JP7217154B2 - RESIST COMPOSITION AND RESIST PATTERN MANUFACTURING METHOD - Google Patents

Description

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

Patent Document 1 describes a resist composition containing any one of compounds represented by the following structural formulas, a resin containing a structural unit having an acid-labile group, and an acid generator.

JP 2012-8553 A

An object of the present invention is to provide a resist composition and a compound capable of producing a resist pattern with a better focus margin (DOF) than the resist pattern formed from the above resist composition.

［式（Ｉ）中、
Ｌ^１は、単結合又は炭素数１～１８の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
Ｗ^１は、炭素数３～２４の炭化水素環を表し、該炭化水素環に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
ｎは、１～３のいずれかの整数を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、炭素数１～６のフッ素化アルキル基を表す。
Ｒ^３は、水素原子又は置換基を有していてもよい炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
ｎが２又は３の時、複数のＲ^１、Ｒ^２及びＲ^３は、同じでも異なっていてもよい。］
〔２〕Ｒ^１及びＲ^２が、トリフルオロメチル基である〔１〕記載のレジスト組成物。
〔３〕Ｒ^３が、水素原子又は置換基を有していてもよい炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる少なくとも１つの－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっている〔１〕又は〔２〕記載のレジスト組成物。
〔４〕Ｗ^１が、単環式の飽和炭化水素環である〔１〕～〔３〕のいずれかに記載のレジスト組成物。
〔５〕酸発生剤が、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、
Ｑ^ｂ１及びＱ^ｂ２は、それぞれ独立に、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１～２４の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、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で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］
〔６〕（１）〔１〕～〔５〕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。
〔７〕式（Ｉ）で表される化合物。

［式（Ｉ）中、
Ｌ^１は、単結合又は炭素数１～１８の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
Ｗ^１は、炭素数３～２４の炭化水素環を表し、該炭化水素環に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
ｎは、１～３のいずれかの整数を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、炭素数１～６のフッ素化アルキル基を表す。
Ｒ^３は、水素原子又は置換基を有していてもよい炭素数１～１８の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
ｎが２又は３の時、複数のＲ^１、Ｒ^２及びＲ^３は、同じでも異なっていてもよい。］ The present invention includes the following inventions.
[1] A resist composition containing a resin containing a structural unit having an acid-labile group, a resin containing a structural unit having a fluorine atom, an acid generator, and a compound represented by formula (I).

[in the formula (I),
L ¹ represents a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —S(O) ₂ — Alternatively, it may be replaced with -CO-.
W ¹ represents a hydrocarbon ring having 3 to 24 carbon atoms, and —CH ₂ — contained in the hydrocarbon ring is replaced with —O—, —S—, —S(O) ₂ — or —CO—. may be
n represents an integer of 1 to 3;
R ¹ and R ² each independently represent a fluorinated alkyl group having 1 to 6 carbon atoms.
R ³ represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, — It may be replaced with S(O) ₂ - or -CO-.
When n is 2 or 3, a plurality of R ¹ , R ² and R ³ may be the same or different. ]
[2] The resist composition of [1], wherein R ¹ and R ² are trifluoromethyl groups.
[3] R ³ represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and at least one —CH ₂ — contained in the hydrocarbon group is —O— or --CO--.
[4] The resist composition according to any one of [ ¹ ] to [3], wherein W1 is a monocyclic saturated hydrocarbon ring.
[5] The resist composition according to any one of [1] to [4], wherein the acid generator is a salt represented by formula (B1).

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO—; A hydrogen atom contained in may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, included in the alicyclic hydrocarbon group- CH ₂ - may be replaced by -O-, -S(O) ₂ - or -CO-.
Z ⁺ represents an organic cation. ]
[6] (1) a step of applying the resist composition according to any one of [1] to [5] onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) A process of heating the composition layer after exposure, and (5) a process of developing the composition layer after heating.
[7] A compound represented by formula (I).

[in the formula (I),
L ¹ represents a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —S(O) ₂ — Alternatively, it may be replaced with -CO-.
W ¹ represents a hydrocarbon ring having 3 to 24 carbon atoms, and —CH ₂ — contained in the hydrocarbon ring is replaced with —O—, —S—, —S(O) ₂ — or —CO—. may be
n represents an integer of 1 to 3;
R ¹ and R ² each independently represent a fluorinated alkyl group having 1 to 6 carbon atoms.
R ³ represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, — It may be replaced with S(O) ₂ - or -CO-.
When n is 2 or 3, a plurality of R ¹ , R ² and R ³ may be the same or different. ]

The present invention provides resist compositions and compounds capable of producing resist patterns with good margin of focus (DOF).

As used herein, "(meth)acrylate" means "at least one of acrylate and methacrylate". Notations such as "(meth)acrylic acid" and "(meth)acryloyl" have the same meaning.
In addition, unless otherwise specified, a group that can be linear, branched and/or cyclic such as an "aliphatic hydrocarbon group" includes any of them. The "aromatic hydrocarbon group" also includes groups in which a hydrocarbon group is bonded to an aromatic ring. Where stereoisomers exist, all stereoisomers are included.
As used herein, the term "solid content of the resist composition" means the total weight of the components excluding the solvent (E), which will be described later, from the total weight of the resist composition.

[Resist composition]
The resist composition of the present invention includes a resin containing a structural unit having an acid-labile group (hereinafter sometimes referred to as "resin (A)"), a resin containing a structural unit having a fluorine atom (hereinafter "resin (X)"). ), an acid generator (hereinafter sometimes referred to as "acid generator (B)") and a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)") . The term "acid-labile group" as used herein means a group having a leaving group, which is eliminated by contact with an acid to form a hydrophilic group (e.g., hydroxy group or carboxy group). .
The resist composition of the present invention preferably contains a solvent (hereinafter sometimes referred to as "solvent (E)").
The resist composition of the present invention may further contain a quencher (hereinafter sometimes referred to as "quencher (C)").

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

［式（１）中、Ｒ^ａ１、Ｒ^ａ２及びＲ^ａ３は、それぞれ独立に、炭素数１～８のアルキル基、炭素数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の非芳香族炭化水素環を形成する。
ｍａ及びｎａは、それぞれ独立して、０又は１を表し、ｍａ及びｎａの少なくとも一方は１を表す。
＊は結合部位を表す。］

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

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

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

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

Examples of alkyl groups for R ^a1 , R ^a2 and R ^a3 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group.
The alicyclic hydrocarbon groups for R ^a1 , R ^a2 and R ^a3 may be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a bonding site). The alicyclic hydrocarbon groups of R ^a1 , R ^a2 and R ^a3 preferably have 3 to 16 carbon atoms.

Groups in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl An ethyl group etc. are mentioned.
Preferably, ma is 0 and na is 1.
-C(R ^a1 )(R ^a2 )(R ^a3 ) when R ^a1 and R ^a2 combine to form a non-aromatic hydrocarbon ring include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents a binding site with -O-.

Ｒ^ａ１’及びＲ^ａ２’のうち、少なくとも１つは水素原子であることが好ましい。
ｎａ’は、好ましくは０である。 Examples of hydrocarbon groups for R ^a1′ , R ^a2′ and R ^a3′ include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, groups formed by combining these groups, and the like.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same groups as those exemplified for R ^a1 , R ^a2 and R ^a3 .
The aromatic hydrocarbon group includes aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group and phenanthryl group.
Examples of the combined group include a group obtained by combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methyl phenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon groups aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, and the like.
When R ^a2′ and R ^a3′ are bonded to each other to form a heterocyclic ring together with the carbon atom to which they are bonded and X, —C(R ^a1′ )(R ^a3′ )—X—R ^a2′ is represented by the following ring. * represents the binding site.

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

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

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

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

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

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

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

R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or *—O—(CH ₂ ) _k01 —CO—O— (provided that k01 is preferably any integer of 1 to 4, more preferably is 1.), more preferably an oxygen atom.
R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 as alkyl groups, alicyclic hydrocarbon groups and groups in which these groups are combined are the groups listed for R ^a1 , R ^a2 and R ^a3 in formula (1) and the same groups as
The alkyl group in R ^a02 , R ^a03 and R ^a04 preferably has 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group.
The alkyl group in R ^a6 and R ^a7 preferably has 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, still more preferably an ethyl group or an isopropyl group.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 preferably have 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms.
It is preferable that the combined group of an alkyl group and an alicyclic hydrocarbon group have a total carbon number of 18 or less.
R ^a02 and R ^a03 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably methyl or ethyl groups.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
R ^a6 and R ^a7 are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, still more preferably an ethyl group or an isopropyl group.
m1 is preferably an integer from 0 to 3, more preferably 0 or 1.
n1 is preferably an integer from 0 to 3, more preferably 0 or 1.
n1' is preferably 0 or 1.

As the structural unit (a1-0), for example, a structural unit represented by any one of formulas (a1-0-1) to (a1-0-12) and R ^a01 in the structural unit (a1-0) Structural units in which the corresponding methyl group is replaced with a hydrogen atom can be mentioned, and structural units represented by any one of formulas (a1-0-1) to (a1-0-10) are preferred.

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

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

When the resin (A) contains the structural unit (a1-0) and/or the structural unit (a1-1) and/or the structural unit (a1-2), the total content of these is the total structure of the resin (A) It is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 mol%, still more preferably 30 to 70 mol%, still more preferably It is 40 to 70 mol %, more preferably 45 to 70 mol %.

