を得た。 Synthesis Example 3: Synthesis of compound represented by formula (I-4)

9.11 parts of the compound represented by the formula (I-4-a) and 50 parts of acetonitrile were mixed and stirred at 40 ° C. for 30 minutes. To the obtained mixture, 10.79 parts of the compound represented by the formula (I-4-b) is added, and the mixture is stirred at 60 ° C. for 1 hour, whereby the compound represented by the formula (I-4-c) is obtained. A solution containing was obtained.

9.42 parts of the compound represented by the formula (I-4-d) is mixed with the obtained solution containing the compound represented by the formula (I-4-c) and stirred at 23 ° C. for 1 hour. Further, the mixture was stirred at 70 ° C. for 18 hours. To the obtained reaction mixture, 200 parts of ethyl acetate and 100 parts of ion-exchanged water were added, followed by stirring and liquid separation. This water washing was performed 5 times. The obtained organic layer was concentrated and then fractionated by column chromatography (silica gel 60-200 mesh; developing solvent: ethyl acetate manufactured by Merck & Co., Inc.), whereby compound 9 represented by the formula (I-4-e) was obtained. .18 parts were obtained.

After 30 parts of tetrahydrofuran was brought to 5 ° C., 0.80 part of lithium aluminum hydride was added, and then a mixed solution of 5.98 parts of the compound represented by the formula (I-4-e) and 20 parts of tetrahydrofuran was added at 5 ° C. Was added dropwise over 1 hour, followed by stirring at 23 ° C. for 12 hours. Furthermore, after stirring at 50 degreeC for 2 hours, it cooled to 5 degreeC. After 12.27 parts of 10% sulfuric acid was added dropwise to the resulting mixture, 100 parts of chloroform and 50 parts of 5% aqueous sodium hydrogen carbonate solution were added and stirred for separation. After adding 50 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the organic layer was washed with water by standing and separating. This washing operation was repeated 5 times. The obtained organic layer was concentrated and then fractionated by column chromatography (silica gel 60-200 mesh; developed solvent: ethyl acetate manufactured by Merck & Co., Inc.), whereby compound 4 represented by the formula (I-4-f) was obtained. .66 parts were obtained.

1.94 parts of the compound represented by the formula (I-4-f), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone are mixed and stirred while the formula (I-4-g) 0.77 part of the compound represented was added and stirred at 60 ° C. for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mixture, followed by liquid separation after stirring. This washing operation was performed 5 times. The obtained organic layer was concentrated and fractionated by column chromatography (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 0.94 parts of a compound represented by the formula (I-4). It was.

MASS: 385.2 [M + H] ⁺

式（Ｉ−５−ａ）で表される化合物９．１１部及びアセトニトリル５０部を混合し、４０℃で３０分間攪拌した。得られた混合物に、式（Ｉ−５−ｂ）で表される化合物１０．７９部を加え、６０℃で１時間攪拌することにより、式（Ｉ−５−ｃ）で表される化合物を含む溶液を得た。

得られた式（Ｉ−５−ｃ）で表される化合物を含む溶液に、式（Ｉ−５−ｄ）で表される化合物１０．６５部を加え、２３℃で１時間攪拌した後、さらに、７０℃で１８時間攪拌した。得られた反応混合物に、酢酸エチル２００部及びイオン交換水１００部を加えた後、攪拌し、分液を行った。水洗を５回行った。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−５−ｅ）で表される化合物１３．６７部を得た。

テトラヒドロフラン６０部を５℃にした後、リチウムアルミニウムハイドライド１．５９部を加え、その後、式（Ｉ−５−ｅ）で表される化合物１２．８０部及びテトラヒドロフラン４０部の混合溶液を、５℃で１時間かけて滴下した後、２３℃で１２時間攪拌した。さらに、５０℃で２時間攪拌した後、５℃まで冷却した。得られた混合物に、１０％硫酸２４．５４部を滴下した後、クロロホルム２００部及び５％炭酸水素ナトリウム水溶液１００部を加えて攪拌し、分液した。得られた有機層にイオン交換水１００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−５−ｆ）で表される化合物１０．８２部を得た。

