JP2022141598A - Carboxylate, carboxylic acid generator, resist composition, and method for producing resist pattern - Google Patents

Abstract

To provide a carboxylate, a carboxylic acid generator, and a resist composition which allow a resist pattern having good line edge roughness to be produced.SOLUTION: There are provided a carboxylate represented by a formula (I), a carboxylic acid generator, and a resist composition. [In the formula, L1 represents a single bond or an optionally substituted hydrocarbon group; R10 represents a group represented by a formula (R10-1) or a formula (R10-2); when L1 is a single bond, R10 is a group represented by a formula (R10-1); Z+ represents an organic cation; ring W represents an alicyclic hydrocarbon group; each R1 independently represents a halogen atom, a hydroxy group, a haloalkyl group, an alkyl group, an alicyclic hydrocarbon group or a group composed of a combination thereof; m1 represents an integer of 0-6; m2 represents an integer of 1-6; and * represents a binding site to L1.]SELECTED DRAWING: None

Description

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

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

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

JP 2014-089440 A JP 2020-152721 A

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

［式（Ｉ）中、
Ｌ¹は、単結合又は置換基を有してもよい炭素数１～６０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。
Ｒ^１０は、式（Ｒ１０－１）又は式（Ｒ１０－２）で表される基を表す。
Ｌ^１が単結合の時、Ｒ^１０は式（Ｒ１０－１）で表される基である。
Ｚ^＋は、有機カチオンを表す。］

［式（Ｒ１０－１）及び式（Ｒ１０－２）中、
環Ｗは、炭素数３～３６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－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｒ^１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のハロアルキル基、炭素数１～１２のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合せた基を表し、該ハロアルキル基、該アルキル基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい。
ｍ１は、０～６のいずれかの整数を表し、ｍ１が２以上のとき、複数のＲ^１は互いに同一であっても異なってもよい。
ｍ２は、１～６のいずれかの整数を表す。
＊は、Ｌ¹との結合部位を表す。］
［２］Ｌ^１が、単結合、置換基を有してもよい炭素数１～１０の鎖式炭化水素基（但し、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。）、置換基を有してもよい炭素数３～２４の環状炭化水素基（但し、該環状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１～８の鎖式炭化水素基と置換基を有してもよい炭素数３～２４の環状炭化水素基とを組み合わせてなる基（但し、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］に記載のカルボン酸発生剤。
［３］＊－Ｌ^１－Ｒ^１０が、式（Ｌ１－０）～式（Ｌ１－５）のいずれかで表される基である［１］又は［２］に記載のカルボン酸発生剤。

［式（Ｌ１－０）～式（Ｌ１－５）中、
環Ｗ、Ｒ^１、ｍ１及びｍ２は、上記と同じ意味を表す。
Ｌ^２は、置換基を有してもよい炭素数１～１０の鎖式炭化水素基、置換基を有してもよい炭素数３～２４の環状炭化水素基又は置換基を有してもよい炭素数３～２４の環状炭化水素基と置換基を有してもよい炭素数１～８の鎖式炭化水素基とを組み合わせた基を表し、該環状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い。
Ｌ^３及びＬ^４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１～８の鎖式炭化水素基を表し、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。
Ｌ^５及びＬ^６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１～１０の鎖式炭化水素基を表し、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。
環Ｗ３は、置換基を有してもよい炭素数３～２４の環状炭化水素基を表し、該環状炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
環Ｗ４及び環Ｗ５は、それぞれ独立に、置換基を有してもよい炭素数３～１８の環状炭化水素基を表し、該環状炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｘ^３は、＊＊－ＣＯ－Ｏ－、＊＊－Ｏ－ＣＯ－、＊＊－Ｏ－ＣＯ－Ｏ－又は＊＊－Ｏ－を表す。
Ｘ^ａ及びＸ^ｂは、それぞれ独立に、－Ｏ－又は－Ｓ－を表す。
Ｘ^０１は、置換基を有してもよい炭素数１～４０の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｒ^２１及びＲ^２２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のハロアルキル基、炭素数１～１２のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合せた基を表し、該ハロアルキル基、該アルキル基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい。
ｍ２１は、０～６のいずれかの整数を表し、ｍ２１が２以上のとき、複数のＲ^２１は互いに同一であっても異なってもよい。
ｍ２２は、０～６のいずれかの整数を表し、ｍ２２が２以上のとき、複数のＲ^２２は互いに同一であっても異なってもよい。
＊は、カルボニル基の炭素原子との結合部位を表す。＊＊は、Ｌ^２との結合部位を表す。］
［４］Ｘ^０１が、式（Ｘ¹－１）、式（Ｘ¹－３）及び式（Ｘ¹－５）～式（Ｘ¹－７）のいずれかで表される基である［３］に記載のカルボン酸発生剤。

［式（Ｘ¹－１）、式（Ｘ¹－３）及び式（Ｘ¹－５）～式（Ｘ¹－７）中、
Ｌ^1１は、単結合又は置換基を有してもよい炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
＊は、結合部位を表す。］
［５］環Ｗが、式（ｗ１－１）で表される環に由来する基、式（ｗ１－２）で表される環に由来する基、式（ｗ１－３）で表される環に由来する基、式（ｗ１－６）で表される環に由来する基又は式（ｗ１－１５）で表される環に由来する基である［１］～［４］のいずれかに記載のカルボン酸発生剤。

［式（ｗ１－１）、式（ｗ１－２）、式（ｗ１－３）、式（ｗ１－６）及び式（ｗ１－１５）中、
該基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。結合部位は任意の位置である。］
［６］ｍ２が、１又は２である［１］～［５］のいずれかに記載のカルボン酸発生剤。
［７］［１］～［６］のいずれかに記載のカルボン酸発生剤、該カルボン酸発生剤以外の酸発生剤及び酸不安定基を有する樹脂を含有するレジスト組成物。
［８］酸不安定基を有する樹脂が、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［７］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。］
［９］酸不安定基を有する樹脂が、式（ａ２－Ａ）で表される構造単位を含む［７］又は［８］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。］
［１０］（１）［７］～［９］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。
［１１］式（Ｉ）で表されるカルボン酸塩。

［式（Ｉ）中、
Ｌ¹は、単結合又は置換基を有してもよい炭素数１～６０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。
Ｒ^１０は、式（Ｒ１０－１）又は式（Ｒ１０－２）で表される基を表す。
Ｌ^１が単結合の時、Ｒ^１０は式（Ｒ１０－１）で表される基である。
Ｚ^＋は、有機カチオンを表す。］

［式（Ｒ１０－１）及び式（Ｒ１０－２）中、
環Ｗは、炭素数３～３６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－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｒ^１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のハロアルキル基、炭素数１～１２のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合せた基を表し、該ハロアルキル基、該アルキル基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい。
ｍ１は、０～６のいずれかの整数を表し、ｍ１が２以上のとき、複数のＲ^１は互いに同一であっても異なってもよい。
ｍ２は、１～６のいずれかの整数を表す。
＊は、Ｌ¹との結合部位を表す。］
［１２］Ｌ^１が、単結合、置換基を有してもよい炭素数１～１０の鎖式炭化水素基（但し、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。）、置換基を有してもよい炭素数３～２４の環状炭化水素基（但し、該環状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１～８の鎖式炭化水素基と置換基を有してもよい炭素数３～２４の環状炭化水素基とを組み合わせてなる基（但し、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［１１］に記載のカルボン酸塩。
［１３］＊－Ｌ^１－Ｒ^１０が、式（Ｌ１－０）～式（Ｌ１－５）のいずれかで表される基である［１１］又は［１２］に記載のカルボン酸塩。

［式（Ｌ１－０）～式（Ｌ１－５）中、
環Ｗ、Ｒ^１、ｍ１及びｍ２は、上記と同じ意味を表す。
Ｌ^２は、置換基を有してもよい炭素数１～１０の鎖式炭化水素基、置換基を有してもよい炭素数３～２４の環状炭化水素基又は置換基を有してもよい炭素数３～２４の環状炭化水素基と置換基を有してもよい炭素数１～８の鎖式炭化水素基とを組み合わせた基を表し、該環状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い。
Ｌ^３及びＬ^４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１～８の鎖式炭化水素基を表し、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。
Ｌ^５及びＬ^６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１～１０の鎖式炭化水素基を表し、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。
環Ｗ３は、置換基を有してもよい炭素数３～２４の環状炭化水素基を表し、該環状炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
環Ｗ４及び環Ｗ５は、それぞれ独立に、置換基を有してもよい炭素数３～１８の環状炭化水素基を表し、該環状炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｘ^３は、＊＊－ＣＯ－Ｏ－、＊＊－Ｏ－ＣＯ－、＊＊－Ｏ－ＣＯ－Ｏ－又は＊＊－Ｏ－を表す。
Ｘ^ａ及びＸ^ｂは、それぞれ独立に、－Ｏ－又は－Ｓ－を表す。
Ｘ^０１は、置換基を有してもよい炭素数１～４０の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｒ^２１及びＲ^２２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のハロアルキル基、炭素数１～１２のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合せた基を表し、該ハロアルキル基、該アルキル基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい。
ｍ２１は、０～６のいずれかの整数を表し、ｍ２１が２以上のとき、複数のＲ^２１は互いに同一であっても異なってもよい。
ｍ２２は、０～６のいずれかの整数を表し、ｍ２２が２以上のとき、複数のＲ^２２は互いに同一であっても異なってもよい。
＊は、カルボニル基の炭素原子との結合部位を表す。＊＊は、Ｌ^２との結合部位を表す。］
［１４］Ｘ^０１が、式（Ｘ¹－１）、式（Ｘ¹－３）及び式（Ｘ¹－５）～式（Ｘ¹－７）のいずれかで表される基である［１３］に記載のカルボン酸塩。

［式（Ｘ¹－１）、式（Ｘ¹－３）及び式（Ｘ¹－５）～式（Ｘ¹－７）中、
Ｌ^1１は、単結合又は置換基を有してもよい炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
＊は、結合部位を表す。］
［１５］環Ｗが、式（ｗ１－１）で表される環に由来する基、式（ｗ１－２）で表される環に由来する基、式（ｗ１－３）で表される環に由来する基、式（ｗ１－６）で表される環に由来する基又は式（ｗ１－１５）で表される環に由来する基である［１１］～［１４］のいずれかに記載のカルボン酸塩。

［式（ｗ１－１）、式（ｗ１－２）、式（ｗ１－３）、式（ｗ１－６）及び式（ｗ１－１５）中、
該基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。結合部位は任意の位置である。］
［１６］ｍ２が、１又は２である［１１］～［１５］のいずれかに記載のカルボン酸塩。 The present invention includes the following inventions.
[1] A carboxylic acid generator containing a carboxylate represented by formula (I).

[in the formula (I),
L ¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 60 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
R ¹⁰ represents a group represented by formula (R10-1) or formula (R10-2).
When L ¹ is a single bond, R ¹⁰ is a group represented by formula (R10-1).
Z ⁺ represents an organic cation. ]

[In the formulas (R10-1) and (R10-2),
Ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—, —CO— or —SO ₂ - may be replaced.
R ¹ is each independently a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these and —CH ₂ — contained in the haloalkyl group, the alkyl group and the alicyclic hydrocarbon group may be replaced with —O— or —CO—.
m1 represents an integer of 0 to 6, and when m1 is 2 or more, multiple R ^1s may be the same or different.
m2 represents an integer of 1 to 6;
* represents the binding site with ^L1 . ]
[2] L ¹ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms (with the proviso that —CH ₂ — contained in the chain hydrocarbon group is —O— or --CO--), optionally substituted cyclic hydrocarbon group having 3 to 24 carbon atoms (with the proviso that --CH ₂ -- contained in the cyclic hydrocarbon group is --O -, -S-, -CO- or -SO ₂ -.) or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms and a substituent a group formed by combining a good cyclic hydrocarbon group having 3 to 24 carbon atoms (with the proviso that —CH ₂ — contained in said chain hydrocarbon group may be replaced with —O— or —CO—; --CH ₂ -- contained in the cyclic hydrocarbon group may be replaced with --O--, --S--, --SO ₂ -- or --CO--).
[3] The carboxylic acid generator according to [1] or [2], wherein *-L ¹ -R ¹⁰ is a group represented by any one of formulas (L1-0) to (L1-5).

[In the formulas (L1-0) to (L1-5),
Ring W, R ¹ , m1 and m2 have the same meanings as above.
L ² is an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may be substituted, or optionally having a substituent —CH ₂ which represents a group obtained by combining a cyclic hydrocarbon group having 3 to 24 carbon atoms and a chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and contained in the cyclic hydrocarbon group; — may be replaced with —O—, —S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—. may be
L ³ and L ⁴ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
L ⁵ and L ⁶ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
Ring W3 represents an optionally substituted cyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, —S—, —CO— Alternatively, it may be replaced with -SO ₂ -.
Ring W4 and ring W5 each independently represent an optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, -S-, -CO- or -SO ₂ - may be substituted.
X3 represents **-CO ^- O-, **-O-CO-, **-O-CO-O- or **-O-.
X ^a and X ^b each independently represent -O- or -S-.
X ⁰¹ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or — SO ₂ - may be substituted.
R ²¹ and R ²² each independently represent a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or these --CH ₂ -- contained in said haloalkyl group, said alkyl group and said alicyclic hydrocarbon group representing a combination of groups may be replaced with --O-- or --CO--.
m21 represents an integer of 0 to 6, and when m21 is 2 or more, multiple R ²¹ may be the same or different.
m22 represents an integer of 0 to 6, and when m22 is 2 or more, multiple R ²² may be the same or different.
* represents the bonding site with the carbon atom of the carbonyl group. ^** represents the binding site with L2. ]
[4] X ⁰¹ is a group represented by formula (X ¹ -1), formula (X ¹ -3) or formula (X ¹ -5) to formula (X ¹ -7) [3 ] The carboxylic acid generator according to .

[In formula (X ¹ -1), formula (X ¹ -3) and formula (X ¹ -5) to formula (X ¹ -7),
L ¹¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
* represents the binding site. ]
[5] Ring W is a group derived from a ring represented by formula (w1-1), a group derived from a ring represented by formula (w1-2), a ring represented by formula (w1-3) A group derived from, a group derived from a ring represented by formula (w1-6) or a group derived from a ring represented by formula (w1-15) according to any one of [1] to [4] carboxylic acid generator.

[In formula (w1-1), formula (w1-2), formula (w1-3), formula (w1-6) and formula (w1-15),
—CH ₂ — included in the group may be replaced with —O—, —S—, —CO— or —SO ₂ —. The binding site can be any position. ]
[6] The carboxylic acid generator according to any one of [1] to [5], wherein m2 is 1 or 2.
[7] A resist composition containing the carboxylic acid generator according to any one of [1] to [6], an acid generator other than the carboxylic acid generator, and a resin having an acid labile group.
[8] The resin having an acid-labile group is 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). The resist composition according to [7], containing at least one selected from the group consisting of:

[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; ]
[9] The resist composition of [7] or [8], wherein the resin having an acid-labile group contains 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. ]
[10] (1) a step of applying the resist composition according to any one of [7] to [9] 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:
[11] A carboxylate represented by formula (I).

[in the formula (I),
L ¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 60 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
R ¹⁰ represents a group represented by formula (R10-1) or formula (R10-2).
When L ¹ is a single bond, R ¹⁰ is a group represented by formula (R10-1).
Z ⁺ represents an organic cation. ]

[In the formulas (R10-1) and (R10-2),
Ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—, —CO— or —SO ₂ - may be replaced.
R ¹ is each independently a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these and —CH ₂ — contained in the haloalkyl group, the alkyl group and the alicyclic hydrocarbon group may be replaced with —O— or —CO—.
m1 represents an integer of 0 to 6, and when m1 is 2 or more, multiple R ^1s may be the same or different.
m2 represents an integer of 1 to 6;
* represents the binding site with ^L1 . ]
[12] L ¹ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms (with the proviso that —CH ₂ — contained in the chain hydrocarbon group is —O— or --CO--), optionally substituted cyclic hydrocarbon group having 3 to 24 carbon atoms (with the proviso that --CH ₂ -- contained in the cyclic hydrocarbon group is --O -, -S-, -CO- or -SO ₂ -.) or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms and a substituent a group formed by combining a good cyclic hydrocarbon group having 3 to 24 carbon atoms (with the proviso that —CH ₂ — contained in said chain hydrocarbon group may be replaced with —O— or —CO—; --CH ₂ -- contained in the cyclic hydrocarbon group may be replaced with --O--, --S--, --SO ₂ -- or --CO--), the carboxylate according to [11].
[13] The carboxylate according to [11] or [12], wherein *-L ¹ -R ¹⁰ is a group represented by any one of formulas (L1-0) to (L1-5).

[In the formulas (L1-0) to (L1-5),
Ring W, R ¹ , m1 and m2 have the same meanings as above.
L ² is an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may be substituted, or optionally having a substituent —CH ₂ which represents a group obtained by combining a cyclic hydrocarbon group having 3 to 24 carbon atoms and a chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and contained in the cyclic hydrocarbon group; — may be replaced with —O—, —S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—. may be
L ³ and L ⁴ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
L ⁵ and L ⁶ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
Ring W3 represents an optionally substituted cyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, —S—, —CO— Alternatively, it may be replaced with -SO ₂ -.
Ring W4 and ring W5 each independently represent an optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, -S-, -CO- or -SO ₂ - may be substituted.
X3 represents **-CO ^- O-, **-O-CO-, **-O-CO-O- or **-O-.
X ^a and X ^b each independently represent -O- or -S-.
X ⁰¹ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or — SO ₂ - may be substituted.
R ²¹ and R ²² each independently represent a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or these --CH ₂ -- contained in said haloalkyl group, said alkyl group and said alicyclic hydrocarbon group representing a combination of groups may be replaced with --O-- or --CO--.
m21 represents an integer of 0 to 6, and when m21 is 2 or more, multiple R ²¹ may be the same or different.
m22 represents an integer of 0 to 6, and when m22 is 2 or more, multiple R ²² may be the same or different.
* represents the bonding site with the carbon atom of the carbonyl group. ^** represents the binding site with L2. ]
[14] X ⁰¹ is a group represented by formula (X ¹ -1), formula (X ¹ -3) or formula (X ¹ -5) to formula (X ¹ -7) [13 ] The carboxylate according to .

[In formula (X ¹ -1), formula (X ¹ -3) and formula (X ¹ -5) to formula (X ¹ -7),
L ¹¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
* represents the binding site. ]
[15] Ring W is a group derived from a ring represented by formula (w1-1), a group derived from a ring represented by formula (w1-2), or a ring represented by formula (w1-3) A group derived from, a group derived from a ring represented by formula (w1-6) or a group derived from a ring represented by formula (w1-15) according to any one of [11] to [14] carboxylate of.

[In formula (w1-1), formula (w1-2), formula (w1-3), formula (w1-6) and formula (w1-15),
—CH ₂ — included in the group may be replaced with —O—, —S—, —CO— or —SO ₂ —. The binding site can be any position. ]
[16] The carboxylate according to any one of [11] to [15], wherein m2 is 1 or 2.

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

As used herein, "(meth)acrylic monomer" means "at least one kind of acrylic monomer and methacrylic monomer". Notations 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—, —SO— 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 bonded, and the valence of these groups may be changed as appropriate depending on the bonding form. "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.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］ [Carboxylate Represented by Formula (I)]
The present invention relates to a carboxylate represented by formula (I) (hereinafter sometimes referred to as "carboxylate (I)" or "salt (I)").
In the salt (I), the negatively charged side is sometimes referred to as "anion (I)" and the positively charged side is referred to as "cation (I)".

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

例えば、シクロアルカンジイル基、シクロアルカントリイル基等の２～３価の脂環式炭化水素基等が挙げられる。
具体的には、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、シクロヘキサン－１，２－ジイル基、シクロヘキサン－１，３－ジイル基、シクロオクタン－１，５－ジイル基、シクロプロパントリイル基、シクロブタントリイル基、シクロペンタントリイル基、シクロヘキサントリイル基、シクロヘプタントリイル基、シクロオクタントリイル基、シクロデカントリイル基等の単環式の脂環式炭化水素基及び
ノルボルナン－１，４－ジイル基、ノルボルナン－２，５－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、デカヒドロナフタレンジイル基、ビシクロ[３．３．０]オクタンジイル基、デカヒドロナフタレントリイル基、アダマンタントリイル基、ノルボルナントリイル基、ビシクロ[３．３．０]オクタントリイル基等の多環式の脂環式炭化水素基が挙げられる。
また、上述した基の水素原子の１つ以上を結合部位に置き換えた基等も挙げられる。
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３～２０であり、より一層好ましくは３～１８であり、さらに一層好ましくは３～１６であり、さらにより好ましくは３～１２である。
芳香族炭化水素基としては、アリーレン基、アレーントリイル基等の２～３価の芳香族炭化水素基等が挙げられる。
具体的には、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、ベンゼントリイル基、ナフタレントリイル基、アントラセントリイル基、ビフェニレントリイル基、フェナントレントリイル基等の芳香族炭化水素基が挙げられる。
また、上述した基の水素原子の１つ以上を結合部位に置き換えた基等も挙げられる。
芳香族炭化水素基の炭素数は、好ましくは６～３６であり、より好ましくは６～２４であり、さらに好ましくは６～２０であり、より一層好ましくは６～１８であり、さらに一層好ましくは６～１４であり、さらにより好ましくは６～１０である。 In formula (I), the hydrocarbon group for L ¹ includes a chain hydrocarbon group, a monocyclic or polycyclic (including spiro ring, condensed ring, bridged ring, etc.) alicyclic hydrocarbon group, Examples include cyclic hydrocarbon groups such as aromatic hydrocarbon groups (including condensed rings with alicyclic hydrocarbon groups, etc.), and groups in which two or more of these groups are combined (e.g., alicyclic hydrocarbon groups or a hydrocarbon group formed from an aromatic hydrocarbon group and a chain hydrocarbon group). The number of carbon atoms in the hydrocarbon group is preferably 1 to 54, more preferably 1 to 48, even more preferably 1 to 42, still more preferably 1 to 38, still more preferably 1 to 36, even more preferably 1-32, even more preferably 1-28.
Examples of chain hydrocarbon groups include divalent to trivalent chain hydrocarbon groups such as alkanediyl groups, alkenediyl groups, alkynediyl groups, alkanetriyl groups, alkenetriyl groups and alkynetriyl groups.
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 groups such as tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl and heptadecane-1,17-diyl alkanediyl group and ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, Branched alkanediyl groups such as 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group are mentioned.
Alkanetriyl groups include methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octanetriyl, nonanetriyl, decanetriyl, and undecanetriyl groups. , dodecanetriyl group, tridecanetriyl group, tetradecanetriyl group, pentadecanetriyl group, hexadecanetriyl group and heptadecanetriyl group.
Examples of the alkenediyl group include ethenediyl, propenediyl, isopropenediyl, butenediyl, isobutenediyl, tert-butenediyl, pentenediyl, hexenediyl, heptenediyl, octenediyl, isooctenediyl, and noneninediyl groups. be done.
The alkenetriyl group includes ethentriyl, propenetriyl, isopropenetriyl, butentriyl, isobutenetriyl, tert-butenetriyl, pententriyl, hexentriyl, heptentriyl, and octentriyl. group, isooctenetriyl group, noneninetriyl group, and the like.
The alkynediyl group includes ethynediyl, propynediyl, isopropynediyl, butynediyl, isobutynediyl, tert-butynediyl, pentynediyl, hexynediyl, octynediyl, nonynediyl, and the like.
Alkynetriyl groups include ethynetriyl, propynetriyl, isopropynetriyl, butynetriyl, isobutynetriyl, tert-butynetriyl, pentynetriyl, hexynetriyl, octynetriyl, nonynetriyl, and the like. are mentioned.
Also included are groups in which one or more of the hydrogen atoms of the above groups are replaced with bonding sites.
The chain hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, and still more preferably 1 to 7, even more preferably 1 to 6, even more preferably 1 to 5, and especially preferably 1 to 4.
Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include the following alicyclic hydrocarbon groups. The binding site can be at any position.

Examples include divalent to trivalent alicyclic hydrocarbon groups such as cycloalkanediyl groups and cycloalkanetriyl groups.
Specifically, cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group , cyclooctane-1,5-diyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclodecanetriyl group, etc. monocyclic alicyclic hydrocarbon groups and norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, decahydro Naphthalenediyl group, bicyclo[3.3.0]octanediyl group, decahydronaphthalenetriyl group, adamantanetriyl group, norbornanetriyl group, bicyclo[3.3.0]octanetriyl group and other polycyclic An alicyclic hydrocarbon group is mentioned.
Also included are groups in which one or more of the hydrogen atoms of the above groups are replaced with bonding sites.
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 20, still more preferably 3 to 18, still more preferably is 3-16, even more preferably 3-12.
The aromatic hydrocarbon group includes divalent to trivalent aromatic hydrocarbon groups such as an arylene group and an arenetriyl group.
Specifically, aromatic hydrocarbons such as phenylene group, naphthylene group, anthrylene group, biphenylene group, phenanthrylene group, benzenetriyl group, naphthalenetriyl group, anthracentriyl group, biphenylenetriyl group and phenanthrenetriyl group. groups.
Also included are groups in which one or more of the hydrogen atoms of the above groups are replaced with bonding sites.
The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, still more preferably 6 to 20, even more preferably 6 to 18, still more preferably 6-14, and more preferably 6-10.

脂環式炭化水素基と鎖式炭化水素基と芳香族炭化水素基とを組み合わせた基としては、脂環式炭化水素基に芳香族炭化水素基と鎖式炭化水素基が結合した基（例えば、＊－脂環式炭化水素基－芳香族炭化水素基－鎖式炭化水素基－等）、芳香族炭化水素基に脂環式炭化水素基と鎖式炭化水素基が結合した基（例えば、＊－芳香族炭化水素基－脂環式炭化水素基－鎖式炭化水素基－等）等が挙げられる。
＊はカルボニル基の炭素原子との結合部位を表す。
組み合わせた基の場合又は置換基を有する場合、上述の基において価数の異なる基（アルキル基、アルカンジイル基、アルカントリイル基、シクロアルキル基、シクロアルカンジイル基、シクロアルカントリイル基等）が含まれていてもよい。 Groups in which two or more types are combined include a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined, a group in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined, and an alicyclic hydrocarbon group. A group obtained by combining a group and an aromatic hydrocarbon group, a group obtained by combining an alicyclic hydrocarbon group, a chain hydrocarbon group and an aromatic hydrocarbon group, and the like. Combination WHEREIN: An alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a chain hydrocarbon group may combine 2 or more types, respectively. Also, any group may be bonded to COO 2 ^— .
Groups in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined include, for example, a group in which an alicyclic hydrocarbon group is bonded to a chain hydrocarbon group (for example, *-chain hydrocarbon group-aliphatic cyclic hydrocarbon group-, etc.), a group in which a chain hydrocarbon group is bonded to an alicyclic hydrocarbon group (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-, etc.), chain hydrocarbon A group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are bonded to a group (e.g., *-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-, etc.), alicyclic hydrocarbon A group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are bonded to a group (e.g., *-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-, etc.), chain hydrocarbon A group in which an alicyclic hydrocarbon group, a chain hydrocarbon group, and an alicyclic hydrocarbon group are bonded to a group (for example, *-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic Cyclic hydrocarbon group -, etc.), a group in which a chain hydrocarbon group, an alicyclic hydrocarbon group and a chain hydrocarbon group are bonded to an alicyclic hydrocarbon group (e.g., *-alicyclic hydrocarbon group- chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-etc.) and the like.
Groups in which an aromatic hydrocarbon group and a chain hydrocarbon group are combined include, for example, a group in which an aromatic hydrocarbon group is bonded to a chain hydrocarbon group (e.g., *-chain hydrocarbon group-aromatic hydrocarbon hydrogen group-, etc.), a group in which a chain hydrocarbon group is bonded to an aromatic hydrocarbon group (e.g., *-aromatic hydrocarbon group-chain hydrocarbon group-, etc.), an aromatic hydrocarbon group in a chain hydrocarbon group A group in which a hydrogen group and a chain hydrocarbon group are bonded (eg, *-chain hydrocarbon group-aromatic hydrocarbon group-chain hydrocarbon group-, etc.) and the like can be mentioned.
Groups in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined include groups in which an aromatic hydrocarbon group is bonded to an alicyclic hydrocarbon group (for example, *-alicyclic hydrocarbon group-aromatic hydrocarbon group-, etc.), a group in which an alicyclic hydrocarbon group is bonded to an aromatic hydrocarbon group (e.g., *-aromatic hydrocarbon group-alicyclic hydrocarbon group-, etc.), alicyclic hydrocarbon group and an aromatic hydrocarbon group condensed (for example, the following groups (the bonding site is at an arbitrary position), etc.), and the like.

Groups in which an alicyclic hydrocarbon group, a chain hydrocarbon group, and an aromatic hydrocarbon group are combined include groups in which an aromatic hydrocarbon group and a chain hydrocarbon group are bonded to an alicyclic hydrocarbon group (for example, , *-alicyclic hydrocarbon group-aromatic hydrocarbon group-chain hydrocarbon group-, etc.), a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are bonded to an aromatic hydrocarbon group (e.g., *--aromatic hydrocarbon group--alicyclic hydrocarbon group--chain hydrocarbon group--etc.).
* represents the bonding site with the carbon atom of the carbonyl group.
In the case of combined groups or in the case of having substituents, groups with different valences in the above groups (alkyl group, alkanediyl group, alkanetriyl group, cycloalkyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) may be included.

組み合わせた基に含まれる－ＣＨ_２－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わった基としては、以下の基等も挙げられる。結合部位は任意の位置とすることができる。

--CH ₂ -- contained in the hydrocarbon group having 1 to 60 carbon atoms in L ¹ may be replaced with --O--, --S--, --SO ₂ -- or --CO--.
When —CH ₂ — contained in the hydrocarbon group having 1 to 60 carbon atoms of L ¹ is replaced with —O—, —S—, —SO ₂ — or —CO—, the number of carbon atoms before replacement is The number of carbon atoms in the hydrogen 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 with —S—), alkoxy group (group in which —CH ₂ — at any position in the alkyl group is replaced with —O—), alkylthio group (any -CH ₂ - at the position is replaced with -S-), alkylsulfonyl group _{(group in which any position of the alkyl group is replaced with -SO 2 -} ), alkoxycarbonyl group (group in which —CH ₂ —CH ₂ — at any position in the alkyl group is replaced with —O—CO-), alkylcarbonyl group ( —CH ₂ — at any position in the alkyl group) is replaced with -CO-), alkylcarbonyloxy group (group in which -CH ₂ -CH ₂ - at any position in the alkyl group is replaced with -CO-O-), oxy group (methylene -CH ₂ - contained in the group is replaced by -O-), carbonyl group (group in which the -CH ₂ - contained in the methylene group is replaced by -CO-), alkanediyloxy group (alkane —CH ₂ — at any position in the diyl group is replaced with —O—), alkanediyloxycarbonyl group (where —CH ₂ —CH ₂ — at any position in the alkanediyl group is , a group substituted with -O-CO-), an alkanediylcarbonyl group (a group in which -CH ₂ - at any position in the alkanediyl group is substituted with -CO-), an alkanediylcarbonyloxy group (alkane —CH ₂ —CH ₂ — at any position in the diyl group is replaced with —CO—O—), alkanediylthio group (—CH ₂ — at any position in the alkanediyl group) is replaced with -S-), alkanediylsulfonyl group (group in which -CH ₂ - at any position in the alkanediyl group is replaced with -SO ₂ -), cycloalkoxy group, cycloalkylalkoxy group, alkoxycarbonyloxy group, aromatic hydrocarbon group-carbonyloxy group, aromatic carbon Examples thereof include hydrogen group-carbonyl group, aromatic hydrocarbon group-oxy group, and groups in which two or more of these groups are combined. Also included are groups in which one or more hydrogen atoms of these groups are replaced with bonding sites.
The alkoxy group includes alkoxy groups having 1 to 17 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy. group, decyloxy group, undecyloxy group, and the like. The alkoxy group preferably has 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
The alkylthio group includes alkylthio groups having 1 to 17 carbon atoms, such as methylthio, ethylthio, propylthio, butylthio and the like. The number of carbon atoms in the alkylthio group is preferably 1-11, more preferably 1-6, even more preferably 1-4, still more preferably 1-3.
The alkylsulfonyl group includes alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl, ethylsulfonyl and propylsulfonyl groups. The number of carbon atoms in the alkylsulfonyl group is preferably 1-11, more preferably 1-6, even more preferably 1-4, still more preferably 1-3.
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 17 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl groups. The alkylcarbonyl group includes alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl group, propionyl group and butyryl group. The alkylcarbonyloxy group includes alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy, propionyloxy and butyryloxy groups. The alkoxycarbonyl group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms. The alkylcarbonyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms. The alkylcarbonyloxy group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms.
The alkanediyloxy group includes alkanediyloxy groups having 1 to 17 carbon atoms, such as methyleneoxy, ethyleneoxy, propanediyloxy, butanediyloxy, and pentanediyloxy groups. The alkanediyloxy group preferably has 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
The alkanediyloxycarbonyl group includes an alkanediyloxycarbonyl group having 2 to 17 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 18 carbon atoms, such as methylenecarbonyl, ethylenecarbonyl, propanediylcarbonyl, butanediylcarbonyl and pentanediylcarbonyl groups. The alkanediylcarbonyloxy group includes an alkanediylcarbonyloxy group having 2 to 17 carbon atoms, such as a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propanediylcarbonyloxy group, a butanediylcarbonyloxy group, and the like. . The alkanediyloxycarbonyl group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms. The alkanediylcarbonyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms. The alkanediylcarbonyloxy group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms.
The alkanediylthio group includes alkanediylthio groups having 1 to 17 carbon atoms, such as methylenethio, ethylenethio and propylenethio groups. The alkanediylthio group preferably has 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
The alkanediylsulfonyl group includes an alkanediylsulfonyl group having 1 to 17 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, a propylenesulfonyl group and the like. The alkanediylsulfonyl group preferably has 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
The cycloalkoxy group includes a cycloalkoxy group having 3 to 17 carbon atoms, such as a cyclohexyloxy group. The cycloalkylalkoxy group includes a cycloalkylalkoxy group having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. The alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. The aromatic hydrocarbon group-carbonyloxy group includes an aromatic hydrocarbon group-carbonyloxy group having 7 to 17 carbon atoms, such as a benzoyloxy group. The aromatic hydrocarbon group-carbonyl group includes an aromatic hydrocarbon group-carbonyl group having 7 to 17 carbon atoms, such as a benzoyl group. The aromatic hydrocarbon group-oxy group includes an aromatic hydrocarbon group-oxy group having 6 to 16 carbon atoms, such as a phenyloxy group.
Examples of groups in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ — include the following groups. Also included are groups represented below in which -O- or -CO- is replaced with -S- or -SO ₂ -. The binding site can be at any position.

Groups in which —CH ₂ — contained in the combined group is replaced with —O—, —S—, —CO— or —SO ₂ — also include the following groups. The binding site can be at any position.

Examples of substituents that L ¹ may have include a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 13 carbon atoms. Examples include a carbonyl group, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 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.
The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a halogen atom.

［式（Ｌ１－０）～式（Ｌ１－５）中、
環Ｗ、Ｒ^１、ｍ１及びｍ２は、上記と同じ意味を表す。
Ｌ^２は、置換基を有してもよい炭素数１～１０の鎖式炭化水素基、置換基を有してもよい炭素数３～２４の環状炭化水素基又は置換基を有してもよい炭素数３～２４の環状炭化水素基と置換基を有してもよい炭素数１～８の鎖式炭化水素基とを組み合わせた基を表し、該環状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い。
Ｌ^３及びＬ^４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１～８の鎖式炭化水素基を表し、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。
Ｌ^５及びＬ^６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１～１０の鎖式炭化水素基を表し、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。
環Ｗ３は、置換基を有してもよい炭素数３～２４の環状炭化水素基を表し、該環状炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
環Ｗ４及び環Ｗ５は、それぞれ独立に、置換基を有してもよい炭素数３～１８の環状炭化水素基を表し、該環状炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｘ^３は、＊＊－ＣＯ－Ｏ－、＊＊－Ｏ－ＣＯ－、＊＊－Ｏ－ＣＯ－Ｏ－又は＊＊－Ｏ－を表す。
Ｘ^ａ及びＸ^ｂは、それぞれ独立に、－Ｏ－又は－Ｓ－を表す。
Ｘ^０１は、置換基を有してもよい炭素数１～４０の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。
Ｒ^２１及びＲ^２２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のハロアルキル基、炭素数１～１２のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合せた基を表し、該ハロアルキル基、該アルキル基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい。
ｍ２１は、０～６のいずれかの整数を表し、ｍ２１が２以上のとき、複数のＲ^２１は互いに同一であっても異なってもよい。
ｍ２２は、０～６のいずれかの整数を表し、ｍ２２が２以上のとき、複数のＲ^２２は互いに同一であっても異なってもよい。
＊は、カルボニル基の炭素原子との結合部位を表す。＊＊は、Ｌ^２との結合部位を表す。］
なお、式（Ｌ１－１）～式（Ｌ１－５）で表される基のうちＬ^１に対応する部分（但し、置換基は除く。）の炭素数合計は、それぞれ６０以下である。
ここでの鎖式炭化水素基と環状炭化水素基との組み合わせは、＊－鎖式炭化水素基－脂環式炭化水素基又は芳香族炭化水素基－、＊－脂環式炭化水素基又は芳香族炭化水素基－鎖式炭化水素基－、＊－鎖式炭化水素基－脂環式炭化水素基又は芳香族炭化水素基－鎖式炭化水素基－、＊－脂環式炭化水素基又は芳香族炭化水素基－鎖式炭化水素基－脂環式炭化水素基又は芳香族炭化水素基－、＊－鎖式炭化水素基－脂環式炭化水素基と芳香族炭化水素基が縮合した基－、＊－脂環式炭化水素基と芳香族炭化水素基が縮合した基－鎖式炭化水素基－、＊－鎖式炭化水素基－脂環式炭化水素基と芳香族炭化水素基が縮合した基－鎖式炭化水素基－等が挙げられる。＊はカルボニル基の炭素原子との結合部位を表す。 L ¹ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms (with the proviso that —CH ₂ — contained in the chain hydrocarbon group is —O— or —CO may be substituted with -), a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (provided that -CH ₂ - contained in the cyclic hydrocarbon group is -O-, - S—, —CO— or —SO ₂ —.) or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms and an optionally substituted carbon number a group consisting of a combination of 3 to 24 cyclic hydrocarbon groups (with the proviso that --CH ₂ -- contained in said chain hydrocarbon group may be replaced by --O-- or --CO--, said cyclic hydrocarbon —CH ₂ — contained in the group may be replaced with —O—, —S—, —SO ₂ — or —CO—), and may have a single bond or a substituent. a chain hydrocarbon group having 1 to 8 carbon atoms (with the proviso that —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—); a cyclic hydrocarbon group having 3 to 20 carbon atoms (provided that —CH ₂ — contained in the cyclic hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ —). or a group formed by combining an optionally substituted C 1-6 chain hydrocarbon group and an optionally substituted C 3-20 cyclic hydrocarbon group (However, -CH _{2 - contained in the chain hydrocarbon group may be replaced with -O- or -CO-, and -CH 2 -} contained in the cyclic hydrocarbon group may be -O-, —S—, —SO ₂ — or —CO—) is more preferred, and a single bond, a chain hydrocarbon group having 1 to 7 carbon atoms which may have a substituent ( provided that —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—), optionally substituted cyclic hydrocarbon having 3 to 18 carbon atoms group (with the proviso that —CH ₂ — contained in the cyclic hydrocarbon group may be replaced with —O— or —CO—) or an optionally substituted chain of 1 to 5 carbon atoms A group formed by combining a hydrocarbon group and a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (provided that —CH ₂ — contained in the chain hydrocarbon group is —O— or may be replaced with -CO-, and -CH ₂ - contained in the cyclic hydrocarbon group may be replaced with -O- or -CO- . ) is more preferred.
*-L ¹ -R ¹⁰ is also preferably a group represented by any one of formulas (L1-0) to (L1-5).

[In the formulas (L1-0) to (L1-5),
Ring W, R ¹ , m1 and m2 have the same meanings as above.
L ² is an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may be substituted, or optionally having a substituent —CH ₂ which represents a group obtained by combining a cyclic hydrocarbon group having 3 to 24 carbon atoms and a chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and contained in the cyclic hydrocarbon group; — may be replaced with —O—, —S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—. may be
L ³ and L ⁴ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
L ⁵ and L ⁶ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
Ring W3 represents an optionally substituted cyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, —S—, —CO— Alternatively, it may be replaced with -SO ₂ -.
Ring W4 and ring W5 each independently represent an optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, -S-, -CO- or -SO ₂ - may be substituted.
X3 represents **-CO ^- O-, **-O-CO-, **-O-CO-O- or **-O-.
X ^a and X ^b each independently represent -O- or -S-.
X ⁰¹ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or — SO ₂ - may be substituted.
R ²¹ and R ²² each independently represent a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or these --CH ₂ -- contained in said haloalkyl group, said alkyl group and said alicyclic hydrocarbon group representing a combination of groups may be replaced with --O-- or --CO--.
m21 represents an integer of 0 to 6, and when m21 is 2 or more, multiple R ²¹ may be the same or different.
m22 represents an integer of 0 to 6, and when m22 is 2 or more, multiple R ²² may be the same or different.
* represents the bonding site with the carbon atom of the carbonyl group. ^** represents the binding site with L2. ]
In addition, the total number of carbon atoms of the portion corresponding to L ¹ among the groups represented by formulas (L1-1) to (L1-5) (excluding substituents) is 60 or less.
Here, the combination of a chain hydrocarbon group and a cyclic hydrocarbon group is represented by: *-chain hydrocarbon group-alicyclic hydrocarbon group or aromatic hydrocarbon group-, *-alicyclic hydrocarbon group or aromatic Group hydrocarbon group-chain hydrocarbon group-, *-chain hydrocarbon group-alicyclic hydrocarbon group or aromatic hydrocarbon group-chain hydrocarbon group-, *-alicyclic hydrocarbon group or aromatic Group hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group or aromatic hydrocarbon group-, *-chain hydrocarbon group-condensed group of alicyclic hydrocarbon group and aromatic hydrocarbon group- , *—a group in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are condensed—a chain hydrocarbon group—, *—a chain hydrocarbon group—an alicyclic hydrocarbon group and an aromatic hydrocarbon group are condensed group--chain hydrocarbon group--and the like. * represents the bonding site with the carbon atom of the carbonyl group.

Examples of substituents that ^each group of formulas (L1-1) to (L1-5) may have include the same groups as the substituents that L1 may have.
The cyclic hydrocarbon group for L ² includes an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a condensed group thereof, and the like, and includes the same groups as those exemplified for L ¹ .
Examples of the chain hydrocarbon group for L ² include the same groups as those exemplified for L ¹ .
Among them, L ² is an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is -O- or -CO- ), an optionally substituted cyclic hydrocarbon group having 3 to 20 carbon atoms (-CH ₂ - contained in the cyclic hydrocarbon group is -O-, -S-, —CO— or —SO ₂ —.) or an optionally substituted C 3-20 cyclic hydrocarbon group and an optionally substituted C 1-6 A group combined with a chain hydrocarbon group (-CH ₂ - contained in the cyclic 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—.), optionally substituted chain hydrocarbon group having 1 to 6 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group may be replaced with -O- or -CO-), optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms (-CH ₂ - contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO ₂ -) or the number of carbon atoms which may have a substituent A group consisting of a combination of a 3-18 cyclic hydrocarbon group and an optionally substituted chain hydrocarbon group having 1-4 carbon atoms (-CH ₂ - contained in the cyclic 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-. ) is more preferred.
Chain hydrocarbon groups for L ³ , L ⁴ , L ⁵ and L ⁶ include the same groups as those exemplified for L ¹ .
Among them, L ³ is preferably a single bond or an optionally substituted chain hydrocarbon group having 1 to 6 carbon atoms, more preferably a single bond or a chain hydrocarbon group having 1 to 4 carbon atoms, A single bond, a methylene group or an ethylene group is more preferred, and a single bond or a methylene group is even more preferred.
L ⁴ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 6 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is -O- or -CO- A single bond or a chain hydrocarbon group having 1 to 5 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO-) is preferred. ) is more preferable, and a single bond or a chain hydrocarbon group having 1 to 4 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO- is more preferred, and a single bond or a chain hydrocarbon group having 1 to 3 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group may be replaced with -O- or -CO- good.) is even more preferred.
L ⁵ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is -O- or -CO- A single bond or a chain hydrocarbon group having 1 to 6 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO-) is preferred. ) is more preferable, and a single bond or a chain hydrocarbon group having 1 to 4 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO- ) is more preferable.
L ⁶ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is -O- or -CO- A single bond or a chain hydrocarbon group having 1 to 6 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO-) is preferred. ) is more preferable, and a single bond or a chain hydrocarbon group having 1 to 4 carbon atoms (-CH ₂ - contained in the chain hydrocarbon group is replaced with -O- or -CO- ) is more preferable.

［式（ｗ１－１）～式（ｗ１－２６）中、
該基は、置換基を有してもよく、該基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。結合部位は任意の位置である。］
ここで、環に由来する基とは、環において任意の位置に結合部位を有し、環に含まれる－ＣＨ_２－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい基を意味する。
環Ｗ３は、置換基を有してもよい炭素数３～２０の環状炭化水素基（該環状炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。）が好ましく、式（ｗ１－１）～式（ｗ１－２６）のいずれかで表される環に由来する基がより好ましく、式（ｗ１－１）～式（ｗ１－３）、式（ｗ１－６）、式（ｗ１－１２）～式（ｗ１－１８）及び式（ｗ１－２２）～式（ｗ１－２６）のいずれかで表される環に由来する基がさらに好ましく、式（ｗ１－１）、式（ｗ１－２）、式（ｗ１－１３）、式（ｗ１－１５）～式（ｗ１－１８）、式（ｗ１－２２）、式（ｗ１－２４）及び式（ｗ１－２６）のいずれかで表される環に由来する基がさらにより好ましい。
環Ｗ４は、置換基を有してもよい炭素数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－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。）が好ましく、式（ｗ１－１）～式（ｗ１－２１）のいずれかで表される環に由来する基がより好ましく、式（ｗ１－１）、式（ｗ１－２）、式（ｗ１－３）又は式（ｗ１－６）で表される環に由来する基がさらに好ましく、式（ｗ１－１）又は式（ｗ１－２）で表される環に由来する基がさらにより好ましい。
環Ｗ５は、置換基を有してもよい炭素数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－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。）が好ましく、式（ｗ１－１）～式（ｗ１－２１）のいずれかで表される環に由来する基がより好ましく、式（ｗ１－１）、式（ｗ１－２）、式（ｗ１－３）又は式（ｗ１－６）で表される環に由来する基がさらに好ましく、式（ｗ１－１）又は式（ｗ１－２）で表される環に由来する基がさらにより好ましい。 The cyclic hydrocarbon groups of ring W3, ring W4 and ring W5 include ^an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a condensed group thereof, and the like. things are mentioned. Ring W3 can also be represented as ^a ring containing ring W4 and Xa, ^Xb and ^X01 .
Examples of ring W3, ring W4 and ring W5 include groups derived from the following rings.

[In the formulas (w1-1) to (w1-26),
The group may have a substituent, and —CH ₂ — contained in the group may be replaced with —O—, —S—, —CO— or —SO ₂ —. The binding site can be any position. ]
Here, a group derived from a ring means a group having a binding site at any position on the ring, and —CH ₂ — contained in the ring is —O—, —S—, —CO— or —SO ₂ —. It means a group which may be substituted.
Ring W3 is an optionally substituted cyclic hydrocarbon group having 3 to 20 carbon atoms (-CH ₂ - contained in the cyclic hydrocarbon group is -O-, -S-, -CO- or - SO ₂ — may be substituted), more preferably a group derived from a ring represented by any one of formulas (w1-1) to (w1-26), and formulas (w1-1) to a ring represented by any one of formula (w1-3), formula (w1-6), formula (w1-12) ~ formula (w1-18) and formula (w1-22) ~ formula (w1-26) A group derived from the formula (w1-1), formula (w1-2), formula (w1-13), formula (w1-15) to formula (w1-18), formula (w1-22), formula A group derived from a ring represented by any one of (w1-24) and formula (w1-26) is even more preferred.
Ring W4 is an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -S-, - may be substituted with CO— or —SO ₂ —), more preferably a group derived from a ring represented by any one of formulas (w1-1) to (w1-21), and formula (w1 -1), a group derived from a ring represented by formula (w1-2), formula (w1-3) or formula (w1-6) is more preferable, and formula (w1-1) or formula (w1-2) A group derived from a ring represented by is even more preferable.
Ring W5 is an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -S-, - may be substituted with CO— or —SO ₂ —), more preferably a group derived from a ring represented by any one of formulas (w1-1) to (w1-21), and formula (w1 -1), a group derived from a ring represented by formula (w1-2), formula (w1-3) or formula (w1-6) is more preferable, and formula (w1-1) or formula (w1-2) A group derived from a ring represented by is even more preferable.

X ³ is preferably **-CO-O-, **-O-CO- or **-O-CO-O-.
X ^a and X ^b are preferably the same atom, more preferably both oxygen atoms.

Examples of the halogen atom, haloalkyl group, alkyl group and alicyclic hydrocarbon group for R ²¹ and R ²² include the same groups as those exemplified for R ¹ .
R ²¹ and R ²² each represent a halogen atom, a hydroxy group, a haloalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the haloalkyl group, the alkyl -CH ₂ - contained in the group and the alicyclic hydrocarbon group may be replaced with -O- or -CO-, and the alkyl group and the alicyclic hydrocarbon group have a halogen atom. may be used.) or a combination thereof is preferred.
m21 is preferably an integer of 0 to 3, more preferably 0, 1 or 2, even more preferably 0 or 1.
m22 is preferably an integer of 0 to 4, more preferably 0, 1, 2 or 4, and even more preferably 0 or 1.

Examples of the hydrocarbon group for X ⁰¹ include cyclic hydrocarbon groups such as chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and groups in which two or more of these groups are combined may be used. , and the same groups as those exemplified for L ¹ .

ここで、Ｌ^1１は、単結合又は置換基を有してもよい炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
なお、上記の基（但し、置換基は除く。）の炭素数合計は、それぞれ４０以下である。
Ｌ^1１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、芳香族炭化水素基等の環状炭化水素基が挙げられ、これらの基から２種以上を組み合わせた基でもよく、Ｌ^１で例示された基と同様のものが挙げられる。
Ｌ^1１は、単結合、置換基を有してもよい炭素数１～８の鎖式炭化水素基、置換基を有してもよい炭素数３～１２の環状炭化水素基又は置換基を有してもよい炭素数３～１２の環状炭化水素基と置換基を有してもよい炭素数１～６の鎖式炭化水素基とを組み合わせた基（該環状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い。）が好ましい。 Examples of X ⁰¹ include the following groups. * represents a binding site. Also, any group may be bonded to ^Xa and ^Xb .

Here, L ¹¹ represents a single bond or a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and —CH ₂ — contained in the hydrocarbon group is —O—, —S— , —SO ₂ — or —CO—.
The total number of carbon atoms in each of the above groups (excluding substituents) is 40 or less.
Examples of the hydrocarbon group for L ¹¹ include cyclic hydrocarbon groups such as chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and a combination of two or more of these groups may also be used. , and the same groups as those exemplified for L ¹ .
L ¹¹ is a single bond, an optionally substituted chain hydrocarbon group of 1 to 8 carbon atoms, an optionally substituted cyclic hydrocarbon group of 3 to 12 carbon atoms, or a substituent A group obtained by combining a cyclic hydrocarbon group having 3 to 12 carbon atoms which may be substituted with a chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent (-CH contained in the cyclic hydrocarbon group _2- may be replaced with -O-, -S-, -CO- or -SO ₂ -, and -CH ₂ - contained in the chain hydrocarbon group may be substituted with -O- or -CO- may be replaced.) is preferred.

［式（Ｘ¹－１）、式（Ｘ¹－３）、式（Ｘ¹－５）～式（Ｘ¹－７）、式（Ｘ¹－１２）及び式（Ｘ¹－１３）中、
Ｌ^1１は、単結合又は置換基を有してもよい炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
＊は、結合部位を表す。］ X ⁰¹ is preferably the following groups. Among them, a group represented by any one of formulas (X ¹ -1), (X ¹ -3), and formulas (X ¹ -5) to (X ¹ -7) is preferable, and a group represented by formula ( X ¹ -1), a group represented by formula (X ¹ -3) or formula (X ¹ -5) is more preferable.

[In formula (X ¹ -1), formula (X ¹ -3), formula (X ¹ -5) to formula (X ¹ -7), formula (X ¹ -12) and formula (X ¹ -13),
L ¹¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
* represents the binding site. ]

［式（Ｘ²－１）、式（Ｘ²－３）、式（Ｘ²－５）～式（Ｘ²－７）、式（Ｘ²－２１）、式（Ｘ²－２３）及び式（Ｘ²－２５）中、
＊は、結合部位を表す。］ X ⁰¹ is, among others, formula (X ² -1), formula (X ² -3), formula (X ² -5) to formula (X ² -7), formula (X ² -21), formula (X ^2-23 ) and groups represented by formulas (X ² -25) are more preferred.

[Formula (X ² -1), Formula (X ² -3), Formula (X ² -5) to Formula (X ² -7), Formula (X ² -21), Formula (X ² -23) and Formula In (X ² -25),
* represents the binding site. ]

例えば、シクロアルキル基、シクロアルカンジイル基等の１～２価の脂環式炭化水素基等が挙げられる。
具体的に、単環式の脂環式炭化水素基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基等の単環式シクロアルキル基、シクロプロパンジイル基、シクロブタンジイル基、シクロペンタンジイル基、シクロヘキサンジイル基、シクロオクタンジイル基等の単環式シクロアルカンジイル基等が挙げられる。多環式の脂環式炭化水素基としては、デカヒドロナフチル基、アダマンチル基、ノルボルニル基、ビシクロ[３．３．０]オクチル基等の多環式シクロアルキル基、デカヒドロナフタレンジイル基、アダマンタンジイル基、ノルボルナンジイル基、ビシクロ[３．３．０]オクタンジイル基等の多環式シクロアルカンジイル基等が挙げられる。
また、脂環式炭化水素基に含まれる－ＣＨ_２－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わった基としては、以下の基等が挙げられる。また、以下に表される基の－Ｏ－又は－ＣＯ－が、－Ｓ－又は－ＳＯ_２－に置き換わったものも挙げられる。結合部位は任意の位置とすることができる。

脂環式炭化水素基の炭素数は、好ましくは３～２４であり、より好ましくは３～２０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であり、さらにより好ましくは３～１０である。
環Ｗは、炭素数３～２０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－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。）が好ましく、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－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。）がより好ましく、式（ｗ１－１）～式（ｗ１－２１）のいずれかで表される環に由来する基がさらに好ましく、式（ｗ１－１）で表される環に由来する基、式（ｗ１－２）で表される環に由来する基、式（ｗ１－３）で表される環に由来する基、式（ｗ１－６）で表される環に由来する基又は式（ｗ１－１５）で表される環に由来する基がより一層好ましく、式（ｗ１－１）で表される環に由来する基又は式（ｗ１－２）で表される環に由来する基がさらに一層好ましい。

［式（ｗ１－１）～式（ｗ１－２１）中、
該基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい。結合部位は任意の位置である。］
ここで、環に由来する基とは、環において任意の位置に結合部位を有し、環に含まれる－ＣＨ_２－が、－Ｏ－、－Ｓ－、－ＣＯ－又は－ＳＯ_２－で置き換わっていてもよい基を意味する。 The alicyclic hydrocarbon group in ring W may be monocyclic or polycyclic (including spiro rings, condensed rings, bridged rings, etc.), and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include the following groups. The binding site can be at any position.

Examples thereof include monovalent to divalent alicyclic hydrocarbon groups such as cycloalkyl groups and cycloalkanediyl groups.
Specific examples of monocyclic alicyclic hydrocarbon groups include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl; monocyclic cycloalkanediyl groups such as propanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cyclooctanediyl group; Polycyclic alicyclic hydrocarbon groups include polycyclic cycloalkyl groups such as decahydronaphthyl group, adamantyl group, norbornyl group, bicyclo[3.3.0]octyl group, decahydronaphthalenediyl group, adamantane polycyclic cycloalkanediyl groups such as a diyl group, a norbornanediyl group, a bicyclo[3.3.0]octanediyl group, and the like;
Examples of groups in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ — include the following groups. Also included are groups represented below in which —O— or —CO— is replaced with —S— or —SO ₂ —. The binding site can be at any position.

The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 24, more preferably 3 to 20, even more preferably 3 to 18, still more preferably 3 to 16, still more preferably is 3-12, even more preferably 3-10.
Ring W is an alicyclic hydrocarbon group having 3 to 20 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO ₂ - may be substituted), and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or may be substituted with —SO ₂ —), more preferably a group derived from a ring represented by any one of formulas (w1-1) to (w1-21), and formula (w1- 1) a group derived from the ring represented by formula (w1-2), a group derived from the ring represented by formula (w1-3), a group derived from the ring represented by formula (w1-6) A group derived from a ring represented by or a group derived from a ring represented by formula (w1-15) is more preferable, and a group derived from a ring represented by formula (w1-1) or formula (w1- A group derived from the ring represented by 2) is even more preferable.

[In the formulas (w1-1) to (w1-21),
—CH ₂ — included in the group may be replaced with —O—, —S—, —CO— or —SO ₂ —. The binding site can be any position. ]
Here, a group derived from a ring means a group having a binding site at any position on the ring, and —CH ₂ — contained in the ring is —O—, —S—, —CO— or —SO ₂ —. It means a group which may be substituted.

ｍ１は、０～５のいずれかの整数であることが好ましく、０～４のいずれかの整数であることがより好ましく、０～３のいずれかの整数であることがさらに好ましく、０、１又は２であることがより一層好ましく、０又は１であることがさらに一層好ましい。
ｍ２は、１～５のいずれかの整数であることが好ましく、１～４のいずれかの整数であることがより好ましく、１、２又は３であることがさらに好ましく、１又は２であることがさらにより好ましい。
Ｒ^１は、ハロゲン原子、ヒドロキシ基、炭素数１～６のハロアルキル基、炭素数１～６のアルキル基、炭素数３～１８の脂環式炭化水素基（該ハロアルキル基、該アルキル基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－で置き換わっていてもよい）又はこれらを組み合せた基が好ましく、ハロゲン原子、ヒドロキシ基、炭素数１～４のアルキル基、炭素数１～４のハロアルキル基又は炭素数１～３のアルコキシ基がより好ましく、ハロゲン原子、ヒドロキシ基、炭素数１～３のペルフルオロアルキル基又は炭素数１～３のアルコキシ基がさらに好ましく、ヨウ素原子、フッ素原子、ヒドロキシ基、トリフルオロメチル基又はメトキシ基がより一層好ましく、ヒドロキシ基がさらに一層好ましい。 Halogen atoms for R ¹ include fluorine, chlorine, bromine and iodine atoms.
The haloalkyl group having 1 to 12 carbon atoms in R ¹ represents an alkyl group having 1 to 12 carbon atoms having a halogen atom, a fluorinated alkyl group having 1 to 12 carbon atoms, a chlorinated alkyl group having 1 to 12 carbon atoms, Examples thereof include alkyl bromide groups having 1 to 12 carbon atoms and alkyl iodide groups having 1 to 12 carbon atoms. Haloalkyl groups include perfluoroalkyl groups having 1 to 12 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3, 3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like. The haloalkyl group preferably has 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.
Examples of the alkyl group having 1 to 12 carbon atoms for R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, and the like. An alkyl group is mentioned. The number of carbon atoms in the alkyl group is preferably 1-9, more preferably 1-6, even more preferably 1-4, still more preferably 1-3.
The alicyclic hydrocarbon group having 3 to 18 carbon atoms for R ¹ includes, for example, monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl groups. Examples include polycyclic cycloalkyl groups such as cycloalkyl groups, norbornyl groups, adamantyl groups, decahydronaphthyl groups, and the like. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3-16, more preferably 3-12, still more preferably 3-10.
When —CH ₂ — contained in the haloalkyl group, alkyl group or alicyclic hydrocarbon group represented by R ¹ is replaced with —O— or —CO—, the number of carbon atoms before the replacement is It is defined as the total number of carbon atoms in the alkyl group or the alicyclic hydrocarbon group. Examples of substituted groups include a hydroxy group (a group in which —CH ₂ — contained in a methyl group is replaced by —O—), a carboxy group (a group in which —CH ₂ —CH ₂ — contained in an ethyl group is replaced by —O -CO-), alkoxy group (group in which -CH ₂ - at any position in the alkyl group is replaced with -O-), alkoxycarbonyl group (any position 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-), haloalkoxy group ( — at any position in the haloalkyl group) a group in which -O- is substituted for CH ₂ -), a haloalkoxycarbonyl group (a group in which -CH ₂ -CH ₂ - at any position in the haloalkyl group is replaced by -O-CO-), haloalkyl Carbonyl group (a group in which —CH ₂ — at any position in the haloalkyl group is replaced with —CO—), haloalkylcarbonyloxy group ( —CH ₂ —CH ₂ — at any position in the haloalkyl group) is a group substituted with -CO-O-), a group in which two or more of these groups are combined, and the like.
The alkoxy group includes alkoxy groups having 1 to 11 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 1-6, more preferably 1-4, still more preferably 1-3.
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 an alkoxycarbonyl group having 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and the like, and the alkylcarbonyl group includes an alkyl group having 2 to 12 carbon atoms. Carbonyl groups include, for example, acetyl, propionyl and butyryl groups, and alkylcarbonyloxy groups include alkylcarbonyloxy groups having 2 to 11 carbon atoms, such as acetyloxy and propionyloxy. group, butyryloxy group, and the like. The alkoxycarbonyl group preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms. The number of carbon atoms in the alkylcarbonyl group is preferably 2-6, more preferably 2-4, still more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2-6, more preferably 2-4, still more preferably 2 or 3.
The haloalkoxy group, haloalkoxycarbonyl group, haloalkylcarbonyl group and haloalkylcarbonyloxy group include a haloalkoxy group having 1 to 11 carbon atoms, a haloalkoxycarbonyl group having 2 to 11 carbon atoms and a haloalkylcarbonyl group having 2 to 12 carbon atoms. , and haloalkylcarbonyloxy groups having 2 to 11 carbon atoms, such as groups in which one or more hydrogen atoms in the above-exemplified groups are replaced with halogen atoms.
Examples of the groups in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced with —O— or —CO— include the following groups. The binding site can be at any position.

m1 is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, further preferably an integer of 0 to 3, 0, 1 or 2 is even more preferred, and 0 or 1 is even more preferred.
m2 is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, further preferably 1, 2 or 3, and 1 or 2 is even more preferred.
R ¹ is a halogen atom, a hydroxy group, a haloalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the haloalkyl group, the alkyl group and the (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O- or -CO-) or a combination of these is preferred, and a halogen atom, a hydroxy group, or a An alkyl group, a haloalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is more preferable, and a halogen atom, a hydroxy group, a perfluoroalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is further preferable. An iodine atom, a fluorine atom, a hydroxy group, a trifluoromethyl group or a methoxy group is more preferred, and a hydroxy group is even more preferred.

Examples of the anion (I) include the following anions. Among them, formula (Ia-1) to formula (Ia-12), formula (Ia-14) to formula (Ia-19), formula (Ia-13), formula (Ia-24), formula (Ia-32 ) to Formula (Ia-42), Formula (Ia-43), Formula (Ia-44), Formula (Ia-63) to Formula (Ia-66) are preferred.

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. 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.

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。

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 ring containing a sulfur atom 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.

Aryl groups such as a phenyl group, a biphenyl group, a naphthyl group and a phenanthryl group can be mentioned as the aromatic hydrocarbon 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.

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.

Carboxylate (I) is a combination of the above-mentioned anions and the above-mentioned organic cations, which can be combined arbitrarily. Carboxylate (I) is preferably represented by Formula (Ia-1) ~ Formula (Ia-12), Formula (Ia-14) ~ Formula (Ia-19), Formula (Ia-13), Formula (Ia -24), represented by any of formulas (Ia-32) to (Ia-42), formula (Ia-43), formula (Ia-44), formula (Ia-63) to formula (Ia-66) and cation (b2-1), cation (b2-2), cation (b2-3) or cation (b2-4).

Carboxylate (I) includes 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. For example, carboxylate (I-1) means a salt consisting of an anion represented by formula (Ia-1) and a cation represented by formula (b2-c-1), and represents the salts shown below. .

Among them, carboxylate (I) includes carboxylate (I-1) to carboxylate (I-12), carboxylate (I-14) to carboxylate (I-19), carboxylic acid Salt (I-23) ~ Carboxylate (I-34), Carboxylate (I-36) ~ Carboxylate (I-41), Carboxylate (I-45) ~ Carboxylate (I-56 ), carboxylate (I-58) to carboxylate (I-63), carboxylate (I-67) to carboxylate (I-78), carboxylate (I-80) to carboxylate (I-85), carboxylate (I-89) to carboxylate (I-100), carboxylate (I-102) to carboxylate (I-107), carboxylate (I-111) ~ Carboxylate (I-122), Carboxylate (I-124) ~ Carboxylate (I-129), Carboxylate (I-133) ~ Carboxylate (I-144), Carboxylate ( I-146) to carboxylate (I-151), carboxylate (I-155) to carboxylate (I-166), carboxylate (I-168) to carboxylate (I-173), Carboxylate (I-177) to Carboxylate (I-188), Carboxylate (I-190) to Carboxylate (I-195), Carboxylate (I-199) to Carboxylate (I -210), carboxylate (I-212) to carboxylate (I-217), carboxylate (I-221) to carboxylate (I-232), carboxylate (I-234) to carboxylate acid salt (I-239), carboxylate (I-243) to carboxylate (I-254), carboxylate (I-256) to carboxylate (I-261), carboxylate (I- 265) to carboxylate (I-276), carboxylate (I-278) to carboxylate (I-283), carboxylate (I-287), carboxylate (I-288), carboxylic acid Salt (I-296) ~ Carboxylate (I-306), Carboxylate (I-307), Carboxylate (I-308), Carboxylate (I-316) ~ Carboxylate (I-326 ), carboxylate (I-327), carboxylate (I-328), carboxylate (I-336) to carboxylate (I-346), carboxylate (I-347), carboxylate (I-348), carboxylate (I-356) to carboxylate (I-366), carboxylate (I-367), carboxylate (I-368), carboxylate (I-376) ~ carboxylic acid Salt (I-386), Carboxylate (I-387), Carboxylate (I-388), Carboxylate (I-396) to Carboxylate (I-406), Carboxylate (I-407 ), carboxylate (I-408), carboxylate (I-416) to carboxylate (I-426), carboxylate (I-427), carboxylate (I-428), carboxylate (I-436) ~ Carboxylate (I-446), Carboxylate (I-447), Carboxylate (I-448), Carboxylate (I-456) ~ Carboxylate (I-466) , carboxylate (I-467), carboxylate (I-468), carboxylate (I-476) to carboxylate (I-486), carboxylate (I-487), carboxylate ( I-488), carboxylate (I-496) ~ carboxylate (I-506), carboxylate (I-507), carboxylate (I-508), carboxylate (I-516) ~ Carboxylate (I-526), Carboxylate (I-527), Carboxylate (I-528), Carboxylate (I-536) to Carboxylate (I-546), Carboxylate (I -547) to carboxylate (I-558), carboxylate (I-560) to carboxylate (I-565), carboxylate (I-569), carboxylate (I-570), carboxylate Acid salt (I-578) to carboxylate (I-588), carboxylate (I-589) to carboxylate (I-600), carboxylate (I-602) to carboxylate (I- 607), carboxylate (I-611), carboxylate (I-612), carboxylate (I-620) to carboxylate (I-630), carboxylate (I-631) to carboxylic acid Salt (I-642), Carboxylate (I-644) to Carboxylate (I-649), Carboxylate (I-653), Carboxylate (I-654), Carboxylate (I-662 ) to carboxylate (I-672), carboxylate (I-673) to carboxylate (I-684), carboxylate (I-686) to carboxylate (I-691), carboxylate (I-695), carboxylate (I-696), carboxylate (I-704) to carboxylate (I-714), carboxylate (I-715), carboxylate (I-716) , carboxylate (I-735), carboxylate (I-736), carboxylate (I-755), carboxylate (I-756), carboxylate (I-77 5), carboxylate (I-776), carboxylate (I-795), carboxylate (I-796), carboxylate (I-815), carboxylate (I-816), carboxylic acid Salt (I-835), Carboxylate (I-836), Carboxylate (I-855), Carboxylate (I-856), Carboxylate (I-875), Carboxylate (I-876) ), carboxylate (I-895), carboxylate (I-896), carboxylate (I-915), carboxylate (I-916), carboxylate (I-935), carboxylate (I-936), carboxylate (I-955), carboxylate (I-956), carboxylate (I-975), carboxylate (I-976), carboxylate (I-995) , carboxylate (I-996), carboxylate (I-1015), carboxylate (I-1016), carboxylate (I-1035), carboxylate (I-1036), carboxylate ( I-1055) to carboxylate (I-1058), carboxylate (I-1067) to carboxylate (I-1070), carboxylate (I-1079) to carboxylate (I-1082), Carboxylate (I-1091) to Carboxylate (I-1094), Carboxylate (I-1103) to Carboxylate (I-1106), Carboxylate (I-1115) to Carboxylate (I -1118), carboxylate (I-1127) to carboxylate (I-1130), carboxylate (I-1139) to carboxylate (I-1142), carboxylate (I-1151) to carboxylate acid salt (I-1154), carboxylate (I-1163) to carboxylate (I-1166), carboxylate (I-1175) to carboxylate (I-1178), carboxylate (I- 1187) to carboxylate (I-1190), carboxylate (I-1199) to carboxylate (I-1202), carboxylate (I-1211) to carboxylate (I-1214), carboxylic acid Salt (I-1223) ~ Carboxylate (I-1226), Carboxylate (I-1235) ~ Carboxylate (I-1238), Carboxylate (I-1247) ~ Carboxylate (I-1250 ) is preferred.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
この反応における溶媒としては、クロロホルム、アセトニトリル、メタノール、イオン交換水等が挙げられる。
反応温度は通常０℃～８０℃であり、反応時間は通常０．５時間～２４時間である。 <Method for producing carboxylate (I)>
Carboxylate (I) can be produced by reacting a salt represented by formula (Ia) with a compound represented by formula (Ib) in the presence of silver oxide in a solvent. can be done.

[In the formula, all symbols have the same meanings as described above. ]
Solvents for this reaction include chloroform, acetonitrile, methanol, ion-exchanged water, and the like.
The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

Examples of the salt represented by formula (Ia) include salts represented by the following formula, which are readily available on the market and can be easily produced by a known production method.

Examples of the compound represented by formula (Ib) include salts represented by the following formula, which are readily available on the market and can be easily produced by known production methods.

[Carboxylic acid generator]
The carboxylic acid generator of the present invention is an acid generator containing carboxylate (I). The carboxylate (I) of the present invention can act as an acid generator in the resist composition. When the carboxylate (I) is used as an acid generator in the resist composition, the acid generator may contain only one kind of carboxylate (I) or two or more kinds of carboxylate (I).
The carboxylic acid generator of the present invention may contain a known carboxylic acid salt in the field of resists other than the carboxylic acid salt (I). In this case, the content ratio (mass ratio) of the carboxylate (I) and the carboxylate other than the carboxylate (I) is usually 1:99 to 100:0, preferably 1:99 to 99. :1, more preferably 2:98-98:2, more preferably 5:95-95:5.

[Resist composition]
The resist composition comprises a carboxylic acid generator containing the carboxylic acid salt (I) of the present invention, an acid generator other than the carboxylic acid generator, and a resin having an acid labile group (hereinafter referred to as "resin (A)"). may be included). The term "acid-labile group" as used herein refers to a group having a leaving group that leaves upon contact with an acid to form a hydrophilic group (e.g., a hydroxy group or a carboxy group). . Examples of acid generators other than carboxylic acid generators include acid generators known in the resist field (hereinafter sometimes referred to as "acid generator (B)").
The resist composition preferably further contains a quencher (hereinafter sometimes referred to as "quencher (C)") and/or a solvent (hereinafter sometimes referred to as "solvent (E)").
In the resist composition of the present invention, the content of carboxylate (I) is preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, based on the solid content of the resist composition. % by mass or less is more preferable, and 1% by mass or more and 25% by mass or less is even more preferable.
In the resist composition of the present invention, the ratio of the contents of the carboxylate (I) and the acid generator (B) (mass ratio; carboxylate (I):acid generator (B), etc.) is Generally, it is 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, still more preferably 5:95 to 95:5.

<Acid generator (B)>
In the resist composition of the present invention, the total content of carboxylate (I) and acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass) per 100 parts by mass of resin (A). parts by mass or more), preferably 55 parts by mass or less (more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less).

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, 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のアルキル基又は炭素数１～６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～２４の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ１^＋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, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO— , 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-.
Z1 ⁺ represents an organic cation. ]

The perfluoroalkyl groups of 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 perfluoro A hexyl group and the like can be mentioned.
Examples of alkyl groups for Q ^b1 and Q ^b2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group.
The acid generator (B) is preferably a fluorine-containing acid generator, at least one of Q ^b1 and Q ^b2 preferably contains a fluorine atom or a perfluoroalkyl group, and at least one of them is a fluorine atom or a perfluoroalkyl group. It is more preferably an alkyl group, each independently more preferably a fluorine atom or a trifluoromethyl group, and still more preferably both a fluorine atom.

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

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

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

［式（ｂ１－４）中、
Ｌ^b8は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
式（ｂ１－５）中、
Ｌ^b9は、炭素数１～２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ｌ^b10は、単結合又は炭素数１～１９の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b9及びＬ^b10の合計炭素数は２０以下である。
式（ｂ１－６）中、
Ｌ^b11は、炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^b12は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b11及びＬ^b12の合計炭素数は２１以下である。
式（ｂ１－７）中、
Ｌ^b13は、炭素数１～１９の２価の飽和炭化水素基を表す。
Ｌ^b14は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ｌ^b15は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b13～Ｌ^b15の合計炭素数は１９以下である。
式（ｂ１－８）中、
Ｌ^b16は、炭素数１～１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ｌ^b17は、炭素数１～１８の２価の飽和炭化水素基を表す。
Ｌ^b18は、単結合又は炭素数１～１７の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b16～Ｌ^b18の合計炭素数は１９以下である。］ Examples of the group represented by 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 C 1-6 divalent saturated hydrocarbon group.
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 the 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 substituted 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 is not replaced with —O—, —S—, —SO ₂ — or —CO— include Examples include groups represented by formulas (Y1) to (Y11) and formulas (Y36) to (Y38).
When —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced with —O—, —S—, —SO ₂ — or —CO—, the number may be 1, or 2 or more. It's okay. 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 —. * represents the binding site with L ^b1 .

The alicyclic hydrocarbon group represented by Y is preferably represented by formulas (Y1) to (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31) and 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), formula (Y30), a group represented by formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), more preferably formula (Y11), formula (Y15), formula (Y20), a group represented by formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) .
The alicyclic hydrocarbon group represented by Y is a spiro ring containing an oxygen atom such as formula (Y28) to formula (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.
Substituents for the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, and an alkyl group having 1 to 16 carbon atoms optionally substituted by a hydroxy group (-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 7 to 21 carbon atoms, aralkyl group, glycidyloxy group, —(CH ₂ ) _ja —CO—O—R ^b1 group or —(CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is a C 1-16 represents an alkyl group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and is included in the alkyl group and the alicyclic hydrocarbon group —CH ₂ — may be replaced with —O—, —SO ₂ — or —CO—, and hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group are may be substituted with 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-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and alicyclic rings having 3 to 18 carbon atoms and aromatic hydrocarbon groups having a hydrocarbon group of formula (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.). 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 formulas A group represented by (Y43) and the like can be mentioned.

Examples of Y include the following.

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 It is a hydrocarbon group, more preferably an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and even more preferably an optionally substituted adamantyl group. , -CH ₂ - constituting the alicyclic hydrocarbon group or adamantyl group may be replaced with -O-, -SO ₂ - or -CO-. Among them, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented by formula (Y42), formula (Y100) to formula (Y114), or formula (Y134) to formula (Y139). .

Examples of the anion in the salt represented by formula (B1) include anions represented by formulas (B1-A-1) to (B1-A-62) [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), Formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-62) Anions are more preferred.

ここでＲⁱ²～Ｒⁱ⁷は、互いに独立に、例えば、炭素数１～４のアルキル基、好ましくはメチル基又はエチル基である。Ｒⁱ⁸は、例えば、炭素数１～１２の脂肪族炭化水素基、好ましくは炭素数１～４のアルキル基、炭素数５～１２の脂環式炭化水素基又はこれらを組合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基又はアダマンチル基である。Ｌ^A41は、単結合又は炭素数１～４のアルカンジイル基である。
Ｑ^b1及びＱ^b2は、上記と同じ意味を表す。
式（Ｂ１）で表される塩におけるアニオンとしては、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, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. 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.

Preferred anions in the salt represented by formula (B1) include anions represented by formulas (B1a-1) to (B1a-40), respectively.

Among them, formula (B1a-1) ~ formula (B1a-3), formula (B1a-7) ~ formula (B1a-16), formula (B1a-18), formula (B1a-19), formula (B1a-22 ) to formula (B1a-40) are preferred.

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. Specific examples include cations represented by any one of formulas (b2-1) to (b2-4) described above.

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 formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a- 19), an anion represented by any one of formulas (B1a-22) to (B1a-40) 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.

<Resin (A)>
The resin (A) contains a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). The resin (A) preferably further contains structural units other than the structural unit (a1). Structural units other than the structural unit (a1) include structural units having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), structural units other than the structural unit (a1) and the structural unit (s). Structural units (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit having a non-eliminating hydrocarbon group described later (hereinafter referred to as "structural unit (a5)" in some cases) and other structural units derived from monomers known in the art.

［式（１）中、Ｒ^a1、Ｒ^a２及びＲ^a3は、それぞれ独立に、炭素数１～８のアルキル基、炭素数２～８のアルケニル基、炭素数３～２０の脂環式炭化水素基、炭素数６～１８の芳香族炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３～２０の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 contained in the resin (A) is a group represented by formula (1) (hereinafter also referred to as group (1)) and/or a group represented by formula (2) (hereinafter referred to as group (2 )) is preferred.

[In formula (1), R ^a1 , R ^a2 and R ^a3 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 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, groups formed by combining these groups, and the like.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same groups as those listed for R ^a1 , R ^a2 and R ^a3 .
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, etc.), an aralkyl group (benzyl group, etc.), an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert- butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups ( p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), alicyclic hydrocarbon groups having an aromatic hydrocarbon group (phenylcyclohexyl group, etc.), and the like.
When R ^a2′ and R ^a3′ are bonded to each other to form a heterocyclic 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. When the resin (A) having a structural unit derived from the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

［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 any integer from 0 to 10;
n1' represents an integer of 0 to 3; ]

R ^a01 , R ^a4 and R ^a5 are preferably a hydrogen atom or a methyl group, 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, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and groups in combination thereof in R ^a02 , R ^a03 and R ^a04 are R ^a1 , R ^a2 and R ^a3 in group (1). Groups similar to the above-mentioned groups can be mentioned.
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 a methyl group, an ethyl group, a phenyl group or a naphthyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, 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 the 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 (A) contains the structural unit (a1-0), its content is usually 5 to 60 mol%, preferably 5 to 50 mol%, based on the total structural units of the resin (A). Yes, more preferably 10 to 40 mol %.
When the resin (A) contains the structural unit (a1-1) and/or the structural unit (a1-2), the total content of these is usually 10 to 95 mol with respect to the total structural units of the resin (A). %, preferably 15 to 85 mol %, more preferably 15 to 80 mol %, still more preferably 20 to 80 mol %, still more preferably 20 to 75 mol %.

［式（ａ１－４）中、
Ｒ^a32は、水素原子、ハロゲン原子、又は、ハロゲン原子を有していてもよい炭素数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 the formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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 alkyl groups for R ^a33 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.
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, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group is more preferable, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group is 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.

Alkanediyl group for A ^a32 includes methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group and 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 and 2-methylbutane-1,4-diyl group.
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.
Hydrocarbon groups for R ^a34 , R ^a35 and R ^a36 include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and groups in which these are combined.
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.

樹脂（Ａ）が、構造単位（ａ１－４）を含む場合、その含有率は、樹脂（Ａ）の全構造単位の合計に対して、５～６０モル％であることが好ましく、５～５０モル％であることがより好ましく、１０～４０モル％であることがさらに好ましい。 --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 preferably bonds to the o-position or p-position of the benzene ring, more preferably to the p-position.
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 structural units and structural units (a1-4) represented by formulas (a1-4-1) to (a1-4-24) is a halogen atom or a haloalkyl group. or a structural unit substituted with an alkyl group, more preferably formula (a1-4-1) ~ formula (a1-4-5), formula (a1-4-10), formula (a1-4-13 ), formula (a1-4-14), formula (a1-4-19), and formula (a1-4-20).

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

式（ａ１－５）中、
Ｒ^a8は、ハロゲン原子を有していてもよい炭素数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 any integer from 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—.

樹脂（Ａ）が、構造単位（ａ１－５）を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１～５０モル％が好ましく、３～４５モル％がより好ましく、５～４０モル％がさらに好ましく、５～３０モル％がさらにより好ましい。 Examples of 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 (A) contains the structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, based on the total structural units of the resin (A). , more preferably 5 to 40 mol %, and even more preferably 5 to 30 mol %.

［式（ａ１－０Ｘ）中、
Ｒ^ｘ１は、水素原子又はメチル基を表す。
Ｒ^ｘ２及びＲ^ｘ３は、それぞれ独立に、炭素数１～６の飽和炭化水素基を表す。
Ａｒ^ｘ１は、炭素数６～３６の芳香族炭化水素基を表す。］ Examples of the structural unit (a1) include structural units represented by formula (a1-0X) (hereinafter sometimes referred to as structural unit (a1-0X)).

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

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

樹脂（Ａ）が、構造単位（ａ１－０Ｘ）を有する場合、その含有率は、樹脂（Ａ）における全モノマーに対して、５～６０モル％であることが好ましく、５～５０モル％であることがより好ましく、１０～４０モル％であることがさらに好ましい。
樹脂（Ａ）は、構造単位（ａ１－０Ｘ）を２種以上含有していてもよい。 Examples of the structural unit (a1-0X) include the following structural units and compounds in which the methyl group corresponding to R ^x1 in the structural unit (a1-0X) is replaced with a hydrogen atom. Structural unit (a1-0X) is preferably structural unit (a1-0X-1) to structural unit (a1-0X-3).

When the resin (A) has the structural unit (a1-0X), the content thereof is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, based on the total monomers in the resin (A). more preferably 10 to 40 mol %.
The resin (A) may contain two or more structural units (a1-0X).

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

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

<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 from 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 group for A ^a52 includes methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and 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 and 2-methylbutane-1,4-diyl group.
A ^a52 is preferably a methylene group or an ethylene group.
A ^a50 is preferably a single bond, *—CO—O— or *—CO—O—A ^a52 —CO—O—, 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 bonded to the meta-position or para-position of the benzene ring, and more preferably bonded to the meta-position. When the phenyl group has two or more hydroxy groups, the two hydroxy groups are preferably bonded to the meta and para positions, respectively.

樹脂（Ａ）中に構造単位（ａ２－Ａ）が含まれる場合の構造単位（ａ２－Ａ）の含有率は、全構造単位に対して、好ましくは５～８０モル％であり、より好ましくは１０～７０モル％であり、さらに好ましくは１５～６５モル％であり、さらにより好ましくは２０～６５モル％である。
構造単位（ａ２－Ａ）は、例えば構造単位（ａ１－４）を用いて重合した後、ｐ－トルエンスルホン酸等の酸で処理することにより、樹脂（Ａ）に含ませることができる。また、アセトキシスチレン等を用いて重合した後、テトラメチルアンモニウムヒドロキシド等のアルカリで処理することにより、構造単位（ａ２－Ａ）を樹脂（Ａ）に含ませることができる。 Examples of the structural unit (a2-A) include structural units derived from 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 A structural unit represented by (a2-2-14), a structural unit represented by formula (a2-2-18) and a structural unit represented by formula (a2-2-3), a structural unit represented by 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 (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol% of the total structural units, more preferably It is 10 to 70 mol %, more preferably 15 to 65 mol %, still more preferably 20 to 65 mol %.
The structural unit (a2-A) can be included in the resin (A), for example, by polymerizing the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Further, the structural unit (a2-A) can be included in the resin (A) by polymerizing with acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide.

式（ａ２－１）中、
Ｌ^a3は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k2－ＣＯ－Ｏ－を表し、
ｋ２は１～７のいずれかの整数を表す。＊は－ＣＯ－との結合部位を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０～１０のいずれかの整数を表す。 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 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) , 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.

樹脂（Ａ）が構造単位（ａ２－１）を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、通常１～４５モル％であり、好ましくは１～４０モル％であり、より好ましくは１～３５モル％であり、さらに好ましくは１～２０モル％であり、さらにより好ましくは１～１０モル％である。 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 (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on the total structural units of the resin (A). Yes, more preferably 1 to 35 mol %, still more preferably 1 to 20 mol %, still more preferably 1 to 10 mol %.

［式（ａ３－１）、式（ａ３－２）、式（ａ３－３）及び式（ａ３－４）中、
Ｌ^ａ４、Ｌ^ａ５及びＬ^ａ６は、それぞれ独立に、－Ｏ－又は＊－Ｏ－（ＣＨ_２）_ｋ３－ＣＯ－Ｏ－（ｋ３は１～７のいずれかの整数を表す。）で表される基を表す。
Ｌ^ａ７は、－Ｏ－、＊－Ｏ－Ｌ^ａ８－Ｏ－、＊－Ｏ－Ｌ^ａ８－ＣＯ－Ｏ－、＊－Ｏ－Ｌ^ａ８－ＣＯ－Ｏ－Ｌ^ａ９－ＣＯ－Ｏ－又は＊－Ｏ－Ｌ^ａ８－Ｏ－ＣＯ－Ｌ^ａ９－Ｏ－を表す。
Ｌ^ａ８及びＬ^ａ９は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
＊はカルボニル基との結合部位を表す。
Ｒ^ａ１８、Ｒ^ａ１９及びＲ^ａ２０は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ２４は、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^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)>
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)).
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 and R ^a20 each independently represent a hydrogen atom or a methyl group.
R ^a24 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have 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 ^a24 include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkyl group for R ^a24 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group, preferably having 1 to 4 carbon atoms. and more preferably a methyl group or an ethyl group.
The alkyl group having a halogen atom for R ^a24 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluoro A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group and the like can be mentioned.

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.)

樹脂（Ａ）が構造単位（ａ３）を含む場合、その合計含有率は、樹脂（Ａ）の全構造単位に対して、通常１～７０モル％であり、好ましくは１～６５モル％であり、より好ましくは１～６０モル％である。
また、構造単位（ａ３－１）、構造単位（ａ３－２）、構造単位（ａ３－３）又は構造単位（ａ３－４）の含有率は、それぞれ、樹脂（Ａ）の全構造単位に対して、１～６０モル％が好ましく、１～５０モル％がより好ましく、１～５０モル％がさらに好ましい。 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 ^a18 , 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 (A) contains the structural unit (a3), the total content is usually 1 to 70 mol%, preferably 1 to 65 mol%, based on the total structural units of the resin (A). , more preferably 1 to 60 mol %.
Further, the content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structural unit (a3-4) is is preferably 1 to 60 mol %, more preferably 1 to 50 mol %, even more preferably 1 to 50 mol %.

［式（ａ４）中、
Ｒ⁴¹は、水素原子又はメチル基を表す。
Ｒ⁴²は、炭素数１～２４のフッ素原子を有する飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。］
Ｒ⁴²で表される飽和炭化水素基は、鎖式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 fluorine atoms, 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、
Ｒ^5ａは、水素原子又はメチル基を表す。
Ｌ^4ａは、単結合又は炭素数１～４のアルカンジイル基を表す。
Ｌ^3ａは、炭素数１～８のペルフルオロアルカンジイル基又は炭素数３～１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ^6ａは、水素原子又はフッ素原子を表す。］ The structural unit (a4) is at least selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3) and formula (a4-4) Structural units represented by one are exemplified.

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

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 perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a perfluoropropane group. -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 ^R5a 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価の脂肪族炭化水素基を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、－Ｏ－、－ＣＯ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は７以下である。〕
＊は結合部位であり、右側の＊が－Ｏ－ＣＯ－Ｒ^a42との結合部位である。］

[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 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 aliphatic 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. is 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（ａ－ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す。
Ａ^a45は、ハロゲン原子を有していてもよい炭素数１～１７の脂肪族炭化水素基を表す。
＊はＲ^a42との結合部位を表す。］
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の脂肪族炭化水素基を表す。 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 an aliphatic 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 an aliphatic hydrocarbon group having 1 to 17 carbon atoms and having at least one halogen atom.

組み合わせにより形成される基としては、１以上のアルキル基又は１以上のアルカンジイル基と、１以上の脂環式炭化水素基とを組み合わせることにより形成される基が挙げられ、－アルカンジイル基－脂環式炭化水素基、－脂環式炭化水素基－アルキル基、－アルカンジイル基－脂環式炭化水素基－アルキル基等が挙げられる。 Aliphatic hydrocarbon groups for A ^a45 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and Alkyl groups such as octadecyl group; 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 (* represents a bonding position.) 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 with 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 optionally having 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の脂肪族炭化水素基を表す。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合部位を表す。］ When R ^a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R ^a42 is more preferably a group represented by formula (a-g2).

[In 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 an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47 and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* represents a bonding site with a carbonyl group. ]

The saturated hydrocarbon group of A ^a46 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
The number of carbon atoms in the aliphatic hydrocarbon group of A ^a47 is preferably 4 to 15, more preferably 5 to 12, 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 of 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 the formula (a-g1) include linear or branched alkanediyl groups and monocyclic or polycyclic divalent Examples thereof include alicyclic saturated hydrocarbon groups, groups formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group, and the like. 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.
Examples of 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 examples below, * and ** each represent a binding site, and ** is the 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。］ As the structural unit represented by formula (a4-1), a structural unit represented by formula (a4-2) is preferable.

[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 alkanediyl group for ^{L44 include the same groups as those exemplified for Aa41 .}
Examples of the saturated hydrocarbon group for R ^f6 include the same groups as those exemplified for R ^a42 .
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－（＊はＡ^f13との結合部位を表す。）を表す。
Ａ^f14は、フッ素原子を有していてもよい炭素数１～１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14の合計炭素数の上限は２０である。］

[In 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, pentyl, hexyl, perfluorohexyl, heptyl, perfluoroheptyl, octyl and perfluorooctyl groups 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. ]

The saturated hydrocarbon group represented by R ^{f22 includes the same saturated hydrocarbon group represented by R a42 .} R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic 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.

樹脂（Ａ）が、構造単位（ａ４）を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１～２０モル％が好ましく、２～１５モル％がより好ましく、３～１０モル％がさらに好ましい。 As the structural unit represented by 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 (A) contains the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, based on the total structural units of the resin (A). ~10 mol% is more preferred.

［式（ａ５－１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３～１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１～８の脂肪族炭化水素基で置換されていてもよい。
Ｌ⁵⁵は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of 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 the formula (a5-1),
^R51 represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group 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 saturated chain 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. The polycyclic divalent alicyclic saturated hydrocarbon group includes 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 formula below, * and ** represent a binding site, and * represents a binding 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 saturated aliphatic 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 aliphatic saturated 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.

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.

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 (L1-4) include the divalent groups shown below.

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

樹脂（Ａ）が、構造単位（ａ５）を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１～３０モル％が好ましく、２～２０モル％がより好ましく、３～１５モル％がさらに好ましい。 Examples of the structural unit (a5-1) include the structural 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 (A) contains the structural unit (a5), the content thereof is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, based on the total structural units of the resin (A). ~15 mol% is more preferred.

<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. A structural unit having a cyclic structure containing a —SO ₂ — group is preferred, and a structural unit having a cyclic structure (sultone ring) containing —SO ₂ —O— is 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、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１～１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１～１２のアルコキシ基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基、グリシジルオキシ基、炭素数２～１２のアルコキシカルボニル基又は炭素数２～４のアルキルカルボニル基を表す。
ｍａは、０～９のいずれかの整数を表す。ｍａが２以上のとき、複数のＲ^４１は同一であっても異なってもよい。
結合部位は任意の位置である。］
Ｘ^１１は、好ましくは酸素原子又はメチレン基であり、より好ましくはメチレン基である。
Ｒ^４１としては、スルトン環の置換基と同様のものが挙げられ、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１～１２のアルキル基が好ましい。 A sultone ring having no substituent is 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.
As R ⁴¹ , the same substituents as those for the sultone ring can be mentioned, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferred.

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

[In formula (T1),
R ⁸ 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, and 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.
m represents any integer from 0 to 9; When m is 2 or more, multiple R ^8s may be the same or different.
The binding site can be any position. ]

Examples of R ⁸ include those similar to those of R ⁴¹ .
ma in formula (T1′) and m in formula (T1) are preferably 0 or 1, more preferably 0.

The ring represented by formula (T1′) and the ring represented by formula (T1) include the following rings. The binding site can be any position.

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

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（Ｉｘ）中、Ｒ^ｘは、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロゲン原子を表す。
Ａ^ｘｘは、酸素原子、－Ｎ（Ｒ^ｃ）－又は硫黄原子を表す。
Ａ^ｘは、炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＣＯ－又は－Ｎ（Ｒ^ｄ）－に置き換わっていてもよい。
Ｘ^１１は、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^４１は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１～１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１～１２のアルコキシ基、炭素数６～１２のアリール基、炭素数７～１２のアラルキル基、グリシジルオキシ基、炭素数２～１２のアルコキシカルボニル基又は炭素数２～４のアルキルカルボニル基を表す。
ｍａは、０～９のいずれかの整数を表す。ｍａが２以上のとき、複数のＲ^４１は同一であっても異なってもよい。
Ｒ^ｃ及びＲ^ｄは、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。］ Structural unit (a6) is preferably a structural unit represented by formula (Ix).

[In formula (Ix), 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 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 replaced.
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 an integer from 0 to 9; When ma is 2 or more, multiple R ⁴¹ may be the same or different.
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 divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group and the like.

Examples of R ⁴¹ , X ¹¹ and ma are the same as those of formula (T1′).
Examples of the sultone ring include those described above, and among these, the above-described sultone ring with a specified binding position is preferable.

Structural units (a6) 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 (A) has the structural unit (a6), the content thereof is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, based on the total structural units of the resin (A), and 3 ~30 mol% is more preferred.

<Structural unit (II)>
The resin (A) may further contain a structural unit that is decomposed by exposure to generate an acid (hereinafter sometimes referred to as "structural unit (II)"). Specific examples of the structural unit (II) include structural units described in JP-A-2016-79235. A structural unit having a group and an organic anion is preferred.

［式（ＩＩ－２－Ａ’）中、
Ｘ^III3は、炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わっていてもよく、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子、ハロゲン原子を有していてもよい炭素数１～６のアルキル基又はヒドロキシ基で置き換わっていてもよい。
Ａ^x1は、炭素数１～８のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、フッ素原子又は炭素数１～６のペルフルオロアルキル基で置換されていてもよい。
ＲＡ^－は、スルホナート基又はカルボキシレート基を表す。
Ｒ^III3は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
ＺＡ^＋は、有機カチオンを表す。］ A structural unit having a sulfonate group or carboxylate group and an organic cation in a side chain is preferably a structural unit represented by formula (II-2-A').

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

Halogen atoms represented by R ^III3 include fluorine, chlorine, bromine and iodine atoms.
The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom represented by R ^III3 includes an alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom represented by R ^a8 . The same can be mentioned.
The alkanediyl group having 1 to 8 carbon atoms represented by A ^x1 includes methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group and pentane-1,5-diyl group. , hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2, 4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. mentioned.
The perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted for A ^x1 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 and the like.
Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X ^III3 include a linear or branched alkanediyl group and a monocyclic or polycyclic bivalent alicyclic saturated hydrocarbon group. and combinations thereof.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , dodecane-1,12-diyl group and other linear alkanediyl groups; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 ,4-diyl group, cycloalkanediyl group such as cyclooctane-1,5-diyl group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane Divalent polycyclic alicyclic saturated hydrocarbon groups such as -2,6-diyl group and the like can be mentioned.
Examples of saturated hydrocarbon groups in which —CH ₂ — is replaced with —O—, —S— or —CO— include divalent groups represented by formulas (X1) to (X53). mentioned. However, each —CH ₂ — contained in the saturated hydrocarbon group has 17 or less carbon atoms before being replaced with —O—, —S— or —CO—. In the formula below, * and ** represent binding sites, and * represents a binding site with ^Ax1 .

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

Examples of ZA ⁺ in formula (II-2-A′) include the same cations Z1 ⁺ in acid generator (B1).

［式（ＩＩ－２－Ａ）中、
Ｒ^III3、Ｘ^III3及びＺＡ^＋は、上記と同じ意味を表す。
ｚ２Ａは、０～６のいずれかの整数を表す。
Ｒ^III2及びＲ^III4は、それぞれ独立して、水素原子、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表し、ｚ２Ａが２以上のとき、複数のＲ^III2及びＲ^III4は互いに同一であってもよいし、異なっていてもよい。
Ｑ^ａ及びＱ^ｂは、それぞれ独立して、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。］
Ｒ^III2、Ｒ^III４、Ｑ^ａ及びＱ^ｂで表される炭素数１～６のペルフルオロアルキル基としては、前述のＱ^ｂ１で表される炭素数１～６のペルフルオロアルキル基と同じものが挙げられる。 The structural unit represented by formula (II-2-A') is preferably a structural unit represented by formula (II-2-A).

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

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

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

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

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

Structural units represented by formula (II-2-A′) include, for example, the following structural units, a group corresponding to a methyl group in R ^III3 is a hydrogen atom, a halogen atom (e.g., a fluorine atom) or a halogen atom Structural units substituted with an alkyl group having 1 to 6 carbon atoms (eg, trifluoromethyl group, etc.) and structural units described in WO 2012/050015 may be mentioned. ZA ⁺ represents an organic cation.

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

[In the formula (II-1-1),
^AII1 represents a single bond or a divalent linking group.
R ^II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^II2 and R ^II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R ^II2 and R ^II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded.
R ^II4 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
A ⁻ represents an organic anion. ]
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^II1 include a phenylene group and a naphthylene group.
The hydrocarbon groups represented by R ^II2 and R ^II3 include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and groups formed by combining these groups.
Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups.
Examples of the combined group include a group obtained by combining an alkyl group and an alicyclic hydrocarbon group described above, an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert- butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups ( p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, and the like.
Halogen atoms represented by R ^II4 include fluorine, chlorine, bromine and iodine atoms.
The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom represented by R ^II4 includes an alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom represented by R ^a8 . The same can be mentioned.
The divalent linking group represented by A ^II1 includes, for example, a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is -O-, -S- or -CO- may be substituted. Specific examples thereof include the same divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by ^XIII3 .

As the structural unit containing a cation in formula (II-1-1), the structural unit represented below and a group corresponding to a methyl group in R ^II4 are a hydrogen atom, a halogen atom (e.g., a fluorine atom) or a halogen Structural units substituted with alkyl groups having 1 to 6 carbon atoms which may have atoms (eg, trifluoromethyl group, etc.), and the like.

Organic anions represented by A ⁻ include sulfonate anions, sulfonylimide anions, sulfonylmethide anions and carboxylate anions. The organic anion represented by A ⁻ is preferably a sulfonate anion, and the sulfonate anion is more preferably an anion contained in the salt represented by the above formula (B1).

Sulfonylimide anions represented by A ⁻ include the following.

Sulfonylmethide anions include the following.

Carboxylate anions include the following.

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

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

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

The resin (A) is preferably a resin composed of structural units (a1) and structural units (s).
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, more preferably structural unit (a1-1) and/or 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 a structural unit represented by formula (a2-A) or a structural unit represented by formula (a2-1). 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 that constitutes the resin (A) may be used alone or in combination of two or more, 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 (A) can be adjusted by adjusting the amount of monomer used for polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 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). As used herein, the weight average molecular weight is a value obtained by gel permeation chromatography under the conditions described in Examples.

<Resins other than resin (A)>
The resist composition of the present invention may be used in combination with a resin other than the resin (A).
Examples of the resin other than the resin (A) include a resin containing the structural unit (a4) or the structural unit (a5) (hereinafter sometimes referred to as resin (X)).
As the resin (X), among others, a resin containing the structural unit (a4) is preferable.
In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total of all structural units of the resin (X). , more preferably 45 mol % or more.
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), more preferably a resin consisting only of the structural unit (a4).
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 (A).
Further, when the resist composition contains the resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the resin (A). , more preferably 1 to 40 parts by mass, still more preferably 1 to 30 parts by mass, and even more preferably 1 to 8 parts by mass.

The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, relative to the solid content of the resist composition. Further, when a resin other than the resin (A) is included, the total content of the resin (A) and the resin other than the resin (A) is 80% by mass or more and 99% by mass with respect to the solid content of the resist composition. It is preferably less than or equal to 90% 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.

<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)>
The quencher (C) is a basic nitrogen-containing organic compound or a salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) (provided, however, that the carboxylate represented by the formula (I) except.) When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15% by mass, based on the solid content of the resist composition. It is more preferably about 01 to 10% by mass, even more preferably about 0.1 to 8% by mass, even more preferably about 0.1 to 7% by mass.
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;

The acidity of a salt that generates an acid weaker than the acid generated from the acid generator (B) 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 (B) has an acid dissociation constant of -3<pKa, preferably -1<. Salts with pKa<7, more preferably salts with 0<pKa<5.
Examples of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) include salts represented by the following formula, and salts represented by the formula (D) described in JP-A-2015-147926. (Hereinafter, it may be referred to as "weak acid inner salt (D)".), and JP 2012-229206, JP 2012-6908, JP 2012-72109, JP 2011-39502 and salts described in JP-A-2011-191745. Preferred is a salt (salt having a carboxylic acid anion) that generates a carboxylic acid having a weaker acidity than the acid generated from the acid generator (B), more preferably a weak acid inner salt (D), Of the weak acid inner salts (D), diphenyliodonium salts containing a phenyl group substituted with a carboxylate anion are more preferred.

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 specific examples include salts represented by the following formulas.

［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。

[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 group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group and 4-propylphenyl group. , 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group , mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-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.

<Other ingredients>
The resist composition of the present invention may optionally 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 carboxylate (I), a resin (A), an acid generator (B), and, if necessary, a resin other than the resin (A), a solvent (E), a quencher ( It can be prepared by mixing C) and other components (F). 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 or the like and the solubility of the resin or the like 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 producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) a step of applying the resist composition of the present invention onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the exposed composition layer; and (5) developing the heated composition layer.
The coating of the resist composition on the substrate can be carried out using a commonly used device such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer, and an organic substrate having a resist film 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, and extreme ultraviolet light (EUV). 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.
After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and pattern is removed.
When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer.
Examples of organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. ether solvents; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole;
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, 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 trace amount of water.
During development, the development may be stopped by replacing the organic developer with a solvent of a different type.
It is preferable to wash the resist pattern after development with a rinsing liquid. 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（Ｉ－５４－ａ）で表される化合物５．００部、ジメチルアミノピリジン０．４５部、トリエチルアミン２．１９部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－５４－ｂ）で表される化合物３．２１部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－５４－ｃ）で表される塩１．３１部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３回繰り返した。得られた有機層を濃縮し、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル２０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－５４）で表される塩１．０９部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４３１．３
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４２５．０ Example 1: Synthesis of salt represented by formula (I-54)

5.00 parts of the compound represented by the formula (I-54-a), 0.45 parts of dimethylaminopyridine, 2.19 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 3.21 parts of the compound represented by (I-54-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 1.31 parts of the salt represented by the formula (I-54-c) was added and stirred at 23° C. for 3 hours. After cooling the resulting mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 10 parts of ion-exchanged water was added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then liquid-separated to obtain an organic layer. This washing operation was repeated three times. The resulting organic layer is concentrated, 20 parts of tert-butyl methyl ether is added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes. 1.09 parts of a salt of the formula are obtained.
MS (ESI (+) Spectrum): M ⁺ 431.3
MS (ESI (-) Spectrum): M ^- 425.0

式（Ｉ－５５－ａ）で表される化合物５．００部、ジメチルアミノピリジン０．３１部、トリエチルアミン１．５１部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－５４－ｂ）で表される化合物２．２１部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－５４－ｃ）で表される塩１．３１部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３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（Ｉ－５５）で表される塩１．１１部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４３１．３
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ５５０．９ Example 2: Synthesis of salt represented by formula (I-55)

5.00 parts of the compound represented by the formula (I-55-a), 0.31 parts of dimethylaminopyridine, 1.51 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 2.21 parts of the compound represented by (I-54-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 1.31 parts of the salt represented by the formula (I-54-c) was added and stirred at 23° C. for 3 hours. After cooling the resulting mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 10 parts of ion-exchanged water was added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then liquid-separated to obtain an organic layer. This washing operation was repeated three times. The resulting organic layer is concentrated, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether are added to the concentration residue, and the mixture is stirred at 23° C. for 30 minutes, then the supernatant is removed and concentrated to obtain the formula ( 1.11 parts of the salt represented by I-55) were obtained.
MS (ESI (+) Spectrum): M ⁺ 431.3
MS (ESI (-) Spectrum): M ^- 550.9

式（Ｉ－５６－ａ）で表される化合物５．２９部、ジメチルアミノピリジン０．４５部、トリエチルアミン２．１９部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－５４－ｂ）で表される化合物３．２１部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－５４－ｃ）で表される塩１．３１部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３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１部及びｔｅｒｔ－ブチルメチルエーテル２０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－５６）で表される塩１．１８部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４３１．３
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４４１．０ Example 3: Synthesis of salt represented by formula (I-56)

5.29 parts of the compound represented by the formula (I-56-a), 0.45 parts of dimethylaminopyridine, 2.19 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 3.21 parts of the compound represented by (I-54-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 1.31 parts of the salt represented by the formula (I-54-c) was added and stirred at 23° C. for 3 hours. After cooling the obtained mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. After adding 10 parts of ion-exchanged water to the obtained mixture and stirring at 23° C. for 30 minutes, the mixture was separated to obtain an organic layer. This washing operation was repeated three times. The obtained organic layer is concentrated, 1 part of acetonitrile and 20 parts of tert-butyl methyl ether are added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes. 1.18 parts of the salt represented by I-56) were obtained.
MS (ESI (+) Spectrum): M ⁺ 431.3
MS (ESI (-) Spectrum): M ^- 441.0

式（Ｉ－５６－ａ）で表される化合物５．２９部、ジメチルアミノピリジン０．４５部、トリエチルアミン２．１９部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－５４－ｂ）で表される化合物３．２１部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－１２－ｃ）で表される塩０．９０部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３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１部及びｔｅｒｔ－ブチルメチルエーテル２０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１２）で表される塩１．２３部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４４１．０ Example 4: Synthesis of salt represented by formula (I-12)

5.29 parts of the compound represented by the formula (I-56-a), 0.45 parts of dimethylaminopyridine, 2.19 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 3.21 parts of the compound represented by (I-54-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 0.90 part of the salt represented by the formula (I-12-c) was added and stirred at 23° C. for 3 hours. After cooling the resulting mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 10 parts of ion-exchanged water was added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then liquid-separated to obtain an organic layer. This washing operation was repeated three times. The obtained organic layer is concentrated, 1 part of acetonitrile and 20 parts of tert-butyl methyl ether are added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes. 1.23 parts of the salt represented by I-12) were obtained.
MS (ESI(+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 441.0

式（Ｉ－１６－ｂ）で表される化合物２．９４部及びアセトニトリル１５部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１６－ｃ）で表される化合物１．６２部を混合し、５０℃で２時間攪拌した。得られた混合物に、式（Ｉ－１６－ａ）で表される塩４．００部を添加し、５０℃で２時間攪拌した後、２３℃まで冷却した。得られた混合物に、クロロホルム２０部及び５％シュウ酸水溶液水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３回繰り返した。得られた有機層を濃縮し、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル２０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１６）で表される塩５．４２部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４５７．０ Example 5: Synthesis of salt represented by formula (I-16)

2.94 parts of the compound represented by the formula (I-16-b) and 15 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes, and then the compound 1.62 represented by the formula (I-16-c) The parts were mixed and stirred at 50° C. for 2 hours. To the resulting mixture, 4.00 parts of the salt represented by the formula (I-16-a) was added, stirred at 50°C for 2 hours, and then cooled to 23°C. 20 parts of chloroform and 10 parts of a 5% aqueous oxalic acid solution were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. After adding 10 parts of ion-exchanged water to the obtained mixture and stirring at 23° C. for 30 minutes, the mixture was separated to obtain an organic layer. This washing operation was repeated three times. The resulting organic layer is concentrated, 20 parts of tert-butyl methyl ether is added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes. 5.42 parts of the salt represented by are obtained.
MS (ESI(+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 457.0

式（Ｉ－５４７－ａ）で表される化合物３．０６部及びメタノール３０部を混合し、２３℃で３０分間攪拌した後、酸化銀１．１６部を添加し、２３℃で８時間撹拌した。得られた混合物に、式（Ｉ－５４７－ｂ）で表される塩６．５２部を添加し、２３℃で１２時間撹拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層にイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。その後、濃縮することにより、式（Ｉ－５４７）で表される塩７．６５部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３０５．０ Example 6: Synthesis of salt represented by formula (I-547)

3.06 parts of the compound represented by the formula (I-547-a) and 30 parts of methanol were mixed and stirred at 23°C for 30 minutes, then 1.16 parts of silver oxide was added and stirred at 23°C for 8 hours. did. To the resulting mixture, 6.52 parts of the salt represented by formula (I-547-b) was added and stirred at 23°C for 12 hours. 50 parts of chloroform and 20 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. Then, by concentrating, 7.65 parts of the salt represented by the formula (I-547) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 305.0

式（Ｉ－５５０－ａ）で表される化合物３．３６部及びメタノール３０部を混合し、２３℃で３０分間攪拌した後、酸化銀１．１６部を添加し、２３℃で８時間撹拌した。得られた混合物に、式（Ｉ－５４７－ｂ）で表される塩６．５２部を添加し、２３℃で１２時間撹拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層にイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。その後、濃縮することにより、式（Ｉ－５５０）で表される塩６．２３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３３５．０ Example 7: Synthesis of salt represented by formula (I-550)

3.36 parts of the compound represented by the formula (I-550-a) and 30 parts of methanol were mixed and stirred at 23°C for 30 minutes, then 1.16 parts of silver oxide was added and stirred at 23°C for 8 hours. did. To the resulting mixture, 6.52 parts of the salt represented by formula (I-547-b) was added and stirred at 23°C for 12 hours. 50 parts of chloroform and 20 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. Then, by concentrating, 6.23 parts of the salt represented by the formula (I-550) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 335.0

式（Ｉ－５７０－ａ）で表される化合物６．００部及びメタノール３０部を混合し、２３℃で３０分間攪拌した後、酸化銀１．１６部を添加し、２３℃で８時間撹拌した。得られた混合物に、式（Ｉ－５４７－ｂ）で表される塩６．５２部を添加し、２３℃で１２時間撹拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層にイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。その後、濃縮することにより、式（Ｉ－５７０）で表される塩８．４６部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ５９９．２ Example 8: Synthesis of salt represented by formula (I-570)

6.00 parts of the compound represented by the formula (I-570-a) and 30 parts of methanol were mixed and stirred at 23°C for 30 minutes, then 1.16 parts of silver oxide was added and stirred at 23°C for 8 hours. did. To the resulting mixture, 6.52 parts of the salt represented by formula (I-547-b) was added and stirred at 23°C for 12 hours. 50 parts of chloroform and 20 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. Then, by concentrating, 8.46 parts of the salt represented by the formula (I-570) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 599.2

式（Ｉ－５８２－ａ）で表される化合物４．２６部及びメタノール３０部を混合し、２３℃で３０分間攪拌した後、酸化銀１．１６部を添加し、２３℃で８時間撹拌した。得られた混合物に、式（Ｉ－５４７－ｂ）で表される塩６．５２部を添加し、２３℃で１２時間撹拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層にイオン交換水２０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。その後、濃縮することにより、式（Ｉ－５８２）で表される塩８．１５部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４２５．０ Example 9: Synthesis of salt represented by formula (I-582)

4.26 parts of the compound represented by the formula (I-582-a) and 30 parts of methanol were mixed and stirred at 23°C for 30 minutes, then 1.16 parts of silver oxide was added and stirred at 23°C for 8 hours. did. To the resulting mixture, 6.52 parts of the salt represented by formula (I-547-b) was added and stirred at 23°C for 12 hours. 50 parts of chloroform and 20 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then separated to obtain an organic layer. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. Then, by concentrating, 8.15 parts of the salt represented by the formula (I-582) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 525.0
MASS (ESI (-) Spectrum): M ^- 425.0

式（Ｉ－５４－ａ）で表される化合物５．００部、ジメチルアミノピリジン０．４５部、トリエチルアミン２．１９部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－５４－ｂ）で表される化合物３．２１部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－５５６－ｃ）で表される塩１．５５部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３回繰り返した。得られた有機層を濃縮し、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル２０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－５５６）で表される塩１．１９部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４２５．０ Example 10: Synthesis of salt represented by formula (I-556)

5.00 parts of the compound represented by the formula (I-54-a), 0.45 parts of dimethylaminopyridine, 2.19 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 3.21 parts of the compound represented by (I-54-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 1.55 parts of the salt represented by the formula (I-556-c) was added and stirred at 23° C. for 3 hours. After cooling the obtained mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. After adding 10 parts of ion-exchanged water to the obtained mixture and stirring at 23° C. for 30 minutes, the mixture was separated to obtain an organic layer. This washing operation was repeated three times. The resulting organic layer is concentrated, 20 parts of tert-butyl methyl ether is added to the concentrated residue, and the mixture is stirred at 23° C. for 30 minutes. 1.19 parts of the salt of the formula are obtained.
MS (ESI (+) Spectrum): M ⁺ 525.0
MS (ESI (-) Spectrum): M ^- 425.0

式（Ｉ－５５－ａ）で表される化合物５．００部、ジメチルアミノピリジン０．３１部、トリエチルアミン１．５１部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－５４－ｂ）で表される化合物２．２１部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－５９９－ｃ）で表される塩１．４２部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３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（Ｉ－５９９）で表される塩１．４９部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４７９．０
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ５５０．９ Example 11: Synthesis of Salt Represented by Formula (I-599)

5.00 parts of the compound represented by the formula (I-55-a), 0.31 parts of dimethylaminopyridine, 1.51 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 2.21 parts of the compound represented by (I-54-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 1.42 parts of the salt represented by the formula (I-599-c) was added and stirred at 23° C. for 3 hours. After cooling the obtained mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. After adding 10 parts of ion-exchanged water to the obtained mixture and stirring at 23° C. for 30 minutes, the mixture was separated to obtain an organic layer. This washing operation was repeated three 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 ( 1.49 parts of the salt represented by I-599) were obtained.
MS (ESI (+) Spectrum): M ⁺ 479.0
MS (ESI (-) Spectrum): M ^- 550.9

式（Ｉ－５５－ａ）で表される化合物５．００部、ジメチルアミノピリジン０．３１部、トリエチルアミン１．５１部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１２２４－ｂ）で表される化合物２．３０部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－５９９－ｃ）で表される塩１．４２部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３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（Ｉ－１２２４）で表される塩０．６８部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ４７９．０
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ５５７．０ Example 12: Synthesis of salt represented by formula (I-1224)

5.00 parts of the compound represented by the formula (I-55-a), 0.31 parts of dimethylaminopyridine, 1.51 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 2.30 parts of the compound represented by (I-1224-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 1.42 parts of the salt represented by the formula (I-599-c) was added and stirred at 23° C. for 3 hours. After cooling the resulting mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 10 parts of ion-exchanged water was added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes, and then liquid-separated to obtain an organic layer. This washing operation was repeated three times. The resulting organic layer is concentrated, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether are added to the concentration residue, and the mixture is stirred at 23° C. for 30 minutes, then the supernatant is removed and concentrated to obtain the formula ( 0.68 parts of the salt represented by I-1224) was obtained.
MS (ESI (+) Spectrum): M ⁺ 479.0
MS (ESI (-) Spectrum): M ^- 557.0

式（Ｉ－５５－ａ）で表される化合物５．００部、ジメチルアミノピリジン０．３１部、トリエチルアミン１．５１部及びジメチルホルムアミド４０部を混合し、２３℃で３０分間攪拌した後、式（Ｉ－１２２４－ｂ）で表される化合物２．３０部及びクロロホルム２０部を添加し、５０℃で５時間攪拌した。得られた混合物を２３℃まで冷却した後、式（Ｉ－５５６－ｃ）で表される塩１．５３部を加え、２３℃で３時間攪拌した。得られた混合物を２３℃まで冷却した後、クロロホルム２０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、分液することにより有機層を得た。得られた混合物に、イオン交換水１０部を添加し、２３℃で３０分間攪拌した後、分液することにより有機層を得た。この水洗操作を３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（Ｉ－１２００）で表される塩０．７４部を得た。
ＭＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ５２５．０
ＭＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ５５７．０ Example 13: Synthesis of Salt Represented by Formula (I-1200)

5.00 parts of the compound represented by the formula (I-55-a), 0.31 parts of dimethylaminopyridine, 1.51 parts of triethylamine and 40 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. 2.30 parts of the compound represented by (I-1224-b) and 20 parts of chloroform were added and stirred at 50° C. for 5 hours. After cooling the obtained mixture to 23° C., 1.53 parts of the salt represented by the formula (I-556-c) was added and stirred at 23° C. for 3 hours. After cooling the obtained mixture to 23° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. After adding 10 parts of ion-exchanged water to the obtained mixture and stirring at 23° C. for 30 minutes, the mixture was separated to obtain an organic layer. This washing operation was repeated three 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 ( 0.74 parts of the salt represented by I-1200) was obtained.
MS (ESI (+) Spectrum): M ⁺ 525.0
MS (ESI (-) Spectrum): M ^- 557.0

The compounds (monomers) used for synthesizing the resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-2-6)" and the like according to their formula numbers.

Synthesis Example 1 [Synthesis of resin A1]
As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-2) are used, and the molar ratio [monomer (a1-2 -6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4-2)] are mixed in a ratio of 53:3:12:32, and , 1.5 times the weight of methyl isobutyl ketone with respect to the total weight of all monomers was mixed into this monomer mixture. 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 p-toluenesulfonic acid solution (2.5% by weight) in an amount of 2.0 times the weight of the total weight of all monomers was added to the polymerization reaction solution, stirred for 12 hours, and then separated. The collected organic layer was poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain Resin A1 having a weight average molecular weight of about 5.3×10 ³ with a yield of 88%. This resin A1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin A2]
As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-13) are used, and the molar ratio [monomer (a1-2 -6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4-13)] are mixed in a ratio of 53:3:12:32, and , 1.5 times the weight of methyl isobutyl ketone with respect to the total weight of all monomers was mixed into this monomer mixture. 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 p-toluenesulfonic acid solution (2.5% by weight) in an amount of 2.0 times the weight of the total weight of all monomers was added to the polymerization reaction solution, stirred for 12 hours, and then separated. The collected organic layer was poured into a large amount of n-heptane to precipitate the resin, filtered and collected to obtain Resin A2 having a weight average molecular weight of about 5.1×10 ³ with a yield of 79%. This resin A2 has the following structural units.

<Preparation of resist composition>
As shown in Table 2, 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.

＜カルボン酸塩（Ｉ）＞
Ｉ－１２：式（Ｉ－１２）で表される塩
Ｉ－１６：式（Ｉ－１６）で表される塩
Ｉ－５４：式（Ｉ－５４）で表される塩
Ｉ－５５：式（Ｉ－５５）で表される塩
Ｉ－５６：式（Ｉ－５６）で表される塩
Ｉ－５４７：式（Ｉ－５４７）で表される塩
Ｉ－５５０：式（Ｉ－５５０）で表される塩
Ｉ－５５６：式（Ｉ－５５６）で表される塩
Ｉ－５７０：式（Ｉ－５７０）で表される塩
Ｉ－５８２：式（Ｉ－５８２）で表される塩
Ｉ－５９９：式（Ｉ－５９９）で表される塩
Ｉ－１２００：式（Ｉ－１２００）で表される塩
Ｉ－１２２４：式（Ｉ－１２２４）で表される塩
＜クエンチャー（Ｃ）＞
ＩＸ－１：
ＩＸ－２：

＜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, A2: Resin A1, Resin A2
<Acid generator (B)>
B1-25: a salt represented by the formula (B1-25); synthesized by the method described in JP-A-2011-126869

<Carboxylate (I)>
I-12: salt represented by formula (I-12) I-16: salt represented by formula (I-16) I-54: salt represented by formula (I-54) I-55: formula Salt represented by (I-55) I-56: Salt represented by formula (I-56) I-547: Salt represented by formula (I-547) I-550: Formula (I-550) Salt represented by I-556: a salt represented by the formula (I-556) I-570: a salt represented by the formula (I-570) I-582: a salt represented by the formula (I-582) I-599: a salt represented by the formula (I-599) I-1200: a salt represented by the formula (I-1200) I-1224: a salt represented by the formula (I-1224) <quencher (C )>
IX-1:
IX-2:

<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. After that, it was pre-baked for 60 seconds on a direct hot plate at the temperature shown in the "PB" column of Table 2 to form a composition layer. The composition layer formed on the wafer is exposed to a line and space pattern (pitch 60 nm/line width 30 nm).
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 2. Next, 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. .
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the effective sensitivity was defined as the exposure dose at which the line width and space width of the line and space pattern with a pitch of 60 nm became 1:1.

比較組成物１、２と比較して、組成物１～１９でのレジストパターンの側壁面の凹凸の振れ幅が小さく、ラインエッジラフネス評価が良好であった。 Line Edge Roughness Evaluation (LER): Line edge roughness was obtained by measuring the unevenness amplitude of the side wall surface of the resist pattern manufactured at effective sensitivity with a scanning electron microscope. Table 3 shows the results.

Compared to Comparative Compositions 1 and 2, Compositions 1 to 19 had a smaller fluctuation width of unevenness on the side wall surface of the resist pattern, and the evaluation of line edge roughness was favorable.

The carboxylate of the present invention and the resist composition containing the carboxylate have good line edge roughness and are useful for fine processing of semiconductors.

Claims (16)

A carboxylic acid generator containing a carboxylate represented by formula (I).

[in the formula (I),
L ¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 60 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
R ¹⁰ represents a group represented by formula (R10-1) or formula (R10-2).
When L ¹ is a single bond, R ¹⁰ is a group represented by formula (R10-1).
Z ⁺ represents an organic cation. ]

[In the formulas (R10-1) and (R10-2),
Ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—, —CO— or —SO ₂ - may be replaced.
R ¹ is each independently a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these and —CH ₂ — contained in the haloalkyl group, the alkyl group and the alicyclic hydrocarbon group may be replaced with —O— or —CO—.
m1 represents an integer of 0 to 6, and when m1 is 2 or more, multiple R ^1s may be the same or different.
m2 represents an integer of 1 to 6;
* represents the binding site with ^L1 . ] L ¹ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms (with the proviso that —CH ₂ — contained in the chain hydrocarbon group is —O— or —CO may be substituted with -), a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (provided that -CH ₂ - contained in the cyclic hydrocarbon group is -O-, - may be substituted with S—, —CO— or —SO ₂ —.) or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms and an optionally substituted carbon number A group consisting of a combination of 3 to 24 cyclic hydrocarbon groups (with the proviso that —CH ₂ — contained in said chain hydrocarbon group may be replaced with —O— or —CO—, and said cyclic hydrocarbon The carboxylic acid generator according to claim 1, wherein -CH ₂ - contained in the group may be replaced with -O-, -S-, -SO ₂ - or -CO-. 3. The carboxylic acid generator according to claim 1, wherein *-L ¹ -R ¹⁰ is a group represented by any one of formulas (L1-0) to (L1-5).

[In the formulas (L1-0) to (L1-5),
Ring W, R ¹ , m1 and m2 have the same meanings as above.
L ² is an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may be substituted, or optionally having a substituent —CH ₂ which represents a group obtained by combining a cyclic hydrocarbon group having 3 to 24 carbon atoms and a chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and contained in the cyclic hydrocarbon group; — may be replaced with —O—, —S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—. may be
L ³ and L ⁴ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
L ⁵ and L ⁶ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
Ring W3 represents an optionally substituted cyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, —S—, —CO— Alternatively, it may be replaced with -SO ₂ -.
Ring W4 and ring W5 each independently represent an optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, -S-, -CO- or -SO ₂ - may be substituted.
X3 represents **-CO ^- O-, **-O-CO-, **-O-CO-O- or **-O-.
X ^a and X ^b each independently represent -O- or -S-.
X ⁰¹ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or — SO ₂ - may be substituted.
R ²¹ and R ²² each independently represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or these --CH ₂ -- contained in said haloalkyl group, said alkyl group and said alicyclic hydrocarbon group representing a combination of groups may be replaced with --O-- or --CO--.
m21 represents an integer of 0 to 6, and when m21 is 2 or more, multiple R ²¹ may be the same or different.
m22 represents an integer of 0 to 6, and when m22 is 2 or more, multiple R ²² may be the same or different.
* represents the bonding site with the carbon atom of the carbonyl group. ^** represents the binding site with L2. ] 3. The group according to claim 3, wherein X ⁰¹ is a group represented by formula (X ¹ -1), formula (X ¹ -3) or formula (X ¹ -5) to formula (X ¹ -7). carboxylic acid generator.

[In formula (X ¹ -1), formula (X ¹ -3) and formula (X ¹ -5) to formula (X ¹ -7),
L ¹¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
* represents the binding site. ] Ring W is a group derived from the ring represented by formula (w1-1), a group derived from the ring represented by formula (w1-2), or derived from the ring represented by formula (w1-3) The carboxylic acid generator according to any one of claims 1 to 4, which is a group, a group derived from a ring represented by formula (w1-6) or a group derived from a ring represented by formula (w1-15). .

[In formula (w1-1), formula (w1-2), formula (w1-3), formula (w1-6) and formula (w1-15),
—CH ₂ — included in the group may be replaced with —O—, —S—, —CO— or —SO ₂ —. The binding site can be any position. ] The carboxylic acid generator according to any one of claims 1 to 5, wherein m2 is 1 or 2. A resist composition comprising the carboxylic acid generator according to any one of claims 1 to 6, an acid generator other than the carboxylic acid generator, and a resin having an acid labile group. A group in which the resin having an acid-labile group comprises 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). 8. The resist composition according to claim 7, comprising at least one selected from.

[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; ] 9. The resist composition according to claim 7, wherein the resin having an acid-labile group contains 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. ] (1) a step of applying the resist composition according to any one of claims 7 to 9 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: A carboxylate represented by formula (I).

[in the formula (I),
L ¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 60 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
R ¹⁰ represents a group represented by formula (R10-1) or formula (R10-2).
When L ¹ is a single bond, R ¹⁰ is a group represented by formula (R10-1).
Z ⁺ represents an organic cation. ]

[In the formulas (R10-1) and (R10-2),
Ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, —S—, —CO— or —SO ₂ - may be replaced.
R ¹ is each independently a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these and —CH ₂ — contained in the haloalkyl group, the alkyl group and the alicyclic hydrocarbon group may be replaced by —O— or —CO—.
m1 represents an integer of 0 to 6, and when m1 is 2 or more, multiple R ^1s may be the same or different.
m2 represents an integer of 1 to 6;
* represents the binding site with ^L1 . ] L ¹ is a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms (with the proviso that —CH ₂ — contained in the chain hydrocarbon group is —O— or —CO may be substituted with -), a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (provided that -CH ₂ - contained in the cyclic hydrocarbon group is -O-, - S—, —CO— or —SO ₂ —.) or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms and an optionally substituted carbon number a group consisting of a combination of 3 to 24 cyclic hydrocarbon groups (with the proviso that --CH ₂ -- contained in said chain hydrocarbon group may be replaced by --O-- or --CO--, said cyclic hydrocarbon The carboxylate according to claim 11, wherein -CH ₂ - contained in the group may be replaced with -O-, -S-, -SO ₂ - or -CO-. 13. The carboxylate according to claim 11, wherein *-L ¹ -R ¹⁰ is a group represented by any one of formulas (L1-0) to (L1-5).

[In the formulas (L1-0) to (L1-5),
Ring W, R ¹ , m1 and m2 have the same meanings as above.
L ² is an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 24 carbon atoms which may be substituted, or optionally having a substituent —CH ₂ which represents a group obtained by combining a cyclic hydrocarbon group having 3 to 24 carbon atoms and a chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and contained in the cyclic hydrocarbon group; — may be replaced with —O—, —S—, —CO— or —SO ₂ —, and —CH ₂ — contained in the chain hydrocarbon group may be replaced with —O— or —CO—. may be
L ³ and L ⁴ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 8 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
L ⁵ and L ⁶ each independently represent a single bond or an optionally substituted chain hydrocarbon group having 1 to 10 carbon atoms, and —CH ₂ — contained in the chain hydrocarbon group is , —O— or —CO—.
Ring W3 represents an optionally substituted cyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, —S—, —CO— Alternatively, it may be replaced with -SO ₂ -.
Ring W4 and ring W5 each independently represent an optionally substituted cyclic hydrocarbon group having 3 to 18 carbon atoms, and —CH ₂ — contained in the cyclic hydrocarbon group is —O—, -S-, -CO- or -SO ₂ - may be substituted.
X3 represents **-CO ^- O-, **-O-CO-, **-O-CO-O- or **-O-.
X ^a and X ^b each independently represent -O- or -S-.
X ⁰¹ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or — SO ₂ - may be substituted.
R ²¹ and R ²² each independently represent a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or these --CH ₂ -- contained in said haloalkyl group, said alkyl group and said alicyclic hydrocarbon group representing a combination of groups may be replaced with --O-- or --CO--.
m21 represents an integer of 0 to 6, and when m21 is 2 or more, multiple R ²¹ may be the same or different.
m22 represents an integer of 0 to 6, and when m22 is 2 or more, multiple R ²² may be the same or different.
* represents the bonding site with the carbon atom of the carbonyl group. ^** represents the binding site with L2. ] 14. The group according to claim 13, wherein X ⁰¹ is a group represented by formula (X ¹ -1), formula (X ¹ -3) or formula (X ¹ -5) to formula (X ¹ -7). carboxylate of.

[In formula (X ¹ -1), formula (X ¹ -3) and formula (X ¹ -5) to formula (X ¹ -7),
L ¹¹ represents a single bond or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —SO ₂ may be substituted with - or -CO-.
* represents the binding site. ] Ring W is a group derived from the ring represented by formula (w1-1), a group derived from the ring represented by formula (w1-2), or derived from the ring represented by formula (w1-3) The carboxylate according to any one of claims 11 to 14, which is a group, a group derived from a ring represented by formula (w1-6) or a group derived from a ring represented by formula (w1-15).

[In formula (w1-1), formula (w1-2), formula (w1-3), formula (w1-6) and formula (w1-15),
—CH ₂ — included in the group may be replaced with —O—, —S—, —CO— or —SO ₂ —. The binding site can be any position. ] The carboxylate according to any one of claims 11 to 15, wherein m2 is 1 or 2.