JP2017120403A - Compound, resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition capable of producing a resist pattern with good line edge roughness.SOLUTION: The resist composition contains a resin (A) having a structural unit derived from a compound represented by formula (I), a resin (X) containing a structural unit represented by formula (a4), and an acid generator. [In the formula (I), Rrepresents an alkyl group which may have a halogen atom, a hydrogen atom, or a halogen atom; Rand Reach represent an alkyl group; R represents a 1-adamantyl group which may have an alkyl group, or *-CHRR; Rand Reach represent a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or a group composed of a combination thereof, or Rand Rare bonded to each other to form an alicyclic hydrocarbon group together with a carbon atom to which they are bonded; Rrepresents a hydrogen atom or a methyl group; and Rrepresents a saturated hydrocarbon group having a fluorine atom.]SELECTED DRAWING: None

Description

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

特許文献２には、下記化合物に由来する構造単位を含む樹脂を含有するレジスト組成物が記載されている。

特許文献３には、下記構造単位からなる樹脂を含有するレジスト組成物が記載されている。

Patent Document 1 describes a resist composition containing a resin containing a structural unit derived from the following compound.

Patent Document 2 describes a resist composition containing a resin containing a structural unit derived from the following compound.

Patent Document 3 describes a resist composition containing a resin composed of the following structural units.

JP 2008-268740 A Japanese Patent Laid-Open No. 11-24274 JP 2009-271253 A

  A resist pattern formed from a resist composition containing the above resin may not always satisfy line edge roughness (LER).

［式（Ｉ）中、
Ｒ^１は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
Ｒは、炭素数１〜８のアルキル基を有してもよい１−アダマンチル基又は＊−ＣＨＲ^４Ｒ^５を表す。＊は結合位を表す。
Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^４及びＲ^５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３〜１８の２価の脂環式炭化水素基を形成する。］

［式（ａ４）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ｒ^a42は、炭素数１〜２４のフッ素原子を有する飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］
〔２〕Ｒは、アダマンチル基又はＲ^４及びＲ^５が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３〜１２の２価の脂環式炭化水素基である〔１〕記載のレジスト組成物。
〔３〕Ｒ^２及びＲ^３は、メチル基である〔１〕又は〔２〕記載のレジスト組成物。
〔４〕式（ａ４）で表される構造単位が、式（ａ４−０）で表される構造単位、式（ａ４−１）で表される構造単位、式（ａ４−２）で表される構造単位及び式（ａ４−３）で表される構造単位からなる群から選ばれる少なくとも一種である〔１〕〜〔３〕のいずれかに記載レジスト組成物。

［式（ａ４−０）中、
Ｒ^f1は、水素原子又はメチル基を表す。
Ｒ^f2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。］

［式（ａ４−１）中、
Ｒ^f3は、水素原子又はメチル基を表す。
Ｌ³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メチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｒ^f4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、Ｌ³及びＲ^f4の合計炭素数の上限は２１である。］

［式（ａ４−２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ⁴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メチレン基は、酸素原子又はカルボニル基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、Ｌ⁴及びＲ^f6の合計炭素数の上限は２１である。］

［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、カルボニルオキシ基又はオキシカルボニル基を表す。
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。］
〔５〕酸発生剤が、式（Ｂ１）で表される塩である〔１〕〜〔４〕のいずれかに記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ¹及びＱ²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−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の１価の脂環式炭化水素基を表し、該アルキル基及び該１価の脂環式炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＳＯ₂−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。］
〔６〕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〔１〕〜〔５〕のいずれかに記載のレジスト組成物。
〔７〕（１）〔１〕〜〔６〕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。
〔８〕式（ＩＡ）で表される化合物。

［式（ＩＡ）中、
Ｒ^１は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
Ｒ^Ａは、炭素数１〜８のアルキル基を有してもよい１−アダマンチル基又は＊−ＣＨＲ^４AＲ^５Aを表す。＊は結合位を表す。
Ｒ^４Ａ及びＲ^５Ａは、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^４Ａ及びＲ^５Ａ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３〜１８の２価の脂環式炭化水素基を形成する。］
〔９〕〔８〕に記載の式（ＩＡ）で表される化合物に由来する構造単位を有する樹脂。 The present invention includes the following inventions.
[1] Resist composition containing resin (A) having a structural unit derived from a compound represented by formula (I), resin (X) containing a structural unit represented by formula (a4), and an acid generator .

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms.
R represents a 1-adamantyl group or * -CHR ⁴ R ⁵ which may have an alkyl group having 1 to 8 carbon atoms. * Represents a bonding position.
R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof, or R ⁴ and R ^5. Are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms together with the carbon atom to which they are bonded. ]

[In the formula (a4),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]
[2] R is an adamantyl group or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms together with carbon atoms to which R ⁴ and R ⁵ are bonded to each other, and the resist composition according to [1] object.
[3] The resist composition according to [1] or [2], wherein R ² and R ³ are methyl groups.
[4] The structural unit represented by the formula (a4) is represented by the structural unit represented by the formula (a4-0), the structural unit represented by the formula (a4-1), or the formula (a4-2). The resist composition according to any one of [1] to [3], which is at least one selected from the group consisting of a structural unit represented by formula (a4-3) and a structural unit represented by formula (a4-3):

[In the formula (a4-0),
R ^f1 represents a hydrogen atom or a methyl group.
R ^f2 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]

[In the formula (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ³ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.
R ^f4 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 ³ and R ^f4 is 21. ]

[In the formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴ and R ^f6 is 21. ]

[In the formula (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a C 1-18 divalent saturated hydrocarbon group which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
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. ]
[5] The resist composition according to any one of [1] to [4], wherein the acid generator is a salt represented by the formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, the alkyl group and the monovalent —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced with —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]
[6] The resist composition according to any one of [1] to [5], further including a salt that generates an acid having a lower acidity than an acid generated from an acid generator.
[7] (1) A step of applying the resist composition according to any one of [1] to [6] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.
[8] A compound represented by the formula (IA).

[In the formula (IA),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms.
R ^A represents a 1-adamantyl group or * -CHR ^4A R ^5A which may have an alkyl group having 1 to 8 carbon atoms. * Represents a bonding position.
R ^4A and R ^5A each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof, or R ^4A and R ^5A are bonded to each other. Then, a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms is formed together with the carbon atom to which they are bonded. ]
[9] A resin having a structural unit derived from the compound represented by the formula (IA) according to [8].

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

In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. The notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning.
In addition, unless otherwise specified, groups such as “aliphatic hydrocarbon group” that can be linear, branched and / or ring include both. The “aromatic hydrocarbon group” also includes a group in which a hydrocarbon group is bonded to an aromatic ring. When stereoisomers exist, all stereoisomers are included.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition.

[Resist composition]
The resist composition of the present invention comprises:
A resin (A) having a structural unit derived from the compound represented by the formula (I),
Resin (X) containing the structural unit represented by Formula (a4) and an acid generator (hereinafter may be referred to as “acid generator (B)”) are contained.
The resist composition preferably contains a quencher (hereinafter sometimes referred to as “quencher (C)”) and / or a solvent (hereinafter sometimes referred to as “solvent (E)”).

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

［式（Ｉ）中、
Ｒ^１は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
Ｒは、炭素数１〜８のアルキル基を有してもよい１−アダマンチル基又は＊−ＣＨＲ^４Ｒ^５を表す。＊は結合位を表す。
Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^４及びＲ^５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３〜１８の２価の脂環式炭化水素基を形成する。］ <Compound (I)>

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms.
R represents a 1-adamantyl group or * -CHR ⁴ R ⁵ which may have an alkyl group having 1 to 8 carbon atoms. * Represents a bonding position.
R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof, or R ⁴ and R ^5. Are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms together with the carbon atom to which they are bonded. ]

Examples of the alkyl group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. Preferably, it is a C1-C4 alkyl group, More preferably, they are a methyl group and an ethyl group.
Examples of the halogen atom for R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having a halogen atom of R ¹ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. A hexyl group, a perchloromethyl group, a perbromomethyl group, a periododomethyl group, etc. are mentioned.
R ¹ is preferably a hydrogen atom or a methyl group.

Examples of the alkyl group for R ² and R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group, and preferably an alkyl group having 1 to 3 carbon atoms. More preferably a methyl group and an ethyl group, and still more preferably a methyl group.

Examples of the alkyl group that the adamantyl group of R may have include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n. -Hexyl group etc. are mentioned, Preferably it is a C1-C4 alkyl group, More preferably, they are a methyl group and an ethyl group.
Examples of the alkyl group of R ⁴ and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group, and preferably an alkyl group having 1 to 3 carbon atoms. More preferably a methyl group and an ethyl group, and still more preferably a methyl group.
The alicyclic hydrocarbon group for R ⁴ and R ⁵ may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group. The alicyclic hydrocarbon group for R ⁴ and R ⁵ preferably has 3 to 12 carbon atoms.
Examples of the group combining the alkyl group of R ⁴ and R ⁵ and the alicyclic hydrocarbon group include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, and a methyl group. Examples thereof include a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, and a norbornylmethyl group.