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

[In formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl It represents an oxy group or a methacryloyloxy group.
la represents an integer of 0 to 4; When la is 2 or more, a plurality of R ^a33 may be the same or different.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^a35 and R ^a36 are bonded to each other to form a C2-C20 divalent hydrocarbon group together with -C-O- to which they are bonded, and -CH ₂ - contained in the hydrocarbon group and the divalent hydrocarbon group is - O- or -S- may be substituted. ]

Examples of alkyl groups for R ^a32 and R ^a33 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, even more preferably a methyl group.
Halogen atoms in R ^a32 and R ^a33 include fluorine, chlorine and bromine atoms.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 , 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, etc. are mentioned.
Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy groups. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.
Alkylcarbonyl groups include acetyl, propionyl and butyryl groups.
An acetyloxy group, a propionyloxy group, a butyryloxy group, etc. are mentioned as an alkylcarbonyloxy group.
Hydrocarbon groups for R ^a34 , R ^a35 and R ^a36 include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups in which these are combined. Examples include the same alkyl groups and alicyclic hydrocarbon groups as R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 .
Aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups.
Examples of the combined group include a group obtained by combining the aforementioned alkyl group and an alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methyl phenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon groups aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cyclohexyl groups such as phenylcyclohexyl group, and the like. In particular, R ^a36 is an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups. are mentioned.

In formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.
la is preferably 0 or 1, more preferably 0.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group.
The hydrocarbon group of R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination of these A group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. The aromatic hydrocarbon group for R ^a36 is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.
--OC(R ^a34 )(R ^a35 )-OR ^a36 in the structural unit (a1-4) is eliminated upon contact with an acid (eg, p-toluenesulfonic acid) to form a hydroxy group.

Examples of structural units (a1-4) include structural units derived from monomers described in JP-A-2010-204646. Preferably, structural units represented by formulas (a1-4-1) to (a1-4-12) and structures in which the hydrogen atom corresponding to R ^a32 in the structural unit (a1-4) is replaced with a methyl group units, more preferably structural units represented by formulas (a1-4-1) to (a1-4-5) and formula (a1-4-10).

When the resin (A) contains the structural unit (a1-4), the content thereof is preferably 10 to 95 mol%, preferably 15 to 90 mol%, based on the total of all structural units of the resin (A). It is more preferably 20 to 85 mol %, even more preferably 20 to 70 mol %, and particularly preferably 20 to 60 mol %.

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

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

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

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

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

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

When the resin (A) contains structural units such as the above (a1-3-1) to (a1-3-7), the content is 10 to 10 to the total structural units of the resin (A). 95 mol % is preferred, 15 to 90 mol % is more preferred, 20 to 85 mol % is even more preferred, 20 to 70 mol % is even more preferred, and 20 to 60 mol % is particularly preferred.

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

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

［式（ａ２－Ａ）中、
Ｒ^a50は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ｒ^a51は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～４のアルキルカルボニル基、炭素数２～４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a50は、単結合又は＊－Ｘ^a51－（Ａ^a52－Ｘ^a52）_nb－を表し、＊は－Ｒ^a50が結合する炭素原子との結合部位を表す。
Ａ^a52は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
Ｘ^a51及びＸ^a52は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－を表す。
ｎｂは、０又は１を表す。
ｍｂは０～４のいずれかの整数を表す。ｍｂが２以上のいずれかの整数である場合、複数のＲ^a51は互いに同一であっても異なってもよい。］ Structural units having a phenolic hydroxy group in structural units (a2) include structural units represented by formula (a2-A) (hereinafter sometimes referred to as “structural unit (a2-A)”).

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

Halogen atoms in R ^a50 include fluorine, chlorine and bromine atoms.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom for R ^a50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2, 3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluoro A hexyl group is mentioned.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, even more preferably a hydrogen atom or a methyl group.
Examples of alkyl groups for R ^a51 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl and hexyl groups.
Alkoxy groups for R ^a51 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy and tert-butoxy groups. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred.
The alkylcarbonyl group for R ^a51 includes an acetyl group, a propionyl group and a butyryl group.
The alkylcarbonyloxy group for R ^a51 includes an acetyloxy group, a propionyloxy group and a butyryloxy group.
R ^a51 is preferably a methyl group.

*-X ^a51 -(A ^a52 -X ^a52 ) _nb - includes *-O-, *-CO-O-, *-O-CO-, *-CO-O-A ^a52 -CO-O-, *-O-CO-A ^a52 -O-, *-O-A ^a52 -CO-O-, *-CO-O-A ^a52 -O-CO-, *-O-CO-A ^a52 -O-CO -, and the like. Among them, *-CO-O-, *-CO-OA ^a52 -CO-O- or * ^{-OA a52} -CO-O- is preferred.

The alkanediyl group includes methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -methylbutane-1,4-diyl group and the like.
A ^a52 is preferably a methylene group or an ethylene group.

A ^a50 is preferably a single bond, *—CO—O— or *—CO—O—A ^a52 —CO—O—, a single bond, *—CO—O— or *—CO—O—CH ₂ -CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

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

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

The structural unit (a2-A) includes structural units represented by formulas (a2-2-1) to (a2-2-6) and formulas (a2-2-1) to (a2-2- In the structural unit represented by 6), a structural unit in which the methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom can be mentioned. Structural unit (a2-A) includes a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), and a structural unit represented by formula (a2-2-6). and the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3) or the structural unit represented by formula (a2-2-6), A structural unit in which the methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom is preferred.

When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol% of the total structural units, more preferably It is 10 to 70 mol %, more preferably 15 to 65 mol %, still more preferably 20 to 65 mol %.
The structural unit (a2-A) can be included in the resin (A), for example, by polymerizing the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Further, the structural unit (a2-A) can be included in the resin (A) by polymerizing with acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide.

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

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

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

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

When the resin (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on the total structural units of the resin (A). more preferably 1 to 35 mol %, still more preferably 1 to 20 mol %, even more preferably 1 to 10 mol %, and still more preferably 1.5 to 5 mol %.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, γ-butyrolactone ring, δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. It's okay. Preferable examples include a γ-butyrolactone ring, an adamantanelactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)).

［式（ａ３－１）、式（ａ３－２）、式（ａ３－３）及び式（ａ３－４）中、
Ｌ^ａ４、Ｌ^ａ５及びＬ^ａ６は、それぞれ独立に、－Ｏ－又は＊－Ｏ－（ＣＨ_２）_ｋ３－ＣＯ－Ｏ－（ｋ３は１～７のいずれかの整数を表す。）で表される基を表す。
Ｌ^ａ７は、－Ｏ－、＊－Ｏ－Ｌ^ａ８－Ｏ－、＊－Ｏ－Ｌ^ａ８－ＣＯ－Ｏ－、＊－Ｏ－Ｌ^ａ８－ＣＯ－Ｏ－Ｌ^ａ９－ＣＯ－Ｏ－又は＊－Ｏ－Ｌ^ａ８－Ｏ－ＣＯ－Ｌ^ａ９－Ｏ－を表す。
Ｌ^ａ８及びＬ^ａ９は、それぞれ独立に、炭素数１～６のアルカンジイル基を表す。
＊はカルボニル基との結合部位を表す。
Ｒ^ａ１８、Ｒ^ａ１９及びＲ^ａ２０は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ２４は、ハロゲン原子を有していてもよい炭素数１～６のアルキル基、水素原子又はハロゲン原子を表す。
Ｘ^ａ３は、－ＣＨ_２－又は酸素原子を表す。
Ｒ^ａ２１は炭素数１～４の脂肪族炭化水素基を表す。
Ｒ^ａ２２、Ｒ^ａ２３及びＲ^ａ２５は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。
ｐ１は０～５のいずれかの整数を表す。
ｑ１は、０～３のいずれかの整数を表す。
ｒ１は、０～３のいずれかの整数を表す。
ｗ１は、０～８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^ａ２１、Ｒ^ａ２２、Ｒ^ａ２３及び／又はＲ^ａ２５は互いに同一であってもよく、異なっていてもよい。］ Structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3) or formula (a3-4). One of these may be contained alone, or two or more may be contained.

[In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4),
L ^a4 , L ^a5 and L ^a6 are each independently represented by —O— or *—O—(CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7); represents a group.
L ^a7 is -O-, * ^{-OL a8} -O-, * ^{-OL a8} -CO-O-, * ^{-OL a8} -CO- ^{OL a9} -CO-O- or * -OL ^a8 -O-CO-L ^a9 -O-.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* represents a bonding site with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
X ^a3 represents —CH ₂ — or an oxygen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer from 0 to 5;
q1 represents an integer of 0 to 3;
r1 represents an integer of 0 to 3;
w1 represents any integer from 0 to 8;
When p1, q1, r1 and/or w1 are 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and/or R ^a25 may be the same or different. ]

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

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

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

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

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

As the structural unit (a3), the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, the structure derived from the monomer described in JP-A-2012-41274 units. As the structural unit (a3), formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2), formula (a3-3- 1), a structural unit represented by any one of formulas (a3-3-2) and formulas (a3-4-1) to (a3-4-12), and in said structural unit, formula (a3-1 ) to R ^a18 , R ^a19 , R ^a20 and R ^a24 in formulas (a3-4) are preferably structural units in which methyl groups are replaced with hydrogen atoms.

When the resin (A) contains the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on the total structural units of the resin (A). , more preferably 10 to 60 mol %, even more preferably 20 to 55 mol %, still more preferably 30 to 50 mol %.
Further, the content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structural unit (a3-4) is 5 to 60 mol % is preferred, 15 to 60 mol % is more preferred, and 20 to 60 mol % is even more preferred.

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

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

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

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

［式（ａ４－０）中、
Ｒ⁵⁴は、水素原子又はメチル基を表す。
Ｌ^4ａは、単結合又は炭素数１～４のアルカンジイル基を表す。
Ｌ^3ａは、炭素数１～８のペルフルオロアルカンジイル基又は炭素数３～１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ⁶⁴は、水素原子又はフッ素原子を表す。］ The structural unit (a4) is at least selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3) and formula (a4-4) Structural units represented by one are exemplified.