式（Ｉ−５−ｆ）で表される化合物２．０８部、Ｎ−メチルピロリジン１．８３部、及びメチルイソブチルケトン２０部を混合し、攪拌しながら、式（Ｉ−５−ｇ）で表される化合物０．７７部を添加し、６０℃で５時間攪拌した。その後、反応混合物にイオン交換水１０部を添加、攪拌後、分液を行った。この水洗の操作を５回行った。得られた有機層を濃縮後、カラムクロマトグラフィー（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）により分取することで、式（Ｉ−５）で表される化合物１．１９部を得た。 Synthesis Example 4: Synthesis of compound represented by formula (I-5)

9.11 parts of the compound represented by the formula (I-5-a) and 50 parts of acetonitrile were mixed and stirred at 40 ° C. for 30 minutes. To the obtained mixture is added 10.79 parts of the compound represented by the formula (I-5-b), and the mixture is stirred at 60 ° C. for 1 hour, whereby the compound represented by the formula (I-5-c) is obtained. A solution containing was obtained.

To the obtained solution containing the compound represented by the formula (I-5-c), 10.65 parts of the compound represented by the formula (I-5-d) was added and stirred at 23 ° C. for 1 hour. Furthermore, it stirred at 70 degreeC for 18 hours. To the obtained reaction mixture, 200 parts of ethyl acetate and 100 parts of ion-exchanged water were added, followed by stirring and liquid separation. Water washing was performed 5 times. After concentrating the obtained organic layer, the compound 13 represented by the formula (I-5-e) is separated by column chromatography (silica gel 60-200 mesh; development solvent: ethyl acetate manufactured by Merck & Co., Inc.). .67 parts were obtained.

After 60 parts of tetrahydrofuran was brought to 5 ° C., 1.59 parts of lithium aluminum hydride was added, and then a mixed solution of 12.80 parts of the compound represented by the formula (I-5-e) and 40 parts of tetrahydrofuran was added at 5 ° C. Was added dropwise over 1 hour, followed by stirring at 23 ° C. for 12 hours. Furthermore, after stirring at 50 degreeC for 2 hours, it cooled to 5 degreeC. After dropping 24.54 parts of 10% sulfuric acid into the obtained mixture, 200 parts of chloroform and 100 parts of 5% aqueous sodium hydrogen carbonate solution were added and stirred for separation. 100 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, then allowed to stand and liquid-separated to wash the organic layer with water. This washing operation was repeated 5 times. After concentrating the obtained organic layer, the compound 10 represented by the formula (I-5-f) is obtained by fractionation by means of column chromatography (silica gel 60-200 mesh; developing solvent: ethyl acetate, manufactured by Merck). .82 parts were obtained.

In the formula (I-5-g), 2.08 parts of the compound represented by the formula (I-5-f), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone are mixed and stirred. 0.77 part of the compound represented was added and stirred at 60 ° C. for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mixture, followed by liquid separation after stirring. This washing operation was performed 5 times. The obtained organic layer was concentrated and fractionated by column chromatography (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.19 parts of the compound represented by the formula (I-5). It was.

MASS: 407.1 [M + H] ⁺

式（Ｉ−２−ａ）で表される化合物９．１１部及びアセトニトリル５０部を混合し、４０℃で３０分間攪拌した。得られた混合物に、式（Ｉ−２−ｂ）で表される化合物１０．７９部を加え、６０℃で１時間攪拌することにより、式（Ｉ−２−ｃ）で表される化合物を含む溶液を得た。

得られた式（Ｉ−２−ｃ）で表される化合物を含む溶液に、式（Ｉ−２−ｄ）で表される化合物９．３１部を加え、２３℃で１時間攪拌した後、さらに、７０℃で１８時間攪拌した。得られた反応混合物に、酢酸エチル２００部及びイオン交換水１００部を加えた後、攪拌し、分液を行った。この水洗を５回行った。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−２−ｅ）で表される化合物１２．１１部を得た。

テトラヒドロフラン６０部を５℃にした後、リチウムアルミニウムハイドライド１．５９部を混合し、その後、式（Ｉ−２−ｅ）で表される化合物１１．８９部及びテトラヒドロフラン４０部の混合溶液を、５℃で１時間かけて滴下した後、５℃で３時間攪拌した。得られた混合物に、１０％硫酸２４．５４部を滴下した後、クロロホルム２００部及び５％炭酸水素ナトリウム水溶液１００部を加えて攪拌し、分液した。得られた有機層にイオン交換水１００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−２−ｆ）で表される化合物４．２８部を得た。