なお、Ｒ^４及びＲ^５が互いに結合して形成する脂環式炭化水素基に含まれる水素原子は、炭素数１〜８のアルキル基で置換されていてもよい。この場合、酸素原子に結合する炭素原子にはアルキル基は置換されない。
Ｒは、好ましくは、単環のシクロアルキル基又は１−アダマンチル基であり、より好ましくは、シクロペンチル基、シクロヘキシル基である。 Examples of —CHR ⁴ R ^{5 in the} case where R ⁴ and R ⁵ are bonded to each other to form a divalent alicyclic hydrocarbon group include the following groups. The divalent alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a monocyclic cycloalkanediyl group. * Represents a bond with -O-.

In addition, the hydrogen atom contained in the alicyclic hydrocarbon group formed by combining R ⁴ and R ⁵ with each other may be substituted with an alkyl group having 1 to 8 carbon atoms. In this case, the alkyl group is not substituted on the carbon atom bonded to the oxygen atom.
R is preferably a monocyclic cycloalkyl group or 1-adamantyl group, and more preferably a cyclopentyl group or a cyclohexyl group.

Examples of the compound (I) include a compound represented by the following formula and a compound in which a methyl group corresponding to R ¹ is replaced with a hydrogen atom.

［式（ＩＡ）中、
Ｒ^１は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
Ｒ^Ａは、炭素数１〜８のアルキル基を有してもよい１−アダマンチル基又は＊−ＣＨＲ^４AＲ^５Aを表す。＊は結合位を表す。
Ｒ^４Ａ及びＲ^５Ａは、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^４Ａ及びＲ^５Ａ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３〜１８の２価の脂環式炭化水素基を形成する。］ <Compound (IA)>

[In the formula (IA),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms.
R ^A represents a 1-adamantyl group or * -CHR ^4A R ^5A which may have an alkyl group having 1 to 8 carbon atoms. * Represents a bonding position.
R ^4A and R ^5A each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof, or R ^4A and R ^5A are bonded to each other. Then, a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms is formed together with the carbon atom to which they are bonded. ]

  Examples of the compound (IA) include compounds represented by the above formulas (I-1) to (I-18).

溶媒としては、クロロホルム、テトラヒドロフラン及びトルエンなどが挙げられる。
塩基触媒としては、ピリジン、ジメチルアミノピリジンなどが挙げられる。
式（ＩＡ−ｂ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場より容易に入手することができる。

化合物（ＩＡ−ａ）は、式（ＩＡ−ｃ）で表される化合物と式（ＩＡ−ｄ）で表される化合物とを触媒の存在下、溶媒中で、反応させることにより製造することができる。

溶媒としては、クロロホルム、テトラヒドロフラン及びトルエンなどが挙げられる。
触媒としては、塩基触媒（例えば、ピリジン、ジメチルアミノピリジン）及び公知のエステル化触媒（例えば、酸触媒やカルボジイミド触媒など）などが挙げられ、塩基触媒及び公知のエステル化触媒を共存させてもよい。
式（ＩＡ−ｃ）で表される化合物は、例えば、以下で表される化合物などが挙げられ、市場より容易に入手できる。

式（ＩＡ−ｄ）で表される化合物は、例えば、以下で表される化合物などが挙げられ、市場より容易に入手できる。

カルボジイミド触媒としては、下記式で表される塩等が挙げられ、市場より容易に入手することができる。

<Method for Producing Compound (IA)>
Compound (IA) can be produced by reacting a compound represented by formula (IA-a) with a compound represented by formula (IA-b) in the presence of a base catalyst in a solvent. . In the following formulae, R ¹ , R ² , R ³ and R are as defined above.

Examples of the solvent include chloroform, tetrahydrofuran and toluene.
Examples of the base catalyst include pyridine and dimethylaminopyridine.
Examples of the compound represented by the formula (IA-b) include compounds represented by the following formula, and can be easily obtained from the market.

Compound (IA-a) can be produced by reacting a compound represented by formula (IA-c) with a compound represented by formula (IA-d) in the presence of a catalyst in a solvent. it can.

Examples of the solvent include chloroform, tetrahydrofuran and toluene.
Examples of the catalyst include a base catalyst (for example, pyridine, dimethylaminopyridine) and a known esterification catalyst (for example, an acid catalyst, a carbodiimide catalyst, etc.), and a base catalyst and a known esterification catalyst may coexist. .
Examples of the compound represented by the formula (IA-c) include compounds represented by the following, and can be easily obtained from the market.

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

Examples of the carbodiimide catalyst include salts represented by the following formulas and can be easily obtained from the market.

The resin (A) may be a homopolymer containing one type of structural unit (I) or a copolymer containing two or more types of structural units (I).
Resin (A) may consist only of structural unit (I), or may contain structural units other than structural unit (I). In resin (A), the content rate of structural unit (I) is 1-100 mol% with respect to all the structural units of resin (A), 3-60 mol% is preferable, and 5-50 mol% is preferable. More preferably, 10-40 mol% is further more preferable.

  The structural unit other than the structural unit (I) that may be contained in the resin (A) is a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). ), Structural units not having acid labile groups (hereinafter sometimes referred to as “structural units (s)”), other structural units (hereinafter referred to as “structural units”). (T) ") and structural units derived from monomers known in the art.

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を形成する。
ｎａは、０又は１を表す。
＊は結合手を表す。］

［式（２）中、Ｒ^a1’及びＲ^a2’は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a3’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a2’及びＲ^a3’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３〜２０の２価の複素環基を形成し、該炭化水素基及び該２価の複素環基に含まれる−ＣＨ₂−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。
＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”). The acid labile group contained in the structural unit (a1) is preferably the following group (1) and / or group (2).

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

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

アルキル基と脂環式炭化水素基とを組み合わせた基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基、メチルアダマンチル基、シクロヘキシルメチル基、メチルシクロヘキシルメチル基、アダマンチルメチル基、ノルボルニルメチル基等が挙げられる。
ｎａは、好ましくは０である。 ^Examples of the alkyl group represented by R ^{a1 to} R ^a3 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.
The alicyclic hydrocarbon group for R ^{a1 to} R ^a3 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 preferably has 3 to 16 carbon atoms.

Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, methyladamantyl group, cyclohexylmethyl group, methylcyclohexylmethyl group, and adamantylmethyl. Group, norbornylmethyl group and the like.
na is preferably 0.

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) when R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group include the following groups. The divalent alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
^{Examples of the} divalent heterocyclic group formed together with the carbon atom and X to which R ^{a2 ′} and R ^{a3 ′} are bonded to each other and X include the following groups. * Represents a bond.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^{a1 to} R ^a3 are alkyl groups in the formula (1), preferably a tert-butoxycarbonyl group), 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- ( And adamantane-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).
At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

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

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

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

  As a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (1), a structural unit represented by the formula (a1-0) is preferably represented by the formula (a1-1). The structural unit represented by a structural unit or a formula (a1-2) is mentioned. These may be used alone or in combination of two or more. In this specification, the structural unit represented by formula (a1-0), the structural unit represented by formula (a1-1), and the structural unit represented by formula (a1-2) are each represented by structural unit (a1). -0), structural unit (a1-1) and structural unit (a1-2), a monomer for deriving structural unit (a1-0), a monomer for deriving structural unit (a1-1), and a structural unit (a1- The monomer that induces 2) may be referred to as monomer (a1-0), monomer (a1-1), and monomer (a1-2), respectively.

［式（ａ１−０）中、
Ｌ^a01は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k01−ＣＯ−Ｏ−を表し、ｋ０１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。］

[In the formula (a1-0),
L ^a01 represents an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 each independently ^represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. ]

［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−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７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３〜１８の脂環式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を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］

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

L ^a01 is preferably an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O— (where k01 is preferably an integer of 1 to 4, more preferably 1, and more preferably). Is an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03, and R ^a04 , the alicyclic hydrocarbon group, and a group obtained by combining these include the same groups as those described for R ^{a1 to} R ^a3 in formula (1).
The alkyl group of R ^a02 , R ^a03 and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon group ^{represented by} R ^a02 , R ^a03 and R ^a04 is preferably an aliphatic hydrocarbon group having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
The group combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less, combining the alkyl group and the alicyclic hydrocarbon group. Examples of such groups include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, and a norbornylmethyl group. It is done.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

L ^a1 and L ^a2 are preferably —O— or ^* —O— (CH ₂ ) _{k1 ′} —CO—O— (where k1 ′ is an integer of 1 to 4, preferably 1). More preferably -O-.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and a group formed by combining these include the same groups as those ^exemplified for R ^{a1 to} R ^a3 of formula (1).
The alkyl group for R ^a6 and R ^a7 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As the structural unit (a1-0), for example, a structural unit represented by any one of the formulas (a1-0-1) to (a1-0-12) is preferable, and the structural units (a1-0-1) to (a1-0-1) The structural unit represented by any one of formulas (a1-0-10) is more preferable.