[In the formula (a4-0),
^R54 represents a hydrogen atom or a methyl group.
L ^4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
^R64 represents a hydrogen atom or a fluorine atom. ]

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

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

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

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

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

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

[In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced with —O— or —CO— may
A ^a41 represents an optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by formula (a-g1). However, at least one of A ^a41 and R ^a42 has a fluorine atom as a substituent.

[In the formula (a-g1),
s represents 0 or 1;
A ^a42 and A ^a44 each independently represent an optionally substituted divalent saturated hydrocarbon group having 1 to 5 carbon atoms.
A ^a43 represents a single bond or an optionally substituted C 1-5 divalent saturated hydrocarbon group.
X ^a41 and X ^a42 each independently represent -O-, -CO-, -CO-O- or -O-CO-.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* is a binding site, and * on the right side is a binding site with --O--CO--R ^a42 . ]

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

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

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

［式（ａ－ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＲ^a42との結合部位を表す。）。
Ａ^a45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。
＊は結合部位を表す。］
ただし、Ｒ^a42－Ｘ^a43－Ａ^a45において、Ｒ^a42がフッ素原子を有しない場合は、Ａ^a45は、少なくとも１つのフッ素原子を有する炭素数１～１７の飽和炭化水素基を表す。 Examples of the substituent that R ^a42 may have include at least one selected from the group consisting of fluorine atoms and groups represented by formulas (a-g3).

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

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

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

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

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

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

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

Alkanediyl group for A ^a41 includes methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group. straight-chain alkanediyl groups such as; Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group can be mentioned.
Examples of substituents in the alkanediyl group represented by A ^a41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

The divalent saturated hydrocarbon groups represented by A ^a42 , A ^a43 and A ^a44 in the group represented by the formula (a-g1) include linear or branched alkanediyl groups and monocyclic divalent alicyclic A saturated hydrocarbon group, a saturated hydrocarbon group formed by combining an alkanediyl group and a divalent saturated alicyclic hydrocarbon group, and the like are included. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
Examples of substituents of the divalent saturated hydrocarbon groups represented by A ^a42 , A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably zero.

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

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

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

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

Examples of the C 1-6 alkanediyl group for L ⁴⁴ include the same groups as those exemplified for A ^a41 .
Examples of the saturated hydrocarbon group for R ^f6 include the same groups as those exemplified for R ^a42 .
The alkanediyl group having 1 to 6 carbon atoms in L ⁴⁴ is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

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

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

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

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

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

Examples of saturated hydrocarbon groups and optionally fluorine-containing saturated hydrocarbon groups for A ^f14 include groups similar to those exemplified for R ^a42 . Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, Fluorination such as 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, perfluorohexyl, heptyl, perfluoroheptyl, octyl and perfluorooctyl groups Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group , a perfluoroadamantylmethyl group, and the like.

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

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

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

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

The saturated hydrocarbon group represented by R ^{f22 includes the same saturated hydrocarbon group represented by R a42 .} R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and an alkyl group having 1 to 10 carbon atoms having a fluorine atom is preferably More preferred is an alkyl group having 1 to 6 carbon atoms and having a fluorine atom.

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

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

When the resin (A) has the structural unit (a4), the content thereof is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, based on the total structural units of the resin (A), and 3 ~10 mol% is more preferred.

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

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

The alicyclic hydrocarbon group for R ⁵² may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl groups and norbornyl groups.
Aliphatic hydrocarbon groups having 1 to 8 carbon atoms are, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2 - alkyl groups such as ethylhexyl groups.
Alicyclic hydrocarbon groups 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X ^III3 include a linear or branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. may be combined.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , dodecane-1,12-diyl group and other linear alkanediyl groups; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 ,4-diyl group, cycloalkanediyl group such as cyclooctane-1,5-diyl group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane Divalent polycyclic alicyclic saturated hydrocarbon groups such as -2,6-diyl group and the like can be mentioned.

Examples of saturated hydrocarbon groups in which —CH ₂ — is replaced with —O—, —S— or —CO— include divalent groups represented by formulas (X1) to (X53). mentioned. However, -CH ₂ - contained in the saturated hydrocarbon group has 17 or less carbon atoms before being replaced with -O-, -S- or -CO-. In the formula below, * and ** represent binding sites, and * represents a binding site with ^Ax1 .

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

Organic cations represented by ZA ⁺ include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred. Specifically, a cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter sometimes referred to as "cation (b2-1)" etc. depending on the formula number) is mentioned.

式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^b4～Ｒ^b6は、それぞれ独立に、炭素数１～３０の鎖式炭化水素基、炭素数３～３６の脂環式炭化水素基又は炭素数６～３６の芳香族炭化水素基を表し、該鎖式炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１～１２のアルコキシ基、炭素数３～１２の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～１８の脂肪族炭化水素基、炭素数２～４のアルキルカルボニル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１～１２のアルコキシ基で置換されていてもよい。
Ｒ^b4とＲ^b5とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０～５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^b7は同一でも異なってもよく、ｎ２が２以上のとき、複数のＲ^b8は同一でも異なってもよい。
Ｒ^b9及びＲ^b10は、それぞれ独立に、炭素数１～３６の鎖式炭化水素基又は炭素数３～３６の脂環式炭化水素基を表す。
Ｒ^b9とＲ^b10とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b11は、水素原子、炭素数１～３６の鎖式炭化水素基、炭素数３～３６の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表す。
Ｒ^b12は、炭素数１～１２の鎖式炭化水素基、炭素数３～１８の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表し、該鎖式炭化水素に含まれる水素原子は、炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１～１２のアルコキシ基又は炭素数１～１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^b11とＲ^b12とは、互いに結合してそれらが結合する－ＣＨ－ＣＯ－を含めて環を形成していてもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b13～Ｒ^b18は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
Ｌ^b31は、硫黄原子又は酸素原子を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０～５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０～４のいずれかの整数を表す。
ｕ２は０又は１を表す。
ｏ２が２以上のとき、複数のＲ^b13は同一又は相異なり、ｐ２が２以上のとき、複数のＲ^b14は同一又は相異なり、ｑ２が２以上のとき、複数のＲ^b15は同一又は相異なり、ｒ２が２以上のとき、複数のＲ^b16は同一又は相異なり、ｓ２が２以上のとき、複数のＲ^b17は同一又は相異なり、ｔ２が２以上のとき、複数のＲ^b18は同一又は相異なる。
脂肪族炭化水素基とは、鎖式炭化水素基及び脂環式炭化水素基を表す。
鎖式炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基及び２－エチルヘキシル基のアルキル基が挙げられる。
特に、Ｒ^b9～Ｒ^b12の鎖式炭化水素基は、好ましくは炭素数１～１２である。
脂環式炭化水素基としては、単環式又は多環式のいずれでもよく、単環式の脂環式炭化水素基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基等のシクロアルキル基が挙げられる。多環式の脂環式炭化水素基としては、デカヒドロナフチル基、アダマンチル基、ノルボルニル基及び下記の基等が挙げられる。

特に、Ｒ^b9～Ｒ^b12の脂環式炭化水素基は、好ましくは炭素数３～１８、より好ましくは炭素数４～１２である。
水素原子が脂肪族炭化水素基で置換された脂環式炭化水素基としては、メチルシクロヘキシル基、ジメチルシクロへキシル基、２－メチルアダマンタン－２－イル基、２－エチルアダマンタン－２－イル基、２－イソプロピルアダマンタン－２－イル基、メチルノルボルニル基、イソボルニル基等が挙げられる。水素原子が脂肪族炭化水素基で置換された脂環式炭化水素基においては、脂環式炭化水素基と脂肪族炭化水素基との合計炭素数が好ましくは２０以下である。
芳香族炭化水素基としては、フェニル基、ビフェニリル基、ナフチル基、フェナントリル基等のアリール基が挙げられる。
なお、芳香族炭化水素基は、鎖式炭化水素基又は脂環式炭化水素基を有していてもよく、炭素数１～１８の鎖式炭化水素基を有する芳香族炭化水素基（トリル基、キシリル基、クメニル基、メシチル基、ｐ－エチルフェニル基、ｐ－ｔｅｒｔ－ブチルフェニル基、２，６－ジエチルフェニル基、２－メチル－６－エチルフェニル基等）、及び炭素数３～１８の脂環式炭化水素基を有する芳香族炭化水素基（ｐ－シクロへキシルフェニル基、ｐ－アダマンチルフェニル基等）等が挙げられる。
水素原子がアルコキシ基で置換された芳香族炭化水素基としては、ｐ－メトキシフェニル基等が挙げられる。
水素原子が芳香族炭化水素基で置換された鎖式炭化水素基としては、ベンジル基、フェネチル基、フェニルプロピル基、トリチル基、ナフチルメチル基、ナフチルエチル基等のアラルキル基が挙げられる。
アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、デシルオキシ基及びドデシルオキシ基等が挙げられる。
アルキルカルボニル基としては、アセチル基、プロピオニル基及びブチリル基等が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられる。
アルキルカルボニルオキシ基としては、メチルカルボニルオキシ基、エチルカルボニルオキシ基、プロピルカルボニルオキシ基、イソプロピルカルボニルオキシ基、ブチルカルボニルオキシ基、ｓｅｃ－ブチルカルボニルオキシ基、ｔｅｒｔ－ブチルカルボニルオキシ基、ペンチルカルボニルオキシ基、ヘキシルカルボニルオキシ基、オクチルカルボニルオキシ基及び２－エチルヘキシルカルボニルオキシ基等が挙げられる。
Ｒ^b4とＲ^b5とが互いに結合してそれらが結合する硫黄原子と一緒になって形成する環は、単環式、多環式、芳香族性、非芳香族性、飽和及び不飽和のいずれの環であってもよい。この環は、炭素数３～１８の環が挙げられ、好ましくは炭素数４～１８の環である。また、硫黄原子を含む環は、３員環～１２員環が挙げられ、好ましくは３員環～７員環であり、例えば下記の環が挙げられる。