式（Ｉ−２−ｆ）で表される化合物１．９３部、Ｎ−メチルピロリジン１．８３部、及びメチルイソブチルケトン２０部を混合し、攪拌しながら、式（Ｉ−２−ｇ）で表される化合物０．７７部を添加し、６０℃で５時間攪拌した。その後、反応混合物にイオン交換水１０部を添加し、攪拌後、分液を行った。この水洗の操作を５回行った。得られた有機層を濃縮後、カラムクロマトグラフィー（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）により分取することで、式（Ｉ−２）で表される化合物１．２１部を得た。 Synthesis Example 5: Synthesis of compound represented by formula (I-2)

9.11 parts of the compound represented by the formula (I-2-a) and 50 parts of acetonitrile were mixed and stirred at 40 ° C. for 30 minutes. To the obtained mixture is added 10.79 parts of the compound represented by the formula (I-2-b), and the mixture is stirred at 60 ° C. for 1 hour, whereby the compound represented by the formula (I-2-c) is obtained. A solution containing was obtained.

To the obtained solution containing the compound represented by the formula (I-2-c), 9.31 parts of the compound represented by the formula (I-2-d) was added and stirred at 23 ° C. for 1 hour. Furthermore, it stirred at 70 degreeC for 18 hours. To the obtained reaction mixture, 200 parts of ethyl acetate and 100 parts of ion-exchanged water were added, followed by stirring and liquid separation. This water washing was performed 5 times. After concentrating the obtained organic layer, the compound 12 represented by the formula (I-2-e) is separated by column chromatography (silica gel 60-200 mesh; developing solvent: ethyl acetate manufactured by Merck & Co., Inc.). .11 parts were obtained.

After making 60 parts of tetrahydrofuran into 5 ° C., 1.59 parts of lithium aluminum hydride is mixed, and then a mixed solution of 11.89 parts of the compound represented by the formula (I-2-e) and 40 parts of tetrahydrofuran is added to 5 parts. After dropwise addition at 1 ° C over 1 hour, the mixture was stirred at 5 ° C for 3 hours. After dropping 24.54 parts of 10% sulfuric acid into the obtained mixture, 200 parts of chloroform and 100 parts of 5% aqueous sodium hydrogen carbonate solution were added and stirred for separation. 100 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, then allowed to stand and liquid-separated to wash the organic layer with water. This washing operation was repeated 5 times. The obtained organic layer was concentrated, and fractionated by column chromatography (silica gel 60-200 mesh; developed solvent: Merced Ltd., developing solvent: ethyl acetate), whereby compound 4 represented by the formula (I-2-f) was obtained. .28 parts were obtained.

1.93 parts of the compound represented by the formula (I-2-f), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone are mixed and stirred while the formula (I-2-g) 0.77 part of the compound represented was added and stirred at 60 ° C. for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mixture, followed by liquid separation after stirring. This washing operation was performed 5 times. The obtained organic layer was concentrated and fractionated by column chromatography (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 1.21 parts of a compound represented by the formula (I-2). It was.

MASS: 383.2 [M + H] ⁺

式（Ｉ−１１−ａ）で表される化合物９．１１部及びアセトニトリル５０部を混合し、４０℃で３０分間攪拌した。得られた混合物に、式（Ｉ−１１−ｂ）で表される化合物１０．７９部を加え、６０℃で１時間攪拌することにより、式（Ｉ−１１−ｃ）で表される化合物を含む溶液を得た。

得られた式（Ｉ−１１−ｃ）で表される化合物を含む溶液に、式（Ｉ−１１−ｄ）で表される化合物９．３１部を加え、２３℃で１時間攪拌した後、さらに、７０℃で１８時間攪拌した。得られた反応混合物に、酢酸エチル２００部及びイオン交換水１００部を加えた後、攪拌し、分液を行った。この水洗を５回行った。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−１１−ｅ）で表される化合物１２．１１部を得た。

テトラヒドロフラン６０部を５℃にした後、リチウムアルミニウムハイドライド３．１８部を混合し、その後、式（Ｉ−１１−ｅ）で表される化合物１１．８９部及びテトラヒドロフラン４０部の混合溶液を、５℃で１時間かけて滴下した後、２３℃で１２時間攪拌した。さらに、５０℃で２時間攪拌した後、５℃まで冷却した。得られた混合物に、１０％硫酸４９．０８部を滴下した後、クロロホルム２００部及び５％炭酸水素ナトリウム水溶液２００部を加えて攪拌し、分液した。得られた有機層にイオン交換水１００部を加え、２３℃で３０分間攪拌した後、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。得られた有機層を濃縮した後、カラムクロマトグラフィー（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）により分取することで、式（Ｉ−１１−ｆ）で表される化合物６．５１部を得た。

式（Ｉ−１１−ｆ）で表される化合物１．９４部、Ｎ−メチルピロリジン１．８３部、及びメチルイソブチルケトン２０部を混合し、攪拌しながら、式（Ｉ−１１−ｇ）で表される化合物０．７７部を添加し、６０℃で５時間攪拌した。その後、反応混合物にイオン交換水１０部を添加し、攪拌後、分液を行った。この水洗の操作を５回行った。得られた有機層を濃縮後、カラムクロマトグラフィー（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）により分取することで、式（Ｉ−１１）で表される化合物０．５６部を得た。 Synthesis Example 6: Synthesis of compound represented by formula (I-11)

9.11 parts of the compound represented by the formula (I-11-a) and 50 parts of acetonitrile were mixed and stirred at 40 ° C. for 30 minutes. To the obtained mixture, 10.79 parts of a compound represented by the formula (I-11-b) is added and stirred at 60 ° C. for 1 hour to obtain a compound represented by the formula (I-11-c). A solution containing was obtained.

To the obtained solution containing the compound represented by the formula (I-11-c), 9.31 parts of the compound represented by the formula (I-11-d) was added and stirred at 23 ° C. for 1 hour. Furthermore, it stirred at 70 degreeC for 18 hours. To the obtained reaction mixture, 200 parts of ethyl acetate and 100 parts of ion-exchanged water were added, followed by stirring and liquid separation. This water washing was performed 5 times. The obtained organic layer was concentrated and then fractionated by column chromatography (silica gel 60-200 mesh; developed solvent: ethyl acetate by Merck & Co., Inc.), whereby compound 12 represented by the formula (I-11-e) was obtained. .11 parts were obtained.

After 60 parts of tetrahydrofuran was brought to 5 ° C., 3.18 parts of lithium aluminum hydride were mixed, and then a mixed solution of 11.89 parts of the compound represented by the formula (I-11-e) and 40 parts of tetrahydrofuran was added to 5 parts. After dropwise addition at 1 ° C over 1 hour, the mixture was stirred at 23 ° C for 12 hours. Furthermore, after stirring at 50 degreeC for 2 hours, it cooled to 5 degreeC. To the obtained mixture, 49.08 parts of 10% sulfuric acid was added dropwise, and then 200 parts of chloroform and 200 parts of 5% aqueous sodium hydrogen carbonate solution were added and stirred to separate the layers. 100 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, then allowed to stand and liquid-separated to wash the organic layer with water. This washing operation was repeated 5 times. The obtained organic layer was concentrated, and fractionated by column chromatography (silica gel 60-200 mesh; developing solvent: ethyl acetate, manufactured by Merck & Co., Inc.), whereby compound 6 represented by formula (I-11-f) was obtained. .51 parts were obtained.

1.94 parts of the compound represented by the formula (I-11-f), 1.83 parts of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone are mixed and stirred while the formula (I-11-g) 0.77 part of the compound represented was added and stirred at 60 ° C. for 5 hours. Thereafter, 10 parts of ion-exchanged water was added to the reaction mixture, followed by liquid separation after stirring. This washing operation was performed 5 times. The obtained organic layer is concentrated, and fractionated by column chromatography (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 0.56 parts of the compound represented by the formula (I-11). It was.

MASS: 385.2 [M + H] ⁺

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

  Hereinafter, these monomers are referred to as “monomer (a1-1-3)” or the like according to the formula number.