In the above structural unit, a structural unit in which a methyl group corresponding to R ^a01 is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a1-0).

As a monomer (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Among these, a monomer represented by any one of formula (a1-1-1) to formula (a1-1-8) is preferable, and any one of formula (a1-1-1) to formula (a1-1-4) is preferable. The monomer represented by is more preferable.

As the monomer (a1-2), 1-methylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclopentan-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcycloheptan-1-yl (meth) acrylate, 1-ethylcyclooctane-1-yl (meth) acrylate, 1-isopropylcyclopentan-1-yl (Meth) acrylate, 1-isopropylcyclohexane-1-yl (meth) acrylate, etc. are mentioned. A monomer represented by any one of the formulas (a1-2-1) to (a1-2-12) is preferable, and the formula (a1-2-3), the formula (a1-2-4), the formula (a1- The monomer represented by 2-9) or formula (a1-2-10) is more preferred, and the monomer represented by formula (a1-2-3) or formula (a1-2-9) is more preferred.

  When the resin (A) includes the structural unit (a1-0) and / or the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is the total structure of the resin (A). It is 10-95 mol% normally with respect to a unit, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

Furthermore, examples of the structural unit (a1) having the group (1) include the following structural units.

樹脂（Ａ）が上記構造単位を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１０〜９５モル％が好ましく、１５〜９０モル％がより好ましく、２０〜８５モル％がさらに好ましい。

When resin (A) contains the said structural unit, the content rate is 10-95 mol% with respect to all the structural units of resin (A), 15-90 mol% is more preferable, 20-85 mol % Is more preferable.

式（ａ１−５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊−（ＣＨ₂）_h3−ＣＯ−Ｌ⁵⁴−を表し、ｈ３は１〜４の整数を表し、＊は、Ｌ⁵¹との結合手を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。 As a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (2), a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”) Is also included).

In formula (a1-5),
R ^a8 represents a C 1-6 alkyl group optionally having a halogen atom, a hydrogen atom, or a halogen atom.
Z ^a1 represents a single bond or * — (CH ₂ ) _h3 —CO—L ⁵⁴ —, h3 represents an integer of 1 to 4, and * represents a bond to L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents 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.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. Groups.
In formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
One of L ⁵² and L ⁵³ is preferably —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—. * Represents a bond to L ^51.

As a monomer which introduce | transduces structural unit (a1-5), the monomer described in Unexamined-Japanese-Patent No. 2010-61117 is mentioned, for example. Among these, monomers represented by formulas (a1-5-1) to (a1-5-4) are preferable, and monomers represented by formula (a1-5-1) or formula (a1-5-2) are preferable. Is more preferable.

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

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

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When a resist pattern is produced from the resist composition of the present invention, when a high energy beam such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, the structural unit (a2) It is preferable to use the structural unit (a2) having a phenolic hydroxy group. When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2), and the structural unit (a2-1) is more preferable. As a structural unit (a2), 1 type may be included independently and 2 or more types may be included.

［式（ａ２−０）中、
Ｒ^a30は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、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。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は互いに同一であっても異なってもよい。］ Examples of the structural unit (a2) having a phenolic hydroxy group include a structural unit represented by the formula (a2-0) (hereinafter sometimes referred to as “structural unit (a2-0)”).

[In the formula (a2-0),
R ^a30 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a31 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 acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ^a31 may be the same as or different from each other. ]

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an n-pentyl group, and an n-hexyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,1. 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -A perfluorohexyl group etc. are mentioned. R ^a30 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 R ^a31 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

Examples of the monomer that derives the structural unit (a2-0) include monomers described in JP 2010-204634 A.
Among them, the structural unit (a2-0) is represented by formula (a2-0-1), formula (a2-0-2), formula (a2-0-3), and formula (a2-0-4), respectively. What is represented is preferable, and what is represented by a formula (a2-0-1) or a formula (a2-0-2) is more preferable.

  The resin (A) containing the structural unit (a2-0) is subjected to a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer that derives the structural unit (a2-0) is protected with a protective group, and then deprotected. It can be manufactured by processing. However, when the deprotection treatment is performed, the acid labile group of the structural unit (a1) needs to be not significantly impaired. Examples of such protecting groups include acetyl groups.

  When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, the content is preferably from 5 to 95 mol% with respect to all the structural units of the resin (A). 80 mol% is more preferable, and 15-80 mol% is further more preferable.

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

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

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

As a structural unit (a2-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A structural unit represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferred, and any one of formula (a2-1-1) to formula (a2-1-4) The structural unit represented is more preferable, and the structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is more preferable.

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

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

  The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These 1 type may be contained independently and 2 or more types may be contained.

［式（ａ３−１）中、
Ｌ^a4は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５の整数を表す。ｐ１が２以上のとき、複数のＲ^a21は互いに同一又は相異なる。
式（ａ３−２）中、
Ｌ^a5は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
Ｒ^a22は、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。
ｑ１は、０〜３の整数を表す。ｑ１が２以上のとき、複数のＲ^a22は互いに同一又は相異なる。
式（ａ３−３）中、
Ｌ^a6は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
Ｒ^a23は、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。
ｒ１は、０〜３の整数を表す。ｒ１が２以上のとき、複数のＲ^a23は互いに同一又は相異なる。
式（ａ３−４）中、
Ｒ^a24は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^ａ２５は、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。
ｗ１は、０〜３の整数を表す。ｗ１が２以上のとき、複数のＲ^ａ２５は互いに同一又は相異なる。
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。
＊はカルボニル基との結合手を表す。
Ｌ^a8及びＬ^a9は、互いに独立に、炭素数１〜６のアルカンジイル基を表す。］

[In the formula (a3-1),
L ^a4 represents —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7).
) Represents a group represented by * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5. When p1 is 2 or more, the plurality of R ^a21 are the same or different from each other.
In formula (a3-2),
L ^a5 represents —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7).
) Represents a group represented by * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, the plurality of R ^a22 are the same or different from each other.
In formula (a3-3),
L ^a6 represents —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7).
) Represents a group represented by * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, the plurality of R ^a23 are the same or different from each other.
In formula (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
w1 represents an integer of 0 to 3. When w1 is 2 or more, the plurality of R ^a25 are the same or different from each other.
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
* Represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. An alkyl group is mentioned.
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group for R ^a24 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. , Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

^Examples of the alkanediyl group represented by L ^a8 and L ^a9 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

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

（式中、Ｒ^ａ２４、Ｌ^ａ７は、上記と同じ意味を表す。） In formula (a3-4),
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.
L ^a7 is preferably —O— or ^* —O—L ^a8 —CO—O—, and more preferably —O—, —O—CH ₂ —CO—O— or —O—C ₂ H. _4- CO-O-.
R ^a25 is preferably a carboxy group, a cyano group, or a methyl group.
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) ′.

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

  As monomers for deriving the structural unit (a3), monomers described in JP 2010-204646 A, monomers described in JP 2000-122294 A, monomers described in JP 2012-41274 A are listed. Can be mentioned. As the structural unit (a3), formula (a3-1-1) to formula (a3-1-4), formula (a3-2-1) to formula (a3-2-4), formula (a3-3) 1) to a structural unit represented by any one of the formula (a3-3-4) and the formula (a3-4-1) to the formula (a3-4-12), the formula (a3-1-1), It is represented by any one of formula (a3-1-2), formula (a3-2-3) to formula (a3-2-4) and formula (a3-4-1) to formula (a3-4-12) The structural unit represented by any one of formulas (a3-4-1) to (a3-4-12) is more preferred, and the structural unit represented by formula (a3-4-1) to formula (a3- The structural unit represented by any one of 4-6) is even more preferable.

In the structural units represented by the following formulas (a3-4-1) to (a3-4-12), compounds in which the methyl group corresponding to R ^a24 is replaced with a hydrogen atom are also structural units (a3-4). ).

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Moreover, the content rate of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), and a structural unit (a3-4) is respectively with respect to all the structural units of resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more preferable.

<Other structural units (t)>
As the structural unit (t), in addition to the structural unit (a2) and the structural unit (a3), a structural unit having a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”) and a non-leaving hydrocarbon group. And a structural unit (hereinafter sometimes referred to as “structural unit (a5)”).

［式（ａ４）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ｒ^a42は、炭素数１〜２４のフッ素原子を有する飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a4)>
The structural unit (a4) is represented below.

[In the formula (a4),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

脂肪族飽和炭化水素基と脂環式飽和炭化水素基とを組み合わせた基としては、アダマンチルメチル基、ノルボルニルメチル基、ペルフルオロアダマンチルメチル基等が挙げられる。 ^Examples of the saturated hydrocarbon group for R ^a42 include an aliphatic saturated hydrocarbon group, an alicyclic saturated hydrocarbon group, and a group obtained by combining these. Examples of the aliphatic saturated hydrocarbon group include linear and branched alkyl groups. Examples of the alicyclic saturated hydrocarbon group include monocyclic and polycyclic alicyclic hydrocarbon groups.
Examples of linear and branched alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl. , N-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.
Examples of the monocyclic aliphatic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic aliphatic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond).

Examples of the group in which an aliphatic saturated hydrocarbon group and an alicyclic saturated hydrocarbon group are combined include an adamantylmethyl group, a norbornylmethyl group, a perfluoroadamantylmethyl group, and the like.

^Examples of the saturated hydrocarbon group having a fluorine atom of R ^a42 include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2 , 2,2-tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1, 2,2,3,3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) B) Methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1 , 1,2,2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,4 Fluorinated alkyl groups such as 5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group and perfluorohexyl group; and alicyclic hydrocarbon groups having fluorine atoms such as perfluorocyclohexyl group and perfluoroadamantyl group .

［式（ａ４−０）中、
Ｒ^f1は、水素原子又はメチル基を表す。
Ｒ^f2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。］
Ｒ^f2の飽和炭化水素基及びフッ素原子を有する飽和炭化水素基は、Ｒ^a42で例示したものと同様の基が挙げられる。 As the structural unit (a4), for example, a structural unit represented by any of the formulas (a4-0) to (a4-3) (hereinafter “structural unit (a4-0) to structural unit (a4-3)”) Is sometimes preferred).

[In the formula (a4-0),
R ^f1 represents a hydrogen atom or a methyl group.
R ^f2 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]
Examples of the saturated hydrocarbon group for R ^{f2 and} the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified for R ^a42 .

Examples of the structural unit (a4-0) include the structural units shown below and structural units in which a methyl group corresponding to R ^f1 is replaced with a hydrogen atom.

［式（ａ４−１）中、
Ｒ^f3は、水素原子又はメチル基を表す。
Ｌ³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メチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｒ^f4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、Ｌ³及びＲ^f4の合計炭素数の上限は２１である。］

[In the formula (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ³ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.
R ^f4 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 ³ and R ^f4 is 21. ]

Examples of the divalent saturated hydrocarbon group for L ³ include an aliphatic saturated hydrocarbon group, an alicyclic saturated hydrocarbon group, and a group obtained by combining these. Examples of the aliphatic saturated hydrocarbon include a linear or branched alkanediyl group. Examples of the alicyclic saturated hydrocarbon group include monocyclic and polycyclic alicyclic hydrocarbon groups.
Examples of the alkanediyl group 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 1-methylpropane-1,3-diyl group. 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
Examples of the divalent alicyclic saturated hydrocarbon group include groups obtained by removing one hydrogen atom from the above-described monovalent alicyclic hydrocarbon group.

Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include the following groups. In the following examples, * and ** each represent a bond.

Examples of the saturated hydrocarbon group for R ^{f4 and} the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified for R ^a42 .

Examples of the structural unit (a4-1) include the structural units shown below and structural units in which a methyl group corresponding to R ^f3 is replaced with a hydrogen atom.

［式（ａ４−２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ⁴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メチレン基は、酸素原子又はカルボニル基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、Ｌ⁴及びＲ^f6の合計炭素数の上限は２１である。］

[In the formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴ and R ^f6 is 21. ]

Examples of the divalent saturated hydrocarbon group for L ⁴ include the same groups as those exemplified for L ³ .
Examples of the saturated hydrocarbon group for R ^{f6 and} the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified for R ^a42 .

As the saturated hydrocarbon group for L ^4, an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

Examples of the structural unit (a4-2) include the structural units shown below and a structural unit in which a methyl group corresponding to R ^f5 is replaced with a hydrogen atom.

［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、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^f14は、フッ素原子を有していてもよい炭素数１〜１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14の合計炭素数の上限は２０である。］

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

Examples of the divalent saturated hydrocarbon group for A ^f13 include the same groups as those exemplified for the divalent saturated hydrocarbon group for L ³ .
The saturated hydrocarbon group which may have a fluorine atom of A ^f13 is preferably a divalent aliphatic saturated hydrocarbon group or a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom. And more preferably a perfluoroalkanediyl group.
Examples of the divalent aliphatic hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; difluoromethylene group, perfluoroethylene group, perfluoro Examples thereof include perfluoroalkanediyl groups such as propanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent alicyclic hydrocarbon group which may have a fluorine atom may be a monocyclic or polycyclic group. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

As the saturated hydrocarbon group for A ^{f14 and} the saturated hydrocarbon group which may have a fluorine atom, the same groups as those exemplified for R ^a42 can be mentioned. Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, Fluorination of 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, Fluorocyclohexyl group, adamantyl group, adamantylmethyl group, norbornyl group, norbornylmethyl group, perfluoro adamantyl group, a perfluoroalkyl adamantylmethyl group and the like are preferable.

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

As the structural unit (a4-3), for example, the structural unit shown below and a structural unit in which a methyl group corresponding to R ^f7 is replaced with a hydrogen atom can be mentioned.

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

［式（ａ５−１）中、
Ｒ^５１は、水素原子又はメチル基を表す。
Ｒ^５２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又はヒドロキシ基で置換されていてもよい。ただし、Ｌ^５１との結合位置にある炭素原子に結合する水素原子は、炭素数１〜８の脂肪族炭化水素基で置換されない。
Ｌ^５１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メチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-leaving hydrocarbon group that the structural unit (a5) has include a linear, branched, or cyclic hydrocarbon group. Especially, it is preferable that a structural unit (a5) contains an alicyclic hydrocarbon group.
As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.

[In the formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the coupling position with the L ⁵¹ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

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

Examples of the divalent saturated hydrocarbon group for L ⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. It is done.
Examples of the divalent aliphatic saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

［式（Ｌ１−１）中、
Ｘ^ｘ１は、カルボニルオキシ基又はオキシカルボニル基を表す。
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、互いに独立に、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^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、互いに独立に、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 the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

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

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

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

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

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

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

L ⁵¹ is preferably a single bond or a group represented by the formula (L1-1).

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

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

The resin (A) is preferably a resin comprising the structural unit (I), the structural unit (a1), and the structural unit (s), that is, a copolymer of the monomer (I), the monomer (a1), and the monomer (s). It is a polymer.
The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group) and a structural unit. It is at least one of (a1-5), more preferably the structural unit (a1-1) or the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably at least one of structural units represented by a γ-butyrolactone ring, a bridged ring containing a γ-butyrolactone ring structure, or an adamantane lactone ring.

  The resin (A) may contain a structural unit derived from a monomer having an adamantyl group (particularly the structural unit (a1-1)) in an amount of 15 mol% or more based on the content of the structural unit (a1). preferable. When the content of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do. The content rate of each structural unit which resin (A) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, further preferably 15,000 or less). The weight average molecular weight is a value determined by gel permeation chromatography.

  As for the content rate of resin (A), 80 to 99 mass% is preferable with respect to solid content of a resist composition. The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Resin (X)>
The resist composition of the present invention is a resin containing the structural unit (a4). However, the resin (X) does not contain the structural unit (I).
In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, and still more preferably 50 mol% or more with respect to all the structural units of the resin (X). .
Examples of the structural unit that the resin (X) may further include a structural unit derived from the structural unit (a1), the structural unit (a2), the structural unit (a3), and other known monomers.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).
The content of the resin (X) in the resist composition is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 with respect to 100 parts by mass of the resin (A). It is -40 mass parts, Most preferably, it is 3-30 mass parts.

  80 mass% or more and 99 mass% or less are preferable with respect to solid content of a resist composition, and, as for the total content rate of resin (A) and resin (X), 90 mass% or more and 99 mass% or less are preferable.

<Acid generator (B)>
Although an acid generator is classified into a nonionic type and an ionic type, any may be used for the acid generator (B) of the resist composition of this invention. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), and sulfones. (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712, etc. The compound which generate | occur | produces an acid by the radiation as described in 1 can be used. Moreover, you may use the compound manufactured by the well-known method. An acid generator (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の１価の脂環式炭化水素基を表し、該メチル基及び該１価の脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).

[In the formula (B1),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the methyl group and the monovalent —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group of Q ¹ and Q ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluoro group. A hexyl group etc. are mentioned.
Q ¹ and Q ² are preferably each independently a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.

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

［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メチレン基は、酸素原子又はカルボニル基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メチレン基は、酸素原子又はカルボニル基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メチレン基は、酸素原子又はカルボニル基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。］ Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include any of formulas (b1-1) to (b1-3) The group represented by these is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * represents a bond with -Y.

[In the formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b4 and L ^b5 is 22 or less.
In formula (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. ]

In Formula (b1-1) to Formula (b1-3), when the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group, the number of carbons before the replacement is represented by the carbon number of the saturated hydrocarbon group. It is a number.
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, The methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

As the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO—, a group represented by the formula (b1-1) or the formula (b1-3) Is preferred.

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

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

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

［式（ｂ１−９）中、
Ｌ^ｂ１９は、単結合又は炭素数１〜２３の２価の飽和炭化水素基を表し、該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、ヒドロキシ基又はアシルオキシ基に置換されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよく、該アシ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、ヒドロキシ基又はアシルオキシ基に置換されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよく、該アシ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^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、ヒドロキシ基又はアシルオキシ基に置換されていてもよい。該アシルオキシ基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよく、該アシ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^ｂ２６の合計炭素数は２１以下である。］ Examples of formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11), respectively.

[In the formula (b1-9),
L ^b19 represents a single bond or a ^C1-C23 divalent saturated hydrocarbon group, and the hydrogen atom contained in the divalent 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 divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an acyloxy group. Also good. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a ^C1-C21 divalent saturated hydrocarbon group, and the hydrogen atom contained in the divalent 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 divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^{b21 to} L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent 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 divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
^However, the total number of carbon atoms of L b24 ^{~L b26} is 21 or less. ]

  In formulas (b1-9) to (b1-11), when a hydrogen atom contained in a divalent saturated hydrocarbon group is substituted with an acyloxy group, the number of carbon atoms in the acyloxy group, CO in the ester bond, and The number of carbon atoms of the divalent saturated hydrocarbon group including the number of O is used.

Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.
Examples of the acyloxy group having a substituent include an oxoadamantylcarbonyloxy group, a hydroxyadamantylcarbonyloxy group, an oxocyclohexylcarbonyloxy group, and a hydroxycyclohexylcarbonyloxy group.

Of the groups represented by formula (b1-1), examples of the group represented by formula (b1-4) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-5) include the following.

Of the groups represented by formula (b1-1), examples of the group represented by formula (b1-6) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-7) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-8) include the following.

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

Of the groups represented by formula (b1-3), examples of the group represented by formula (b1-9) include the following.

Of the groups represented by the formula (b1-3), examples of the group represented by the formula (b1-10) include the following.

Of the groups represented by formula (b1-3), examples of the group represented by formula (b1-11) include the following.

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y11).
When —CH ₂ — contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO—, the number may be one, or two or more There may be multiple. Examples of such a group include groups represented by formula (Y12) to formula (Y38).

  That is, Y represents a hydrogen atom contained in an alicyclic hydrocarbon group, each substituted with an oxygen atom, and the two oxygen atoms together with an alkanediyl group having 1 to 8 carbon atoms form a ketal ring. Alternatively, a structure in which an oxygen atom is bonded to each of different carbon atoms may be included. However, when a spiro ring such as formula (Y28) to formula (Y33) is formed, the alkanediyl group between two oxygens preferably has one or more fluorine atoms. Of the alkanediyl groups contained in the ketal structure, those in which the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom are preferred.

  Among them, a group represented by any one of Formula (Y1) to Formula (Y20), Formula (Y30), and Formula (Y31) is preferable, and Formula (Y11), Formula (Y15), and Formula (Y Y16), a group represented by the formula (Y20), a formula (Y30) or a formula (Y31) can be mentioned, and a group represented by the formula (Y11), the formula (Y15) or the formula (Y30) is more preferable. It is done.

Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, Glycidyloxy group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms) Or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (ja represents an integer of 0 to 4).
Examples of the substituent for the monovalent alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 carbon atoms. -16 monovalent alicyclic hydrocarbon group, C1-C12 alkoxy group, C6-C18 monovalent aromatic hydrocarbon group, C7-C21 aralkyl group, C2-C2 4 acyl group, glycidyloxy group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, monovalent fat having 3 to 16 carbon atoms) Represents a cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4).

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the monovalent aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group, mesityl group. Groups, biphenyl groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of Y include the following.

In addition, when Y is a methyl group and L ^b1 is a C1-C17 divalent linear or branched saturated hydrocarbon group, the divalent saturated hydrocarbon at the bonding position with Y The group —CH ₂ — is preferably replaced by —O— or —CO—. In this case, —CH ₂ — contained in the alkyl group of Y is not replaced with —O— or —CO—.

Y is preferably a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent. The methylene group constituting the group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented by the following.

As the sulfonate anion in the salt represented by the formula (B1), an anion represented by the formula (B1-A-1) to the formula (B1-A-46) [hereinafter, anion (B1 -A-1) "or the like. ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula An anion represented by any one of (B1-A-33) and formulas (B1-A-36) to (B1-A-40) is more preferable.

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.
R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. More preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
L ⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and Q ² are the same as described above.
Specific examples of the sulfonate anion in the salt represented by the formula (B1) include the anions described in JP 2010-204646 A.

Examples of the sulfonate anion in the salt represented by the preferable formula (B1) include anions represented by the formulas (B1a-1) to (B1a-22), respectively.

［式（ｂ２−１）〜式（ｂ２−４）において、
Ｒ^ｂ４〜Ｒ^ｂ６は、互いに独立に、炭素数１〜３０の１価の脂肪族炭化水素基、炭素数３〜３６の１価の脂環式炭化水素基又は炭素数６〜３６の１価の芳香族炭化水素基を表し、該１価の脂肪族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１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の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１価の脂肪族炭化水素基、炭素数２〜４のアシ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１価の芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。
Ｒ^ｂ４とＲ^ｂ５とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ７及びＲ^ｂ８は、互いに独立に、ヒドロキシ基、炭素数１〜１２の１価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、互いに独立に、０〜５の整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一であっても異なってもよく、ｎ２が２以上のとき、複数のＲ^ｂ８は同一であっても異なってもよい。
Ｒ^ｂ９及びＲ^ｂ１０は、互いに独立に、炭素数１〜３６の１価の脂肪族炭化水素基又は炭素数３〜３６の１価の脂環式炭化水素基を表す。
Ｒ^ｂ９とＲ^ｂ１０とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−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１価の脂肪族炭化水素基、炭素数３〜３６の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１〜１２の１価の脂肪族炭化水素基、炭素数３〜１８の１価の脂環式炭化水素基又は炭素数６〜１８の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化水素に含まれる水素原子は、炭素数６〜１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の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、一緒になってそれらが結合する−ＣＨ−ＣＯ−を含む環を形成していてもよく、該環に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ−又は−ＣＯ−に置き換わってもよい。
Ｒ^ｂ１３〜Ｒ^ｂ１８は、互いに独立に、ヒドロキシ基、炭素数１〜１２の１価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、−Ｓ−又は−Ｏ−を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、互いに独立に、０〜５の整数を表す。
ｑ２及びｒ２は、互いに独立に、０〜４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は同一であっても異なってもよく、ｐ２が２以上のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数のＲ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異なってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］ Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) Is preferable.
Examples of the organic cation of Z ⁺ include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation, and preferably organic sulfonium cation or organic iodonium cation. More preferably, an arylsulfonium cation is mentioned.
Z ⁺ in the formula (B1) is preferably a cation represented by any one of the formulas (b2-1) to (b2-4) [hereinafter referred to as “cation (b2-1)” or the like depending on the formula number, etc. There is a case. ].

[In Formula (b2-1)-Formula (b2-4),
R ^{b4 to} R ^b6 are each independently a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent group having 6 to 36 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or a monovalent alicyclic carbon group having 3 to 12 carbon atoms. It may be substituted with a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the monovalent alicyclic hydrocarbon group is a halogen atom or a carbon number 1 to 18 Which may be substituted with a monovalent aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, the hydrogen atom contained in the monovalent aromatic hydrocarbon group is a halogen atom, hydroxy Group or an alkoxy group having 1 to 12 carbon atoms may be substituted.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b7 and R ^b8 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 represent the integer of 0-5 independently of each other.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b11 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic carbon group having 6 to 18 carbon atoms. Represents a hydrogen group.
R ^b12 represents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. And a hydrogen atom contained in the monovalent aliphatic hydrocarbon may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the monovalent aromatic hydrocarbon group The hydrogen atom to be substituted may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may together form a ring containing —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring is —O—, —SO—. Alternatively, it may be replaced by -CO-.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more The plurality of R ^b15 may be the same or different. When r2 is 2 or more, the plurality of R ^b16 may be the same or different. When s2 is 2 or more, the plurality of R ^b17 is ^They may be the same or different, and when t2 is 2 or more, the plurality of R ^b18 may be the same or different. ]

中でも、Ｒ^ｂ９〜Ｒ^ｂ１２の１価の脂環式炭化水素基の炭素数は、好ましくは３〜１８であり、より好ましくは４〜１２である。 Monovalent aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2 -The alkyl group of an ethylhexyl group is mentioned. Among these, the monovalent aliphatic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic monovalent alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclo And cycloalkyl groups such as a hexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

Among ^them, the number of carbon atoms of the monovalent alicyclic hydrocarbon group R ^{b9 to R b12} is preferably 3 to 18, more preferably from 4 to 12.

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

Examples of the monovalent aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p- Examples thereof include aryl groups such as an adamantylphenyl group, a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
When the monovalent aromatic hydrocarbon group includes a monovalent aliphatic hydrocarbon group or a monovalent alicyclic hydrocarbon group, the monovalent aliphatic hydrocarbon group or carbon having 1 to 18 carbon atoms A monovalent alicyclic hydrocarbon group having a number of 3 to 18 is preferred.
Examples of the monovalent aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the monovalent aliphatic hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group. .