Ｒ^b9とＲ^b10とが一緒になって形成する環は、単環式、多環式、芳香族性、非芳香族性、飽和及び不飽和のいずれの環であってもよい。この環は、３員環～１２員環が挙げられ、好ましくは３員環～７員環である。例えば、チオラン－１－イウム環（テトラヒドロチオフェニウム環）、チアン－１－イウム環、１，４－オキサチアン－４－イウム環等が挙げられる。
Ｒ^b11とＲ^b12とが一緒になって形成する環は、単環式、多環式、芳香族性、非芳香族性、飽和及び不飽和のいずれの環であってもよい。この環は、３員環～１２員環が挙げられ、好ましくは３員環～７員環である。オキソシクロヘプタン環、オキソシクロヘキサン環、オキソノルボルナン環、オキソアダマンタン環等が挙げられる。

In formulas (b2-1) to (b2-4),
R ^b4 to R ^b6 each independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms; The hydrogen atom contained in the chain hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. It may be substituted, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. It may be substituted, and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be —O—, —S— or -CO- may be substituted.
R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5;
When m2 is 2 or more, multiple R ^b7 may be the same or different, and when n2 is 2 or more, multiple R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be —O—, —S— or -CO- may be substituted.
R ^b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are alkoxy groups having 1 to 12 carbon atoms or 1 to 1 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may be bonded to each other to form a ring including —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring may be —O—, —S - or -CO- may be substituted.
R ^b13 to R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5;
q2 and r2 each independently represent an integer of 0 to 4;
u2 represents 0 or 1;
When o2 is 2 or more, multiple R ^b13 are the same or different, when p2 is 2 or more, multiple R ^b14 are the same or different, and when q2 is 2 or more, multiple R ^b15 are the same or different. , when r2 is 2 or more, the plurality of R ^b16 are the same or different; when s2 is 2 or more, the plurality of R ^b17 are the same or different; when t2 is 2 or more, the plurality of R ^b18 are the same or different; different.
An aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
Chain hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. mentioned.
In particular, chain hydrocarbon groups of R ^b9 to R ^b12 preferably have 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo Cycloalkyl groups such as a heptyl group, a cyclooctyl group, and a cyclodecyl group can be mentioned. The polycyclic alicyclic hydrocarbon group includes decahydronaphthyl group, adamantyl group, norbornyl group and the following groups.

In particular, the alicyclic hydrocarbon groups of R ^b9 to R ^b12 preferably have 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
Alicyclic hydrocarbon groups in which hydrogen atoms are substituted with aliphatic hydrocarbon groups include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, and 2-ethyladamantan-2-yl group. , 2-isopropyladamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.
The aromatic hydrocarbon group includes aryl groups such as phenyl group, biphenylyl group, naphthyl group and phenanthryl group.
The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms (tolyl group , xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and 3 to 18 carbon atoms aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.) having an alicyclic hydrocarbon group of
Aromatic hydrocarbon groups in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group and the like.
Chain hydrocarbon groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl and naphthylethyl groups.
Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups.
An acetyl group, a propionyl group, a butyryl group, etc. are mentioned as an alkylcarbonyl group.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group and a pentylcarbonyloxy group. , hexylcarbonyloxy group, octylcarbonyloxy group and 2-ethylhexylcarbonyloxy group.
The ring formed by R ^b4 and R ^b5 bonded together with the sulfur atom to which they are bonded may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. may be a ring of This ring includes a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Further, the ring containing a sulfur atom includes a 3- to 12-membered ring, preferably a 3- to 7-membered ring, and examples thereof include the following rings.

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

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

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

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

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

［式（ＩＩ－２－Ａ）中、Ｒ^ＩＩＩ３、Ｘ^ＩＩＩ３及びＺＡ^＋は、上記と同じ意味を表す。
ｚは、０～６のいずれかの整数を表す。
Ｒ^ＩＩＩ２及びＲ^ＩＩＩ４は、それぞれ独立して、水素原子、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表し、ｚが２以上のとき、複数のＲ^ＩＩＩ２及びＲ^ＩＩＩ４は互いに同一であってもよいし、異なっていてもよい。
Ｑ^ａ及びＱ^ｂは、それぞれ独立して、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。］
Ｒ^ＩＩＩ２、Ｒ^ＩＩＩ４、Ｑ^ａ及びＱ^ｂで表される炭素数１～６のペルフルオロアルキル基としては、前述のＡ^ｘ１の置換基である炭素数１～６のペルフルオロアルキル基と同じものが挙げられる。 The structural unit represented by formula (II-2-A') is preferably a structural unit represented by formula (II-2-A).

[In formula (II-2-A), R ^III3 , X ^III3 and ZA ⁺ have the same meanings as above.
z represents any integer from 0 to 6;
R ^III2 and R ^III4 each independently represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, and when z is 2 or more, a plurality of R ^III2 and R ^III4 are the same may be different.
Q ^a and Q ^b each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. ]
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R ^III2 , R ^III4 , Q ^a and Q ^b include the same perfluoroalkyl group having 1 to 6 carbon atoms as the substituent of A ^x1 described above. be done.

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

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

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

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

The structural unit represented by formula (II-2-A′) includes, for example, the following structural units and structural units described in International Publication No. 2012/050015. ZA ⁺ represents an organic cation.

［式（ＩＩ－１－１）中、
Ａ^ＩＩ１は、単結合又は２価の連結基を表す。
Ｒ^ＩＩ１は、炭素数６～１８の２価の芳香族炭化水素基を表す。
Ｒ^ＩＩ２及びＲ^ＩＩ３は、それぞれ独立して、炭素数１～１８の炭化水素基を表し、Ｒ^ＩＩ２及びＲ^ＩＩ３は互いに結合してそれらが結合する硫黄原子とともに環を形成していてもよい。
Ｒ^II4は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１～６のアルキル基を表す。
Ａ^－は、有機アニオンを表す。］
Ｒ^ＩＩ１で表される炭素数６～１８の２価の芳香族炭化水素基としては、フェニレン基及びナフチレン基等が挙げられる。
Ｒ^ＩＩ２及びＲ^ＩＩ３で表される炭化水素基としては、Ｒ^ａ３’で表される炭化水素基と同じものが挙げられる。
Ｒ^ＩＩ４で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられる。
Ｒ^ＩＩ４で表されるハロゲン原子を有していてもよい炭素数１～６のアルキル基としては、Ｒ^ａ８で表されるハロゲン原子を有していてもよい炭素数１～６のアルキル基と同じものが挙げられる。
Ａ^ＩＩ１で表される２価の連結基としては、例えば、炭素数１～１８の２価の飽和炭化水素基が挙げられ、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ－又は－ＣＯ－で置き換わっていてもよい。具体的には、Ｘ^ＩＩＩ３で表される炭素数１～１８の２価の飽和炭化水素基と同じものが挙げられる。 A structural unit having a sulfonio group and an organic anion in a side chain is preferably a structural unit represented by formula (II-1-1).

[In the formula (II-1-1),
^AII1 represents a single bond or a divalent linking group.
R ^II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^II2 and R ^II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R ^II2 and R ^II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded.
R ^II4 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
A ⁻ represents an organic anion. ]
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^II1 include a phenylene group and a naphthylene group.
The hydrocarbon groups represented by R ^II2 and R ^II3 include the same hydrocarbon groups as those represented by R ^a3′ .
Halogen atoms represented by ^RII4 include fluorine, chlorine, bromine and iodine atoms.
The alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 includes an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 . The same can be mentioned.
The divalent linking group represented by A ^II1 includes, for example, a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is -O-, -S- or -CO- may be substituted. Specific examples thereof include the same divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by X ^III3 .

Examples of structural units containing cations in formula (II-1-1) include structural units represented below.

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

Sulfonylimide anions represented by A ⁻ include the following.

Sulfonylmethide anions include the following.

Carboxylate anions include the following.

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

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

Resin (A) may have structural units other than the structural units described above, and examples of such structural units include structural units well known in the art.
Resin (A) is preferably a resin composed of structural unit (a1) and structural unit (s), that is, a copolymer of monomer (a1) and monomer (s).
Structural unit (a1) is preferably a group consisting of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group) is at least one selected from, more preferably structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2) (preferably a cyclohexyl group, or the structural unit having a cyclopentyl group) It is at least two selected from the group consisting of, more preferably at least two selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2).
Structural unit (s) is preferably at least one selected from the group consisting of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably a structural unit represented by formula (a2-1) or a structural unit represented by formula (a2-A). Structural unit (a3) is preferably a group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-4) is at least one selected from

Each structural unit that constitutes the resin (A) may be used alone or in combination of two or more. Using a monomer that induces these structural units, it is produced by a known polymerization method (e.g., radical polymerization method). can do. The content of each structural unit in the resin (A) can be adjusted by adjusting the amount of monomer used for polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, further preferably is 15,000 or less). As used herein, the weight average molecular weight is a value obtained by gel permeation chromatography under the conditions described in Examples.

<Resin (X)>
Resin (X) is a resin containing a structural unit having a fluorine atom. Examples of the resin (X) include a resin consisting only of the structural unit (a4), a resin consisting of the structural unit (a4) and the structural unit (a5), and the like.
In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total of all structural units of the resin (X). , more preferably 45 mol % or more.
Structural units that the resin (X) may further include structural units (a1), structural units (a2), structural units (a3), and structural units derived from other known monomers. Among them, the resin (X) is preferably a resin consisting only of the structural unit (a4) and/or the structural unit (a5), more preferably a resin consisting only of the structural unit (a4).
Each structural unit that constitutes the resin (X) may be used alone or in combination of two or more. Using a monomer that induces these structural units, the resin (X) is produced by a known polymerization method (e.g., radical polymerization method). can do. The content of each structural unit in the resin (X) can be adjusted by adjusting the amount of the monomer used for polymerization.
The weight average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight-average molecular weight of resin (X) is the same as for resin (A).
When the resist composition contains resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of resin (A). It is preferably 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass.

