JP2023098702A - Resist composition and method for producing resist pattern - Google Patents

Abstract

To provide a resist composition from which a resist pattern having good resolution can be produced.SOLUTION: The resist composition contains a resin (A1) containing a structural unit represented by formula (I1) and a resin (A2) containing a structural unit represented by formula (I2). [In the formulae, Yb1 represents a single bond or an optionally substituted alicyclic hydrocarbon group; and X0 represents a single bond or an optionally substituted hydrocarbon group, provided that an atom adjacent to CO2- is a carbon atom which is not substituted with a fluorine atom.]SELECTED DRAWING: None

Description

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

Patent Document 1 describes a resist composition containing a resin containing a structural unit derived from a salt represented by the following formula.

Patent Document 2 describes a resist composition containing a resin containing a structural unit derived from a carboxylate represented by the following formula.

Patent Document 3 describes a resist composition containing a resin containing a structural unit derived from a salt represented by the following formula and a resin containing a structural unit derived from a carboxylate represented by the following formula. there is

JP 2007-197718 A JP 2011-037834 A JP 2011-195812 A

The present invention provides a resist composition that forms a resist pattern with better resolution than the resist pattern formed by the above resist composition.

［式（Ｉ１）及び式（Ｉ２）中、
Ｑ^ｂ１及びＱ^ｂ２は、それぞれ独立に、水素原子、フッ素原子、炭素数１～６のペルフルオロアルキル基又は炭素数１～６のアルキル基を表す。
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^ｂ１は、単結合又は置換基を有していてもよい炭素数３～２４の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－Ｓ－又は－ＳＯ_２－に置き換わっていてもよい。
Ｘ^０は、単結合又は置換基を有してもよい炭素数１～７２の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい。但し、ＣＯ_２ ^－に隣接する原子は炭素原子であり、該炭素原子にフッ素原子は置換しない。
Ｒ^１０及びＲ^２０は、それぞれ独立に、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｘ^１０及びＸ^２０は、それぞれ独立に、単結合、＊－Ｏ－＊＊、＊－ＣＯ－Ｏ－＊＊、＊－Ｏ－ＣＯ－Ｏ－＊＊又は＊－Ａｘ－Ｐｈ－Ａｙ－＊＊を表す。
Ａｘ及びＡｙは、それぞれ独立に、単結合、エーテル結合、エステル結合及び炭酸エステル結合から構成される群から選択される１種の結合種を表す。
Ｐｈは、置換基を有していてもよいフェニレン基を表す。
＊は、Ｒ^１０又はＲ^２０が結合した炭素原子との結合部位を表し、＊＊はＬ^１０又はＬ^２０との結合部位を表す。
Ｌ^１０及びＬ^２０は、それぞれ独立に、単結合又は置換基を有してもよい炭素数１～３６の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ１^＋及びＺ２^＋は、それぞれ独立に、有機カチオンを表す。］
［２］Ｙ^ｂ１が、単結合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（該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－Ｓ－又は－ＳＯ_２－に置き換わっていてもよい。）である［１］に記載のレジスト組成物。
［３］Ｙ^ｂ１が、シクロヘキサンジイル基、アダマンタンジイル基、ノルボルナンジイル基、アダマンタンラクトンジイル基又はノルボルナンラクトンジイル基である［２］に記載のレジスト組成物。
［４］Ｘ^０が、単結合であるか、置換基を有してもよい炭素数１～７２の脂肪族炭化水素基（該脂肪族炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい。）又は置換基を有してもよい炭素数６～３６の芳香族炭化水素基を含む（但し、ＣＯ_２ ^－に隣接する原子は炭素原子であり、該炭素原子にフッ素原子は置換しない。）［１］～［３］のいずれかに記載のレジスト組成物。
［５］Ｘ^０が、単結合であるか、フッ素原子、炭素数１～４のペルフルオロアルキル基もしくはヒドロキシ基を有してもよい炭素数１～１８の鎖式炭化水素基（該鎖式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。）、フッ素原子、炭素数１～４のペルフルオロアルキル基もしくはヒドロキシ基を有してもよい炭素数３～３６の脂環式炭化水素基（該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい。）、炭素数３～３６の脂環式炭化水素基と炭素数１～１８の鎖式炭化水素基とを組み合わせた基（該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよく、該鎖式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該脂環式炭化水素基及び該鎖式炭化水素基は、フッ素原子、炭素数１～４のペルフルオロアルキル基又はヒドロキシ基を有してもよい。）、フッ素原子、炭素数１～４のペルフルオロアルキル基もしくはヒドロキシ基を有してもよい炭素数６～３６の芳香族炭化水素基、又は、炭素数６～３６の芳香族炭化水素基と炭素数１～１８の鎖式炭化水素基とを組み合わせた基（該鎖式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該芳香族炭化水素基及び該鎖式炭化水素基は、フッ素原子、炭素数１～４のペルフルオロアルキル基又はヒドロキシ基を有してもよい。）を含む（但し、ＣＯ_２ ^－に隣接する原子は炭素原子であり、該炭素原子にフッ素原子は置換しない。）［４］に記載のレジスト組成物。
［６］Ｘ^０は、脂環式炭化水素基を含み、該脂環式炭化水素基は、炭素数５もしくは６のシクロアルカンジイル基、アダマンタンジイル基、ノルボルナンジイル基、アダマンタンラクトンジイル基、ノルボルナンラクトンジイル基、又は、アダマンタンジイル基と該アダマンタンジイル基とスピロで結合した炭素数５もしくは６のシクロアルカンジイル基（該アダマンタンジイル基、ノルボルナンジイル基及びシクロアルカンジイル基は、フッ素原子、炭素数１～４のペルフルオロアルキル基もしくはヒドロキシ基を有してもよく、該アダマンタンジイル基、ノルボルナンジイル基及びシクロアルカンジイル基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。）を含む（但し、ＣＯ_２ ^－に隣接する原子は炭素原子であり、該炭素原子にフッ素原子は置換しない。）［５］に記載のレジスト組成物。
［７］Ｘ^１０及びＸ^２０が、それぞれ独立に、単結合又は式（Ｘ^１－１）、式（Ｘ^１－８）及び式（Ｘ^１－２’）～式（Ｘ^１－７’）のいずれかで表される基である［１］～［６］のいずれかに記載のレジスト組成物。

［式（Ｘ^１－１）、式（Ｘ^１－８）及び式（Ｘ^１－２’）～式（Ｘ^１－７’）中、
＊、＊＊は結合部位であり、＊＊はＬ^1０又はＬ^2０との結合部位を表す。
Ｒｘは、ハロゲン原子、ヒドロキシ基、炭素数１～６のフッ化アルキル基、炭素数１～１８のアルキル基又は炭素数１～６のアルコキシ基を表す。
ｍｘは、０～４のいずれかの整数を表す。］
［８］Ｘ^１０及びＸ^２０が、それぞれ独立に、単結合又は式（Ｘ^１－１）～式（Ｘ^１－７）のいずれかで表される基である［７］に記載のレジスト組成物。

［式（Ｘ^１－１）～式（Ｘ^１－７）中、
＊、＊＊は結合部位であり、＊＊はＬ^1０又はＬ^2０との結合部位を表す。］
［９］Ｘ^１０及びＸ^２０が、それぞれ独立に、単結合又は式（Ｘ^１－１）、式（Ｘ^１－４）及び式（Ｘ^１－５）のいずれかで表される基である［８］に記載のレジスト組成物。
［１０］Ｌ^１０及びＬ^２０が、それぞれ独立に、単結合、炭素数１～６のアルカンジイル基（但し、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。）、炭素数３～１８の環状炭化水素基（但し、該環状炭化水素基は、置換基を有してもよく、該環状炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。）又は炭素数１～６のアルカンジイル基と炭素数３～１８の環状炭化水素基とを組み合わせてなる基（但し、該環状炭化水素基は、置換基を有してもよく、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く、該環状炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。）である［１］～［９］のいずれかに記載のレジスト組成物。
［１１］樹脂（Ａ１）及び樹脂（Ａ２）の少なくともいずれか一方が、さらに、酸不安定基を有する構造単位を含む［１］～［１０］のいずれかに記載のレジスト組成物。
［１２］酸不安定基を有する構造単位が、式（ａ１－０）で表される構造単位、式（ａ１－１）で表される構造単位及び式（ａ１－２）で表される構造単位からなる群より選ばれる少なくとも１種を含む［１１］に記載のレジスト組成物。

［式（ａ１－０）、式（ａ１－１）及び式（ａ１－２）中、
Ｌ^a01、Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、－Ｏ－又は＊－Ｏ－（ＣＨ_２）_ｋ１－ＣＯ－Ｏ－を表し、ｋ１は１～７のいずれかの整数を表し、＊は－ＣＯ－との結合部位を表す。
Ｒ^a01、Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基又はこれらを組み合わせた基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１～８のアルキル基、炭素数２～８のアルケニル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基又はこれらを組合せることにより形成される基を表す。
ｍ１は０～１４のいずれかの整数を表す。
ｎ１は０～１０のいずれかの整数を表す。
ｎ１’は０～３のいずれかの整数を表す。］
［１３］樹脂（Ａ１）及び樹脂（Ａ２）の少なくともいずれか一方が、さらに、式（ａ２－Ａ）で表される構造単位を含む［１］～［１２］のいずれかに記載のレジスト組成物。

［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いてもよい炭素数１～６のアルキル基を表す。
Ｒ^a51は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～１２のアルコキシアルキル基、炭素数２～１２のアルコキシアルコキシ基、炭素数２～４のアルキルカルボニル基、炭素数２～４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a50は、単結合又は＊－Ｘ^a51－（Ａ^a52－Ｘ^a52）_nｂ－を表し、＊は－Ｒ^a50が結合する炭素原子との結合部位を表す。
Ａ^a52は、炭素数１～６のアルカンジイル基を表す。
Ｘ^a51及びＸ^a52は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ｎｂは、０又は１を表す。
ｍｂは、０～４のいずれかの整数を表す。ｍｂが２以上のいずれかの整数である場合、複数のＲ^a51は互いに同一であっても異なっていてもよい。］
［１４］さらに、酸発生剤を含有する［１］～［１３］のいずれかに記載のレジスト組成物。
［１５］酸発生剤が、式（Ｂ１）で表される塩を含む［１４］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、水素原子、フッ素原子、炭素数１～６のペルフルオロアルキル基又は炭素数１～６のアルキル基を表す。
Ｌ^ｂ１は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～２４の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］
［１６］さらに、酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩を含有する［１４］又は［１５］に記載のレジスト組成物。
［１７］（１）［１］～［１６］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 containing a resin (A1) containing a structural unit represented by formula (I1) and a resin (A2) containing a structural unit represented by formula (I2).

[In the formulas (I1) and (I2),
Q ^b1 and Q ^b2 each independently represent a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO— , a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y ^b1 represents a single bond or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O— , —CO—, —S— or —SO ₂ —.
X ⁰ represents a single bond or an optionally substituted hydrocarbon group having 1 to 72 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO - or -SO ₂ - may be substituted. However, the atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom.
R ¹⁰ and R ²⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
X ¹⁰ and X ²⁰ are each independently a single bond, *-O-**, *-CO-O-**, *-O-CO-O-** or *-Ax-Ph-Ay-* * represents.
Ax and Ay each independently represent one type of bond selected from the group consisting of a single bond, an ether bond, an ester bond and a carbonate bond.
Ph represents a phenylene group optionally having a substituent.
* represents the bonding site with the carbon atom to which ^R10 or ^R20 is bonded, and ** represents the bonding site with ^L10 or ^L20 .
L ¹⁰ and L ²⁰ each independently represent a single bond or an optionally substituted hydrocarbon group having 1 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— , —S—, —SO ₂ — or —CO—.
Z1 ⁺ and Z2 ⁺ each independently represent an organic cation. ]
[2] Y ^b1 is a single bond or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms (the —CH ₂ — contained in the alicyclic hydrocarbon group is —O -, -CO-, -S- or -SO ₂ -).
[3] The resist composition according to [2], wherein Y ^b1 is a cyclohexanediyl group, adamantanediyl group, norbornanediyl group, adamantanelactonediyl group or norbornanelactonediyl group.
[4] X ⁰ is a single bond or an optionally substituted aliphatic hydrocarbon group having 1 to 72 carbon atoms (-CH ₂ - contained in the aliphatic hydrocarbon group is -O -, -S-, -CO- or -SO ₂ -) or optionally substituted aromatic hydrocarbon groups having 6 to 36 carbon atoms (with the proviso that CO ₂ ^- is a carbon atom, and the carbon atom is not substituted with a fluorine atom.) The resist composition according to any one of [1] to [3].
[5] X ⁰ is a single bond or a chain hydrocarbon group having 1 to 18 carbon atoms optionally having a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group (the chain hydrocarbon —CH ₂ — contained in a hydrogen group may be replaced with —O— or —CO—.), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group. 3 to 36 alicyclic hydrocarbon groups (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -; ), a group obtained by combining an alicyclic hydrocarbon group having 3 to 36 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms (the —CH ₂ — contained in the alicyclic hydrocarbon group is —O -, -S-, -CO- or -SO ₂ -, and -CH ₂ - contained in the chain hydrocarbon group may be replaced with -O- or -CO-, The alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a C 1-4 perfluoroalkyl group or a hydroxy group.), a fluorine atom, a C 1-4 perfluoro an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have an alkyl group or a hydroxy group, or an aromatic hydrocarbon group having 6 to 36 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms; —CH ₂ — contained in the combined group (the chain hydrocarbon group may be replaced with —O— or —CO—, and the aromatic hydrocarbon group and the chain hydrocarbon group may be substituted with a fluorine atom , may have a C 1-4 perfluoroalkyl group or a hydroxy group) (However, the atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom.) The resist composition according to [4].
[6] X ⁰ includes an alicyclic hydrocarbon group, which is a cycloalkanediyl group having 5 or 6 carbon atoms, an adamantanediyl group, a norbornanediyl group, an adamantanelactonediyl group, norbornane A lactonediyl group, or an adamantanediyl group and a cycloalkanediyl group having 5 or 6 carbon atoms spiro-bonded to the adamantanediyl group (the adamantanediyl group, norbornanediyl group and cycloalkanediyl group are fluorine atoms, carbon atoms may have 1 to 4 perfluoroalkyl groups or hydroxy groups, and —CH ₂ — contained in the adamantanediyl group, norbornanediyl group and cycloalkanediyl group is replaced with —O— or —CO—; (The atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom.) [5].
[7] X ¹⁰ and X ²⁰ are each independently a single bond or formula (X ¹ -1), formula (X ¹ -8) and formula (X ¹ -2′) to formula (X ¹ -7′) The resist composition according to any one of [1] to [6], which is a group represented by any one of

[In formula (X ¹ -1), formula (X ¹ -8) and formula (X ¹ -2′) to formula (X ¹ -7′),
*, ** is a binding site, and ** represents a binding site with ^L10 or ^L20 .
Rx represents a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
mx represents any integer from 0 to 4; ]
[8] The resist composition according to [7], wherein X ¹⁰ and X ²⁰ are each independently a single bond or a group represented by any one of formulas (X ¹ -1) to (X ¹ -7) thing.

[In the formulas (X ¹ -1) to (X ¹ -7),
*, ** is a binding site, and ** represents a binding site with ^L10 or ^L20 . ]
[9] X ¹⁰ and X ²⁰ are each independently a single bond or a group represented by formula (X ¹ -1), formula (X ¹ -4) or formula (X ¹ -5) The resist composition according to [8].
[10] L ¹⁰ and L ²⁰ are each independently a single bond and an alkanediyl group having 1 to 6 carbon atoms (with the proviso that —CH ₂ — contained in the alkanediyl group is —O— or —CO— ), a cyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the cyclic hydrocarbon group may have a substituent, and -CH ₂ - contained in the cyclic hydrocarbon group is , —O—, —S—, —SO ₂ — or —CO—.) or a combination of an alkanediyl group having 1 to 6 carbon atoms and a cyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the cyclic hydrocarbon group may have a substituent, —CH ₂ — contained in the alkanediyl group may be replaced with —O— or —CO—, and the cyclic -CH ₂ - contained in the hydrocarbon group may be replaced with -O-, -S-, -SO ₂ - or -CO-). resist composition.
[11] The resist composition according to any one of [1] to [10], wherein at least one of resin (A1) and resin (A2) further comprises a structural unit having an acid-labile group.
[12] The structural unit having an acid-labile group is a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structure represented by formula (a1-2). The resist composition according to [11], containing at least one selected from the group consisting of units.

[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 an integer of 1 to 7, * is represents the binding site with -CO-.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom, a halogen atom or an optionally halogenated alkyl group having 1 to 6 carbon atoms.
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, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or represents a combined group.
R ^a6 and R ^a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. It represents a hydrocarbon group or a group formed by combining these groups.
m1 represents any integer from 0 to 14;
n1 represents any integer from 0 to 10;
n1' represents an integer of 0 to 3; ]
[13] The resist composition according to any one of [1] to [12], wherein at least one of resin (A1) and resin (A2) further comprises a structural unit represented by formula (a2-A). thing.

[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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, It represents an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or *-X ^a51 -(A ^a52 -X ^a52 ) _nb -, and * represents a bonding site with the carbon atom to which -R ^a50 bonds.
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent -O-, -CO-O- or -O-CO-.
nb represents 0 or 1;
mb represents an integer from 0 to 4; When mb is any integer of 2 or more, multiple R ^a51 may be the same or different. ]
[14] The resist composition according to any one of [1] to [13], further containing an acid generator.
[15] The resist composition of [14], wherein the acid generator contains a salt represented by formula (B1).

[In formula (B1),
Q ^b1 and Q ^b2 each independently represent a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO— , a 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 24 carbon atoms, included in the alicyclic hydrocarbon group- CH ₂ - may be replaced by -O-, -S-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ]
[16] The resist composition according to [14] or [15], further comprising a salt that generates an acid weaker in acidity than the acid generated from the acid generator.
[17] (1) A step of applying the resist composition according to any one of [1] to [16] onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) 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.

By using a resist composition using the salt of the present invention, a resist pattern can be produced with good resolution.

As used herein, "(meth)acrylic monomer" means "at least one of acrylic monomer and methacrylic monomer". Descriptions such as "(meth)acrylate" and "(meth)acrylic acid" have the same meaning. Any of the groups described in this specification that can have both a linear structure and a branched structure may be used. When —CH ₂ — contained in a hydrocarbon group or the like is replaced with —O—, —S—, —CO— or —SO ₂ —, the same examples apply to each group. A "combined group" means a group in which two or more of the exemplified groups are combined by appropriately changing their valence numbers, bonding forms, and the like. "Derived from" or "derived from" refers to the polymerization of a polymerizable C=C bond contained in the molecule to a single bond (--C--C-- group). Where stereoisomers exist, all stereoisomers are included.
As used herein, "the solid content of the resist composition" means the total amount of components excluding the solvent (E) described below from the total amount of the resist composition.

［式（Ｉ１）及び式（Ｉ２）中の全ての符号は、前記と同じである。］
本発明のレジスト組成物は、２種以上の樹脂（Ａ１）又は２種以上の樹脂（Ａ２）を含んでいてもよい。また、樹脂（Ａ１）は、２種以上の構造単位（Ｉ１）を含んでいてもよい。樹脂（Ａ２）は、２種以上の構造単位（Ｉ２）を含んでいてもよい。
本発明のレジスト組成物は、さらに酸発生剤、カルボン酸発生剤又はその両方を含んでいてもよい。ここでの酸発生剤及びカルボン酸発生剤は、構造単位（Ｉ１）を誘導する塩（Ｉ１－ｓ）及び構造単位（Ｉ２）を誘導するカルボン酸塩（Ｉ２－ｓ）を含んでいてもよい。
本発明のレジスト組成物は、レジスト分野で公知の酸発生剤（以下「酸発生剤（Ｂ）」という場合がある）、クエンチャー（以下「クエンチャー（Ｃ）」という場合がある）、樹脂（Ａ１）及び樹脂（Ａ２）以外の樹脂及び／又は溶剤（以下「溶剤（Ｅ）」という場合がある）をさらに含有することが好ましい。 [Resist composition]
The resist composition of the present invention comprises a resin (A1) containing a structural unit represented by formula (I1) (hereinafter sometimes referred to as structural unit (I1)) and a structural unit represented by formula (I2) (hereinafter sometimes referred to as structural unit (I2)) and a resin (A2) containing the structural unit (I2).

[All symbols in formulas (I1) and (I2) are the same as above. ]
The resist composition of the present invention may contain two or more resins (A1) or two or more resins (A2). Moreover, the resin (A1) may contain two or more structural units (I1). The resin (A2) may contain two or more structural units (I2).
The resist composition of the present invention may further contain an acid generator, a carboxylic acid generator, or both. The acid generator and the carboxylic acid generator here may contain a salt (I1-s) from which the structural unit (I1) is derived and a carboxylate (I2-s) from which the structural unit (I2) is derived. .
The resist composition of the present invention comprises an acid generator (hereinafter sometimes referred to as "acid generator (B)"), a quencher (hereinafter sometimes referred to as "quencher (C)"), and a resin known in the field of resists. It is preferable to further contain a resin and/or a solvent (hereinafter sometimes referred to as "solvent (E)") other than (A1) and resin (A2).

［式（Ｉ１）及び式（Ｉ１－ｓ）中、全ての符号はそれぞれ前記と同じ意味を表す。］ [Resin A1]
Resin A1 contains a structural unit (I1) represented by formula (I1).
<Structural unit (I1)>
Structural unit (I1) is derived from, for example, a salt represented by formula (I1-s) capable of functioning as an acid generator (hereinafter sometimes referred to as salt (I1-s)), and salt (I1- The double bond of CH ₂ ═C—R ¹⁰ contained in s) is cleaved.
Of the salt (I1-s), the negatively charged side is sometimes called "anion (I1-a)" and the positively charged side is sometimes called "cation (I1-c)".

[In formulas (I1) and (I1-s), all symbols have the same meanings as described above. ]

The perfluoroalkyl groups 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 and the like can be mentioned.
Examples of alkyl groups represented by Q ^b1 and Q ^b2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n- Examples thereof include hexyl group and the like, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
At least one of Q ^b1 and Q ^b2 preferably contains a fluorine atom or a perfluoroalkyl group, each independently more preferably a fluorine atom or a perfluoroalkyl group, and a fluorine atom or a trifluoromethyl group is more preferable, and it is even more preferable that both are fluorine atoms.