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

The ring that R ^b4 and R ^b5 may form together with the sulfur atom to which they are bonded is any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. There may be. As this ring, a C3-C18 ring is mentioned, Preferably a C4-C18 ring is mentioned. Moreover, as a ring containing a sulfur atom, 3-membered ring-12-membered ring are mentioned, Preferably 3-membered ring-7-membered ring are mentioned, Specifically, the following ring is mentioned.

The ring formed by R ^b9 and R ^b10 together with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Good. Examples of the ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Examples thereof include a thiolane-1-ium ring (tetrahydrothiophenium ring) and thian-1-ium ring. Ring, 1,4-oxathian-4-ium ring and the like.
The ring formed by ^combining R ^b11 and R ^b12 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of the ring include 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. It is done.

  Among cations (b2-1) to cations (b2-4), cations (b2-1) are 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 (B1) is a combination of the above-described sulfonate anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B1) is preferably an anion and a cation (b2) represented by any of the formulas (B1a-1) to (B1a-3) and (B1a-7) to (B1a-15). -1) or a combination with a cation (b2-3).

  Preferred examples of the acid generator (B1) include those represented by formulas (B1-1) to (B1-40), and preferably include formulas (B1-1) and formula (B) containing an arylsulfonium cation. B1-2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7), formula (B1-11), formula (B1-12), formula (B1) -13), formula (B1-14), formula (B1-13), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-24), formula (B1- 25), Formula (B1-26), Formula (B1-29), Formula (B1-31), Formula (B1-32), Formula (B1-33), Formula (B1-34), Formula (B1-35) ), Formula (B1-36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40). It is.

The content of the acid generator (B1) is preferably 30% by mass or more and 100% by mass or less, and more preferably 50% by mass or more and 100% by mass or less, with respect to the total amount of the acid generator (B). Preferably, it is more preferably substantially only the acid generator (B1).
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less). The resist composition of the present invention may contain one or more acid generators (B).

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

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

<Quencher (C)>
The resist composition of the present invention may contain a quencher (hereinafter sometimes referred to as “quencher (C)”). The quencher (C) may be a basic nitrogen-containing organic compound or a salt that generates an acid having a lower acidity than the acid generator (B).

<Basic nitrogen-containing organic compound>
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

  Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine , Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, Triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyl Cyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldinonylamine Decylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4 , 4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methyl Imidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4, 4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine and the like are preferable, diisopropylaniline is preferable, and 2,6-diisopropylaniline is particularly preferable.

  As ammonium salts, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

<Salt that generates acid with low acidity>
The acidity in a salt that generates an acid having a weaker acidity than the acid generated from the acid generator is indicated by an acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator is a salt in which the pKa of the acid generated from the salt is usually -3 <pKa, preferably -1 <pKa <7. More preferably, the salt is 0 <pKa <5. Examples of the salt that generates an acid weaker than the acid generated from the acid generator include a salt represented by the following formula, a weak acid inner salt represented by the formula (D), and JP 2012-229206 A, JP Examples include salts described in JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A, and JP 2011-191745 A.

［式（Ｄ）中、
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１〜１２の１価の炭化水素基、炭素数１〜６のアルコキシ基、炭素数２〜７のアシル基、炭素数２〜７のアシルオキシ基、炭素数２〜７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０〜４の整数を表し、ｍ’が２以上の場合、複数のＲ^D1は同一又は相異なり、ｎ’が２以上の場合、複数のＲ^D2は同一又は相異なる。］

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

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

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

In the formula (D), R ^D1 and R ^D2 each independently represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 2 to 2 carbon atoms. Preferred are an acyl group having 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom.
m ′ and n ′ are each independently preferably an integer of 0 to 2, and more preferably 0. When m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n ′ is 2 or more, the plurality of R ^D2 are the same or different.

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

  The weak acid inner salt (D) can be produced by the method described in “Tetrahedron Vol. 45, No. 19, p6281-6296”. A commercially available compound can be used as the weak acid inner salt (D).

  The content of the quencher (C) is preferably 0.01 to 5% by mass, more preferably 0.01 to 4% by mass, and particularly preferably 0.01 to 3% by mass in the solid content of the resist composition. % By mass.

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

<Preparation of resist composition>
The resist composition of the present invention comprises the resin (X), the resin (A) and the acid generator (B) of the present invention, and the quencher (C), solvent (E) and other components used as necessary. 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 select an appropriate temperature from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (E), such as resin. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) A step of applying the resist composition of the present invention on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

  The resist composition can be applied onto the substrate by a commonly used apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

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

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

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

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

  In the resist composition of the present invention, the resin (X) tends to have a high distribution on the surface in the composition layer, and elution of the acid generator or the like into the immersion exposure liquid during immersion exposure can be suppressed. . Further, the advancing contact angle and the receding contact angle caused by the resin (X) exhibit water repellency and enable high-speed scanning exposure without leaving water droplets.

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

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

Moreover, the structure of the compound was confirmed by measuring a molecular peak using mass spectrometry (LC: Model 1100 manufactured by Agilent, MASS: LC / MSD manufactured by Agilent). In the following examples, the value of this molecular peak is indicated by “MASS”.
The receding contact angle (RCA) and the advancing contact angle (ACA) were confirmed by measuring using “DM-700” manufactured by Kyowa Interface Science Co., Ltd.

式（Ｉ−１−ａ）で表される化合物２５部、式（Ｉ−１−ｂ）で表される化合物２０．６８部及びクロロホルム１１２．５部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、ピリジン２８．４９部及び式（Ｉ−１−ｃ）で表される化合物６９．０５部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した。得られた反応物に、クロロホルム２６０部及び５％塩酸２１１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液１６６部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１−ｄ）で表される化合物３５．８９部を得た。

式（Ｉ−１−ｄ）で表される化合物３０部、テトラヒドロフラン１５０部、トリエチルアミン１５．１６部及びジメチルアミノピリジン１．０６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−１−ｅ）で表される化合物２７．３１部を添加した後、２３℃に昇温し、さらに、２３℃で２時間攪拌した。得られた反応物に、酢酸エチル６７０部及び５％塩酸１２８部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、１０％炭酸カリウム水溶液１１０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水２００部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１）で表される化合物３４．３２部を得た。 Example 1 [Synthesis of Compound Represented by Formula (I-1)]

25 parts of the compound represented by the formula (I-1-a), 20.68 parts of the compound represented by the formula (I-1-b) and 112.5 parts of chloroform were added and stirred at 23 ° C. for 30 minutes. . The obtained mixed solution was cooled to 5 ° C., 28.49 parts of pyridine and 69.05 parts of a compound represented by the formula (I-1-c) were added, the temperature was raised to 23 ° C., and further 23 ° C. For 18 hours. To the obtained reaction product, 260 parts of chloroform and 211 parts of 5% hydrochloric acid were charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The collected organic layer was charged with 185 parts of ion exchange water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 166 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The collected organic layer was charged with 185 parts of ion exchange water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The collected organic layer was concentrated. The obtained concentrated mass is fractionated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the formula (I-1-d). 35.89 parts of the compound represented were obtained.

30 parts of the compound represented by the formula (I-1-d), 150 parts of tetrahydrofuran, 15.16 parts of triethylamine and 1.06 part of dimethylaminopyridine were added and stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 27.31 parts of the compound represented by formula (I-1-e) was added, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 2 hours. . The obtained reaction product was charged with 670 parts of ethyl acetate and 128 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 110 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 200 parts of ion exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated 4 times. The collected organic layer was concentrated. The obtained concentrated mass is fractionated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-1). 34.32 parts of compound were obtained.

  MS (mass spectrometry): 240.1 (molecular ion peak)

式（Ｉ−２０−ａ）で表される化合物１４．１９部、式（Ｉ−２０−ｂ）で表される化合物１０．３４部及びクロロホルム１００部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、ピリジン１４．２５部及び式（Ｉ−２０−ｃ）で表される化合物３４．５３部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した。得られた反応物に、クロロホルム１５０部及び５％塩酸１０６部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１００部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液８３部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１００を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 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−２０−ｄ）で表される化合物１６．６６部を得た。

式（Ｉ−２０−ｄ）で表される化合物１６．２２部、テトラヒドロフラン１００部、トリエチルアミン７．５８部及びジメチルアミノピリジン０．５３部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−２０−ｅ）で表される化合物１３．６６部を添加した後、２３℃に昇温し、さらに、２３℃で２時間攪拌した。得られた反応物に、酢酸エチル２００部及び５％塩酸６４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、１０％炭酸カリウム水溶液５５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１００部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 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−２０）で表される化合物１４．４９部を得た。 Example 2 [Synthesis of Compound Represented by Formula (I-20)]

14.19 parts of the compound represented by the formula (I-20-a), 10.34 parts of the compound represented by the formula (I-20-b) and 100 parts of chloroform were added and stirred at 23 ° C. for 30 minutes. . The obtained mixed solution was cooled to 5 ° C., 14.25 parts of pyridine and 34.53 parts of a compound represented by the formula (I-20-c) were added, the temperature was raised to 23 ° C., and further 23 ° C. For 18 hours. To the obtained reaction product, 150 parts of chloroform and 106 parts of 5% hydrochloric acid were added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 100 parts of ion exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 83 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with ion-exchanged water 100, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The collected organic layer was concentrated. The obtained concentrated mass is separated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the formula (I-20-d). 16.66 parts of the compound represented were obtained.

16.22 parts of a compound represented by the formula (I-20-d), 100 parts of tetrahydrofuran, 7.58 parts of triethylamine and 0.53 part of dimethylaminopyridine were added and stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 13.66 parts of the compound represented by the formula (I-20-e) were added, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 2 hours. . The obtained reaction product was charged with 200 parts of ethyl acetate and 64 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 55 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 100 parts of ion exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated 4 times. The collected organic layer was concentrated. The obtained concentrated mass is separated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-20). 14.49 parts of the above compound were obtained.

  MS (mass spectrometry): 254.2 (molecular ion peak)

式（Ｉ−２−ａ）で表される化合物２５部、式（Ｉ−２−ｂ）で表される化合物２４．０５部及びクロロホルム１２０部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、ピリジン２８．４９部及び式（Ｉ−２−ｃ）で表される化合物６９．０５部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した。得られた反応物に、クロロホルム２６０部及び５％塩酸２１１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液１６６部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 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−２−ｄ）で表される化合物３６．０９部を得た。

式（Ｉ−２−ｄ）で表される化合物３２．４４部、テトラヒドロフラン１５０部、トリエチルアミン１５．１６部及びジメチルアミノピリジン１．０６部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−２−ｅ）で表される化合物２７．３１部を添加した後、２３℃に昇温し、さらに、２３℃で２時間攪拌した。得られた反応物に、酢酸エチル６７０部及び５％塩酸１２８部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、１０％炭酸カリウム水溶液１１０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水２００部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 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−２）で表される化合物３４．６６部を得た。 Example 3 [Synthesis of Compound Represented by Formula (I-2)]

25 parts of the compound represented by the formula (I-2-a), 24.05 parts of the compound represented by the formula (I-2-b) and 120 parts of chloroform were added and stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 28.49 parts of pyridine and 69.05 parts of a compound represented by the formula (I-2-c) were added, the temperature was raised to 23 ° C., and further 23 ° C. For 18 hours. To the obtained reaction product, 260 parts of chloroform and 211 parts of 5% hydrochloric acid were charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The collected organic layer was charged with 185 parts of ion exchange water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 166 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The collected organic layer was charged with 185 parts of ion exchange water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The collected organic layer was concentrated. The obtained concentrated mass was fractionated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the formula (I-2-d) 36.09 parts of the compound represented were obtained.

32.44 parts of the compound represented by the formula (I-2-d), 150 parts of tetrahydrofuran, 15.16 parts of triethylamine and 1.06 part of dimethylaminopyridine were added and stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 27.31 parts of the compound represented by the formula (I-2-e) was added, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 2 hours. . The obtained reaction product was charged with 670 parts of ethyl acetate and 128 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 110 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 200 parts of ion exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated 4 times. The collected organic layer was concentrated. The obtained concentrated mass is separated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-2). This gave 34.66 parts of the compound.

  MS (mass spectrometry): 254.2 (molecular ion peak)

式（Ｉ−６−ａ）で表される化合物２５部、式（Ｉ−６−ｂ）で表される化合物３６．５６部及びクロロホルム１２０部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、ピリジン２８．４９部及び式（Ｉ−６−ｃ）で表される化合物６９．０５部を添加し、２３℃に昇温し、さらに、２３℃で１８時間攪拌した。得られた反応物に、クロロホルム２６０部及び５％塩酸２１１部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液１６６部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水１８５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 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−６−ｄ）で表される化合物３５．１５部を得た。

式（Ｉ−６−ｄ）で表される化合物２０．７６部、テトラヒドロフラン１５０部、トリエチルアミン７．５８部及びジメチルアミノピリジン０．５３部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を５℃まで冷却し、式（Ｉ−６−ｅ）で表される化合物１３．６６部を添加した後、２３℃に昇温し、さらに、２３℃で２時間攪拌した。得られた反応物に、酢酸エチル３００部及び５％塩酸６４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、１０％炭酸カリウム水溶液５５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、イオン交換水２００部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 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−６）で表される化合物１７．１９部を得た。 Example 4 [Synthesis of Compound Represented by Formula (I-6)]

25 parts of the compound represented by the formula (I-6-a), 36.56 parts of the compound represented by the formula (I-6-b) and 120 parts of chloroform were added and stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 28.49 parts of pyridine and 69.05 parts of a compound represented by the formula (I-6-c) were added, the temperature was raised to 23 ° C., and further 23 ° C. For 18 hours. To the obtained reaction product, 260 parts of chloroform and 211 parts of 5% hydrochloric acid were charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The collected organic layer was charged with 185 parts of ion exchange water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 166 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The collected organic layer was charged with 185 parts of ion exchange water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The collected organic layer was concentrated. The obtained concentrated mass was fractionated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the formula (I-6-d). 35.15 parts of the compound represented were obtained.

20.76 parts of a compound represented by the formula (I-6-d), 150 parts of tetrahydrofuran, 7.58 parts of triethylamine and 0.53 part of dimethylaminopyridine were added and stirred at 23 ° C. for 30 minutes. The obtained mixed solution was cooled to 5 ° C., 13.66 parts of the compound represented by the formula (I-6-e) was added, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 2 hours. . To the obtained reaction product, 300 parts of ethyl acetate and 64 parts of 5% hydrochloric acid were charged, stirred at 23 ° C. for 30 minutes, allowed to stand and liquid-separated to wash the organic layer. The recovered organic layer was charged with 55 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 200 parts of ion exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated 4 times. The collected organic layer was concentrated. The obtained concentrated mass is separated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-6). 17.19 parts of compound were obtained.

  MS (mass spectrometry): 306.2 (molecular ion peak)

以下、これらのモノマーを式番号に応じて「モノマー（ａ１−１−３）」等という。 Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below.

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

Example 5 [Synthesis of Resin A1]
As a monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-1), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is 30:14: 15: 2.5: 38.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A1 (copolymer) having a weight average molecular weight of 8.2 × 10 ^{3 in} a yield of 63%. It was. This resin A1 has the following structural units.

Example 6 [Synthesis of Resin A2]
As a monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-1), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is 15:14: 30: 2.5: 38.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A2 (copolymer) having a weight average molecular weight of 8.8 × 10 ^{3 in} a yield of 75%. It was. This resin A2 has the following structural units.

Example 7 [Synthesis of Resin A3]
As the monomer, the monomer (a1-2-9), the monomer (I-1), the monomer (a2-1-1) and the monomer (a3-4-2) were used, and the molar ratio [monomer (a1-2-9 ): Monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is mixed at 14: 45: 2.5: 38.5, 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and the resin was filtered to obtain a resin A3 (copolymer) having a weight average molecular weight of 9.3 × 10 ^{3 in} a yield of 88%. It was. This resin A3 has the following structural units.

Example 8 [Synthesis of Resin A4]
As the monomer, the monomer (a1-2-9), the monomer (I-1), the monomer (a2-1-1) and the monomer (a3-4-2) were used, and the molar ratio [monomer (a1-2-9 ): Monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is mixed at 29: 30: 2.5: 38.5, 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A4 (copolymer) having a weight average molecular weight of 9.1 × 10 ^{3 in} a yield of 84%. It was. This resin A4 has the following structural units.

Example 9 [Synthesis of Resin A5]
As the monomer, the monomer (a1-2-9), the monomer (I-1), the monomer (a2-1-1) and the monomer (a3-4-2) were used, and the molar ratio [monomer (a1-2-9 ): Monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is mixed at 45: 14: 2.5: 38.5, 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A5 (copolymer) having a weight average molecular weight of 8.9 × 10 ^{3 in} a yield of 85%. It was. This resin A5 has the following structural units.

実施例１１〔樹脂Ａ７の合成〕
モノマーとして、モノマー（Ｉ−１）、モノマー（ａ２−１−１）及びモノマー（ａ３−４−２）を用い、そのモル比〔モノマー（Ｉ−１）：モノマー（ａ２−１−１）：モノマー（ａ３−４−２）〕が５９：２．５：３８．５となるように混合し、全モノマー量の１．５質量倍のプロピレングリコールモノメチルエーテルアセテートを加えて溶液とした。この溶液に、開始剤としてアゾビスイソブチロニトリル及びアゾビス（２，４−ジメチルバレロニトリル）を全モノマー量に対して各々、１ｍｏｌ％及び３ｍｏｌ％添加し、これらを７５℃で約５時間加熱した。得られた反応混合物を、大量のメタノール／水混合溶媒に注いで樹脂を沈殿させ、この樹脂をろ過した。得られた樹脂を再び、メタノール／水混合溶媒に注いでリパルプし、この樹脂をろ過することにより、重量平均分子量８．２×１０³の樹脂Ａ７（共重合体）を収率７８％で得た。この樹脂Ａ７は、以下の構造単位を有するものである。

Example 10 [Synthesis of Resin A6]
As the monomer, monomer (a1-1-3), monomer (I-1), monomer (a2-1-1) and monomer (a3-4-2) were used, and the molar ratio [monomer (a1-1-3) ): Monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is mixed at 15: 44: 2.5: 38.5, 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A6 (copolymer) having a weight average molecular weight of 7.9 × 10 ^{3 in} a yield of 76%. It was. This resin A6 has the following structural units.

Example 11 [Synthesis of Resin A7]
As the monomer, monomer (I-1), monomer (a2-1-1) and monomer (a3-4-2) were used, and the molar ratio [monomer (I-1): monomer (a2-1-1): The monomer (a3-4-2)] was mixed at 59: 2.5: 38.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and the resin was filtered to obtain a resin A7 (copolymer) having a weight average molecular weight of 8.2 × 10 ^{3 in} a yield of 78%. It was. This resin A7 has the following structural units.

Synthesis Example 1 [Synthesis of Resin A8]
As the monomer, the monomer (a1-2-9), the monomer (I-13), the monomer (a2-1-1) and the monomer (a3-4-2) were used, and the molar ratio [monomer (a1-2-9 ): Monomer (I-13): monomer (a2-1-1): monomer (a3-4-2)] is mixed so that 29: 30: 2.5: 38.5. 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A8 (copolymer) having a weight average molecular weight of 9.5 × 10 ^{3 in} a yield of 89%. It was. This resin A8 has the following structural units.

Synthesis Example 2 [Synthesis of Resin A9]
As the monomer, monomer (I-13), monomer (a2-1-1) and monomer (a3-4-2) were used, and the molar ratio [monomer (I-13): monomer (a2-1-1): The monomer (a3-4-2)] was mixed at 59: 2.5: 38.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A9 (copolymer) having a weight average molecular weight of 9.8 × 10 ^{3 in} a yield of 87%. It was. This resin A9 has the following structural units.

Example 12 [Synthesis of Resin A10]
As the monomer, the monomer (a1-2-9), the monomer (I-2), the monomer (a2-1-1) and the monomer (a3-4-2) were used, and the molar ratio [monomer (a1-2-9 ): Monomer (I-2): monomer (a2-1-1): monomer (a3-4-2)] is mixed at 29: 30: 2.5: 38.5, 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and the resin was filtered to obtain a resin A10 (copolymer) having a weight average molecular weight of 8.8 × 10 ^{3 in} a yield of 81%. It was. This resin A10 has the following structural units.

Example 13 [Synthesis of Resin A11]
As the monomer, monomer (a1-2-9), monomer (I-6), monomer (a2-1-1) and monomer (a3-4-2) were used, and the molar ratio [monomer (a1-2-9 ): Monomer (I-6): monomer (a2-1-1): monomer (a3-4-2)] is mixed at 29: 30: 2.5: 38.5, 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A11 (copolymer) having a weight average molecular weight of 8.2 × 10 ^{3 in} a yield of 78%. It was. This resin A11 has the following structural units.

Example 14 [Synthesis of Resin A12]
As the monomer, the monomer (a1-2-9), the monomer (I-20), the monomer (a2-1-1) and the monomer (a3-4-2) were used, and the molar ratio [monomer (a1-2-9 ): Monomer (I-20): monomer (a2-1-1): monomer (a3-4-2)] is mixed at 29: 30: 2.5: 38.5, 1.5 mass times propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A12 (copolymer) having a weight average molecular weight of 9.3 × 10 ^{3 in} a yield of 84%. It was. This resin A12 has the following structural units.

Synthesis Example 3 [Synthesis of Resin AX1]
As the monomer, monomer (IX-1), monomer (a2-1-1) and monomer (a3-4-2) were used, and their molar ratio [monomer (IX-1): monomer (a2-1-1): The monomer (a3-4-2)] was mixed at 59: 2.5: 38.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and the resin was filtered to obtain a resin AX1 (copolymer) having a weight average molecular weight of 9.4 × 10 ^{3 in} a yield of 70%. It was. This resin AX1 has the following structural units.

Synthesis Example 4 [Synthesis of Resin AX2]
As the monomer, monomer (IX-2), monomer (a2-1-1) and monomer (a3-4-2) were used, and the molar ratio [monomer (IX-2): monomer (a2-1-1): The monomer (a3-4-2)] was mixed at 59: 2.5: 38.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin AX2 (copolymer) having a weight average molecular weight of 8.8 × 10 ^{3 in} a yield of 84%. It was. This resin AX2 has the following structural units.

Synthesis Example 5 [Synthesis of Resin X1]
As the monomer, monomer (a5-1-1) and monomer (a4-0-12) were used, and the molar ratio [monomer (a5-1-1): monomer (a4-0-12)] was 50:50. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 3 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added based on the total amount of monomers, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin X1 (copolymer) having a weight average molecular weight of 1.0 × 10 ^{4 in} a yield of 91%. Got in. This resin X1 has the following structural units.

<Preparation of resist composition>
Each of the components shown below was mixed in parts by mass shown in Table 1, dissolved in a solvent, and filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２−ヘプタノン ２０部
γ−ブチロラクトン ３．５部 <Resin (A)>
A1 to A12, AX1, AX2, X1: Resin A1 to Resin A12, Resin AX1, Resin AX2, Resin X1
<Acid generator (B)>
B1-5: a salt represented by the formula (B1-5) (synthesized according to Examples in Japanese Patent Application Laid-Open No. 2015-200886)
B1-21: a salt represented by the formula (B1-21) (synthesized according to Examples in Japanese Patent Application Laid-Open No. 2015-200886)
B1-22: a salt represented by the formula (B1-22) (synthesized according to Examples in Japanese Patent Application Laid-Open No. 2015-200886)
<Quencher (C)>
D1: (Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts

<Manufacture of resist pattern and its evaluation>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer, and baked under the conditions of 205 ° C. and 60 seconds, whereby an organic layer having a thickness of 78 nm. An antireflection film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After the application, this silicon wafer was pre-baked on a direct hot plate at a temperature described in the “PB” column of Table 1 for 60 seconds to form a composition layer on the silicon wafer.
An ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, Annual σ _out = 0.85 σ _in = 0.65 XY− pol. Illumination], using a mask for forming a trench pattern (pitch 120 nm / trench width 40 nm), the exposure amount was changed stepwise to perform exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

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

<Line edge roughness evaluation (LER)>
About the obtained resist pattern, the fluctuation width of the unevenness | corrugation of a wall surface was observed and measured with the scanning electron microscope. This swing is
A circle having a thickness of 3.3 nm or less
What exceeded 3.3 nm was set as x. The results are shown in Table 2. A numerical value in parentheses indicates a swing width (nm).

  From the above results, it can be seen that according to the resist composition of the present invention, a resist pattern can be produced with good line edge roughness.

  The resist composition of the present invention can produce a resist pattern with good line edge roughness, and is useful for fine processing of semiconductors.

Claims (9)

A resist composition comprising a resin (A) having a structural unit derived from a compound represented by formula (I), a resin (X) containing a structural unit represented by formula (a4), and an acid generator.

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms.
R represents a 1-adamantyl group or * -CHR ⁴ R ⁵ which may have an alkyl group having 1 to 8 carbon atoms. * Represents a bonding position.
R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof, or R ⁴ and R ^5. Are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms together with the carbon atom to which they are bonded. ]

[In the formula (a4),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ] 2. The resist composition according to claim 1, wherein R is a 1-adamantyl group or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms together with carbon atoms to which R ⁴ and R ⁵ are bonded to each other. . The resist composition according to claim 1, wherein R ² and R ³ are methyl groups. The structural unit represented by the formula (a4) is a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), or a structural unit represented by the formula (a4-2). The resist composition according to claim 1, which is at least one selected from the group consisting of structural units represented by formula (a4-3):

[In the formula (a4-0),
R ^f1 represents a hydrogen atom or a methyl group.
R ^f2 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]

[In the formula (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ³ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.
R ^f4 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 ³ and R ^f4 is 21. ]

[In the formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴ and R ^f6 is 21. ]

[In the formula (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a C 1-18 divalent saturated hydrocarbon group which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
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. ] The resist composition according to claim 1, wherein the acid generator is a salt represented by the formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the methyl group and the monovalent —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced with —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]   The resist composition according to claim 1, further comprising a salt that generates an acid having a lower acidity than an acid generated from the acid generator. (1) The process of apply | coating the resist composition in any one of Claims 1-6 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: A compound represented by formula (IA).

[In the formula (IA),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represents an alkyl group having 1 to 4 carbon atoms.
R ^A represents a 1-adamantyl group or * -CHR ^4A R ^5A which may have an alkyl group having 1 to 8 carbon atoms. * Represents a bonding position.
R ^4A and R ^5A each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof, or R ^4A and R ^5A are bonded to each other. Then, a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms is formed together with the carbon atom to which they are bonded. ]   A resin having a structural unit derived from the compound represented by formula (IA) according to claim 8.