The total content of resin (A) and resin (X) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90 to 99% by mass, based on the solid content of the resist composition. preferable. The solid content and resin content of the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator (B) may be either nonionic or ionic. Nonionic acid generators include sulfonate esters (eg 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg disulfone, ketosulfone, sulfonyldiazomethane) and the like. Typical ionic acid generators are onium salts containing onium cations (eg, diazonium salts, phosphonium salts, sulfonium salts and iodonium salts). The anions of the onium salts include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, and the like.
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, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. A compound that generates an acid upon exposure to radiation as described in 1. above can be used. Moreover, you may use the compound manufactured by the well-known method. The acid generator (B) may be used in combination of two or more.

［式（Ｂ１）中、
Ｑ^ｂ１及びＱ^ｂ２は、それぞれ独立に、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－Ｓ（Ｏ）_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generator (B1)").

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced with —O— or —CO— , a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, included in the alicyclic hydrocarbon group- CH ₂ - may be replaced by -O-, -S(O) ₂ - or -CO-.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl groups represented by Q ^b1 and Q ^b2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and A perfluorohexyl group and the like can be mentioned.
Q ^b1 and Q ^b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both a fluorine atom.

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

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

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

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

In the groups represented by formulas (b1-1) to (b1-3), when —CH ₂ — contained in the saturated hydrocarbon group is replaced with —O— or —CO—, carbon before replacement Let the number be the number of carbon atoms of the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include those similar to the saturated hydrocarbon group for ^Lb1 .

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 a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO—.
The group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced with —O— or —CO— is represented by formula (b1-1) or formula (b1-3). are preferred.

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

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

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

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

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

In addition, in the group represented by formula (b1-9) to the group represented by formula (b1-11), when the hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, it is substituted Let the previous carbon number be the carbon number of this saturated hydrocarbon group.

The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

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

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

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

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

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

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

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

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

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

Ｙで表される脂環式炭化水素基としては、好ましくは式（Ｙ１）～式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）～式（Ｙ４１）のいずれかで表される基であり、より好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ１６）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）～式（Ｙ３１）又は式（Ｙ３９）～式（Ｙ４０）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ２０）、式（Ｙ３０）、式（Ｙ３９）又は式（Ｙ４０）で表される基である。
Ｙで表される脂環式炭化水素基が式（Ｙ２８）～式（Ｙ３５）、式（Ｙ３９）又は式（Ｙ４０）等の、酸素原子を含むスピロ環である場合には、２つの酸素原子間のアルカンジイル基は、１以上のフッ素原子を有することが好ましい。また、ケタール構造に含まれるアルカンジイル基のうち、酸素原子に隣接するメチレン基には、フッ素原子が置換されていないのが好ましい。 The alicyclic hydrocarbon group represented by Y includes groups represented by formulas (Y1) to (Y11) and formulas (Y36) to (Y38).
When —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced with —O—, —S(O) ₂ — or —CO—, the number may be 1 or 2 or more. good. Such groups include groups represented by formulas (Y12) to (Y35) and formulas (Y39) to (Y41).

The alicyclic hydrocarbon group represented by Y is preferably represented by formulas (Y1) to (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), and formula (Y39). to a group represented by any one of formula (Y41), more preferably formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30) to a group represented by formula (Y31) or formula (Y39) to formula (Y40), more preferably formula (Y11), formula (Y15), formula (Y20), formula (Y30), formula (Y39) or a group represented by formula (Y40).
When the alicyclic hydrocarbon group represented by Y is a spiro ring containing an oxygen atom such as formulas (Y28) to (Y35), formula (Y39) or formula (Y40), two oxygen atoms The intervening alkanediyl groups preferably have one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

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

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Examples of alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and adamantyl groups.
The alicyclic hydrocarbon group may have a chain hydrocarbon group such as a methylcyclohexyl group and a dimethylcyclohexyl group.
Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, biphenylyl, naphthyl, anthryl, and phenanthryl groups.
The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms (tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and lipids having 3 to 18 carbon atoms. Examples thereof include aromatic hydrocarbon groups having a cyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.).
Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group and nonyl. group, decyl group, undecyl group, dodecyl group and the like.
Alkyl groups substituted with a hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups.
Aralkyl groups include benzyl, phenethyl, phenylpropyl, naphthylmethyl and naphthylethyl groups.
Examples of alkylcarbonyl groups include acetyl group, propionyl group and butyryl group.

Examples of Y include the following.

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

Examples of the sulfonate anion in the salt represented by formula (B1) include anions represented by formulas (B1-A-1) to (B1-A-55) [hereinafter referred to as "anion (B1 -A-1)”, etc. ] is preferable, formula (B1-A-1) ~ formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ formula (B1-A-40), represented by any of formula (B1-A-47) ~ formula (B1-A-55) Anions are more preferred.

ここで、Ｒ^ｉ２～Ｒ^ｉ７は、それぞれ独立に、例えば、炭素数１～４のアルキル基、好ましくはメチル基又はエチル基である。Ｒ^ｉ８は、例えば、炭素数１～１２の脂肪族炭化水素基、好ましくは炭素数１～４のアルキル基、炭素数５～１２の脂環式炭化水素基又はこれらを組合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基又はアダマンチル基である。Ｌ^Ａ４１は、単結合又は炭素数１～４のアルカンジイル基である。
Ｑ^ｂ１及びＱ^ｂ２は、上記と同じ意味を表す。
式（Ｂ１）で表される塩におけるスルホン酸アニオンとしては、具体的には、特開２０１０－２０４６４６号公報に記載されたアニオンが挙げられる。

Here, R ⁱ² to R ⁱ⁷ are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ^A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ^b1 and Q ^b2 have the same meanings as above.
Specific examples of the sulfonate anion in the salt represented by formula (B1) include anions described in JP-A-2010-204646.

Preferred examples of the sulfonate anion in the salt represented by formula (B1) include anions represented by formulas (B1a-1) to (B1a-34).

Among them, formula (B1a-1) ~ formula (B1a-3) and formula (B1a-7) ~ formula (B1a-16), formula (B1a-18), formula (B1a-19), formula (B1a-22 ) to Formula (B1a-30) are preferred.

Examples of the organic cation for Z ⁺ include the same as ZA ⁺ in the structural unit represented by formula (II-2-A').

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

The acid generator (B) preferably includes those represented by formulas (B1-1) to (B1-48), respectively. Among them, those containing an arylsulfonium cation are preferred, and formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~ Formula (B1-14), Formula (B1-20) ~ Formula (B1-26), Those represented by formula (B1-29) and formulas (B1-31) to (B1-48) are particularly preferred.

In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin (A). is. The resist composition of the present invention may contain one type of acid generator (B) alone, or may contain a plurality of types.

[Compound (I)]
In formula (I), the divalent hydrocarbon group represented by L ¹ includes an alkanediyl group, a monocyclic or polycyclic bivalent alicyclic saturated hydrocarbon group, and a divalent aromatic hydrocarbon group. A hydrogen group and the like may be mentioned, and a divalent hydrocarbon group in which two or more of these groups are combined may be used.

The alkanediyl groups include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane- 1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group linear alkanediyl groups such as groups;
ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group can be mentioned.
The monocyclic alicyclic saturated hydrocarbon group includes a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group. and monocyclic cycloalkanediyl groups such as
Polycyclic alicyclic saturated hydrocarbon groups include norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like. and polycyclic cycloalkanediyl groups.
Aromatic hydrocarbon groups include phenylene group, naphthylene group, anthrylene group, methylphenylene group, isopropylphenylene group, tert-butylphenylene group, adamantylphenylene group, xylylene group, isopropylphenylene group, trimethylphenylene group, biphenylene group and phenanthrylene group. 2,6-diethylphenylene group, 2-methyl-6-ethylphenylene group and other divalent aromatic hydrocarbon groups.
As the divalent hydrocarbon group in which two or more types are combined, -cycloalkanediyl group-alkanediyl group-, -alkanediyl group-cycloalkanediyl group-alkanediyl group-, -alkanediyl group-aromatic hydrocarbon group- and the like.

—CH ₂ — contained in the divalent hydrocarbon group having 1 to 18 carbon atoms represented by L ¹ is replaced with —O—, —S—, —CO— or —S(O) ₂ — good too.
When —CH ₂ — contained in the divalent hydrocarbon group having 1 to 18 carbon atoms represented by L ¹ is replaced with —O—, —S—, —CO— or —S(O) ₂ — , the number of carbon atoms before substitution is the number of carbon atoms of the hydrocarbon group.

The divalent hydrocarbon group having 1 to 18 carbon atoms represented by L ¹ is an alkanediyl group having 1 to 12 carbon atoms (-CH ₂ - contained in the alkanediyl group is -O- or -CO- ), a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms (-CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -S-, - may be substituted with CO— or —S(O) ₂ —), an alicyclic hydrocarbon group having 3 to 12 carbon atoms (the —CH ₂ — contained in the alicyclic hydrocarbon group is —O may be substituted with -, -S-, -CO- or -S(O) ₂ -) and an alkanediyl group having 1 to 6 carbon atoms (-CH ₂ - contained in the alkanediyl group is - may be substituted with O- or -CO-).
L ¹ is a single bond, an alkanediyl group having 1 to 12 carbon atoms (--CH ₂ -- contained in the alkanediyl group may be replaced with --O-- or --CO--) or 3 carbon atoms. to 12 alicyclic hydrocarbon groups (-CH ₂ - contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -S(O) ₂ - ) and an alkanediyl group having 1 to 6 carbon atoms (-CH ₂ - contained in the alkanediyl group may be replaced with -O- or -CO-). is preferred, a single bond or an alkanediyl group having 1 to 6 carbon atoms is more preferred, a single bond or a methylene group is even more preferred, and a single bond is even more preferred.