Synthesis Example 7 [Synthesis of Resin A1]
As the monomer, the monomer (a2-2-1), the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-1) were used, and their molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-1)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A1 having a weight average molecular weight of about 6.2 × 10 ³ in a yield of 61%. This resin A1 has the following structural units.

Synthesis Example 8 [Synthesis of Resin A2]
As the monomer, the monomer (a2-2-1), the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-3) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-3)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A2 having a weight average molecular weight of about 6.1 × 10 ³ in a yield of 66%. This resin A2 has the following structural units.

Synthesis Example 9 [Synthesis of Resin A3]
As the monomer, monomer (a2-2-1), monomer (a1-1-3), monomer (a1-2-6) and monomer (I-4) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-4)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A3 having a weight average molecular weight of about 6.4 × 10 ³ with a yield of 68%. This resin A3 has the following structural units.

Synthesis Example 10 [Synthesis of Resin A4]
As the monomer, a monomer (a2-2-1), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I-5) are used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-5)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A4 having a weight average molecular weight of about 6.0 × 10 ³ in a yield of 60%. This resin A4 has the following structural units.

Synthesis Example 11 [Synthesis of Resin A5]
As the monomer, the monomer (a2-2-1), the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-7) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-7)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A5 having a weight average molecular weight of about 6.4 × 10 ³ in a yield of 66%. This resin A5 has the following structural units.

Synthesis Example 12 [Synthesis of Resin A6]
As the monomer, a monomer (a2-2-1), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (I-8) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-8)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain Resin A6 having a weight average molecular weight of about 6.6 × 10 ³ in a yield of 63%. This resin A6 has the following structural units.

Synthesis Example 13 [Synthesis of Resin A7]
As the monomer, the monomer (a2-2-1), the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-9) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-9)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A7 having a weight average molecular weight of about 6.3 × 10 ³ in a yield of 65%. This resin A7 has the following structural units.

Synthesis Example 14 [Synthesis of Resin A8]
As the monomer, the monomer (a2-2-1), the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-10) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-10)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A8 having a weight average molecular weight of about 6.5 × 10 ³ with a yield of 68%. This resin A8 has the following structural units.

Synthesis Example 15 [Synthesis of Resin A9]
As the monomer, monomer (a2-2-1), monomer (a1-1-3), monomer (a1-2-6) and monomer (I-2) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-2)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain Resin A9 having a weight average molecular weight of about 6.8 × 10 ³ with a yield of 65%. This resin A9 has the following structural units.

Synthesis Example 16 [Synthesis of Resin A10]
As the monomer, the monomer (a2-2-1), the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-11) are used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (I-11)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain Resin A10 having a weight average molecular weight of about 6.6 × 10 ³ in a yield of 60%. This resin A10 has the following structural units.

Synthesis Example 17 [Synthesis of Resin AX1]
As the monomer, the monomer (a2-2-1), the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (IX-3) were used, and the molar ratio [monomer (a2-2-1) ): Monomer (a1-1-3): monomer (a1-2-6): monomer (IX-3)] in a ratio of 37: 25: 20: 18, and this monomer mixture. In addition, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, Heated at about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain a resin AX1 having a weight average molecular weight of about 6.5 × 10 ³ in a yield of 60%. This resin AX1 has the following structural units.

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

＜酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩＞
Ｄ１：特開２０１１−３９５０２号公報記載の方法で合成

Ｄ２：（東京化成工業（株）製）

＜塩基性化合物：クエンチャー（Ｃ）＞
Ｃ１：（東京化成工業（株）製）

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ４００部
プロピレングリコールモノメチルエーテル １５０部
γ−ブチロラクトン ５部 <Resin>
A1 to A10, AX1: Resin A1 to Resin A10, Resin AX1
<Acid generator (B)>
B1-43: a salt represented by the formula (B1-43) (synthesized according to Examples in JP-A-2016-47815)

<Salt that generates an acid with a lower acidity than the acid generated from the acid generator>
D1: synthesized by the method described in JP2011-39502A

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

<Basic compound: Quencher (C)>
C1: (Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 150 parts γ-butyrolactone 5 parts

(Electron beam exposure evaluation of resist composition: alkali development)
A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds. This silicon wafer was spin-coated with a resist composition so that the film thickness of the composition layer was 0.04 μm. Thereafter, the composition layer was formed by pre-baking on a direct hot plate for 60 seconds at the temperature shown in the “PB” column of Table 1. A line-and-space pattern was directly drawn on the composition layer formed on the wafer using an electron beam drawing machine ("HL-800D 50 keV" manufactured by Hitachi, Ltd.) while changing the exposure stepwise. .
After exposure, post exposure baking is performed for 60 seconds on the hot plate at the temperature shown in the “PEB” column of Table 1, and then paddle development is performed for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. A resist pattern was obtained.
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and space width of the 60 nm line and space pattern were 1: 1 was defined as effective sensitivity.