The divalent saturated hydrocarbon group for L ^b1 includes a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic bivalent alicyclic saturated hydrocarbon group, and these A group formed by combining two or more of the groups may also be used.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group , tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-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, and 2-methylbutane-1,4-diyl group;
monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; alicyclic saturated hydrocarbon group;
Polycyclic bivalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group and the like.

Groups in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced with —O— or —CO— include, for example, formulas (b1-1) to (b1-3) The group represented by any one of is mentioned. In addition, in the groups represented by formulas (b1-1) to (b1-3) and the groups represented by formulas (b1-4) to (b1-11) which are specific examples thereof, * and * * represents the binding site and * represents the binding site with -Y ^b1 .

［式（ｂ１－１）中、
Ｌ^ｂ２は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ３は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
ただし、Ｌ^ｂ２とＬ^ｂ３との炭素数合計は、２２以下である。
式（ｂ１－２）中、
Ｌ^ｂ４は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ５は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
ただし、Ｌ^ｂ４とＬ^ｂ５との炭素数合計は、２２以下である。
式（ｂ１－３）中、
Ｌ^ｂ６は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
Ｌ^ｂ７は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
ただし、Ｌ^ｂ６とＬ^ｂ７との炭素数合計は、２３以下である。］

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

L ^b2 is preferably a single bond, a methylene group, —CH(CF ₃ )—, —C(CF ₃ ) ₂ —.
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, hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms, methylene group, - CH(CF ₃ )—, —C(CF ₃ ) ₂ — are preferred.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO—.

［式（ｂ１－４）中、
Ｌ^ｂ８は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
式（ｂ１－５）中、
Ｌ^ｂ９は、炭素数１～２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ｌ^ｂ１０は、単結合又は炭素数１～１９の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ９及びＬ^ｂ１０の合計炭素数は２０以下である。
式（ｂ１－６）中、
Ｌ^ｂ１１は、炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^ｂ１２は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ１１及びＬ^ｂ１２の合計炭素数は２１以下である。
式（ｂ１－７）中、
Ｌ^ｂ１３は、炭素数１～１９の２価の飽和炭化水素基を表す。
Ｌ^ｂ１４は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ｌ^ｂ１５は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ１３～Ｌ^ｂ１５の合計炭素数は１９以下である。
式（ｂ１－８）中、
Ｌ^ｂ１６は、炭素数１～１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ｌ^ｂ１７は、炭素数１～１８の２価の飽和炭化水素基を表す。
Ｌ^ｂ１８は、単結合又は炭素数１～１７の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ１６～Ｌ^ｂ１８の合計炭素数は１９以下である。］ The group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced with —O— or —CO— is represented by formula (b1-1) or formula (b1-3). are preferred.
Examples of the group represented by formula (b1-1) include groups represented by formulas (b1-4) to (b1-8).

[In formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO—.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In formula (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is replaced with —O— or —CO— good too.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b13 to L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO—.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b16 to L ^b18 is 19 or less. ]

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

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

[In formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group being substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group; good too. --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 a 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 a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group; good too. --CH ₂ -- contained in the alkylcarbonyloxy group 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 a 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 a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group; good too. --CH ₂ -- contained in the alkylcarbonyloxy group 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 ^b24 , L ^b25 and L ^b26 is 21 or less. ]

In addition, in the group represented by formula (b1-9) to the group represented by formula (b1-11), when the hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, it is replaced Let the previous carbon number be the carbon number of this saturated hydrocarbon group.
The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

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

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

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

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

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

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

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

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

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

Examples of alicyclic hydrocarbon groups in which —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y ^b1 is not replaced with —O—, —S—, —SO ₂ — or —CO— 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 ^b1 is replaced with —O—, —S—, —SO ₂ — or —CO—, the number thereof may be 1 or 2. It can be more than that. Such groups include groups represented by formulas (Y12) to (Y35) and formulas (Y39) to (Y43). —O— or —CO— in groups represented by formulas (Y12) to (Y35) and formulas (Y39) to (Y43) may be replaced with —S— or —SO ₂ —. The binding site can be at any position.

Ｙ^ｂ１で表される脂環式炭化水素基としては、好ましくは式（Ｙ１）～式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）～式（Ｙ４３）のいずれかで表される基であり、より好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ１６）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）で表される基である。

The alicyclic hydrocarbon group represented by ^Yb1 is preferably represented by formulas (Y1) to (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) ) to a group represented by any one of formula (Y43), more preferably formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), a group represented by formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), more preferably formula (Y11), formula (Y15), a group represented by formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) be.

Examples of substituents for the alicyclic hydrocarbon group represented by Y ^b1 include halogen atoms, hydroxy groups, cyano groups, and alkyl groups having 1 to 16 carbon atoms optionally substituted by hydroxy groups (included in the alkyl groups). —CH ₂ — may be replaced with —O— or —CO—.), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, 7 to 21 aralkyl groups, glycidyloxy groups, —(CH ₂ ) _ja —CO—O—R ^b1 groups or —(CH ₂ ) _ja —O—CO—R ^b1 groups (wherein R ^b1 is the number of carbon atoms represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, the alkyl group and the alicyclic hydrocarbon —CH ₂ — included in the group may be replaced with —O—, —SO ₂ — or —CO— and is included in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group. A hydrogen atom may be replaced by a hydroxy group or a fluorine atom, and ja represents an integer of 0 to 4).

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Examples of alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, norbornyl and adamantyl groups. The alicyclic hydrocarbon group may have a chain hydrocarbon group, such as a methylcyclohexyl group and a dimethylcyclohexyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3-12, more preferably 3-10.
Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms (tolyl group, xylyl group, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and carbon An aromatic hydrocarbon group having an alicyclic hydrocarbon group of number 3 to 18 (p-adamantylphenyl group, p-cyclohexylphenyl group, etc.) is preferred. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-14, more preferably 6-10.
Examples of alkyl groups 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. The number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-6, still more preferably 1-4.
Alkyl groups substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Aralkyl groups include benzyl, phenethyl, phenylpropyl, naphthylmethyl and naphthylethyl groups.
The groups in which —CH ₂ — contained in the alkyl group is replaced with —O—, —SO ₂ —, —CO—, etc. include an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, or Groups in which these are combined, and the like are included.
Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. The alkoxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
The alkylsulfonyl group includes a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group and the like. The number of carbon atoms in the alkylsulfonyl group is preferably 1-12, more preferably 1-6, still more preferably 1-4.
Examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl groups. The alkoxycarbonyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
Examples of alkylcarbonyl groups include acetyl group, propionyl group and butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably 2-12, more preferably 2-6, still more preferably 2-4.
The alkylcarbonyloxy group includes, for example, an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2-12, more preferably 2-6, still more preferably 2-4.
Examples of the combined group include, for example, a group in which an alkoxy group and an alkyl group are combined, a group in which an alkoxy group and an alkoxy group are combined, a group in which an alkoxy group and an alkylcarbonyl group are combined, an alkoxy group and an alkylcarbonyloxy group, and and the like.
Examples of groups in which an alkoxy group and an alkyl group are combined include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group and an ethoxymethyl group. The alkoxyalkyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
Groups in which an alkoxy group and an alkoxy group are combined include alkoxyalkoxy groups such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group. The alkoxyalkoxy group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
Groups in which an alkoxy group and an alkylcarbonyl group are combined include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group and an ethoxypropionyl group. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably 3-13, more preferably 3-7, still more preferably 3-5.
Groups in which an alkoxy group and an alkylcarbonyloxy group are combined include alkoxyalkylcarbonyloxy groups such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, and an ethoxypropionyloxy group. The number of carbon atoms in the alkoxyalkylcarbonyloxy group is preferably 3-13, more preferably 3-7, still more preferably 3-5.
Groups in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced with —O—, —SO ₂ —, —CO—, etc. include formulas (Y12) to (Y35), formulas (Y39) to A group represented by (Y43) and the like can be mentioned.

［式（ｗ１－１）～式（ｗ１－２４）中、
該基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい。結合部位は任意の位置である。］ an alicyclic hydrocarbon group for Y ^b1 (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -CO-, -S- or -SO ₂ -); is, among others, an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -CO-, -S- or -SO ₂ - It may be substituted with ), more preferably a group represented by any one of formula (w1-1) ~ formula (w1-24), formula (w1-1) ~ formula (w1-6) and a group represented by any one of formulas (w1-12) to (w1-24) is more preferable, and formulas (w1-1) to (w1-3), formulas ( w1-15) and a group represented by formula (w1-22) are even more preferred.

[In the formulas (w1-1) to (w1-24),
--CH ₂ -- contained in the group may be replaced with --O--, --S--, --CO-- or --SO ₂ --. The binding site can be any position. ]

Y ^b1 is preferably a single bond or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, more preferably a single bond or an optionally substituted carbon number 3 to 20 alicyclic hydrocarbon groups, more preferably a single bond or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, still more preferably having a substituent a cyclohexanediyl group optionally having a substituent, an adamantanediyl group optionally having a substituent, a norbornanediyl group optionally having a substituent, an adamantanelactonediyl group optionally having a substituent, or —CH ₂ — which is an optionally substituted norbornane lactone diyl group and constitutes the alicyclic hydrocarbon group, cyclohexanediyl group, adamantanediyl group or norbornanediyl group, is —O—, —S— , —CO— or —SO ₂ —.
The substituents that Y ^b1 may have include a hydroxy group, a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms optionally substituted by a hydroxy group (the —CH ₂ — contained in the alkyl group is , —O— or —CO—.) or an alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferable, and a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or An alkoxy group having 1 to 6 carbon atoms is more preferred. Halogen atoms, alkyl groups, alkoxy groups, and alicyclic hydrocarbon groups include the same groups as those described above. Among them, a fluorine atom, a hydroxy group, a methyl group and an ethyl group are preferred.

［式（Ｘ１０）中、
Ａｘは、Ｒ^１０が結合した炭素原子と結合する結合種を表し、単結合、エーテル結合、エステル結合及び炭酸エステル結合から構成される群から選択される１種の結合種を表す。
Ａｙは、Ｌ^１０と結合する結合種を表し、単結合、エーテル結合、エステル結合及び炭酸エステル結合から構成される群から選択される１種の結合種を表す。
Ａｘ及びＡｙのどちらかの一方が、単結合である場合、他方は、エーテル結合、エステル結合及び炭酸エステル結合から構成される群から選択される１種であることが好ましい。
Ｒｘは、ハロゲン原子、ヒドロキシ基、炭素数１～６のフッ化アルキル基、炭素数１～１８のアルキル基又は炭素数１～６のアルコキシ基を表す。中でも、フッ素原子、ヨウ素原子、トリフルオロメチル基、メチル基又はエチル基が好ましい。
ｍｘは、０～４のいずれかの整数を表し、０、１又は２が好ましい。ｍｘが２以上の整数の場合、複数のＲｘは互いに同じでも異なっていてもよい。］
フェニレン基におけるＡｙの結合位置は、Ａｘの結合位置に対して、ｍ位又はｐ位であることが好ましく、ｐ位であることがより好ましい。
Ｘ^１０としては、例えば、以下の式（Ｘ^１－１）、式（Ｘ^１－２’）～式（Ｘ^１－７’）及び式（Ｘ^１－８）で表される基が挙げられる。＊は－Ｒ^１０が結合する炭素原子との結合部位を表す。＊＊は、Ｌ^１０との結合部位を表す。

式（Ｘ^１－２’）～式（Ｘ^１－７’）で表される基の具体例としては、以下の基が挙げられる。

なかでも、Ｘ^１０は、単結合又は式（Ｘ^１－１）～式（Ｘ^１－７）のいずれかで表される基であることが好ましく、単結合又は式（Ｘ^１－１）、式（Ｘ^１－３）、式（Ｘ^１－４）及び式（Ｘ^１－５）のいずれかで表される基であることがより好ましく、単結合、式（Ｘ^１－１）で表される基、式（Ｘ^１－４）で表される基又は式（Ｘ^１－５）で表される基であることがさらに好ましい。 The halogen atom for R ¹⁰ includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The alkyl group for R ¹⁰ includes the same groups as those for Q ^b1 and Q ^b2 within the range of 1 to 6 carbon atoms.
The alkyl group having 1 to 6 carbon atoms and having a halogen atom for R ¹⁰ is a fluorinated alkyl group having 1 to 6 carbon atoms, a chlorinated alkyl group having 1 to 6 carbon atoms, a brominated alkyl group having 1 to 6 carbon atoms, a carbon Iodide alkyl groups of numbers 1 to 6 and the like can be mentioned. Specifically, the alkyl group having a halogen atom includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluoro hexyl group, perchloromethyl group, perbromomethyl group, periodomethyl group and the like.
The number of carbon atoms in the alkyl group, alkyl fluoride group, alkyl chloride group, alkyl bromide group, and alkyl iodide group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2. be.
R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom or a methyl group, still more A methyl group is preferred.
When X ¹⁰ is a group represented by *-Ax-Ph-Ay-**, it is preferably a linking group represented by the following formula (X10).

[In the formula (X10),
Ax represents a bond type that bonds with the carbon atom to which ^R10 is bonded, and represents one bond type selected from the group consisting of a single bond, an ether bond, an ester bond and a carbonate bond.
Ay represents a bond type that binds to ^L10 , and represents one bond type selected from the group consisting of a single bond, an ether bond, an ester bond and a carbonate bond.
When one of Ax and Ay is a single bond, the other is preferably one selected from the group consisting of an ether bond, an ester bond and a carbonate bond.
Rx represents a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Among them, fluorine atom, iodine atom, trifluoromethyl group, methyl group and ethyl group are preferable.
mx represents an integer of 0 to 4, preferably 0, 1 or 2. When mx is an integer of 2 or more, multiple Rx may be the same or different. ]
The bonding position of Ay in the phenylene group is preferably m-position or p-position, more preferably p-position, with respect to the bonding position of Ax.
Examples of X ¹⁰ include groups represented by the following formulas (X ¹ -1), formulas (X ¹ -2′) to (X ¹ -7′) and formulas (X ¹ -8). . * represents the binding site to the carbon atom to which ^-R10 is bound. ** represents the binding site with ^L10 .

Specific examples of the groups represented by formulas (X ¹ -2′) to (X ¹ -7′) include the following groups.

Among them, X ¹⁰ is preferably a single bond or a group represented by any one of formulas (X ¹ -1) to (X ¹ -7), and a single bond or formula (X ¹ -1), It is more preferably a group represented by any one of formula (X ^1-3 ), formula (X ^1-4 ) and formula (X ^1-5 ), a single bond represented by formula (X ^1-1 ) is more preferably a group represented by formula (X ¹ -4) or a group represented by formula (X ¹ -5).

The hydrocarbon group having 1 to 36 carbon atoms of L ¹⁰ includes a divalent aliphatic hydrocarbon group (alkanediyl group, alkenediyl group, divalent chain hydrocarbon group such as alkynediyl group and divalent alicyclic hydrocarbon groups), divalent aromatic hydrocarbon groups, and the like, and divalent hydrocarbon groups in which two or more of these groups are combined may be used.

具体的に、単環式の２価の脂環式炭化水素基としては、シクロブタン－１，３－ジイル基、シクロペンタン－１，３－ジイル基、シクロヘキサン－１，４－ジイル基、シクロヘキセン－３，６－ジイル基、シクロオクタン－１，５－ジイル基等の単環式シクロアルカンジイル基が挙げられ、多環式の２価の脂環式炭化水素基としては、ノルボルナン－１，４－ジイル基、ノルボルナン－２，５－ジイル基、５－ノルボルネン－２，３－ジイル基、アダマンタン－１，５－ジイル基、アダマンタン－２，６－ジイル基等の多環式シクロアルカンジイル基が挙げられる。
脂環式炭化水素基の炭素数は、好ましくは３～１８であり、より好ましくは３～１６であり、さらに好ましくは３～１２である。
２価の芳香族炭化水素基としては、フェニレン基、ナフチレン基、アントリレン基、ビフェニレン基、フェナントリレン基等が挙げられる。芳香族炭化水素基の炭素数は、好ましくは６～１８であり、より好ましくは６～１４であり、さらに好ましくは６～１０である。
２種以上を組み合わせた炭化水素基としては、アルカンジイル基と脂環式炭化水素基及び／又は芳香族炭化水素基とを組み合わせた基等が挙げられ、－脂環式炭化水素基－アルカンジイル基－、－アルカンジイル基－脂環式炭化水素基－、－アルカンジイル基－脂環式炭化水素基－アルカンジイル基－、－アルカンジイル基－芳香族炭化水素基－、－芳香族炭化水素基－アルカンジイル基－等が挙げられる。 The alkanediyl groups include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, 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 linear alkanediyl groups such as groups;
ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group can be mentioned.
Alkenediyl groups include ethenediyl, propenediyl, isopropenediyl, butenediyl, isobutenediyl, tert-butenediyl, pentenediyl, hexenediyl, heptenediyl, octenediyl, isooctenediyl, and nonenediyl groups. .
The alkynediyl group includes ethynediyl, propynediyl, isopropynediyl, butynediyl, isobutynediyl, tert-butynediyl, pentynediyl, hexynediyl, octynediyl, nonynediyl, and the like.
The chain hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 1 to 9 carbon atoms, still more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3.
The divalent alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic. Examples of the divalent alicyclic hydrocarbon group include groups represented below. The binding site can be at any position.

Specifically, the monocyclic divalent alicyclic hydrocarbon group includes a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclohexene- monocyclic cycloalkanediyl groups such as 3,6-diyl group and cyclooctane-1,5-diyl group; Polycyclic cycloalkanediyl groups such as -diyl group, norbornane-2,5-diyl group, 5-norbornene-2,3-diyl group, adamantane-1,5-diyl group and adamantane-2,6-diyl group are mentioned.
The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and still more preferably 3 to 12 carbon atoms.
The divalent aromatic hydrocarbon group includes a phenylene group, naphthylene group, anthrylene group, biphenylene group, phenanthrylene group and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, still more preferably 6-10.
Hydrocarbon groups in which two or more types are combined include groups in which an alkanediyl group and an alicyclic hydrocarbon group and/or an aromatic hydrocarbon group are combined, and the like, - alicyclic hydrocarbon group - alkanediyl group -, - alkanediyl group - alicyclic hydrocarbon group -, - alkanediyl group - alicyclic hydrocarbon group - alkanediyl group -, - alkanediyl group - aromatic hydrocarbon group -, - aromatic hydrocarbon group--alkanediyl group--and the like.

—CH ₂ — contained in the hydrocarbon group having 1 to 36 carbon atoms in L ¹⁰ may be replaced with —O—, —S—, —CO— or —SO ₂ —.
When the hydrocarbon group having 1 to 36 carbon atoms in L ¹⁰ has a substituent, or —CH ₂ — contained in the hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ — If there is, the number of carbon atoms before the substitution is the number of carbon atoms in the hydrocarbon group.
The group in which —CH ₂ — contained in the hydrocarbon group is replaced by —O—, —S—, —SO ₂ — or —CO— includes a hydroxy group (the —CH ₂ — contained in the methyl group, -O-), carboxy group (group in which -CH ₂ -CH ₂ - contained in the ethyl group is replaced by -O-CO-), thiol group (-CH ₂ contained in the methyl group - is replaced by -S-), carbonyl group (group in which -CH ₂ - contained in the methylene group is replaced by -CO-), sulfonyl group (group in which -CH ₂ - contained in the methylene group is , a group substituted for -SO ₂ -), an oxy group (a group substituted -O- for -CH ₂ - contained in a methylene group), a thio group (a group substituted for -CH ₂ - contained in a methylene group, -S- substituted), alkoxy group (group in which -CH ₂ - at any position contained in the alkyl group is substituted with -O-), alkoxycarbonyl group (any position contained in the alkyl group of —CH ₂ —CH ₂ — is replaced with —O—CO—), an alkylcarbonyl group (a group in which —CH ₂ — at any position in an alkyl group is replaced with —CO—), Alkylcarbonyloxy group (a group in which —CH ₂ —CH ₂ — at any position in the alkyl group is replaced with —CO—O-), alkanediyloxy group (any position in the alkanediyl group -CH ₂ - is replaced with -O-), alkanediyloxycarbonyl group (any position of -CH ₂ -CH ₂ - contained in the alkanediyl group is replaced with -O-CO- group), alkanediylcarbonyl group (a group in which —CH ₂ — at any position contained in the alkanediyl group is replaced with —CO—), alkanediylcarbonyloxy group (any position contained in the alkanediyl group of —CH ₂ —CH ₂ — is replaced with —CO—O—), alkylthio group (group in which —CH ₂ — at any position in the alkyl group is replaced with —S—), alkyl A sulfonyl group (a group in which —CH ₂ — at any position in an alkyl group is replaced with —SO ₂ —), an alkanediylsulfonyl group (a group in which —CH ₂ — at any position in an alkanediyl group is , a group substituted with -SO ₂ -), an alkanediylthio group (a group in which -CH ₂ - at any position in the alkanediyl group is substituted with -S-), a cycloalkoxy group, a cycloalkylalkoxy group , an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyloxy group, an aromatic hydrocarbon group-carbonyl group, an aromatic hydrocarbon group-oxy group, a combination of two or more of these groups, and the like. .
Alkoxy groups include those having 1 to 35 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, group, decyloxy group, undecyloxy group, and the like. The number of carbon atoms in the alkoxy group is preferably 1 to 17, more preferably 1 to 11, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. is.
An alkoxycarbonyl group, an alkylcarbonyl group and an alkylcarbonyloxy group represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above alkyl group or alkoxy group.
The alkoxycarbonyl group includes alkoxycarbonyl groups having 2 to 35 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl groups. The alkylcarbonyl group includes alkylcarbonyl groups having 2 to 36 carbon atoms, such as acetyl group, propionyl group and butyryl group. The alkylcarbonyloxy group includes alkylcarbonyloxy groups having 2 to 35 carbon atoms, such as acetyloxy, propionyloxy and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group is preferably 2 to 17, more preferably 2 to 11, still more preferably 2 to 6, still more preferably 2 to 4. and even more preferably 2-3.
The alkanediyloxy group includes alkanediyloxy groups having 1 to 35 carbon atoms, such as methyleneoxy, ethyleneoxy, propanediyloxy, butanediyloxy, and pentanediyloxy groups. The number of carbon atoms in the alkanediyloxy group is preferably 1 to 17, more preferably 1 to 11, still more preferably 1 to 6, even more preferably 1 to 4, still more preferably 1 ~3.
The alkanediyloxycarbonyl group includes an alkanediyloxycarbonyl group having 2 to 35 carbon atoms, such as a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propanediyloxycarbonyl group, a butanediyloxycarbonyl group, and the like. . The alkanediylcarbonyl group includes alkanediylcarbonyl groups having 2 to 36 carbon atoms, such as methylenecarbonyl, ethylenecarbonyl, propanediylcarbonyl, butanediylcarbonyl and pentanediylcarbonyl groups. The alkanediylcarbonyloxy group includes an alkanediylcarbonyloxy group having 2 to 35 carbon atoms, such as a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propanediylcarbonyloxy group, a butanediylcarbonyloxy group, and the like. . The number of carbon atoms in the alkanediyloxycarbonyl group, alkanediylcarbonyl group, and alkanediylcarbonyloxy group is preferably 2 to 17, more preferably 2 to 11, still more preferably 2 to 6, and still more preferably. is 2-4, and even more preferably 2-3.
The alkylthio group includes alkylthio groups having 1 to 35 carbon atoms, such as methylthio, ethylthio and propylthio groups. The number of carbon atoms in the alkylthio group is preferably 1 to 17, more preferably 1 to 11, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. is.
The alkylsulfonyl group includes alkylsulfonyl groups having 1 to 35 carbon atoms, such as methylsulfonyl, ethylsulfonyl and propylsulfonyl groups. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 17, more preferably 1 to 11, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3.
The alkanediylsulfonyl group includes an alkanediylsulfonyl group having 1 to 35 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, a propylenesulfonyl group and the like. The number of carbon atoms in the alkanediylsulfonyl group is preferably 1 to 17, more preferably 1 to 11, still more preferably 1 to 6, even more preferably 1 to 4, still more preferably 1 ~3.
The alkanediylthio group includes alkanediylthio groups having 1 to 35 carbon atoms, such as methylenethio, ethylenethio and propylenethio groups. The number of carbon atoms in the alkanediylthio group is preferably 1 to 17, more preferably 1 to 11, still more preferably 1 to 6, still more preferably 1 to 4, and still more preferably 1 ~3.
The cycloalkoxy group includes a cycloalkoxy group having 3 to 35 carbon atoms, such as a cyclohexyloxy group. The cycloalkylalkoxy group includes a cycloalkylalkoxy group having 4 to 35 carbon atoms, such as a cyclohexylmethoxy group. The alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having 2 to 34 carbon atoms, such as a butoxycarbonyloxy group. The cycloalkoxy group and cycloalkylalkoxy group preferably have 3 to 17 carbon atoms, more preferably 3 to 11 carbon atoms, and still more preferably 3 to 6 carbon atoms. The number of carbon atoms in the alkoxycarbonyloxy group is preferably 2 to 17, more preferably 2 to 11, still more preferably 2 to 6, still more preferably 2 to 4, still more preferably 2 ~3. The aromatic hydrocarbon group-carbonyloxy group includes an aromatic hydrocarbon group having 7 to 35 carbon atoms-carbonyloxy group, such as benzoyloxy group. The aromatic hydrocarbon group-carbonyl group includes an aromatic hydrocarbon group having 7 to 36 carbon atoms-carbonyl group, such as benzoyl group. The aromatic hydrocarbon group-oxy group includes an aromatic hydrocarbon group-oxy group having 6 to 35 carbon atoms, such as a phenyloxy group.
In addition, the groups in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ — include the groups represented below. . -O- or -CO- in the groups represented below may be replaced with -S- or -SO ₂ -. The binding site can be at any position.

Substituents which the hydrocarbon group of L ¹⁰ may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (the —CH ₂ — contained in the alkyl group is —O— or — may be substituted with CO—) and groups in which these are combined.
L ¹⁰ is substantially a _hydroxy group, a carboxy group, an ^alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl can have substituents such as groups, alkylcarbonyloxy groups, and the like.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
The hydrocarbon group having 1 to 36 carbon atoms for L ¹⁰ may have one substituent or multiple substituents.

L ¹⁰ is a single bond, an alkanediyl group having 1 to 6 carbon atoms (with the proviso that —CH ₂ — contained in the alkanediyl group may be replaced with —O— or —CO—); 3 to 18 cyclic hydrocarbon groups (provided that the cyclic hydrocarbon group may have a substituent, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, —S—, — SO ₂ — or —CO—) or a group formed by combining an alkanediyl group having 1 to 6 carbon atoms and a cyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the cyclic hydrocarbon group may have a substituent, -CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-, and -CH ₂ - contained in the cyclic hydrocarbon group may be substituted with —O—, —S—, —SO ₂ — or —CO—), and is preferably a single bond and an alkanediyl group having 1 to 4 carbon atoms (provided that the alkanediyl —CH ₂ — contained in the group may be replaced with —O— or —CO—), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the alicyclic hydrocarbon group contains (-CH ₂ -) may be replaced with -O-, -S-, -SO ₂ - or -CO-), optionally substituted aromatic hydrocarbons having 6 to 18 carbon atoms. a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (with the proviso that —CH ₂ — contained in the alkanediyl group is —O— or may be replaced with -CO-, and -CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -SO ₂ - or -CO-). or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (with the proviso that —CH ₂ — may be substituted with —O— or —CO—), and is more preferably a single bond and an alkanediyl group having 1 to 4 carbon atoms (with the proviso that —CH ₂ — contained in the alkanediyl group may be replaced with —O— or —CO—), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (with the proviso that —CH ₂ — contained in the alicyclic hydrocarbon group is — O— or —CO—.), a phenylene group which may have a substituent, an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. Groups to be combined (with the proviso that —CH ₂ — contained in the alkanediyl group may be replaced with —O— or —CO—, and —CH ₂ — contained in the alicyclic hydrocarbon group is -O- or -CO- may be substituted. ) or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and a phenylene group which may have a substituent (with the proviso that —CH ₂ — contained in the alkanediyl group is —O— or —CO is more preferably a single bond or an alkanediyl group having 1 to 4 carbon atoms (with the proviso that —CH ₂ — contained in the alkanediyl group is —O— or —CO - may be substituted.) is even more preferable.

Examples of the anion (I1-a) include the following anions.

In the anions represented by formulas (I1-a-1) to (I1-a-15), the anion in which the methyl group corresponding to R ¹⁰ in formula (I1) is replaced with a hydrogen atom is also an anion (I1-a ) can be cited as a specific example. Among them, anions represented by formulas (I1-a-1) to (I1-a-6) are preferable.

［式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^b4～Ｒ^b6は、それぞれ独立に、炭素数１～３０の鎖式炭化水素基、炭素数３～３６の脂環式炭化水素基又は炭素数６～３６の芳香族炭化水素基を表し、該鎖式炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１～１２のアルコキシ基、炭素数３～１２の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～１８の脂肪族炭化水素基、炭素数２～４のアルキルカルボニル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基、炭素数１～１８の脂肪族炭化水素基、炭素数１～１２のフッ化アルキル基又は炭素数１～１２のアルコキシ基で置換されていてもよい。
Ｒ^b4とＲ^b5とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ハロゲン原子、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のフッ化アルキル基又は炭素数１～１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０～５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^b7は同一でも異なってもよく、ｎ２が２以上のとき、複数のＲ^b8は同一でも異なってもよい。
Ｒ^b9及びＲ^b10は、それぞれ独立に、炭素数１～３６の鎖式炭化水素基又は炭素数３～３６の脂環式炭化水素基を表す。
Ｒ^b9とＲ^b10とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b11は、水素原子、炭素数１～３６の鎖式炭化水素基、炭素数３～３６の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表す。
Ｒ^b12は、炭素数１～１２の鎖式炭化水素基、炭素数３～１８の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表し、該鎖式炭化水素基に含まれる水素原子は、炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１～１２のアルコキシ基又は炭素数１～１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^b11とＲ^b12とは、互いに結合してそれらが結合する－ＣＨ－ＣＯ－を含めて環を形成していてもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b13～Ｒ^b18は、それぞれ独立に、ハロゲン原子、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基、炭素数１～１２のフッ化アルキル基又は炭素数１～１２のアルコキシ基を表す。
Ｒ^b13とＲ^b14とは、互いに結合してそれらが結合するベンゼン環と一緒になって硫黄原子を含む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。
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。］
ｕ２が０のとき、ｏ２、ｐ２、ｑ２及びｒ２のうちいずれか１つは１以上であり、Ｒ^b13～Ｒ^b1６のうち少なくとも１つはハロゲン原子であることが好ましく、ｕ２が１のとき、ｏ２、ｐ２、ｓ２、ｔ２、ｑ２及びｒ２のうちいずれか１つは１以上であり、Ｒ^b13～Ｒ^b18のうち少なくとも１つはハロゲン原子であることが好ましい。
さらに、ｕ２が０のとき、ｒ２は１以上であることが好ましく、１であることがさらに好ましい。また、ｕ２が０、かつ、ｒ２が１以上のとき、Ｒ^ｂ１６がハロゲン原子であることが好ましい。 Organic cations of Z1 ⁺ include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specifically, a cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" etc. depending on the formula number) is mentioned.

[In formulas (b2-1) to (b2-4),
R ^b4 to R ^b6 each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms; The hydrogen atom contained in the chain hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. It may be substituted, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. It may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or a carbon It may be substituted with 1 to 12 alkoxy groups.
R ^b4 and R ^b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be —O—, —S— or -CO- may be substituted.
R ^b7 and R ^b8 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. .
m2 and n2 each independently represent an integer of 0 to 5;
When m2 is 2 or more, multiple R ^b7 may be the same or different, and when n2 is 2 or more, multiple 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 to each other to form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be —O—, —S— or -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 the chain hydrocarbon group The hydrogen atoms contained may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are alkoxy groups having 1 to 12 carbon atoms or 1 carbon atoms. It may be optionally 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 may be —O—, —S - or -CO- may be substituted.
R ^b13 to R ^b18 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. .
R ^b13 and R ^b14 may be bonded to each other to form a sulfur atom-containing ring together with the benzene ring to which they are bonded, and —CH ₂ — contained in the ring may be —O—, -S- or -CO- may be substituted.
L ^b31 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5;
q2 and r2 each independently represent an integer of 0 to 4;
u2 represents 0 or 1;
When o2 is 2 or more, multiple R ^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, the plurality of R ^b16 are the same or different; when s2 is 2 or more, the plurality of R ^b17 are the same or different; when t2 is 2 or more, the plurality of R ^b18 are the same or different; different. ]
When u2 is 0, any one of o2, p2, q2 and r2 is 1 or more, and at least one of R ^b13 to R ^b16 is preferably a halogen atom; Any one of o2, p2, s2, t2, q2 and r2 is 1 or more, and at least one of R ^b13 to R ^b18 is preferably a halogen atom.
Furthermore, when u2 is 0, r2 is preferably 1 or more, more preferably 1. Further, when u2 is 0 and r2 is 1 or more, ^Rb16 is preferably a halogen atom.

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.
Chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. mentioned.
In particular, chain hydrocarbon groups of R ^b9 to R ^b12 preferably have 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo Cycloalkyl groups such as a heptyl group, a cyclooctyl group, and a cyclodecyl group can be mentioned. The polycyclic alicyclic hydrocarbon group includes decahydronaphthyl group, adamantyl group, norbornyl group and the following groups.

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

Alicyclic hydrocarbon groups in which hydrogen atoms are substituted with aliphatic hydrocarbon groups include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, and 2-ethyladamantan-2-yl group. , 2-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 carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.
A fluorinated alkyl group represents an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, and includes a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluorobutyl group, and the like. The number of carbon atoms in the fluorinated alkyl group is preferably 1-9, more preferably 1-6, still more preferably 1-4.

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

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

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

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

カチオン（ｂ２－２）としては、以下のカチオンが挙げられる。

カチオン（ｂ２－３）としては、以下のカチオンが挙げられる。

カチオン（ｂ２－４）としては、以下のカチオンが挙げられる。

Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferred.
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 salt (I1-s) is a combination of the aforementioned anion (I1-a) and the aforementioned organic cation Z1 ⁺ (cation (I1-c)), which can be combined in any desired manner. The salt (I1-s) is preferably an anion represented by any one of formulas (I1-a-1) to (I1-a-6), a cation (b2-1), a cation (b2- 2), cation (b2-3) or combination with cation (b2-4).

中でも、塩（Ｉ１－ｓ）は、塩（Ｉ１－ｓ－１）～塩（Ｉ１－ｓ－６）、塩（Ｉ１－ｓ－１５）～塩（Ｉ１－ｓ－２０）、塩（Ｉ１－ｓ－２９）～塩（Ｉ１－ｓ－３４）、塩（Ｉ１－ｓ－４３）～塩（Ｉ１－ｓ－４８）、塩（Ｉ１－ｓ－５７）～塩（Ｉ１－ｓ－６２）、塩（Ｉ１－ｓ－７１）～塩（Ｉ１－ｓ－７６）、塩（Ｉ１－ｓ－８５）～塩（Ｉ１－ｓ－９０）、塩（Ｉ１－ｓ－９９）～塩（Ｉ１－ｓ－１０４）、塩（Ｉ１－ｓ－１１３）～塩（Ｉ１－ｓ－１１８）、塩（Ｉ１－ｓ－１２７）～塩（Ｉ１－ｓ－１３２）、塩（Ｉ１－ｓ－１４１）～塩（Ｉ１－ｓ－１４６）、塩（Ｉ１－ｓ－１５５）～塩（Ｉ１－ｓ－１６０）、塩（Ｉ１－ｓ－１６９）～塩（Ｉ１－ｓ－１７４）、塩（Ｉ１－ｓ－１８３）～塩（Ｉ１－ｓ－１８８）、塩（Ｉ１－ｓ－１９７）～塩（Ｉ１－ｓ－２０２）、塩（Ｉ１－ｓ－２１１）～塩（Ｉ１－ｓ－２１６）、塩（Ｉ１－ｓ－２２５）～塩（Ｉ１－ｓ－２４０）であることが好ましい。 Salts (I1-s) include salts listed in Table 1. In the table below, each code represents the code attached to the structure representing the anion or cation described above, and "~" represents the combination of salt (I1-s) and anion (I1-a) or cation (I1-c). Indicates that each corresponds. For example, salt (I1-s-1) means a salt consisting of an anion represented by formula (I1-a-1) and a cation represented by formula (b2-c-1), and the following salts represents

Among them, salt (I1-s) includes salt (I1-s-1) to salt (I1-s-6), salt (I1-s-15) to salt (I1-s-20), salt (I1- s-29) to salt (I1-s-34), salt (I1-s-43) to salt (I1-s-48), salt (I1-s-57) to salt (I1-s-62), Salt (I1-s-71) ~ Salt (I1-s-76), Salt (I1-s-85) ~ Salt (I1-s-90), Salt (I1-s-99) ~ Salt (I1-s -104), salt (I1-s-113) to salt (I1-s-118), salt (I1-s-127) to salt (I1-s-132), salt (I1-s-141) to salt (I1-s-146), salt (I1-s-155) to salt (I1-s-160), salt (I1-s-169) to salt (I1-s-174), salt (I1-s- 183) ~ Salt (I1-s-188), Salt (I1-s-197) ~ Salt (I1-s-202), Salt (I1-s-211) ~ Salt (I1-s-216), Salt ( I1-s-225) to salt (I1-s-240).

The content of the structural unit (I1) may be 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 0.8 mol, based on the total structural units of the resin (A1). % or more, more preferably 1 mol % or more. Further, it is 100 mol % or less, preferably 50 mol % or less, more preferably 30 mol % or less, and still more preferably 10 mol % or less. Specifically, it is 0.1 to 100 mol%, preferably 0.5 to 50 mol%, more preferably 0.8 to 30 mol%, still more preferably 1 to 10 mol%. be.

［式（Ｉ２）及び式（Ｉ２－ｓ）中、全ての符号はそれぞれ前記と同じ意味を表す。］ [Resin A2]
Resin A2 contains a structural unit (I2) represented by formula (I2).
<Structural unit (I2)>
Structural unit (I2) is derived from, for example, a carboxylate represented by formula (I2-s) capable of functioning as a carboxylic acid generator (hereinafter sometimes referred to as carboxylate (I2-s)). , in which the double bond of CH ₂ ═C—R ²⁰ contained in the carboxylate (I2-s) is cleaved.
Of the carboxylates (I2-s), the negatively charged side is sometimes referred to as "anion (I2-a)" and the positively charged side is sometimes referred to as "cation (I2-c)".

[In formulas (I2) and (I2-s), all symbols have the same meanings as above. ]

In the formulas (I2) and (I2-s), the hydrocarbon group represented by X ⁰ includes an aliphatic hydrocarbon group (a chain hydrocarbon group such as an alkanediyl group, an alkenediyl group, an alkynediyl group, and an alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups in which these are combined. -CH ₂ - contained in the hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -. In the hydrocarbon group, the atoms adjacent to CO ₂ ^— are preferably carbon atoms, and in the aliphatic hydrocarbon groups, the atoms adjacent to CO ₂ ^— are more preferably carbon atoms. Also, the carbon atom is not substituted with a fluorine atom.
The alkanediyl groups include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, 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 linear alkanediyl groups such as groups;
ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group can be mentioned.
Alkenediyl groups include ethenediyl, propenediyl, isopropenediyl, butenediyl, isobutenediyl, tert-butenediyl, pentenediyl, hexenediyl, heptenediyl, octenediyl, isooctenediyl, and nonenediyl groups. .
Examples of alkynediyl groups include ethynediyl, propynediyl, isopropynediyl, butynediyl, isobutynediyl, tert-butynediyl, pentynediyl, hexynediyl, octynediyl, and nonynediyl groups.
The chain hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 9 carbon atoms, still more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4.
As a group in which —CH ₂ — contained in a chain hydrocarbon group is replaced by —O—, —S—, —CO— or —SO ₂ —, among the hydrocarbon groups of the hydrocarbon groups of L ¹⁰ , chain Examples thereof include the same groups in which —CH ₂ — contained in the hydrocarbon group of the formula is replaced with —O—, —S—, —SO ₂ — or —CO—.
The substitution in the alkenediyl group and the alkynediyl group may include a carbon-carbon double bond or a carbon-carbon triple bond at any position in the examples of the substitution in the alkanediyl group described above.

具体的に、単環式の２価の脂環式炭化水素基としては、シクロブタン－１，３－ジイル基、シクロペンタン－１，３－ジイル基、シクロヘキサン－１，４－ジイル基、シクロヘキセン－３，６－ジイル基、シクロオクタン－１，５－ジイル基等の単環式シクロアルカンジイル基が挙げられ、多環式の２価の脂環式炭化水素基としては、ノルボルナン－１，４－ジイル基、ノルボルナン－２，５－ジイル基、５－ノルボルネン－２，３－ジイル基、アダマンタン－１，５－ジイル基、アダマンタン－２，６－ジイル基等の多環式シクロアルカンジイル基が挙げられる。
脂環式炭化水素基の炭素数は、好ましくは３～３６であり、より好ましくは３～２４であり、さらに好ましくは３～１８であり、より一層好ましくは３～１６であり、さらに一層好ましくは３～１２である。
脂環式炭化水素基に含まれる－ＣＨ₂－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わった基としては、具体的に、下記の基等が挙げられる。結合部位は任意の位置とすることができる。

脂環式炭化水素基としては、式（ｙ１）～式（ｙ１１）、式（ｙ４４）～式（ｙ４８）、式（ｙ５９）～式（ｙ６１）のいずれかで表される基が好ましく、式（ｙ３）、式（ｙ４）、式（ｙ９）、式（ｙ１１）のいずれかで表される基がより好ましい。
脂環式炭化水素基に含まれる－ＣＨ₂－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わった基としては、式（ｙ１２）～式（ｙ２０）、式（ｙ２６）、式（ｙ２７）、式（ｙ３０）、式（ｙ３１）、式（ｙ３９）～式（ｙ４３）、式（ｙ４９）～式（ｙ７１）のいずれかで表される基が好ましく、式（ｙ１４）、式（ｙ１５）、式（ｙ１６）、式（ｙ２０）、式（ｙ２６）、式（ｙ２７）、式（ｙ３０）、式（ｙ３１）、式（ｙ３９）、式（ｙ４０）、式（ｙ４２）、式（ｙ４３）、式（ｙ４９）～式（ｙ５８）、式（ｙ６２）～式（ｙ７１）のいずれかで表される基がより好ましい。 The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic. Examples of the alicyclic hydrocarbon group include groups represented below. The binding site can be at any position.

Specifically, the monocyclic divalent alicyclic hydrocarbon group includes a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclohexene- monocyclic cycloalkanediyl groups such as 3,6-diyl group and cyclooctane-1,5-diyl group; Polycyclic cycloalkanediyl groups such as -diyl group, norbornane-2,5-diyl group, 5-norbornene-2,3-diyl group, adamantane-1,5-diyl group and adamantane-2,6-diyl group are mentioned.
The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36, more preferably 3 to 24, even more preferably 3 to 18, still more preferably 3 to 16, still more preferably is 3-12.
Specific examples of the group in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ — include the following groups. The binding site can be at any position.

The alicyclic hydrocarbon group is preferably a group represented by any one of formulas (y1) to (y11), formulas (y44) to (y48), and formulas (y59) to (y61). A group represented by any one of formula (y3), formula (y4), formula (y9), and formula (y11) is more preferred.
Groups in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ — include formulas (y12) to (y20), formula ( y26), formula (y27), formula (y30), formula (y31), formula (y39) ~ formula (y43), formula (y49) ~ formula (y71) is preferably a group represented by formula ( y14), formula (y15), formula (y16), formula (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (y39), formula (y40), formula ( y42), formula (y43), formulas (y49) to (y58), and groups represented by formulas (y62) to (y71) are more preferred.

The aromatic hydrocarbon group includes phenylene group, naphthylene group, anthrylene group, biphenylene group, phenanthrylene group and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, even more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6-10.
Hydrocarbon groups in which two or more types are combined include groups in which an alkanediyl group and an alicyclic hydrocarbon group and/or an aromatic hydrocarbon group are combined, and the like, - alicyclic hydrocarbon group - alkanediyl group -, - alkanediyl group - alicyclic hydrocarbon group -, - alkanediyl group - alicyclic hydrocarbon group - alkanediyl group -, - alkanediyl group - aromatic hydrocarbon group -, - aromatic hydrocarbon group--alkanediyl group--and the like.
When —CH ₂ — contained in the hydrocarbon group represented by X ⁰ is replaced with —O—, —S—, —CO— or —SO ₂ —, the number of carbon atoms before the replacement is referred to as the number of carbon atoms in the hydrocarbon group. is the total carbon number of Moreover, when a substituent is bonded to the hydrocarbon group represented by X ⁰ , the number of carbon atoms before substitution is taken as the total number of carbon atoms of the 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、ナフチル基等のアリール基が挙げられる。 The hydrocarbon group represented by X ⁰ may have one or more substituents.
Examples of substituents include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and an alkylcarbonyl group having 2 to 13 carbon atoms. , an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a combination thereof.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group and nonyl group.
Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy. group, dodecyloxy group, and the like.
An alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms and an alkylcarbonyloxy group having 2 to 13 carbon atoms are groups in which a carbonyl group or a carbonyloxy group is bonded to the alkyl group or alkoxy group described above. represents
The alkoxycarbonyl group having 2 to 13 carbon atoms includes methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like, and the alkylcarbonyl group having 2 to 13 carbon atoms includes acetyl group, propionyl group, butyryl group and the like. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include acetyloxy group, propionyloxy group and butyryloxy group.
Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include groups shown below. ** represents the binding site with ^X0 .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as phenyl group and naphthyl group.

Examples of the combined group include a group obtained by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group obtained by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and carbon A group obtained by combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkyl group having 1 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms. and a group in which a halogen atom and an alkyl group having 1 to 12 carbon atoms are combined.
Groups in which a hydroxy group and an alkyl group having 1 to 12 carbon atoms are combined include a hydroxyalkyl group having 1 to 12 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group.
Examples of groups 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, and a carbon number such as a tolyl group and a xylyl group. 7-22 alkylaryl groups are included.
Examples of groups in which an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined include a cyclohexylphenyl group and the like.
Examples of groups in which an alkyl group having 1 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms are combined include a cycloalkylalkyl group having 4 to 24 carbon atoms such as a cyclohexylmethyl group, a methylcyclohexyl group and the like. Examples thereof include alkylcycloalkyl groups having 4 to 24 carbon atoms.
Groups in which a halogen atom and an alkyl group having 1 to 12 carbon atoms are combined include a perfluoroalkyl group having 1 to 12 carbon atoms such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a nonafluorobutyl group. are mentioned.

The hydrocarbon group represented by X ⁰ is preferably an optionally substituted aliphatic hydrocarbon group having 1 to 72 carbon atoms (-CH ₂ - contained in the aliphatic hydrocarbon group is —O—, —S—, —CO— or —SO ₂ —.) or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent,
More preferably, an optionally substituted chain hydrocarbon group having 1 to 18 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO- ), an optionally substituted alicyclic hydrocarbon group having 3 to 36 carbon atoms (the —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—, —CO— or —SO ₂ —.), an optionally substituted C 3-36 alicyclic hydrocarbon group and an optionally substituted C 1- 18 chain hydrocarbon group (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ - --CH ₂ -- contained in the chain hydrocarbon group may be replaced with --O-- or --CO--), an optionally substituted aromatic hydrocarbon group having 6 to 36 carbon atoms; A group obtained by combining a hydrogen group or an optionally substituted aromatic hydrocarbon group having 6 to 36 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms which may have a substituent (the chain —CH ₂ — contained in the hydrocarbon group of the formula may be replaced with —O— or —CO—.),

More preferably, *-chain hydrocarbon group-, *-alicyclic hydrocarbon group-, *-group combining an alicyclic hydrocarbon group and a chain hydrocarbon group-, *-alicyclic carbonization Hydrogen group-chain hydrocarbon group-, *-chain hydrocarbon group-alicyclic hydrocarbon group-, *-group combining alicyclic hydrocarbon group and chain hydrocarbon group-chain hydrocarbon group Group -, *-chain hydrocarbon group-group combining alicyclic hydrocarbon group and chain hydrocarbon group-, *-aromatic hydrocarbon group-, *-chain hydrocarbon group-aromatic hydrocarbon hydrogen group-, *-aromatic hydrocarbon group-chain hydrocarbon group-, *-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-, *-chain hydrocarbon group- Alicyclic hydrocarbon group-chain hydrocarbon group-, *-group combining alicyclic hydrocarbon group and chain hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-,*- chain hydrocarbon group-group combining alicyclic hydrocarbon group and chain hydrocarbon group-chain hydrocarbon group-, *-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon Group - alicyclic hydrocarbon group - or * - chain hydrocarbon group - group combining alicyclic hydrocarbon group and chain hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group —(—CH ₂ — contained in the alicyclic hydrocarbon group may be replaced with —O—, —S—, —CO— or —SO ₂ —, and contained in the chain hydrocarbon group —CH ₂ — may be replaced by —O— or —CO—, and the alicyclic hydrocarbon group, the aromatic hydrocarbon group and the chain hydrocarbon group may have a substituent. * represents the bonding site with the carbon atom of —COO ^— .),
More preferably, *-alicyclic hydrocarbon group- (-CH ₂ - contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO ₂ -. and the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom.* represents the bonding site with the carbon atom of —COO ^— .), *—alicyclic hydrocarbon group. The group -chain hydrocarbon group- (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -, and the chain —CH ₂ — contained in the formula hydrocarbon group may be replaced with —O— or —CO—, and the alicyclic hydrocarbon group and the chain hydrocarbon group have a fluorine atom or a hydroxy group. * represents the bonding site to the carbon atom of ^—COO— ), *—chain hydrocarbon group—alicyclic hydrocarbon group—(—CH ₂ contained in the chain hydrocarbon group — may be replaced with —O— or —CO—, and —CH ₂ — contained in the alicyclic hydrocarbon group may be —O—, —S—, —CO— or —SO ₂ —. The chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group.* represents the bonding site with the carbon atom of —COO ^— .) , *—aromatic hydrocarbon group— (the aromatic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding site with the carbon atom of —COO ^— .) or *—chain Formula hydrocarbon group -aromatic hydrocarbon group- (-CH ₂ - contained in said chain hydrocarbon group may be replaced with -O- or -CO-, said chain hydrocarbon group and said aromatic group hydrocarbon group may have a fluorine atom or a hydroxy group.* represents the bonding site with the carbon atom of ^-COO- ),

Even more preferably, *-monocyclic alicyclic hydrocarbon group- (-CH ₂ - contained in the monocyclic alicyclic hydrocarbon group is -O-, -S-, -CO- or —SO ₂ —, and the monocyclic alicyclic hydrocarbon group may have a hydroxyl group or a fluorine atom.* is the bonding site with the carbon atom of —COO ^— ), *—polycyclic alicyclic hydrocarbon group— (—CH ₂ — contained in the polycyclic alicyclic hydrocarbon group is —O—, —S—, —CO— or —SO ₂ —, and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom.* is the bonding site with the carbon atom of —COO ^— ), *—polycyclic alicyclic hydrocarbon group—chain hydrocarbon group—(—CH ₂ — contained in the polycyclic alicyclic hydrocarbon group is —O—, — S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—, and the polycyclic The alicyclic hydrocarbon group and the chain hydrocarbon group of the formula may have a fluorine atom or a hydroxy group.* represents the bonding site with the carbon atom of —COO ^— .), *—chain formula Hydrocarbon group—polycyclic alicyclic hydrocarbon group—(—CH ₂ — contained in said chain hydrocarbon group may be replaced with —O— or —CO—, and said polycyclic —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced with —O—, —S—, —CO— or —SO ₂ —, and the chain hydrocarbon group and the polycyclic The alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group.* represents the bonding site with the carbon atom of ^—COO— .), *—aromatic hydrocarbon group—(the aromatic hydrocarbon The hydrogen group may have a fluorine atom or a hydroxy group.* represents the bonding site with the carbon atom of ^—COO— .) or *—chain hydrocarbon group—aromatic hydrocarbon group—(the chain —CH ₂ — contained in the formula hydrocarbon group may be replaced with —O— or —CO—, and the chain hydrocarbon group and the aromatic hydrocarbon group have a fluorine atom or a hydroxy group. * represents the bonding site with the carbon atom of —COO ^— .
However, in the above groups, the atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom.

［式（ｗ１－１）～式（ｗ１－２８）中、
該基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－に置き換わっていてもよい。結合部位は任意の位置である。］
より具体的に、上記の単環式の脂環式炭化水素基は、炭素数５もしくは６のシクロアルカンジイル基（該シクロアルカンジイル基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。）であることが好ましく、上記の多環式の脂環式炭化水素基は、アダマンタンジイル基、ノルボルナンジイル基、アダマンタンラクトンジイル基、ノルボルナンラクトンジイル基、又は、アダマンタンジイル基と該アダマンタンジイル基とスピロで結合した炭素数５もしくは６のシクロアルカンジイル基（該アダマンタンジイル基、ノルボルナンジイル基及びシクロアルカンジイル基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。）であることが好ましく、上記の芳香族炭化水素基は、フェニレン基であることが好ましい。ここで、該アダマンタンジイル基及びノルボルナンジイル基に含まれる－ＣＨ_２－ＣＨ_２－は、－Ｏ－ＣＯ－に置き換わっていてもよく、該シクロアルカンジイル基は、アセタール環であってもよい。
上記の基において、鎖式炭化水素基は、炭素数１～１２の鎖式炭化水素基（該鎖式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。）であることが好ましく、炭素数１～８の鎖式炭化水素基（該鎖式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。）であることがより好ましく、炭素数１～６のアルカンジイル基（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。）であることがさらに好ましい。また、フッ素原子を有することも好ましい。
上記の基において、置換基は、フッ素原子、ヒドロキシ基、炭素数１～４のアルキル基、炭素数３～１０の脂環式炭化水素基又はこれらを組み合わせた基であることが好ましく、フッ素原子、ヒドロキシ基又は炭素数１～４のペルフルオロアルキル基であることがより好ましい。 In the above groups, the alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 24 carbon atoms, still more preferably 3 to 18 carbon atoms, and still more preferably 3 to 16 carbon atoms. Yes, and even more preferably between 3 and 12. The chain hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 9 carbon atoms, still more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, even more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6-10.
In the above groups, the alicyclic hydrocarbon group or aromatic hydrocarbon group is an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms (included in the group- CH ₂ — may be replaced with —O—, —S—, —CO— or —SO ₂ —.), and any one of formulas (w1-1) to (w1-28) It is more preferably a group represented by any of formulas (w1-1) to (w1-6) and formulas (w1-12) to (w1-26). More preferably, formula (w1-1) ~ formula (w1-3), formula (w1-6), formula (w1-15) ~ formula (w1-17), formula (w1-22) and formula (w1 -25) is even more preferred.

[In the formulas (w1-1) to (w1-28),
--CH ₂ -- contained in the group may be replaced with --O--, --S--, --CO-- or --SO ₂ --. The binding site can be any position. ]
More specifically, the above monocyclic alicyclic hydrocarbon group is a cycloalkanediyl group having 5 or 6 carbon atoms (-CH ₂ - contained in the cycloalkanediyl group is -O- or -CO - may be substituted), and the polycyclic alicyclic hydrocarbon group is an adamantanediyl group, a norbornanediyl group, an adamantanelactonediyl group, a norbornanelactonediyl group, or adamantane A cycloalkanediyl group having 5 or 6 carbon atoms spiro-bonded to a diyl group and said adamantanediyl group (-CH ₂ - contained in said adamantanediyl group, norbornanediyl group and cycloalkanediyl group is -O- or - may be substituted with CO—), and the above aromatic hydrocarbon group is preferably a phenylene group. Here, —CH ₂ —CH ₂ — contained in the adamantanediyl group and the norbornanediyl group may be replaced with —O—CO—, and the cycloalkanediyl group may be an acetal ring.
In the above groups, the chain hydrocarbon group is a chain hydrocarbon group having 1 to 12 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO- ), and a chain hydrocarbon group having 1 to 8 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group may be replaced with -O- or -CO- ), and an alkanediyl group having 1 to 6 carbon atoms (-CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-). is more preferred. Moreover, it is also preferable to have a fluorine atom.
In the above groups, the substituent is preferably a fluorine atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a group combining these. , a hydroxy group, or a perfluoroalkyl group having 1 to 4 carbon atoms.

More specifically, X ⁰ is preferably a single bond or an optionally substituted aliphatic hydrocarbon group having 1 to 72 carbon atoms (-CH _2- may be replaced with -O-, -S-, -CO- or -SO ₂ -) or optionally substituted aromatic hydrocarbon groups having 6 to 36 carbon atoms is a
More preferably, it is a single bond or a chain hydrocarbon group having 1 to 18 carbon atoms optionally having a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group (the chain hydrocarbon group —CH ₂ — contained may be replaced with —O— or —CO—.), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group, optionally having 3 to 36 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -), carbon A group obtained by combining an alicyclic hydrocarbon group of number 3 to 36 with a chain hydrocarbon group of 1 to 18 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, - S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—, and the alicyclic The formula hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group.), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a hydroxy group, or a group obtained by combining an aromatic hydrocarbon group having 6 to 36 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the aromatic hydrocarbon group and the chain hydrocarbon group may contain a fluorine atom, a carbon number may have 1 to 4 perfluoroalkyl groups or hydroxy groups),
More preferably, it is a single bond or a chain hydrocarbon group having 1 to 12 carbon atoms optionally having a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group (the chain hydrocarbon group —CH ₂ — contained may be replaced with —O— or —CO—.), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group having 3 to 18 carbon atoms. (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -), carbon A group obtained by combining an alicyclic hydrocarbon group of 3 to 18 numbers and a chain hydrocarbon group of 1 to 8 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, - S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—, and the alicyclic The formula hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group.), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a hydroxy group, or a group obtained by combining an aromatic hydrocarbon group having 6 to 18 carbon atoms and a chain hydrocarbon group having 1 to 8 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the aromatic hydrocarbon group and the chain hydrocarbon group may contain a fluorine atom, a carbon number may have 1 to 4 perfluoroalkyl groups or hydroxy groups),
more preferably a single bond, an alkanediyl group having 1 to 6 carbon atoms, a cycloalkanediyl group having 5 or 6 carbon atoms, an adamantanediyl group, a norbornanediyl group, an adamantanelactonediyl group, a norbornanelactonediyl group, a phenylene group, a combination of an alkanediyl group having 1 to 6 carbon atoms and a cycloalkanediyl group having 5 or 6 carbon atoms, an adamantanediyl group, a norbornanediyl group or a phenylene group, or an adamantanediyl group and a carbon number of 5 or 6 (-CH ₂ - contained in the alkanediyl group, the cycloalkanediyl group, the adamantanediyl group and the norbornanediyl group is replaced with -O- or -CO- The alkanediyl group, the cycloalkanediyl group, the adamantanediyl group, the norbornanediyl group, the adamantanelactonediyl group, the norbornanelactonediyl group and the phenylene group each contain a fluorine atom and 1 to 1 carbon atoms. may have 4 perfluoroalkyl groups or hydroxy groups),
Still more preferably, a cyclohexanediyl group, an adamantanediyl group, a hydroxyadamantanediyl group, a norbornanelactonediyl group, a group obtained by combining an alkanediyl group having 1 to 6 carbon atoms and an adamantanediyl group (- CH ₂ — may be replaced with —O— or —CO—), a phenylene group, or a hydroxyphenylene group.
However, in the above groups, the atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom.
In addition, X ⁰ includes an alicyclic hydrocarbon group, and the alicyclic hydrocarbon group is a cycloalkanediyl group having 5 or 6 carbon atoms, an adamantanediyl group, a norbornanediyl group, an adamantanelactonediyl group, norbornanelactone A diyl group, or an adamantanediyl group and a cycloalkanediyl group having 5 or 6 carbon atoms spiro-bonded to the adamantanediyl group (the adamantanediyl group, norbornanediyl group and cycloalkanediyl group are fluorine atoms and carbon atoms of 1 -CH ₂ - contained in the adamantanediyl group, norbornanediyl group and cycloalkanediyl group may be replaced with -O- or -CO- good.) is also preferred. Here, —CH ₂ —CH ₂ — contained in the adamantanediyl group and the norbornanediyl group may be replaced with —O—CO—, and the cycloalkanediyl group may be an acetal ring.

R ²⁰ , X ²⁰ and L ²⁰ are each independent of R ¹⁰ , X ¹⁰ and L ¹⁰ in formula (I1), and the same ones are exemplified, and the same ones are preferred.
Examples of the anion (I2-a) include the following anions.

Organic cations of Z2 ⁺ include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Examples of the Z2 ⁺ organic cation include those similar to the Z1 ⁺ organic cation in the formula (I1).

The carboxylate (I2-s) is a combination of the above-described anion (I2-a) and the above-described organic cation Z2 ⁺ (cation (I2-c)), which can be combined arbitrarily. The carboxylate (I2-s) is preferably an anion represented by any one of formulas (I2-a-1) to (I2-a-12), a cation (b2-1), and a cation ( b2-2), cations (b2-3) or combinations with cations (b2-4).

Carboxylate (I2-s) includes salts listed in Table 2. In the table below, each code represents the code attached to the structure representing the anion or cation described above, and "~" is the combination of salt (I2-s) and anion (I2-a) or cation (I2-c). Indicates that each corresponds. For example, carboxylate (I2-s-1) means a salt consisting of an anion represented by formula (I2-a-1) and a cation represented by formula (b2-c-1). represents the salt shown.

Among them, as the carboxylate (I2-s), carboxylate (I2-s-1) to carboxylate (I2-s-12), carboxylate (I2-s-28) to carboxylate (I2-s-39), carboxylate (I2-s-55) to carboxylate (I2-s-66), carboxylate (I2-s-82) to carboxylate (I2-s-93) ), carboxylate (I2-s-109) to carboxylate (I2-s-120), carboxylate (I2-s-136) to carboxylate (I2-s-147), carboxylate ( I2-s-163) ~ Carboxylate (I2-s-174), Carboxylate (I2-s-190) ~ Carboxylate (I2-s-201), Carboxylate (I2-s-217) ~ Carboxylate (I2-s-228), Carboxylate (I2-s-244) ~ Carboxylate (I2-s-255), Carboxylate (I2-s-271) ~ Carboxylate (I2 -s-282), carboxylate (I2-s-298) to carboxylate (I2-s-309), carboxylate (I2-s-325) to carboxylate (I2-s-336), Carboxylate (I2-s-352) ~ Carboxylate (I2-s-363), Carboxylate (I2-s-379) ~ Carboxylate (I2-s-390), Carboxylate (I2- s-406) to carboxylate (I2-s-417) are preferred.
The content of the structural unit (I2) is 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 0.8 mol%, based on the total structural units of the resin (A2). % or more, more preferably 1 mol % or more. Further, it is 100 mol % or less, preferably 50 mol % or less, more preferably 30 mol % or less, and still more preferably 10 mol % or less. Specifically, it is 0.1 to 100 mol%, preferably 0.5 to 50 mol%, more preferably 0.8 to 30 mol%, still more preferably 1 to 10 mol%. be.

The resin (A1) and the resin (A2) are each a structural unit (hereinafter sometimes referred to as "structural unit (a1)") having an acid-labile group in addition to the structural unit (I1) and structural unit (I2). may further include Here, the "acid-labile group" is a structural unit having a leaving group, and the leaving group is eliminated by contact with an acid, resulting in a structural unit having a hydrophilic group (e.g., a hydroxy group or a carboxyl group). means a group that converts to
It is preferable that the resin (A1) and the resin (A2) further contain a structural unit other than the structural unit (a1). Structural units other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), other structural units (hereinafter referred to as "structural unit (t)"). may be called) and structural units known in the art.

［式（１）中、Ｒ^ａ１、Ｒ^ａ２及びＲ^ａ３は、それぞれ独立に、炭素数１～８のアルキル基、炭素数２～８のアルケニル基、炭素数３～２０の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３～２０の非芳香族炭化水素環を形成する。
ｍａ及びｎａは、それぞれ独立して、０又は１を表し、ｍａ及びｎａの少なくとも一方は１を表す。
＊は結合部位を表す。］

［式（２）中、Ｒ^ａ１’及びＲ^ａ２’は、それぞれ独立に、水素原子又は炭素数１～１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１～２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３～２０の複素環を形成し、該炭化水素基及び該複素環に含まれる－ＣＨ_２－は、－Ｏ－又は－Ｓ－で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
ｎａ’は、０又は１を表す。
＊は結合部位を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)").
The acid-labile group that may be contained in the resin (A1) and the resin (A2) is a group represented by formula (1) (hereinafter also referred to as group (1)) and/or represented by formula (2). (hereinafter also referred to as group (2)) is preferred.

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

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

Ｒ^ａ１、Ｒ^ａ２及びＲ^ａ３における芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニル基、フェナントリル基等のアリール基が挙げられる。
組み合わせた基としては、上述したアルキル基と脂環式炭化水素基とを組み合わせた基（例えば、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のアルキルシクロアルキル基又はシクロアルキルアルキル基）、ベンジル基等のアラルキル基、アルキル基を有する芳香族炭化水素基（ｐ－メチルフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、２，６－ジエチルフェニル基、２－メチル－６－エチルフェニル基等）、脂環式炭化水素基を有する芳香族炭化水素基（ｐ－シクロヘキシルフェニル基、ｐ－アダマンチルフェニル基等）、フェニルシクロヘキシル基等のアリール－シクロアルキル基等が挙げられる。
好ましくは、ｍａは０であり、ｎａは１である。
Ｒ^a1及びＲ^a2が互いに結合して非芳香族炭化水素環を形成する場合の－Ｃ（Ｒ^a1）（Ｒ^a2）（Ｒ^a3）としては、下記の環が挙げられる。非芳香族炭化水素環は、好ましくは炭素数３～１２である。＊は－Ｏ－との結合部位を表す。

Examples of alkyl groups for R ^a1 , R ^a2 and R ^a3 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group.
The alkenyl group for R ^a1 , R ^a2 and R ^a3 includes ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, A nonenyl group is mentioned.
The alicyclic hydrocarbon groups for R ^a1 , R ^a2 and R ^a3 may be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bonding site). The alicyclic hydrocarbon groups of R ^a1 , R ^a2 and R ^a3 preferably have 3 to 16 carbon atoms.

Examples of aromatic hydrocarbon groups for R ^a1 , R ^a2 and R ^a3 include aryl groups such as phenyl, naphthyl, anthryl, biphenyl and phenanthryl groups.
Examples of the combined group include groups obtained by combining the above alkyl groups and alicyclic hydrocarbon groups (e.g., methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl a dimethyl group, an alkylcycloalkyl group such as a norbornylethyl group or a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p- cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, and the like.
Preferably, ma is 0 and na is 1.
-C(R ^a1 )(R ^a2 )(R ^a3 ) when R ^a1 and R ^a2 combine to form a non-aromatic hydrocarbon ring include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents a binding site with -O-.

Ｒ^ａ１’及びＲ^ａ２’のうち、少なくとも１つは水素原子であることが好ましい。
ｎａ’は、好ましくは０である。 Examples of hydrocarbon groups for R ^a1′ , R ^a2′ and R ^a3′ include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and groups formed by combining these groups.
Examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and combined group are the same as the groups exemplified for R ^a1 , R ^a2 and R ^a3 .
When R ^a2′ and R ^a3′ are bonded to each other to form a heterocyclic ring together with the carbon atom to which they are bonded and X, —C(R ^a1′ )(R ^a2′ )—X—R ^a3′ is represented by the following ring. * represents the binding site.

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

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

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

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

Among (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferred. If the resin (A1) and the resin (A2) each having structural units derived from the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group are used in the resist composition, the resolution of the resist pattern can be improved. can be improved.

［式（ａ１－０）、式（ａ１－１）及び式（ａ１－２）中、
Ｌ^a01、Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、－Ｏ－又は＊－Ｏ－（ＣＨ_２）_ｋ１－ＣＯ－Ｏ－を表し、ｋ１は１～７のいずれかの整数を表し、＊は－ＣＯ－との結合部位を表す。
Ｒ^a01、Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基又はこれらを組み合わせた基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１～８のアルキル基、炭素数２～８のアルケニル基、炭素数３～１８の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基又はこれらを組合せることにより形成される基を表す。
ｍ１は０～１４のいずれかの整数を表す。
ｎ１は０～１０のいずれかの整数を表す。
ｎ１’は０～３のいずれかの整数を表す。］ As a structural unit derived from a (meth)acrylic monomer having a group (1), a structural unit represented by formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)), formula ( a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter referred to as structural unit (a1-2) There is a case.) is mentioned. Preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2), more preferably structural unit (a1- 1) and at least one structural unit selected from the group consisting of structural units (a1-2). 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 an integer of 1 to 7, * is represents the binding site with -CO-.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom, a halogen atom or an optionally halogenated alkyl group having 1 to 6 carbon atoms.
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, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Represents a combined group.
R ^a6 and R ^a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. It represents a hydrocarbon group or a group formed by combining these groups.
m1 represents any integer from 0 to 14;
n1 represents an integer from 0 to 10;
n1' represents an integer of 0 to 3; ]

R ^a01 , R ^a4 and R ^a5 are preferably a hydrogen atom or a methyl group, more preferably a methyl group.
L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or *—O—(CH ₂ ) _k01 —CO—O— (provided that k01 is preferably any integer of 1 to 4, more preferably is 1.), more preferably an oxygen atom.
The alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the groups in which these are combined for R ^a02 , R ^a03 and R ^a04 are the groups listed for R ^a1 , R ^a2 and R ^a3 in group (1). and the same groups as
The alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and groups in which these are combined for R ^a6 and R ^a7 are the groups listed for R ^a1 , R ^a2 and R ^a3 in formula (1) and the same groups as
The alkyl group for R ^a02 , R ^a03 and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group.
The alkyl group for R ^a6 and R ^a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, still more preferably an ethyl group or an isopropyl group. or a t-butyl group.
The alkenyl group for R ^a6 and R ^a7 is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably an ethenyl group, propenyl group, isopropenyl group or butenyl group.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 preferably have 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms.
The aromatic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 preferably have 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
It is preferable that the combined group of an alkyl group and an alicyclic hydrocarbon group have a total carbon number of 18 or less.
It is preferable that the combined group of an alkyl group and an aromatic hydrocarbon group have a total carbon number of 18 or less.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably methyl group, ethyl group, phenyl group or naphthyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
R ^a6 and R ^a7 are each independently preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group , ethyl, isopropyl, t-butyl, ethenyl, phenyl or naphthyl, more preferably ethyl, isopropyl, t-butyl, ethenyl or phenyl.
m1 is preferably an integer from 0 to 3, more preferably 0 or 1.
n1 is preferably an integer from 0 to 3, more preferably 0 or 1.
n1' is preferably 0 or 1.

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

Examples of the structural unit (a1-1) include structural units derived from monomers described in JP-A-2010-204646. Among them, a structural unit represented by any one of formulas (a1-1-1) to (a1-1-7) and a methyl group corresponding to R ^a4 in structural unit (a1-1) is a hydrogen atom or a halogen atom. , a haloalkyl group or other alkyl group is preferred, and a structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) is more preferred.

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

When the resin (A1) or the resin (A2) contains the structural unit (a1-0), the content thereof may be 5 mol% or more with respect to the total structural units of the resin (A1) or the resin (A2). , preferably at least 10 mol %. Further, it is 80 mol % or less, preferably 75 mol % or less, and more preferably 70 mol % or less. Specifically, it is 5 to 80 mol %, preferably 5 to 75 mol %, more preferably 10 to 70 mol %.
When the resin (A1) or the resin (A2) contains the structural unit (a1-1) and/or the structural unit (a1-2), the total content of these is the total structure of the resin (A1) or the resin (A2) It may be 10 mol % or more, preferably 15 mol % or more, more preferably 20 mol % or more, based on the unit. Also, it is 90 mol % or less, preferably 85 mol % or less, more preferably 80 mol % or less, even more preferably 75 mol % or less, and even more preferably 70 mol % or less. Specifically, it is 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 75 mol%, still more preferably 20 to 70 mol %.

［式（ａ１－４）中、
Ｒ^a32は、水素原子、ハロゲン原子、又は、ハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～１２のアルコキシアルキル基、炭素数２～１２のアルコキシアルコキシ基、炭素数２～４のアルキルカルボニル基、炭素数２～４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a30は、単結合又は^＊－Ｘ^a31－（Ａ^a32－Ｘ^a32）_nc－を表し、＊は－Ｒ^a32が結合する炭素原子との結合部位を表す。
Ａ^a32は、炭素数１～６のアルカンジイル基を表す。
Ｘ^a31及びＸ^a32は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ｎｃは、０又は１を表す。
ｌａは０～４のいずれかの整数を表す。ｌａが２以上のいずれかの整数である場合、複数のＲ^a33は互いに同一であっても異なっていてもよい。
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。］ Structural units having group (2) in structural unit (a1) include structural units represented by formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4)”). .

[In 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, and a carbon number It represents an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a30 represents a single bond or ^* -X ^a31 -(A ^a32 -X ^a32 ) _nc -, and * represents a bonding site with the carbon atom to which -R ^a32 is bonded.
A ^a32 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a31 and X ^a32 each independently represent -O-, -CO-O- or -O-CO-.
nc represents 0 or 1;
la represents an integer of 0 to 4; When la is any integer of 2 or more, the plurality of R ^a33 may be the same or different.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^a35 and R ^a36 are bonded to each other to form a C2-C20 divalent hydrocarbon group together with -C-O- to which they are bonded, and -CH ₂ - contained in the hydrocarbon group and the divalent hydrocarbon group is - O- or -S- may be substituted. ]

Halogen atoms in R ^a32 and R ^a33 include fluorine, chlorine and bromine atoms.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom for R ^a32 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 perfluoro A hexyl group is mentioned.
R ^a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, even more preferably a hydrogen atom or a methyl group.
Examples of the alkyl group for R ^a33 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
The alkoxy group for R ^a33 includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy and hexyloxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.
Alkoxyalkyl groups for R ^a33 include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl and tert-butoxymethyl groups. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, even more preferably a methoxymethyl group.
The alkoxyalkoxy group for R ^a33 includes a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group and a tert-butoxymethoxy group. mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group.
The alkylcarbonyl group for R ^a33 includes an acetyl group, a propionyl group and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group.
The alkylcarbonyloxy group for R ^a33 includes an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group.
R ^a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, a fluorine atom, an iodine atom, a hydroxy group, a methyl A group, methoxy group, ethoxy group, ethoxyethoxy group or ethoxymethoxy group is more preferable, and fluorine atom, iodine atom, hydroxy group, methyl group, methoxy group or ethoxyethoxy group is more preferable.

*-X ^a31 -(A ^a32 -X ^a32 ) _nc - includes *-O-, *-CO-O-, *-O-CO-, *-CO-O-A ^a32 -CO-O-, *-O-CO- ^Aa32 -O-, *-O- ^Aa32 -CO-O-, *-CO-O- ^Aa32 -O-CO-, *-O-CO- ^Aa32 -O-CO -, are included. Among them, *-CO-O-, *-CO-O-A ^a32 -CO-O- or *-O-A ^a32 -CO-O- is preferred.

The alkanediyl groups include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -methylbutane-1,4-diyl group and the like.
A ^a32 is preferably a methylene group or an ethylene group.

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

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

Aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups.
Examples of the combined group include groups obtained by combining the above alkyl groups and alicyclic hydrocarbon groups (e.g., methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl a dimethyl group, an alkylcycloalkyl group such as a norbornylethyl group or a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p- cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, and the like. In particular, R ^a36 is an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups. are mentioned.

R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferably a methyl group or an ethyl group.
The hydrocarbon group of R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination of these A group 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.
--OC(R ^a34 )(R ^a35 )-OR ^a36 in the structural unit (a1-4) is eliminated upon contact with an acid (eg, p-toluenesulfonic acid) to form a hydroxy group.
-OC(R ^a34 )(R ^a35 )-OR ^a36 is preferably attached to the m-position or p-position of the benzene ring.

Examples of structural units (a1-4) include structural units derived from monomers described in JP-A-2010-204646. Preferably, the hydrogen atom corresponding to R ^a32 in the structural units and structural units (a1-4) represented by formulas (a1-4-1) to (a1-4-24) is a halogen atom, a haloalkyl group, or Examples include structural units substituted with alkyl groups, more preferably formulas (a1-4-1) to (a1-4-5), formulas (a1-4-10), and formulas (a1-4-13) , formula (a1-4-14), formula (a1-4-19), and formula (a1-4-20).

When the resin (A1) or the resin (A2) contains the structural unit (a1-4), its content is 3 to 80 mol with respect to the total of all structural units of the resin (A1) or the resin (A2). %, more preferably 5 to 75 mol%, even more preferably 7 to 70 mol%, even more preferably 7 to 65 mol%, and 10 to 60 mol% It is even more preferred to have

［式（ａ１－５）中、
Ｒ^a8は、ハロゲン原子を有していてもよい炭素数１～６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊－（ＣＨ₂）_h3－ＣＯ－Ｌ⁵⁴－を表し、ｈ３は１～４のいずれかの整数を表し、＊は、Ｌ⁵¹との結合部位を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、－Ｏ－又は－Ｓ－を表す。
ｓ１は、１～３のいずれかの整数を表す。
ｓ１’は、０～３のいずれかの整数を表す。］ Structural units derived from (meth)acrylic monomers having group (2) include structural units represented by formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”). be done.

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

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

Examples of structural units (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among them, structural units represented by formulas (a1-5-1) to (a1-5-4) are preferable, and represented by formula (a1-5-1) or formula (a1-5-2) Structural units are more preferred.

When the resin (A1) or the resin (A2) contains the structural unit (a1-5), its content is 1 to 50 mol% with respect to the total structural units of the resin (A1) or the resin (A2). Preferably, 3 to 45 mol % is more preferred, 5 to 40 mol % is even more preferred, and 5 to 30 mol % is even more preferred.

The structural unit (a1) also includes the following structural units.

When the resin (A1) or the resin (A2) contains structural units such as (a1-3-1) to (a1-3-7), the content of the resin (A1) or the resin (A2) 10 to 95 mol% is preferred, 15 to 90 mol% is more preferred, 20 to 85 mol% is still more preferred, 20 to 70 mol% is even more preferred, and 20 to 60 mol% is particularly preferred, relative to all structural units. preferable.

樹脂（Ａ１）又は樹脂（Ａ２）が、（ａ１－６－１）～（ａ１－６－３）のような構造単位を含む場合、その含有率は、樹脂（Ａ１）又は樹脂（Ａ２）の全構造単位に対して、１０～６０モル％が好ましく、１５～５５モル％がより好ましく、２０～５０モル％がさらに好ましく、２０～４５モル％がさらにより好ましく、２０～４０モル％が特に好ましい。 The structural unit (a1) also includes the following structural units.

When the resin (A1) or the resin (A2) contains structural units such as (a1-6-1) to (a1-6-3), the content of the resin (A1) or the resin (A2) 10 to 60 mol% is preferred, 15 to 55 mol% is more preferred, 20 to 50 mol% is still more preferred, 20 to 45 mol% is even more preferred, and 20 to 40 mol% is particularly preferred, relative to the total structural units. preferable.

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

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

［式（ａ２－Ａ）中、
Ｒ^a50は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｒ^a51は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～１２のアルコキシアルキル基、炭素数２～１２のアルコキシアルコキシ基、炭素数２～４のアルキルカルボニル基、炭素数２～４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a50は、単結合又は＊－Ｘ^a51－（Ａ^a52－Ｘ^a52）_nb－を表し、＊は－Ｒ^a50が結合する炭素原子との結合部位を表す。
Ａ^a52は、炭素数１～６のアルカンジイル基を表す。
Ｘ^a51及びＸ^a52は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ｎｂは、０又は１を表す。
ｍｂは０～４のいずれかの整数を表す。ｍｂが２以上のいずれかの整数である場合、複数のＲ^a51は互いに同一であっても異なっていてもよい。］ Structural units having a phenolic hydroxy group in structural units (a2) include structural units represented by 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, It represents an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or *-X ^a51 -(A ^a52 -X ^a52 ) _nb -, and * represents a bonding site with the carbon atom to which -R ^a50 bonds.
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent -O-, -CO-O- or -O-CO-.
nb represents 0 or 1;
mb represents an integer of 0 to 4; When mb is any integer of 2 or more, multiple R ^a51 may be the same or different. ]

Halogen atoms in R ^a50 and R ^a51 include fluorine, chlorine and bromine atoms.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom for 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 perfluoro A hexyl group is mentioned.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, even more preferably a hydrogen atom or a methyl group.
Examples of alkyl groups for R ^a51 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl and hexyl groups. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
Alkoxy groups for R ^a51 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy and tert-butoxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.
Alkoxyalkyl groups for R ^a51 include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl and tert-butoxymethyl groups. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, even more preferably a methoxymethyl group.
The alkoxyalkoxy group for R ^a51 includes a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group and a tert-butoxymethoxy group. mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group.
The alkylcarbonyl group for R ^a51 includes an acetyl group, a propionyl group and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group.
The alkylcarbonyloxy group for R ^a51 includes an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group.
R ^a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, a fluorine atom, an iodine atom, a hydroxy group, a methyl A group, methoxy group, ethoxy group, ethoxyethoxy group or ethoxymethoxy group is more preferable, and fluorine atom, iodine atom, hydroxy group, methyl group, methoxy group or ethoxyethoxy group is more preferable.

*-X ^a51 -(A ^a52 -X ^a52 ) _nb - includes *-O-, *-CO-O-, *-O-CO-, *-CO-O-A ^a52 -CO-O-, *-O-CO-A ^a52 -O-, *-O-A ^a52 -CO-O-, *-CO-O-A ^a52 -O-CO-, *-O-CO-A ^a52 -O-CO -, are included. Among them, *-CO-O-, *-CO-OA ^a52 -CO-O- or *-OA ^a52 -CO-O- is preferred.

The alkanediyl groups include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -methylbutane-1,4-diyl group and the like.
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—, a single bond, *—CO—O— or *—CO—O—CH ₂ --CO--O-- is more preferred, and a single bond or *--CO--O-- is even more preferred.

mb is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.
At least one hydroxy group is preferably attached to the m-position or p-position of the benzene ring. When the phenyl group contains two or more hydroxy groups, the two hydroxy groups are preferably bonded to the m-position and p-position, respectively.

Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577.
The structural unit (a2-A) includes structural units represented by formulas (a2-2-1) to (a2-2-24) and formulas (a2-2-1) to (a2-2-24). ) in which the methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group. Structural unit (a2-A) includes structural units represented by formulas (a2-2-1) to (a2-2-4), structural units represented by formula (a2-2-6), and structural units represented by formula ( a2-2-8), structural units represented by formulas (a2-2-12) to (a2-2-18) and formulas (a2-2-1) to (a2- 2-4), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), and formulas (a2-2-12) to In the structural unit represented by formula (a2-2-18), it is preferably a structural unit in which the methyl group corresponding to R ^a50 in structural unit (a2-A) is replaced with a hydrogen atom. -3), structural unit represented by formula (a2-2-4), structural unit represented by formula (a2-2-8), formula (a2-2-12) to formula Structural unit represented by (a2-2-14), structural unit represented by formula (a2-2-18) and structural unit represented by formula (a2-2-3), formula (a2-2- 4), structural units represented by formula (a2-2-8), structural units represented by formulas (a2-2-12) to (a2-2-14), and formula ( a2-2-18), the structural unit is more preferably a structural unit in which the methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom, and the structural unit represented by the formula (a2-2- 3), a structural unit represented by formula (a2-2-4), a structural unit represented by formula (a2-2-8) and a structural unit represented by formula (a2-2-3) the structural unit represented by formula (a2-2-4), the structural unit represented by formula (a2-2-8), the methyl group corresponding to R ^a50 in structural unit (a2-A) is more preferably a structural unit in which is replaced with a hydrogen atom.

When the structural unit (a2-A) is contained in the resin (A1) or the resin (A2), the content of the structural unit (a2-A) is preferably at least 5 mol% of the total structural units. , more preferably 10 mol % or more, still more preferably 15 mol % or more, and even more preferably 20 mol % or more. Also, it is preferably 80 mol % or less, more preferably 70 mol % or less, and still more preferably 65 mol % or less. Specifically, it is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, even more preferably 15 to 65 mol %, still more preferably 20 to 65 mol %.
The structural unit (a2-A) is incorporated into the resin (A1) and the resin (A2) by, for example, polymerizing the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. be able to. Moreover, the structural unit (a2-A) can be included in the resin (A1) and the resin (A2) by polymerizing with acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide.

［式（ａ２－１）中、
Ｌ^a3は、－Ｏ－又は＊－Ｏ－（ＣＨ₂）_k2－ＣＯ－Ｏ－を表し、
ｋ２は１～７のいずれかの整数を表す。＊は－ＣＯ－との結合部位を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０～１０のいずれかの整数を表す。］ A structural unit having an alcoholic hydroxy group in the structural unit (a2) includes a structural unit represented by formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)").

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

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

Examples of structural units (a2-1) include structural units derived from monomers described in JP-A-2010-204646. Structural units represented by any one of formulas (a2-1-1) to (a2-1-6) are preferred, and any one of formulas (a2-1-1) to (a2-1-4) Structural units represented by the formula (a2-1-1) or (a2-1-3) are more preferable.

When the resin (A1) or the resin (A2) contains the structural unit (a2-1), the content thereof may be 1 mol% or more with respect to the total structural units of the resin (A1) or the resin (A2). , is preferably 2 mol % or more. Also, it is 45 mol % or less, preferably 40 mol % or less, more preferably 35 mol % or less, still more preferably 20 mol % or less, and even more preferably 10 mol % or less. Specifically, it is 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, still more preferably 1 to 20 mol%, still more preferably It is 1 to 10 mol %.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, γ-butyrolactone ring, δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. It's okay. Preferable examples include 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)).

［式（ａ３－１）、式（ａ３－２）、式（ａ３－３）及び式（ａ３－４）中、
Ｌ^ａ４、Ｌ^ａ５及びＬ^ａ６は、それぞれ独立に、－Ｏ－又は＊－Ｏ－（ＣＨ_２）_k3－ＣＯ－Ｏ－（ｋ３は１～７のいずれかの整数を表す。）で表される基を表す。
Ｌ^ａ７は、－Ｏ－、＊－Ｏ－Ｌ^ａ８－Ｏ－、＊－Ｏ－Ｌ^ａ８－ＣＯ－Ｏ－、＊－Ｏ－Ｌ^ａ８－ＣＯ－Ｏ－Ｌ^ａ９－ＣＯ－Ｏ－又は＊－Ｏ－Ｌ^ａ８－Ｏ－ＣＯ－Ｌ^ａ９－Ｏ－を表す。
Ｌ^ａ８及びＬ^ａ９は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
＊はカルボニル基との結合部位を表す。
Ｒ^ａ１８、Ｒ^ａ１９、Ｒ^ａ２０及びＲ^ａ２４は、それぞれ独立に、ハロゲン原子を有していてもよい炭素数１～６のアルキル基、水素原子又はハロゲン原子を表す。
Ｘ^ａ３は、－ＣＨ_２－又は酸素原子を表す。
Ｒ^ａ２１は炭素数１～４の脂肪族炭化水素基を表す。
Ｒ^ａ２２、Ｒ^ａ２３及びＲ^ａ２５は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。
ｐ１は０～５のいずれかの整数を表す。
ｑ１は、０～３のいずれかの整数を表す。
ｒ１は、０～３のいずれかの整数を表す。
ｗ１は、０～８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^ａ２１、Ｒ^ａ２２、Ｒ^ａ２３及び／又はＲ^ａ２５は互いに同一であっても異なっていてもよい。］ Structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3) or formula (a3-4). One of these may be contained alone, or two or more 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 an integer of 1 to 7); represents a group.
L ^a7 is -O-, *-OL ^a8 -O-, *-OL ^a8 -CO-O-, *-OL ^a8 -CO-OL ^a9 -CO-O- or * -OL ^a8 -O-CO-L ^a9 -O-.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* represents a bonding site with a carbonyl group.
R ^a18 , R ^a19 , R ^a20 and R ^a24 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
X ^a3 represents —CH ₂ — or an oxygen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer from 0 to 5;
q1 represents an integer of 0 to 3;
r1 represents an integer of 0 to 3;
w1 represents any integer from 0 to 8;
When p1, q1, r1 and/or w1 are 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and/or R ^a25 may be the same or different. ]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group. be done.
Halogen atoms in R ^a18 , R ^a19 , R ^a20 and R ^a24 include fluorine, chlorine, bromine and iodine atoms.
Examples of alkyl groups for R ^a18 , R ^a19 , R ^a20 and R ^a24 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. , preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
The alkyl group having a halogen atom for R ^a18 , R ^a19 , R ^a20 and R ^a24 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, and a perfluorotert -butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like.

The alkanediyl group for L ^a8 and L ^a9 includes methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5 -diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group, 2-methylbutane-1,4-diyl group and the like.

In formulas (a3-1) to (a3-3), L ^a4 to L ^a6 are each independently preferably —O— or *—O—(CH ₂ ) _k3 —CO—O—, k3 is an integer of 1 to 4, more preferably -O- and *-O-CH ₂ -CO-O-, more preferably an oxygen atom.
R ^a18 to R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

（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, still more preferably a hydrogen atom or a methyl group is.
R ^a25 is preferably a carboxy group, a cyano group or a methyl group.
L ^a7 is preferably -O- or *-OL ^a8 -CO-O-, more preferably -O-, -O-CH ₂ -CO-O- or -O-C ₂ H ₄ - It is CO—O—.
w1 is preferably an integer from 0 to 2, more preferably 0 or 1.
In particular, formula (a3-4) is preferably formula (a3-4)'.

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

As the structural unit (a3), the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, the structure derived from the monomer described in JP-A-2012-41274 units. As the structural unit (a3), formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2), formula (a3-3- 1), a structural unit represented by any one of formulas (a3-3-2) and formulas (a3-4-1) to (a3-4-12), and in said structural unit, formula (a3-1 ) to R ^a19 , R ^a20 and R ^a24 in formulas ⁽ a3-4) are preferably structural units in which methyl groups are replaced with hydrogen atoms.

When the resin (A1) or the resin (A2) contains the structural unit (a3), the total content is 1 mol% or more with respect to the total structural units of the resin (A1) or the resin (A2), It is preferably 3 mol % or more, more preferably 5 mol % or more, still more preferably 10 mol % or more. Also, it is 70 mol % or less, preferably 65 mol % or less, and more preferably 60 mol % or less. Specifically, it is 1 to 70 mol %, preferably 3 to 65 mol %, more preferably 5 to 60 mol %.
Further, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is the content of the resin (A1) or the resin (A2), respectively. It is preferably 1 mol % or more, more preferably 3 mol % or more, still more preferably 5 mol % or more, relative to all structural units. Also, it is preferably 60 mol % or less, more preferably 55 mol % or less, and still more preferably 50 mol % or less. Specifically, it is preferably 1 to 60 mol %, more preferably 3 to 55 mol %, even more preferably 5 to 50 mol %.

［式（ａ４）中、
Ｒ⁴¹は、水素原子又はメチル基を表す。
Ｒ⁴²は、炭素数１～２４のハロゲン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、鎖式飽和炭化水素基及び単環又は多環の脂環式飽和炭化水素基、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)>
Structural units (a4) include the following structural units.

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

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

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

［式（ａ４－０）中、
Ｒ⁵⁴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。
Ｒ⁶⁴は、水素原子又はフッ素原子を表す。］ The structural unit (a4) includes a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), and a structural unit represented by formula (a4-4). .

[In the formula (a4-0),
^R54 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.
^R64 represents a hydrogen atom or a fluorine atom. ]

The alkanediyl group for L ^4a includes linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, ethane-1,1-diyl, branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group; be done.

The perfluoroalkanediyl group for L ^3a includes a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a perfluoropropane-2,2 -diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2 -diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like.
The perfluorocycloalkanediyl group for L ^3a includes a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

L ^4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group.
L ^3a is preferably a C 1-6 perfluoroalkanediyl group, more preferably a C 1-3 perfluoroalkanediyl group.

Examples of the structural unit (a4-0) include structural units shown below and structural units in which the methyl group corresponding to R ⁵⁴ in the structural unit (a4-0) in the following structural units is replaced with a hydrogen atom.

［式（ａ４－１）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ｒ^a42は、置換基を有していてもよい炭素数１～２０の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ａ^a41は、置換基を有していてもよい炭素数１～６のアルカンジイル基又は式（ａ－ｇ１）で表される基を表す。ただし、Ａ^ａ４１及びＲ^ａ４２のうち少なくとも１つは、置換基としてハロゲン原子（好ましくはフッ素原子）を有する。

〔式（ａ－ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１～５の２価の飽和炭化水素基を表す。
Ａ^a43は、単結合又は置換基を有していてもよい炭素数１～５の２価の飽和炭化水素基を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、－Ｏ－、－ＣＯ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は７以下である。〕
＊は結合部位であり、右側の＊が－Ｏ－ＣＯ－Ｒ^a42との結合部位である。］ Structural units (a4) include structural units represented by formula (a4-1).

[In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced with —O— or —CO— may
A ^a41 represents an optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by 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 an optionally substituted divalent saturated hydrocarbon group having 1 to 5 carbon atoms.
A ^a43 represents a single bond or an optionally substituted C 1-5 divalent saturated hydrocarbon group.
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 binding site, and * on the right side is a binding site with --O--CO--R ^a42 . ]

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

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

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

［式（ａ－ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す。
Ａ^a45は、ハロゲン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。
＊はＲ^a42との結合部位を表す。］
ただし、Ｒ^a42－Ｘ^a43－Ａ^a45において、Ｒ^a42がハロゲン原子を有しない場合は、Ａ^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の飽和炭化水素基を表す。 Examples of substituents possessed by R ^a42 include at least one selected from the group consisting of halogen atoms and groups represented by formulas (a-g3). A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom.

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, *--O--CO-- or *--CO--O--.
A ^a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* represents the binding site with ^Ra42 . ]
However, in R ^a42 -X ^a43 -A ^a45 , when R ^a42 does not have a halogen atom, A ^a45 represents a C 1-17 saturated hydrocarbon group having at least one halogen atom.

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

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

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 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 having 1 to 1 carbon atoms. A perfluoroalkyl group having 6 carbon atoms, particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl and perfluorooctyl groups. A perfluorocyclohexyl group etc. are mentioned as a perfluorocycloalkyl group.
When R ^a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), the total carbon number of R ^a42 including the number of carbon atoms contained in the group represented by formula (a-g3) The number is preferably 15 or less, more preferably 12 or less. When it has a group represented by formula (a-g3) as a substituent, the number thereof is preferably one.

［式（ａ－ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数１～１７の２価の飽和炭化水素基を表す。
Ｘ^a44は、＊＊－Ｏ－ＣＯ－又は＊＊－ＣＯ－Ｏ－を表す（＊＊はＡ^a46との結合部位を表す。）。
Ａ^a47は、ハロゲン原子を有していてもよい炭素数１～１７の飽和炭化水素基を表す。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合部位を表す。］ When R ^a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R ^a42 is more preferably a group represented by formula (a-g2).

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

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

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

Alkanediyl group for A ^a41 includes methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group straight-chain alkanediyl groups such as; A branched alkanediyl group such as a 2-methylbutane-1,4-diyl group can be mentioned.
Examples of substituents on 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 groups represented by A ^a42 , A ^a43 and A ^a44 in the group represented by formula (a-g1) include linear or branched alkanediyl groups and monocyclic or polycyclic divalent An alicyclic saturated hydrocarbon group, a divalent saturated hydrocarbon group formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group, and the like are included. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
Substituents of the divalent saturated hydrocarbon groups 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 zero.

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

As the structural unit represented by formula (a4-1), the following structural units and the methyl group corresponding to R ^a41 in the structural unit represented by formula (a4-1) in the following structural units is replaced with a hydrogen atom. Structural units replaced are included.

［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。］ Structural units (a4) include structural units represented by formula (a4-2) and structural units represented by formula (a4-3).

[In formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴⁴ represents an alkanediyl group having 1 to 6 carbon atoms, and --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 and a fluorine atom.
However, the upper limit of the total carbon number of L ⁴⁴ and R ^f6 is 21. ]

Examples of the C 1-6 alkanediyl group for L ⁴⁴ include the same groups as those exemplified for A ^a41 .
Examples of the saturated hydrocarbon group for R ^f6 include the same groups as those exemplified for R ⁴² .
The alkanediyl group for L ⁴⁴ is preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an ethylene group.

Examples of structural units represented by formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11). A structural unit in which the methyl group corresponding to R ^f5 in the structural unit (a4-2) is replaced with a hydrogen atom is also included 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との結合部位を表す。）。
Ａ^f14は、フッ素原子を有していてもよい炭素数１～１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14の合計炭素数の上限は２０である。］

[In formula (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a C 1-18 divalent saturated hydrocarbon group which may have a fluorine atom.
X ^f12 represents *--O--CO-- or *--CO--O-- (* represents a binding site with A ^f13 ).
A ^f14 represents a C 1-17 saturated hydrocarbon group 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 for L ⁵ include the same groups as those exemplified for the alkanediyl group for A ^a41 .

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

Examples of saturated hydrocarbon groups and optionally fluorine-containing saturated hydrocarbon groups for A ^f14 include groups similar to those exemplified for R ^a42 . Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, Fluorination such as 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, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group , a perfluoroadamantylmethyl group, and the like.

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

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

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

Examples of the saturated hydrocarbon group for R ^f22 include those similar to the saturated hydrocarbon group for R ^a42 . R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and an alkyl group having 1 to 10 carbon atoms having a fluorine atom is preferably More preferred is an alkyl group having 1 to 6 carbon atoms and having a fluorine atom.

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

As the structural unit represented by formula (a4-4), for example, in structural units represented by the following structural units and structural units represented by the following formulas, the methyl group corresponding to R ^f21 in structural unit (a4-4) is hydrogen Structural units replaced with atoms are included.

When the resin (A1) or the resin (A2) contains the structural unit (a4), the content thereof is preferably 1 to 20 mol% with respect to the total structural units of the resin (A1) or the resin (A2). 2 to 15 mol % is more preferable, and 3 to 10 mol % is even more preferable.

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

[In formula (a5-1),
^R51 represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. .
L ⁵⁵ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO— . ]

The alicyclic hydrocarbon group for R ⁵² may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl groups and norbornyl groups.
Aliphatic hydrocarbon groups having 1 to 8 carbon atoms are, for example, 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 ethylhexyl groups.
A 3-methyladamantyl group etc. are mentioned as an alicyclic hydrocarbon group which has a substituent.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

The divalent saturated hydrocarbon group for L ⁵⁵ includes a divalent saturated chain hydrocarbon group and a saturated divalent alicyclic hydrocarbon group, preferably a saturated chain divalent hydrocarbon group. .
Examples of divalent chain saturated hydrocarbon groups include alkanediyl groups such as methylene, ethylene, propanediyl, butanediyl and pentanediyl groups.
The bivalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. The monocyclic alicyclic saturated hydrocarbon group includes cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

［式（Ｌ１－１）中、
Ｘ^x1は、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＬ^x1との結合部位を表す。）。
Ｌ^x1は、炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x2は、単結合又は炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x1及びＬ^x2の合計炭素数は、１６以下である。
式（Ｌ１－２）中、
Ｌ^x3は、炭素数１～１７の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x4は、単結合又は炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x3及びＬ^x4の合計炭素数は、１７以下である。
式（Ｌ１－３）中、
Ｌ^x5は、炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x6及びＬ^x7は、それぞれ独立に、単結合又は炭素数１～１４の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x5、Ｌ^x6及びＬ^x7の合計炭素数は、１５以下である。
式（Ｌ１－４）中、
Ｌ^x8及びＬ^x9は、単結合又は炭素数１～１２の２価の脂肪族飽和炭化水素基を表す。
Ｗ^x1は、炭素数３～１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^x8、Ｌ^x9及びＷ^x1の合計炭素数は、１５以下である。］ Groups in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ is replaced with —O— or —CO— include, for example, formulas (L1-1) to (L1-4) and the group represented by In the following formulas, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom.

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

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

式（Ｌ１－２）で表される基としては、例えば、以下に示す２価の基が挙げられる。

式（Ｌ１－３）で表される基としては、例えば、以下に示す２価の基が挙げられる。

式（Ｌ１－４）で表される基としては、例えば、以下に示す２価の基が挙げられる。

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

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

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

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

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

樹脂（Ａ１）又は樹脂（Ａ２）が、構造単位（ａ５）を含む場合、その含有率は、樹脂（Ａ１）又は樹脂（Ａ２）の全構造単位に対して、１～３０モル％が好ましく、２～２０モル％がより好ましく、３～１５モル％がさらに好ましい。 Examples of the structural unit (a5-1) include structural units shown below and structural units in which the methyl group corresponding to R ⁵¹ in the structural unit (a5-1) in the following structural units is replaced with a hydrogen atom.

When the resin (A1) or the resin (A2) contains the structural unit (a5), the content thereof is preferably 1 to 30 mol% with respect to the total structural units of the resin (A1) or the resin (A2). 2 to 20 mol % is more preferable, and 3 to 15 mol % is even more preferable.

<Structural unit (a6)>
Structural unit (a6) is a structural unit having a —SO ₂ — group, and preferably has a —SO ₂ — group in its side chain.
A structural unit having a —SO ₂ — group may have a linear structure having a —SO ₂ — group, or may have a branched structure having a —SO ₂ — group, It may have a cyclic structure (monocyclic and polycyclic structures) having a —SO ₂ — group. Structural units having a cyclic structure containing —SO ₂ — groups are preferred, and structural units having a cyclic structure (sultone ring) containing —SO ₂ —O— are more preferred.

The sultone ring includes rings represented by the following formulas (T ¹ -1), (T ¹ -2), (T ¹ -3) and (T ¹ -4). The binding site can be at any position. The sultone ring may be monocyclic, but preferably polycyclic. A polycyclic sultone ring means a bridged ring containing —SO ₂ —O— as an atomic group constituting the ring, and is represented by formulas (T ¹ -1) and (T ¹ -2). ring. The sultone ring may further contain a heteroatom in addition to —SO ₂ —O— as an atomic group constituting the ring, like the ring represented by formula (T ¹ -2). A heteroatom includes an oxygen atom, a sulfur atom or a nitrogen atom, preferably an oxygen atom.

The sultone ring may have a substituent, and examples of the substituent include a halogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a hydroxy group, a halogen atom, a hydroxy group, a cyano group, and 1 carbon atom. alkoxy groups of up to 12 carbon atoms, aryl groups of 6 to 12 carbon atoms, aralkyl groups of 7 to 12 carbon atoms, glycidyloxy groups, alkoxycarbonyl groups of 2 to 12 carbon atoms and alkylcarbonyl groups of 2 to 4 carbon atoms, and the like. be done.

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

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

[in the formula (T1′),
X ¹¹ represents an oxygen atom, a sulfur atom or a methylene group.
R ⁴¹ is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. aralkyl group having 7 to 12 carbon atoms, glycidyloxy group, alkoxycarbonyl group having 2 to 12 carbon atoms or alkylcarbonyl group having 2 to 4 carbon atoms.
ma represents any integer from 0 to 9; When ma is 2 or more, multiple R ⁴¹ may be the same or different.
The binding site can be any position. ]
X ¹¹ is preferably an oxygen atom or a methylene group, more preferably a methylene group.
Examples of R ⁴¹ include the same substituents as those described above for the sultone ring, and preferably an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group.
ma is preferably 0 or 1, more preferably 0.

The ring represented by formula (T1') includes the following rings. The binding site can be any position. Among them, the binding site is preferably at the 1st or 3rd position.

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

［式（ａ６－０）中、
Ｒ^ｘは、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロゲン原子を表す。
Ａ^ｘｘは、酸素原子、－Ｎ（Ｒ^ｃ）－又は硫黄原子を表す。
Ａ^ｘは、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－、－ＣＯ－又は－Ｎ（Ｒ^ｄ）－に置き換わっていてもよい。
Ｘ^１１、Ｒ^４１、ｍａは、上記と同じ意味を表す。
Ｒ^ｃ及びＲ^ｄは、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。］ Structural unit (a6) is preferably a structural unit represented by formula (a6-0).

[In the formula (a6-0),
R ^x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ^xx represents an oxygen atom, -N(R ^c )- or a sulfur atom.
A ^x 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 is —O—, —CO— or —N(R ^d )- may be substituted.
X ¹¹ , R ⁴¹ and ma have the same meanings as above.
R ^c and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

Halogen atoms for R ^x include fluorine, chlorine, bromine and iodine atoms.
The alkyl group for R ^x includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. and preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
The alkyl group having a halogen atom for R ^x includes, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. , perfluorohexyl group, trichloromethyl group, tribromomethyl group and triiodomethyl group.
R ^x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group.

The divalent saturated hydrocarbon group for A ^x includes a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic bivalent alicyclic saturated hydrocarbon group. A combination of two or more of the groups may also be used.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, 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, heptadecane-1, linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4- a branched alkanediyl group such as a diyl group;
monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; alicyclic saturated hydrocarbon group;
Polycyclic bivalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group and the like.
The bonding position of ^Ax to the sultone ring can be any position, but the 1-position is preferred.

Structural units (a6-0) include the following structural units.

Among them, structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferred, and structural units represented by formulas (a6-1), (a6-2), (a6-7) and (a6-8) are more preferred.
When the resin (A1) or the resin (A2) contains the structural unit (a6), the content thereof is preferably 1 to 50 mol% with respect to the total structural units of the resin (A1) or the resin (A2). 2 to 40 mol % is more preferable, and 3 to 30 mol % is even more preferable.

The resin (A1) is preferably a resin composed of the structural unit (I1), the structural unit (a1) and the structural unit (s), that is, the salt (I1-s), the monomer (a1) and the monomer (s) is a copolymer of
Resin (A2) is preferably a resin comprising structural unit (I2), structural unit (a1) and structural unit (s), that is, carboxylate (I2-s), monomer (a1) and monomer (s ) is a copolymer with
Structural unit (a1) is preferably a group consisting of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group) is at least one selected from, more preferably at least two, still more preferably at least two selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2).
Structural unit (s) is preferably at least one selected from the group consisting of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably structural unit (a2-1) or structural unit (a2-A). Structural unit (a3) is preferably a group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-4) is at least one selected from

Each structural unit constituting the resin (A1) and the resin (A2) may be used alone or in combination of two or more. legal). The content of each structural unit in the resin (A1) or the resin (A2) can be adjusted by adjusting the amount of the monomer used for polymerization.
The weight average molecular weights of resin (A1) and resin (A2) are preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or more). 000 or less, more preferably 15,000 or less). As used herein, the weight average molecular weight is a value obtained by gel permeation chromatography under the conditions described in Examples.
The content ratio of resin (A1) and resin (A2) is preferably 1:100 to 100:1, more preferably 10:90 to 90:10, and 30:70 to 70:30. more preferably 40:60 to 60:40.

<Resins other than resin (A1) and resin (A2)>
In the resist composition of the present invention, resins other than resin (A1) and resin (A2) may be used in combination. For example, the resist composition can contain other resins in addition to resin (A1) and resin (A2).
Other resins include resins containing the structural unit (a1) described above (hereinafter sometimes referred to as resin (AA), provided that structural units (I1) and structural units (I2) are not included).
In addition to the structural unit (a1), the resin (AA) preferably further contains structural units other than the structural unit (a1). Structural units other than structural unit (a1) include structural unit (s), structural unit (t), and structural units known in the art. Structural unit (a1) is preferably at least one selected from the group consisting of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2), more preferably at least two and more preferably at least two selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). Structural unit (s) is preferably at least one selected from the group consisting of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably structural unit (a2-1) or structural unit (a2-A). Structural unit (a3) is preferably a group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-4) is at least one selected from
Each structural unit constituting the resin (AA) may be used alone or in combination of two or more types, and is produced by a known polymerization method (e.g., radical polymerization method) using a monomer that leads to these structural units. be able to. The content of each structural unit in the resin (AA) can be adjusted by adjusting the amount of monomer used for polymerization. The weight average molecular weight of the resin (AA) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, further preferably is 15,000 or less).

Further, as another resin, a resin containing the structural unit (a4) or the structural unit (a5) (provided that the structural unit (I1), the structural unit (I2) and the structural unit (a1) are not included. Hereinafter referred to as "resin (X )” may also be mentioned.
As the resin (X), among others, a resin containing the structural unit (a4) is preferable.
When the resin (X) contains the structural unit (a4), the content of the structural unit (a4) in the resin (X) may be 20 mol% or more with respect to the total of all structural units in the resin (X). 30 mol % or more is preferable, 40 mol % or more is more preferable, and 45 mol % or more is even more preferable. Further, it is 100 mol % or less, preferably 80 mol % or less, more preferably 70 mol % or less, still more preferably 60 mol % or less, and even more preferably 55 mol % or less. Specifically, it is 20 to 100 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. When the resin (X) contains the structural unit (a5), the content of the structural unit (a5) may be 20 mol% or more, such as 30 mol% or more, based on the total of all structural units of the resin (X). is preferred, 40 mol % or more is more preferred, and 45 mol % or more is even more preferred. Further, it is 100 mol % or less, preferably 80 mol % or less, more preferably 70 mol % or less, still more preferably 60 mol % or less, and even more preferably 55 mol % or less. Specifically, it is 20 to 100 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. Further, when the resin (X) contains the structural unit (a4) and the structural unit (a5), the total content of the structural unit (a4) and the structural unit (a5) is the total of all structural units of the resin (X). On the other hand, it is 40 mol % or more, preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more. Furthermore, 100 mol% or less is mentioned. Specifically, it is 40 to 100 mol %, preferably 60 to 100 mol %, more preferably 70 to 100 mol %, even more preferably 80 to 100 mol %.
Structural units that the resin (X) may further include structural units (a2), structural units (a3), and structural units derived from other known monomers. Among them, the resin (X) is preferably a resin consisting only of the structural unit (a4) and/or the structural unit (a5).
Each structural unit that constitutes the resin (X) may be used alone or in combination of two or more. Using a monomer that induces these structural units, the resin (X) is produced by a known polymerization method (e.g., radical polymerization method). can do. The content of each structural unit in the resin (X) can be adjusted by adjusting the amount of the monomer used for polymerization.
The weight average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight-average molecular weight of resin (X) is the same as for resin (A1) and resin (A2).

When the resist composition of the present invention contains the resin (AA), its content is preferably 1 to 200 parts by mass with respect to the total 100 parts by mass of the resin (A1) and the resin (A2), and more It is preferably 10 to 150 parts by mass, more preferably 50 to 150 parts by mass, even more preferably 60 to 140 parts by mass, and even more preferably 70 to 140 parts by mass.
When the resist composition of the present invention contains the resin (X), its content is preferably 1 to 60 mass parts with respect to a total of 100 mass parts of the resin (A1), the resin (A2) and the resin (AA). parts, more preferably 1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and even more preferably 1 to 8 parts by mass.

The total content of the resin (A1), the resin (A2) and the resin (AA) in the resist composition is preferably 20% by mass or more and 100% by mass or less with respect to the solid content of the resist composition, and is 40% by mass. % or more and 100 mass % or less, more preferably 50 mass % or more and 99 mass % or less. The total content of resin (A1), resin (A2), resin (AA) and resin (X) is preferably 80% by mass or more and 99% by mass or less relative to the solid content of the resist composition. It is more preferably 99% by mass or more and more preferably 90% by mass or more and 99% by mass or less. The solid content and resin content of the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography.

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

Examples of the acid generator (B) include JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. A compound that generates an acid upon exposure to radiation as described in 1. above can be used. Moreover, you may use the compound manufactured by the well-known method. The acid generator (B) may be used in combination of two or more.

［式（Ｂ１）中、
Ｑ^ｂ１及びＱ^ｂ２は、それぞれ独立に、水素原子、フッ素原子、炭素数１～６のペルフルオロアルキル基又は炭素数１～６のアルキル基を表す。
Ｌ^ｂ１は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～２４の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generator (B1)").

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO— , a 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 24 carbon atoms, included in the alicyclic hydrocarbon group- CH ₂ - may be replaced by -O-, -S-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ]

Q ^b1 , Q ^b2 , and L ^b1 include the same groups as Q ^b1 , Q ^b2 , and L ^b1 in formula (I1) described above, and are preferably the same groups.
An optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms in Y (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -S-, -SO ₂ which may be substituted with - or -CO-) includes the same groups as Y ^b1 in formula (I1) described above, and is preferably the same group.

The alicyclic hydrocarbon group represented by Y is a spiro ring containing an oxygen atom such as formulas (Y28) to (Y35), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) In some cases it is preferred that the alkanediyl group between the two oxygen atoms has one or more fluorine atoms. Further, among 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 substituents of 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, -( CH ₂ ) _ja —CO—O—R ^b1 group or —(CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and —CH ₂ — contained in the alkyl group and the alicyclic hydrocarbon group is —O— , —SO ₂ — or —CO—, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group is replaced with a hydroxy group or a fluorine atom ja represents any integer from 0 to 4.) and the like.
Y is preferably an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, more preferably an optionally substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms A hydrocarbon group, more preferably an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, still more preferably an optionally substituted adamantyl group or a substituted is a norbornyl group optionally having a group, and —CH ₂ — constituting the alicyclic hydrocarbon group, adamantyl group or norbornyl group is —O—, —S—, —SO ₂ — or —CO— may be replaced by Specifically, the following are mentioned.

なかでも、Ｙは、好ましくはアダマンチル基、ヒドロキシアダマンチル基、オキソアダマンチル基、ノルボルナンラクトン基又は式（Ｙ４２）、式（Ｙ１００）～式（Ｙ１１４）、式（Ｙ１３４）～式（Ｙ１３９）で表される基である。

Among them, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, a norbornanelactone group or represented by formula (Y42), formula (Y100) to formula (Y114), formula (Y134) to formula (Y139). is a group.

Examples of the anion in the salt represented by formula (B1) include anions represented by formulas (B1-A-1) to (B1-A-65) [hereinafter referred to as "anion (B1-A -1)”, etc. ] is preferable, formula (B1-A-1) ~ formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), represented by any of formulas (B1-A-36) to (B1-A-40), formulas (B1-A-47) to (B1-A-65) Anions are more preferred.

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の鎖式炭化水素基、好ましくは炭素数１～４のアルキル基、炭素数５～１２の脂環式炭化水素基又はこれらを組合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基又はアダマンチル基である。Ｌ^Ａ４１は、単結合又は炭素数１～４のアルカンジイル基である。Ｑ^ｂ１及びＱ^ｂ２は、上記と同じ意味を表す。
式（Ｂ１）で表される塩におけるアニオンとしては、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 each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ^A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q ^b1 and Q ^b2 have the same meaning as above.
Specific examples of the anion in the salt represented by formula (B1) include the anions described in JP-A-2010-204646.

Anions in the salt represented by Formula (B1) are preferably anions represented by Formulas (B1a-1) to (B1a-43).

スルホニルメチドアニオンとしては、以下のものが挙げられる。

Among them, formula (B1a-1) ~ formula (B1a-4), formula (B1a-7) ~ formula (B1a-11), formula (B1a-14) ~ formula (B1a-30) and formula (B1a-35 ) to Formula (B1a-41) are preferred.
Moreover, the following are mentioned as a sulfonylimide anion.

Sulfonylmethide anions include the following.

Organic cations for Z ⁺ include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, organic phosphonium cations, and the like. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Examples of the Z ⁺ cation include those similar to the Z 1 ⁺ cation in the formula (I1).

The acid generator (B) is a combination of the aforementioned anions and the aforementioned organic cations, and these can be combined arbitrarily. As the acid generator (B), preferably formulas (B1a-1) to (B1a-4), formulas (B1a-7) to (B1a-11), formulas (B1a-14) to (B1a- 30) and an anion represented by any one of formulas (B1a-35) to (B1a-41), and cation (b2-1), cation (b2-2), cation (b2-3) or cation (b2 -4).

As the acid generator (B), those represented by formulas (B1-1) to (B1-60) are preferred. Among them, those containing an arylsulfonium cation are preferable, and formulas (B1-1) to (B1-3), formulas (B1-5) to (B1-7), formulas (B1-11) to (B1-14) ), formulas (B1-20) to (B1-26), formulas (B1-29), and formulas (B1-31) to (B1-60) are particularly preferred.

Moreover, the resist composition of the present invention may contain a salt (I1-s) as an acid generator. The content of the salt (I1-s) is preferably 1 part by mass or less, preferably 0.1 part by mass or less, relative to 100 parts by mass of the resin (A1).

In the resist composition of the present invention, the content of the acid generator is preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass, based on the solid content of the resist composition. 45 mass % or less, more preferably 1 mass % or more and 40 mass % or less, and still more preferably 3 mass % or more and 40 mass % or less. When the resin (A) or the like is included, the content of the acid generator is preferably 1 part by mass or more and 45 parts by mass or less with respect to a total of 100 parts by mass of the resin (A1), the resin (A2) and the resin (AA). , more preferably 1 part by mass or more and 40 parts by mass or less, and still more preferably 3 parts by mass or more and 35 parts by mass or less.

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

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

<Quencher (C)>
Examples of the quencher (C) include salts that generate an acid that is weaker in acidity than the acid generated from the acid generator, and basic nitrogen-containing organic compounds. The content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, based on the solid content of the resist composition. About 0.1 to 8% by mass is more preferable, and about 0.1 to 7% by mass is even more preferable.

<Salt that generates an acid with a weaker acidity than the acid generated from the acid generator>
The acidity of a salt that generates an acid that is weaker than the acid generated from the acid generator is indicated by the acid dissociation constant (pKa). The salt that generates an acid weaker in acidity than the acid generated from the acid generator is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3<pKa, preferably -1<pKa<7. and more preferably a salt with 0<pKa<5.
Examples of the salt that generates an acid that is weaker in acidity than the acid generated from the acid generator include salts represented by the following formula, and salts represented by the formula (D) described in JP-A-2015-147926 (hereinafter referred to as Sometimes referred to as "weak acid inner salt (D)".), and JP 2012-229206, JP 2012-6908, JP 2012-72109, JP 2011-39502 and patent Examples thereof include salts described in JP-A-2011-191745. The salt that generates an acid weaker in acidity than the acid generated by the acid generator is preferably a salt that generates a carboxylic acid that is weaker in acidity than the acid generated by the acid generator (a salt having a carboxylic acid anion). More preferably, it is the weak acid inner salt (D), and among the weak acid inner salts (D), diphenyl iodonium salts containing a phenyl group substituted with a carboxylate anion are more preferred.

［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のアシル基、炭素数２～７のアシルオキシ基、炭素数２～７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０～４のいずれかの整数を表し、ｍ’が２以上の場合、複数のＲ^D1は同一であっても異なってもよく、ｎ’が２以上の場合、複数のＲ^D2は同一であっても異なってもよい。］
Ｒ^D1及びＲ^D2の炭化水素基としては、鎖式炭化水素基、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。
鎖式炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ノニル基等のアルキル基が挙げられる。
脂環式炭化水素基としては、単環式及び多環式のいずれでもよく、飽和及び不飽和のいずれでもよい。シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロノニル基、シクロドデシル基等のシクロアルキル基、ノルボニル基、アダマンチル基等が挙げられる。
芳香族炭化水素基としては、フェニル基、１－ナフチル基、２－ナフチル基、２－メチルフェニル基、３－メチルフェニル基、４－メチルフェニル基、４－エチルフェニル基、４－プロピルフェニル基、４－イソプロピルフェニル基、４－ブチルフェニル基、４－ｔ－ブチルフェニル基、４－ヘキシルフェニル基、４－シクロヘキシルフェニル基、アントリル基、ｐ－アダマンチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、ビフェニル基、フェナントリル基、２，６－ジエチルフェニル基、２－メチル－６－エチルフェニル基等のアリール基等が挙げられる。
これらを組み合わせることにより形成される基としては、アルキル－シクロアルキル基、シクロアルキル－アルキル基、アラルキル基（例えば、フェニルメチル基、１－フェニルエチル基、２－フェニルエチル基、１－フェニル－１－プロピル基、１－フェニル－２－プロピル基、２－フェニル－２－プロピル基、３－フェニル－１－プロピル基、４－フェニル－１－ブチル基、５－フェニル－１－ペンチル基、６－フェニル－１－ヘキシル基等）等が挙げられる。
アルコキシ基としては、メトキシ基、エトキシ基等が挙げられる。
アシル基としては、アセチル基、プロパノイル基、ベンゾイル基、シクロヘキサンカルボニル基等が挙げられる。
アシルオキシ基としては、上記アシル基にオキシ基（－Ｏ－）が結合した基等が挙げられる。
アルコキシカルボニル基としては、上記アルコキシ基にカルボニル基（－ＣＯ－）が結合した基等が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられる。
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、炭素数１～６のアルコキシ基、炭素数２～４のアシル基、炭素数２～４のアシルオキシ基、炭素数２～４のアルコキシカルボニル基、ニトロ基又はハロゲン原子が好ましい。
ｍ’及びｎ’は、それぞれ独立に、０～２のいずれかの整数であることが好ましく、０であることがより好ましい。ｍ’が２以上の場合、複数のＲ^D1は同一であっても異なってもよく、ｎ’が２以上の場合、複数のＲ^D2は同一であっても異なってもよい。
より具体的には、以下の塩が挙げられる。

As the weak acid inner salt (D), diphenyliodonium having an iodonium cation to which two phenyl groups are bonded and a carboxylate anion substituted by at least one of the two phenyl groups bonded to the iodonium cation. Salts are preferred, and examples thereof include salts represented by the following formulas.

[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 acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, and a carbon number represents 2 to 7 alkoxycarbonyl groups, nitro groups or halogen atoms;
m' and n' each independently represent an integer of 0 to 4, and when m' is 2 or more, the plurality of R ^D1 may be the same or different, and n' is 2 or more , the plurality of R ^D2 may be the same or different. ]
Examples of hydrocarbon groups for R ^D1 and R ^D2 include chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, groups formed by combining these groups, and the like.
Chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group and nonyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be saturated or unsaturated. cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group and cyclododecyl group; norbornyl group; adamantyl group;
Aromatic hydrocarbon groups include phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl and 4-propylphenyl groups. , 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group , mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and the like.
Groups formed by combining these groups include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, aralkyl groups (e.g., phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1 -propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6 -phenyl-1-hexyl group, etc.).
The alkoxy group includes a methoxy group, an ethoxy group, and the like.
The acyl group includes acetyl group, propanoyl group, benzoyl group, cyclohexanecarbonyl group and the like.
Examples of the acyloxy group include groups in which an oxy group (--O--) is bonded to the above acyl group.
Examples of the alkoxycarbonyl group include groups in which a carbonyl group (--CO--) is bonded to the above alkoxy group.
A fluorine atom, a chlorine atom, a bromine atom etc. are mentioned as a halogen atom.
R ^D1 and R ^D2 each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, and an acyl group having 2 to 4 carbon atoms. Acyloxy groups having 2 to 4 carbon atoms, alkoxycarbonyl groups having 2 to 4 carbon atoms, nitro groups or halogen atoms are preferred.
Each of m' and n' is preferably an integer of 0 to 2, more preferably 0. When m' is 2 or more, multiple R ^D1 may be the same or different, and when n' is 2 or more, multiple R ^D2 may be the same or different.
More specific examples include the following salts.

Basic nitrogen-containing organic compounds include amines and ammonium salts. Amines include aliphatic amines and aromatic amines. Aliphatic amines include primary, secondary and tertiary amines.
Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tri heptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, tri isopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3 , 3′-diethyldiphenylmethane, 2,2′-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4- 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, Aromatic amines such as diisopropylaniline are preferred, and 2,6-diisopropylaniline is more preferred.
Ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethyl ammonium hydroxide, tetra-n-butylammonium salicylate and choline;

Further, the resist composition of the present invention may contain a carboxylate (I2-s) as a carboxylic acid generator. The content of the carboxylate (I2-s) is preferably 1 part by mass or less, preferably 0.1 part by mass or less, relative to 100 parts by mass of the resin (A2).

<Other ingredients>
If necessary, the resist composition of the present invention may contain components other than the components described above (hereinafter sometimes referred to as "other components (F)"). Other components (F) are not particularly limited, and additives known in the field of resists, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc., can be used.

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A1) containing a structural unit (I1) and a resin (A2) containing a structural unit (I2), optionally a resin (AA), an acid generator (B), a resin (X ), resin (A1), resin (A2), resin (AA) and resin other than resin (X), solvent (E), quencher (C) and other components (F), etc. be able to. The mixing order is arbitrary and not particularly limited. The temperature during mixing can be appropriately selected from 10 to 40° C. depending on the type of resin and the solubility of the resin in the solvent (E). An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is also not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for manufacturing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) a step of applying the resist composition of the present invention onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the exposed composition layer; and (5) developing the heated composition layer.
The coating of the resist composition on the substrate can be carried out using a commonly used device such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer, and an organic substrate having a resist film or the like formed on the surface thereof. Before applying the resist composition, the substrate may be washed, and an antireflection film or the like may be formed on the substrate.
By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is carried out, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a decompression device. The heating temperature is preferably 50 to 200° C., and the heating time is preferably 10 to 180 seconds. Moreover, the pressure for drying under reduced pressure is preferably about 1 to 1.0×10 ⁵ Pa.
The resulting composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an _F2 excimer laser (wavelength: 157 nm) that emits a laser beam in the ultraviolet region, a solid-state laser source (YAG or semiconductor laser etc.) and emits harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, electron beam, extreme ultraviolet light (EUV), etc. can be done. In the present specification, these irradiations with radiation may be collectively referred to as "exposure". During exposure, exposure is usually performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.
The exposed composition layer is subjected to a heat treatment (so-called post-exposure bake) in order to promote the deprotection reaction at the acid-labile groups. The heating temperature is usually about 50 to 200°C, preferably about 70 to 150°C. A chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating. Moreover, before the development, the steps of applying a resist composition, drying, exposing, and heating may be repeatedly performed on the exposed composition layer.
The composition layer after heating is usually developed using a developer using a developing device. The developing method includes a dipping method, a paddle method, a spraying method, a dynamic dispensing method, and the like. The development temperature is preferably, for example, 5 to 60° C., and the development time is preferably, for example, 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. Examples thereof include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove water remaining on the substrate and pattern.
When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer.
Examples of organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. ether solvents; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole;
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably substantially only the organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and/or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and substantially contains butyl acetate and/or 2-heptanone. - more preferably only heptanone.
The organic developer may contain a surfactant. In addition, the organic developer may contain a very small amount of water.
During development, the development may be stopped by replacing the organic developer with a solvent of a different type.
It is preferable to wash the resist pattern after development with a rinsing liquid. The rinse 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, preferably an alcohol solvent or an ester solvent.
After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and pattern.

<Application>
The resist composition of the present invention is a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure. It is suitable as a resist composition for line (EB) exposure or as a resist composition for EUV exposure, and is useful for microfabrication of semiconductors.

EXAMPLES The present invention will be described more specifically with reference to examples. In the examples, "%" and "parts" representing the content or amount used are based on mass unless otherwise specified.
A weight average molecular weight is the value calculated|required by the gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows.
Column: TSKgel Multipore HXL-M x 3+guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL/min
Detector: RI detector Column temperature: 40℃
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)
The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent Model 1100, MASS: Agilent Model LC/MSD). In the following examples, the value of this molecular ion peak is indicated by "MASS".

式（Ｉ１－１－ａ）で表される塩４．３８部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１－ｂ）で表される化合物１．６２部を添加し、５０℃に昇温後、５０℃で２時間撹拌した。得られた反応混合物に、式（Ｉ－１－ｃ）で表される化合物２．５０部を添加し、５０℃で１０時間撹拌した。得られた反応混合物を２３℃まで冷却した後、イオン交換水２５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２５部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、濃縮残渣に、アセトニトリル３部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ１－１）で表される塩５．４９部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４０７．１ Synthesis Example 1: Synthesis of Salt Represented by Formula (I1-1)

After mixing 4.38 parts of the salt represented by the formula (I1-1-a) and 50 parts of chloroform and stirring at 23° C. for 30 minutes, 1.62 of the compound represented by the formula (I-1-b) After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 2.50 parts of the compound represented by formula (I-1-c) was added to the obtained reaction mixture, and the mixture was stirred at 50° C. for 10 hours. After cooling the resulting reaction mixture to 23° C., 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. After adding 25 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated 5 times. The obtained organic layer is concentrated, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether are added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes, then the supernatant is removed and concentrated to obtain the formula ( 5.49 parts of the salt represented by I1-1) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 407.1

式（Ｉ１－１６９－ａ）で表される塩６．５６部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１－ｂ）で表される化合物１．６２部を添加し、５０℃に昇温後、５０℃で２時間撹拌した。得られた反応混合物に、式（Ｉ－１－ｃ）で表される化合物２．５０部を添加し、５０℃で１０時間撹拌した。得られた反応混合物を２３℃まで冷却した後、イオン交換水２５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２５部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、濃縮残渣に、アセトニトリル３部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ１－１６９）で表される塩４．２１部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４８１．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４０７．１ Synthesis Example 2: Synthesis of Salt Represented by Formula (I1-169)

After mixing 6.56 parts of the salt represented by the formula (I1-169-a) and 50 parts of chloroform and stirring at 23° C. for 30 minutes, 1.62 of the compound represented by the formula (I-1-b) After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 2.50 parts of the compound represented by formula (I-1-c) was added to the obtained reaction mixture, and the mixture was stirred at 50° C. for 10 hours. After cooling the resulting reaction mixture to 23° C., 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. After adding 25 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated 5 times. The obtained organic layer is concentrated, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether are added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes, then the supernatant is removed and concentrated to obtain the formula ( 4.21 parts of the salt represented by I1-169) were obtained.
MASS (ESI (+) Spectrum): M ⁺ 481.0
MASS (ESI (-) Spectrum): M ^- 407.1

式（Ｉ－２－ｃ）で表される化合物２．６４部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１－ｂ）で表される化合物１．６２部を添加し、５０℃に昇温後、５０℃で２時間撹拌した。得られた反応混合物に、式（Ｉ１－１６９－ａ）で表される塩６．４２部を添加し、５０℃で１０時間撹拌した。得られた反応混合物を２３℃まで冷却した後、イオン交換水２５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２５部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、濃縮残渣に、アセトニトリル３部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ１－１７０）で表される塩６．９４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４８１．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４０７．１ Synthesis Example 3: Synthesis of Salt Represented by Formula (I1-170)

2.64 parts of the compound represented by the formula (I-2-c) and 50 parts of chloroform were mixed and stirred at 23° C. for 30 minutes, and then 1.62 parts of the compound represented by the formula (I-1-b) After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 6.42 parts of the salt represented by the formula (I1-169-a) was added to the obtained reaction mixture and stirred at 50° C. for 10 hours. After cooling the resulting reaction mixture to 23° C., 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. After adding 25 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated 5 times. The obtained organic layer is concentrated, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether are added to the concentration residue, and after stirring at 23° C. for 30 minutes, the supernatant is removed and concentrated to obtain the formula ( 6.94 parts of the salt represented by I1-170) were obtained.
MASS (ESI (+) Spectrum): M ⁺ 481.0
MASS (ESI (-) Spectrum): M ^- 407.1

式（Ｉ－２２５－ｃ）で表される化合物０．８６部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１－ｂ）で表される化合物１．６２部を添加し、５０℃に昇温後、５０℃で２時間撹拌した。得られた反応混合物に、式（Ｉ１－２２５－ａ）で表される塩４．９３部を添加し、５０℃で１０時間撹拌した。得られた反応混合物を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：クロロホルム／メタノール＝１／１）分取することにより、式（Ｉ１－２２５）で表される塩０．９６部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２９７．０ Synthesis Example 4: Synthesis of Salt Represented by Formula (I1-225)

0.86 parts of the compound represented by the formula (I-225-c) and 50 parts of chloroform were mixed and stirred at 23° C. for 30 minutes, and then 1.62 of the compound represented by the formula (I-1-b) After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 4.93 parts of the salt represented by the formula (I1-225-a) was added to the obtained reaction mixture and stirred at 50° C. for 10 hours. The resulting reaction mixture was concentrated, and the concentrated mass was collected by column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: chloroform/methanol=1/1). 0.96 parts of the salt represented by the formula (I1-225) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 297.0

式（Ｉ－２－ｃ）で表される化合物２．６４部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１－ｂ）で表される化合物１．６２部を添加し、５０℃に昇温後、５０℃で２時間撹拌した。得られた反応混合物に、式（Ｉ１－１５６－ａ）で表される塩６．８６部を添加し、５０℃で１０時間撹拌した。得られた反応混合物を２３℃まで冷却した後、イオン交換水２５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２５部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、濃縮残渣に、アセトニトリル３部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ１－１５６）で表される塩８．０９部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４０７．１ Synthesis Example 5: Synthesis of Salt Represented by Formula (I1-156)

2.64 parts of the compound represented by the formula (I-2-c) and 50 parts of chloroform were mixed and stirred at 23° C. for 30 minutes, and then 1.62 parts of the compound represented by the formula (I-1-b) After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 6.86 parts of the salt represented by the formula (I1-156-a) was added to the obtained reaction mixture and stirred at 50° C. for 10 hours. After cooling the resulting reaction mixture to 23° C., 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. After adding 25 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated 5 times. The obtained organic layer is concentrated, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether are added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes, then the supernatant is removed and concentrated to obtain the formula ( 8.09 parts of the salt represented by I1-156) were obtained.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 407.1

式（Ｉ－１６７ａ－ｃ）で表される化合物１．４８部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１－ｂ）で表される化合物１．６２部を添加し、５０℃に昇温後、５０℃で２時間撹拌した。得られた反応混合物に、式（Ｉ１－１５６－ａ）で表される塩６．８６部を添加し、５０℃で１０時間撹拌した。得られた反応混合物を２３℃まで冷却した後、イオン交換水２５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水２５部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、濃縮残渣に、アセトニトリル３部及びｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ１－１６７ａ）で表される塩７．０３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２９１．０ Synthesis Example 6: Synthesis of Salt Represented by Formula (I1-167a)

1.48 parts of the compound represented by the formula (I-167a-c) and 50 parts of chloroform were mixed and stirred at 23° C. for 30 minutes, and then 1.62 of the compound represented by the formula (I-1-b) After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 6.86 parts of the salt represented by the formula (I1-156-a) was added to the obtained reaction mixture and stirred at 50° C. for 10 hours. After cooling the resulting reaction mixture to 23° C., 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. After adding 25 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated 5 times. The obtained organic layer is concentrated, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether are added to the concentration residue, and after stirring at 23° C. for 30 minutes, the supernatant is removed and concentrated to obtain the formula ( 7.03 parts of the salt represented by I1-167a) are obtained.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 291.0

式（Ｉ－２－ｃ）で表される化合物５．２８部、アセトニトリル３０部及び酸化銀２．３２部を混合し、２３℃で４時間攪拌して、ろ過した。得られた濾物に、ｔｅｒｔ－ブチルメチルエーテル２０部を添加し、２３℃で３０分間攪拌して、ろ過することにより、式（Ｉ－２－ｄ）で表される塩５．８６部を得た。

式（Ｉ２－１－ｃ）で表される塩２．９９部、式（Ｉ－２－ｄ）で表される塩３．７１部、メタノール２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌した。得られた混合物に、炭酸カリウム０．４４部を添加し、２３℃で５時間攪拌した。得られた反応物に、クロロホルム６０部及びイオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水３０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を７回繰り返した。得られた有機層を濃縮することにより、濃縮残差に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ２－１）で表される塩４．６３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２６３．１ Synthesis Example 7: Synthesis of Salt Represented by Formula (I2-1)

5.28 parts of the compound represented by the formula (I-2-c), 30 parts of acetonitrile and 2.32 parts of silver oxide were mixed, stirred at 23° C. for 4 hours, and filtered. 20 parts of tert-butyl methyl ether was added to the resulting filtrate, stirred at 23° C. for 30 minutes, and filtered to obtain 5.86 parts of the salt represented by the formula (I-2-d). Obtained.

Mix 2.99 parts of the salt represented by the formula (I2-1-c), 3.71 parts of the salt represented by the formula (I-2-d), 20 parts of methanol and 10 parts of ion-exchanged water, 23 C. for 30 minutes. 0.44 parts of potassium carbonate was added to the obtained mixture, and the mixture was stirred at 23° C. for 5 hours. 60 parts of chloroform and 10 parts of ion-exchanged water were added to the obtained reactant, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated seven times. By concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether is added to the concentration residue, and after stirring at 23° C. for 30 minutes, the supernatant is removed and concentrated to obtain the formula (I2 4.63 parts of the salt represented by -1) were obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 263.1

式（Ｉ２－３２５－ｃ）で表される塩５．１６部、式（Ｉ－２－ｄ）で表される塩３．７１部、メタノール２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌した。得られた混合物に、炭酸カリウム０．４４部を添加し、２３℃で５時間攪拌した。得られた反応物に、クロロホルム６０部及びイオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水３０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を７回繰り返した。得られた有機層を濃縮することにより、濃縮残差に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ２－３２５）で表される塩７．０１部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４８１．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２６３．１ Synthesis Example 8: Synthesis of Salt Represented by Formula (I2-325)

Mix 5.16 parts of the salt represented by the formula (I2-325-c), 3.71 parts of the salt represented by the formula (I-2-d), 20 parts of methanol and 10 parts of ion-exchanged water, 23 C. for 30 minutes. 0.44 parts of potassium carbonate was added to the obtained mixture, and the mixture was stirred at 23° C. for 5 hours. 60 parts of chloroform and 10 parts of ion-exchanged water were added to the obtained reactant, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated seven times. By concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether is added to the concentration residue, and after stirring at 23° C. for 30 minutes, the supernatant is removed and concentrated to obtain the formula (I2 -325) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 481.0
MASS (ESI (-) Spectrum): M ^- 263.1

式（Ｉ２－２９８－ｃ）で表される塩５．６１部、式（Ｉ－２－ｄ）で表される塩３．７１部、メタノール２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌した。得られた混合物に、炭酸カリウム０．４４部を添加し、２３℃で５時間攪拌した。得られた反応物に、クロロホルム６０部及びイオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水３０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を７回繰り返した。得られた有機層を濃縮することにより、濃縮残差に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ２－２９８）で表される塩７．０１部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２６３．１ Synthesis Example 9: Synthesis of Salt Represented by Formula (I2-298)

Mix 5.61 parts of the salt represented by the formula (I2-298-c), 3.71 parts of the salt represented by the formula (I-2-d), 20 parts of methanol and 10 parts of ion-exchanged water, 23 C. for 30 minutes. 0.44 parts of potassium carbonate was added to the obtained mixture, and the mixture was stirred at 23° C. for 5 hours. 60 parts of chloroform and 10 parts of ion-exchanged water were added to the obtained reactant, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated seven times. By concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether is added to the concentration residue, and after stirring at 23° C. for 30 minutes, the supernatant is removed and concentrated to obtain the formula (I2 -298) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 263.1

式（Ｉ－３０２－ｃ）で表される化合物４．１２部、アセトニトリル３０部及び酸化銀２．３２部を混合し、２３℃で４時間攪拌して、ろ過した。得られた濾物に、ｔｅｒｔ－ブチルメチルエーテル２０部を添加し、２３℃で３０分間攪拌して、ろ過することにより、式（Ｉ－３０２－ｄ）で表される塩４．６８部を得た。

式（Ｉ２－２９８－ｃ）で表される塩５．６１部、式（Ｉ－３０２－ｄ）で表される塩３．１３部、メタノール２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌した。得られた混合物に、炭酸カリウム０．４４部を添加し、２３℃で５時間攪拌した。得られた反応物に、クロロホルム６０部及びイオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、イオン交換水３０部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を７回繰り返した。得られた有機層を濃縮することにより、濃縮残差に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ２－３０２）で表される塩４．６３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２０５．１ Synthesis Example 10: Synthesis of Salt Represented by Formula (I2-302)

4.12 parts of the compound represented by formula (I-302-c), 30 parts of acetonitrile and 2.32 parts of silver oxide were mixed, stirred at 23° C. for 4 hours, and filtered. 20 parts of tert-butyl methyl ether was added to the resulting filtrate, stirred at 23° C. for 30 minutes, and filtered to obtain 4.68 parts of the salt represented by the formula (I-302-d). Obtained.

Mix 5.61 parts of the salt represented by the formula (I2-298-c), 3.13 parts of the salt represented by the formula (I-302-d), 20 parts of methanol and 10 parts of ion-exchanged water, 23 C. for 30 minutes. 0.44 parts of potassium carbonate was added to the obtained mixture, and the mixture was stirred at 23° C. for 5 hours. 60 parts of chloroform and 10 parts of ion-exchanged water were added to the obtained reactant, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 30 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the organic layer was taken out by liquid separation. This washing operation was repeated seven times. By concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether is added to the concentration residue, and after stirring at 23° C. for 30 minutes, the supernatant is removed and concentrated to obtain the formula (I2 -302) to obtain 4.63 parts of the salt.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 205.1

式（ＩＸ２－１－ｃ）で表される化合物４．４４部、アセトニトリル３０部及び酸化銀２．３２部を混合し、２３℃で４時間攪拌して、ろ過した。得られた濾物に、ｔｅｒｔ－ブチルメチルエーテル２０部を添加し、２３℃で３０分間攪拌して、ろ過することにより、式（ＩＸ２－１－ｄ）で表される塩３．９５部を得た。

式（Ｉ２－１－ｃ）で表される塩２．９９部、式（ＩＸ２－１－ｄ）で表される塩３．２９部、アセトニトリル３０部を混合し、２３℃で３０分間攪拌した。得られた混合物に、炭酸カリウム０．４４部を添加し、２３℃で５時間攪拌した。得られた反応混合物を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：クロロホルム／メタノール＝１／１）分取することにより、式（ＩＸ２－１）で表される塩０．４８部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２２１．１ Synthesis Example 11: Synthesis of Salt Represented by Formula (IX2-1)

4.44 parts of the compound represented by formula (IX2-1-c), 30 parts of acetonitrile and 2.32 parts of silver oxide were mixed, stirred at 23° C. for 4 hours, and filtered. 20 parts of tert-butyl methyl ether was added to the resulting filtrate, stirred at 23° C. for 30 minutes, and filtered to obtain 3.95 parts of the salt represented by the formula (IX2-1-d). Obtained.

2.99 parts of the salt represented by the formula (I2-1-c), 3.29 parts of the salt represented by the formula (IX2-1-d), and 30 parts of acetonitrile were mixed and stirred at 23° C. for 30 minutes. . 0.44 parts of potassium carbonate was added to the obtained mixture, and the mixture was stirred at 23° C. for 5 hours. The resulting reaction mixture was concentrated, and the concentrated mass was collected by column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: chloroform/methanol=1/1). 0.48 parts of the salt represented by the formula (IX2-1) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 221.1

Synthesis of Resin The compounds (monomers) used in synthesizing Resin (A1), Resin (A2) and Resin (AA) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-3)" and the like according to their formula numbers.

Synthesis Example 12 [Synthesis of Resin A1-1]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I1-1), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I1-1)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain Resin A1-1 having a weight average molecular weight of about 5.4×10 ³ with a yield of 60%. rice field. This resin A1-1 has the following structural units.

Synthesis Example 13 [Synthesis of Resin A1-2]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I1-169), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I1-169)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain resin A1-2 having a weight average molecular weight of about 5.5×10 ³ with a yield of 64%. rice field. This resin A1-2 has the following structural units.

Synthesis Example 14 [Synthesis of Resin A1-3]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I1-170), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I1-170)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain Resin A1-3 having a weight average molecular weight of about 5.3×10 ³ with a yield of 67%. rice field. This resin A1-3 has the following structural units.

Synthesis Example 15 [Synthesis of resin A1-4]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I1-225), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I1-225)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain Resin A1-4 having a weight average molecular weight of about 5.3×10 ³ with a yield of 52%. rice field. This resin A1-4 has the following structural units.

Synthesis Example 16 [Synthesis of resin A1-5]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I1-156), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I1-156)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain Resin A1-5 having a weight average molecular weight of about 5.2×10 ³ with a yield of 69%. rice field. This resin A1-5 has the following structural units.

Synthesis Example 17 [Synthesis of resin A1-6]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I1-167a), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I1-167a)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain resin A1-6 having a weight average molecular weight of about 5.5×10 ³ with a yield of 65%. rice field. This resin A1-6 has the following structural units.

Synthesis Example 18 [Synthesis of Resin A2-1]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I2-1), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I2-1)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain resin A2-1 having a weight average molecular weight of about 5.5×10 ³ with a yield of 66%. rice field. This resin A2-1 has the following structural units.

Synthesis Example 19 [Synthesis of Resin A2-2]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I2-325), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I2-325)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain resin A2-2 having a weight average molecular weight of about 5.4×10 ³ with a yield of 60%. rice field. This resin A2-2 has the following structural units.

Synthesis Example 20 [Synthesis of resin A2-3]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I2-298), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I2-298)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain resin A2-3 having a weight average molecular weight of about 5.3×10 ³ with a yield of 68%. rice field. This resin A2-3 has the following structural units.

Synthesis Example 21 [Synthesis of resin A2-4]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( I2-302), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (I2-302)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain resin A2-4 having a weight average molecular weight of about 5.4×10 ³ with a yield of 67%. rice field. This resin A2-4 has the following structural units.

Synthesis Example 22 [Synthesis of Resin AX2-1]
As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2), monomer (a1-4-2) and monomer ( IX2-1), the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1 -4-2): Monomer (IX2-1)] are mixed in a ratio of 20:32:3:16:25:4, and further, to this monomer mixture, , and 1.5 times the mass of methyl isobutyl ketone. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) was added to the polymerization reaction solution in an amount of 2.0 times the weight of the total weight of all the monomers, stirred for 12 hours, and then separated. The collected organic layer is poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain resin AX2-1 having a weight average molecular weight of about 5.5×10 ³ with a yield of 51%. rice field. This resin AX2-1 has the following structural units.

Synthesis Example 23 [Synthesis of Resin AA1]
Using monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-2) as monomers, The molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2)] is , 20:32:3:20:25, and this monomer mixture was further mixed with methyl isobutyl ketone in an amount of 1.5 times the mass of the total mass of all the monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers. C. for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5% by weight) in an amount of 2.0 times the total weight of all monomers was added to the polymerization reaction solution, stirred for 12 hours, and separated. The collected organic layer was poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain Resin AA1 having a weight average molecular weight of about 5.5×10 ³ with a yield of 68%. This resin AA1 has the following structural units.

<Preparation of resist composition>
As shown in Table 3, a resist composition was prepared by mixing the following components and filtering the resulting mixture through a fluororesin filter having a pore size of 0.2 μm.

＜クエンチャー（Ｃ）＞
Ｃ１：特開２０１１－３９５０２号公報記載の方法で合成

＜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 １００部
γ－ブチロラクトン ５部 <Resin>
A1-1 to A1-6, A2-1 to A2-4, AX2-1, AA1: Resin A1-1 to Resin A1-6, Resin A2-1 to Resin A2-4, Resin AX2-1, Resin AA1
<Acid generator>
B1-25: a salt represented by the formula (B1-25); synthesized by the method described in JP-A-2011-126869

<Quencher (C)>
C1: synthesized by the method described in JP-A-2011-39502

<Solvent>
Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts

(Evaluation of resist composition by electron beam exposure: organic solvent development)
A 6-inch silicon wafer was treated with hexamethyldisilazane at 90° C. for 60 seconds on a direct hotplate. This silicon wafer was spin-coated with the resist composition so that the film thickness of the composition layer was 0.04 μm. Then, it was pre-baked on a direct hot plate at the temperature shown in the "PB" column of Table 3 for 60 seconds to form a composition layer. A line and space pattern (pitch: 36 to 72 nm) was formed on the composition layer formed on the wafer using an electron beam lithography machine [“ELS-F125 125 keV” manufactured by Elionix Co., Ltd.] with stepwise changes in the exposure dose. /line width 18-36 nm) were directly written.
After the exposure, post-exposure baking was performed for 60 seconds on a hot plate at the temperature shown in the "PEB" column of Table 3. Then, the composition layer on the silicon wafer was developed using butyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a developer by a dynamic dispensing method at 23° C. for 20 seconds to obtain a resist pattern. .
Effective sensitivity was defined as the amount of exposure at which the line width and space width of the 36 nm line-and-space pattern were 1:1 in the resulting resist pattern.

比較組成物１～４と比較し、組成物１～２４は解像度の評価が良好であった。 <Resolution evaluation>
In the effective sensitivity, the resist pattern was observed with a scanning electron microscope, and the resolved minimum line width was defined as the resolution. Table 4 shows the results. Resolution (nm) is indicated.

Compared with Comparative Compositions 1-4, Compositions 1-24 were evaluated as good in terms of resolution.

INDUSTRIAL APPLICABILITY The resist composition of the present invention provides a resist pattern with good resolution, is suitable for fine processing of semiconductors, and is industrially extremely useful.

Claims (17)

A resist composition containing a resin (A1) containing a structural unit represented by formula (I1) and a resin (A2) containing a structural unit represented by formula (I2).

[In the formulas (I1) and (I2),
Q ^b1 and Q ^b2 each independently represent a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO— , a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y ^b1 represents a single bond or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O— , —CO—, —S— or —SO ₂ —.
X ⁰ represents a single bond or an optionally substituted hydrocarbon group having 1 to 72 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO - or -SO ₂ - may be substituted. However, the atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom.
R ¹⁰ and R ²⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
X ¹⁰ and X ²⁰ are each independently a single bond, *-O-**, *-CO-O-**, *-O-CO-O-** or *-Ax-Ph-Ay-* * represents.
Ax and Ay each independently represent one type of bond selected from the group consisting of a single bond, an ether bond, an ester bond and a carbonate bond.
Ph represents a phenylene group optionally having a substituent.
* represents the bonding site with the carbon atom to which ^R10 or ^R20 is bonded, and ** represents the bonding site with ^L10 or ^L20 .
L ¹⁰ and L ²⁰ each independently represent a single bond or an optionally substituted hydrocarbon group having 1 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O— , —S—, —SO ₂ — or —CO—.
Z1 ⁺ and Z2 ⁺ each independently represent an organic cation. ] Y ^b1 is a single bond or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, - CO-, -S- or -SO ₂ - may be substituted). 3. The resist composition according to claim 2, wherein ^Yb1 is a cyclohexanediyl group, adamantanediyl group, norbornanediyl group, adamantanelactonediyl group or norbornanelactonediyl group. X ⁰ is a single bond or an optionally substituted aliphatic hydrocarbon group having 1 to 72 carbon atoms (-CH ₂ - contained in the aliphatic hydrocarbon group is -O-, - may be substituted with S—, —CO— or ^—SO ₂ —) _or optionally substituted aromatic hydrocarbon groups having 6 to 36 carbon atoms (provided that The atoms are carbon atoms, and the carbon atoms are not substituted with fluorine atoms.) The resist composition of Claim 1. X ⁰ is a single bond or a chain hydrocarbon group of 1 to 18 carbon atoms optionally having a fluorine atom, a perfluoroalkyl group of 1 to 4 carbon atoms or a hydroxy group (the chain hydrocarbon group —CH ₂ — contained may be replaced with —O— or —CO—.), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group, optionally having 3 to 36 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -), carbon A group obtained by combining an alicyclic hydrocarbon group of number 3 to 36 with a chain hydrocarbon group of 1 to 18 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, - S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—, and the alicyclic The formula hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group.), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a hydroxy group, or a group obtained by combining an aromatic hydrocarbon group having 6 to 36 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and the aromatic hydrocarbon group and the chain hydrocarbon group may contain a fluorine atom, a carbon number (It may have 1 to 4 perfluoroalkyl groups or hydroxy groups.) (provided that the atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom.) Claim 4 The resist composition described in . X ⁰ includes an alicyclic hydrocarbon group, and the alicyclic hydrocarbon group is a cycloalkanediyl group having 5 or 6 carbon atoms, an adamantanediyl group, a norbornanediyl group, an adamantanelactonediyl group, a norbornanelactonediyl group , or an adamantanediyl group and a cycloalkanediyl group having 5 or 6 carbon atoms spiro-bonded to the adamantanediyl group (the adamantanediyl group, norbornanediyl group and cycloalkanediyl group are fluorine atoms, carbon atoms of 1 to 4 —CH ₂ — contained in the adamantanediyl group, norbornanediyl group and cycloalkanediyl group may be replaced with —O— or —CO—. ), provided that the atom adjacent to CO ₂ ^— is a carbon atom, and the carbon atom is not substituted with a fluorine atom. X ¹⁰ and X ²⁰ are each independently a single bond or any one of formula (X ¹ -1), formula (X ¹ -8) and formula (X ¹ -2') to formula (X ¹ -7') 2. The resist composition according to claim 1, which is a group represented by:

[In formula (X ¹ -1), formula (X ¹ -8) and formula (X ¹ -2′) to formula (X ¹ -7′),
*, ** is a binding site, and ** represents a binding site with ^L10 or ^L20 .
Rx represents a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
mx represents any integer from 0 to 4; ] 8. The resist composition according to claim 7, wherein X ¹⁰ and X ²⁰ are each independently a single bond or a group represented by any one of formulas (X ¹ -1) to (X ¹ -7).

[In the formulas (X ¹ -1) to (X ¹ -7),
*, ** is a binding site, and ** represents a binding site with ^L10 or ^L20 . ] 8. X ¹⁰ and X ²⁰ are each independently a single bond or a group represented by any one of formulas (X ¹ -1), (X ¹ -4) and (X ¹ -5) The resist composition described in . L ¹⁰ and L ²⁰ are each independently a single bond and an alkanediyl group having 1 to 6 carbon atoms (with the proviso that —CH ₂ — contained in the alkanediyl group is replaced with —O— or —CO—; ), a cyclic hydrocarbon group having 3 to 18 carbon atoms (wherein the cyclic hydrocarbon group may have a substituent, and —CH ₂ — contained in the cyclic hydrocarbon group is —O -, -S-, -SO ₂ - or -CO-) or a group formed by combining an alkanediyl group having 1 to 6 carbon atoms and a cyclic hydrocarbon group having 3 to 18 carbon atoms ( However, the cyclic hydrocarbon group may have a substituent, and —CH ₂ — contained in the alkanediyl group may be replaced with —O— or —CO—, and the cyclic hydrocarbon group may be substituted with —O— or —CO—. -CH ₂ - contained in may be replaced with -O-, -S-, -SO ₂ - or -CO-). 2. The resist composition according to claim 1, wherein at least one of resin (A1) and resin (A2) further comprises a structural unit having an acid labile group. The structural unit having an acid-labile group consists of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2). 12. The resist composition according to claim 11, comprising at least one selected from the group.

[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 an integer of 1 to 7, * is represents the binding site with -CO-.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom, a halogen atom or an optionally halogenated alkyl group having 1 to 6 carbon atoms.
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, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Represents a combined group.
R ^a6 and R ^a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. It represents a hydrocarbon group or a group formed by combining these groups.
m1 represents any integer from 0 to 14;
n1 represents any integer from 0 to 10;
n1' represents an integer of 0 to 3; ] 2. The resist composition according to claim 1, wherein at least one of resin (A1) and resin (A2) further comprises a structural unit represented by formula (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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, It represents an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or *-X ^a51 -(A ^a52 -X ^a52 ) _nb -, and * represents a bonding site with the carbon atom to which -R ^a50 bonds.
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent -O-, -CO-O- or -O-CO-.
nb represents 0 or 1;
mb represents an integer from 0 to 4; When mb is any integer of 2 or more, multiple R ^a51 may be the same or different. ] 2. The resist composition according to claim 1, further comprising an acid generator. 15. The resist composition according to claim 14, wherein the acid generator contains a salt represented by formula (B1).

[In formula (B1),
Q ^b1 and Q ^b2 each independently represent a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO— , a 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 24 carbon atoms, included in the alicyclic hydrocarbon group- CH ₂ - may be replaced by -O-, -S-, -SO ₂ - or -CO-.
Z ⁺ represents an organic cation. ] 15. The resist composition according to claim 14, further comprising a salt that generates an acid weaker in acidity than the acid generated from the acid generator. (1) a step of applying the resist composition according to any one of claims 1 to 16 onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the composition layer after exposure; and (5) developing the composition layer after heating;
A method of manufacturing a resist pattern comprising: