JP2021130808A - Resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

To provide a resin and a resist composition capable of producing a resist pattern with good CD uniformity (CDU).SOLUTION: The resin containing structural units represented by formula (I) and formula (III) and the resist composition are provided. [X1 is a single bond or -CO-O-*; X2 is -CO-O-*, -O-* or the like; and Ar1, Ar2 and Ar11 are each an optionally substituted aromatic hydrocarbon group.]SELECTED DRAWING: None

Description

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

Patent Document 1 describes a resin having the following structural units.

Patent Document 2 describes a resist composition containing a resin having the following structural units.

Japanese Unexamined Patent Publication No. 10-186642 Japanese Unexamined Patent Publication No. 2016-089125

An object of the present invention is to provide a resin that forms a resist pattern having better CD uniformity (CDU) than a resist pattern formed by a resist composition containing the above resin.

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ｘ^１は、単結合又は−ＣＯ−Ｏ−＊（＊は、Ａｒ^１との結合位を表す。）を表す。
Ｘ^２は、−ＣＯ−Ｏ−＊、−Ｏ−＊、−Ｏ−ＣＯ−＊、−Ｏ−ＣＯ−（ＣＨ_２）_ｍｍ−Ｏ−＊又は−Ｏ−（ＣＨ_２）_ｎｎ−ＣＯ−Ｏ−＊（＊は、Ａｒ^２との結合位を表す。）を表す。
ｍｍ及びｎｎは、０又は１を表す。
Ａｒ^１及びＡｒ^２は、それぞれ独立に、置換基を有していてもよい炭素数６〜３６の芳香族炭化水素基を表す。
Ｒ^２は、それぞれ独立に、水素原子又は酸不安定基を表すか、Ｒ^２が２以上存在するとき、２つのＲ^２が一緒になってアセタール環構造を有する基を形成していてもよい。
ｎは、１〜３のいずれかの整数を表す。ｎが２以上のいずれかの整数である場合、複数のＲ^２は互いに同一であっても異なってもよい。］

［式（ＩＩＩ）中、
Ｒ¹¹は、水素原子又はメチル基を表す。
Ｒ¹²、Ｒ¹³及びＲ¹⁴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、Ｒ¹²及びＲ¹³は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の脂環式炭化水素基を形成する。
Ｘ¹¹は、単結合、−ＣＯ−Ｏ−＊又は−ＣＯ−ＮＲ¹⁵−＊を表し、＊はＡｒ¹¹との結合手を表し、Ｒ¹⁵は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｘ¹²は、単結合、＊−Ｏ−Ｌ¹¹−又は＊−ＣＯ−Ｏ−Ｌ¹²−を表し、＊はＡｒ¹¹との結合手を表し、Ｌ¹¹及びＬ¹²は、それぞれ独立に、炭素数１〜４のアルカンジイル基を表す。
Ａｒ¹¹は、置換基を有していてもよい炭素数６〜２０の芳香族炭化水素基を表す。］
［２］Ｘ^１が、単結合である［１］記載の樹脂。
［３］Ｘ^２が、−ＣＯ−Ｏ−＊又は−Ｏ−＊（＊は、Ａｒ^２との結合位を表す。）である［１］又は［２］記載の樹脂。
［４］ｎが、１又は２である［１］〜［３］のいずれかに記載の樹脂。
［５］Ｒ^２における酸不安定基が、式（１ａ）で表される基又は式（２ａ）で表される基である［１］〜［４］のいずれかに記載の樹脂。

［式（１ａ）中、Ｒ^aa1、Ｒ^aa2及びＲ^aa3は、それぞれ独立に、置換基を有していてもよい炭素数１〜８のアルキル基、置換基を有していてもよい炭素数２〜８のアルケニル基、置換基を有していてもよい炭素数３〜２０の脂環式炭化水素基、もしくは置換基を有していてもよい炭素数６〜１８の芳香族炭化水素基を表すか、又はＲ^aa1及びＲ^aa2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の脂環式炭化水素基を形成する。
ｎａａは、０又は１を表す。
＊は結合手を表す。］

［式（２ａ）中、Ｒ^aa1’及びＲ^aa2’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^aa3’は、炭素数１〜２０の炭化水素基を表すか、又はＲ^aa2’及びＲ^aa3’は互いに結合してそれらが結合する−Ｃ−Ｘ^ａ−とともに炭素数３〜２０の複素環基を形成し、該炭化水素基及び該複素環基に含まれる−ＣＨ_２−は、−Ｏ−又は−Ｓ−で置き換わってもよい。
Ｘ^aは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］
［６］Ｒ^２が水素原子であるか、又はｎが２以上であって、２つのＲ^２が一緒になってアセタール環構造を有する基を形成している［１］〜［５］のいずれかに記載の樹脂。
［７］Ｘ¹¹及びＸ¹²が、ともに単結合である［１］〜［６］のいずれかに記載の樹脂。
［８］式（ａ２−Ａ）で表される構造単位をさらに含む［１］〜［７］のいずれかに記載の樹脂。

［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もよい。］
［９］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種をさらに含む［１］〜［８］のいずれかに記載の樹脂。

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表し、ｋ１は１〜７のいずれかの整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組合せた基を表す。
ｍ１は、０〜１４のいずれかの整数を表す。
ｎ１は、０〜１０のいずれかの整数を表す。
ｎ１’は、０〜３のいずれかの整数を表す。］
［１０］［１］〜［９］のいずれかに記載の樹脂と、酸発生剤とを含有するレジスト組成物。
［１１］酸発生剤が、式（Ｂ１）で表される塩を含む［１０］記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ^ｂ１及びＱ^ｂ２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜２４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（Ｏ）_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］
［１２］酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する［１０］又は［１１］記載のレジスト組成物。
［１３］（１）［１０］〜［１２］のいずれかに記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程、を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resin containing a structural unit represented by the formula (I) and a structural unit represented by the formula (III).

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
X ¹ represents a single bond or -CO-O- * (* represents the binding ^{site with Ar 1).}
X ² is -CO-O- *, _{-O- *, -O-CO- *, -O-CO- (CH 2} ) _mm- O- * or -O- (CH ₂ ) _nn- CO-O. -* (* Represents the binding ^{site with Ar 2).}
mm and nn represent 0 or 1.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent.
Each of R ² independently represents a hydrogen atom or an acid unstable group, or ^{when two or more R 2} are present, the two R ² may be combined to form a group having an acetal ring structure. ..
n represents an integer of 1 to 3. When n is any integer of 2 or more, the plurality of R ^2s may be the same or different from each other. ]

[In equation (III),
R ¹¹ represents a hydrogen atom or a methyl group.
R ¹² , R ¹³ and R ¹⁴ independently have 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 20 carbon atoms, and 6 to 18 carbon atoms. R ¹² and R ¹³ bond with each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.
X ¹¹ represents a single bond, -CO-O-* or -CO-NR ¹⁵ - * represents * represents a bond to Ar ^11, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Represents.
X ¹² represents a single bond, * - O-L ¹¹ - or * -CO-O-L ¹² - represents * represents a bond to Ar ^11, L ¹¹ and L ¹² independently represents a carbon Represents an alkanediyl group of numbers 1 to 4.
Ar ¹¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. ]
[2] The resin according to [1], wherein ^{X 1 is a single bond.}
[3] The resin according to [1] or [2] ^{, wherein X 2} is -CO-O- * or -O- * (* ^{represents a binding site with Ar 2).}
[4] The resin according to any one of [1] to [3], wherein n is 1 or 2.
[5] Acid labile groups in ^{R 2} is a group represented by the group or the formula represented by the formula (1a) (2a) [1 ] ~ [4] resin according to any one of.

[In the formula (1a), ^Raa1 , ^Raa2 and ^Raa3 independently have an alkyl group having 1 to 8 carbon atoms which may have a substituent and a carbon number which may have a substituent. An alkenyl group of 2 to 8, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. Or, ^Raa1 and ^Raa2 bond with each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.
naa represents 0 or 1.
* Represents a bond. ]

Wherein (2a), R ^{aa1 'and} R ^aa2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^{aa3 'is} a hydrocarbon group having 1 to 20 carbon atoms represents or R ^{aa2 'and} R ^aa3' is bonded to -C-X a to which they are attached to one another ^- to form together with heterocyclic group having 3 to 20 carbon atoms, the hydrocarbon group and heterocyclic group The included −CH ₂₋ may be replaced by −O− or −S−.
X ^a represents an oxygen atom or a sulfur atom.
* Represents a bond. ]
[6] or R ² is a hydrogen atom, or n is at least 2 and [1] to form a group having an acetal ring structure two R ² are taken together either to [5] The resin described in Crab.
[7] The resin according to any one of [1] to [6], wherein both ^{X 11} and X ^{12 are single bonds.}
[8] The resin according to any one of [1] to [7], which further contains a structural unit represented by the formula (a2-A).

[In formula (a2-A),
R ^a50 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a51 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 of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or ^* −X ^a51 − (A ^a52 −X ^a52 ) _nb −, and * represents a binding site with a carbon atom to which ^{−R a50 is bonded.}
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 independently represent -O-, -CO-O- or -O-CO-, respectively.
nb represents 0 or 1.
mb represents any integer from 0 to 4. When mb is any integer of 2 or more, the plurality of Ra ^51s may be the same or different from each other. ]
[9] Any of [1] to [8] further comprising at least one selected from the group consisting of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2). The resin described in.

[In the formula (a1-1) and the formula (a1-2),
^La1 and ^La2 independently represent -O- or * -O- (CH ₂ ) _k1- CO-O-, k1 represents an integer of 1 to 7, and * represents -CO-. Represents a bond with.
R ^a4 and R ^a5 independently represent a hydrogen atom or a methyl group, respectively.
R ^a6 and R ^a7 independently have an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group or a group combining these groups.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]
[10] A resist composition containing the resin according to any one of [1] to [9] and an acid generator.
[11] The resist composition according to [10], wherein the acid generator contains a salt represented by the formula (B1).

[In equation (B1),
Q ^b1 and Q ^b2 independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH _2- may be replaced with −O−, −S (O) _{2− or −CO−.}
Z ⁺ represents an organic cation. ]
[12] The resist composition according to [10] or [11], which further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[13] (1) A step of applying the resist composition according to any one of [10] to [12] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
A method for producing a resist pattern, which comprises (4) a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

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

In the present specification, the "(meth) acrylic monomer" is _{derived from a monomer having a structure of "CH 2} = CH-CO-" and a monomer having a structure of "CH ₂ = C (CH ₃ ) -CO-". Means at least one species selected from the group. Similarly, "(meth) acrylate" and "(meth) acrylic acid" are "at least one selected from the group consisting of acrylate and methacrylate" and "at least one selected from the group consisting of acrylic acid and methacrylic acid, respectively". Means. When a structural unit having "CH ₂ = C (CH ₃ ) -CO-" or "CH ₂ = CH-CO-" is exemplified, a structural unit having both groups is similarly exemplified. It shall be. In addition, any of the groups described in the present specification that can have both a linear structure and a branched structure may be used. The “combined group” means a group obtained by binding two or more of the exemplified groups, and the valence of these groups may be appropriately changed depending on the bonding form. "Derived" or "derived" means that the polymerizable C = C bond contained in the molecule becomes a -CC- group by polymerization. If stereoisomers are present, they include all stereoisomers.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

〔resin〕
The resin of the present invention has a structural unit represented by the formula (I) (hereinafter, may be referred to as a structural unit (I)) and a structural unit represented by the formula (III) (hereinafter, the structural unit (III)). It is a resin (hereinafter, may be referred to as "resin (A)") containing (may be referred to as "resin (A)").

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ｘ^１は、単結合又は−ＣＯ−Ｏ−＊（＊は、Ａｒ^１との結合位を表す。）を表す。
Ｘ^２は、−ＣＯ−Ｏ−＊、−Ｏ−＊、−Ｏ−ＣＯ−＊、−Ｏ−ＣＯ−（ＣＨ_２）_ｍｍ−Ｏ−＊又は−Ｏ−（ＣＨ_２）_ｎｎ−ＣＯ−Ｏ−＊（＊は、Ａｒ^２との結合位を表す。）を表す。
ｍｍ及びｎｎは、０又は１を表す。
Ａｒ^１及びＡｒ^２は、それぞれ独立に、置換基を有していてもよい炭素数６〜３６の芳香族炭化水素基を表す。
Ｒ^２は、それぞれ独立に、水素原子又は酸不安定基を表すか、Ｒ^２が２以上存在するとき、２つのＲ^２が一緒になってアセタール環構造を有する基を形成していてもよい。
ｎは、１〜３のいずれかの整数を表す。ｎが２以上のいずれかの整数である場合、複数のＲ^２は互いに同一であっても異なってもよい。］ <Structural unit (I)>
The structural unit (I) is represented by the following formula.

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
X ¹ represents a single bond or -CO-O- * (* represents the binding ^{site with Ar 1).}
X ² is -CO-O- *, _{-O- *, -O-CO- *, -O-CO- (CH 2} ) _mm- O- * or -O- (CH ₂ ) _nn- CO-O. -* (* Represents the binding ^{site with Ar 2).}
mm and nn represent 0 or 1.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent.
Each of R ² independently represents a hydrogen atom or an acid unstable group, or ^{when two or more R 2} are present, the two R ² may be combined to form a group having an acetal ring structure. ..
n represents an integer of 1 to 3. When n is any integer of 2 or more, the plurality of R ^2s may be the same or different from each other. ]

Examples of the divalent aromatic hydrocarbon group of Ar ¹ and Ar ² include a benzenediyl group, a naphthalenediyl group, an anthracenediyl group and the like.
Examples of the trivalent or tetravalent aromatic hydrocarbon group of Ar ² include a benzenetriyl group, a benzenetetrayl group, a naphthalenetriyl group, a naphthalenetetrayl group, an anthracene triyl group, an anthracene tetrayl group and the like. ..
The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, even more preferably 6 to 10, and even more preferably. It is 6.
As the substituent of the aromatic hydrocarbon group, a hydroxy group, a halogen atom, a cyano group, and an alkyl group having 1 to 16 carbon atoms (-CH ₂ − contained in the alkyl group is replaced with −O− or −CO−. (May be), an alkyl fluorinated group having 1 to 12 carbon atoms (-CH ₂ − contained in the alkyl fluorinated group may be replaced with -O- or -CO-), and the number of carbon atoms. Examples thereof include an alicyclic hydrocarbon group of 3 to 12, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group combining these groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group having 1 to 16 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. .. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4.
_{When -CH 2} − contained in an alkyl group is replaced with -O- or -CO-, the number of carbon atoms before the replacement is taken as the total number of carbon atoms of the alkyl group. _{The groups in which -CH 2} − contained in the alkyl group is replaced with -O- or -CO- are hydroxy groups (groups in which -CH ₂ − contained in the methyl group is replaced with -O-) and carboxy groups. A group (a group in which −CH ₂ −CH ₂ − contained in an ethyl group is replaced with −O—CO−) and an alkoxy group (−CH ₂ − at an arbitrary position contained in an alkyl group is −O−. (Group replaced by), alkoxycarbonyl group (group in which −CH ₂ −CH ₂ − at any position contained in the alkyl group is replaced by −O—CO−), alkylcarbonyl group (included in the alkyl group) -CH ₂ − at an arbitrary position is replaced with −CO −, and an alkylcarbonyloxy group (a group in which −CH ₂ −CH ₂ − at an arbitrary position contained in an alkyl group is replaced with −CO−O−) is replaced with −CO−O−. Group) and the like.
Examples of the alkoxy group include an alkoxy group having 1 to 15 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group and a nonyloxy group. Examples thereof include a group, a decyloxy group, an undecyloxy group, a dodecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 11, still more preferably 1 to 6, and even more preferably 1 to 4.
The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group.

Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 15 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include an alkylcarbonyl group having 2 to 16 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a butyryl group. Examples of the alkylcarbonyloxy group include an alkylcarbonyloxy group having 2 to 15 carbon atoms, and examples thereof include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkoxycarbonyl group has preferably 2 to 13 carbon atoms, more preferably 2 to 11 carbon atoms, still more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkylcarbonyl group preferably has 2 to 13 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkylcarbonyloxy group preferably has 2 to 13 carbon atoms, more preferably 2 to 11 carbon atoms, still more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
Examples of the alkyl fluoride group having 1 to 12 carbon atoms include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group and a 1,1,2,2-tetrafluoroethyl group. Perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluoropentyl group, 2, Examples thereof include an alkyl fluoride group such as a 2,3,3,4,5,5,5-nonafluoropentyl group and a perfluorohexyl group. The alkyl fluoride group preferably has 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.
_{When −CH 2} − contained in the alkyl fluoride group is replaced with −O − or −CO −, the number of carbon atoms before the replacement is taken as the total number of carbon atoms of the alkyl fluoride group. As a group in which −CH ₂ − contained in the alkyl fluoride group is replaced with −O − or −CO −, an alkoxyfluorinated group (−CH ₂ − at an arbitrary position contained in the alkyl fluoride group is used as a group. -O-replaced group), fluorinated alkoxycarbonyl group (a group in which -CH ₂ -CH _{2- at} any position contained in the fluorinated alkyl group is replaced with -O-CO-), alkyl fluorinated A carbonyl group (a group in which −CH ₂ − at an arbitrary position contained in an alkyl fluoride group is replaced with −CO −), an alkyl fluorinated carbonyloxy group (a group at an arbitrary position contained in an alkyl fluoride group). CH ₂ −CH ₂₋ is replaced with −CO−O−) and the like.
Examples of the fluorinated alkoxy group, the fluorinated alkoxycarbonyl group, the fluorinated alkylcarbonyl group and the fluorinated alkylcarbonyloxy group include a fluorinated alkoxy group having 1 to 11 carbon atoms, a fluorinated alkoxycarbonyl group having 2 to 11 carbon atoms, and carbon. Examples thereof include an alkylcarbonyl fluorinated group having a number of 2 to 12 and an alkylcarbonyloxy group having a number of 2 to 11 carbon atoms, and one or more hydrogen atoms of the groups exemplified above may be replaced with a fluorine atom.
The alicyclic hydrocarbon group having 3 to 12 carbon atoms may be either a monocyclic or polycyclic group, and examples thereof include the groups shown below. ** is a bond with an aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
The combined group in the substituent of the aromatic hydrocarbon group includes a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Examples thereof include a group in which the above is combined, a group in which an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined, and the like.
Examples of the group in which the hydroxy group and the alkyl group having 1 to 12 carbon atoms are combined include a hydroxyalkyl group having 1 to 12 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the group in which an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms are combined include an alkoxyalkoxy group having 2 to 24 carbon atoms such as an ethoxyethoxy group.
Examples of the group in which an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined include an aralkyl group having 7 to 22 carbon atoms such as a benzyl group.

The substituents are a halogen atom, an alkyl fluoride group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a hydroxy group, an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, and carbon. It is preferably an alkylcarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyloxy group having 2 to 11 carbon atoms, a halogen atom, an alkylfluorinated group having 1 to 6 carbon atoms, a hydroxy group, and an alkoxy having 1 to 11 carbon atoms. More preferably, it is a group, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyloxy group having 2 to 11 carbon atoms, and a halogen atom, a hydroxy group, or 1 to 1 carbon atoms. It is more preferably an alkyl fluoride group of 6 or an alkoxy group having 1 to 11 carbon atoms.

［式（１ａ）中、Ｒ^aa1、Ｒ^aa2及びＲ^aa3は、それぞれ独立に、置換基を有していてもよい炭素数１〜８のアルキル基、置換基を有していてもよい炭素数２〜８のアルケニル基、置換基を有していてもよい炭素数３〜２０の脂環式炭化水素基、もしくは置換基を有していてもよい炭素数６〜１８の芳香族炭化水素基を表すか、又はＲ^aa1及びＲ^aa2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の脂環式炭化水素基を形成する。
ｎａａは、０又は１を表す。
＊は結合手を表す。］

［式（２ａ）中、Ｒ^aa1’及びＲ^aa2’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^aa3’は、炭素数１〜２０の炭化水素基を表すか、又はＲ^aa2’及びＲ^aa3’は互いに結合してそれらが結合する−Ｃ−Ｘ^ａ−とともに炭素数３〜２０の複素環基を形成し、該炭化水素基及び該複素環基に含まれる−ＣＨ_２−は、−Ｏ−又は−Ｓ−で置き換わってもよい。
Ｘ^aは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］ The acid labile groups of R ^2, upon contact with an acid (e.g. p- toluenesulfonic acid) groups represented by R ² eliminated, meaning a group which forms a hydroxyl group.
When R ² in structural units used in the preparation of the resin (A) (I) is an acid labile group, the resin (A), by contact with acid, the R ² and desorption (R ² to a hydrogen atom (Conversion) may be carried out, and the desorption rate thereof is preferably 40% to 100%, more preferably 60% to 100%, still more preferably 100%.
Examples of the acid unstable group include a group represented by the formula (1a) (hereinafter, sometimes referred to as “acid unstable group (1a)”) and a group represented by the formula (2a) (hereinafter, depending on the case). "Acid unstable group (2a)") and the like.

[In the formula (1a), ^Raa1 , ^Raa2 and ^Raa3 independently have an alkyl group having 1 to 8 carbon atoms which may have a substituent and a carbon number which may have a substituent. An alkenyl group of 2 to 8, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. Or, ^Raa1 and ^Raa2 bond with each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.
naa represents 0 or 1.
* Represents a bond. ]

Wherein (2a), R ^{aa1 'and} R ^aa2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^{aa3 'is} a hydrocarbon group having 1 to 20 carbon atoms represents or R ^{aa2 'and} R ^aa3' is bonded to -C-X a to which they are attached to one another ^- to form together with heterocyclic group having 3 to 20 carbon atoms, the hydrocarbon group and heterocyclic group The included −CH ₂₋ may be replaced by −O− or −S−.
X ^a represents an oxygen atom or a sulfur atom.
* Represents a bond. ]

Ｒ^aa1、Ｒ^aa2及びＲ^aa3の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。Ｒ^aa1、Ｒ^aa2及びＲ^aa3の芳香族炭化水素基の炭素数は、好ましくは６〜１４であり、より好ましくは６〜１０である。 ^{Examples of the alkyl group of Raa1} , ^Raa2 and Raa3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group. Be done. ^{The alkyl groups of Raa1} , ^Raa2 and ^Raa3 have preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
The alkenyl group of R ^aa1, R ^aa2 and R ^aa3, ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert- butenyl, pentenyl, hexenyl, heptenyl group, octynyl group, Isookuchiniru group, Nonenyl group is mentioned.
^{The alicyclic hydrocarbon groups of Raa1} , ^Raa2 and ^Raa3 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a bond). R ^aa1, the number of carbon atoms in the alicyclic hydrocarbon group R ^aa2 and R ^aa3 is preferably 3 to 16, more preferably from 3 to 12.

^{Examples of the aromatic hydrocarbon groups of Raa1} , ^Raa2 and ^Raa3 include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group. ^{The aromatic hydrocarbon groups of Raa1} , ^Raa2 and ^Raa3 have preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.

Examples of the substituent of the alkyl group having 1 to 8 carbon atoms which may have a substituent include an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 to 18 carbon atoms. Aromatic hydrocarbon groups of. Examples of the substituent of the alkenyl group having 2 to 8 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 to 18 carbon atoms. Aromatic hydrocarbon groups of. Examples of the substituent of the alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 6 to 18 carbon atoms. Aromatic hydrocarbon groups of. Examples of the substituent of the aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 3 to 20 carbon atoms. An alicyclic hydrocarbon group can be mentioned. More specifically, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group (p-) having an alicyclic hydrocarbon group, a group, a trill group, a xsilyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned.
naa is preferably 1.

^{Examples of -C (R aa1} ) (R ^aa2 ) (R ^{aa3 ) when Raa1} and ^Raa2 are bonded to each other to form an alicyclic hydrocarbon group include the following groups. The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms, and more preferably 3 to 12 carbon atoms. * Represents a bond with -O-.

The group represented by the formula (1a) is a 1,1-dialkylalkoxycarbonyl group (a group in which ^Raa1 , ^Raa2 and ^Raa3 are alkyl groups in the formula (1a), preferably a tert-butoxycarbonyl group). , 2-alkyladamantan-2-yloxycarbonyl group (in formula (1a), ^Raa1 , ^Raa2 and the carbon atom to which they are bonded form an adamantyl group and ^Raa3 is an alkyl group) and 1- (adamantan-1-yl) -1-alkyl alkoxycarbonyl group (wherein (1a), R ^aa1 and R ^aa2 is an alkyl group, R ^aa3 is group an adamantyl group).

Ｒ^aa1'及びＲ^aa2'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。 ^{Examples of the hydrocarbon groups of Raa1'} , ^Raa2' and ^Raa3' 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 include the same groups as those mentioned in ^Raa1 , ^Raa2 and ^Raa3.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl group) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group (p-) having an alicyclic hydrocarbon group, a group, a trill group, a xsilyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned.
If R ^{aa2 'and} R ^aa3' together with the carbon atoms and X ^a binding to which they are attached together form a heterocyclic ^{group, -C (R aa1 ') (} R aa2') -X a - (R aa3 ' ) Examples include the following groups. * Represents a bond.

Of R ^aa1'and R ^aa2' , at least one is preferably a hydrogen atom.

Specific examples of the acid unstable group (1a) include the following groups. * Represents a bond.

構造単位（Ｉ）において、複数のＲ^２は同一であっても異なっていてもよい。 Specific examples of the acid unstable group (2a) include the following groups. * Represents a bond.

In the structural unit (I), the plurality of R ^2s may be the same or different.

［式（３ａ）中、Ｒ^ab1及びＲ^ab2は、それぞれ独立に、水素原子、炭素数１〜８のアルキル基、もしくは炭素数３〜２０の脂環式炭化水素基を表すか、又はＲ^ab1及びＲ^ab2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の脂環式炭化水素基を形成し、該アルキル基及び該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わってもよい。
＊は酸素原子との結合手を表す。］
アルキル基及び脂環式炭化水素基としては、Ｒ^aa1、Ｒ^aa2及びＲ^aa3で挙げた基と同様の基が挙げられる。
基（３ａ）としては、以下で表される基等が挙げられる。＊は酸素原子との結合手を表す。

また、２つのＲ^２が一緒になってアセタール環構造を有する基を形成している場合、＊−Ａｒ^２−（Ｏ−Ｒ^２）_２としては、以下で表される基（但し、ベンゼン環は、置換基を有していてもよい。）等が挙げられる。＊はＸ^２との結合手を表す。

When two R ² form a group having an acetal ring structure together * - The (R ²⁾ _2, a group represented by the formula (3a) (hereinafter also "group (3a ) ”.) Etc. can be mentioned.

[In formula (3a), R ^ab1 and R ^ab2 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^ab1. And R ^ab2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and the alkyl group and −CH ₂ − contained in the alicyclic hydrocarbon group are , -O- or -CO- may be replaced.
* Represents a bond with an oxygen atom. ]
Examples of the alkyl group and the alicyclic hydrocarbon group include groups similar to those mentioned in ^Raa1 , ^Raa2 and ^Raa3.
Examples of the group (3a) include groups represented by the following. * Represents a bond with an oxygen atom.

Also, when two R ² form a group having an acetal ring structure together, * - Ar 2 - The ^{(O-R 2)} _2, group (represented below, the benzene ring May have a substituent.) And the like. * Represents a bond with ^{X 2.}

The acid labile groups in R ^2, is preferably an acid labile group (2a).
R ² is a group represented by hydrogen atom or formula (2a), it is preferred that two R ² form a group having an acetal ring structure together, or a hydrogen atom, it is more preferred that two R ² form a group having an acetal ring structure together.
Ar ¹ is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent, and is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. It is more preferable that it is an aromatic hydrocarbon group having 6 to 18 carbon atoms, further preferably it is an aromatic hydrocarbon group having 6 to 10 carbon atoms, and it is a benzenediyl group. Is even more preferable.
Ar ² is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent, and is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. It is more preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, further preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, a benzenediyl group and a benzenetri. It is even more preferably an yl group or a benzenetetrayl group, and even more preferably a benzenediyl group or a benzenetriyl group.
n is preferably 1 or 2, more preferably 2.
The bonding position of −O-R ² in Ar ² may be any of the о position, the m position, and the p position with respect to the bonding position of ^{X 2.}
X ² is preferably -CO-O- *, -O- * or -O-CO- *, and more preferably -CO-O- * or -O- *.
Resin (A), when R ² contains a structural unit (I) is a hydrogen atom, the amount of the structural unit wherein R ² is a hydrogen atom (I), relative to the total amount of the structural units (I), preferably Is 40 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 100 mol%.

Examples of the structural unit (I) include the structural units described below. The structural unit (I) includes a structural unit (I-1) to a structural unit (I-14), a structural unit (I-17) to a structural unit (I-20), and a structural unit (I-25) to a structural unit. (I-28), structural unit (I-33) to structural unit (I-58), structural unit (I-67) to structural unit (I-92) are preferable, and structural unit (I-1) to structural unit. (I-8), structural unit (I-13), structural unit (I-14), structural unit (I-17) to structural unit (I-20), structural unit (I-25) to structural unit (I) -28), structural unit (I-33) to structural unit (I-58), structural unit (I-67), structural unit (I-68), structural unit (I-71), structural unit (I-72) ), The structural unit (I-81), and the structural unit (I-82) are more preferable.

Formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11), formula (I-13), formula. (I-15), formula (I-17), formula (I-19), formula (I-21), formula (I-23), formula (I-25), formula (I-27), formula ( I-29), formula (I-31), formula (I-33), formula (I-35), formula (I-37), formula (I-39), formula (I-41), formula (I) -43), formula (I-45), formula (I-47), formula (I-49), formula (I-51), formula (I-53), formula (I-55) to formula (I-). 70), formula (I-71), formula (I-73), formula (I-75), formula (I-77), formula (I-79), formula (I-81), formula (I-83). ), Formula (I-85), Formula (I-87), Formula (I-89), Formula (I-91), respectively, ^{the hydrogen atom corresponding to R 1} is replaced with a methyl group. Structural units, as well as formulas (I-2), formulas (I-4), formulas (I-6), formulas (I-8), formulas (I-10), formulas (I-12), formulas ( I-14), formula (I-16), formula (I-18), formula (I-20), formula (I-22), formula (I-24), formula (I-26), formula (I) -28), formula (I-30), formula (I-32), formula (I-34), formula (I-36), formula (I-38), formula (I-40), formula (I-) 42), formula (I-44), formula (I-46), formula (I-48), formula (I-50), formula (I-52), formula (I-54), formula (I-72). ), Equation (I-74), Equation (I-76), Equation (I-78), Equation (I-80), Equation (I-82), Equation (I-84), Equation (I-86). , In the structural units represented by the formulas (I-88), (I-90), and (I-92), the structural units in ^{which the methyl group corresponding to R 1} is replaced with a hydrogen atom are also structural units ( I).

The content of the structural unit (I) in the resin (A) is preferably 3 to 80 mol%, more preferably 5 to 60 mol%, still more preferably 5 to 55, based on the total structural units. It is mol%, more preferably 5 to 50 mol%.
In the resin (A), the structural unit (I) may contain only one type, or may contain two or more types.

［式（ＩＩＩ）中、
Ｒ¹¹は、水素原子又はメチル基を表す。
Ｒ¹²、Ｒ¹³及びＲ¹⁴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、Ｒ¹²及びＲ¹³は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の脂環式炭化水素基を形成する。
Ｘ¹¹は、単結合、−ＣＯ−Ｏ−＊又は−ＣＯ−ＮＲ¹⁵−＊を表し、＊はＡｒ¹¹との結合手を表し、Ｒ¹⁵は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｘ¹²は、単結合、＊−Ｏ−Ｌ¹¹−又は＊−ＣＯ−Ｏ−Ｌ¹²−を表し、＊はＡｒ¹¹との結合手を表し、Ｌ¹¹及びＬ¹²は、それぞれ独立に、炭素数１〜４のアルカンジイル基を表す。
Ａｒ¹¹は、置換基を有していてもよい炭素数６〜２０の芳香族炭化水素基を表す。］ <Structural unit (III)>
The structural unit (III) is represented by the following formula.

[In equation (III),
R ¹¹ represents a hydrogen atom or a methyl group.
R ¹² , R ¹³ and R ¹⁴ independently have 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 20 carbon atoms, and 6 to 18 carbon atoms. R ¹² and R ¹³ bond with each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.
X ¹¹ represents a single bond, -CO-O-* or -CO-NR ¹⁵ - * represents * represents a bond to Ar ^11, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Represents.
X ¹² represents a single bond, * - O-L ¹¹ - or * -CO-O-L ¹² - represents * represents a bond to Ar ^11, L ¹¹ and L ¹² independently represents a carbon Represents an alkanediyl group of numbers 1 to 4.
Ar ¹¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. ]

Ｒ¹²、Ｒ¹³及びＲ¹⁴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。Ｒ¹²、Ｒ¹³及びＲ¹⁴の芳香族炭化水素基の炭素数は、好ましくは６〜１４であり、より好ましくは６〜１０である。
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。
Ｒ¹²及びＲ¹³が互いに結合してそれらが結合する炭素原子とともに脂環式炭化水素基を形成する場合、−Ｃ（Ｒ¹²）（Ｒ¹³）（Ｒ¹⁴）としては、下記の基が挙げられる。脂環式炭化水素基の炭素数は、好ましくは３〜１６であり、より好ましくは３〜１２である。＊は−Ｏ−との結合部位を表す。

Examples ^{of the alkyl group in R 12} , R ¹³ and R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, a heptyl group, an octyl group and the like. The alkyl groups of R ¹² , R ¹³ and R ¹⁴ have preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
The alkenyl groups in R ¹² , R ¹³ and R ¹⁴ include ethenyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, tert-butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octynyl groups and isooctynyl groups. Nonenyl group is mentioned.
The alicyclic hydrocarbon group in R ¹² , R ¹³ and R ¹⁴ may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a binding site). The alicyclic hydrocarbon groups of R ¹² , R ¹³ and R ¹⁴ preferably have 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms.

Examples of the aromatic hydrocarbon group in R ¹² , R ¹³ and R ¹⁴ include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group. The aromatic hydrocarbon groups of R ¹² , R ¹³ and R ¹⁴ have preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl group) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group (p-) having an alicyclic hydrocarbon group, a group, a trill group, a xsilyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned.
When R ¹² and R ¹³ are bonded to each other to form an alicyclic hydrocarbon group together with the carbon atom to which they are bonded, the following groups are mentioned as ^{-C (R 12} ) (R ¹³ ) (R ^14). Be done. The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms, and more preferably 3 to 12 carbon atoms. * Represents the binding site with -O-.

The ^{alkanediyl groups in L 11} and L ¹² include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a butane-1,3 group. -Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like can be mentioned.
L ¹¹ and L ¹² are independently, preferably a methylene group or an ethylene group, and more preferably a methylene group.
X ¹¹ is preferably single-bonded or -CO-O- *, more preferably single-bonded.
X ¹² is preferably a single bond or * -O-L ¹¹ -, more preferably an a single bond.

Examples of the aromatic hydrocarbon group in Ar ¹¹ include a phenylene group, a 1-naphthylene group, a 2-naphthylene group, a 1-anthrylene group, a 9-anthrylene group, a 1-phenanthrylene group and a 2-phenanthrylene group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.
Examples of the substituent that Ar ¹¹ may have include the same groups as those exemplified as the substituents that ^{Ar 1} and Ar ^{2 may have.}
Ar ¹¹ is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, more preferably a phenylene group or a naphthylene group, and further preferably a phenylene group. ..

Examples of the structural unit (III) include structural units represented by the formulas (III-1) to (III-36), respectively, and are represented by the formulas (III-1) to (III-9), respectively. The structural unit is preferably represented by the formula (III-1), the formula (III-2), the formula (III-4), the formula (III-5), the formula (III-7) or the formula (III-8), respectively. The structural unit to be used is more preferable, and the structural unit represented by the formula (III-1), the formula (III-2), the formula (III-5) or the formula (III-8) is further preferable.

In the structural units represented by the formulas (III-1) to (III-9), the formulas (III-16) to the formula (III-21), and the formulas (III-28) to the formula (III-30), respectively. , ^{A structural unit in which a hydrogen atom corresponding to R 11} is replaced with a methyl group, and formulas (III-10) to (III-15), formulas (III-22) to (III-27), and formula (III-27). In the structural units represented by the formulas (III-31) to (III-36), the structural unit in ^{which the methyl group corresponding to R 11} is replaced with a hydrogen atom is also mentioned as the structural unit (III).

The content of the structural unit (III) in the resin (A) is preferably 3 to 80 mol%, preferably 5 to 75 mol%, based on the total structural units of the resin (A) in terms of the shape of the resist pattern. More preferably, 10 to 70 mol% is further preferable.
In the resin (A), the structural unit (III) may contain only one type or two or more types.

The resin (A) of the present invention may be a polymer containing one or more structural units other than the structural unit (I) and the structural unit (III). As the structural unit other than the structural unit (I) and the structural unit (III), the structural unit having an acid instability group other than the structural unit (I) and the structural unit (III) (hereinafter referred to as “structural unit (a1)”). ), A structural unit other than the structural unit having an acid instability group and having a halogen atom (hereinafter, may be referred to as “structural unit (a4)”), and an acid instability other than the structural unit (I). Examples include a structural unit having no group (hereinafter sometimes referred to as “structural unit (s)”), a structural unit having a non-eliminating hydrocarbon group (hereinafter sometimes referred to as “structural unit (a5)”), and the like. .. Here, the acid-labile group means a group having a leaving group, and the leaving group is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group).

［式（１）中、Ｒ^ａ１、Ｒ^ａ２及びＲ^ａ３は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数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 unstable group (hereinafter, may be referred to as “monomer (a1)”).
The acid-unstable group contained in the resin (A) is a group represented by the formula (1) (hereinafter, also referred to as a group (1)) and / or a group represented by the formula (2) (hereinafter, a group (2). ) Is also preferable.

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

[In the formula (2), R ^a1'and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Represented, R ^a2'and R ^a3' are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and are contained in the hydrocarbon group and the heterocycle-CH ₂ -May be replaced by -O- or -S-.
X represents an oxygen atom or a sulfur atom.
na'represents 0 or 1.
* Represents the 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 the alkyl group in R ^a1 , Ra ² and Ra 3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
^Examples of the alkenyl group in R ^a1 , Ra ² and Ra 3 include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octynyl group and an isooctynyl group. Nonenyl group is mentioned.
The alicyclic hydrocarbon group in R ^a1 , Ra ² and Ra ³ may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a binding site). The alicyclic hydrocarbon groups of R ^a1 , Ra ² and Ra ³ preferably have 3 to 16 carbon atoms.

Examples of the aromatic hydrocarbon group in R ^a1 , Ra ² and Ra ³ include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group.
As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl group) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group (p-) having an alicyclic hydrocarbon group, a group, a trill group, a xsilyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned.
Preferably, ma is 0 and na is 1.
^{Examples of -C (R a1} ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R a ² are bonded to each other to form a non-aromatic hydrocarbon ring include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * Represents the binding site with -O-.

Ｒ^ａ１’及びＲ^ａ２’のうち、少なくとも１つは水素原子であることが好ましい。
ｎａ’は、好ましくは０である。 Examples of the hydrocarbon group in R ^a1' , R ^a2' and R ^a3' include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group formed by combining these.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same groups as those mentioned in ^{Ra 1} , Ra ² and Ra ^3.
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl group) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group (p-) having an alicyclic hydrocarbon group, a group, a trill group, a xsilyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned.
When R ^a2'and R ^a3' are bonded to each other to form a heterocycle together with the carbon atom and X to which they are bonded, -C (R ^a1' ) (R ^a2' )-X-R ^a3'is as follows. Ring of. * Represents the binding site.

Of R ^{a1 'and R a2',} it is preferable that at least one is a hydrogen atom.
na'is preferably 0.

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

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

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

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

［式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a01、Ｌ^ａ１及びＬ^ａ２は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表し、ｋ１は１〜７のいずれかの整数を表し、＊は−ＣＯ−との結合部位を表す。
Ｒ^a01、Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組み合わせた基を表す。
Ｒ^ａ６及びＲ^ａ７は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組合せることにより形成される基を表す。
ｍ１は０〜１４のいずれかの整数を表す。
ｎ１は０〜１０のいずれかの整数を表す。
ｎ１’は０〜３のいずれかの整数を表す。］ As the structural unit derived from the (meth) acrylic monomer having the group (1), the structural unit represented by the formula (a1-0) (hereinafter, may be referred to as the structural unit (a1-0)), the formula ( The structural unit represented by a1-1) (hereinafter, may be referred to as a structural unit (a1-1)) or the structural unit represented by the formula (a1-2) (hereinafter, referred to as a structural unit (a1-2)). In some cases.) Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more.

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

R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
L ^{a01, L a1} and ^{L a2} are preferably oxygen atom or _{* -O- (CH 2) k01 -CO} -O- and is (however, k01 is preferably either 1 to 4 integer, more preferably Is 1.), More preferably an oxygen atom.
The alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^{a7 and the group in which these are combined include R a1 of} the group (1). Groups similar to those mentioned in R ^a2 and R ^{a3 can be mentioned.}
The alkyl group in R ^a02 , R ^a03 , and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
The alkyl group in R ^a6 and R ^a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, and further preferably an ethyl group or an isopropyl group. Or it is a t-butyl group.
The alkenyl group in R ^a6 and R ^a7 is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an ethenyl group, a propenyl group, an isopropenyl group or a butenyl group.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 have preferably 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms.
The ^{number of carbon atoms of the aromatic hydrocarbon groups of R a02} , R ^a03 , R ^a04 , R ^a6 and R ^a7 is preferably 6 to 12, and more preferably 6 to 10.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination with these alkyl groups and the alicyclic hydrocarbon group.
The group in which the alkyl group and the aromatic hydrocarbon group are combined preferably has a total carbon number of 18 or less in which the alkyl group and the aromatic hydrocarbon group are combined.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group.
^Ra04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
R ^a6 and R ^a7 are 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, and more preferably a methyl group. , Ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group or naphthyl group, more preferably ethyl group, isopropyl group, t-butyl group, ethenyl group or phenyl group.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1'is preferably 0 or 1.

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

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

The structural unit (a1-2) corresponds to the structural unit represented by any of the formulas (a1-2-1) to (a1-2-12) and R ^{a5 in the structural unit (a1-2).} Structural units in which a methyl group is replaced with a hydrogen atom include formulas (a1-2-2), formulas (a1-2-5), formulas (a1-2-6) and formulas (a1-2-10) to. The structural unit represented by any of the formula (a1-2-12) is preferable.

When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 80 mol%, preferably 5 to 75 mol%, based on all the structural units of the resin (A). Yes, more preferably 10 to 70 mol%.
When the resin (A) contains a structural unit (a1-1) and / or a structural unit (a1-2), the total content of these is usually 10 to 90 mol with respect to the total structural unit of the resin (A). %, Preferably 15-85 mol%, more preferably 20-80 mol%, even more preferably 20-75 mol%, even more preferably 20-70 mol%.

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

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

Examples of the halogen atom in R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
^{Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in Ra32} include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, and a 2,2,2-trifluoroethyl group. 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2 3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluoro Hexyl group is mentioned.
R ^a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group in Ra33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group.
^Examples of the alkoxy group in Ra33 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.
^Examples of the alkoxyalkyl group in Ra33 include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.
^Examples of the alkoxyalkoxy group in Ra33 include methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, and tert-butoxymethoxy group. Can be mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group.
^{Examples of the alkylcarbonyl group in Ra33} include an acetyl group, a propionyl group, a butyryl group and the like. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.
The alkylcarbonyloxy group in R ^a33, acetyloxy group, and a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.
R ^a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, and is preferably a fluorine atom, an iodine atom, a hydroxy group or a methyl. A group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group is more preferable, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group is further preferable.

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

The ^{alkanediyl group in A a32} includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Examples include groups and 2-methylbutane-1,4-diyl groups.
A ^a32 is preferably a methylene group or an ethylene group.

A ^a30 is preferably single bond, * -CO-O- or * -CO-O-A ^a32- CO-O-, and is preferably single bond, * -CO-O- or * -CO-O-CH. _{It is more preferably 2-} CO-O-, and even more preferably a single bond or * -CO-O-.

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 even more preferably 0.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group, aromatic hydrocarbon group and a group formed by combining these.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
The alicyclic hydrocarbon group may be either a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a binding site).

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl group) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group (p-) having an alicyclic hydrocarbon group, a group, a trill group, a xsilyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned. In particular, ^Ra36 includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups. Can be mentioned.

R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. It is a group to be formed, 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. Alkyl group and alicyclic hydrocarbon group for R ^a36 is preferably unsubstituted. Aromatic hydrocarbon group for R ^a36 is an aromatic ring preferably has an aryloxy group having 6 to 10 carbon atoms.
^{-OC (R a34) (R a35} ) -O-R a36 in the structural unit (a1-4) is desorbed by contact with an acid (e.g. p- toluenesulfonic acid) to form a hydroxy group.
^{-OC (R a34) (R a35} ) -O-R a36 is preferably bonded to the o- or p- position of the benzene ring, and more preferably binds to the p- position.

Examples of the structural unit (a1-4) include a structural unit derived from a monomer described in JP-A-2010-204646. Preferably, hydrogen atom corresponding to ^{R a32} in equation (a1-4-1) represented respectively to Formula (a1-4-18) structural units and structural units (a1-4) is replaced by a methyl group structure Units are mentioned, and more preferably, the formulas (a1-4-1) to (a1-4-5), formulas (a1-4-10), formulas (a1-4-13), and formulas (a1-4) are used. The structural units represented by -14) can be mentioned.

When the resin (A) contains the structural units (a1-4), the content thereof is preferably 1 to 60 mol%, preferably 2 to 50 mol%, based on the total of all the structural units of the resin (A). It is more preferably mol%, and even more preferably 3-40 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。 Examples of the structural unit derived from the (meth) acrylic monomer having the group (2) include a structural unit represented by the formula (a1-5) (hereinafter, may be referred to as “structural unit (a1-5)”). Be done.

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

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Alkyl groups having 1 to 6 carbon atoms which may have a halogen atom include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group and trifluoro. Methyl group can be mentioned.
In the formula (a1-5), R ^a8 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
Of L ⁵² and L ⁵³ , it is preferable that one is −O− and the other is −S−.
s1 is preferably 1.
s1'is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * -CH _2- CO-O-.

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

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

Moreover, the following structural unit is also mentioned as a structural unit (a1).

When the resin (A) contains the structural units such as (a1-3-1) to (a1-3-7) described above, the content rate thereof is 10 to 10 with respect to all the structural units of the resin (A). 95 mol% is preferable, 15 to 90 mol% is more preferable, 20 to 85 mol% is further preferable, 20 to 70 mol% is further more preferable, and 20 to 60 mol% is particularly preferable.

樹脂（Ａ）が上記、（ａ１−６−１）〜（ａ１−６−３）のような構造単位を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１０〜６０モル％が好ましく、１５〜５５モル％がより好ましく、２０〜５０モル％がさらに好ましく、２０〜４５モル％がさらにより好ましく、２０〜４０モル％が特に好ましい。 Moreover, the following structural unit is also mentioned as a structural unit (a1).

When the resin (A) contains structural units such as (a1-6-1) to (a1-6-3) described above, the content thereof is 10 to 10 with respect to all the structural units of the resin (A). 60 mol% is preferable, 15 to 55 mol% is more preferable, 20 to 50 mol% is further preferable, 20 to 45 mol% is further more preferable, and 20 to 40 mol% is particularly preferable.

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

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

［式（ａ２−Ａ）中、
Ｒ^a50は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数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は互いに同一でも異なっていてもよい。］ Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter, may be referred to as “structural unit (a2-A)”).

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

^Examples of the halogen atom in R ^a50 and R a51 include a fluorine atom, a chlorine atom and a bromine atom.
^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in Ra50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, and a 2,2,2-trifluoroethyl group. 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2 3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluoro 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, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group in Ra51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
^Examples of the alkoxy group in Ra51 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.
^Examples of the alkoxyalkyl group in Ra51 include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.
^Examples of the alkoxyalkoxy group in Ra51 include methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, and tert-butoxymethoxy group. Can be mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group.
^Examples of the alkylcarbonyl group in Ra51 include an acetyl group, a propionyl group, a butyryl group and the like. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.
^Examples of the alkylcarbonyloxy group in Ra51 include an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.
R ^a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, and is preferably a fluorine atom, an iodine atom, a hydroxy group or a methyl. A group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group is more preferable, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group is further preferable.

* -X ^a51- (A ^a52- X ^a52 ) _nb- is * -O-, * -CO-O-, * -O-CO-, * -CO-O-A ^{a52-CO-O-, * -O-CO-A a52 -O} -, * - O-A a52 -CO-O -, * - CO-O-A a52 -O-CO -, * - O-CO-A a52 -O-CO -, Can be mentioned. Of these, * ^{-CO-O-, * -CO-O-A a52-} CO-O- or * -O-A ^a52- CO-O- are preferable.

The ^{alkanediyl group in A a52} includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Examples include groups and 2-methylbutane-1,4-diyl groups.
A ^a52 is preferably a methylene group or an ethylene group.

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

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

Examples of the structural unit (a2-A) include monomer-derived structural units described in JP-A-2010-204634 and JP-A-2012-12577.

As the structural unit (a2-A), the structural unit represented by the formulas (a2-2-1) to (a2-2-16) and the formulas (a2-2-1) to (a2-2-16) are used. ^{), The structural unit in which the methyl group corresponding to Ra50} in the structural unit (a2-A) is replaced with a hydrogen atom can be mentioned. The structural unit (a2-A) is represented by a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), and a formula (a2-2-6). Structural units, structural units represented by the formula (a2-2-8), structural units represented by the formulas (a2-2-12) to (a2-2-14), and structures in these structural units. ^{It is preferable that the methyl group corresponding to Ra50} in the unit (a2-A) is a structural unit in which a hydrogen atom is replaced.

When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 1 to 80 mol%, more preferably 1 to 80 mol%, based on the total structural units. It is 3 to 70 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 50 mol%.
The structural unit (a2-A) can be included in the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Further, the structural unit (a2-A) can be contained in the resin (A) by polymerizing with acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide.

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

In equation (a2-1),
^La3 represents −O− or * −O− (CH ₂ ) _k2 −CO−O−.
k2 represents any integer from 1 to 7. * Represents the binding site with -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 independently represent a hydrogen atom, a methyl group or a hydroxy group, respectively.
o1 represents any integer from 0 to 10.

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

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

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

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

［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位を表す。
Ｒ^ａ１８、Ｒ^ａ１９及びＲ^ａ２０は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ２４は、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｘ^ａ３は、−ＣＨ_２−又は酸素原子を表す。
Ｒ^ａ２１は炭素数１〜４の脂肪族炭化水素基を表す。
Ｒ^ａ２２、Ｒ^ａ２３及びＲ^ａ２５は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５のいずれかの整数を表す。
ｑ１は、０〜３のいずれかの整数を表す。
ｒ１は、０〜３のいずれかの整数を表す。
ｗ１は、０〜８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^ａ２１、Ｒ^ａ２２、Ｒ^ａ２３及び／又はＲ^ａ２５は互いに同一でも異なっていてもよい。］ The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). One of these may be contained alone, or two or more thereof may be contained.

[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4),
L ^a4 , ^{La 5} and ^{La 6} are independently represented by -O- or * -O- (CH ₂ ) _k3 -CO-O- (k3 represents an integer of 1 to 7). Represents a group.
L ^{a7 is, -O -, * - O-} L a8 -O -, * - O-L a8 -CO-O -, * - O-L a8 -CO-O-L a9 -CO-O- or * -O-L ^a8- O-CO-L ^a9- O-represented.
^{La 8} and ^{La 9} each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents the binding site with the carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
^Ra24 represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
X ^a3 is, -CH ₂ - represents an or an oxygen atom.
Ra ²¹ 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 any integer from 0 to 3.
r1 represents any integer from 0 to 3.
w1 represents any integer from 0 to 8.
When p1, q1, r1 and / or w1 is 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same or different from each other. ]

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

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

In the formula (a3-1) ~ formula ^(a3-3), L a4 ^{~L a6} are each independently preferably -O- _{or, * - O- (CH 2)} k3 -CO-O- in, k3 Is an integer of 1 to 4, more preferably -O- and * -O-CH _2- CO-O-, and even more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently, preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are independently, preferably an integer of 0 to 2, and more preferably 0 or 1.

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

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

The structural unit (a3) is a structure derived from the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and the monomer described in JP-A-2012-41274. The unit is mentioned. The structural unit (a3) includes the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula (a3-2-2), and the formula (a3-3-3). 1), the structural unit represented by any of the formulas (a3-3-2) and the formulas (a3-4-1) to (a3-4-12), and in the structural unit, the formula (a3-1). ) ^R a18 in ~ formula ^{(a3-4), R a19, R} a20 and structural units in which a methyl group is replaced by a hydrogen atom corresponding to ^{R a24} are preferred.

When the resin (A) contains the structural unit (a3), the total content thereof is usually 1 to 70 mol%, preferably 3 to 65 mol%, based on all the structural units of the resin (A). , More preferably 5 to 60 mol%.
Further, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is set with respect to all the structural units of the resin (A), respectively. Therefore, 1 to 60 mol% is preferable, 3 to 50 mol% is more preferable, and 5 to 50 mol% is further preferable.

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

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

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

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

［式（ａ４−０）中、
Ｒ⁵⁴は、水素原子又はメチル基を表す。
Ｌ^4ａは、単結合又は炭素数１〜４のアルカンジイル基を表す。
Ｌ^3ａは、炭素数１〜８のペルフルオロアルカンジイル基又は炭素数３〜１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ⁶⁴は、水素原子又はフッ素原子を表す。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4). ..

[In equation (a4-0),
R ⁵⁴ 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 ⁶⁴ represents a hydrogen atom or a fluorine atom. ]

^Examples of the alkanediyl group in L 4a include a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and an ethane-1,1-diyl group. Bifurcated 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 can be mentioned. Be done.

The perfluoroalkanediyl group in L ^3a includes a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a perfluoropropane-2,2. -Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2 -Diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like can be mentioned.
^Examples of the perfluorocycloalkanediyl group in L 3a include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantandiyl group and the like.

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

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

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

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

[In equation (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and −CH ₂ − contained in the saturated hydrocarbon group is replaced with −O− or −CO−. You may.
A ^a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (ag1). However, ^{at least one of Aa41} and ^Ra42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In the formula (ag1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 independently represent -O-, -CO-, -CO-O- or -O-CO-, respectively.
However, the total number of carbon atoms of ^{A a42} , A ^a43 , A ^a44 , X ^a41 and X ^{a42 is 7 or less.} ]
* Is the binding site, and * on the right is the binding site with -O-CO-R ^a42 . ]

^Examples of the saturated hydrocarbon group in Ra42 include a chain hydrocarbon group, a monocyclic or polycyclic saturated alicyclic hydrocarbon group, and a group formed by combining these.

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

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

［式（ａ−ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、＊−Ｏ−ＣＯ−又は＊−ＣＯ−Ｏ−を表す。
Ａ^a45は、ハロゲン原子を有していてもよい炭素数１〜１７の飽和炭化水素基を表す。
＊はＲ^a42との結合部位を表す。］
ただし、Ｒ^a42−Ｘ^a43−Ａ^a45において、Ｒ^a42がハロゲン原子を有しない場合は、Ａ^a45は、少なくとも１つのハロゲン原子を有する炭素数１〜１７の飽和炭化水素基を表す。 ^{Examples of the substituent contained in} R a42 include at least one selected from the group consisting of a halogen atom and a group represented by the formula (ag3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

[In the formula (ag3),
X ^a43 represents an oxygen atom, a carbonyl group, * -O-CO- or * -CO-O-.
A ^a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* Represents the binding site with ^Ra42. ]
However, in R ^a42- X ^a43- A ^a45 , when R ^a42 does not have a halogen atom, A ^a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms 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。 Saturated hydrocarbon groups in A ^a45 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group. Alkyl groups such as groups; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; and decahydronaphthyl group, adamantyl group, norbornyl group and the following groups ( * Indicates a bonding site.) Examples thereof include a polycyclic alicyclic hydrocarbon group.

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

R ^a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (ag3).
When R ^a42 is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably having 1 to 1 carbon atoms. It is a perfluoroalkyl group of 6, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^{a42 is a saturated hydrocarbon group having a group represented by the formula (ag3)} , the total carbon of R a42 including the number of carbon atoms contained in the group represented by the formula (ag3). The number is preferably 15 or less, more preferably 12 or less. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.

［式（ａ−ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数１〜１７の２価の飽和炭化水素基を表す。
Ｘ^a44は、＊＊−Ｏ−ＣＯ−又は＊＊−ＣＯ−Ｏ−を表す（＊＊はＡ^a46との結合部位を表す。）。
Ａ^a47は、ハロゲン原子を有していてもよい炭素数１〜１７の飽和炭化水素基を表す。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合部位を表す。］ When R ^a42 is a saturated hydrocarbon group having a group represented by the formula ( ^{ag3), R a42} is more preferably a group represented by the formula (ag2).

[In the formula (ag2),
A ^a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents **-O-CO- or **-CO-O- (** represents the binding site with ^{A a46).}
A ^a47 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of ^{A a46} , A ^a47 and X ^{a44 is 18 or less, and at least one of A a46} and A ^a47 has at least one halogen atom.
* Represents the binding site with the carbonyl group. ]

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

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

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

^{The divalent saturated hydrocarbon group represented by A a42} , A ^a43 and A ^{a44 in} the group represented by the formula (ag1) includes a linear or branched alkanediyl group and a monocyclic divalent alicyclic group. Examples thereof include a saturated hydrocarbon group and a divalent saturated hydrocarbon group formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, Examples thereof include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
^Examples of the substituent of the divalent saturated hydrocarbon group represented by A a42, A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

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

As the structural unit represented by the formula (a4-1), the methyl group corresponding to ^Ra41 in the structural unit shown below and the structural unit represented by the formula (a4-1) in the following structural unit is a hydrogen atom. Examples include replaced structural units.

［式（ａ４−２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ⁴⁴は、炭素数１〜６のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｒ^f6は、炭素数１〜２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ⁴⁴及びＲ^f6の合計炭素数の上限は２１である。］ Examples of the structural unit represented by the formula (a4-1) include a structural unit represented by the formula (a4-2) and a structural unit represented by the formula (a4-3).

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

^Examples of the alkanediyl group having 1 to 6 carbon atoms of L ⁴⁴ include the same groups as those exemplified in A a41.
Examples of the saturated hydrocarbon group of R ^f6 include the same groups as those exemplified in ^{R 42.}
As the ^{alkanediyl group in L 44,} an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

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

［式（ａ４−３）中、
Ｒ^f7は、水素原子又はメチル基を表す。
Ｌ⁵は、炭素数１〜６のアルカンジイル基を表す。
Ａ^f13は、フッ素原子を有していてもよい炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｘ^f12は、＊−Ｏ−ＣＯ−又は＊−ＣＯ−Ｏ−を表す（＊はＡ^f13との結合部位を表す。）。
Ａ^f14は、フッ素原子を有していてもよい炭素数１〜１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14の合計炭素数の上限は２０である。］

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

^Examples of the alkanediyl group in L ⁵ include the same groups as those exemplified in the alkanediyl group of A a41.

The ^{divalent saturated hydrocarbon group which may have a fluorine atom in A f13} preferably has a divalent chain saturated hydrocarbon group which may have a fluorine atom and a fluorine atom. It is also a good divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalcandiyl group.
Examples of the divalent chain saturated hydrocarbon group which may have a fluorine atom include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group; a difluoromethylene group and a perfluoroethylene group. Examples thereof include a perfluoroalkanediyl group such as a perfluoropropanediyl group, a perfluorobutandyl group and a perfluoropentanediyl group.
The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either a monocyclic type or a polycyclic type. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantandiyl group, a norbornanediyl group, a perfluoroadamantandiyl group and the like.

Examples of the saturated hydrocarbon group of A ^{f14 and} the saturated hydrocarbon group which may have a fluorine atom include the same groups as those exemplified in ^Ra42. Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,5,5,5-Nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group, etc. Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group , Perfluoroadamantylmethyl group and the like are preferable.

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

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

［式（ａ４−４）中、
Ｒ^f21は、水素原子又はメチル基を表す。
Ａ^f21は、−（ＣＨ₂）_j1−、−（ＣＨ₂）_j2−Ｏ−（ＣＨ₂）_j3−又は−（ＣＨ₂）_j4−ＣＯ−Ｏ−（ＣＨ₂）_j5−を表す。
ｊ１〜ｊ５は、それぞれ独立に、１〜６のいずれかの整数を表す。
Ｒ^f22は、フッ素原子を有する炭素数１〜１０の飽和炭化水素基を表す。］ The structural unit (a4) also includes a structural unit represented by the formula (a4-4).

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

^Examples of the saturated hydrocarbon group of R ^f22 include those similar to the saturated hydrocarbon group represented by R a42. R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic 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 preferable. More preferably, an alkyl group having 1 to 6 carbon atoms having a fluorine atom is further preferable.
In the formula (a4-4), as A ^f21 , − (CH ₂ ) _j1 − is preferable, an ethylene group or a methylene group is more preferable, and a methylene group is further preferable.

樹脂（Ａ）が、構造単位（ａ４）を有する場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１〜２０モル％が好ましく、２〜１５モル％がより好ましく、３〜１０モル％がさらに好ましい。 As the structural unit represented by the formula (a4-4), for example, in the following structural unit and the structural unit represented by the following formula, the methyl group corresponding to ^{R f21 in the structural unit (a4-4) is hydrogen.} Examples include structural units that have been replaced by atoms.

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

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

[In equation (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ..
L ⁵⁵ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. .. ]

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[In formula (II-2-A'),
X ^III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group may be replaced with -O-, -S- or -CO-. Often, the hydrogen atom contained in the saturated hydrocarbon group may be replaced with a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a hydroxy group.
A ^x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
RA ⁻ represents a sulfonate group or a carboxylate group.
R ^III3 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
ZA ⁺ represents an organic cation. ]

Examples of the halogen atom represented by R ^III3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3, the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 The same can be mentioned.
The ^{alkanediyl group having 1 to 8 carbon atoms represented by A x1} includes a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2, 4-Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Can be mentioned.
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms that may be substituted in A ^x1 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, and a perfluorotert. -Butyl group, perfluoropentyl group, perfluorohexyl group and the like can be mentioned.

Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X ^III3 include a linear or branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. And these may be combined.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-Diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decan-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group and other linear alkanediyl groups; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , Pentan-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 , 4-Diyl group, cyclooctane-1,5-Diyl group and other cycloalkanediyl groups and other divalent monocyclic alicyclic saturated hydrocarbon groups; norbornan-1,4-diyl group, norbornan-2, Examples thereof include divalent polycyclic alicyclic saturated hydrocarbon groups such as 5-diyl group, adamantan-1,5-diyl group and adamantan-2,6-diyl group.

_{When -CH 2-} contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO-, for example, a divalent group represented by the formulas (X1) to (X53) is used. Can be mentioned. _{However, the number of carbon atoms before -CH 2-} contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following formula, * and ** represent the binding site, and * represents the binding site with A ^x1 .

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

Examples ^{of the organic cation represented by ZA +} include an organic onium cation, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an aryl sulfonium cation is more preferable. Specific examples thereof include cations represented by any of the formulas (b2-1) to (b2-4) described later.

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

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

The ^{R III2,} R III4, ^Q perfluoroalkyl group having 1 to 6 carbon atoms represented by ^a and ^{Q b,} include those similar to the perfluoroalkyl group having 1 to 6 carbon atoms represented by below of ^{Q b1} ..

［式（ＩＩ−２−Ａ−１）中、
Ｒ^ＩＩＩ２、Ｒ^ＩＩＩ３、Ｒ^ＩＩＩ４、Ｑ^a、Ｑ^b、ｚ及びＺＡ^＋は、上記と同じ意味を表す。
Ｒ^ＩＩＩ５は、炭素数１〜１２の飽和炭化水素基を表す。
Ｘ^Ｉ2は、炭素数１〜１１の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−ＣＯ−に置き換わっていてもよく、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子又はヒドロキシ基で置換されていてもよい。］ The structural unit represented by the formula (II-2-A) is preferably the structural unit represented by the formula (II-2-A-1).

[In formula (II-2-A-1),
R ^III2 , R ^III3 , R ^III4 , Q ^a , Q ^b , z and ZA ⁺ have the same meanings as above.
R ^III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
X ^I2 represents a divalent saturated hydrocarbon group of 1 to 11 carbon atoms, -CH ₂ contained in the saturated hydrocarbon group - is -O -, - it is replaced in S- or -CO- Often, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group. ]

Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ^III5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Examples thereof include a linear or branched alkyl group such as a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
Examples of the divalent saturated hydrocarbon group represented by X ^I2, are the same as those of the divalent saturated hydrocarbon group represented by X ^III3.

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

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

As the structural unit represented by the formula (II-2-A'), for example, the following structural unit, the ^{group corresponding to the methyl group of R III3} , is a hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen atom. Examples thereof include structural units replaced with alkyl groups having 1 to 6 carbon atoms (for example, trifluoromethyl groups, etc.) and structural units described in International Publication No. 2012/050015. ZA ⁺ represents an organic cation.

［式（ＩＩ−１−１）中、
Ａ^ＩＩ１は、単結合又は２価の連結基を表す。
Ｒ^ＩＩ１は、炭素数６〜１８の２価の芳香族炭化水素基を表す。
Ｒ^ＩＩ２及びＲ^ＩＩ３は、それぞれ独立して、炭素数１〜１８の炭化水素基を表し、Ｒ^ＩＩ２及びＲ^ＩＩ３は互いに結合してそれらが結合する硫黄原子とともに環を形成していてもよい。
Ｒ^ＩＩ４は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数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。 The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1).

[In formula (II-1-1),
A ^II1 represents a single bond or a divalent linking group.
R ^II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^II2 and R ^II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R ^II2 and R ^II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded.
R ^II4 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
A ⁻ represents an organic anion. ]
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^{II1 include a phenylene group and a naphthylene group.}
Examples of the hydrocarbon group represented by R ^II2 and R ^II3 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-). Aromatic hydrocarbon group having an alicyclic hydrocarbon group (butylphenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) Examples thereof include an aryl-cycloalkyl group such as a p-cyclohexylphenyl group and a p-adamantylphenyl group) and a phenylcyclohexyl group.
Examples of the halogen atom represented by R ^II4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 The same can be mentioned.
Examples of the divalent linking group represented by A ^II1 include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and −CH ₂ − contained in the divalent saturated hydrocarbon group is It may be replaced by -O-, -S- or -CO-. Specifically, the same divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by ^{X III3 can be mentioned.}

As the structural unit containing a cation in the formula (II-1-1), the structural unit represented by the following, the ^{group corresponding to the methyl group of R II4} is a hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen. Examples thereof include a structural unit in which an alkyl group having 1 to 6 carbon atoms (for example, a trifluoromethyl group or the like) which may have an atom is replaced.

Examples of the organic anion represented by A ⁻ include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylic acid anion. The ^{organic anion represented by A −} is preferably a sulfonic acid anion, and examples of the sulfonic acid anion include the same as the anion represented by the formula (B1) described later.

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

Examples of the sulfonylmethide anion include the following.

Examples of the carboxylic acid anion include the following.

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

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

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

The resin (A) is preferably a resin composed of a structural unit (I) and a structural unit (III), a structural unit (I), a structural unit (III), a structural unit (a1-1), and a structural unit (a1-). Resin consisting of 2), resin consisting of structural unit (I), structural unit (III) and structural unit (a1-1), structural unit (I), structural unit (III) and structural unit (a1-2) Resin consisting of, structural unit (I), structural unit (III), and resin consisting of structural unit (s), structural unit (I), structural unit (III), structural unit (a1), and structural unit (s). Resin consisting of, structural unit (I), structural unit (III), structural unit (a1), structural unit (a1-1), structural unit (s), structural unit (I) and structural unit ( Resin consisting of III), structural unit (a1), structural unit (a1-2) and structural unit (s), structural unit (I), structural unit (III), structural unit (a1-1) and structural unit ( Resin composed of a1-2) and structural unit (s), resin composed of structural unit (I), structural unit (III), structural unit (a1-1) and structural unit (s), structural unit (I) Resin consisting of a structural unit (III), a structural unit (a1-2), and a structural unit (s), a structural unit (I), a structural unit (III), a structural unit (a1-1), and a structural unit (a1-). A resin composed of 2), a structural unit (s), a structural unit (a4) and / or a structural unit (a5), or a structural unit (I), a structural unit (III), a structural unit (a1-1), and a structure. A resin consisting only of a unit (a1-2) and a structural unit (a4), more preferably a resin composed of a structural unit (I) and a structural unit (III), a structural unit (I) and a structural unit (III). Resin consisting of a structural unit (a1-1) and a structural unit (a1-2), a structural unit (I), a structural unit (III), a structural unit (a1-1), a structural unit (a1-2), and a structure. Resin consisting of unit (s), resin consisting of structural unit (I), structural unit (III), structural unit (a1-1) and structural unit (s), structural unit (I) and structural unit (III) Resin consisting of structural unit (a1-2) and structural unit (s), resin consisting of structural unit (I), structural unit (III) and structural unit (s), structural unit (I) and structural unit ( Resin composed of III), structural unit (a1) and structural unit (s), structural unit (I), structural unit (III), structural unit (a1), structural unit (a1-1) and structural unit (s) Resin consisting of, structural unit (I), structural unit (III) and structural unit (a1) It is a resin composed of a structural unit (a1-2) and a structural unit (s).

The structural unit (a1) is preferably a structural unit (a1-4). The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably at least one selected from the group consisting of the structural unit (a2-1) and the structural unit (a2-A). The structural unit (a3) is preferably a group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4). At least one of the choices.

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

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

<Resin other than resin (A)>
The resin other than the resin (A) may be a resin that does not contain the structural unit (I) or the structural unit (III). Examples of such a resin include a resin in which the structural unit (I) is removed from the resin (A) (hereinafter, may be referred to as “resin (AY)”), and the structural unit (III) is removed from the resin (A). Examples thereof include a resin (hereinafter, may be referred to as “resin (AZ)”), a resin composed of only a structural unit (a4) and a structural unit (a5) (hereinafter, may be referred to as a resin (X)) and the like.

As the resin (X), a resin containing the structural unit (a4) is particularly preferable.
In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total of all the structural units of the resin (X). , 45 mol% or more is more preferable.
Examples of the structural unit that the resin (X) may further include include a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers. Above all, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5).
Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, a radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weights of the resin (AY), the resin (AZ), and the resin (X) are independently, preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60), respectively. 000 or less). The means for measuring the weight average molecular weight of the resin (AY) and the resin (X) is the same as that of the resin (A).
When the resist composition of the present invention contains a resin (AY), the total content thereof is usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) with respect to 100 parts by mass of the resin (A). Is.
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). It is even more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and even more preferably 1 to 8 parts by mass.

In the resist composition of the present invention, the resin (A) may be used in combination with a resin other than the resin (A), and when a resin other than the resin (A) is used in combination, the resin containing a structural unit having an acid unstable group is used. And / or a resin containing a structural unit having a fluorine atom is preferably used in combination, and a resin (AY), a resin (AZ) and / or a resin (X) is more preferably used in combination.
The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. When a resin other than the resin (A) is contained, the total content of the resin (A) and the resin other than the resin (A) is 80% by mass or more and 99% by mass with respect to the solid content of the resist composition. It is preferably 90% by mass or more and 99% by mass or less. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

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

Examples of the acid generator (B) include Japanese Patent Application Laid-Open No. 63-26653, Japanese Patent Application Laid-Open No. 55-164824, Japanese Patent Application Laid-Open No. 62-69263, Japanese Patent Application Laid-Open No. 63-146038, and Japanese Patent Application Laid-Open No. 63-163452. Kaisho 62-153853, Japanese Patent Application Laid-Open No. 63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. A compound that generates an acid by the radiation described in the above can be used. Moreover, you may use the compound produced by the 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、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜２４の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ（Ｏ）_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 fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter, may be referred to as “acid generator (B1)”).

[In equation (B1),
Q ^b1 and Q ^b2 independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH _2- may be replaced with −O−, −S (O) _{2− or −CO−.}
Z1 ⁺ represents an organic cation. ]

The ^{perfluoroalkyl groups represented by Q b1} and Q ^b2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and Examples include a perfluorohexyl group.
It is preferable that Q ^b1 and Q ^b2 are independently fluorine atoms or trifluoromethyl groups, and it is more preferable that both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group in L ^b1 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a group formed by combining two or more of the groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl Group, Octane-1,8-Diyl Group, Nonan-1,9-Diyl Group, Decane-1,10-Diyl Group, Undecane-1,11-Diyl Group, Dodecane-1,12-Diyl Group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group. Alcandiyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. The group etc. can be mentioned.

_{Examples of the group in which -CH 2-} contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced with -O- or -CO- include formulas (b1-1) to (b1-3). The group represented by any of the above can be mentioned. In addition, in the groups represented by the formulas (b1-1) to (b1-3) and the groups represented by the formulas (b1-4) to (b1-11) which are specific examples thereof, * and * * Represents a bond and * represents a bond with -Y.

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

[In equation (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. _{-CH 2-} contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of ^{L b2} and L ^{b3 is 22 or less.}
In equation (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. _{-CH 2-} contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of ^{L b4} and L ^{b5 is 22 or less.}
In equation (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. _{-CH 2-} contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of ^{L b6} and L ^{b7 is 23 or less.}
* And ** represent a bond, and * represents a bond with Y. ]

In the groups represented by the formulas (b1-1) to (b1-3), when -CH _2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the carbon before the replacement is performed. Let the number be the number of carbon atoms of the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of ^{L b1.}
L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. _{-CH 2-} contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

［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。
＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。］
Ｌ^b8は、好ましくは炭素数１〜４の２価の飽和炭化水素基である。
Ｌ^b9は、好ましくは炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b10は、好ましくは単結合又は炭素数１〜１９の２価の飽和炭化水素基であり、より好ましくは単結合又は炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b11は、好ましくは炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b12は、好ましくは単結合又は炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b13は、好ましくは炭素数１〜１２の２価の飽和炭化水素基である。
Ｌ^b14は、好ましくは単結合又は炭素数１〜６の２価の飽和炭化水素基である。
Ｌ^b15は、好ましくは単結合又は炭素数１〜１８の２価の飽和炭化水素基であり、より好ましくは単結合又は炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b16は、好ましくは炭素数１〜１２の２価の飽和炭化水素基である。
Ｌ^b17は、好ましくは炭素数１〜６の２価の飽和炭化水素基である。
Ｌ^b18は、好ましくは単結合又は炭素数１〜１７の２価の飽和炭化水素基であり、より好ましくは単結合又は炭素数１〜４の２価の飽和炭化水素基である。 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 the formula (b1-1) or the formula (b1-3). Is preferred.
Examples of the group represented by the formula (b1-1) include the groups represented by the formulas (b1-4) to (b1-8), respectively.

[In equation (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In equation (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total number of carbon atoms of ^{L b9} and L ^{b10 is 20 or less.}
In equation (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total number of carbon atoms of ^{L b11} and L ^{b12 is 21 or less.}
In equation (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group is replaced with -O- or -CO-. May be good.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total number of carbon atoms of ^{L b13 to} L ^{b15 is 19 or less.}
In equation (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. ..
However, the total number of carbon atoms of ^{L b16 to} L ^{b18 is 19 or less.}
* And ** represent a bond, and * represents a bond with Y. ]
L ^b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

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

[In equation (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. May be good. _{The −CH 2} − contained in the alkylcarbonyloxy group may be replaced with −O− or −CO−, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total number of carbon atoms of ^{L b19} and L ^{b20 is 23 or less.}
In equation (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. May be good. _{The −CH 2} − contained in the alkylcarbonyloxy group may be replaced with −O− or −CO−, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of ^{L b21} , L ^b22 and L ^{b23 is 21 or less.}
In equation (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. May be good. _{The −CH 2} − contained in the alkylcarbonyloxy group may be replaced with −O− or −CO−, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, L ^b24, the total number of carbon atoms of L ^b25 and L ^b26 is 21 or less.
* And ** represent a bond, and * represents a bond with Y. ]

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

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-4) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-5) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-6) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-7) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-8) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-2) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-9) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-10) include the following.

(* And ** represent a bond, * represents a bond with Y.)

（＊及び＊＊は結合手を表し、＊はＹとの結合手を表す。） Examples of the group represented by the formula (b1-11) include the following.

(* And ** represent a bond, * represents a bond with Y.)

Ｙで表される脂環式炭化水素基としては、好ましくは式（Ｙ１）〜式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）〜式（Ｙ４３）のいずれかで表される基であり、より好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ１６）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）で表される基である。
Ｙで表される脂環式炭化水素基が式（Ｙ２８）〜式（Ｙ３５）、式（Ｙ３９）〜式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）等の酸素原子を含むスピロ環である場合には、２つの酸素原子間のアルカンジイル基は、１以上のフッ素原子を有することが好ましい。また、ケタール構造に含まれるアルカンジイル基のうち、酸素原子に隣接するメチレン基には、フッ素原子が置換されていないのが好ましい。 Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y11) and formulas (Y36) to (Y38).
_{When -CH 2-} contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -S (O) _2- or -CO-, the number may be one or two or more. good. Examples of such groups include groups represented by formulas (Y12) to (Y35) and formulas (Y39) to (Y43). * Represents a bond with ^{L b1.}

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

As the substituent of the methyl group represented by Y, a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, and-( CH ₂ ) _ja- CO-O-R ^b1 group or-(CH ₂ ) _ja- O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms and having 3 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 the alkyl group and −CH ₂ − contained in the alicyclic hydrocarbon group are −O−. , -SO _2- or -CO- may be replaced, 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. May represent ja represents any integer from 0 to 4) and the like.
As the substituent of the alicyclic hydrocarbon group represented by Y, an alkyl group having 1 to 16 carbon atoms which may be substituted with a halogen atom, a hydroxy group or a hydroxy group (-CH2- contained in the alkyl group). May be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 21 carbon atoms. Group, glycidyloxy group,-(CH ₂ ) _ja- CO-O-R ^b1 group or-(CH ₂ ) _ja- O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl having 1 to 16 carbon atoms. Represents a 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 _- is, -O _-, - SO 2 - or -CO- may be replaced to a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and aromatic hydrocarbon group, hydroxy It may be replaced with a group or a fluorine atom. Ja represents an integer of 0 to 4) and the like.

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

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group, more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and even more preferably an adamantyl group which may have a substituent. _{, -CH 2-} constituting the alicyclic hydrocarbon group or adamantyl group may be replaced with -CO-, -S (O) _{2- or -CO-.} Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the formulas (Y42) and the formulas (Y100) to (Y114).

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

Here, R ^{i2 to} R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, independently of each other. ^Ri8 is formed, for example, by a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. Group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. ^LA41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q ^b1 and Q ^b2 have the same meanings as described above.
Specific examples of the anion in the salt represented by the formula (B1) include the anion described in JP-A-2010-204646.

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

Among them, equations (B1a-1) to (B1a-3), equations (B1a-7) to (B1a-16), equations (B1a-18), equations (B1a-19), equations (B1a-22). )-Anion represented by any of the formulas (B1a-38) is preferable.

式（ｂ２−１）〜式（ｂ２−４）において、
Ｒ^b4〜Ｒ^b6は、それぞれ独立に、炭素数１〜３０の鎖式炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜３６の芳香族炭化水素基を表し、該鎖式炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数３〜１２の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜１８の脂肪族炭化水素基、炭素数２〜４のアルキルカルボニル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基、炭素数１〜１８の脂肪族炭化水素基、炭素数１〜１２のフッ化アルキル基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。
Ｒ^b4とＲ^b5とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−又は−ＣＯ−に置き換わってもよい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ハロゲン原子、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数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又は炭素数１〜１２のアルコキシ基を表す。
Ｌ^b31は、硫黄原子又は酸素原子を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０〜５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０〜４のいずれかの整数を表す。
ｕ２は０又は１を表す。
ｏ２が２以上のとき、複数のＲ^b13は同一又は相異なり、ｐ２が２以上のとき、複数のＲ^b14は同一又は相異なり、ｑ２が２以上のとき、複数のＲ^b15は同一又は相異なり、ｒ２が２以上のとき、複数のＲ^b16は同一又は相異なり、ｓ２が２以上のとき、複数のＲ^b17は同一又は相異なり、ｔ２が２以上のとき、複数のＲ^b18は同一又は相異なる。 Examples of the Z1 ⁺ organic cation include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an aryl sulfonium cation is more preferable. Specifically, the cation represented by any of the formulas (b2-1) to (b2-4) (hereinafter, may be referred to as "cation (b2-1)" or the like depending on the formula number). Can be mentioned.

In equations (b2-1) to (b2-4),
R ^{b4 to} R ^b6 independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the chain hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. It may be substituted, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted, and the hydrogen atom is a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms or carbon. It may be substituted with an alkoxy group of numbers 1-12.
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 is −O−, −S− or −O−, −S− or. It may be replaced with −CO−.
R ^b7 and R ^b8 independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 independently represent a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and −CH ₂ − contained in the ring may be −O−, −S− or −O−, −S− or. It may be replaced with −CO−.
R ^b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The contained hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or 1 carbon atom. It may be substituted with ~ 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may form a ring including −CH—CO− to which they are bonded to each other, and −CH ₂₋ contained in the ring is −O−, −S. It may be replaced with − or −CO−.
R ^{b13 to} R ^b18 independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
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, a plurality of R ^b13s are the same or different, when p2 is 2 or more, a plurality of R ^b14s are the same or different, and when q2 is 2 or more, a plurality of R ^b15s are the same or different. when r2 is 2 or more, plural R ^b16 same or different, when s2 is 2 or more, plural R ^b17 same or different, when t2 is 2 or more, plural R ^b18 same or different different.

特に、Ｒ^b9〜Ｒ^b12の脂環式炭化水素基は、好ましくは炭素数３〜１８、より好ましくは炭素数４〜１２である。 The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
The chain hydrocarbon group includes an alkyl group of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group. Can be mentioned.
In particular, ^{the chain hydrocarbon 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, and a cyclo. Cycloalkyl groups such as heptyl group, cyclooctyl group and cyclodecyl group can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

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

The alicyclic hydrocarbon group in which the hydrogen atom is substituted with an aliphatic hydrocarbon group includes a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, and a 2-ethyladamantan-2-yl group. , 2-Isopropyl adamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which the hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.
The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms having a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and perfluorobutyl. The alkyl fluoride group preferably has 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.

Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a biphenyl group, a naphthyl group and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and the aromatic hydrocarbon group having a chain hydrocarbon group (trill group, xsilyl group, cumenyl group, mesityl). Aromatic hydrocarbon group having an alicyclic hydrocarbon group (group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) p-cyclohexylphenyl group, p-adamantylphenyl group, etc.) and the like.
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 preferable.
Examples of the aromatic hydrocarbon group in which the hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the chain hydrocarbon group in which the hydrogen atom is substituted with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group.

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

The ^{ring formed by R b4} and R ^b5 bonding to each other and together with the sulfur atom to which they are bonded can be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. It may be a ring of. Examples of this ring include a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Further, the ring containing a sulfur atom may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include the following rings. * Represents a bond.

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

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

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

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

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

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

As the acid generator (B), those represented by the formulas (B1-1) to (B1-56) are preferably mentioned. 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 formulas (B1-14). ), Formulas (B1-20) to formulas (B1-26), formulas (B1-29), and formulas (B1-31) to formulas (B1-56) are particularly preferable.

本発明のレジスト組成物においては、酸発生剤の含有率は、前述の樹脂（Ａ）１００質量部に対して、好ましくは１質量部以上４５質量部以下、より好ましくは１質量部以上４０質量部以下、さらに好ましくは３質量部以上４０質量部以下、さらにより好ましくは１０質量部以上４０質量部以下である。

In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more and 45 parts by mass or less, and more preferably 1 part by mass or more and 40 parts by mass with respect to 100 parts by mass of the resin (A) described above. Parts or less, more preferably 3 parts by mass or more and 40 parts by mass or less, still more preferably 10 parts by mass or more and 40 parts by mass or less.

<Solvent (E)>
The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. % Or less. The content of the solvent (E) can be measured by a known analytical means such as liquid chromatography or gas chromatography.
Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate. Esters; ketones such as acetone, methylisobutylketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One type of solvent (E) may be used alone, or two or more types may be used.

<Quencher (C)>
Examples of the quencher (C) include a basic nitrogen-containing organic compound or a salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B). When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15% by mass based on the solid content of the resist composition, and 0. It is more preferably about 01 to 10% by mass, further preferably about 0.1 to 5% by mass, and even more preferably about 0.1 to 3% by mass.
Examples of the basic nitrogen-containing organic compound include amine and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.
Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, tri Heptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, tri Isopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3 , 3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-di) Pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethane, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ) Ethan, di (2-pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicorylamine, bipyridine and the like. Aromatic amines such as diisopropylaniline are preferred, and 2,6-diisopropylaniline is more preferred.
Ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl. Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

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

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

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

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

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

<Use>
The resist composition of the present invention includes a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly electrons. It is suitable as a resist composition for linear (EB) exposure or a resist composition for EUV exposure, and is useful for fine processing of semiconductors.

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

式（Ｉ−１７−ａ）で表される化合物２０部、式（Ｉ−１７−ｃ）で表される化合物２．２８部、酢酸エチル１００部及びテトラヒドロフラン１５部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ−１７−ｂ）で表される化合物６．５５部を添加し、２３℃で１８時間攪拌した。得られた反応マスに、ｎ−ヘプタン２０部及びイオン交換水７０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水６０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を４回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１７−ｄ）で表される化合物７．４８部を得た。

式（Ｉ−１７−ｅ）で表される化合物５．９０部、式（Ｉ−１７−ｆ）で表される化合物７．１０部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、６０℃で１時間攪拌した。得られた混合物に、式（Ｉ−１７−ｄ）で表される化合物７．２６部を添加し、６０℃で１時間攪拌した。得られた反応マスを２３℃まで冷却した後、酢酸エチル１００部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を４回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−１７）で表される化合物９．４４部を得た。
ＭＡＳＳ（質量分析）：３１３．１［Ｍ＋Ｈ］^＋ Synthesis Example 1: Synthesis of the compound represented by the formula (I-17)

20 parts of the compound represented by the formula (I-17-a), 2.28 parts of the compound represented by the formula (I-17-c), 100 parts of ethyl acetate and 15 parts of tetrahydrofuran are mixed and 30 at 23 ° C. Stir for minutes. To the obtained mixed solution, 6.55 parts of the compound represented by the formula (I-17-b) was added, and the mixture was stirred at 23 ° C. for 18 hours. To the obtained reaction mass, 20 parts of n-heptane and 70 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 60 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 4 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 7.48 parts of the compound represented by the formula (I-17-d) was obtained.

5.90 parts of the compound represented by the formula (I-17-e), 7.10 parts of the compound represented by the formula (I-17-f) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. Then, the mixture was stirred at 60 ° C. for 1 hour. To the obtained mixture, 7.26 parts of the compound represented by the formula (I-17-d) was added, and the mixture was stirred at 60 ° C. for 1 hour. The obtained reaction mass was cooled to 23 ° C., 100 parts of ethyl acetate and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 4 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 9.44 parts of the compound represented by the formula (I-17) was obtained.
MASS (Mass Spectrometry): 313.1 [M + H] ⁺

式（Ｉ−２５−ａ）で表される化合物５．００部、式（Ｉ−１７−ｄ）で表される化合物１０．３９部、ジメチルホルムアミド５０部及び炭酸カリウム１１．１４部を混合し、２３℃で３０分間攪拌した後、１２０℃で１８時間攪拌した。得られた混合物を２３℃まで冷却した後、イオン交換水１５０部及び酢酸エチル１５０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１５０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３回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−２５−ｂ）で表される化合物１０．６１部を得た。

式（Ｉ−２５−ｃ）で表される化合物１７．１６部、式（Ｉ−２５−ｄ）で表される化合物５．３９部及びテトラヒドロフラン１２０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、５℃で、式（Ｉ−２５−ｂ）で表される化合物１０．５８部を３０分かけて添加し、２３℃に昇温後、２３℃で１２時間攪拌した後、ろ過した。得られたろ液に、イオン交換水１００部及び酢酸エチル２００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１００部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を３回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−２５）で表される化合物６．８２部を得た。
ＭＡＳＳ（質量分析）：２８５．１［Ｍ＋Ｈ］^＋ Synthesis Example 2: Synthesis of the compound represented by the formula (I-25)

5.00 parts of the compound represented by the formula (I-25-a), 10.39 parts of the compound represented by the formula (I-17-d), 50 parts of dimethylformamide and 11.14 parts of potassium carbonate are mixed. After stirring at 23 ° C. for 30 minutes, the mixture was stirred at 120 ° C. for 18 hours. The obtained mixture was cooled to 23 ° C., 150 parts of ion-exchanged water and 150 parts of ethyl acetate were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 150 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 10.61 part of the compound represented by the formula (I-25-b) was obtained.

17.16 parts of the compound represented by the formula (I-25-c), 5.39 parts of the compound represented by the formula (I-25-d) and 120 parts of tetrahydrofuran were mixed and stirred at 23 ° C. for 30 minutes. After that, it was cooled to 5 ° C. To the obtained mixture, 10.58 parts of the compound represented by the formula (I-25-b) was added at 5 ° C. over 30 minutes, the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 12 hours. , Filtered. To the obtained filtrate, 100 parts of ion-exchanged water and 200 parts of ethyl acetate were added, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to remove the organic layer. To the obtained organic layer, 100 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 6.82 parts of the compound represented by the formula (I-25) was obtained.
MASS (Mass Spectrometry): 285.1 [M + H] ⁺

式（ＩＩＩ−８−ａ）で表される化合物５部、式（ＩＩＩ−８−ｂ）で表される化合物５．４７部及びアセトニトリル２５部を混合し、２３℃で３０分間攪拌した後、６０℃で１時間攪拌した。得られた混合物に、式（ＩＩＩ−８−ｃ）で表される化合物４．６２部及び式（ＩＩＩ−８−ｄ）で表される化合物５．１４部を添加し、６０℃で１時間攪拌した。得られた反応マスを２３℃まで冷却した後、酢酸エチル１５０部及び１Ｎ塩酸３５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、イオン交換水４５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を４回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（ＩＩＩ−８）で表される化合物５．３０部を得た。
ＭＡＳＳ（質量分析）：２４５．２［Ｍ＋Ｈ］^＋ Synthesis Example 3: Synthesis of the compound represented by the formula (III-8)

After mixing 5 parts of the compound represented by the formula (III-8-a), 5.47 parts of the compound represented by the formula (III-8-b) and 25 parts of acetonitrile and stirring at 23 ° C. for 30 minutes, The mixture was stirred at 60 ° C. for 1 hour. To the obtained mixture, 4.62 parts of the compound represented by the formula (III-8-c) and 5.14 parts of the compound represented by the formula (III-8-d) were added, and the mixture was added at 60 ° C. for 1 hour. Stirred. The obtained reaction mass was cooled to 23 ° C., 150 parts of ethyl acetate and 35 parts of 1N hydrochloric acid were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. Forty-five parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 4 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 5.30 parts of the compound represented by the formula (III-8) was obtained.
MASS (Mass Spectrometry): 245.2 [M + H] ⁺

式（Ｉ−４３−ａ）で表される化合物５．００部、式（Ｉ−１７−ｃ）で表される化合物０．００８部及びトルエン５０部を混合し、２３℃で３０分間攪拌した後、１００℃まで昇温した。得られた混合溶液に、１００℃で、式（Ｉ−４３−ｂ）で表される化合物６．１９部を滴下し、１１０℃で２時間攪拌した後、２３℃まで冷却した。得られた混合物に、酢酸エチル２５部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、イオン交換水３０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−４３−ｄ）で表される化合物５．８５部を得た。

式（Ｉ−１７−ｅ）で表される化合物４．２０部、式（Ｉ−１７−ｆ）で表される化合物５．０６部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、６０℃で１時間攪拌した。得られた混合物に、式（Ｉ−４３−ｄ）で表される化合物５．７９部を添加し、６０℃で１時間攪拌した。得られた反応マスを２３℃まで冷却した後、酢酸エチル１００部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、イオン交換水５０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３回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝１０／１）分取することにより、式（Ｉ−４３）で表される化合物３．１０部を得た。
ＭＡＳＳ（質量分析）：２９７．１［Ｍ＋Ｈ］^＋ Synthesis Example 4: Synthesis of compound represented by formula (I-43)

5.00 parts of the compound represented by the formula (I-43-a), 0.008 parts of the compound represented by the formula (I-17-c) and 50 parts of toluene were mixed and stirred at 23 ° C. for 30 minutes. After that, the temperature was raised to 100 ° C. To the obtained mixed solution, 6.19 parts of the compound represented by the formula (I-43-b) was added dropwise at 100 ° C., and the mixture was stirred at 110 ° C. for 2 hours and then cooled to 23 ° C. To the obtained mixture, 25 parts of ethyl acetate and 30 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the recovered organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. By concentrating the obtained organic layer, 5.85 parts of the compound represented by the formula (I-43-d) was obtained.

4.20 parts of the compound represented by the formula (I-17-e), 5.06 parts of the compound represented by the formula (I-17-f) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. Then, the mixture was stirred at 60 ° C. for 1 hour. To the obtained mixture, 5.79 parts of the compound represented by the formula (I-43-d) was added, and the mixture was stirred at 60 ° C. for 1 hour. The obtained reaction mass was cooled to 23 ° C., 100 parts of ethyl acetate and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1). As a result, 3.10 parts of the compound represented by the formula (I-43) was obtained.
MASS (Mass Spectrometry): 297.1 [M + H] ⁺

式（Ｉ−４３）で表される化合物２．９５部、ｐ−トルエンスルホン酸１．８９部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、６０℃で１０時間攪拌した。得られた混合物を２３℃まで冷却した後、酢酸エチル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３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−３３）で表される化合物１．９５部を得た。
ＭＡＳＳ（質量分析）：２５７．１［Ｍ＋Ｈ］^＋ Synthesis Example 5: Synthesis of the compound represented by the formula (I-33)

2.95 parts of the compound represented by the formula (I-43), 1.89 parts of p-toluenesulfonic acid and 30 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then stirred at 60 ° C. for 10 hours. The obtained mixture was cooled to 23 ° C., 50 parts of ethyl acetate and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. By concentrating the obtained organic layer, 1.95 parts of the compound represented by the formula (I-33) was obtained.
MASS (Mass Spectrometry): 257.1 [M + H] ⁺

式（Ｉ−６７−ａ）で表される化合物２０部、式（Ｉ−１７−ｃ）で表される化合物２．２８部、酢酸エチル１００部及びテトラヒドロフラン１４部を混合し、２３℃で３０分間攪拌した後、１０℃まで冷却した。得られた混合溶液に、１０℃で、式（Ｉ−１７−ｂ）で表される化合物６．５５部を滴下し、２３℃に昇温後、２３℃で２時間攪拌した。得られた混合物に、イオン交換水７０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝１０／１）分取することにより、式（Ｉ−６７−ｄ）で表される化合物８．７５部を得た。

式（Ｉ−１７−ｅ）で表される化合物６．４０部、式（Ｉ−１７−ｆ）で表される化合物７．７０部及びアセトニトリル３２部を混合し、２３℃で３０分間攪拌した後、６０℃で１時間攪拌した。得られた混合物に、式（Ｉ−６７−ｄ）で表される化合物８．６５部を添加し、６０℃で１時間攪拌した。得られた反応マスを２３℃まで冷却した後、酢酸エチル１００部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を４回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−６７）で表される化合物９．８４部を得た。
ＭＡＳＳ（質量分析）：３１３．１［Ｍ＋Ｈ］^＋ Synthesis Example 6: Synthesis of the compound represented by the formula (I-67)

20 parts of the compound represented by the formula (I-67-a), 2.28 parts of the compound represented by the formula (I-17-c), 100 parts of ethyl acetate and 14 parts of tetrahydrofuran are mixed and 30 at 23 ° C. After stirring for minutes, the mixture was cooled to 10 ° C. 6.55 parts of the compound represented by the formula (I-17-b) was added dropwise to the obtained mixed solution at 10 ° C., the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 2 hours. 70 parts of ion-exchanged water was added to the obtained mixture, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1). As a result, 8.75 parts of the compound represented by the formula (I-67-d) was obtained.

6.40 parts of the compound represented by the formula (I-17-e), 7.70 parts of the compound represented by the formula (I-17-f) and 32 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. Then, the mixture was stirred at 60 ° C. for 1 hour. To the obtained mixture, 8.65 parts of the compound represented by the formula (I-67-d) was added, and the mixture was stirred at 60 ° C. for 1 hour. The obtained reaction mass was cooled to 23 ° C., 100 parts of ethyl acetate and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 4 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 9.84 parts of the compound represented by the formula (I-67) was obtained.
MASS (Mass Spectrometry): 313.1 [M + H] ⁺

式（Ｉ−６７）で表される化合物５．００部、１Ｎ塩酸２０部及びアセトニトリル３０部を混合し、２３℃で１０時間攪拌した。得られた混合物を、酢酸エチル５０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３回繰り返した。得られた有機層を濃縮した後、ｎ−ヘプタン１００部を添加し、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｉ−６８）で表される化合物３．７５部を得た。
ＭＡＳＳ（質量分析）：２４１．１［Ｍ＋Ｈ］^＋ Synthesis Example 7: Synthesis of the compound represented by the formula (I-68)

5.00 parts of the compound represented by the formula (I-67), 20 parts of 1N hydrochloric acid and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 10 hours. 50 parts of ethyl acetate was added to the obtained mixture, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. After concentrating the obtained organic layer, 100 parts of n-heptane was added, the mixture was stirred at 23 ° C. for 30 minutes, and then filtered to obtain 3.75 parts of the compound represented by the formula (I-68). rice field.
MASS (Mass Spectrometry): 241.1 [M + H] ⁺

式（Ｉ−２５−ａ）で表される化合物２．５０部、式（Ｉ−４３−ｄ）で表される化合物４．７４部、ジメチルホルムアミド２５部及び炭酸カリウム５．５７部を混合し、２３℃で３０分間攪拌した後、１２０℃で１８時間攪拌した。得られた混合物を２３℃まで冷却した後、イオン交換水８０部及び酢酸エチル８０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８０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３回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−４９−ｂ）で表される化合物５．０１部を得た。

式（Ｉ−２５−ｃ）で表される化合物８．５８部、式（Ｉ−２５−ｄ）で表される化合物２．７０部及びテトラヒドロフラン６０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、５℃で、式（Ｉ−４９−ｂ）で表される化合物５．００部を３０分かけて添加し、２３℃に昇温後、２３℃で１２時間攪拌した後、ろ過した。得られたろ液に、イオン交換水１００部及び酢酸エチル２００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１００部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を３回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−４９）で表される化合物３．２２部を得た。
ＭＡＳＳ（質量分析）：２６９．１［Ｍ＋Ｈ］^＋ Synthesis Example 8: Synthesis of the compound represented by the formula (I-49)

2.50 parts of the compound represented by the formula (I-25-a), 4.74 parts of the compound represented by the formula (I-43-d), 25 parts of dimethylformamide and 5.57 parts of potassium carbonate are mixed. After stirring at 23 ° C. for 30 minutes, the mixture was stirred at 120 ° C. for 18 hours. The obtained mixture was cooled to 23 ° C., 80 parts of ion-exchanged water and 80 parts of ethyl acetate were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 80 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 5.01 part of the compound represented by the formula (I-49-b) was obtained.

8.58 parts of the compound represented by the formula (I-25-c), 2.70 parts of the compound represented by the formula (I-25-d) and 60 parts of tetrahydrofuran were mixed and stirred at 23 ° C. for 30 minutes. After that, it was cooled to 5 ° C. To the obtained mixture, 5.00 parts of the compound represented by the formula (I-49-b) was added at 5 ° C. over 30 minutes, the temperature was raised to 23 ° C., and the mixture was stirred at 23 ° C. for 12 hours. , Filtered. To the obtained filtrate, 100 parts of ion-exchanged water and 200 parts of ethyl acetate were added, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to remove the organic layer. To the obtained organic layer, 100 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 3.22 parts of the compound represented by the formula (I-49) was obtained.
MASS (Mass Spectrometry): 269.1 [M + H] ⁺

式（Ｉ−４９）で表される化合物２．６７部、ｐ−トルエンスルホン酸１．８９部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、６０℃で１０時間攪拌した。得られた混合物を２３℃まで冷却した後、酢酸エチル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３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−３７）で表される化合物１．６９部を得た。
ＭＡＳＳ（質量分析）：２２９．１［Ｍ＋Ｈ］^＋ Synthesis Example 9: Synthesis of the compound represented by the formula (I-37)

2.67 parts of the compound represented by the formula (I-49), 1.89 parts of p-toluenesulfonic acid and 30 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then stirred at 60 ° C. for 10 hours. The obtained mixture was cooled to 23 ° C., 50 parts of ethyl acetate and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. By concentrating the obtained organic layer, 1.69 parts of the compound represented by the formula (I-37) was obtained.
MASS (Mass Spectrometry): 229.1 [M + H] ⁺

式（Ｉ−８１−ａ）で表される化合物５．００部、式（Ｉ−１７−ｃ）で表される化合物０．００８部及びトルエン５０部を混合し、２３℃で３０分間攪拌した後、１００℃まで昇温した。得られた混合溶液に、１００℃で、式（Ｉ−８１−ｂ）で表される化合物７．０５部を添加し、１１０℃で２時間攪拌した後、２３℃まで冷却した。得られた混合物に、酢酸エチル２５部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、イオン交換水３０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を３回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝１０／１）分取することにより、式（Ｉ−８１−ｄ）で表される化合物２．１９部を得た。

式（Ｉ−１７−ｅ）で表される化合物１．４０部、式（Ｉ−１７−ｆ）で表される化合物１．６９部及びアセトニトリル２０部を混合し、２３℃で３０分間攪拌した後、６０℃で１時間攪拌した。得られた混合物に、式（Ｉ−８１−ｄ）で表される化合物２．１２部を添加し、６０℃で１時間攪拌した。得られた反応マスを２３℃まで冷却した後、酢酸エチル５０部及びイオン交換水２５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、イオン交換水２５部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。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、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ；関東化学（株）製、展開溶媒：ｎ−ヘプタン／酢酸エチル＝１０／１）分取することにより、式（Ｉ−８１）で表される化合物１．０３部を得た。
ＭＡＳＳ（質量分析）：３１３．１［Ｍ＋Ｈ］^＋ Synthesis Example 10: Synthesis of the compound represented by the formula (I-81)

5.00 parts of the compound represented by the formula (I-81-a), 0.008 parts of the compound represented by the formula (I-17-c) and 50 parts of toluene were mixed and stirred at 23 ° C. for 30 minutes. After that, the temperature was raised to 100 ° C. To the obtained mixed solution, 7.05 parts of the compound represented by the formula (I-81-b) was added at 100 ° C., the mixture was stirred at 110 ° C. for 2 hours, and then cooled to 23 ° C. To the obtained mixture, 25 parts of ethyl acetate and 30 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the recovered organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1). As a result, 2.19 parts of the compound represented by the formula (I-81-d) was obtained.

1.40 parts of the compound represented by the formula (I-17-e), 1.69 parts of the compound represented by the formula (I-17-f) and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. Then, the mixture was stirred at 60 ° C. for 1 hour. To the obtained mixture, 2.12 parts of the compound represented by the formula (I-81-d) was added, and the mixture was stirred at 60 ° C. for 1 hour. The obtained reaction mass was cooled to 23 ° C., 50 parts of ethyl acetate and 25 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the recovered organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1). As a result, 1.03 parts of the compound represented by the formula (I-81) was obtained.
MASS (Mass Spectrometry): 313.1 [M + H] ⁺

式（Ｉ−８１）で表される化合物１．０３部、ｐ−トルエンスルホン酸０．６３部及びアセトニトリル１０部を混合し、２３℃で３０分間攪拌した後、６０℃で１０時間攪拌した。得られた混合物を２３℃まで冷却した後、酢酸エチル３０部及びイオン交換水１５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１５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３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ−７１）で表される化合物０．３８部を得た。
ＭＡＳＳ（質量分析）：２５７．１［Ｍ＋Ｈ］^＋ Synthesis Example 11: Synthesis of the compound represented by the formula (I-71)

1.03 parts of the compound represented by the formula (I-81), 0.63 parts of p-toluenesulfonic acid and 10 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then stirred at 60 ° C. for 10 hours. The obtained mixture was cooled to 23 ° C., 30 parts of ethyl acetate and 15 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. By concentrating the obtained organic layer, 0.38 part of the compound represented by the formula (I-71) was obtained.
MASS (Mass Spectrometry): 257.1 [M + H] ⁺

以下、これらのモノマーを式番号に応じて「モノマー（ａ１−１−１）」等という。 Synthesis of resin The compounds (monomers) used in the synthesis of resin are shown below.

Hereinafter, these monomers will be referred to as "monomer (a1-1-1)" or the like according to the formula number.

Example 1 [Synthesis of resin A1]
As the monomer, a monomer (a1-4-2), a monomer (III-8), a monomer (a1-2-6) and a monomer (I-17) are used, and their molar ratio [monomer (a1-4-2): Monomer (III-8): Monomer (a1-2-6): Monomer (I-17)] are mixed in a ratio of 19:25:38:18, and the total monomer is further added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A1 weight-average molecular weight of about 5.4 × 10 ³ in 84% yield. This resin A1 has the following structural units (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (a1-4-2) and the monomer (I-17) is 100%).

Example 2 [Synthesis of resin A2]
As the monomer, a monomer (a1-4-2), a monomer (III-8), a monomer (a1-2-6) and a monomer (I-17) are used, and their molar ratio [monomer (a1-4-2): Monomer (III-8): Monomer (a1-2-6): Monomer (I-17)] are mixed in a ratio of 19:25:38:18, and the total monomer is further added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, the polymerization reaction solution was cooled to 15 ° C., an aqueous p-toluenesulfonic acid solution was added, and the mixture was stirred for 6 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A2 weight-average molecular weight of about 5.6 × 10 ³ in 76% yield. This resin A2 has the following structural units (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (a1-4-2) and the monomer (I-17) is 64%).

Example 3 [Synthesis of resin A3]
As the monomer, a monomer (a1-4-2), a monomer (III-8) and a monomer (I-17) are used, and their molar ratio [monomer (a1-4-2): monomer (III-8): monomer ( I-17)] was mixed in a ratio of 19:63:18, and the monomer mixture was further mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A3 weight average molecular weight of about 5.2 × 10 ³ in 76% yield. This resin A3 has the following structural units (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (a1-4-2) and the monomer (I-17) is 100%).

Example 4 [Synthesis of resin A4]
Monomers (III-8) and monomer (I-17) are used as the monomers, and the mixture is mixed so that the molar ratio [monomer (III-8): monomer (I-17)] is 63:37. Further, this monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A4 weight average molecular weight of about 5.1 × 10 ³ in 77% yield. This resin A4 has the following structural unit (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (I-17) is 100%).

Example 5 [Synthesis of resin A5]
Monomers (III-1) and monomer (I-17) are used as the monomers, and the mixture is mixed so that the molar ratio [monomer (III-1): monomer (I-17)] is 63:37. Further, this monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A5 weight average molecular weight of about 5.8 × 10 ³ in 79% yield. This resin A5 has the following structural unit (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (I-17) is 100%).

Example 6 [Synthesis of resin A6]
As the monomers, the monomer (a1-4-2), the monomer (III-8), the monomer (a1-2-6), the monomer (a2-1-3), the monomer (a3-4-2) and the monomer (I-). 17) is used and its molar ratio [monomer (a1-4-2): monomer (III-8): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2) ): Monomer (I-17)] is mixed in a ratio of 12:20:35: 3:15:15, and further, 1.5 is added to this monomer mixture with respect to the total mass of all the monomers. A mass-folded methylisobutylketone was mixed. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A6 weight average molecular weight of about 5.2 × 10 ³ in 77% yield. This resin A6 has the following structural units (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (a1-4-2) and the monomer (I-17) is 100%).

Example 7 [Synthesis of Resin A7]
As the monomer, a monomer (III-8), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I-17) are used, and their molar ratio [monomer (III-8): monomer (monomer) a2-1-3): Monomer (a3-4-2): Monomer (I-17)] is mixed so as to have a ratio of 55: 3: 15: 27, and further, all the monomers are added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A7 weight average molecular weight of about 5.0 × 10 ³ in 66% yield. This resin A7 has the following structural unit (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (I-17) is 100%).

Example 8 [Synthesis of resin A8]
As the monomers, the monomer (I-17), the monomer (III-1), the monomer (a1-1-1), the monomer (a2-1-1), the monomer (a7-1) and the monomer (a3-1-1). [Monomer (I-17): Monomer (III-1): Monomer (a1-1-1): Monomer (a2-1-1): Monomer (a7-1): Monomer (a3-) 1-1)] was mixed so as to be 20:15:35: 5: 5: 20, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.1 mol% and 3.3 mol%, respectively, based on the total amount of monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was dissolved again in propylene glycol monomethyl ether acetate, an aqueous p-toluenesulfonic acid solution was added, and the mixture was stirred for about 6 hours, and then separated to recover the organic layer. The recovered organic layer is poured into a methanol / water mixed solvent to precipitate a resin, and the resin is filtered to obtain a resin A8 (copolymer) having ^{a weight average molecular weight of 5.7 × 10 3 in a yield of 81%.} Obtained. This resin A8 has the following structural unit (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (I-17) is 100%).

Example 9 [Synthesis of Resin A9]
Monomers (III-8) and monomer (I-25) are used as the monomers, and the mixture is mixed so that the molar ratio [monomer (III-8): monomer (I-25)] is 63:37. Further, this monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A9 weight average molecular weight of about 5.2 × 10 ³ in 77% yield. This resin A9 has the following structural unit (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (I-25) is 100%).

Example 10 [Synthesis of Resin A10]
As the monomer, a monomer (a1-4-2), a monomer (III-8), a monomer (a1-2-6) and a monomer (I-33) are used, and their molar ratio [monomer (a1-4-2): Monomer (III-8): Monomer (a1-2-6): Monomer (I-33)] are mixed in a ratio of 19:25:38:18, and the total monomer is further added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A10 weight average molecular weight of about 5.3 × 10 ³ in 82% yield. This resin A10 has the following structural units.

Example 11 [Synthesis of resin A11]
As the monomer, a monomer (a1-4-2), a monomer (III-8) and a monomer (I-33) are used, and their molar ratio [monomer (a1-4-2): monomer (III-8): monomer ( I-33)] was mixed in a ratio of 19:63:18, and the monomer mixture was further mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A11 weight average molecular weight of about 5.1 × 10 ³ in 75% yield. This resin A11 has the following structural units.

Example 12 [Synthesis of Resin A12]
Monomer (III-8) and monomer (I-33) are used as the monomer, and the mixture is mixed so that the molar ratio [monomer (III-8): monomer (I-33)] is 63:37. Further, this monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Thereafter, the polymerization reaction solution, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A12 weight average molecular weight of about 5.0 × 10 ³ in 73% yield. This resin A12 has the following structural units.

Example 13 [Synthesis of Resin A13]
Monomers (III-1) and monomer (I-33) are used as the monomers, and the mixture is mixed so that the molar ratio [monomer (III-1): monomer (I-33)] is 63:37. Further, this monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Thereafter, the polymerization reaction solution, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A13 weight average molecular weight of about 5.4 × 10 ³ in 71% yield. This resin A13 has the following structural units.

Example 14 [Synthesis of resin A14]
As the monomer, acetoxystyrene, monomer (III-8), monomer (a1-2-6) and monomer (I-43) are used, and their molar ratios are [acetoxystyrene: monomer (III-8): monomer (a1-2). -6): Monomer (I-43)] was mixed in a ratio of 37:20:32:11, and the monomer mixture was further multiplied by 1.5 by mass with respect to the total mass of all the monomers. Methyl isobutyl ketone was mixed. Azobisisobutyronitrile as an initiator was added to the obtained mixture so as to be 7 mol% based on the total number of moles of all the monomers, and this was heated at 85 ° C. for about 5 hours to carry out polymerization. rice field. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The resulting organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and recovered, the resin weight average molecular weight of about 5.1 × 10 ³ A14 (copolymer) Yield 72 Obtained in%. This resin A14 has the following structural units.

Example 15 [Synthesis of Resin A15]
As the monomers, the monomer (a1-4-2), the monomer (III-8), the monomer (a1-2-6), the monomer (a2-1-3), the monomer (a3-4-2) and the monomer (I-). 33) is used and its molar ratio [monomer (a1-4-2): monomer (III-8): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2) ): Monomer (I-33)] is mixed in a ratio of 12:20:35: 3:15:15, and further, 1.5 is added to this monomer mixture with respect to the total mass of all the monomers. A mass-folded methylisobutylketone was mixed. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A15 weight average molecular weight of about 5.1 × 10 ³ in 79% yield. This resin A15 has the following structural units.

Example 16 [Synthesis of Resin A16]
As the monomer, a monomer (III-8), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I-33) are used, and their molar ratio [monomer (III-8): monomer (monomer (III-8)): a2-1-3): Monomer (a3-4-2): Monomer (I-33)] is mixed so as to have a ratio of 55: 3: 15: 27, and further, all the monomers are added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Thereafter, the polymerization reaction solution, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A16 weight average molecular weight of about 5.1 × 10 ³ in 68% yield. This resin A16 has the following structural units.

Example 17 [Synthesis of Resin A17]
As the monomers, the monomer (I-33), the monomer (III-1), the monomer (a1-1-1), the monomer (a2-1-1), the monomer (a7-1) and the monomer (a3-1-1). [Monomer (I-33): Monomer (III-1): Monomer (a1-1-1): Monomer (a2-1-1): Monomer (a7-1): Monomer (a3-) 1-1)] was mixed so as to be 20:15:35: 5: 5: 20, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.1 mol% and 3.3 mol%, respectively, based on the total amount of monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is dissolved again in propylene glycol monomethyl ether acetate, poured into a mixed solvent of methanol / water to precipitate the resin, and the resin is filtered to obtain a resin A17 ^{having a weight average molecular weight of 5.6 × 10 3 (} Copolymer) was obtained in a yield of 77%. This resin A17 has the following structural units.

Example 18 [Synthesis of resin A18]
As the monomer, a monomer (a1-4-2), a monomer (III-8), a monomer (a1-2-6) and a monomer (I-68) are used, and their molar ratio [monomer (a1-4-2): Monomer (III-8): Monomer (a1-2-6): Monomer (I-68)] was mixed in a ratio of 19:25:38:18, and the total monomer was further added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A18 weight average molecular weight of about 5.1 × 10 ³ in 75% yield. This resin A18 has the following structural units.

Example 19 [Synthesis of Resin A19]
As the monomer, acetoxystyrene, monomer (III-8), monomer (a1-2-6) and monomer (I-67) are used, and their molar ratios are [acetoxystyrene: monomer (III-8): monomer (a1-2). -6): Monomer (I-67)] was mixed in a ratio of 37:20:32:11, and the monomer mixture was added 1.5 times by mass with respect to the total mass of all the monomers. Methylisobutylketone was mixed. Azobisisobutyronitrile as an initiator was added to the obtained mixture so as to be 7 mol% based on the total number of moles of all the monomers, and this was heated at 85 ° C. for about 5 hours to carry out polymerization. rice field. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The resulting organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and recovered, yield 78 resin A19 (copolymer) is the weight average molecular weight of about 5.3 × 10 ³ Obtained in%. This resin A19 has the following structural units.

Example 20 [Synthesis of Resin A20]
Monomer (III-8) and monomer (I-37) are used as the monomer, and the mixture is mixed so that the molar ratio [monomer (III-8): monomer (I-37)] is 63:37. Further, this monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Thereafter, the polymerization reaction solution, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A20 weight average molecular weight of about 5.1 × 10 ³ in 75% yield. This resin A20 has the following structural units.

Example 21 [Synthesis of resin A21]
As the monomer, acetoxystyrene, monomer (III-8), monomer (a1-2-6) and monomer (I-49) are used, and their molar ratios are [acetoxystyrene: monomer (III-8): monomer (a1-2). -6): Monomer (I-49)] was mixed in a ratio of 37:20:32:11, and the monomer mixture was added 1.5 times by mass with respect to the total mass of all the monomers. Methyl isobutyl ketone was mixed. Azobisisobutyronitrile as an initiator was added to the obtained mixture so as to be 7 mol% based on the total number of moles of all the monomers, and this was heated at 85 ° C. for about 5 hours to carry out polymerization. rice field. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The resulting organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and recovered, yield 70 resin A21 (copolymer) is the weight average molecular weight of about 5.4 × 10 ³ Obtained in%. This resin A21 has the following structural units.

Example 22 [Synthesis of Resin A22]
As the monomer, a monomer (III-8), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I-37) are used, and their molar ratio [monomer (III-8): monomer (monomer) a2-1-3): Monomer (a3-4-2): Monomer (I-37)] is mixed so as to have a ratio of 55: 3: 15: 27, and further, all the monomers are added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Thereafter, the polymerization reaction solution, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A22 weight average molecular weight of about 5.3 × 10 ³ in 70% yield. This resin A22 has the following structural units.

Example 23 [Synthesis of resin A23]
Monomer (III-8) and monomer (I-71) are used as the monomer, and the mixture is mixed so that the molar ratio [monomer (III-8): monomer (I-71)] is 63:37. Further, this monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Thereafter, the polymerization reaction solution, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A23 weight average molecular weight of about 5.4 × 10 ³ in 66% yield. This resin A23 has the following structural units.

Example 24 [Synthesis of Resin A24]
As the monomer, acetoxystyrene, monomer (III-8), monomer (a1-2-6) and monomer (I-81) are used, and their molar ratios are [acetoxystyrene: monomer (III-8): monomer (a1-2). -6): Monomer (I-81)] was mixed so that the ratio was 37:20:32:11, and the monomer mixture was added 1.5 times by mass with respect to the total mass of all the monomers. Methyl isobutyl ketone was mixed. Azobisisobutyronitrile as an initiator was added to the obtained mixture so as to be 7 mol% based on the total number of moles of all the monomers, and this was heated at 85 ° C. for about 5 hours to carry out polymerization. rice field. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The resulting organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and recovered, yield 62 resin A24 (copolymer) is the weight average molecular weight of about 5.5 × 10 ³ Obtained in%. This resin A24 has the following structural units.

Example 25 [Synthesis of Resin A25]
As the monomer, a monomer (III-8), a monomer (a2-1-3), a monomer (a3-4-2) and a monomer (I-71) are used, and the molar ratio [monomer (III-8): monomer (monomer (III-8)): a2-1-3): Monomer (a3-4-2): Monomer (I-71)] is mixed so as to have a ratio of 55: 3: 15: 27, and further, all the monomers are added to this monomer mixture. Methyl isobutyl ketone was mixed in an amount of 1.5 times by mass based on the total mass of the above. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Thereafter, the polymerization reaction solution, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin A25 weight average molecular weight of about 5.4 × 10 ³ in 60% yield. This resin A25 has the following structural units.

Synthesis Example 12 [Synthesis of resin AX1]
As the monomer, a monomer (ax-1), a monomer (ax-2) and a monomer (I-17) are used, and their molar ratios are [monomer (ax-1): monomer (ax-2): monomer (I-17). ] Was mixed at a ratio of 30:30:40, and further, 1.5 times by mass of methyl isobutyl ketone was mixed with this monomer mixture with respect to the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.2 mol% and 3.6 mol%, respectively, based on the total amount of monomers, and these were added 73. It was heated at ° C. for about 5 hours. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours and then separated. The recovered organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and collection, to obtain a resin AX1 weight average molecular weight of about 5.4 × 10 ³ in 66% yield. This resin AX1 has the following structural unit (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (I-17) is 100%).

Synthesis Example 13 [Synthesis of resin AX2]
As the monomers, the monomer (a1-4-2), the monomer (III-1), the monomer (a1-1-1), the monomer (a2-1-1), the monomer (a7-1) and the monomer (a3-1-1). 1) is used, and the molar ratio [monomer (a1-4-2): monomer (III-1): monomer (a1-1-1): monomer (a2-1-1): monomer (a7-1): The monomer (a3-1-1)] was mixed so as to be 20:15:35: 5: 5: 20, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomer was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.1 mol% and 3.3 mol%, respectively, based on the total amount of monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was dissolved again in propylene glycol monomethyl ether acetate, an aqueous p-toluenesulfonic acid solution was added, and the mixture was stirred for about 6 hours, and then separated to recover the organic layer. The recovered organic layer is poured into a methanol / water mixed solvent to precipitate a resin, and the resin is filtered to obtain a resin AX2 (copolymer) having ^{a weight average molecular weight of 5.7 × 10 3 in a yield of 83%.} Obtained. This resin AX2 has the following structural unit (the elimination rate of the ethoxyethyl group in all the ethoxyethyl groups of the monomer (a1-4-2) is 100%).

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

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

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ４００部
プロピレングリコールモノメチルエーテル １５０部
γ−ブチロラクトン ５部 <Resin>
A1 to A25, AX1, AX2: Resin A1 to Resin A25, Resin AX1, Resin AX2
<Acid generator (B)>
B1-43: Salt represented by the formula (B1-43) (synthesized according to an example of JP-A-2016-47815)

<Quencher (C)>
C1: Synthesized by the method described in JP2011-39502.

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

(Evaluation of electron beam exposure of resist composition)
A 6 inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds. The resist composition was spin-coated on this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, on a direct hot plate, a composition layer was formed by prebaking at the temperature shown in the “PB” column of Table 1 for 60 seconds. A contact hole pattern (hole pitch 40 nm / hole) is used on the composition layer formed on the wafer by using an electron beam drawing machine [“ELS-F125 125keV” manufactured by Elionix Inc.] and the exposure amount is changed stepwise. Diameter 17 nm) was drawn directly.
After exposure, post-exposure baking is performed on a hot plate at the temperature shown in the “PEB” column of Table 1 for 60 seconds, and further paddle development is performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. , A resist pattern was obtained.

In the resist pattern obtained after development, the exposure amount at which the formed hole diameter was 17 nm was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In the effective sensitivity, the hole diameter of the pattern formed with the hole diameter of 17 nm was measured 24 times per hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was determined by measuring the average hole diameter of a pattern formed with a hole diameter of 17 nm at 400 points on the same wafer as a population.
The results are shown in Table 2. The numbers in the table indicate the standard deviation (nm).

Since the resist composition containing the resin of the present invention is excellent in CD uniformity (CDU) of the obtained resist pattern, it is suitable for microfabrication of semiconductors and is extremely useful in industry.

Claims (13)

A resin containing a structural unit represented by the formula (I) and a structural unit represented by the formula (III).

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
X ¹ represents a single bond or -CO-O- * (* represents the binding ^{site with Ar 1).}
X ² is -CO-O- *, _{-O- *, -O-CO- *, -O-CO- (CH 2} ) _mm- O- * or -O- (CH ₂ ) _nn- CO-O. -* (* Represents the binding ^{site with Ar 2).}
mm and nn represent 0 or 1.
Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent.
Each of R ² independently represents a hydrogen atom or an acid unstable group, or ^{when two or more R 2} are present, the two R ² may be combined to form a group having an acetal ring structure. ..
n represents an integer of 1 to 3. When n is any integer of 2 or more, the plurality of R ^2s may be the same or different from each other. ]

[In equation (III),
R ¹¹ represents a hydrogen atom or a methyl group.
R ¹² , R ¹³ and R ¹⁴ independently have 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 20 carbon atoms, and 6 to 18 carbon atoms. R ¹² and R ¹³ bond with each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.
X ¹¹ represents a single bond, -CO-O-* or -CO-NR ¹⁵ - * represents * represents a bond to Ar ^11, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Represents.
X ¹² represents a single bond, * - O-L ¹¹ - or * -CO-O-L ¹² - represents * represents a bond to Ar ^11, L ¹¹ and L ¹² independently represents a carbon Represents an alkanediyl group of numbers 1 to 4.
Ar ¹¹ represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. ] The resin according to claim 1, wherein X ^{1 is a single bond.} The resin according to claim 1 or 2, wherein X ² is -CO-O- * or -O- * (* ^{represents a binding site with Ar 2).} The resin according to any one of claims 1 to 3, wherein n is 1 or 2. Acid labile group in R ² is a resin according to claim 1 is a group represented by the group or the formula represented by the formula (1a) (2a).

[In the formula (1a), ^Raa1 , ^Raa2 and ^Raa3 independently have an alkyl group having 1 to 8 carbon atoms which may have a substituent and a carbon number which may have a substituent. An alkenyl group of 2 to 8, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. Or, ^Raa1 and ^Raa2 bond with each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.
naa represents 0 or 1.
* Represents a bond. ]

Wherein (2a), R ^{aa1 'and} R ^aa2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^{aa3 'is} a hydrocarbon group having 1 to 20 carbon atoms represents or R ^{aa2 'and} R ^aa3' is bonded to -C-X a to which they are attached to one another ^- to form together with heterocyclic group having 3 to 20 carbon atoms, the hydrocarbon group and heterocyclic group The included −CH ₂₋ may be replaced by −O− or −S−.
X ^a represents an oxygen atom or a sulfur atom.
* Represents a bond. ] Or R ² is a hydrogen atom, or n is at least 2 and a resin according to claim 1 which forms a group having an acetal ring structure two R ² are taken together .. The resin according to any one of claims 1 to 6, wherein X ¹¹ and X ^{12 are both single bonds.} The resin according to any one of claims 1 to 7, further comprising a structural unit represented by the formula (a2-A).

[In formula (a2-A),
R ^a50 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a51 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 of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or ^* −X ^a51 − (A ^a52 −X ^a52 ) _nb −, and * represents a binding site with a carbon atom to which ^{−R a50 is bonded.}
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 independently represent -O-, -CO-O- or -O-CO-, respectively.
nb represents 0 or 1.
mb represents any integer from 0 to 4. When mb is any integer of 2 or more, the plurality of Ra ^51s may be the same or different from each other. ] The resin according to any one of claims 1 to 8, further comprising at least one selected from the group consisting of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2).

[In the formula (a1-1) and the formula (a1-2),
^La1 and ^La2 independently represent -O- or * -O- (CH ₂ ) _k1- CO-O-, k1 represents an integer of 1 to 7, and * represents -CO-. Represents a bond with.
R ^a4 and R ^a5 independently represent a hydrogen atom or a methyl group, respectively.
R ^a6 and R ^a7 independently have an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group or a group combining these groups.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ] A resist composition containing the resin according to any one of claims 1 to 9 and an acid generator. The resist composition according to claim 10, wherein the acid generator contains a salt represented by the formula (B1).

[In equation (B1),
Q ^b1 and Q ^b2 independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH _2- may be replaced with −O−, −S (O) _{2− or −CO−.}
Z ⁺ represents an organic cation. ] The resist composition according to claim 10 or 11, further comprising a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. (1) A step of applying the resist composition according to any one of claims 10 to 12 onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A step of heating the composition layer after exposure, and (5) A step of developing the composition layer after heating,
A method for producing a resist pattern including.