  Line edge roughness evaluation (LER): The width of unevenness on the side wall surface of a resist pattern manufactured with effective sensitivity was measured with a scanning electron microscope to determine line edge roughness. The results are shown in Table 2.

(Electron beam exposure evaluation of resist composition: butyl acetate development)
A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds. This silicon wafer was spin-coated with a resist composition so that the film thickness of the composition layer was 0.04 μm. Thereafter, the composition layer was formed by pre-baking on a direct hot plate for 60 seconds at the temperature shown in the “PB” column of Table 1. A line-and-space pattern was directly drawn on the composition layer formed on the wafer using an electron beam drawing machine ("HL-800D 50 keV" manufactured by Hitachi, Ltd.) while changing the exposure stepwise. .
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature shown in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer was developed by a dynamic dispensing method at 23 ° C. for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution to obtain a resist pattern. .
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and space width of the 60 nm line and space pattern were 1: 1 was defined as effective sensitivity.

  Line edge roughness evaluation (LER): The width of unevenness on the side wall surface of a resist pattern manufactured with effective sensitivity was measured with a scanning electron microscope to determine line edge roughness. The results are shown in Table 3.

  Since the resist composition of the present invention is excellent in line edge roughness (LER) of the resulting resist pattern, it is suitable for fine processing of semiconductors and is extremely useful industrially.

Claims (8)

A resist composition comprising a resin containing a structural unit derived from the compound represented by formula (I), an acid generator, and a salt that generates an acid having a lower acidity than an acid generated from the acid generator.

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms.
Ar represents a C6-C36 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents a divalent group having —CO—O—, —O—CO—, —O—CO—O— or —O—.
R ⁴ represents an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (—CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—, -CO- or -S (O) _2- may be substituted.), Or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms and having 1 to 18 carbon atoms. An aliphatic hydrocarbon group (-CH ₂ — contained in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is replaced by —O—, —S—, —CO— or —S (O) ₂ —; May be present). ] The resist composition according to claim 1, wherein R ² is an alkyl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom. X ¹ is * —CO—O— or * —O—A ¹¹ —CO—O— (* represents a bond with Ar, and A ¹¹ represents an alkanediyl group having 1 to 6 carbon atoms). The resist composition according to claim 1 or 2. R ⁴ is an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms, a hydroxy group or a halogen atom (—CH ₂ contained in the alicyclic hydrocarbon group). -May be replaced by -O-, -S-, -CO- or -S (O) _2- .) The resist composition according to any one of claims 1 to 3. The resist composition according to any one of claims 1 to 4, wherein the acid having a lower acidity than the acid generated from the acid generator is a salt represented by the formula (C1) or a salt represented by the formula (D). object.

[In the formula (C1),
R ^A represents an optionally substituted hydrocarbon group having 1 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or It may be replaced by —SO ₂ —.
Z ⁶⁺ represents an organic cation. ]

[In the formula (D),
R ^D1 and R ^D2 are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 7 carbon atoms, or an alkylcarbonyloxy group having 2 to 7 carbon atoms. Represents an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group, or a halogen atom.
m ′ and n ′ each independently represents an integer of 0 to 4, and when m ′ is 2 or more, a plurality of R ^D1 are the same or different, and when n ′ is 2 or more, a plurality of R ^D2 is the same or different. ]   The resist composition according to claim 1, wherein the resin further comprises a structural unit having an acid labile group. The resist composition according to any one of claims 1 to 6, wherein the acid generator contains a salt represented by the formula (B1).

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
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 by —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 an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —S (O) ₂ —, or —CO—.
Z ⁺ represents an organic cation. ] (1) The process of apply | coating the resist composition in any one of Claims 1-7 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: