JP7019292B2 - Method for manufacturing resist composition and resist pattern - Google Patents

Description

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

Patent Document 1 describes a resist composition containing triphenylsulfonium nonafluorobutane sulfonate as a resin consisting of a combination of the following structural units and an acid generator.

Patent Document 2 describes a resist composition containing triphenylsulfonium nonafluorobutane sulfonate as a resin consisting of a combination of the following structural units and an acid generator.

Japanese Patent Application Laid-Open No. 2003-167347 Japanese Unexamined Patent Publication No. 2007-272194

The resist pattern formed from the resist composition containing the above resin may not always be satisfied with the mask error factor (MEF).

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ｒ^２は、炭素数３～１８の飽和脂環式炭化水素基を有する飽和炭化水素基を表す。
Ｘ^１は、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ－Ｏ－を表す。
Ａ^１は、炭素数１～１２の２価の炭化水素基又は^＊－Ａ^２－Ｘ^２－（Ａ^３－Ｘ^３）_ａ－（Ａ^４）_ｂ－を表す。＊は酸素原子との結合手を表す。但し、Ｘ^１が、－Ｏ－の時、Ａ^１は、メチレン基にはならない。
Ａ^２、Ａ^３及びＡ^４は、それぞれ独立に、炭素数１～１２の２価の炭化水素基を表す。
Ｘ^２及びＸ^３は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ－Ｏ－を表す。］

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＳＯ₂－又は－ＣＯ－に置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］
〔２〕Ｘ^１は、－Ｏ－又は－ＣＯ－Ｏ－である〔１〕記載のレジスト組成物。
〔３〕Ｒ^２は、炭素数３～１２の飽和脂環式炭化水素基又は炭素数１～６のアルカンジイル基と炭素数３～１２の脂環式炭化水素基とが組み合わせられた基である〔１〕又は〔２〕記載のレジスト組成物。
〔４〕さらに、式（ａ４）で表される構造単位を含む樹脂（Ｘ）を有する〔１〕～〔３〕のいずれかに記載レジスト組成物。

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

［式（ａ４－０）中、
Ｒ^f1は、水素原子又はメチル基を表す。
Ｒ^f2は、炭素数１～２０のフッ素原子を有する飽和炭化水素基を表す。］

［式（ａ４－１）中、
Ｒ^f3は、水素原子又はメチル基を表す。
Ｌ³は、炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｒ^f4は、炭素数１～２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ³及びＲ^f4の合計炭素数の上限は２１である。］

［式（ａ４－２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ⁴は、炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｒ^f6は、炭素数１～２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ⁴及びＲ^f6の合計炭素数の上限は２１である。］

［式（ａ４－３）中、
Ｒ^f7は、水素原子又はメチル基を表す。
Ｌ⁵は、炭素数１～６のアルカンジイル基を表す。
Ａ^f13は、フッ素原子を有していてもよい炭素数１～１８の２価の飽和炭化水素基を表す。
Ｘ^f12は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^f14は、フッ素原子を有していてもよい炭素数１～１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14の合計炭素数の上限は２０である。］
〔６〕酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する〔１〕～〔５〕のいずれかに記載のレジスト組成物。
〔７〕（１）〔１〕～〔６〕のいずれかに記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resist composition containing a resin (A) containing a structural unit derived from a compound represented by the formula (I) and a structural unit having an acid unstable group, and a salt represented by the formula (B1).

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a saturated hydrocarbon group having a saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms.
X ¹ represents —O—, —CO—O—, —O—CO— or —O—CO—O—.
A ¹ represents a divalent hydrocarbon group having 1 to 12 carbon atoms or ^* -A ² -X ^2- (A ³ -X ³ ) _a- (A ⁴ ) _b- . * Represents a bond with an oxygen atom. However, when X ¹ is −O—, A ¹ does not become a methylene group.
A ² , A ³ and A ⁴ each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms.
X ² and X ³ independently represent —O—, —CO—O—, —O—CO— or —O—CO—O—, respectively. ]

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon. -CH _2- contained in the hydrogen group may be replaced with -O-, -SO _2- or -CO-.
Z ⁺ represents an organic cation. ]
[2] The resist composition according to [1], wherein X ¹ is —O— or —CO—O—.
[3] R ² is a saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms or a group in which an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms are combined. The resist composition according to [1] or [2].
[4] The resist composition according to any one of [1] to [3], further comprising a resin (X) containing a structural unit represented by the formula (a4).

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

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

[In equation (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ³ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f4 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ³ and R ^{f 4} is 21. ]

[In equation (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f6 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴ and R f ⁶ is 21. ]

[In equation (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 has a fluorine atom, and the upper limit of the total carbon number of L ⁵ , A ^f13 and A ^f14 is 20. ]
[6] The resist composition according to any one of [1] to [5], which further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[7] (1) A step of applying the resist composition according to any one of [1] to [6] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A method for producing a resist pattern, which comprises a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

By using the resist composition of the present invention, a resist pattern can be produced with a good mask error factor (MEF).

As used herein, the term "(meth) acrylate" means "at least one of acrylate and methacrylate," respectively. Notations such as "(meth) acrylic acid" and "(meth) acryloyl" have the same meaning.
Unless otherwise specified, "aliphatic hydrocarbon groups" are carbonized into linear and branched hydrocarbon groups, and "aliphatic hydrocarbon groups" are carbonized into cyclic hydrocarbon groups and / or cyclic hydrocarbon groups. It means a group to which a hydrogen group is bonded. The "aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bonded to an aromatic ring. If a steric isomer is present, it includes all steric isomers.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

[Resist composition]
The resist composition of the present invention is
A resin (A) containing a structural unit derived from a compound represented by the formula (I) and a structural unit having an acid unstable group and a salt represented by the formula (B1) (hereinafter referred to as “acid generator (B1)”). May contain.).
Further, the resist composition includes a resin (X) and / or a quencher (hereinafter, may be referred to as “quencher (C)”) and / or a solvent (hereinafter, “solvent”) containing a structural unit represented by the formula (a4). (E) ”) is preferably contained.

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

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ｒ^２は、炭素数３～１８の飽和脂環式炭化水素基を有する飽和炭化水素基を表す。
Ｘ^１は、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ－Ｏ－を表す。
Ａ^１は、炭素数１～１２の２価の炭化水素基又は^＊－Ａ^２－Ｘ^２－（Ａ^３－Ｘ^３）_ａ－Ａ^４－を表す。＊は酸素原子との結合手を表す。但し、Ｘ^１が、－Ｏ－の時、Ａ^１は、メチレン基にはならない。
ａは０又は１を表す。
Ａ^２、Ａ^３及びＡ^４は、それぞれ独立に、炭素数１～１２の２価の炭化水素基を表す。
Ｘ^２及びＸ^３は、それぞれ独立に、－Ｏ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は－Ｏ－ＣＯ－Ｏ－を表す。］ <Compound (I)>

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a saturated hydrocarbon group having a saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms.
X ¹ represents —O—, —CO—O—, —O—CO— or —O—CO—O—.
A ¹ represents a divalent hydrocarbon group having 1 to 12 carbon atoms or ^* -A ² -X ^2- (A ³ -X ³ ) _a -A ^4- . * Represents a bond with an oxygen atom. However, when X ¹ is −O—, A ¹ does not become a methylene group.
a represents 0 or 1.
A ² , A ³ and A ⁴ each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms.
X ² and X ³ independently represent —O—, —CO—O—, —O—CO— or —O—CO—O—, respectively. ]

The saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms is a monocyclic group which is a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group;
Examples thereof include polycyclic groups such as a norbornyl group and an adamantyl group.
Examples of the saturated hydrocarbon group having a saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms in ^R2 include a saturated hydrocarbon group having a cyclopentyl group, a saturated hydrocarbon group having a cyclohexyl group, and a saturated hydrocarbon group having a norbornyl group. Examples thereof include a saturated hydrocarbon group having a group and an adamantyl group. Among them, a saturated hydrocarbon group having a cyclopentyl group, a saturated hydrocarbon group having a cyclohexyl group, and a saturated hydrocarbon group having an adamantyl group are preferable, and a saturated hydrocarbon group having an adamantyl group and a saturated hydrocarbon group having a cyclohexyl group are preferable. More preferably, a saturated hydrocarbon group having an adamantyl group is further preferable.

The saturated hydrocarbon group having a saturated alicyclic hydrocarbon group is formed by combining a saturated alicyclic hydrocarbon group and a linear or branched saturated hydrocarbon group and a saturated alicyclic hydrocarbon group. Group is preferred. However, the carbon atom bonded to X ¹ does not form an acid unstable group.
Among them, a saturated alicyclic hydrocarbon group and a group formed by combining a linear saturated alicyclic hydrocarbon group and a saturated alicyclic hydrocarbon group are more preferable, and a saturated alicyclic hydrocarbon group and a saturated alicyclic hydrocarbon group are preferable. , A group formed by combining an alkanediyl group and a saturated alicyclic hydrocarbon group is more preferable, and an adamantyl group, a cyclohexyl group, **-(CH ₂ ) _m -adamantyl group or **- (CH ₂ ). The _n -cyclohexyl group is particularly preferred. Here, m and n each independently represent an integer of 1 to 3.
Examples of the linear or branched hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and an octyl group. And 2-ethylhexyl groups.
R ² is preferably an adamantyl group, a cyclohexyl group, a **-CH ₂ -adamantyl group or a **-CH ₂ -cyclohexyl group.
** represents a bond with X ¹ .

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms of A ¹ , A ² , A ³ and A ⁴ include an alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and the like. Examples thereof include divalent aromatic hydrocarbon groups, and two or more of these groups may be combined.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl group, Octane-1,8-Diyl group, Nonan-1,9-Diyl group, Decan-1,10-Diyl group, Undecan-1,11-Diyl group, Dodecan-1,12-Diyl group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group. Alcandiyl group;
Etan-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. Group;
Examples thereof include a divalent aromatic hydrocarbon group such as a phenylene group, a tosilene group, a naphthylene group, a biphenylene group, a xylylene group and an anthrasenylene group.

^* -A ² -X ^1- (A ³ -X ² ) _a -A ^4- , ^* -A ² -O-A ^4- , ^* -A ² -CO-O-A ^4- , ^* -A ² -O-CO-A ^4- , ^* -A ² -O-CO-O-A ^4- , ^* -A ² -CO-O-A ³ -CO-O-A ^4- , ^* -A ^2- O-CO-A ³ -O-A ^4- , ^* -A ² -O-CO-O-A ³ -O-A ^4- , ^* -A ² -O-A ³ -CO-O-A ^4- , ^* -A ² -CO-O-A ³ -O-CO-A ^4- , ^* -A ² -O-CO-A ³ -O-CO-A ^4- , ^* -A ² -O-A ³ -O ^- A 4-- can be mentioned. Among them, ^* -A ² -O-A ^4- , ^* -A ² -CO-O-A ^4- , ^* -A ² -O-CO-O-A ⁴ -or ^* -A ² -O-A ³ -OA ⁴ -is preferable. * Represents a bond with an oxygen atom.

A ¹ is preferably a divalent alkanediyl group having 1 to 6 carbon atoms or ^* -A ² -X ¹ -A ^4- , and a divalent alkanediyl group having 1 to 6 carbon atoms, -CH ₂ . -CH ₂ -O-CH ₂ -CH _2- , -Ad-CO-O-CH _2- , -Ad-CO-O-CH ₂ -CH _2- , -Ad-O-CO-O-CH _2- Alternatively, it is more preferably -Ad-O-CO-O-CH ₂ -CH _2- (Ad represents an adamantandiyl group), and a divalent alkanediyl group having 1 to 6 carbon atoms or -CH _2- . It is more preferably CH ₂ -O-CH ₂ -CH _2- , and particularly preferably a methylene group, an ethylene group or -CH ₂ -CH ₂ -O-CH ₂ -CH _2- .
A ² , A ³ and A ⁴ are each independently, preferably a divalent alkanediyl group having 1 to 6 carbon atoms or a polycyclic divalent alicyclic saturated hydrocarbon group.
X ¹ is preferably —O— or —CO—O— (—CO— in —CO ^— O— binds to A1), more preferably —O—.

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

The resin (A) may be a polymer containing one type of structural unit (I) or a copolymer containing two or more types of structural unit (I).
The resin (A) may be a polymer containing a structural unit (I) and a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”), or may be a structural unit (I). ), The structural unit (a1), and a polymer containing structural units other than the structural unit (I) and the structural unit (a1).
In the resin (A), the content of the structural unit (I) is 1 to 100 mol%, preferably 3 to 60 mol%, and 4 to 40 mol% with respect to all the structural units of the resin (A). More preferably, 5 to 20 mol% is further preferable.

The "acid-unstable group" is a structural unit having a leaving group, and the leaving group is removed by contact with an acid, and the structural unit is converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Means the group to do.

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

［式（２）中、Ｒ^a1’及びＲ^a2’は、それぞれ独立に、水素原子又は炭素数１～１２の炭化水素基を表し、Ｒ^a3’は、炭素数１～２０の炭化水素基を表すか、Ｒ^a2’及びＲ^a3’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３～２０の２価の複素環基を形成し、該炭化水素基及び該２価の複素環基に含まれる－ＣＨ₂－は、－Ｏ－又は－Ｓ－で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid unstable group (hereinafter, may be referred to as “monomer (a1)”). As the acid unstable group contained in the structural unit (a1), the following groups (1) and / or groups (2) are preferable.

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

[In the formula (2), R ^a1'and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Represented, R ^a2'and R ^a3' are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and the hydrocarbon group and the divalent complex are formed. -CH _2- contained in the ring group may be replaced with -O- or -S-.
X represents an oxygen atom or a sulfur atom.
* Represents a bond. ]

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

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

Examples of -C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R a ² are bonded to each other to form a divalent alicyclic hydrocarbon group include the following groups. The divalent alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. * Represents a bond with -O-.

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

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^a1 to R ^a3 are alkyl groups in the formula (1), preferably a tert-butoxycarbonyl group). 2-Alkyl adamantan-2-yloxycarbonyl group (in formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- (group) and 1- (in the formula (1)). Examples thereof include adamantan-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups and R ^a3 is an adamantyl group).
Of R ^a1'and R ^a2' , at least one is preferably a hydrogen atom.

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

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

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

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

［式（ａ１－０）中、
Ｌ^a01は、酸素原子又は^＊－Ｏ－（ＣＨ₂）_k00－ＣＯ－Ｏ－を表し、ｋ００は１～７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。］

[In equation (a1-0),
^La01 represents an oxygen atom or ^* -O- (CH ₂ ) _k00 -CO-O-, k00 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these groups. ]

［式（ａ１－１）及び式（ａ１－２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k1－ＣＯ－Ｏ－を表し、ｋ１は１～７の整数を表し、＊は－ＣＯ－との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１～８のアルキル基、炭素数３～１８の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表す。
ｍ１は０～１４の整数を表す。
ｎ１は０～１０の整数を表す。
ｎ１’は０～３の整数を表す。］

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

^La01 is preferably an oxygen atom or ^* -O- (CH ₂ ) _k01 -CO-O- (where k01 is preferably an integer of 1 to 4, more preferably 1), more preferably. Is an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03 and R ^a04 , the alicyclic hydrocarbon group and the group combining these groups include the same groups as those mentioned in R ^a1 to R ^a3 of the formula (1).
The alkyl group of R ^a02 , R ^a03 and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 and R ^a04 are preferably aliphatic hydrocarbon groups having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

L ^a1 and L ^a2 are preferably -O- or ^* -O- (CH ₂ ) _k1' -CO-O- (where k1'is an integer of 1 to 4, preferably 1). Yes), more preferably -O-.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group and the group formed by combining them include the same groups as those mentioned in R ^a1 to R ^a3 of the formula (1).
The alkyl groups of R ^a6 and R ^a7 are preferably alkyl groups having 1 to 6 carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably 3 to 6 or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1'is preferably 0 or 1.

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

In the above structural unit, a structural unit in which a methyl group corresponding to ^Ra01 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a1-0).

Examples of the monomer (a1-1) include the monomers described in JP-A-2010-204646. Among them, the monomers represented by any of the formulas (a1-1-1) to (a1-1-8) are preferable, and any of the formulas (a1-1-1) to (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include 1-methylcyclopentane-1-yl (meth) acrylate, 1-ethylcyclopentane-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, and the like. 1-Ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcycloheptane-1-yl (meth) acrylate, 1-ethylcyclooctane-1-yl (meth) acrylate, 1-isopropylcyclopentane-1-yl Examples thereof include (meth) acrylate and 1-isopropylcyclohexane-1-yl (meth) acrylate. Monomers represented by any of the formulas (a1-2-1) to (a1-2-12) are preferable, and formulas (a1-2-3), formulas (a1-2-4), and formulas (a1-) are preferable. The monomer represented by 2-9) or the formula (a1-2-10) is more preferable, and the monomer represented by the formula (a1-2-3) or the formula (a1-2-9) is further preferable.

When the resin (A) contains a structural unit (a1-0) and / or a structural unit (a1-1) and / or a 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%, and more preferably 20 to 85 mol% with respect to the unit.
When the resin (A) contains the above structural units, the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, and 20 to 85 mol% with respect to all the structural units of the resin (A). % Is more preferable.

Further, as the structural unit (a1) having the group (1), it is bonded to the main chain of the following structural unit and the structural unit represented by the formulas (a1-4-4) to (a1-4-8). Examples thereof include structural units in which a hydrogen atom is replaced with a methyl group.

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

When the resin (A) contains the above structural units, the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, and 20 to 85 mol% with respect to all the structural units of the resin (A). % Is more preferable.

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

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

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

Examples of the monomer for deriving the structural unit (a1-5) include the monomers described in JP-A-2010-61117. Among them, the monomers represented by the formulas (a1-5-1) to (a1-5-4) are preferable, and the monomers represented by the formula (a1-5-1) or the formula (a1-5-2) are preferable. Is more preferable.

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

In addition to the structural unit (I) and the structural unit having an acid unstable group, the resin (A) of the present invention may be further referred to as a monomer having no acid unstable group (hereinafter referred to as "monomer (s)"). ) And / or other structural units described below, for example, structural units having a halogen atom in addition to the structural units (a2) and (a3) (hereinafter referred to as “structural unit (a4)”) and non-desorbed hydrocarbon groups. It may have a structural unit (hereinafter, referred to as “structural unit (a5)”) or the like (hereinafter, may be referred to as “structural unit (t)”).

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

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

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

[In equation (a2-0),
R ^a30 represents an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or Represents a methacryloyloxy group.
ma represents an integer from 0 to 4. When ma is an integer of 2 or more, the plurality of Ra ^31s may be the same or different from each other. ]

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an n-pentyl group, an n-hexyl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, and 1,1,. 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -Perfluorohexyl group and the like can be mentioned. R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Of these, 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.
Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group having 2 to 4 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
The ma is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.

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

The resin (A) containing the structural unit (a2-0) undergoes a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer inducing the structural unit (a2-0) is protected with a protecting group, and then deprotected. It can be manufactured by processing. However, when performing the deprotection treatment, it is necessary to carry out the deprotection treatment so as not to significantly impair the acid unstable group of the structural unit (a1). Examples of such a protecting group include an acetyl group and the like.

When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, the content thereof is preferably 5 to 95 mol% with respect to all the structural units of the resin (A), and 10 to 10 to 80 mol% is more preferable, and 15-80 mol% is even more preferable.

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

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

In the formula (a2-1), ^La3 is preferably —O—, —O— (CH ₂ ) _f1 -CO—O— (the f1 is an integer of 1 to 4), and more preferably. Is -O-.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

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

When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on all the structural units of the resin (A). Yes, more preferably 1 to 35 mol%, still more preferably 2 to 20 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocyclic ring such as β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a fused ring of a monocyclic lactone ring and another ring. But it may be. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure.

The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). One of these may be contained alone, or two or more thereof may be contained.

［式（ａ３－１）中、
Ｌ^a4は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k3－ＣＯ－Ｏ－（ｋ３は１～７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
Ｒ^a21は炭素数１～４の脂肪族炭化水素基を表す。
ｐ１は０～５の整数を表す。ｐ１が２以上のとき、複数のＲ^a21は互いに同一又は相異なる。
式（ａ３－２）中、
Ｌ^a5は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k3－ＣＯ－Ｏ－（ｋ３は１～７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。
ｑ１は、０～３の整数を表す。ｑ１が２以上のとき、複数のＲ^a22は互いに同一又は相異なる。
式（ａ３－３）中、
Ｌ^a6は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k3－ＣＯ－Ｏ－（ｋ３は１～７の整数を表す。
）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。
ｒ１は、０～３の整数を表す。ｒ１が２以上のとき、複数のＲ^a23は互いに同一又は相異なる。
式（ａ３－４）中、
Ｒ^a24は、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^a25は、カルボキシ基、シアノ基又は炭素数１～４の脂肪族炭化水素基を表す。
ｗ１は、０～３の整数を表す。ｗ１が２以上のとき、複数のＲ^a25は互いに同一又は相異なる。
Ｌ^a7は、－Ｏ－、^＊－Ｏ－Ｌ^a8－Ｏ－、^＊－Ｏ－Ｌ^a8－ＣＯ－Ｏ－、^＊－Ｏ－Ｌ^a8－ＣＯ－Ｏ－Ｌ^a9－ＣＯ－Ｏ－又は^＊－Ｏ－Ｌ^a8－Ｏ－ＣＯ－Ｌ^a9－Ｏ－を表す。
＊はカルボニル基との結合手を表す。
Ｌ^a8及びＬ^a9は、互いに独立に、炭素数１～６のアルカンジイル基を表す。］

[In equation (a3-1),
L ^a4 represents -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 is an integer of 1 to 7).
) Represents a group. * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer from 0 to 5. When p1 is 2 or more, a plurality of ^Ra21s are the same or different from each other.
In equation (a3-2),
L ^a5 represents -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 is an integer of 1 to 7).
) Represents a group. * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, a plurality of ^Ra22s are the same or different from each other.
In equation (a3-3),
L ^a6 represents -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 is an integer of 1 to 7).
) Represents a group. * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, a plurality of ^Ra23s are the same or different from each other.
In equation (a3-4),
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
R ^a25 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
w1 represents an integer of 0 to 3. When w1 is 2 or more, a plurality of ^Ra25s are the same or different from each other.
L ^a7 is -O-, ^* -OL ^a8 -O-, ^{* -OL a8} -CO-O-, ^* -OL ^a8 -CO- ^{OL a9} -CO-O- or ^* -O-L ^a8 -O-CO-L ^a9 -O-represented.
* Represents a bond with a carbonyl group.
^La8 and ^La9 represent an alkanediyl group having 1 to 6 carbon atoms independently of each other. ]

Examples of the aliphatic hydrocarbon group of R ^a21 , R ^a22 , R ^a23 and R ^a25 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Alkyl groups can be mentioned.
Examples of the halogen atom of R ^a24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group of R ^a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Alkyl groups having a halogen atom of R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. Examples thereof include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

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

In the formulas (a3-1) to (a3-3), ^La4 to ^La6 are independently, preferably -O- or k3 is an integer of 1 to 4 * -O- (CH ₂ ). ) A group represented by _k3 -CO-O-, more preferably -O- and * -O-CH ₂ -CO-O-, still more preferably an oxygen atom.
R ^a18 to R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently, preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are independently, preferably integers of 0 to 2, and more preferably 0 or 1.

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

(In the formula, R ^a24 and ^La 7 have the same meanings as above.)

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

In the structural units represented by the following formulas (a3-4-1) to (a3-4-12), the compound in which the methyl group corresponding to R ^a24 is replaced with a hydrogen atom is also a structural unit (a3-4). ) Can be mentioned as a specific example.

When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). , More preferably 10-60 mol%.
Further, the contents of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) and the structural unit (a3-4) are the respective contents with respect to all the structural units of the resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is further preferable.

When the resin (A) has a structural unit (a4) and / or a structural unit (a5) described later, the content of the structural unit (a4) is 1 to 20 with respect to all the structural units of the resin (A). Mol% is preferred, 2-15 mol% is more preferred, and 3-10 mol% is even more preferred. The content of the structural unit (a5) is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, still more preferably 3 to 15 mol%, based on all the structural units of the resin (A).

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

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

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (A) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, still more preferable). Is 15,000 or less). The weight average molecular weight is a value obtained by gel permeation chromatography.

The content of the resin (A) is preferably 80% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (X)>
The resist composition of the present invention contains a resin containing the structural unit (a4). However, the resin (X) does not include the structural unit (I). The resin (X) preferably contains a structural unit represented by the formula (a5) (hereinafter, may be referred to as “structural unit (a5)”).

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

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

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

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

Examples of the saturated hydrocarbon group having a fluorine atom of R ^a42 include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, and a 2,2,2-trifluoroethyl group. Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2 , 2,2-Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1, 2,2,3,3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) 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, 2,3,3,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ) Ethyl group, 1,1,2,2,3,3,4,5,5-decafluorohexyl group, 1,1,2,2,3,4,4,5,5,6 , 6-Dodecafluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group and other fluoroalkyl groups; perfluorocyclohexyl group, perfluoroadamantyl group and other alicyclic hydrocarbon groups having a fluorine atom.

［式（ａ４－０）中、
Ｒ^f1は、水素原子又はメチル基を表す。
Ｒ^f2は、炭素数１～２０のフッ素原子を有する飽和炭化水素基を表す。］ The structural unit (a4) is, for example, a structural unit represented by any of the equations (a4-0) to (a4-3) (hereinafter, “structural unit (a4-0) to structural unit (a4-3)). ") Is preferable.

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

Examples of the saturated hydrocarbon group of R ^f2 and the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified in R ^a42 .

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

［式（ａ４－１）中、
Ｒ^f3は、水素原子又はメチル基を表す。
Ｌ³は、炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｒ^f4は、炭素数１～２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ³及びＲ^f4の合計炭素数の上限は２１である。］

[In equation (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ³ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f4 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ³ and R ^{f 4} is 21. ]

Examples of the divalent saturated hydrocarbon group of L ³ include an aliphatic saturated hydrocarbon group, an alicyclic saturated hydrocarbon group, and a group combining these. Aliphatic saturated hydrocarbons include linear and branched alkanediyl groups. Examples of the alicyclic saturated hydrocarbon group include monocyclic and polycyclic alicyclic hydrocarbon groups.
The linear and branched alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group and 1-methylpropane-1. , 3-Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
Examples of the divalent alicyclic saturated hydrocarbon group include a group obtained by removing one hydrogen atom from the above-mentioned monovalent alicyclic hydrocarbon group.

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

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

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

［式（ａ４－２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ⁴⁴は、炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｒ^f6は、炭素数１～２０のフッ素原子を有する飽和炭化水素基を表す。
ただし、Ｌ⁴⁴及びＲ^f6の合計炭素数の上限は２１である。］

[In equation (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴⁴ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f6 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴⁴ and R ^f6 is 21. ]

Examples of the divalent saturated hydrocarbon group of L ⁴⁴ include the same groups as those exemplified in L ³ .
Examples of the saturated hydrocarbon group of R ^f6 and the saturated hydrocarbon group having a fluorine atom include the same groups as those exemplified in R ^a42 .

As the saturated hydrocarbon group of ^L44 , an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

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

［式（ａ４－３）中、
Ｒ^f7は、水素原子又はメチル基を表す。
Ｌ⁵は、炭素数１～６のアルカンジイル基を表す。
Ａ^f13は、フッ素原子を有していてもよい炭素数１～１８の２価の飽和炭化水素基を表す。
Ｘ^f12は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^f14は、フッ素原子を有していてもよい炭素数１～１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14の合計炭素数の上限は２０である。］

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

Examples of the alkanediyl group of L ⁵ include the same groups as those exemplified for the alkanediyl group in the divalent saturated hydrocarbon group of L ³ .

Examples of the divalent saturated hydrocarbon group of A ^f13 include the same groups as those exemplified for the divalent saturated hydrocarbon group of L ³ .
As the saturated hydrocarbon group which may have a fluorine atom of A ^f13 , a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom are preferable. And more preferably a perfluoroalkandyl group.
Examples of the divalent aliphatic hydrocarbon group which may have a fluorine atom include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group; a difluoromethylene group, a perfluoroethylene group and a perfluoro. Examples thereof include a perfluoroarcandyl group such as a propanediyl group, a perfluorobutanediyl group and a perfluoropentanediyl group.
The divalent alicyclic hydrocarbon group which may have a fluorine atom may be a group containing either a monocyclic or polycyclic group. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantandiyl group, a norbornanediyl group, a perfluoroadamantandiyl group and the like.

Examples of the saturated hydrocarbon group of A ^f14 and the saturated hydrocarbon group which may have a fluorine atom include the same groups as those exemplified in R ^a42 . Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, Fluorination of 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group, etc. Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group , Perfluoroadamantylmethyl group and the like are preferable.

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

Examples of the structural unit (a4-3) include the structural unit shown below and the structural unit in which the methyl group corresponding to R ^f7 is replaced with a hydrogen atom.

［式（ａ５－１）中、
Ｒ^５１は、水素原子又はメチル基を表す。
Ｒ^５２は、炭素数３～１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１～８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。ただし、Ｌ^５５との結合位置にある炭素原子に結合する水素原子は、炭素数１～８の脂肪族炭化水素基で置換されない。
Ｌ^５５は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表す。］ <Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group of the structural unit (a5) include a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably contains an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).

[In equation (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or a hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the bonding position with L ⁵⁵ is not substituted with the 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. ]

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

Examples of the divalent saturated hydrocarbon group of ^L55 include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. Be done.
Examples of the divalent aliphatic saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl group and a norbornanediyl group.

樹脂（Ｘ）において、構造単位（ａ４）の含有率は、樹脂（Ｘ）の全構造単位に対して、４０モル％以上が好ましく、４５モル％以上がより好ましく、５０モル％以上がさらに好ましい。
樹脂（Ｘ）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、２０～６０モル％が好ましく、２５～５５モル％がより好ましく、３０～５０モル％がさらに好ましい。
樹脂（Ｘ）がさらに有していてもよい構造単位としては、構造単位（ａ１）、構造単位（ａ２）、構造単位（ａ３）及び当該分野で公知のモノマーに由来する構造単位が挙げられる。
樹脂（Ｘ）を構成する各構造単位は、１種のみ又は２種以上を組み合わせて用いてもよく、これら構造単位を誘導するモノマーを用いて、公知の重合法（例えばラジカル重合法）によって製造することができる。樹脂（Ｘ）が有する各構造単位の含有率は、重合に用いるモノマーの使用量で調整できる。
樹脂（Ｘ）の重量平均分子量は、好ましくは、６，０００以上（より好ましくは７，０００以上）、８０，０００以下（より好ましくは６０，０００以下）である。樹脂（Ｘ）の重量平均分子量の測定手段は、樹脂（Ａ）の場合と同様である。
レジスト組成物中の樹脂（Ｘ）の含有量は、樹脂（Ａ）１００質量部に対して、好ましくは１～６０質量部であり、より好ましくは２～５０質量部であり、さらに好ましくは２～４０質量部であり、特に好ましくは３～３０質量部である。 Examples of the structural unit (a5-1) include the following structural units and structural units in which a methyl group corresponding to R ⁵¹ is replaced with a hydrogen atom.

In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, still more preferably 50 mol% or more, based on all the structural units of the resin (X). ..
When the resin (X) has a structural unit (a5), the content thereof is preferably 20 to 60 mol%, more preferably 25 to 55 mol%, and 30 to 30 mol% with respect to all the structural units of the resin (A). It is more preferably ~ 50 mol%.
Examples of the structural unit that the resin (X) may further include include a structural unit (a1), a structural unit (a2), a structural unit (a3), and a structural unit derived from a monomer known in the art.
Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that of the resin (A).
The content of the resin (X) in the resist composition is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 with respect to 100 parts by mass of the resin (A). It is about 40 parts by mass, and particularly preferably 3 to 30 parts by mass.

The total content of the resin (A) and the resin (X) is preferably 80% by mass or more and 99% by mass or less, and preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition.

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１～２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３～１８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ_２－又は－ＣＯ－に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ <Acid generator (B)>
The resist composition of the present invention contains an acid generator (B1).

[In formula (B1),
^Q1 and ^Q2 independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon. -CH _2- contained in the hydrogen group may be replaced with -O-, -SO _2- or -CO-.
Z ⁺ represents an organic cation. ]

The perfluoroalkyl groups of ^Q1 and ^Q2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. A hexyl group and the like can be mentioned.
^Q1 and ^Q2 are preferably fluorine atoms or trifluoromethyl groups independently of each other, and more preferably both are fluorine atoms.

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

［式（ｂ１－１）中、
Ｌ^ｂ２は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ３は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^ｂ２とＬ^ｂ３との炭素数合計は、２２以下である。
式（ｂ１－２）中、
Ｌ^ｂ４は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^ｂ５は、単結合又は炭素数１～２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^ｂ４とＬ^ｂ５との炭素数合計は、２２以下である。
式（ｂ１－３）中、
Ｌ^ｂ６は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
Ｌ^ｂ７は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよく、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ただし、Ｌ^ｂ６とＬ^ｂ７との炭素数合計は、２３以下である。］ Examples of the group in which -CH _2- in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO- are any of the formulas (b1-1) to (b1-3). The group represented by is mentioned. In the formulas (b1-1) to (b1-3) and the following specific examples, * represents a bond with −Y.

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

In the formulas (b1-1) to (b1-3), when the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group, the number of carbon atoms before the replacement is the carbon of the saturated hydrocarbon group. Let it be a number.
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L ^b1 .

L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single-bonded or divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. The methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

The group in which _-CH2- in the divalent saturated hydrocarbon group of L ^b1 is replaced with -O- or -CO- is a group represented by the formula (b1-1) or the formula (b1-3). Is preferable.

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

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

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

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

[In equation (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be good. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In equation (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b21 to L ^b23 is 21 or less.
In equation (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b24 to L ^b26 is 21 or less. ]

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

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

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-4) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-5) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-6) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-7) include the following.

Among the groups represented by the formula (b1-1), the groups represented by the formula (b1-8) include the following.

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

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-9) include the following.

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-10) include the following.

Among the groups represented by the formula (b1-3), the groups represented by the formula (b1-11) include the following.

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11).
When -CH _2- contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO _2- or -CO-, the number may be one or two or more. There may be more than one. Examples of such a group include groups represented by the formulas (Y12) to (Y38).

That is, in Y, two hydrogen atoms contained in the alicyclic hydrocarbon group are each replaced with an oxygen atom, and the two oxygen atoms are combined with an arcandyl group having 1 to 8 carbon atoms to form a ketal ring. Alternatively, it may contain a structure in which an oxygen atom is bonded to different carbon atoms. However, when forming a spiro ring of the formulas (Y28) to (Y33), it is preferable that the alkanediyl group between the two oxygens has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, those in which the fluorine atom is not substituted in the methylene group adjacent to the oxygen atom are preferable.

Among them, the alicyclic hydrocarbon group of Y is preferably a group represented by any one of the formula (Y1) to the formula (Y20), the formula (Y30), and the formula (Y31), and more preferably the formula (Y11). ), Formula (Y15), formula (Y16), formula (Y20), formula (Y30) or formula (Y31), more preferably formula (Y11), formula (Y15) or formula (Y30). ) Is the group represented by.

Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Glycidyloxy group or-(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms. Alternatively, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms is represented. Ja represents an integer of 0 to 4) and the like.
Substituents of the monovalent alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkyl group containing a hydroxy group having 1 to 12 carbon atoms, and 3 carbon atoms. ~ 16 monovalent alicyclic hydrocarbon groups, 1-12 carbons alkoxy groups, 6-18 carbons monovalent aromatic hydrocarbon groups, 7-21 carbon aralkyl groups, 2 ~ carbons Acylic group of 4, glycidyloxy group or-(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms and a monovalent fat having 3 to 16 carbon atoms. A cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms is represented. Ja represents an integer of 0 to 4) and the like.

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

Examples of Y include the following.

When Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon at the bond position with Y is used. It is preferable that the -CH _2- of the group is replaced with -O- or -CO-.

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

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions represented by the formulas (B1-A-1) to (B1-A-46) [hereinafter, "anion (B1)" according to the formula number. -A-1) "and so on. ] Are preferable, and the formulas (B1-A-1) to (B1-A-4), formulas (B1-A-9), formulas (B1-A-10), and formulas (B1-A-24) to formulas (B1-A-24) to formulas are preferable. Anions represented by any of (B1-A-33) and formulas (B1-A-36) to (B1-A-40) are more preferable.

Here, R ⁱ² to R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. It is a group formed by the above, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
L4 is a single bond or an alkanediyl group having 1 to ⁴ carbon atoms.
^Q1 and ^Q2 are the same as above.
Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions described in JP-A-2010-204646.

Examples of the sulfonic acid anion in the salt represented by the preferred formula (B1) include anions represented by the formulas (B1a-1) to (B1a-22).

Among them, the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-16), the formulas (B1a-18), the formulas (B1a-19), and the formulas (B1a-22). ) Is preferred.
Examples of the Z ⁺ organic cation include an organic onium cation, for example, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation, and the like, preferably an organic sulfonium cation or an organic iodine cation. These include, more preferably aryl sulfonium cations.
Z ⁺ in the formula (B1) is preferably a cation represented by any of the formulas (b2-1) to (b2-4) [hereinafter, "cation (b2-1)" or the like according to the formula number. In some cases. ].

［式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^ｂ４～Ｒ^ｂ６は、互いに独立に、炭素数１～３０の１価の脂肪族炭化水素基、炭素数３～３６の１価の脂環式炭化水素基又は炭素数６～３６の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１～１２のアルコキシ基、炭素数３～１２の１価の脂環式炭化水素基又は炭素数６～１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～１８の１価の脂肪族炭化水素基、炭素数２～４のアシル基又はグリシジルオキシ基で置換されていてもよく、該１価の芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１～１２のアルコキシ基で置換されていてもよい。
Ｒ^ｂ４とＲ^ｂ５とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ７及びＲ^ｂ８は、互いに独立に、ヒドロキシ基、炭素数１～１２の１価の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
ｍ２及びｎ２は、互いに独立に、０～５の整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一であっても異なってもよく、ｎ２が２以上のとき、複数のＲ^ｂ８は同一であっても異なってもよい。
Ｒ^ｂ９及びＲ^ｂ１０は、互いに独立に、炭素数１～３６の１価の脂肪族炭化水素基又は炭素数３～３６の１価の脂環式炭化水素基を表す。
Ｒ^ｂ９とＲ^ｂ１０とは、それらが結合する硫黄原子とともに環を形成してもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ１１は、水素原子、炭素数１～３６の１価の脂肪族炭化水素基、炭素数３～３６の１価の脂環式炭化水素基又は炭素数６～１８の１価の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１～１２の１価の脂肪族炭化水素基、炭素数３～１８の１価の脂環式炭化水素基又は炭素数６～１８の１価の芳香族炭化水素基を表し、該１価の脂肪族炭化水素に含まれる水素原子は、炭素数６～１８の１価の芳香族炭化水素基で置換されていてもよく、該１価の芳香族炭化水素基に含まれる水素原子は、炭素数１～１２のアルコキシ基又は炭素数１～１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^ｂ１１とＲ^ｂ１２とは、一緒になってそれらが結合する－ＣＨ－ＣＯ－を含む環を形成していてもよく、該環に含まれる－ＣＨ_２－は、－Ｏ－、－ＳＯ－又は－ＣＯ－に置き換わってもよい。
Ｒ^ｂ１３～Ｒ^ｂ１８は、互いに独立に、ヒドロキシ基、炭素数１～１２の１価の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
Ｌ^ｂ３１は、－Ｓ－又は－Ｏ－を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、互いに独立に、０～５の整数を表す。
ｑ２及びｒ２は、互いに独立に、０～４の整数を表す。
ｕ２は、０又は１を表す。
ｏ２が２以上のとき、複数のＲ^ｂ１３は同一であっても異なってもよく、ｐ２が２以上のとき、複数のＲ^ｂ１４は同一であっても異なってもよく、ｑ２が２以上のとき、複数のＲ^ｂ１５は同一であっても異なってもよく、ｒ２が２以上のとき、複数のＲ^ｂ１６は同一であっても異なってもよく、ｓ２が２以上のとき、複数のＲ^ｂ１７は同一であっても異なってもよく、ｔ２が２以上のとき、複数のＲ^ｂ１８は同一であっても異なってもよい。］

[In equations (b2-1) to (b2-4),
R ^b4 to R ^b6 are independent of each other, a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group represents a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, and a monovalent alicyclic hydrocarbon having 3 to 12 carbon atoms. It may be substituted with a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the monovalent alicyclic hydrocarbon group is a halogen atom and 1 to 18 carbon atoms. It may be substituted with a monovalent aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is a halogen atom or hydroxy. It may be substituted with a group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b7 and R ^b8 independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 represent integers from 0 to 5 independently of each other.
When m2 is 2 or more, the plurality of R ^b7s may be the same or different, and when n2 is 2 or more, the plurality of R ^b8s may be the same or different.
R ^b9 and R ^b10 independently represent a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be replaced with -O-, -SO- or -CO-. ..
R ^b11 is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Represents a hydrogen group.
R ^b12 contains a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the monovalent aromatic hydrocarbon group. The hydrogen atom may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may be used together to form a ring containing -CH-CO- to which they are bound, and -CH _2- contained in the ring is -O-, -SO-. Alternatively, it may be replaced with -CO-.
R ^b13 to R ^b18 independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents —S— or —O—.
o2, p2, s2, and t2 represent integers from 0 to 5 independently of each other.
q2 and r2 represent integers from 0 to 4 independently of each other.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13s may be the same or different, when p2 is 2 or more, a plurality of R ^b14s may be the same or different, and when q2 is 2 or more. , A plurality of R ^b15s may be the same or different, and when r2 is 2 or more, a plurality of R ^b16s may be the same or different, and when s2 is 2 or more, a plurality of R ^b17s may be present. It may be the same or different, and when t2 is 2 or more, a plurality of R ^b18s may be the same or different. ]

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

Among them, the monovalent alicyclic hydrocarbon group of R ^b9 to R ^b12 preferably has 3 to 18 carbon atoms, and more preferably 4 to 12 carbon atoms.

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

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

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

The rings that R ^b4 and R ^b5 may form with the sulfur atoms to which they are attached are monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. There may be. Examples of this ring include a ring having 3 to 18 carbon atoms, and preferably a ring having 4 to 18 carbon atoms. Examples of the ring containing a sulfur atom include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and specific examples thereof include the following rings.

The ring formed by R ^b9 and R ^b10 together with the sulfur atom to which they are bonded may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. good. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include a thiolan-1-ium ring (tetrahydrothiophenium ring) and a thian-1-ium. Rings, 1,4-oxatian-4-ium rings and the like can be mentioned.
The ring formed by R ^b11 and R ^b12 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring. Be done.

Among the cations (b2-1) to cations (b2-4), cations (b2-1) are preferable.

Examples of the cation (b2-1) include the following cations.

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

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

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

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

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

The acid generator (B1) may be used alone or may contain two or more. Further, in the resist composition of the present invention, in addition to the acid generator (B1), known acid generators such as JP-A-63-26653, JP-A-55-164824, JP-A-62-69263 can be used. No., Japanese Patent Application Laid-Open No. 63-146038, Japanese Patent Application Laid-Open No. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849 , 137, German Patent No. 3914407, European Patent No. 126,712, etc., which generate acid by radiation can be used. Further, a compound produced by a known method may be used. These may be only one kind, or two or more kinds may be used in combination.

The content of the acid generator (B1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass or less, and substantially, with respect to the total amount of the acid generator (B). It is more preferable that only the acid generator (B1) is used.
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). (Below). The resist composition of the present invention may contain one kind of acid generator (B) or a plurality of kinds.

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

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

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

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

Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine. , Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, Triheptylamine, 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, Triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino- 3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-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) ethen, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyl) Oxy) ethane, di (2-pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicorylamine, bipyridine and the like. , Preferably diisopropylaniline, and particularly preferably 2,6-diisopropylaniline.

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

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

［式（Ｄ）中、
Ｒ^D1及びＲ^D2は、それぞれ独立に、炭素数１～１２の１価の炭化水素基、炭素数１～６のアルコキシ基、炭素数２～７のアシル基、炭素数２～７のアシルオキシ基、炭素数２～７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０～４の整数を表し、ｍ’が２以上の場合、複数のＲ^D1は同一であっても異なってもよく、ｎ’が２以上の場合、複数のＲ^D2は同一であっても異なってもよい。］

[In formula (D),
R ^D1 and R ^D2 independently have a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, and an acyloxy group having 2 to 7 carbon atoms. Represents an alkoxycarbonyl group, a nitro group or a halogen atom having 2 to 7 carbon atoms.
m'and n'independently represent integers from 0 to 4, and when m'is 2 or more, a plurality of R ^D1s may be the same or different, and when n'is 2 or more, they may be different. The plurality of R ^D2s may be the same or different. ]

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

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

In the formula (D), R ^D1 and R ^D2 independently have an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms, respectively. A acyl group of 4 and an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group or a halogen atom are preferable.
For m'and n', an integer of 0 to 2 is preferable, and 0 is more preferable, respectively. When m'is 2 or more, the plurality of R ^D1s may be the same or different, and when n'is 2 or more, the plurality of R ^D2s may be the same or different.

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

The weak acid intramolecular salt (D) can be produced by the method described in "Tetrahedron Vol. 45, No. 19, p6281-6296". Further, as the weak acid intramolecular salt (D), a commercially available compound can be used.

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

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

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

<Manufacturing method of resist pattern>
The method for producing a resist pattern of the present invention is
(1) A step of applying the resist composition of the present invention onto a substrate,
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
It includes (4) a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

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

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a depressurizing device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure for drying under reduced pressure is preferably about ¹ to 1.0 × 105 Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. The exposure light source includes a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excima laser (wavelength 157 nm) that emits laser light in the ultraviolet region, and a solid-state laser light source (YAG or semiconductor laser). Etc.), and various ones such as those that radiate harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, those that irradiate electron beams, super-ultraviolet light (EUV), etc. are used. Can be done. In addition, in this specification, irradiation of these radiations may be generically referred to as "exposure". At the time of exposure, the exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, it may be exposed by direct drawing without using a mask.

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

The heated composition layer is usually developed using a developer and a developer. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense method. The development temperature is preferably 5 to 60 ° C., and the development time is preferably 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any alkaline aqueous solution used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) can be mentioned. The alkaline developer may contain a surfactant.
After development, it is preferable to wash the resist pattern with ultrapure water and then remove the substrate and the water remaining on the pattern.

When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter, may be referred to as "organic developer") is used as the developer.
Examples of the organic solvent contained in the organic developer include a ketone solvent such as 2-hexanone and 2-heptanone; a glycol ether ester solvent such as propylene glycol monomethyl ether acetate; an ester solvent such as butyl acetate; and a glycol such as propylene glycol monomethyl ether. Examples include an ether solvent; an amide solvent such as N, N-dimethylacetamide; an aromatic hydrocarbon solvent such as anisole, and the like.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and further preferably substantially only the organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and substantially butyl acetate and / or 2 -It is more preferable that it is only heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a small amount of water.
At the time of development, the development may be stopped by substituting with a solvent of a type different from that of the organic developer.

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

In the resist composition of the present invention, the resin (X) tends to have a high distribution on the surface in the composition layer, and can suppress elution of an acid generator or the like into an immersion exposure liquid during immersion exposure. .. Further, the above-mentioned forward contact angle and backward contact angle caused by the resin (X) exert water repellency and enable high-speed scan exposure without leaving water droplets.

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

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part" indicating the content or the 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.
Equipment: HLC-8120GPC type (manufactured by Tosoh)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh)

The structure of the compound was confirmed by measuring the molecular peak using mass spectrometry (LC: Agilent 1100 type, MASS: Agilent LC / MSD type). In the following examples, the value of this molecular peak is indicated by "MASS".

式（Ｉ－１－ａ）で表される化合物１０部、トリエチルアミン１１．６６部及びクロロホルム５０部を添加した後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合溶液に、５℃で、式（Ｉ－１－ｂ）で表される化合物１６．８１部を１時間かけて滴下し、２３℃で２４時間攪拌した。得られた反応溶液に、１Ｎ塩酸１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－１－ｃ）で表される化合物１５．７２部を得た。

式（Ｉ－１－ｃ）で表される化合物１５．７２部、トリエチルアミン８．２９部及び式（Ｉ－１－ｄ）で表される化合物７４．９７部を添加した。その後、８０℃で４時間攪拌し、２３℃まで冷却した。得られた反応溶液に、イオン交換水７５部及びクロロホルム７５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－１－ｅ）で表される化合物１１．６９部を得た。

式（Ｉ－１－ｅ）で表される化合物１１．６９部、式（Ｉ－１－ｆ）で表される化合物５．１３部及びクロロホルム５０部を添加し。その後、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物１３．７０部及びジメチルアミノピリジン０．７３部を仕込み、２３℃で４時間攪拌した。得られた反応溶液に、イオン交換水２５部及びクロロホルム２５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：酢酸エチル）分取することにより、式（Ｉ－１）で表される化合物１１．２２部を得た。
ＭＳ（質量分析）：２６４．２（分子イオンピーク） Synthesis Example 1: Synthesis of a compound represented by the formula (I-1)

After adding 10 parts of the compound represented by the formula (I-1-a), 11.66 parts of triethylamine and 50 parts of chloroform, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixed solution, 16.81 part of the compound represented by the formula (I-1-b) was added dropwise at 5 ° C. over 1 hour, and the mixture was stirred at 23 ° C. for 24 hours. 16.67 parts of 1N hydrochloric acid was added to the obtained reaction solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 16.67 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 16.67 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 15.72 parts of the compound represented by the formula (I-1-c) was obtained.

15.72 parts of the compound represented by the formula (I-1-c), 8.29 parts of triethylamine and 74.97 parts of the compound represented by the formula (I-1-d) were added. Then, the mixture was stirred at 80 ° C. for 4 hours and cooled to 23 ° C. 75 parts of ion-exchanged water and 75 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 50 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 50 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 11.69 parts of the compound represented by the formula (I-1-e) was obtained.

11.69 parts of the compound represented by the formula (I-1-e), 5.13 parts of the compound represented by the formula (I-1-f) and 50 parts of chloroform were added. Then, the mixture was stirred at 23 ° C. for 30 minutes. 13.70 parts of the compound represented by the formula (I-1-g) and 0.73 parts of dimethylaminopyridine were added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 4 hours. 25 parts of ion-exchanged water and 25 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 17 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 17 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 17 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. The recovered organic layer is concentrated, and the concentrated mass is separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: ethyl acetate) to obtain a compound represented by the formula (I-1). 11.22 copies were obtained.
MS (Mass Spectrometry): 264.2 (Molecular Ion Peak)

式（Ｉ－５－ａ）で表される化合物１０部、トリエチルアミン１１．６６部及びクロロホルム５０部を添加し。その後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合溶液に、５℃で、式（Ｉ－５－ｂ）で表される化合物１５．３９部を１時間かけて滴下し、２３℃で２４時間攪拌した。得られた反応溶液に、１Ｎ塩酸１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－５－ｃ）で表される化合物１６．６８部を得た。

式（Ｉ－５－ｃ）で表される化合物１６．６８部、トリエチルアミン８．２９部及び式（Ｉ－５－ｄ）で表される化合物７５部を添加した。その後、８０℃で４時間攪拌し、２３℃まで冷却した。得られた反応溶液に、イオン交換水７５部及びクロロホルム７５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－５－ｅ）で表される化合物１２．５２部を得た。

式（Ｉ－５－ｅ）で表される化合物１２．５２部、式（Ｉ－５－ｆ）で表される化合物５．１３部及びクロロホルム５０部を添加し、その後、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－５－ｇ）で表される化合物１３．７０部及びジメチルアミノピリジン０．７３部を仕込み、２３℃で４時間攪拌した。得られた反応溶液に、イオン交換水２５部及びクロロホルム２５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：酢酸エチル）分取することにより、式（Ｉ－５）で表される化合物１０．９１部を得た。
ＭＳ（質量分析）：２７８．２（分子イオンピーク） Synthesis Example 2: Synthesis of a compound represented by the formula (I-5)

10 parts of the compound represented by the formula (I-5a), 11.66 parts of triethylamine and 50 parts of chloroform were added. Then, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixed solution, 15.39 parts of the compound represented by the formula (I-5-b) was added dropwise at 5 ° C. over 1 hour, and the mixture was stirred at 23 ° C. for 24 hours. 16.67 parts of 1N hydrochloric acid was added to the obtained reaction solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 16.67 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 16.67 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 16.68 parts of the compound represented by the formula (I-5-c) was obtained.

16.68 parts of the compound represented by the formula (I-5-c), 8.29 parts of triethylamine and 75 parts of the compound represented by the formula (I-5d) were added. Then, the mixture was stirred at 80 ° C. for 4 hours and cooled to 23 ° C. 75 parts of ion-exchanged water and 75 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 50 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 50 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 12.52 parts of the compound represented by the formula (I-5-e) was obtained.

12.52 parts of the compound represented by the formula (I-5-e), 5.13 parts of the compound represented by the formula (I-5-f) and 50 parts of chloroform were added, and then at 23 ° C. for 30 minutes. Stirred. 13.70 parts of the compound represented by the formula (I-5-g) and 0.73 parts of dimethylaminopyridine were added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 4 hours. 25 parts of ion-exchanged water and 25 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 17 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 17 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 17 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. The recovered organic layer was concentrated. The concentrated mass was fractionated from a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: ethyl acetate) to obtain 10.91 part of the compound represented by the formula (I-5).
MS (Mass Spectrometry): 278.2 (Molecular Ion Peak)

式（Ｉ－９－ａ）で表される化合物１８．３１部、ピリジン１０．４７部及びテトラヒドロフラン１００部を添加し、その後、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－９－ｂ）で表される化合物１４．９４部を１時間かけて添加し、２３℃で８時間攪拌した。得られた反応溶液に、ｎ－ヘプタン３００部及び５％塩酸６１．４７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水３０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－９－ｃ）で表される化合物２６．４２部を得た。

式（Ｉ－９－ｄ）で表される化合物１１．９２部、テトラヒドロフラン６０部、炭酸カリウム９．５７部、ヨウ化カリウム１．１５部及びを添加し、その後、２３℃で３０分間攪拌した後、５０℃まで昇温した。得られた混合溶液に、式（Ｉ－９－ｃ）で表される化合物２６．３８部を１時間かけて添加し、５０℃で２時間攪拌した。得られた反応溶液に、ｎ－ヘプタン１４０部及び５％塩酸５０．５２部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、飽和炭酸水素ナトリウム水溶液２４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：ｎ－ヘプタン／酢酸エチル＝２０／１）分取することにより、式（Ｉ－９）で表される化合物２８．９２部を得た。
ＭＳ（質量分析）：２７８．２（分子イオンピーク） Synthesis Example 3: Synthesis of the compound represented by the formula (I-9)

18.31 parts of the compound represented by the formula (I-9-a), 10.47 parts of pyridine and 100 parts of tetrahydrofuran were added, and then the mixture was stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 14.94 parts of the compound represented by the formula (I-9-b) was added over 1 hour, and the mixture was stirred at 23 ° C. for 8 hours. The obtained reaction solution was charged with 300 parts of n-heptane and 61.47 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 30 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 4 times. By concentrating the recovered organic layer, 26.42 parts of the compound represented by the formula (I-9-c) was obtained.

11.92 parts of the compound represented by the formula (I-9-d), 60 parts of tetrahydrofuran, 9.57 parts of potassium carbonate, 1.15 parts of potassium iodide and the like were added, and then the mixture was stirred at 23 ° C. for 30 minutes. After that, the temperature was raised to 50 ° C. To the obtained mixed solution, 26.38 parts of the compound represented by the formula (I-9-c) was added over 1 hour, and the mixture was stirred at 50 ° C. for 2 hours. 140 parts of n-heptane and 50.52 parts of 5% hydrochloric acid were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 70 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 24 parts of a saturated aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 70 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was concentrated by repeating such a washing operation 5 times. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 20/1) and represented by the formula (I-9). 28.92 parts of the compound was obtained.
MS (Mass Spectrometry): 278.2 (Molecular Ion Peak)

式（Ｉ－１３－ａ）で表される化合物２０部、ピリジン１０．４７部及びテトラヒドロフラン１００部を添加し、その後、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１３－ｂ）で表される化合物１４．９４部を１時間かけて添加し、２３℃で２時間攪拌した。得られた反応溶液に、ｎ－ヘプタン３００部及び５％塩酸６１．４７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水３０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を４回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－１３－ｃ）で表される化合物２８．００部を得た。

式（Ｉ－１３－ｄ）で表される化合物１１．９２部、テトラヒドロフラン６０部、炭酸カリウム９．５７部、ヨウ化カリウム１．１５部及びを添加し、その後、２３℃で３０分間攪拌した後、５０℃まで昇温した。得られた混合溶液に、式（Ｉ－１３－ｃ）で表される化合物２８．００部を１時間かけて添加し、５０℃で２時間攪拌した。得られた反応溶液に、ｎ－ヘプタン１４０部及び５％塩酸５０．５２部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、飽和炭酸水素ナトリウム水溶液２４部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水７０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した回収された有機層を濃縮した。得られた濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：ｎ－ヘプタン／酢酸エチル＝２０／１）分取することにより、式（Ｉ－１３）で表される化合物３１．７７部を得た。
ＭＳ（質量分析）：２９２．２（分子イオンピーク） Synthesis Example 4: Synthesis of the compound represented by the formula (I-13)

20 parts of the compound represented by the formula (I-13-a), 10.47 parts of pyridine and 100 parts of tetrahydrofuran were added, and then the mixture was stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 14.94 parts of the compound represented by the formula (I-13-b) was added over 1 hour, and the mixture was stirred at 23 ° C. for 2 hours. The obtained reaction solution was charged with 300 parts of n-heptane and 61.47 parts of 5% hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 30 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated 4 times. By concentrating the recovered organic layer, 28.00 parts of the compound represented by the formula (I-13-c) was obtained.

11.92 parts of the compound represented by the formula (I-13-d), 60 parts of tetrahydrofuran, 9.57 parts of potassium carbonate, 1.15 parts of potassium iodide and the like were added, and then the mixture was stirred at 23 ° C. for 30 minutes. After that, the temperature was raised to 50 ° C. To the obtained mixed solution, 28.00 parts of the compound represented by the formula (I-13-c) was added over 1 hour, and the mixture was stirred at 50 ° C. for 2 hours. 140 parts of n-heptane and 50.52 parts of 5% hydrochloric acid were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 70 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 24 parts of a saturated aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 70 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was concentrated by repeating such a washing operation 5 times. The obtained concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 20/1) and represented by the formula (I-13). 31.77 parts of the compound was obtained.
MS (Mass Spectrometry): 292.2 (Molecular Ion Peak)

式（Ｉ－１－ｃ）で表される化合物１５．７２部、トリエチルアミン８．２９部及び式（Ｉ－３６－ｄ）で表される化合物１００部を添加した。その後、８０℃で４時間攪拌し、２３℃まで冷却した。得られた反応溶液に、イオン交換水７５部及びクロロホルム７５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－３６－ｅ）で表される化合物１４．５８部を得た。

式（Ｉ－３６－ｅ）で表される化合物１４．３１部、式（Ｉ－１－ｆ）で表される化合物５．１３部及びクロロホルム５０部を添加し。その後、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物１３．７０部及びジメチルアミノピリジン０．７３部を仕込み、２３℃で４時間攪拌した。得られた反応溶液に、イオン交換水２５部及びクロロホルム２５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：酢酸エチル）分取することにより、式（Ｉ－３６）で表される化合物１２．１９部を得た。
ＭＳ（質量分析）：３０８．２（分子イオンピーク） Synthesis Example 5: Synthesis of the compound represented by the formula (I-36)

15.72 parts of the compound represented by the formula (I-1-c), 8.29 parts of triethylamine and 100 parts of the compound represented by the formula (I-36-d) were added. Then, the mixture was stirred at 80 ° C. for 4 hours and cooled to 23 ° C. 75 parts of ion-exchanged water and 75 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 50 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 50 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 14.58 parts of the compound represented by the formula (I-36-e) was obtained.

14.31 parts of the compound represented by the formula (I-36-e), 5.13 parts of the compound represented by the formula (I-1-f) and 50 parts of chloroform were added. Then, the mixture was stirred at 23 ° C. for 30 minutes. 13.70 parts of the compound represented by the formula (I-1-g) and 0.73 parts of dimethylaminopyridine were added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 4 hours. 25 parts of ion-exchanged water and 25 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 17 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 17 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 17 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. The recovered organic layer is concentrated, and the concentrated mass is separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: ethyl acetate) to form a compound represented by the formula (I-36). 12.19 copies were obtained.
MS (Mass Spectrometry): 308.2 (Molecular Ion Peak)

式（Ｉ－５－ｃ）で表される化合物１６．６８部、トリエチルアミン８．２９部及び式（Ｉ－３６－ｄ）で表される化合物１００部を添加した。その後、８０℃で４時間攪拌し、２３℃まで冷却した。得られた反応溶液に、イオン交換水７５部及びクロロホルム７５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－４０－ｅ）で表される化合物１５．４１部を得た。

式（Ｉ－５－ｅ）で表される化合物１５．１４部、式（Ｉ－５－ｆ）で表される化合物５．１３部及びクロロホルム５０部を添加し、その後、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－５－ｇ）で表される化合物１３．７０部及びジメチルアミノピリジン０．７３部を仕込み、２３℃で４時間攪拌した。得られた反応溶液に、イオン交換水２５部及びクロロホルム２５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：酢酸エチル）分取することにより、式（Ｉ－４０）で表される化合物１３．４２部を得た。
ＭＳ（質量分析）：３２２．２（分子イオンピーク） Synthesis Example 6: Synthesis of a compound represented by the formula (I-40)

16.68 parts of the compound represented by the formula (I-5-c), 8.29 parts of triethylamine and 100 parts of the compound represented by the formula (I-36-d) were added. Then, the mixture was stirred at 80 ° C. for 4 hours and cooled to 23 ° C. 75 parts of ion-exchanged water and 75 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 50 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 50 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 15.41 parts of the compound represented by the formula (I-40-e) was obtained.

15.14 parts of the compound represented by the formula (I-5-e), 5.13 parts of the compound represented by the formula (I-5-f) and 50 parts of chloroform were added, and then at 23 ° C. for 30 minutes. Stirred. 13.70 parts of the compound represented by the formula (I-5-g) and 0.73 parts of dimethylaminopyridine were added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 4 hours. 25 parts of ion-exchanged water and 25 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 17 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 17 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 17 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. The recovered organic layer was concentrated. The concentrated mass was fractionated from a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: ethyl acetate) to obtain 13.42 parts of the compound represented by the formula (I-40).
MS (Mass Spectrometry): 322.2 (Molecular Ion Peak)

式（Ｉ－２－ａ）で表される化合物８．００部、トリエチルアミン１１．６６部及びクロロホルム５０部を添加した後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合溶液に、５℃で、式（Ｉ－１－ｂ）で表される化合物１６．８１部を１時間かけて滴下し、２３℃で２４時間攪拌した。得られた反応溶液に、１Ｎ塩酸１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１６．６７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－２－ｃ）で表される化合物１０．２９部を得た。

式（Ｉ－２－ｃ）で表される化合物１２．１７部、トリエチルアミン８．２９部及び式（Ｉ－１－ｄ）で表される化合物７４．９７部を添加した。その後、８０℃で４時間攪拌し、２３℃まで冷却した。得られた反応溶液に、イオン交換水７５部及びクロロホルム７５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層に、濃縮することにより、式（Ｉ－２－ｅ）で表される化合物１１．８８部を得た。

式（Ｉ－２－ｅ）で表される化合物８．５９部、式（Ｉ－１－ｆ）で表される化合物５．１３部及びクロロホルム５０部を添加し。その後、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物１３．７０部及びジメチルアミノピリジン０．７３部を仕込み、２３℃で４時間攪拌した。得られた反応溶液に、イオン交換水２５部及びクロロホルム２５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、１Ｎ塩酸１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、５％炭酸水素ナトリウム水溶液１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。回収された有機層に、イオン交換水１７部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ 展開溶媒：酢酸エチル）分取することにより、式（Ｉ－１）で表される化合物８．０４部を得た。
ＭＳ（質量分析）：２１２．１（分子イオンピーク） Synthesis Example 7: Synthesis of the compound represented by the formula (I-2)

After adding 8.00 parts of the compound represented by the formula (I-2-a), 11.66 parts of triethylamine and 50 parts of chloroform, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixed solution, 16.81 part of the compound represented by the formula (I-1-b) was added dropwise at 5 ° C. over 1 hour, and the mixture was stirred at 23 ° C. for 24 hours. 16.67 parts of 1N hydrochloric acid was added to the obtained reaction solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 16.67 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 16.67 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 10.29 parts of the compound represented by the formula (I-2-c) was obtained.

12.17 parts of the compound represented by the formula (I-2-c), 8.29 parts of triethylamine and 74.97 parts of the compound represented by the formula (I-1-d) were added. Then, the mixture was stirred at 80 ° C. for 4 hours and cooled to 23 ° C. 75 parts of ion-exchanged water and 75 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 50 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 50 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 50 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. By concentrating the recovered organic layer, 11.88 parts of the compound represented by the formula (I-2-e) was obtained.

8.59 parts of the compound represented by the formula (I-2-e), 5.13 parts of the compound represented by the formula (I-1-f) and 50 parts of chloroform were added. Then, the mixture was stirred at 23 ° C. for 30 minutes. 13.70 parts of the compound represented by the formula (I-1-g) and 0.73 parts of dimethylaminopyridine were added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 4 hours. 25 parts of ion-exchanged water and 25 parts of chloroform were added to the obtained reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The recovered organic layer was charged with 17 parts of 1N hydrochloric acid, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. The recovered organic layer was charged with 17 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. 17 parts of ion-exchanged water was charged into the recovered organic layer, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer. Such a washing operation was repeated three times. The recovered organic layer is concentrated, and the concentrated mass is separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: ethyl acetate) to obtain a compound represented by the formula (I-1). 8.04 copies were obtained.
MS (Mass Spectrometry): 212.1 (Molecular Ion Peak)

Resin synthesis The compounds (monomers) used in the resin synthesis are shown below.

以下、これらのモノマーを式番号に応じて「モノマー（ａ１－１－３）」等という。

Hereinafter, these monomers will be referred to as "monomer (a1-1-3)" or the like according to the formula number.

Synthesis Example 8 [Synthesis of resin A1]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (I-1), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molars thereof are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)] is 35:14: The mixture was mixed so as to have a ratio of 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A1 (copolymer) having a weight average molecular weight of 7.9 × 10 ³ in a yield of 65%. rice field. This resin A1 has the following structural units.

Synthesis Example 9 [Synthesis of resin A2]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (I-5), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and their molars are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-5): monomer (a2-1-1): monomer (a3-4-2)] is 35:14: The mixture was mixed so as to have a ratio of 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A2 (copolymer) having a weight average molecular weight of 8.2 × 10 ³ in a yield of 62%. rice field. This resin A2 has the following structural units.

Synthesis Example 10 [Synthesis of resin A3]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (I-9), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and their molars are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-9): monomer (a2-1-1): monomer (a3-4-2)] is 35:14: The mixture was mixed so as to have a ratio of 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A3 (copolymer) having a weight average molecular weight of 8.4 × 10 ³ in a yield of 60%. rice field. This resin A3 has the following structural units.

Synthesis Example 11 [Synthesis of resin A4]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (I-13), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and their molars are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-13): monomer (a2-1-1): monomer (a3-4-2)] is 35:14: The mixture was mixed so as to have a ratio of 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a mixed methanol / water solvent to repulp, and the resin is filtered to obtain a resin A4 (copolymer) having a weight average molecular weight of 8.8 × 10 ³ in a yield of 58%. rice field. This resin A4 has the following structural units.

Synthesis Example 12 [Synthesis of resin A5]
As the monomer, a monomer (a1-1-1), a monomer (a2-1-1), a monomer (a3-4-2) and a monomer (I-1) are used, and the molar ratio [monomer (a1-1-1)] is used. ): Monomer (a2-1-1): Monomer (a3-4-2): Monomer (I-1)] are mixed so as to be 35:15:35:15, and 1.5 mass of the total amount of the monomer. Double the amount of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total amount of the monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a mixed methanol / water solvent to repulp, and the resin is filtered to obtain a resin A5 (copolymer) having a weight average molecular weight of 9.9 × 10 ³ in a yield of 88%. rice field. This resin A5 has the following structural units.

Synthesis Example 13 [Synthesis of resin A6]
As the monomer, a monomer (a1-1-1), a monomer (a2-1-1), a monomer (a3-1-1) and a monomer (I-1) are used, and the molar ratio [monomer (a1-1-1)] is used. ): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (I-1)] are mixed so as to be 35:15:35:15, and 1.5 mass of the total amount of the monomer. Double the amount of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total amount of the monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A6 (copolymer) having a weight ^average molecular weight of 1.0 × 104 in a yield of 86%. rice field. This resin A6 has the following structural units.

Synthesis Example 14 [Synthesis of resin A7]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (I-36), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and their molars are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-36): monomer (a2-1-1): monomer (a3-4-2)] is 35:14: The mixture was mixed so as to have a ratio of 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A7 (copolymer) having a weight average molecular weight of 8.2 × 10 ³ in a yield of 63%. rice field. This resin A7 has the following structural units.

Synthesis Example 15 [Synthesis of resin A8]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (I-40), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and their molars are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-40): monomer (a2-1-1): monomer (a3-4-2)] is 35:14: The mixture was mixed so as to have a ratio of 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A8 (copolymer) having a weight average molecular weight of 8.4 × 10 ³ in a yield of 60%. rice field. This resin A8 has the following structural units.

Synthesis Example 16 [Synthesis of resin A9]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (I-2), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and their molars are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-2): monomer (a2-1-1): monomer (a3-4-2)] is 35:14: The mixture was mixed so as to have a ratio of 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of the monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of monomers, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin A9 (copolymer) having a weight average molecular weight of 7.8 × 10 ³ in a yield of 66%. rice field. This resin A9 has the following structural units.

Synthesis Example 17 [Synthesis of resin AX1]
As the monomer, a monomer (a1-1-1), a monomer (a2-1-1), a monomer (a3-1-1) and a monomer (a5-1-1) are used, and the molar ratio [monomer (a1-1-1)] is used. -1): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (a5-1-1)] are mixed so as to be 35:15:35:15, and the total amount of the monomer is adjusted. 1.5 times by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total amount of the monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin AX1 (copolymer) having a weight average molecular weight of 1.0 × 10 ⁴ in a yield of 80%. rice field. This resin AX1 has the following structural units.

Synthesis Example 18 [Synthesis of resin AX2]
As the monomer, a monomer (a1-1-1), a monomer (a2-1-1), a monomer (a3-2-1) and a monomer (a5-1-2) are used, and the molar ratio [monomer (a1-1-1)] is used. -1): Monomer (a2-1-1): Monomer (a3-2-1): Monomer (a5-1-2)] are mixed so as to be 35:15:35:15, and the total amount of the monomer is adjusted. 1.5 times by mass of propylene glycol monomethyl ether acetate was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.9 mol% and 2.7 mol%, respectively, based on the total amount of the monomers, and these were added at 75 ° C. It was heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is again poured into a methanol / water mixed solvent to repulp, and the resin is filtered to obtain a resin AX2 ⁽ copolymer) having a weight average molecular weight of 1.0 × 104 in a yield of 84%. rice field. This resin AX2 has the following structural units.

Synthesis Example 19 [Synthesis of resin X1]
As the monomer, a monomer (a5-1-1) and a monomer (a4-0-12) are used, and the molar ratio [monomer (a5-1-1): monomer (a4-0-12)] is 50:50. Methyl isobutyl ketone was added in an amount 1.2% by mass of the total amount of the monomers to prepare a solution. Azobis (2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 3 mol% based on the total amount of monomers, and the mixture was heated at 70 ° C. for about 5 hours. The obtained reaction mixture is poured into a large amount of a mixed methanol / water solvent to precipitate a resin, and the resin is filtered to obtain a resin X1 (copolymer) having a weight average molecular weight of 1.0 × 10 ⁴ in a yield of 91%. I got it in. This resin X1 has the following structural units.

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

＜クエンチャー（Ｃ）＞
Ｄ１：（東京化成工業（株）製）

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２－ヘプタノン ２０部
γ－ブチロラクトン ３．５部 <Resin (A)>
A1 to A9, AX1, AX2, X1: Resin A1 to Resin A9, Resin AX1, Resin AX2, Resin X1
<Acid generator (B)>
B1-5: Salt represented by the formula (B1-5) (synthesized according to the synthesis example of JP-A-2015-200886)
B1-21: Salt represented by the formula (B1-21) (synthesized according to the synthesis example of JP-A-2015-200886)
B1-22: Salt represented by the formula (B1-22) (synthesized according to a synthesis example of JP-A-2015-200886)
BX-1: Triphenylsulfonium nonafluorobutane sulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)

<Quencher (C)>
D1: (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
Propylene Glycol Monomethyl Ether Acetate 265 Parts Propylene Glycol Monomethyl Ether 20 Parts 2-Heptanone 20 Parts γ-Butyrolactone 3.5 Parts

<Manufacturing of resist pattern and its evaluation>
An organic antireflection film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to cause organic reflection on the wafer with a film thickness of 78 nm. An anti-reflective film was formed. Next, the above resist composition was applied (spin coated) on the organic antireflection film so that the film thickness after drying was 85 nm. After coating, the silicon wafer was prebaked on a direct hot plate at the temperature listed in the "PB" column of Table 1 for 60 seconds to form a composition layer. A contact hole pattern (hole pitch 90 nm) was used on a silicon wafer on which a composition layer was formed with an ArF excimer stepper for immersion exposure (XT: 1900Gi; ASML, NA = 1.35, 3/4 Anal XY polarization). / Using a mask for forming a hole diameter (55 nm), the exposure amount was changed stepwise for exposure. Ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed on a hot plate at the temperature listed in the “PEB” column of Table 1 for 60 seconds. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution at 23 ° C. for 20 seconds by the dynamic dispensing method to obtain a negative resist pattern. Manufactured.

In the resist pattern obtained after development, the exposure amount having a hole diameter of 45 nm formed by using the mask was defined as the effective sensitivity.

<Mask error factor (MEF) evaluation>
In terms of effective sensitivity, a resist pattern was formed using a mask having a mask hole diameter (hole diameter of a translucent portion of the mask) of 57 nm, 56 nm, 55 nm, 54 nm, and 53 nm (hole pitch is 90 nm, respectively). The slope of the regression line when the hole diameter of the resist pattern formed (transferred) on the substrate by exposure was plotted on the vertical axis with the mask hole diameter on the horizontal axis was calculated as the MEF value.
Those with a MEF value of 5.2 or less are evaluated as having a good MEF, and are marked with ○.
Those having a MEF value of more than 5.2 were evaluated as having poor MEF and were evaluated as x.
The results are shown in Table 2. The numbers in parentheses indicate the MEF value.

From the above results, it can be seen that the resist composition of the present invention can produce a resist pattern with a good mask error factor (MEF).

The resist composition of the present invention is suitable for microfabrication of semiconductors because a resist pattern can be produced with a good mask error factor (MEF).

Claims (8)

A resist composition containing a resin (A) containing a structural unit derived from a compound represented by the formula (I) and a structural unit having an acid unstable group, and a salt represented by the formula (B1).

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² is a combination of an alkanediyl group having 1 to 6 carbon atoms bonded to X ¹ and an alicyclic hydrocarbon group having 3 to 12 carbon atoms bonded to the alkanediyl group having 1 to 6 carbon atoms. Is the basis and
The carbon atom bonded to the alkanediyl group having 1 to 6 carbon atoms and contained in the alicyclic hydrocarbon group having 3 to 12 carbon atoms does not form an acid unstable group.
X ¹ represents —O—, —CO—O—, —O—CO— or —O—CO—O—.
A ¹ represents a divalent hydrocarbon group having 1 to 12 carbon atoms or ^* -A ² -X ^2- (A ³ -X ³ ) _a -A ^4- . * Represents a bond with an oxygen atom. However, when X ¹ is −O—, A ¹ does not become a methylene group.
a represents 0 or 1.
A ² , A ³ and A ⁴ each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms.
X ² and X ³ independently represent —O—, —CO—O—, —O—CO— or —O—CO—O—, respectively. ]

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon. -CH _2- contained in the hydrogen group may be replaced with -O-, -SO _2- or -CO-.
Z ⁺ represents an organic cation. ] A resin (A) containing a structural unit derived from a compound represented by the formula (I) and a structural unit having an acid unstable group.
An acid generator containing a salt represented by the formula (B1) and
A resist composition containing a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.

[In formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents a saturated hydrocarbon group having a saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the carbon atom bonded to X ¹ does not form an acid unstable group.
X ¹ represents —O—, —CO—O—, —O—CO— or —O—CO—O—.
A ¹ represents a divalent hydrocarbon group having 1 to 12 carbon atoms or ^* -A ² - X ^2- (A ³ - X ³ ) _a -A ^4- . * Represents a bond with an oxygen atom. However, when X ¹ is −O—, A ¹ does not become a methylene group.
a represents 0 or 1.
A ² , A ³ and A ⁴ each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms.
X ² and X ³ independently represent —O—, —CO—O—, —O—CO— or —O—CO—O—, respectively. ]

[In formula (B1),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon. -CH _2- contained in the hydrogen group may be replaced with -O-, -SO _2- or -CO-.
Z ⁺ represents an organic cation. ] The resist composition according to claim 1 or 2 , wherein X ¹ is —O— or —CO—O—. The resist composition according to claim 2, wherein R ² is a saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms bonded to X ¹ or which is dependent on claim 2 . R ² is a combination of an alkanediyl group having 1 to 6 carbon atoms bonded to X ¹ and an alicyclic hydrocarbon group having 3 to 12 carbon atoms bonded to the alkanediyl group having 1 to 6 carbon atoms. Is the basis and
According to claim 2 or claim 2, the carbon atom bonded to the alkanediyl group having 1 to 6 carbon atoms and contained in the alicyclic hydrocarbon group having 3 to 12 carbon atoms does not form an acid unstable group. Item 3. The resist composition according to Item 3. The resist composition according to any one of claims 1 to 5 , further comprising a resin (X) containing a structural unit represented by the formula (a4).

[In equation (a4),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ] The structural unit represented by the formula (a4) is the structural unit represented by the formula (a4-0), the structural unit represented by the formula (a4-1), and the structural unit represented by the formula (a4-2). The resist composition according to claim 6 , which is at least one selected from the group consisting of structural units represented by the formula (a4-3).

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

[In equation (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ³ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f4 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ³ and R ^{f 4} is 21. ]

[In equation (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
R ^f6 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴ and R f ⁶ is 21. ]

[In equation (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 has a fluorine atom, and the upper limit of the total carbon number of L ⁵ , A ^f13 and A ^f14 is 20. ] (1) A step of applying the resist composition according to any one of claims 1 to 7 onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) Step of heating the composition layer after exposure, and (5) Step of developing the composition layer after heating,
A method for manufacturing a resist pattern including.