The hydrocarbon ring represented by W1 includes ^a monocyclic or polycyclic saturated hydrocarbon ring, a monocyclic or polycyclic unsaturated hydrocarbon ring, and an aromatic hydrocarbon ring.
Monocyclic saturated hydrocarbon rings include cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, and cyclooctane.
The polycyclic saturated hydrocarbon ring includes norbornane, adamantane and the like.
Aromatic hydrocarbon rings include benzene, naphthalene, anthracene, methylbenzene, tert-butylbenzene, adamantylbenzene group, toluene group, xylene group, cumene, mesitylene, biphenyl, phenanthrene, 2,6-diethylbenzene, 2-methyl- 6-ethylbenzene and the like.
--CH ₂ -- contained in the hydrocarbon ring having 3 to 24 carbon atoms represented by W ¹ may be replaced with --O--, --S--, --S(O) ₂ -- or --CO--.
When —CH ₂ — contained in the hydrocarbon ring having 3 to 24 carbon atoms represented by W ¹ is replaced with —O—, —S—, —S(O) ₂ — or —CO—, is taken as the carbon number of the hydrocarbon ring.
W ¹ is preferably a monocyclic or polycyclic saturated hydrocarbon ring or aromatic hydrocarbon ring (with the proviso that —CH ₂ — contained in the saturated hydrocarbon ring and aromatic hydrocarbon ring is , —O—, —S—, —S(O) ₂ — or —CO—), more preferably a monocyclic or polycyclic saturated hydrocarbon ring, and a monocyclic A saturated hydrocarbon ring of the formula is more preferred, and cyclohexane is even more preferred.

Fluorinated alkyl groups for R ¹ and R ² include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2 , 2,2-trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2, 3,3-hexafluoropropyl group, perfluoropropyl group, perfluoroethylmethyl group, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2 -tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2, 3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis(trifluoro)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, 2,2,3,3,4,4,5,5,5 - nonafluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5 , 6,6-dodecafluorohexyl group, perfluorohexyl group and the like.
Among them, R ¹ and R ² are preferably a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a trifluoromethyl group or a perfluoroethyl group, even more preferably a trifluoromethyl group. .

The hydrocarbon group represented by R ³ includes an aliphatic hydrocarbon group (a (linear or branched) chain aliphatic hydrocarbon group such as an alkyl group, an alkenyl group or an alkynyl group, and an alicyclic hydrocarbon group ), aromatic hydrocarbon groups, groups combining these groups, and the like.
The alkyl group includes alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. The number of carbon atoms in the alkyl group is preferably 1-9, more preferably 1-6, still more preferably 1-4.
Alkenyl groups include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl and nonenyl groups.
Examples of alkynyl groups include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, tert-butynyl, pentynyl, hexynyl, octynyl and nonynyl groups.
The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be saturated or unsaturated. The alicyclic hydrocarbon group includes monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl, norbornyl, and adamantyl. and polycyclic cycloalkyl groups such as
As the alicyclic hydrocarbon group represented by R ³ , groups represented by formulas (Y1) to (Y41) (* represents a bonding site) are preferable, and formulas (Y1) to (Y20), It is more preferably a group represented by any one of formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) or formula (Y40), and formula (Y3), ( Y4), formula (Y9), formula (Y11), formula (Y14), formula (Y15), formula (Y20), formula (Y30), formula (Y39) or a group represented by formula (Y40) is more preferred. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3-18, more preferably 3-16, still more preferably 3-12.

Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, biphenyl, anthryl, phenanthryl, and binaphthyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-14, more preferably 6-10.
Examples of combined groups include alicyclic hydrocarbon groups-chain aliphatic hydrocarbon groups-*, such as adamantylmethyl group, adamantylethyl group, adamantylpropyl group, cyclohexylmethyl group, cyclohexylethyl group, and cyclohexylpropyl group, and methyladamantyl. Chain aliphatic hydrocarbon groups such as groups - alicyclic hydrocarbon groups - *, chain aliphatic hydrocarbon groups such as tolyl groups and xylyl groups - aromatic hydrocarbon groups - *, chains such as methylcyclohexylmethyl groups Formula aliphatic hydrocarbon group-alicyclic hydrocarbon group-chain aliphatic hydrocarbon group-*, aromatic hydrocarbon group such as benzyl group-chain aliphatic hydrocarbon group-*, chain formula such as tolylmethyl group Aliphatic hydrocarbon group-aromatic hydrocarbon group-chain aliphatic hydrocarbon group-* and the like. Here, * represents a bonding site with an oxygen atom.
Among them, alicyclic hydrocarbon group-chain aliphatic hydrocarbon group-* and chain aliphatic hydrocarbon group-alicyclic hydrocarbon group-chain aliphatic hydrocarbon group-* are preferred, and alicyclic A hydrocarbon group--a chain aliphatic hydrocarbon group--* is more preferable.

When —CH ₂ — contained in the hydrocarbon group represented by R ³ is replaced with —O—, —S—, —CO— or —S(O) ₂ —, the number of carbon atoms before replacement is The total number of carbon atoms in the hydrocarbon group. In addition, when a substituent is bonded to the hydrocarbon group represented by R ³ , the number of carbon atoms before substitution is taken as the total number of carbon atoms of the hydrocarbon group.
The hydrocarbon group represented by R ³ may have one or more substituents.
Examples of substituents include a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, and an alkylcarbonyl group having 2 to 13 carbon atoms. 13 alkylcarbonyloxy groups or groups in which these groups are combined, and the like.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy. group, dodecyloxy group, and the like.
An alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms and an alkylcarbonyloxy group having 2 to 13 carbon atoms are groups in which a carbonyl group or a carbonyloxy group is bonded to the alkyl group or alkoxy group described above. represents The alkoxycarbonyl group having 2 to 13 carbon atoms includes methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like, and the alkylcarbonyl group having 2 to 13 carbon atoms includes acetyl group, propionyl group, butyryl group and the like. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include acetyloxy group, propionyloxy group and butyryloxy group.
The substituent possessed by R ³ is preferably a fluorine atom or a hydroxy group.

R ³ is preferably a hydrogen atom, a fluorine atom or a chain aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a hydroxy group (provided that —CH ₂ — may be replaced with —O—, —S—, —CO— or —S(O) ₂ —.), 3 to 3 carbon atoms optionally having a fluorine atom or a hydroxy group 18 alicyclic hydrocarbon group (with the proviso that —CH ₂ — contained in said alicyclic hydrocarbon group may be replaced with —O—, —CO— or —S(O) ₂ —); Or a group obtained by combining a chain aliphatic hydrocarbon group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have a fluorine atom or a hydroxy group (wherein the chain —CH ₂ — contained in the aliphatic hydrocarbon group may be replaced with —O— or —CO—, and —CH ₂ — contained in the alicyclic hydrocarbon group may be —O—, —CO - or -S(O) ₂ -), more preferably a chain aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a hydrogen atom or a fluorine atom ( provided that —CH ₂ — contained in the chain aliphatic hydrocarbon group may be replaced with —O— or —CO—) or A group obtained by combining a chain aliphatic hydrocarbon group and an alicyclic hydrocarbon group having 3 to 12 carbon atoms (with the proviso that —CH ₂ — contained in the chain aliphatic hydrocarbon group is —O— or — may be substituted with CO-, and -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted with -O-, -CO- or -S(O) ₂ -); , and more preferably a chain aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a hydrogen atom or a fluorine atom (provided that at least one —CH ₂ — contained in the aliphatic hydrocarbon group is , —O— or —CO—), or a chain aliphatic hydrocarbon group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have a fluorine atom (provided that at least one —CH ₂ — contained in said chain aliphatic hydrocarbon group is replaced with —O— or —CO— and contained in said alicyclic hydrocarbon group —CH ₂ — may be replaced with —O— or —CO—), and more preferably a hydrogen atom, an alkoxyalkyl group, a tertiary alkyl group, an alkoxycarbonyl group (t-butoxycarbonyl group , pentoxycarbonyl group, etc.), fluorinated alkylcarbonyl group, cycloalkyl group-oxycarbonyl-alkyl group (-CH ₂ - contained in the cycloalkyl group may be replaced with -O- or -CO- ), more preferably a hydrogen atom, an alkoxyalkyl group or an alkoxycarbonyl group, and particularly preferably a hydrogen atom.

Examples of compound (I) include compounds represented by the following formula.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
溶媒としては、クロロホルム、アセトニトリル、テトラヒドロフラン、ジメチルホルムアミド等が挙げられる。
反応は、通常１５～８０℃の温度範囲で、０．５～２４時間行われる。
式（Ｉ－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、また、公知の合成方法により容易に製造できる。

<Method for producing compound (I)>
Compound (I) can be obtained by reacting a compound represented by formula (Ia) and a compound represented by formula (Ib) in a solvent.

(In the formula, all symbols have the same meanings as described above.)
Solvents include chloroform, acetonitrile, tetrahydrofuran, dimethylformamide and the like.
The reaction is usually carried out in the temperature range of 15-80° C. for 0.5-24 hours.
Examples of the compound represented by the formula (Ib) include compounds represented by the following formula, which are readily available on the market and can be easily produced by known synthetic methods.

The content of compound (I) is usually 0.001 to 20% by mass, preferably 0.005 to 15% by mass, more preferably 0.01 to 10% by mass, based on the solid content of the resist composition. .
Compound (I) functions as a quencher in the resist composition.

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

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

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

The weak acid inner salt (D) includes the following salts.

When the resist composition contains the quencher (C), the content of the quencher (C) is usually 0.01 to 5% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resist composition. 3% by mass.

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

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

<Method for manufacturing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) a step of applying the resist composition of the present invention onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the exposed composition layer; and (5) developing the heated composition layer.
The coating of the resist composition on the substrate can be carried out using a commonly used device such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be washed, and an antireflection film or the like may be formed on the substrate.
By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is carried out, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a decompression device. The heating temperature is preferably 50 to 200° C., and the heating time is preferably 10 to 180 seconds. Moreover, the pressure for drying under reduced pressure is preferably about 1 to 1.0×10 ⁵ Pa.
The resulting composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an F2 excimer laser ₍ wavelength: 157 nm) that emits a laser beam in the ultraviolet region, a solid-state laser source (YAG or semiconductor laser etc.) and emits harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, electron beam, and extreme ultraviolet light (EUV). can be done. In the present specification, these irradiations with radiation may be collectively referred to as "exposure". During exposure, exposure is usually performed through a mask corresponding to the desired pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.
The exposed composition layer is subjected to a heat treatment (so-called post-exposure bake) in order to promote the deprotection reaction at the acid-labile groups. The heating temperature is usually about 50 to 200°C, preferably about 70 to 150°C.
The composition layer after heating is usually developed using a developer using a developing device. The developing method includes a dipping method, a paddle method, a spraying method, a dynamic dispensing method, and the like. The development temperature is preferably, for example, 5 to 60° C., and the development time is preferably, for example, 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. Examples thereof include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant.
After development, the resist pattern is preferably washed with ultrapure water, and then water remaining on the substrate and pattern is removed.
When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer.
Examples of organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. ether solvents; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole;
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably substantially only the organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and/or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and substantially contains butyl acetate and/or 2-heptanone. - more preferably only heptanone.
The organic developer may contain a surfactant. In addition, the organic developer may contain a trace amount of water.
During development, the development may be stopped by replacing the organic developer with a solvent of a different type.
It is preferable to wash the resist pattern after development with a rinsing liquid. The rinse liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent.
After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and pattern.

<Application>
The resist composition of the present invention is a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure, particularly ArF It is suitable as a resist composition for thick films (thickness 150 nm to 1000 nm) for excimer laser exposure, and is useful for microfabrication of semiconductors.

EXAMPLES The present invention will be described more specifically with reference to examples. In the examples, "%" and "parts" representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value obtained 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)
Further, the structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent Model 1100, MASS: Agilent Model LC/MSD). In the following examples, the value of this molecular ion peak is indicated by "MASS".

式（Ｉ－１－ａ）で表される化合物１０部、メタノール８０部及び１０％水酸化ナトリウム水溶液８．００部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム１００部及びイオン交換水５０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水５０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エチル）分取することにより、式（Ｉ－１－ｂ）で表される化合物４．２８部を得た。

式（Ｉ－１－ｂ）で表される化合物４．２８部、アセトニトリル３５部及び式（Ｉ－１－ｃ）で表される化合物１．８８部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ－１）で表される化合物３．６７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：５２７．１ ［Ｍ＋Ｈ］^＋ Example 1: Synthesis of compound represented by formula (I-1)

10 parts of the compound represented by formula (I-1-a), 80 parts of methanol and 8.00 parts of 10% aqueous sodium hydroxide solution were mixed and stirred at 23° C. for 18 hours. 100 parts of chloroform and 50 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 50 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. The obtained organic layer is concentrated, and the concentrated mass is collected by column (Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain formula (I-1). 4.28 parts of the compound represented by -b) are obtained.

4.28 parts of the compound represented by the formula (I-1-b), 35 parts of acetonitrile and 1.88 parts of the compound represented by the formula (I-1-c) were mixed and stirred at 23° C. for 18 hours. . 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 3.67 parts of the compound represented by the formula (I-1) was obtained.
MASS (ESI(+) Spectrum): 527.1 [M+H] ⁺

式（Ｉ－１－ａ）で表される化合物５．００部、ジメチルホルムアミド３０部、トリエチルアミン２．２２部及びヨウ化カリウム１．００部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ－３－ａ）で表される化合物２．８４部を加え、５℃で３０分間攪拌した後、さらに、２３℃で８時間撹拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮した後、濃縮残渣に、メタノール４０部及び１０％水酸化ナトリウム水溶液４．００部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エチル）分取することにより、式（Ｉ－３－ｃ）で表される化合物２．６１部を得た。

式（Ｉ－３－ｃ）で表される化合物２．６１部、アセトニトリル３５部及び式（Ｉ－１－ｃ）で表される化合物０．８９部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ－３）で表される化合物３．６７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：６１５．１ ［Ｍ＋Ｈ］^＋ Example 2: Synthesis of compound represented by formula (I-3)

5.00 parts of the compound represented by the formula (I-1-a), 30 parts of dimethylformamide, 2.22 parts of triethylamine and 1.00 parts of potassium iodide were mixed and stirred at 23° C. for 30 minutes. Cooled to °C. To the resulting mixture, 2.84 parts of the compound represented by formula (I-3-a) was added, stirred at 5°C for 30 minutes, and then stirred at 23°C for 8 hours. 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. After concentrating the obtained organic layer, 40 parts of methanol and 4.00 parts of 10% aqueous sodium hydroxide solution were mixed with the concentration residue, and the mixture was stirred at 23° C. for 18 hours. 50 parts of chloroform and 25 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. The obtained organic layer is concentrated, and the concentrated mass is collected by column (Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain formula (I-3). 2.61 parts of the compound represented by -c) are obtained.

2.61 parts of the compound represented by the formula (I-3-c), 35 parts of acetonitrile and 0.89 parts of the compound represented by the formula (I-1-c) were mixed and stirred at 23° C. for 18 hours. . 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 3.67 parts of the compound represented by the formula (I-3) was obtained.
MASS (ESI(+) Spectrum): 615.1 [M+H] ⁺

式（Ｉ－１－ｂ）で表される化合物４．３２部、ジメチルホルムアミド３０部及びトリエチルアミン１．１１部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ－３－ａ）で表される化合物１．４２部を加え、５℃で３０分間攪拌した後、さらに、２３℃で２時間撹拌することにより、式（Ｉ－７－ａ）で表される化合物を含む溶液を得た。式（Ｉ－７－ａ）で表される化合物を含む溶液に、ピリジン１．９０部及び式（Ｉ－７－ｂ）で表される化合物５．４６部を加え、４０℃で２時間撹拌した後、２３℃まで冷却した。得られた混合物に、ｐ－トルエンスルホン酸６．８８部を添加した後、２３℃で４時間撹拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エチル）分取することにより、式（Ｉ－７－ｃ）で表される化合物１．６２部を得た。

式（Ｉ－７－ｃ）で表される化合物１．０３部、アセトニトリル２０部及び式（Ｉ－１－ｃ）で表される化合物０．２５部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ－７）で表される化合物１．０１部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：８１９．０ ［Ｍ＋Ｈ］^＋ Example 3: Synthesis of compound represented by formula (I-7)

4.32 parts of the compound represented by the formula (I-1-b), 30 parts of dimethylformamide and 1.11 parts of triethylamine were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, 1.42 parts of the compound represented by formula (I-3-a) was added, stirred at 5°C for 30 minutes, and further stirred at 23°C for 2 hours to give formula (I A solution containing the compound represented by -7-a) was obtained. To the solution containing the compound represented by formula (I-7-a), 1.90 parts of pyridine and 5.46 parts of the compound represented by formula (I-7-b) were added and stirred at 40°C for 2 hours. After that, it was cooled to 23°C. After adding 6.88 parts of p-toluenesulfonic acid to the obtained mixture, the mixture was stirred at 23° C. for 4 hours. 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. The obtained organic layer is concentrated, and the concentrated mass is collected by column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain formula (I-7). 1.62 parts of the compound represented by -c) are obtained.

1.03 parts of the compound represented by the formula (I-7-c), 20 parts of acetonitrile and 0.25 parts of the compound represented by the formula (I-1-c) were mixed and stirred at 23° C. for 18 hours. . 50 parts of chloroform and 25 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 1.01 parts of the compound represented by the formula (I-7) was obtained.
MASS (ESI(+) Spectrum): 819.0 [M+H] ⁺

式（Ｉ－１－ａ）で表される化合物５．００部、ジメチルホルムアミド３０部、トリエチルアミン２．２２部及びヨウ化カリウム１．００部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ－５－ａ）で表される化合物６．５６部を加え、５℃で３０分間攪拌した後、さらに、２３℃で８時間撹拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮した後、濃縮残渣に、メタノール４０部及び１０％水酸化ナトリウム水溶液４．００部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エチル）分取することにより、式（Ｉ－５－ｃ）で表される化合物３．２９部を得た。

式（Ｉ－５－ｃ）で表される化合物３．１７部、アセトニトリル３５部及び式（Ｉ－１－ｃ）で表される化合物０．８９部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ－５）で表される化合物３．８８部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：７２７．２ ［Ｍ＋Ｈ］^＋ Example 4: Synthesis of compound represented by formula (I-5)

5.00 parts of the compound represented by the formula (I-1-a), 30 parts of dimethylformamide, 2.22 parts of triethylamine and 1.00 parts of potassium iodide were mixed and stirred at 23° C. for 30 minutes. Cooled to °C. To the resulting mixture, 6.56 parts of the compound represented by formula (I-5-a) was added, stirred at 5°C for 30 minutes, and then stirred at 23°C for 8 hours. 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. After concentrating the obtained organic layer, 40 parts of methanol and 4.00 parts of 10% aqueous sodium hydroxide solution were mixed with the concentration residue, and the mixture was stirred at 23° C. for 18 hours. 50 parts of chloroform and 25 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. The obtained organic layer is concentrated, and the concentrated mass is collected by column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain formula (I-5). 3.29 parts of the compound represented by -c) are obtained.

