JP7042878B2 - 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.

特許文献２には、下記式で表される塩を酸発生剤として含有するレジスト組成物が記載
されている。

Patent Document 1 describes a salt represented by the following formula.

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

Japanese Unexamined Patent Publication No. 2011-46694 Japanese Unexamined Patent Publication No. 2012-229206

In the resist composition containing the above salt, the CD uniformity of the obtained resist pattern (CDU)
) Was not always satisfactory.

［式（Ｉ）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、該飽和炭化水素基に含まれる
－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該飽和炭化水素基に含ま
れる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ａｄは、アダマンタントリイル基を表す。
Ｚ^＋は、有機カチオンを表す。］
［２］Ｌ^b1が、式（ｂ１－１）～式（ｂ１－３）のいずれかで表される基であり、＊は
ＣＱ¹Ｑ²との結合位を表す［１］記載の塩。

［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。］
［３］［１］又は［２］記載の塩を有効成分として含有する酸発生剤。
［４］式（Ｉ０）で表される塩と酸不安定基を有する樹脂とを含有するレジスト組成物
。

［式（Ｉ）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、該飽和炭化水素基に含まれる
－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該飽和炭化水素基に含ま
れる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ａｄ_１は、アダマンタンジイル基又はアダマンタントリイル基を表す。
ｎは、１又は２を表す。
Ｚ^＋は、有機カチオンを表す。］
［５］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含有する［４］に
記載のレジスト組成物。
［６］（１）［４］又は［５］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 salt represented by the formula (I).

[In formula (I),
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 saturated hydrocarbon group may be replaced with -O- or -CO-, and the saturated hydrocarbon group may be replaced. The hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Ad represents an adamantane triyl group.
Z ⁺ represents an organic cation. ]
[2] The salt according to [1], wherein L ^b1 is a group represented by any of the formulas (b1-1) to (b1-3), and * represents a binding position with CQ ¹ Q ² .

[In equation (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. 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 bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. 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 bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. 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. ]
[3] An acid generator containing the salt according to [1] or [2] as an active ingredient.
[4] A resist composition containing a salt represented by the formula (I0) and a resin having an acid unstable group.

[In formula (I),
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 saturated hydrocarbon group may be replaced with -O- or -CO-, and the saturated hydrocarbon group may be replaced. The hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Ad ₁ represents an adamantane diyl group or an adamantane triyl group.
n represents 1 or 2.
Z ⁺ represents an organic cation. ]
[5] The resist composition according to [4], which contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[6] (1) A step of applying the resist composition according to [4] or [5] 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.

Provided are salts capable of producing a resist pattern with good CD uniformity (CDU).

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.
Further, unless otherwise specified, a group capable of taking a linear, branched and / or ring such as "aliphatic hydrocarbon group" includes any of them. 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.

［式（Ｉ）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、該飽和炭化水素基に含まれる
－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該飽和炭化水素基に含ま
れる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ａｄは、アダマンタントリイル基を表す。
Ｚ^＋は、有機カチオンを表す。］ [Salt (I)]
The salt of the present invention is a salt having the following formula (I) (hereinafter, may be referred to as “salt (I)”).

[In formula (I),
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 saturated hydrocarbon group may be replaced with -O- or -CO-, and the saturated hydrocarbon group may be replaced. The hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Ad represents an adamantane triyl group.
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.
Q ¹ and Q ² are independently, preferably a trifluoromethyl group or a fluorine atom, and more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group represented by L ^b1 include an alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and two or more of these groups. It may be a combination of.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4
-Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1
, 7-Diyl group, Octane-1,8-Diyl group, Nonane-1,9-Diyl group, Decane-1
, 10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group,
Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-
1,15-Diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-
Linear alkanediyl groups such as diyl groups;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-
Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 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;
Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-
Examples thereof include a polycyclic divalent alicyclic saturated hydrocarbon group such as a 1,5-diyl group and an adamantane-2,6-diyl group.

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。 The group in which the methylene group contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced with an oxygen atom or a carbonyl group is represented by any of the formulas (b1-1) to (b1-3). Group is mentioned. In the equations (b1-1) to (b1-3) and the following specific examples, * represents a bond with CQ ¹ Q ² .

In equation (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. 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 bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. 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 bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. 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 saturated hydrocarbon group. The number of carbon atoms in.
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 an alkanediyl 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 saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. , The methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

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、該飽和炭化水素
基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b9及びＬ^b10の合計炭素数は２０以下である。
式（ｂ１－６）中、
Ｌ^b11は、炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^b12は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b11及びＬ^b12の合計炭素数は２１以下である。
式（ｂ１－７）中、
Ｌ^b13は、炭素数１～１９の２価の飽和炭化水素基を表す。
Ｌ^b14は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表す。
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^b14及び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^b17及びＬ^b18の合計炭素数は１９以下である。 Among them, the group represented by the formula (b1-1) or the formula (b1-3) is preferable.
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 saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
However, the total number of carbon atoms of L ^b9 and L ^b10 is 20 or less.
In equation (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the 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 saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
However, the total carbon number of L ^b13 , L ^b14 and 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 saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
However, the total carbon number of L ^b16 , L ^b17 and L ^b18 is 19 or less.

L ^b8 is preferably an alkanediyl 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 preferably represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 preferably represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b18 preferably represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably represents a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

式（ｂ１－９）中、
Ｌ^b19は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b20は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はア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、該飽和炭化水素
基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b22は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^b23は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はア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^b22及びＬ^b23の合計炭素数は２１以下である。
式（ｂ１－１１）中、
Ｌ^b24は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b25は、炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^b26は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該飽和炭化水素
基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はア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^b25及び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 saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an acyloxy group. .. 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 saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an acyloxy group. .. 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 , L ^b22 and L ^b23 is 21 or less.
In equation (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an acyloxy group. .. 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 , L ^b25 and L ^b26 is 21 or less.

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

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, and an oxocyclohexylcarbonyloxy group.
Hydroxycyclohexylcarbonyloxy group and the like can be mentioned.

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.

Ａｄのアダマンタントリイル基の３つの結合手は、任意の位置とすることができる。

The three bonds of the adamantane triyl group of Ad can be at any position.

Examples of the anion of the salt (I) include anions represented by the following.

式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^b4～Ｒ^b6は、それぞれ独立に、炭素数１～３０の脂肪族炭化水素基、炭素数３～３６
の脂環式炭化水素基又は炭素数６～３６の芳香族炭化水素基を表し、該脂肪族炭化水素基
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
の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該
脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～１８の脂肪族炭化水
素基、炭素数２～４のア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、一緒になってそれらが結合する硫黄原子を含む環を形成してもよく、
該環に含まれるメチレン基は、酸素原子、スルフィニル基又はカルボニル基に置き換わっ
てもよい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基
又は炭素数１～１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０～５の整数を表す。
ｍ２が２以上のとき、複数のＲ^b7は同一でも異なってもよく、ｎ２が２以上のとき、複
数のＲ^b8は同一でも異なってもよい。
Ｒ^b9及びＲ^b10は、それぞれ独立に、炭素数１～３６の脂肪族炭化水素基又は炭素数３
～３６の脂環式炭化水素基を表す。
Ｒ^b9とＲ^b10とは、一緒になってそれらが結合する硫黄原子を含む環を形成してもよく
、該環に含まれるメチレン基は、酸素原子、スルフィニル基又はカルボニル基に置き換わ
ってもよい。
Ｒ^b11は、水素原子、炭素数１～３６の脂肪族炭化水素基、炭素数３～３６の脂環式炭
化水素基又は炭素数６～１８の芳香族炭化水素基を表す。
Ｒ^b12は、炭素数１～１２の脂肪族炭化水素基、炭素数３～１８の脂環式炭化水素基又
は炭素数６～１８の芳香族炭化水素基を表し、該脂肪族炭化水素に含まれる水素原子は、
炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含ま
れる水素原子は、炭素数１～１２のアルコキシ基又は炭素数１～１２のアルキルカルボニ
ルオキシ基で置換されていてもよい。
Ｒ^b1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、該環に含まれるメチレン基は、酸素原子、スルフィニル基又はカルボニル基
に置き換わってもよい。
Ｒ^b13～Ｒ^b18は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基
又は炭素数１～１２のアルコキシ基を表す。
Ｌ^b31は、硫黄原子又は酸素原子を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０～５の整数を表す。
ｑ２及びｒ２は、それぞれ独立に、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は同一又は相異なり、ｐ２が２以上のとき、複数の
Ｒ^b14は同一又は相異なり、ｑ２が２以上のとき、複数のＲ^b15は同一又は相異なり、ｒ２
が２以上のとき、複数のＲ^b16は同一又は相異なり、ｓ２が２以上のとき、複数のＲ^b17は
同一又は相異なり、ｔ２が２以上のとき、複数のＲ^b18は同一又は相異なる。 Examples of the cation Z ⁺ in the salt (I) include an organic onium cation, for example, an organic sulfonium cation, an organic iodinenium cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation, and the like, and an organic sulfonium cation or an organic cation is preferable. It is an iodonium cation, more preferably an aryl sulfonium cation.
Among them, a cation represented by any of the formulas (b2-1) to (b2-4) (hereinafter, may be referred to as “cation (b2-1)” or the like depending on the formula number) is preferable.

In equations (b2-1) to (b2-4),
R ^b4 to R ^b6 are independently aliphatic hydrocarbon groups having 1 to 30 carbon atoms and 3 to 36 carbon atoms.
Represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, and 3 carbon atoms. ~ 12
May be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom and has 1 to 18 carbon atoms. It may be substituted with an aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, a hydroxy group or 1 to 12 carbon atoms. It may be substituted with the alkoxy group of.
R ^b4 and R ^b5 may be combined to form a ring containing sulfur atoms to which they are bonded.
The methylene group contained in the ring may be replaced with an oxygen atom, a sulfinyl group or a carbonyl group.
R ^b7 and R ^b8 independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.
When m2 is 2 or more, 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.
Each of R ^b9 and R ^b10 independently has an aliphatic hydrocarbon group having 1 to 36 carbon atoms or 3 carbon atoms.
Represents ~ 36 alicyclic hydrocarbon groups.
R ^b9 and R ^b10 may be combined to form a ring containing a sulfur atom to which they are bonded, and the methylene group contained in the ring may be replaced with an oxygen atom, a sulfinyl group or a carbonyl group. ..
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is contained in the aliphatic hydrocarbon group. Hydrogen atom is
It may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy having 1 to 12 carbon atoms. It may be substituted with a group.
R ^b1 and R ^b12 may be combined to form a ring containing —CH—CO— to which they are bonded, and the methylene group contained in the ring may be an oxygen atom, a sulfinyl group or a carbonyl group. It may be replaced.
R ^b13 to R ^b18 independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5.
q2 and r2 each independently represent an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13s are the same or different, when p2 is 2 or more, a plurality of R ^b14s are the same or different, and when q2 is 2 or more, a plurality of R ^b15s are the same or different. , R2
When is 2 or more, the plurality of R ^b16s are the same or different, when s2 is 2 or more, the plurality of R ^b17s are the same or different, and when t2 is 2 or more, the plurality of R ^b18s are the same or different.

特に、Ｒ^b9～Ｒ^b12の脂環式炭化水素基は、好ましくは炭素数３～１８、より好ましく
は炭素数４～１２である。 Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like.
Examples thereof include alkyl groups of n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group and 2-ethylhexyl group. Especially, R ^b9 ~
The aliphatic hydrocarbon group of R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cyclo. Cycloalkyl groups such as heptyl group, cyclooctyl group and cyclodecyl group can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

In particular, the alicyclic hydrocarbon 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 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, a methylnorbornyl group, an isobornyl group and the like. Can be mentioned. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group and p-adamantylphenyl group. , Biphenylyl group, naphthyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and other aryl groups.
When the aromatic hydrocarbon group contains an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, the aliphatic hydrocarbon group having 1 to 18 carbon atoms or the alicyclic hydrocarbon group having 3 to 18 carbon atoms Groups are preferred.
Examples of the 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 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 ring containing a sulfur atom formed by R ^b4 and R ^b5 together may be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. .. This ring has 3 to 18 carbon atoms.
The ring is preferably a ring having 4 to 18 carbon atoms. In addition, the ring containing a sulfur atom has 3
A member ring to a 12-membered ring can be mentioned, and a 3-membered ring to a 7-membered ring is preferable. The following rings are mentioned.

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

Among the cations (b2-1) to cations (b2-4), the cation (b2) is preferable.
-1).
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 salt (I) is a combination of the above-mentioned sulfonic acid anion and organic cation. These anions and cations can be combined arbitrarily. Specific examples of the salt (I) are shown in Table 1.
In Table 1, the salt (I-1) is the salt shown below.

Among them, the salt (I) is salt (I-1), salt (I-2), salt (I-3), salt (I-6),
Salt (I-7), salt (I-8), salt (I-9), salt (I-12), salt (I-13), salt (I)
-14), salt (I-15), salt (I-18), salt (I-19), salt (I-20), salt (I)
-21), salt (I-24) salt (I-25), salt (I-26), salt (I-27), salt (I-
30), salt (I-31), salt (I-32), salt (I-33), salt (I-36), salt (I-)
37), salt (I-38), salt (I-39) and salt (I-42) are preferred.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
酸としては、塩酸等が挙げられる。
溶媒としては、アセトニトリル、ジメチルホルムアミド、メチルイソブチルケトン、ク
ロロホルム、テトラヒドロフラン及びトルエン等が挙げられる。 The salt represented by the formula (I1) (L ^b1 represents * -CO-O- (* represents the binding position with CQ ¹ Q ² ).
The salt (I)) in the case of the group represented by is obtained, for example, by reacting the salt represented by the formula (I1-a) with water in the presence of an acid in a solvent.

(In the formula, all the symbols have the same meanings as described above.)
Examples of the acid include hydrochloric acid and the like.
Examples of the solvent include acetonitrile, dimethylformamide, methyl isobutyl ketone, chloroform, tetrahydrofuran, toluene and the like.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。） The salt represented by the formula (I1-a) is, for example, a salt represented by the formula (I1-b) and a salt represented by the formula (I1-b).
It can be produced by reacting the compound represented by c) in a solvent such as acetonitrile.

(In the formula, all the symbols have the same meanings as described above.)

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
式（Ｉ１－ｄ）で表される化合物は、例えば、以下で表される化合物などが挙げられ、
特開２００８－１２７３６７号公報に記載された方法で製造することができる。

The compounds represented by the formula (I1-b) are the compound represented by the formula (I1-d) and the compound represented by the formula (I1-d).
It can be obtained by reacting with the compound represented by e) in a solvent such as acetonitrile.

(In the formula, all the symbols have the same meanings as described above.)
Examples of the compound represented by the formula (I1-d) include compounds represented by the following.
It can be produced by the method described in JP-A-2008-127365.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
塩基触媒としては、トリエチルアミン、水酸化ナトリウムなどが挙げられる。
溶剤としては、アセトン、メタノールなどが挙げられる。 The compounds represented by the formula (I1-c) are the compound represented by the formula (I1-f) and the compound represented by the formula (I1-f).
It can be obtained by reacting the compound represented by g) in a solvent in the presence of a base catalyst.

(In the formula, all the symbols have the same meanings as described above.)
Examples of the base catalyst include triethylamine and sodium hydroxide.
Examples of the solvent include acetone and methanol.

Examples of the compound represented by the formula (I1-f) include compounds represented by the following.
Easily available on the market.

式（Ｉ２－ａ）で表される塩は、例えば、式（Ｉ２－ｂ）で表される塩と、式（Ｉ２－
ｃ）で表される化合物とを、塩基触媒存在下、溶媒中で反応させることにより製造するこ
とができる。塩基触媒としては、炭酸カリウム、ヨウ化カリウム、トリエチルアミン、水
酸化ナトリウムなどが挙げられる。溶剤としては、テトラヒドロフラン、クロロホルムな
どが挙げられる。

式（Ｉ２－ｂ）で表される化合物は、例えば、以下で表される化合物などが挙げられ、
特開２００８－１２７３６７号公報に記載された方法で製造することができる。

The salt represented by the formula (I2) (L ^b1 is * -CO-O-CH ₂ -CO-O- (* is CQ ¹ Q ² )
The salt (I)) in the case of a group represented by (representing a bond position with) is, for example, a reaction between a salt represented by the formula (I2-a) and water in a solvent in the presence of an acid. Can be obtained by

The salt represented by the formula (I2-a) is, for example, a salt represented by the formula (I2-b) and a salt represented by the formula (I2-b).
It can be produced by reacting the compound represented by c) in a solvent in the presence of a base catalyst. Examples of the base catalyst include potassium carbonate, potassium iodide, triethylamine, sodium hydroxide and the like. Examples of the solvent include tetrahydrofuran, chloroform and the like.

Examples of the compound represented by the formula (I2-b) include compounds represented by the following.
It can be produced by the method described in JP-A-2008-127365.

The compounds represented by the formula (I2-c) are the compound represented by the formula (I1-c) and the compound represented by the formula (I2-c).
It can be obtained by reacting the compound represented by d) in a solvent in the presence of a base catalyst. Examples of the base catalyst include potassium carbonate, potassium iodide, triethylamine, sodium hydroxide and the like. Examples of the solvent include tetrahydrofuran, chloroform and the like.

［式（Ｉ）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、該飽和炭化水素基に含まれる
－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該飽和炭化水素基に含ま
れる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ａｄ_１は、アダマンタンジイル基又はアダマンタントリイル基を表す。
ｎは、１又は２を表す。
Ｚ^＋は、有機カチオンを表す。］
Ａｄのアダマンタンジイル基及びアダマンタントリイル基の結合手は、任意の位置とす
ることができる。 [Acid generator]
The acid generator of the present invention is an acid generator containing a salt (I) as an active ingredient. In the acid generator of the present invention, a salt (I0) may be used as the active ingredient instead of the salt (I). The acid generator of the present invention may contain the salt (I) alone, or may contain two or more kinds of the salt (I).
The acid generator of the present invention is an acid generator known in the resist field other than the salt (I) and the salt (I0) (
Hereinafter, it may be referred to as "acid generator (B)").

[In formula (I),
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 saturated hydrocarbon group may be replaced with -O- or -CO-, and the saturated hydrocarbon group may be replaced. The hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Ad ₁ represents an adamantane diyl group or an adamantane triyl group.
n represents 1 or 2.
Z ⁺ represents an organic cation. ]
The bond of the adamantane diyl group and the adamantane triyl group of Ad can be at any position.

Examples of the salt (I0) other than the salt (I) include salts represented by the following.

上記の塩において、カチオン（ｂ２－ｃ－１）が、式（ｂ２－１）～式（ｂ２－４）の
いずれかで表されるカチオンに置き換わったものも、塩（Ｉ０）として挙げられる。

In the above salt, a salt (I0) in which the cation (b2-c-1) is replaced with a cation represented by any of the formulas (b2-1) to (b2-4) is also mentioned.

When the salt (I) and / or the salt (I0) and the acid generator (B) are contained as the acid generator,
The ratio of the content of the salt (I) and / or the salt (I0) to the acid generator (B) (mass ratio; salt (I) and / or salt (I0): acid generator (B)) is usually used. , 1:99 to 99: 1, preferably 2: 9
8 to 98: 2, more preferably 5:95 to 95: 5, still more preferably 10:90 to 90
: 10.

[Resist composition]
The resist composition of the present invention comprises the above-mentioned acid generator containing a resin having an acid unstable group (hereinafter sometimes referred to as "resin (A)") and a salt (I) and / or a salt (I0). contains. Here, the "acid-unstable group" is a structural unit having a leaving group, the leaving group being removed by contact with an acid, and the constituent unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Means the group that converts to.
The resist composition further preferably contains a quencher (hereinafter, may be referred to as “quencher (C)”) and preferably contains a solvent (hereinafter, may be referred to as “solvent (E)”). ..

<Acid generator>
The resist composition of the present invention preferably contains a salt (I0) as an acid generator. When the salt (I0) is used as an acid generator, the content of the salt (I0) is 1 with respect to the resin (A).
It is preferably about 20% by mass, more preferably 2 to 15% by mass.

<Acid generator (B)>
As the acid generator (B), a known acid generator can be used, and either an ionic acid generator or a nonionic acid generator may be used. An ionic acid generator is preferred. Examples of the ionic acid generator include an ionic acid generator composed of a combination of an anion constituting the salt (I) and a cation other than the cation Z ⁺ , and an ionic acid generator composed of a combination of a known cation and a known anion. Agents are mentioned.

Examples of the acid generator (B) include organic sulfonic acids and organic sulfonium salts. For example, JP2013-68914A, JP2013-3155A, JP2013-1.
Examples thereof include acid generators described in Japanese Patent Publication No. 1905. Specifically, equations (B1-1) to equations (B1)
A salt represented by any of -40) can be mentioned. Among them, those containing an arylsulfonium cation are preferable, and formulas (B1-1), formulas (B1-2), formulas (B1-3), and formulas (B1-6) are preferable.
), Equation (B1-7), Equation (B1-11), Equation (B1-12), Equation (B1-13), Equation (B)
1-14), formula (B1-20), formula (B1-21), formula (B1-22), formula (B1-23)
), Equation (B1-24), Equation (B1-25), Equation (B1-26), Equation (B1-29), Equation (B1-29)
B1-31), formula (B1-32), formula (B1-33), formula (B1-34), formula (B1-3)
5), the salt represented by any of the formula (B1-36), the formula (B1-37), the formula (B1-38), the formula (B1-39) or the formula (B1-40) is more preferable.

The acid generator (B) may contain one kind alone or two or more kinds.
The content of the acid generator (B) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and 3 to 15% by mass with respect to the resin (A). Is more preferable.
When the salt (I0) and the acid generator (B) are used as the acid generator in the resist composition, the content of the salt (I0) and the acid generator (B) is preferable with respect to the resin (A). Is 1.5
It is mass% or more (more preferably 3% by mass or more), preferably 40% by mass or less (more preferably 35% by mass or less).

<Resin (A)>
The resin (A) has a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”). It is preferable that the resin (A) further contains a structural unit other than the structural unit (a1). Structural units other than the structural unit (a1) include a structural unit having no acid unstable group (hereinafter, may be referred to as “structural unit (s)”), a structural unit (a1), and a structural unit (s).
) And other structural units derived from monomers known in the art.

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

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

[In the formula (1), R ^a1 to R ^a3 are independently alkyl groups having 1 to 8 carbon atoms and 3 carbon atoms.
Represents an alicyclic hydrocarbon group of ~ 20 or a group combining these, or R ^a1 and R ^a2 are divalent alicyclic hydrocarbons having 3 to 20 carbon atoms together with carbon atoms to which they are bonded to each other. Form a group.
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. Represent or R ^a2'and R ^a3'
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 heterocyclic group contained-CH _2- , -O- or -S- may be replaced.
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、シクロヘキシルメチル基
、アダマンチルメチル基、ノルボルニルエチル基等が挙げられる。
ｎａは、好ましくは０である。 The alkyl groups of R ^a1 to R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, and the like.
Examples thereof include an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group.
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 is preferably an alicyclic hydrocarbon group having 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 cyclohexylmethyl group, an adamantylmethyl group, a norbornylethyl group and the like. Can be mentioned.
na is preferably 0.

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

The group represented by the formula (1) is a 1,1-dialkylalkoxycarbonyl group (formula (1).
), Groups in which R ^a1 to R ^a3 are alkyl groups, preferably tert-butoxycarbonyl groups), 2-alkyladamantane-2-yloxycarbonyl groups (R ^a1 in formula (1),
R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantane-1-yl) -1-alkylalkoxycarbonyl group (formula (formula).
1) Among the groups, R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Ｒ^a1’及びＲ^a2’のうち、少なくとも１つは水素原子であることが好ましい。 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 groups.
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, tolyl 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.
R ^a2'and R ^a3'bond to each other to form with the carbon atoms and X to which they bond 2
Examples of the valence heterocyclic group include the following groups. * Represents a bond.

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, preferably, the number of carbon atoms is 5 to 20.
Examples thereof include those having an alicyclic hydrocarbon group of. 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
Two or more types may be used in combination. In the present specification, the structural unit represented by the formula (a1-0), the formula (a).
The structural unit represented by 1-1) and the structural unit represented by the formula (a1-2) are referred to as a structural unit (a1-0), a structural unit (a1-1), and a structural unit (a1-2), respectively. , Structural unit (a1-
Monomer for inducing 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.

In the resin (A), the content of the structural unit (a1) is preferably 10 to 99 mol%, more preferably 20 to 97 mol%, and further, with respect to all the structural units of the resin (A). It is preferably 30 to 95 mol%.

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

[In equation (a1-0),
^La01 represents an oxygen atom or ^* -O- (CH ₂ ) _k01 -CO-O-, k01 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 are independently alkyl groups having 1 to 8 carbon atoms and 3 to 3 carbon atoms, respectively.
Represents 18 alicyclic hydrocarbon groups or a combination thereof. ]

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

[In 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), and more. It is preferably 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 groups of R ^a02 , R ^a03 and R ^a04 preferably have 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 preferably has 8 or less carbon atoms, and more preferably 6 or less 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. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, a norbornylmethyl group and the like. Be done.
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). ), More preferably -O
-.
R ^a4 and R ^a5 are preferably methyl groups.
As the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group and the group combining these,
Examples thereof 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 preferably have 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably an alicyclic hydrocarbon group having 8 or less carbon atoms, and more preferably an alicyclic hydrocarbon group having 6 or less carbon atoms.
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.

Examples of the structural unit (a1-0) include equations (a1-0-1) to equations (a1-0-12).
The structural unit represented by any of the above is preferable, and the formulas (a1-0-1) to (a1-0-10) are preferable.
The structural unit represented by any of the above 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 one 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, and 1-methylcyclohexane-1-yl (meth). Acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcycloheptane-1-yl (meth) acrylate,
1-Ethylcyclooctane-1-yl (meth) acrylate, 1-isopropylcyclopentane-1-yl (meth) acrylate, 1-isopropylcyclohexane-1-yl (1-isopropylcyclohexane-1-yl)
Meta) Acrylate and the like can be mentioned. 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 (a) are preferable.
Monomers represented by the formulas 1-2-9) and the formula (a1-2-10) are more preferable, and the monomers represented by the formula (a1-2-10) are more preferable.
The monomers represented by 2-3) and the formula (a1-2-9) are more 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). For the unit
It is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20.
It is ~ 85 mol%.

式（ａ１－３）中、
Ｒ^a9は、ヒドロキシ基を有していてもよい炭素数１～３の脂肪族炭化水素基、カルボキ
シ基、シアノ基、水素原子又は－ＣＯＯＲ^a13を表す。
Ｒ^a13は、炭素数１～８の脂肪族炭化水素基、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ることにより形成される基を表し、該脂肪族炭化水素基及び該脂環
式炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよく、該脂肪族炭
化水素基及び該脂環式炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換
わっていてもよい。
Ｒ^a10、Ｒ^a11及びＲ^a12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ることにより形成される基を表すか、Ｒ
^a10及びＲ^a11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。 Further, as the structural unit (a1) having the group (1), a structural unit represented by the formula (a1-3) can also be mentioned. The structural unit represented by the formula (a1-3) may be referred to as a structural unit (a1-3). Further, the monomer for inducing the structural unit (a1-3) is referred to as the monomer (a1-3).
In some cases.

In equation (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a carboxy group, a cyano group, a hydrogen atom or -COOR ^a13 , which may have a hydroxy group.
R ^a13 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these groups, the aliphatic hydrocarbon group and the said group. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group, and the aliphatic hydrocarbon group and -CH _2- contained in the alicyclic hydrocarbon group are -O- or. It may be replaced with -CO-.
R ^a10 , R ^a11 and R ^a12 are independently alkyl groups having 1 to 8 carbon atoms and 3 to 3 carbon atoms, respectively.
Represents 20 alicyclic hydrocarbon groups or groups formed by combining them, or R
^a10 and R ^a11 are bonded to each other, and 2 with 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
It forms a valent alicyclic hydrocarbon group.

Here, -COOR ^a13 includes, for example, a group in which a carbonyl group is bonded to an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the aliphatic hydrocarbon group which may have a hydroxy group of R ^a9 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a 2-hydroxyethyl group.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^a13 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and n. -Hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group and the like can be mentioned.
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ^a13 include cyclopentyl group, cyclopropyl group, adamantyl group, adamantylmethyl group, 1-adamantyl-1-methylethyl group and 2-oxo-oxolan-3-. Examples thereof include an yl group and a 2-oxo-oxolan-4-yl group.
Alkyl groups of R ^a10 to R ^a12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-.
Examples thereof include a hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-octyl group and the like.
The alicyclic hydrocarbon group of R ^a10 to R ^a12 may be either a monocyclic or polycyclic group, and the monocyclic alicyclic hydrocarbon group may be, for example, a cyclopropyl group, a cyclobutyl group or a cyclopentyl. Examples thereof include a cycloalkyl group such as a group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, and a 1- (adamantan-1-yl) alkane-.
1-Il group, norbornyl group, methylnorbornyl group, isobornyl group and the like can be mentioned.
As -C (R ^a10 ) (R ^a11 ) (R ^a12 ) when R ^a10 and R ^a11 are bonded to each other to form a divalent alicyclic hydrocarbon group together with the carbon atom to which they are bonded. , The following groups are preferred.

Specifically, the monomer (a1-3) is 5-norbornene-2-carboxylic acid-tert.
-Butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl,
5-Norbornene-2-carboxylic acid 1-methylcyclohexyl, 5-norbornene-2-
2-Methyl-2-adamantyl Carboxylic Acid, 5-Norbornen-2-Carboxylic Acid 2-ethyl-2-adamantyl, 5-Norbornen-2-Carboxylic Acid 1- (4-Methylcyclohexyl) -1-methylethyl, 5- Norbornen-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornen-2-carboxylic acid 1-methyl-1
-(4-Oxocyclohexyl) ethyl and 5-norbornene-2-carboxylic acid 1- (1)
-Adamantyl) -1-methylethyl and the like can be mentioned.

Since the resin (A) containing the structural unit (a1-3) contains a three-dimensionally bulky structural unit, it is higher than the resist composition of the present invention containing such a resin (A). A resist pattern can be obtained at a resolution. Further, since a rigid norbornane ring is introduced into the main chain, the obtained resist pattern tends to have excellent dry etching resistance.

When the resin (A) contains structural units (a1-3), the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). 20-8
5 mol% is more preferred.

［式（ａ１－４）中、
Ｒ^a32は、水素原子、ハロゲン原子、又は、ハロゲン原子を有してもよい炭素数１～６
のアルキル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基、炭素数１～６の
アルコキシ基、炭素数２～４のアシル基、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。
ｌａは０～４の整数を表す。ｌａが２以上である場合、複数のＲ^a33は互いに同一であ
っても異なってもよい。
Ｒ^a34及びＲ^a35はそれぞれ独立に、水素原子又は炭素数１～１２の炭化水素基を表し、
Ｒ^a36は、炭素数１～２０の炭化水素基を表すか、Ｒ^a35及びＲ^a36は互いに結合してそれ
らが結合するＣ－Ｏとともに炭素数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。
］ As the structural unit (a1) having a group represented by the group (2), the structural unit represented by the formula (a1-4) (hereinafter, may be referred to as “structural unit (a1-4)”). Can be mentioned.

[In equation (a1-4),
R ^a32 may have a hydrogen atom, a halogen atom, or a halogen atom and has 1 to 6 carbon atoms.
Represents the alkyl group of.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an 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.
la represents an integer from 0 to 4. When la is 2 or more, a plurality of Ra ^33s may be the same or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
R ^a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^a35 and R ^a36 are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with CO to which they are bonded. , -CH _2- contained in the hydrocarbon group and the divalent heterocyclic group may be replaced with -O- or -S-.
]

Examples of the alkyl group of R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group and the like. The alkyl group has 1 carbon atom.
Alkyl groups of -4 are preferred, methyl or ethyl groups are more preferred, and methyl groups are even more preferred.
Examples of the halogen atom of R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group that 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-
Examples thereof include a hexyl group and an n-perfluorohexyl 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 and the like. 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 include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
Examples of the hydrocarbon groups of R ^a34 and R ^a35 include groups similar to those of R a1'and R ^{a2' in} the formula (2).
R ^a36 includes an alkyl group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms.
Examples thereof include aromatic hydrocarbon groups having 6 to 18 carbon atoms or groups formed by combining them.

In the formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and even more preferably a methoxy group.
For la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. A group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms and 3 to 1 carbon atoms.
It is an alicyclic aliphatic hydrocarbon group of 8 or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. When the aromatic hydrocarbon group in R ^a36 has a substituent, the aryloxy group having 6 to 10 carbon atoms is preferable as the substituent.

As the monomer for deriving the structural unit (a1-4), for example, Japanese Patent Application Laid-Open No. 2010-204646
Examples thereof include the monomers described in the publication. Above all, equations (a1-4-1) to equations (a1-4)
The monomers represented by -8) are preferable, and the formulas (a1-4-1) to (a1-4-5) are preferable.
) And the monomers represented by the formula (a1-4-8), respectively, are more preferable.

When the resin (A) has a structural unit (a1-4), the content thereof is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). , 20
It is more preferably ~ 85 mol%.

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.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group and an ethyl group.
Examples thereof include 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.
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.
Of L ⁵² and L ⁵³ , it is preferable that one 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-.

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

Examples of the structural unit (a) having an acid unstable group in the resin (A) include the structural unit (a1-0).
At least one selected from the group consisting of structural units (a1-1), structural units (a1-2) and structural units (a1-5) is preferable, at least two or more are more preferable, and structural units (a1-1). And a combination of structural units (a1-2), a combination of structural units (a1-1) and structural units (a1-5), a combination of structural units (a1-1) and structural units (a1-0), structural units ( A combination of a1-2) and structural unit (a1-0), structural unit (a1-
5) Combination of structural unit (a1-0), structural unit (a1-0), structural unit (a1-0)
1) and combination of structural unit (a1-2), structural unit (a1-0), structural unit (a1-
The combination of 1) and the structural unit (a1-5) is more preferable, and the combination of the structural unit (a1-1) and the structural unit (a1-2), the structural unit (a1-1) and the structural unit (a1-5).
The combination of is even more preferable.
The structural unit (a1) preferably includes the structural unit (a1-1).

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid unstable group (hereinafter, may be referred to as “monomer (s)”). As the monomer for deriving the structural unit (s), a monomer having no acid unstable group known in the resist field can be used.
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 a structure 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 producing a resist pattern from the resist composition of the present invention, KrF is used as an exposure light source.
When using a high-energy beam such as an excimer laser (248 nm), electron beam or EUV (ultraviolet light), the structural unit (a2) is a structural unit having a phenolic hydroxy group (the structural unit (a2)).
It is preferable to use a2). When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) is a structural unit (a2) having an alcoholic hydroxy group.
) Is preferable, and it is more preferable to use 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. ]

Alkyl groups having 1 to 6 carbon atoms which may have a halogen atom of R ^a30 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 Groups, n-perfluorohexyl group and the like can be mentioned. R ^a3
0 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 of R ^a31 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 include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
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 JP-A-2010-2046.
Examples thereof include the monomers described in Japanese Patent Publication No. 34.
Among them, the structural unit (a2-0) includes the formula (a2-0-1), the formula (a2-0-2), and the like.
Those represented by the formulas (a2-0-3) and (a2-0-4) are preferable, and the formulas (a) are preferable.
The structural unit represented by 2-0-1) 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 possessed by 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－を表し、
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 —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

As the monomer for inducing the structural unit (a2-1), for example, Japanese Patent Application Laid-Open No. 2010-2046
Examples thereof include the monomers described in Japanese Patent Publication No. 46. Equation (a2-1-1) to Equation (a2-1-6)
) Is preferable, and formulas (a2-1-1) to (a2-1-4) are preferable.
The monomer represented by any of the above is more preferable, and the formula (a2-1-1) or the formula (a2-1-1) is preferable.
The monomer represented by 3) is more 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. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or γ
-A bridge ring containing a butyrolactone ring structure can be mentioned.

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

［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。
Ｌ^a7は、－Ｏ－、^＊－Ｏ－Ｌ^a8－Ｏ－、^＊－Ｏ－Ｌ^a8－ＣＯ－Ｏ－、^＊－Ｏ－Ｌ^a8－Ｃ
Ｏ－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。
ｗ１は、０～８の整数を表す。ｗ１が２以上のとき、複数のＲ^ａ２５は互いに同一であ
ってもよく、異なってもよい。］

[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.
L ^a7 is -O-, ^* -OL ^a8 -O-, ^{* -OL a8} -CO-O-, ^* -OL ^a8 -C
Represents O- ^{OL a9} -CO-O- or ^* -OL ^a8 -O-CO-L ^a9 -O-.
* Represents a bond with a carbonyl group.
^La8 and ^La9 represent an alkanediyl group having 1 to 6 carbon atoms independently of each other.
w1 represents an integer of 0 to 8. When w1 is 2 or more, the plurality of Ra ^25s may be the same or different from each other. ]

The aliphatic hydrocarbon groups of R ^a21 , R ^a22 , R ^a23 and R ^a25 include a methyl group, an ethyl group and n.
-Alkyl groups such as propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group 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 a methylene group, an ethylene group, and a propane-1,
3-Diyl group, Propane-1,2-Diyl group, Butane-1,4-Diyl group, Pentane-1
, 5-Diyl group, Hexane-1,6-Diyl group, Butane-1,3-Diyl group, 2-Methylpropane-1,3-Diyl group, 2-Methylpropane-1,2-Diyl group, Pentane- 1,
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 ^* —OL ^a8 −CO—O—, and more preferably.
-O-, -O-CH ₂ -CO-O- or -OC 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 monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and JP-A-201.
Examples thereof include the monomers described in Japanese Patent Publication No. 2-41274. As a structural unit (a3),
Equations (a3-1-1) to (a3-1-4), equations (a3-2-1) to equations (a3-2-4),
Formulas (a3-3-1) to formulas (a3-3-4) and formulas (a3-4-1) to formulas (a3-4-12)
) Is preferable, and the formula (a3-1-1) and the formula (a3-1-2) are preferable.
, Formula (a3-2-3) to formula (a3-2-4) and formula (a3-4-1) to formula (a3-4-1)
The structural unit represented by any of 2) is more preferable, and the formulas (a3-4-1) to (a3-4) are more preferable.
The structural unit represented by any one of -12) is more preferable, and the formulas (a3-4-1) to (a) are more preferable.
The structural unit represented by any of 3-4-6) is even more preferable.

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

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.

<Other structural units (t)>
As the structural unit (t), a structural unit having a halogen atom in addition to the structural unit (a2) and the structural unit (a3) (hereinafter, sometimes referred to as “structural unit (a4)”) and a non-desorbed hydrocarbon group are used. Examples thereof include a structural unit (s) having a structure unit (s) (hereinafter, may be referred to as a “structural unit (a5)”).

［式（ａ４－０）中、
Ｒ⁵は、水素原子又はメチル基を表す。
Ｌ⁴は、単結合又は炭素数１～４の脂肪族飽和炭化水素基を表す。
Ｌ³は、炭素数１～８のペルフルオロアルカンジイル基又は炭素数３～１２のペルフル
オロシクロアルカンジイル基を表す。
Ｒ⁶は、水素原子又はフッ素原子を表す。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0).

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

Examples of the aliphatic saturated hydrocarbon group of L ⁴ include an alkanediyl group having 1 to 4 carbon atoms.
For example, a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a linear alkanediyl group, and an alkyl group (particularly, a methyl group, Those having a side chain of (ethyl group, etc.), ethane-1,1-diyl group, propane-1,2
-Diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2
Examples thereof include branched alkanediyl groups such as -methylpropane-1,2-diyl group.

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

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

Examples of the structural unit ( ^a4-0 ) include the structural unit shown below and the structural unit in which the methyl group corresponding to R5 in the following structural unit is replaced with a hydrogen atom.

［式（ａ４－１）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ｒ^a42は、置換基を有していてもよい炭素数１～２０の炭化水素基を表し、該炭化水素
基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。
Ａ^a41は、置換基を有していてもよい炭素数１～６のアルカンジイル基又は式（ａ－ｇ
１）で表される基を表す。

〔式（ａ－ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１～５の脂肪族
炭化水素基を表す。
Ａ^a43は、単結合又は置換基を有していてもよい炭素数１～５の脂肪族炭化水素基を表
す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、－Ｏ－、－ＣＯ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ
－を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は７以下である。〕
＊で表される２つの結合手のうち、右側の＊が－Ｏ－ＣＯ－Ｒ^a42との結合手である。
］ Examples of the structural unit (a4) include a structural unit represented by the equation (a4-1).

[In equation (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-. good.
A ^a41 is an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a formula (ag).
Represents the group represented by 1).

[In the formula (ag1),
s represents 0 or 1.
A a ⁴² and A a ⁴⁴ each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a single bond or a substituent.
X ^a41 and X ^a42 are independently -O-, -CO-, -CO-O- or -O-CO, respectively.
-Represents.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
Of the two bonds represented by *, the * on the right side is the bond with -O-CO-R ^a42 .
]

The hydrocarbon groups of R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like.
In addition, a group formed by combining these can be mentioned.
The chain and cyclic aliphatic hydrocarbon groups may have a carbon-carbon unsaturated bond, but chain and cyclic aliphatic saturated hydrocarbon groups are preferable. The aliphatic saturated hydrocarbon group is a fat formed by combining a linear or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group. Examples include group hydrocarbon groups.

芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニリル基
、フェナントリル基及びフルオレニル基が挙げられる。 Chain-type aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-decyl. Examples thereof include a group, an n-dodecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group and an n-octadecyl group. The cyclic aliphatic hydrocarbon group includes a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* is a bond). Represent a hand.
) Etc., a polycyclic alicyclic hydrocarbon group can be mentioned.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthryl group and a fluorenyl group.

［式（ａ－ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、カルボニルオキシ基又はオキシカルボニル基を表
す。
Ａ^a45は、少なくとも１つのハロゲン原子を有する炭素数１～１７の脂肪族炭化水素基
を表す。
＊は結合手を表す。］ Examples of R ^a42 include a halogen atom or a group represented by the formula (ag3) as a substituent. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
It is preferably a fluorine atom.

[In the formula (ag3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.
* Represents a bond. ]

Examples of the aliphatic hydrocarbon group of A ^a45 include the same groups as those exemplified in R ^a42 .
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (ag3). ..
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably having a carbon number of carbons. It is a perfluoroalkyl group of 1 to 6, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (ag3), the formula (a) is used.
-The total number of carbon atoms of the aliphatic hydrocarbon group is 15 including the number of carbon atoms contained in the group represented by g3).
The following is preferable, and 12 or less is more preferable. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (ag3), the formula (a) is used.
-The total number of carbon atoms of the aliphatic hydrocarbon group is 15 including the number of carbon atoms contained in the group represented by g3).
The following is preferable, and 12 or less is more preferable. When the group represented by the formula (ag3) is used as a substituent, the number thereof is preferably one.

［式（ａ－ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数１～１７の脂肪族炭化水素基を表す
。
Ｘ^a44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^a47は、ハロゲン原子を有していてもよい炭素数１～１７の脂肪族炭化水素基を表す
。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47の
うち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合手を表す。］ The aliphatic hydrocarbon group having a group represented by the formula (ag3) is more preferably the formula (a-).
It is a group represented by g2).

[In the formula (ag2),
A ^a46 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents a carbonyloxy group or an oxycarbonyl group.
A ^a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47 and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* Represents a bond with a carbonyl group. ]

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

Partial structure represented by * -A ^a46- X ^a44 -A ^a47 (* is a bond with a carbonyl group)
A more preferable structure of the above is the following structure.

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

The aliphatic hydrocarbon groups of A ^a42 , A ^a43 and A ^a44 in the group (a-g1) may have a carbon-carbon unsaturated bond, but are chain-type and cyclic-type aliphatic saturated hydrocarbon groups. In addition, a group formed by combining these is preferable. The aliphatic saturated hydrocarbon group includes
Examples thereof include a linear or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic hydrocarbon group formed by combining an alkyl group and an alicyclic hydrocarbon group.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2
-Diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-
Examples thereof include a methylpropane-1,3-diyl group and a 2-methylpropane-1,2-diyl group.
Examples of the substituent of the aliphatic hydrocarbon group of A ^a42 , A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

Examples of the group (ag1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group include the following groups. In the following examples, * and ** represent the bond, respectively, and ** is the bond with -O-CO-R ^a42 .

［式（ａ４－２）中、
Ｒ^f1は、水素原子又はメチル基を表す。
Ａ^f1は、炭素数１～６のアルカンジイル基を表す。
Ｒ^f2は、フッ素原子を有する炭素数１～１０の炭化水素基を表す。］ As the structural unit represented by the formula (a4-1), the structural unit represented by the formula (a4-2) and the formula (a4-3) is preferable.

[In equation (a4-2),
R ^f1 represents a hydrogen atom or a methyl group.
A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms.
R ^f2 represents a hydrocarbon group having a fluorine atom and having 1 to 10 carbon atoms. ]

The alkanediyl group of A ^f1 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , Hexine-1,6-diyl group and other linear alkanediyl groups; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1
, 2-Diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups can be mentioned.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic type and a group formed by a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
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.
-Includes octyl group and 2-ethylhexyl group.
The alicyclic hydrocarbon group may be a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and a cycloheptyl group.
Cycloalkyl groups such as a cyclooctyl group, a cycloheptyl group and a cyclodecyl group can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, and 2-.
Examples thereof include an alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, a norbornyl group, a methylnorbornyl group and an isobornyl group.

Examples of the hydrocarbon group having a fluorine atom of R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
As the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 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, 1,1,2,2,3,3,4,4,5
, 5-Decafluorohexyl group, 1,1,2,2,3,4,4,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group and other fluorinated alkyl The group is mentioned.
Examples of the alicyclic hydrocarbon group having a fluorine atom include a fluorocycloalkyl group such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

As A ^f1 in the formula (a4-2), an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.
As R ^f2 , an alkyl fluoride group having 1 to 6 carbon atoms is preferable.

［式（ａ４－３）中、
Ｒ^f11は、水素原子又はメチル基を表す。
Ａ^f11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の脂肪族炭化水素基を表す。
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の脂肪族炭化水素基を表す。
ただし、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有する脂肪族炭化水素基を
表す。］

[In equation (a4-3),
R ^f11 represents a hydrogen atom or a methyl group.
A ^f11 represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents an aliphatic 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 an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 represents an aliphatic hydrocarbon group having a fluorine atom. ]

Examples of the alkanediyl group of A ^f11 include the same groups as the alkanediyl group of A ^f1 .

The aliphatic hydrocarbon group of A ^f13 includes a chain type and a cyclic type aliphatic hydrocarbon group, and a divalent aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f13 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain-type aliphatic hydrocarbon group which may have a fluorine atom include a methylene group.
Alkanediyl groups such as ethylene group, propanediyl group, butanediyl group and pentandiyl group; perfluoroalkandyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group can be mentioned. ..
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a group containing either a monocyclic or polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantandiyl group, a norbornanediyl group, and a perfluoroadamantandiyl group.

The aliphatic hydrocarbon group of A ^f14 includes either a chain type or a cyclic type, and an aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon is
It may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f14 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Chain-type aliphatic hydrocarbon groups that may have a fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 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, pentyl group, hexyl group, perfluorohexyl group, Examples thereof include a heptyl group, a perfluoroheptyl group, an octyl group and a perfluorooctyl group.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl group and the like.

In the formula ( ^a4-3 ), A f11 is preferably an ethylene group.
The aliphatic hydrocarbon group of A ^f13 is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and has 2 carbon atoms.
The aliphatic hydrocarbon group of ~ 3 is more preferable.
The aliphatic hydrocarbon group of A ^f14 is preferably an aliphatic hydrocarbon group having 3 to 12 carbon atoms, and more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms. 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 represented by the formula (a4-2) include the structural unit shown below and the structural unit in which the methyl group corresponding to R ^f1 in the following structural unit is replaced with a hydrogen atom.

Examples of the structural unit represented by the formula (a4-3) include the structural unit shown below and the structural unit in which the methyl group corresponding to R ^f11 in the following structural unit is replaced with a hydrogen atom.

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

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

Examples of the hydrocarbon group having a fluorine atom of R ^f22 include the same hydrocarbon group of R ^f2 in the formula (a4-2). R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom. Preferably, it has 1 to 6 carbon atoms having a fluorine atom.
Alkyl groups of are more preferred.

In the formula (a4-4), as A ^f21 , − (CH ₂ ) _j1 − is preferable, an ethylene group or a methylene group is more preferable, and a methylene group is further preferable.

Examples of the structural unit represented by the formula (a4-4) include the following structural unit and the structural unit in which the methyl group corresponding to R ^f21 is replaced with a hydrogen atom in the following structural unit. Be done.

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

［式（ａ５－１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３～１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水
素原子は炭素数１～８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。但
し、Ｌ⁵¹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。
Ｌ⁵¹は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基
に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group of the structural unit (a5) include a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably 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 ⁵¹ is not substituted with the aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

The alicyclic hydrocarbon group of R ⁵² may be either a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, and the like.
Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group,
Alkyl groups such as a hexyl group, an octyl group and a 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 L ⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent aliphatic saturated hydrocarbon group is preferable. ..
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.

式（Ｌ１－１）中、
Ｘ^x1は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ｌ^x1は、炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x2は、単結合又は炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x1及びＬ^x2の合計炭素数は、１６以下である。
式（Ｌ１－２）中、
Ｌ^x3は、炭素数１～１７の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x4は、単結合又は炭素数１～１６の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x3及びＬ^x4の合計炭素数は、１７以下である。
式（Ｌ１－３）中、
Ｌ^x5は、炭素数１～１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x6及びＬ^x7は、それぞれ独立に、単結合又は炭素数１～１４の２価の脂肪族飽和炭化
水素基を表す。
ただし、Ｌ^x5、Ｌ^x6及びＬ^x7の合計炭素数は、１５以下である。
式（Ｌ１－４）中、
Ｌ^x8及びＬ^x9は、単結合又は炭素数１～１２の２価の脂肪族飽和炭化水素基を表す。
Ｗ^x1は、炭素数３～１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^x8、Ｌ^x9及びＷ^x1の合計炭素数は、１５以下である。 Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include groups represented by the formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

In equation (L1-1),
X ^x1 represents a carbonyloxy group or an oxycarbonyl group.
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total number of carbon atoms of L ^x 1 and L ^{x 2} is 16 or less.
In equation (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total number of carbon atoms of L ^x3 and L ^x4 is 17 or less.
In formula (L1-3),
L ^{x 5} represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6 and L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x 1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9 and W ^x1 is 15 or less.

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

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

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

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

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

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

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

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

The resin (A) is preferably a resin composed of a structural unit (a1) and a structural unit (s), that is, a copolymer of a monomer (a1) and a monomer (s).
The structural unit (a1) is preferably at least one selected from a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably a structural unit (a1). At least two kinds selected from a1-1) and 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 selected from the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-4). At least one kind.

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).
00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30)
000 or less, more preferably 15,000 or less).

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Examples of such a resin include a resin consisting of only the structural unit (s), a resin containing the structural unit (a4) (however, the resin does not include the structural unit (a1); hereinafter may be referred to as “resin (X)”) and the like. Can be mentioned. Among them, a resin containing the structural unit (a4) is preferable.
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). ..
Examples of the structural unit that the resin (X) may further include include a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7.0).
00 or more), 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).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further, with respect to 100 parts by mass of the resin (A). It is preferably 2 to 40 parts by mass, and particularly preferably 3 to 30 parts by mass.

The total content of the resin (A) and the resin other than the resin (A) 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 with respect to the solid content of the resist composition. .. In the present specification, the "solid content of the resist composition" is defined as the total amount of the resist composition.
It means the total of the components excluding the solvent (E) described later. 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.

<Solvent (E)>
The content of the solvent (E) is usually 90% by mass or more, preferably 92% by mass in the resist composition.
As mentioned above, it is more preferably 94% by mass or more, and usually 99.9% by mass or less, preferably 99.
It is less than mass%. 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. The solvent (E) may contain one kind alone or two or more kinds.

<Quencher (C)>
Examples of the quencher (C) include a basic nitrogen-containing organic compound or a salt that generates an acid having a weaker acidity than the acid generated from the salt (I) and the acid generator (B).
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.

The quencher (C) includes 1-naphthylamine, 2-naphthylamine, aniline, etc.
Diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N
-Methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, Tripropylamine, Tributylamine, Tripentylamine, Trihexylamine, Triheptylamine, Trioctylamine, Trinonylamine, Tridecylamine, Methyldibutylamine, Methyldipentylamine, Methyldihexylamine, Methyldicyclohexylamine, Methyldiheptyl Amine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine,
Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, tri Isopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3 , 3'-diethyldiphenylmethane, piperazine, morpholin, piperidine and a hindered amine compound having a piperidine skeleton described in JP-A-11-52575, imidazole, 4
-Methylimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethane, 1,2
-Di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyl)
Pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicorylamine, bipyridine and the like. And preferably diisopropylaniline,
Particularly preferred is 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.

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

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

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

In the weak acid intramolecular salt (D), the hydrocarbon groups of R ^D1 and R ^D2 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 t-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. For example, cyclopropyl group, cyclobutyl group, cyclopentyl group,
Examples thereof include a cycloalkyl group such as a cyclohexyl group, a cyclononyl group and a cyclododecyl group, a norbonyl group and an adamantyl group.
The monovalent aromatic hydrocarbon group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and 2
-Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group,
4-t-Butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group,
Anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-
Aryl groups such as 6-ethylphenyl and the like can be mentioned.
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 so on.

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 are independently alkyl groups having 1 to 8 carbon atoms.
Cycloalkyl group with 3 to 10 carbon atoms, alkoxy group with 1 to 6 carbon atoms, acyl group with 2 to 4 carbon atoms, acyloxy group with 2 to 4 carbon atoms, alkoxycarbonyl group with 2 to 4 carbon atoms, nitro group or Halogen atoms are preferred.
For m'and n', an integer of 0 to 2 is preferable, and 0 is more preferable, respectively. m'
When is 2 or more, the plurality of R ^D1s are the same or different, and when n'is 2 or more, the plurality of R ^D2s are the same or different.

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

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

<Other ingredients>
If necessary, the resist composition contains components other than the above-mentioned components (hereinafter, “other components (F)).
May be said. ) May be contained. As the other component (F), additives known in the field of resist, for example, a sensitizer, a dissolution inhibitor, a surfactant, a stabilizer, a dye and the like can be used.

<Preparation of resist composition>
The resist composition comprises an acid generator containing a resin (A) and a salt (I) and / or a salt (I0), and if necessary, a resin other than the resin (A), an acid generator (B), and a solvent. It can be prepared by mixing (E), the quencher (C) and the other component (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. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying
For example, it is carried out by evaporating the solvent using a heating device such as a hot plate (so-called prebaking), 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 1 to 1.
About 0 × 10 ⁵ Pa is preferable.

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 a resist composition, an alkaline developer is used as the developer. The alkaline developer may be any alkaline aqueous solution used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline). 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 a resist composition, 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.
It is more preferably 95% by mass or more and 100% by mass or less, and it is further preferable that it is substantially only an organic solvent.
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 50% by mass or more and 10
It is preferably 0% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and further preferably substantially only butyl acetate and / or 2-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. As a rinse liquid,
There is no particular limitation as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

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

A more specific description will be given 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 is mass spectrometry (LC is Agilent 1100 type, MASS is A.
It was confirmed by measuring the molecular peak using an Agilent LC / MSD type). In the following examples, the value of this molecular peak is indicated by "MASS".

式（Ｉ－２－ａ）で表される化合物１．００部及びメタノール３０部を添加し、２３℃
で３０分間攪拌した。得られた混合溶液に、トリエチルアミン０．９３部を添加し、式（
Ｉ－２－ｂ）で表される化合物０．７４部を３０分かけて滴下し、さらに、２３℃で１８
時間攪拌した。得られた反応混合物に、クロロホルム５０部を添加撹拌した。得られた混
合物に、イオン交換水２０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出
した。この操作を３回繰り返した。得られた有機層を濃縮することにより、式（Ｉ－２－
ｃ）で表される化合物１．２４部を得た。

式（Ｉ－２－ｃ）で表される化合物０．９７部、テトラヒドロフラン７．５０部及びピ
リジン０．２８部を添加し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた
混合溶液に、式（Ｉ－２－ｄ）で表される化合物０．４０部を添加し、２３℃まで昇温し
、さらに、２３℃で１時間攪拌した。得られた反応混合物に、クロロホルム５０部及び５
％塩酸２．５８部を添加撹拌し、分液して有機層を取り出した。得られた有機層に、イオ
ン交換水２０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られ
た有機層に、１０％炭酸カリウム水溶液１．４７部を加えて２３℃で３０分間攪拌し、分
液して有機層を取り出した。得られた有機層に、イオン交換水２０部を加えて２３℃で３
０分間攪拌し、分液して有機層を取り出した。この操作を４回繰り返した。得られた有機
層を濃縮することにより、式（Ｉ－２－ｅ）で表される化合物０．８４部を得た。

式（Ｉ－２－ｆ）で表される塩０．８０部及びクロロホルム１０部を添加し、２３℃で
３０分間攪拌した。得られた混合溶液に、炭酸カリウム０．１５部及びヨウ化カリウム０
．０３部を添加し、その後、式（Ｉ－２－ｅ）で表される化合物０．７０部を添加し、２
３℃で１時間攪拌した。得られた反応物に、クロロホルム２０部及びイオン交換水１０部
を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られた有機層にイオ
ン交換水１０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られ
た有機層を濃縮し、得られた残渣に、アセトニトリル１．４５部及び酢酸エチル２３．２
０部を加えて攪拌し、上澄液を除去した。得られた残渣を濃縮することにより、式（Ｉ－
２－ｇ）で表される塩１．０９部を得た。

式（Ｉ－２―ｇ）で表される塩１．０９部及びアセトニトリル１０部を仕込み、２３℃
で３０分間攪拌した。これに、１％塩酸０．３３部を添加し、８０℃で３時間攪拌し、濃
縮することにより、式（Ｉ－２）で表される塩０．９１部を得た。 Example 1: Synthesis of salt represented by the formula (I-2)

1.00 part of the compound represented by the formula (I-2-a) and 30 parts of methanol were added, and the temperature was 23 ° C.
Was stirred for 30 minutes. To the obtained mixed solution, 0.93 part of triethylamine was added, and the formula (
0.74 parts of the compound represented by I-2-b) was added dropwise over 30 minutes, and further, 18 at 23 ° C.
Stir for hours. To the obtained reaction mixture, 50 parts of chloroform was added and stirred. To the obtained mixture, 20 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and the mixture was separated to remove the organic layer. This operation was repeated 3 times. By concentrating the obtained organic layer, the formula (I-2-
1.24 parts of the compound represented by c) was obtained.

0.97 parts of the compound represented by the formula (I-2-c), 7.50 parts of tetrahydrofuran and 0.28 parts of pyridine were added, and the mixture was stirred at 23 ° C. for 30 minutes and then cooled to 5 ° C. To the obtained mixed solution, 0.40 part of the compound represented by the formula (I-2-d) was added, the temperature was raised to 23 ° C., and the mixture was further stirred at 23 ° C. for 1 hour. 50 parts of chloroform and 5 parts of chloroform are added to the obtained reaction mixture.
2.58 parts of% hydrochloric acid was added and stirred, and the liquid was separated to take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to take out the organic layer. To the obtained organic layer, 1.47 parts of a 10% potassium carbonate aqueous solution was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to remove the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added and 3 at 23 ° C.
The mixture was stirred for 0 minutes, the liquid was separated, and the organic layer was taken out. This operation was repeated 4 times. By concentrating the obtained organic layer, 0.84 part of the compound represented by the formula (I-2-e) was obtained.

0.80 part of the salt represented by the formula (I-2-f) and 10 parts of chloroform were added, and the mixture was stirred at 23 ° C. for 30 minutes. In the obtained mixed solution, 0.15 part of potassium carbonate and 0 of potassium iodide
.. 03 parts were added, and then 0.70 parts of the compound represented by the formula (I-2-e) was added, and 2 parts were added.
The mixture was stirred at 3 ° C. for 1 hour. To the obtained reaction product, 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to take out the organic layer. The obtained organic layer was concentrated, and 1.45 parts of acetonitrile and 23.2 parts of ethyl acetate were added to the obtained residue.
0 part was added and stirred, and the supernatant was removed. By concentrating the obtained residue, the formula (I-
1.09 parts of a salt represented by 2-g) was obtained.

1.09 parts of salt and 10 parts of acetonitrile represented by the formula (I-2-g) were charged, and the temperature was 23 ° C.
Was stirred for 30 minutes. To this, 0.33 part of 1% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 3 hours and concentrated to obtain 0.91 part of the salt represented by the formula (I-2).

MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 455.1

式（Ｉ－３－ａ）で表される塩４．８３部及びアセトニトリル３０部を仕込み、２３℃
で３０分間攪拌した。その後、式（Ｉ－３－ｂ）で表される化合物１．７０部を添加し、
６０℃で１時間攪拌した。得られた反応溶液をろ過した後、回収されたろ液を濃縮した。
得られた濃縮物に、クロロホルム３０部及びイオン交換水１５部を加え、２３℃で３０分
間攪拌した。その後、静置し、分液して有機層を得た。得られた有機層に、イオン交換水
１５部を加え、２３℃で３０分間攪拌した。この水洗の操作をさらに３回行った。得られ
た有機層に活性炭１．００部を仕込み、２３℃で３０分間攪拌し、ろ過した。ろ液を濃縮
し、得られた濃縮物に、ｔｅｒｔ－ブチルメチルエーテル１００部を加えて攪拌した後、
ろ過することにより、式（Ｉ－３－ｃ）で表される塩４．９０部を得た。

式（Ｉ－３－ｃ）で表される塩１．４５部、式（Ｉ－３－ｄ）で表される化合物０．８
８部及びアセトニトリル３０部を添加し、さらに、２３℃で６時間攪拌した後、ろ過した
。回収されたろ液を濃縮した後、得られた濃縮物に、クロロホルム３０部及びイオン交換
水１５部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られた有機
層にイオン交換水１５部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した
。この操作を５回繰り返した。得られた有機層を濃縮し、得られた残渣に、ｔｅｒｔ－ブ
チルメチルエーテル２０部を加えて攪拌し、上澄液を除去した。得られた残渣を濃縮する
ことにより、式（Ｉ－３－ｅ）で表される塩１．４８部を得た。

得られた式（Ｉ－３－ｅ）で表される塩１．００部、クロロホルム１０部及びメタノー
ル１０部を添加し、２３℃で３０分間攪拌した。得られた混合溶液に、ｐ－トルエンスル
ホン酸０．０４部を添加し、６０℃で１８時間攪拌した。得られた反応物を２３℃まで冷
却した後、クロロホルム２０部及びイオン交換水１０部を加えて２３℃で３０分間攪拌し
、分液して有機層を取り出した。得られた有機層にイオン交換水１０部を加えて２３℃で
３０分間攪拌し、分液して有機層を取り出した。得られた有機層を濃縮することにより、
式（Ｉ－３）で表される塩０．６２部を得た。 Example 2: Synthesis of salt represented by formula (I-3)

4.83 parts of salt and 30 parts of acetonitrile represented by the formula (I-3-a) were charged, and the temperature was 23 ° C.
Was stirred for 30 minutes. Then, 1.70 parts of the compound represented by the formula (I-3-b) was added, and the compound was added.
The mixture was stirred at 60 ° C. for 1 hour. After filtering the obtained reaction solution, the recovered filtrate was concentrated.
To the obtained concentrate, 30 parts of chloroform and 15 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. Then, it was allowed to stand and separated to obtain an organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes. This washing operation was performed three more times. 1.00 part of activated carbon was charged into the obtained organic layer, stirred at 23 ° C. for 30 minutes, and filtered. The filtrate was concentrated, 100 parts of tert-butylmethyl ether was added to the obtained concentrate, and the mixture was stirred.
By filtration, 4.90 parts of a salt represented by the formula (I-3-c) was obtained.

1.45 parts of salt represented by formula (I-3-c), compound 0.8 represented by formula (I-3-d)
8 parts and 30 parts of acetonitrile were added, and the mixture was further stirred at 23 ° C. for 6 hours and then filtered. After concentrating the recovered filtrate, 30 parts of chloroform and 15 parts of ion-exchanged water were added to the obtained concentrate, and the mixture was stirred at 23 ° C. for 30 minutes, separated, and the organic layer was taken out. 15 parts of ion-exchanged water was added to the obtained organic layer, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to take out the organic layer. This operation was repeated 5 times. The obtained organic layer was concentrated, 20 parts of tert-butyl methyl ether was added to the obtained residue, and the mixture was stirred to remove the supernatant. By concentrating the obtained residue, 1.48 parts of a salt represented by the formula (I-3-e) was obtained.

1.00 part of the obtained salt represented by the formula (I-3-e), 10 parts of chloroform and 10 parts of methanol were added, and the mixture was stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 0.04 part of p-toluenesulfonic acid was added, and the mixture was stirred at 60 ° C. for 18 hours. After cooling the obtained reaction product to 23 ° C., 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes, separated and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to take out the organic layer. By concentrating the obtained organic layer
0.62 parts of the salt represented by the formula (I-3) was obtained.

MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 485.1

式（Ｉ－１－ａ）で表される塩１．００部及びアセトニトリル１０部を添加し、２３℃
で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｂ）で表される化合物０．４０
部を添加し、さらに、７０℃で２時間攪拌することにより、式（Ｉ－１－ｃ）で表される
塩を含む溶液を得た。

式（Ｉ－１－ｃ）で表される塩を含む溶液に、式（Ｉ－２－ｃ）で表される化合物０．
７１部を添加し、さらに、２３℃で１２時間攪拌した後、ろ過した。回収されたろ液を濃
縮した後、得られた濃縮物に、クロロホルム３０部及びイオン交換水１５部を加えて２３
℃で３０分間攪拌し、分液して有機層を取り出した。得られた有機層にイオン交換水１５
部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この操作を５回繰り
返した。得られた有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球
状、中性）１００－２１０μｍ 展開溶媒：クロロホルム／メタノール＝１／１）分取す
ることにより、式（Ｉ－１－ｄ）で表される塩０．２２部を得た。

式（Ｉ－２―ｇ）で表される塩０．２０部及びアセトニトリル１０部を仕込み、２３℃
で３０分間攪拌した。これに、１％塩酸０．０６部を添加し、８０℃で３時間攪拌し、濃
縮することにより、式（Ｉ－１）で表される塩０．０９部を得た。 Example 3: Synthesis of salt represented by formula (I-1)

1.00 part of the salt represented by the formula (I-1-a) and 10 parts of acetonitrile were added, and the temperature was 23 ° C.
Was stirred for 30 minutes. Compound 0.40 represented by the formula (I-1-b) is added to the obtained mixed solution.
A portion was added, and the mixture was further stirred at 70 ° C. for 2 hours to obtain a solution containing a salt represented by the formula (I-1-c).

In a solution containing a salt represented by the formula (I-1-c), the compound represented by the formula (I-2-c) 0.
71 parts were added, and the mixture was further stirred at 23 ° C. for 12 hours and then filtered. After concentrating the recovered filtrate, 30 parts of chloroform and 15 parts of ion-exchanged water are added to the obtained concentrate 23.
The mixture was stirred at ° C. for 30 minutes and separated to remove the organic layer. Ion-exchanged water 15 in the obtained organic layer
The portion was added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. This operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mass was separated by a column (Kanto Chemical silica gel 60N (spherical, neutral) 100-210 μm developing solvent: chloroform / methanol = 1/1) to formulate (I-1-). 0.22 parts of the salt represented by d) was obtained.

0.20 parts of salt and 10 parts of acetonitrile represented by the formula (I-2-g) were charged, and the temperature was 23 ° C.
Was stirred for 30 minutes. To this, 0.06 part of 1% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 3 hours and concentrated to obtain 0.09 part of the salt represented by the formula (I-1).

MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 397.0

式（Ｉ－２６－ａ）で表される塩０．７５部及びクロロホルム１０部を添加し、２３℃
で３０分間攪拌した。得られた混合溶液に、炭酸カリウム０．１５部及びヨウ化カリウム
０．０３部を添加し、さらに式（Ｉ－２－ｅ）で表される化合物０．７０部を添加し、２
３℃で１時間攪拌した。得られた反応物に、クロロホルム２０部及びイオン交換水１０部
を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られた有機層にイオ
ン交換水１０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。得られ
た有機層を濃縮した。得られた残渣に、アセトニトリル１部及び酢酸エチル２５部を加え
て攪拌し、上澄液を除去した。得られた残渣を濃縮することにより、式（Ｉ－２６－ｂ）
で表される塩０．８９部を得た。

式（Ｉ－２６―ｂ）で表される塩０．５０部及びアセトニトリル１０部を仕込み、２３
℃で３０分間攪拌した。これに、１％塩酸０．１８部を添加し、８０℃で３時間攪拌し、
濃縮することにより、式（Ｉ－２６）で表される塩０．２８部を得た。 Example 4: Synthesis of salt represented by formula (I-26)

0.75 parts of the salt represented by the formula (I-26-a) and 10 parts of chloroform were added, and the temperature was 23 ° C.
Was stirred for 30 minutes. To the obtained mixed solution, 0.15 part of potassium carbonate and 0.03 part of potassium iodide were added, and 0.70 part of the compound represented by the formula (I-2-e) was further added, and 2
The mixture was stirred at 3 ° C. for 1 hour. To the obtained reaction product, 20 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to take out the organic layer. The obtained organic layer was concentrated. To the obtained residue, 1 part of acetonitrile and 25 parts of ethyl acetate were added and stirred, and the supernatant was removed. By concentrating the obtained residue, the formula (I-26-b)
0.89 parts of salt represented by is obtained.

0.50 parts of salt and 10 parts of acetonitrile represented by the formula (I-26-b) were charged, and 23
The mixture was stirred at ° C for 30 minutes. To this, 0.18 part of 1% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 3 hours.
By concentrating, 0.28 part of the salt represented by the formula (I-26) was obtained.

MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 455.1

式（Ｂ１－５－ａ）で表される塩５０．４９部及びクロロホルム２５２．４４部を反応
器に仕込み、２３℃で３０分間攪拌した。その後、これに、式（Ｂ１－５－ｂ）で表され
る化合物１６．２７部を滴下し、２３℃で１時間攪拌することにより、式（Ｂ１－５－ｃ
）で表される塩を含む溶液を得た。得られた式（Ｂ１－５－ｃ）で表される塩を含む溶液
に、式（Ｂ１－５－ｄ）で表される塩４８．８０部及びイオン交換水８４．１５部を添加
し、２３℃で１２時間攪拌した。得られた反応液が２層に分離していたので、クロロホル
ム層を分液して取り出し、更に、該クロロホルム層にイオン交換水８４．１５部を添加し
、水洗した。この操作を５回繰り返した。得られたクロロホルム層に、活性炭３．８８部
を添加攪拌し、ろ過した。回収されたろ液を濃縮し、得られた残渣に、アセトニトリル１
２５．８７部を添加攪拌し、濃縮した。得られた残渣に、アセトニトリル２０．６２部及
びｔｅｒｔ－ブチルメチルエーテル３０９．３０部を加えて２３℃で３０分間攪拌し、上
澄み液を除去し、濃縮した。得られた残渣に、ｎ－ヘプタン２００部を添加、２３℃で３
０分間攪拌し、ろ過することにより、式（Ｂ１－５）で表される塩６１．５４部を得た。 Synthesis example 1: Synthesis of salt represented by the formula (B1-5)

50.49 parts of the salt represented by the formula (B1-5-a) and 252.44 parts of chloroform were charged into the reactor, and the mixture was stirred at 23 ° C. for 30 minutes. Then, 16.27 parts of the compound represented by the formula (B1-5-b) was added dropwise thereto, and the mixture was stirred at 23 ° C. for 1 hour to obtain the formula (B1-5-c).
) Was obtained. To the obtained solution containing the salt represented by the formula (B1-5-c), 48.80 parts of the salt represented by the formula (B1-5-d) and 84.15 parts of ion-exchanged water were added. The mixture was stirred at 23 ° C. for 12 hours. Since the obtained reaction solution was separated into two layers, the chloroform layer was separated and taken out, and 84.15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. 3.88 parts of activated carbon was added to the obtained chloroform layer, stirred, and filtered. The recovered filtrate was concentrated, and acetonitrile 1 was added to the obtained residue.
25.87 parts were added and stirred, and the mixture was concentrated. To the obtained residue, 20.62 parts of acetonitrile and 309.30 parts of tert-butyl methyl ether were added, and the mixture was stirred at 23 ° C. for 30 minutes to remove the supernatant and concentrated. To the obtained residue, 200 parts of n-heptane was added, and 3 at 23 ° C.
The mixture was stirred for 0 minutes and filtered to obtain 61.54 parts of a salt represented by the formula (B1-5).

MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (-) Spectrum): M ^- 339.1

Synthesis Example 2 [Synthesis of salt represented by formula (B1-21)]

Formula (B1-21) obtained by the method described in Japanese Patent Application Laid-Open No. 2008-209917.
30.00 parts of the compound represented by −b), 35.50 parts of the salt represented by the formula (B1-21-a), 100 parts of chloroform and 50 parts of ion-exchanged water were charged and stirred at 23 ° C. for 15 hours. ..
Since the obtained reaction solution was separated into two layers, the chloroform layer was separated and taken out, and further.
30 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer is concentrated, 100 parts of tert-butylmethyl ether is added to the obtained residue, the mixture is stirred at 23 ° C. for 30 minutes, and filtered to obtain a salt represented by the formula (B1-21-c) 48. I got 57 copies.

式（Ｂ１－２１－ｃ）で表される塩２０．００部、式（Ｂ１－２１－ｄ）で表される化
合物２．８４部及びモノクロロベンゼン２５０部を仕込み、２３℃で３０分間攪拌した。
得られた混合液に、二安息香酸銅（ＩＩ）０．２１部を添加し、更に、１００℃で１時間
攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム２００部及びイ
オン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収
された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を
取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮した。得られた残渣
を、アセトニトリル５３．５１部に溶解し、濃縮し、ｔｅｒｔ－ブチルメチルエーテル１
１３．０５部を加えて攪拌し、ろ過することにより、式（Ｂ１－２１）で表される塩１０
．４７部を得た。

20.00 parts of the salt represented by the formula (B1-21-c), 2.84 parts of the compound represented by the formula (B1-21-d) and 250 parts of monochlorobenzene were charged and stirred at 23 ° C. for 30 minutes. ..
To the obtained mixed solution, 0.21 part of copper (II) dibenzoate was added, and the mixture was further stirred at 100 ° C. for 1 hour. The obtained reaction solution was concentrated. To the obtained residue, 200 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes, separated into liquids, and the organic layer was taken out. 50 parts of ion-exchanged water was added to the recovered organic layer, the mixture was stirred at 23 ° C. for 30 minutes, and the liquid was separated to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated. The obtained residue was dissolved in 53.51 parts of acetonitrile, concentrated, and tert-butylmethyl ether 1
The salt 10 represented by the formula (B1-21) is obtained by adding 13.05 parts, stirring, and filtering.
.. I got 47 copies.

MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 339.1

式（Ｂ１－２２－ａ）で表される塩１１．２６部、式（Ｂ１－２２－ｂ）で表される化
合物１０．００部、クロロホルム５０部及びイオン交換水２５部を仕込み、２３℃で１５
時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取
り出し、更に、該クロロホルム層にイオン交換水１５部を添加し、水洗した。この操作を
５回繰り返した。クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ－ブチルメチルエ
ーテル５０部を加えて２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１－２２－
ｃ）で表される塩１１．７５部を得た。 Synthesis Example 3 [Synthesis of salt represented by formula (B1-22)]

11.26 parts of the salt represented by the formula (B1-22-a), 10.00 parts of the compound represented by the formula (B1-22-b), 50 parts of chloroform and 25 parts of ion-exchanged water were charged at 23 ° C. At 15
Stir for hours. Since the obtained reaction solution was separated into two layers, the chloroform layer was separated and taken out, and 15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer is concentrated, 50 parts of tert-butylmethyl ether is added to the obtained residue, the mixture is stirred at 23 ° C. for 30 minutes, and filtered to obtain the formula (B1-22-).
11.75 parts of salt represented by c) was obtained.

式（Ｂ１－２２－ｃ）で表される塩１１．７１部、式（Ｂ１－２２－ｄ）で表される化
合物１．７０部及びモノクロロベンゼン４６．８４部を仕込み、２３℃で３０分間攪拌し
た。得られた混合液に、二安息香酸銅（ＩＩ）０．１２部を添加し、更に、１００℃で３
０分間攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム５０部及
びイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出
した。回収された有機層にイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、
分液して有機層を取り出した。この水洗操作を８回繰り返した。得られた有機層を濃縮し
た。得られた残渣に、ｔｅｒｔ－ブチルメチルエーテル５０部を加えて攪拌し、ろ過する
ことにより、式（Ｂ１－２２）で表される塩６．８４部を得た。

11.71 parts of the salt represented by the formula (B1-22-c), 1.70 parts of the compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged and charged at 23 ° C. for 30 minutes. Stirred. To the obtained mixed solution, 0.12 part of copper (II) dibenzoate was added, and further, 3 at 100 ° C.
The mixture was stirred for 0 minutes. The obtained reaction solution was concentrated. To the obtained residue, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and separated to remove the organic layer. 12.50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes.
The liquid was separated and the organic layer was taken out. This washing operation was repeated 8 times. The obtained organic layer was concentrated. To the obtained residue, 50 parts of tert-butylmethyl ether was added, stirred, and filtered to obtain 6.84 parts of a salt represented by the formula (B1-22).

MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 323.0

Synthesis of Resin (A) The compounds (monomers) used for the synthesis of resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-2)" or the like according to the formula number.

Synthesis Example 4 [Synthesis of resin A1]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (
Using a2-1-1) and a monomer (a3-4-2), their molar ratio [monomer (a1-1-1)
-3): Monomer (a1-2-9): Monomer (a2-1-1): Monomer (a3-4-)
2)] was mixed so as to be 45: 14: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5% by mass of the total amount of monomers was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1 mol% and 3 mol%, respectively, based on the total amount of the monomers, and these were added to 75.
It was heated at ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin is dissolved again in propylene glycol monomethyl ether acetate, and the obtained solution is poured into a methanol / water mixed solvent to precipitate the resin, and the resin is filtered. Molecular weight 7
.. A 9 × 10 ³ resin A1 (copolymer) was obtained in a yield of 70%. This resin A1 has the following structural units.

Synthesis Example 5 [Synthesis of resin X1]
As the monomer, a monomer (a5-1-1) and a monomer (a4-0-12) were used.
Mix so that the molar ratio [monomer (a5-1-1): monomer (a4-0-12)] is 50:50, and add 1.2% by mass of methyl isobutyl ketone to the solution. And said. 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 is mixed by the mass part shown in Table 2 and dissolved in a solvent, and then the pore size is 0.2.
A resist composition was prepared by filtering with a μm fluororesin filter.

Ｂ１－５：式（Ｂ１－５）で表される塩
Ｂ１－２１：式（Ｂ１－２１）で表される塩
Ｂ１－２２：式（Ｂ１－２２）で表される塩
Ｂ１－Ｘ：特開２０１２－２２９２０６号公報の実施例に従って合成

＜弱酸分子内塩（Ｄ）＞
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, X1: Resin A1, Resin X1
<Acid generator (B)>
I-1: Salt represented by the formula (I-1) I-2: Salt represented by the formula (I-2) I-3: Salt represented by the formula (I-3) I-26: Formula represented by the formula (I-3) Salt represented by (I-26) I0-1: Synthesized according to Examples of JP-A-2011-46694

B1-5: Salt represented by the formula (B1-5) B1-21: Salt represented by the formula (B1-21) B1-22: Salt represented by the formula (B1-22) B1-X: Special Synthesized according to the examples of Kai 2012-229206

<Weak acid intramolecular salt (D)>
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>
By applying an organic antireflection film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) to a silicon wafer and baking it at 205 ° C. for 60 seconds, organic reflection with a film thickness of 78 nm is performed on the wafer. 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 shown in the “PB” column of Table 2 for 60 seconds to form a composition layer. ArF excimer stepper for immersion exposure (XT: 1900Gi; ASML, NA = 1.35, 3) on a silicon wafer on which a composition layer is formed.
/ 4Annular XY polarization) with contact hole pattern (hole pitch 90n)
Using a mask for forming m / 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 2 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 50 nm formed by using the mask was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In the effective sensitivity, the hole diameter of the pattern formed by the mask having a hole diameter of 55 nm was measured 24 times for one hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was obtained by measuring the average hole diameter of a pattern formed by a mask with a hole diameter of 70 nm at 400 points on the same wafer as a population.
"○" when the standard deviation is 2.00 nm or less,
When the standard deviation was larger than 2.00 nm, it was judged as “x”.
The results are shown in Table 3. The numbers in parentheses indicate the standard deviation (nm).

From the above results, it can be seen that the salt, acid generator of the present invention and the resist composition using the same can produce a resist pattern with good CD uniformity.

The salt, acid generator of the present invention and the resist composition using the same are suitable for microfabrication of semiconductors because they are excellent in CD uniformity of the obtained resist pattern.

Claims (4)

A resist composition containing an acid generator containing a salt represented by the formula (I0) and a resin having an acid unstable group.

[In formula (I0),
Q ¹ and Q ² independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 is a group represented by any one of the formula (b1-1), the formula (b1-2) and the formula (b1-3), and * represents the binding position with CQ ¹ Q ² .

(In equation (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In equation (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
However, the total number of carbon atoms of L ^b4 and L ^b5 is 22 or less.
In equation (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. )
Ad ₁ represents an adamantane diyl group.
n represents 1.
Z ⁺ represents an organic cation. ] The resist composition according to claim 1, which contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. A group in which a resin having an acid unstable group consists of a structural unit represented by the formula (a1-0), a structural unit represented by the formula (a1-1), and a structural unit represented by the formula (a1-2). The resist composition according to claim 1 or 2 , which comprises at least one selected from.

[In equation (a1-0),
^La01 represents an oxygen atom or ^* -O- (CH ₂ ) _k01 -CO-O-, k01 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.
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. ] (1) A step of applying the resist composition according to any one of claims 1 to 3 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.