3.17 parts of the compound represented by the formula (I-5-c), 35 parts of acetonitrile and 0.89 parts of the compound represented by the formula (I-1-c) were mixed and stirred at 23° C. for 18 hours. . 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 3.88 parts of the compound represented by formula (I-5) was obtained.
MASS (ESI(+) Spectrum): 727.2 [M+H] ⁺

式（Ｉ－１－ａ）で表される化合物５．００部、ジメチルホルムアミド３０部、トリエチルアミン２．２２部及びヨウ化カリウム１．００部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ－２７－ａ）で表される化合物７．４０部を加え、５℃で３０分間攪拌した後、さらに、２３℃で８時間撹拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮した後、濃縮残渣に、メタノール４０部及び１０％水酸化ナトリウム水溶液４．００部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エチル）分取することにより、式（Ｉ－２７－ｃ）で表される化合物３．４０部を得た。

式（Ｉ－２７－ｃ）で表される化合物３．３１部、アセトニトリル３５部及び式（Ｉ－１－ｃ）で表される化合物０．８９部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ－２７）で表される化合物３．６９部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：７５５．２ ［Ｍ＋Ｈ］^＋ Example 5: Synthesis of compound represented by formula (I-27)

5.00 parts of the compound represented by the formula (I-1-a), 30 parts of dimethylformamide, 2.22 parts of triethylamine and 1.00 parts of potassium iodide were mixed and stirred at 23° C. for 30 minutes. Cooled to °C. To the resulting mixture, 7.40 parts of the compound represented by formula (I-27-a) was added, stirred at 5°C for 30 minutes, and then stirred at 23°C for 8 hours. 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. After concentrating the obtained organic layer, 40 parts of methanol and 4.00 parts of 10% aqueous sodium hydroxide solution were mixed with the concentration residue, and the mixture was stirred at 23° C. for 18 hours. 50 parts of chloroform and 25 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. The obtained organic layer is concentrated, and the concentrated mass is collected by column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain the compound of formula (I-27). 3.40 parts of the compound represented by -c) are obtained.

3.31 parts of the compound represented by the formula (I-27-c), 35 parts of acetonitrile and 0.89 parts of the compound represented by the formula (I-1-c) were mixed and stirred at 23° C. for 18 hours. . 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 3.69 parts of the compound represented by the formula (I-27) was obtained.
MASS (ESI(+) Spectrum): 755.2 [M+H] ⁺

式（Ｉ－１－ａ）で表される化合物５．００部、ジメチルホルムアミド３０部、トリエチルアミン２．２２部及びヨウ化カリウム１．００部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ－１８－ａ）で表される化合物７．２９部を加え、５℃で３０分間攪拌した後、さらに、２３℃で８時間撹拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮した後、濃縮残渣に、メタノール４０部及び１０％水酸化ナトリウム水溶液４．００部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム５０部及びイオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水２５部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：酢酸エチル）分取することにより、式（Ｉ－１８－ｃ）で表される化合物４．２９部を得た。

式（Ｉ－１８－ｃ）で表される化合物４．２３部、アセトニトリル３５部及び式（Ｉ－１－ｃ）で表される化合物０．８９部を混合し、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム８０部及びイオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。得られた有機層に、イオン交換水４０部を加え、２３℃で３０分間攪拌し、分液することにより有機層を得た。この水洗の操作を５回行った。得られた有機層を濃縮することにより、式（Ｉ－１８）で表される化合物４．１３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：９３９．３ ［Ｍ＋Ｈ］^＋ Example 6: Synthesis of compound represented by formula (I-18)

5.00 parts of the compound represented by the formula (I-1-a), 30 parts of dimethylformamide, 2.22 parts of triethylamine and 1.00 parts of potassium iodide were mixed and stirred at 23° C. for 30 minutes. Cooled to °C. To the resulting mixture, 7.29 parts of the compound represented by formula (I-18-a) was added, stirred at 5°C for 30 minutes, and then stirred at 23°C for 8 hours. 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. After concentrating the obtained organic layer, 40 parts of methanol and 4.00 parts of 10% aqueous sodium hydroxide solution were mixed with the concentration residue, and the mixture was stirred at 23° C. for 18 hours. 50 parts of chloroform and 25 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. The obtained organic layer is concentrated, and the concentrated mass is collected by column (Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain formula (I-18). 4.29 parts of the compound represented by -c) are obtained.

4.23 parts of the compound represented by the formula (I-18-c), 35 parts of acetonitrile and 0.89 parts of the compound represented by the formula (I-1-c) were mixed and stirred at 23° C. for 18 hours. . 80 parts of chloroform and 40 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. 40 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. By concentrating the obtained organic layer, 4.13 parts of the compound represented by the formula (I-18) was obtained.
MASS (ESI(+) Spectrum): 939.3 [M+H] ⁺

Synthesis of Resin Compounds (monomers) used for synthesizing resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-3)" and the like according to their formula numbers.

Synthesis Example 1: Synthesis of Resin A1 As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1) and monomer (a3-1-1) are used, The molar ratio [monomer (a1-1-3):monomer (a1-2-9):monomer (a2-1-1):monomer (a3-1-1)] was 14:45:2.5:38. 5, and propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers was added to obtain a solution. To this solution, 1 mol % and 3 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the total amount of monomers, respectively, and these were heated at 73° C. for about 5 hours. bottom. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered. The resulting resin is again dissolved in propylene glycol monomethyl ether acetate, the resulting solution is poured into a methanol/water mixed solvent to precipitate the resin, and the resin is filtered. Resin A1 with a molecular weight of 7.9×10 ³ was obtained with a yield of 88%. This resin A1 has the following structural units.

Synthesis Example 2 Synthesis of Resin X1 Monomer (a4-1-4) was used as a monomer, and methyl isobutyl ketone was added in an amount 1.5 times the total amount of monomers to form a solution. To this solution, 0.7 mol % and 2.1 mol % of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators to the total amount of monomers, respectively, and these were stirred at 75°C. Heated for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate the resin, which was filtered to obtain Resin X1 having a weight average molecular weight of 1.7×10 ⁴ with a yield of 77%. This resin X1 has the following structural units.

<Preparation of resist composition>
As shown in Table 1, a resist composition was prepared by mixing the following components and filtering the resulting mixture through a fluororesin filter having a pore size of 0.2 μm.

＜クエンチャー（Ｃ）＞
クエンチャーＣ１：（特開２０１２－８５５３号公報の実施例に従って合成）

クエンチャーＣ２：（特開２０１２－８５５３号公報の実施例に従って合成）

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート 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>
A1, X1: Resin A1, Resin X1
<Acid generator>
B1-21: a salt represented by the formula (B1-21) (synthesized according to the examples of JP-A-2012-224611)
B1-22: a salt represented by the formula (B1-22) (synthesized according to the examples of JP-A-2012-224611)

<Quencher (C)>
Quencher C1: (synthesized according to the examples of JP-A-2012-8553)

Quencher C2: (synthesized according to the examples of JP-A-2012-8553)

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

<Production of resist pattern>
An organic antireflection film composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205° C. for 60 seconds to form an organic film 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 (prebaking) was 170 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature indicated in the "PB" column of Table 1 for 60 seconds to form a composition layer on the silicon wafer.
A space pattern (pitch 240 nm/ Using a mask for forming a space width of 90 nm, exposure was performed by changing the exposure dose stepwise. Ultrapure water was used as the liquid immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on a hot plate at the temperature listed in the "PEB" column of Table 1. Next, the composition layer on the silicon wafer was puddle-developed at 23° C. for 60 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer to produce a resist pattern.

In the obtained resist pattern, the effective sensitivity was defined as the exposure dose at which the width of the space pattern was 90 nm.

<Focus margin evaluation (DOF)>
A resist pattern was produced in the same manner as described above, except that exposure was performed while changing the focus stepwise in terms of effective sensitivity. In the obtained resist pattern, the DOF (nm) was defined as the focus range where the width of the space pattern was 90 nm±5% (85.5 to 94.5 nm). Table 2 shows the results.

From the above results, it can be seen that the resist composition of the present invention can produce a thick resist pattern having a film thickness of 150 to 1000 nm with an excellent focus margin (DOF).

INDUSTRIAL APPLICABILITY According to the resist composition of the present invention, since a resist pattern can be produced with an excellent focus margin, it is useful for microfabrication of semiconductors.

Claims (6)

A resist composition comprising a resin containing a structural unit having an acid-labile group, a resin containing a structural unit having a fluorine atom, an acid generator, and a compound represented by formula (I).

[in the formula (I),
L ¹ represents a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —S(O) ₂ — Alternatively, it may be replaced with -CO-.
W ¹ represents a hydrocarbon ring having 3 to 24 carbon atoms, and —CH ₂ — contained in the hydrocarbon ring is replaced with —O—, —S—, —S(O) ₂ — or —CO—. may be
n represents an integer of 1 to 3;
R ¹ and R ² each independently represent a fluorinated alkyl group having 1 to 6 carbon atoms.
R ³ represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, — It may be replaced by S(O) ₂ -- or --CO--.
When n is 2 or 3, a plurality of R ¹ , R ² and R ³ may be the same or different. ] 2. The resist composition of claim 1, wherein ^R1 and ^R2 are trifluoromethyl groups. R ³ represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and at least one —CH ₂ — contained in the hydrocarbon group is —O— or —CO 3. The resist composition according to claim 1 or 2, wherein - is replaced. 4. The resist composition according to claim 1, wherein W ¹ is a monocyclic saturated hydrocarbon ring. 5. The resist composition according to any one of claims 1 to 4, wherein the acid generator is a salt represented by formula (B1).

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO—; A hydrogen atom contained in may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, included in the alicyclic hydrocarbon group- CH ₂ -- may be replaced by --O--, --SO ₂ -- or --CO--.
Z ⁺ represents an organic cation. ] (1) a step of applying the resist composition according to any one of claims 1 to 5 onto a substrate;
(2) a step of drying the applied composition to form a composition layer;
(3) exposing the composition layer;
(4) heating the composition layer after exposure; and (5) developing the composition layer after heating;
A method of manufacturing a resist pattern comprising: