JP7032270B2 - Method for producing salt, acid generator, resist composition and resist pattern - Google Patents

Description

The present invention relates to a salt for an acid generator used for fine processing of a semiconductor, an acid generator containing the salt, 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及び該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。

特許文献３には、下記式で表される塩及び該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。

特許文献４には、下記式で表される酸発生剤、酸不安定基を有する樹脂及び塩基性化合物を含有するレジスト組成物も記載されている。

Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator.

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

Patent Document 3 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator.

Patent Document 4 also describes a resist composition containing an acid generator represented by the following formula, a resin having an acid unstable group, and a basic compound.

Japanese Unexamined Patent Publication No. 2013-060424 Japanese Unexamined Patent Publication No. 2007-197432 Japanese Unexamined Patent Publication No. 2014-160143 Japanese Unexamined Patent Publication No. 2008-13551

An object of the present invention is to provide a resist composition containing a salt capable of producing a resist pattern having a better line edge roughness (LER) than a resist pattern formed from the resist composition containing the salt. And.

［式（Ｉ）中、
Ｒ^１及びＲ^２は、それぞれ独立に、ヒドロキシ基又は式（Ｒ－１）で表される基を表す。但し、Ｒ^１及びＲ^２の少なくとも一つは、式（Ｒ－１）で表される基を表す。

（式（Ｒ－１）中、
Ｑ^ｒ1及びＱ^ｒ2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。
Ｒ^ｒ1及びＲ^ｒ2は、それぞれ独立に、水素原子、フッ素原子又は炭素数１～６のペルフルオロアルキル基を表す。
ｚ^ｒは、０～６のいずれかの整数を表し、ｚが２以上のとき、複数のＲ^ｒ1及びＲ^ｒ2は互いに同一であっても異なってもよい。
Ｘ^ｒ1は、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－又は－Ｏ－を表す。
Ｌ^ｒ1は、単結合又は炭素数１～２８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－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－Ｓ（Ｏ）₂－に置き換わっていてもよい。
＊はＡｒ^１又はＡｒ^２との結合位を表す。
ＺＲ⁺は有機カチオンを表す。）
Ａｒ^１は、置換基を有していてもよい炭素数６～３６の芳香族炭化水素環を表す。
Ａｒ^２は、置換基を有していてもよい炭素数６～３６の芳香族炭化水素環を表す。］
［２］Ａｒ^１が、置換基を有してもよいベンゼン又は置換基を有してもよいナフタレンである［１］に記載の塩。
［３］Ａｒ^２が、置換基を有していてもよいベンゼンである［１］又は［２］に記載の塩。
［４］Ｘ^ｒ1が、＊－ＣＯ－Ｏ－又は＊－Ｏ－ＣＯ－（但し、＊は、Ｃ（Ｒ^ｒ1）（Ｒ^ｒ2）又はＣ（Ｑ^ｒ1）（Ｑ^ｒ2）との結合位を表す。）である［１］～［３］のいずれかに記載の塩。
［５］Ｌ^ｒ1が、単結合、アルカンジイル基（但し、該アルカンジイル基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。）又はアルカンジイル基と脂環式飽和炭化水素基とを組み合わせてなる基（但し、該組み合わせてなる基におけるアルカンジイル基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該脂環式飽和炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＣＯ－又は－Ｓ（Ｏ）_２－に置き換わっていてもよい。）である［１］～［４］のいずれかに記載の塩。
［６］［１］～［５］のいずれかに記載の塩を含有する酸発生剤。
［７］［６］記載の酸発生剤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。
［８］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［７］に記載のレジスト組成物。
［９］（１）［７］又は［８］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),
R ¹ and R ² each independently represent a hydroxy group or a group represented by the formula (R-1). However, at least one of R ¹ and R ² represents a group represented by the formula (R-1).

(In formula (R-1),
Q ^r1 and Q ^r2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
R ^r1 and R ^r2 independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms.
z ^r represents an integer of 0 to 6, and when z is 2 or more, a plurality of R ^r1 and R ^r2 may be the same as or different from each other.
X ^r1 represents -CO-O-, -O-CO-, -O-CO-O- or -O-.
L ^r1 represents a single bond or a divalent saturated hydrocarbon group having 1 to 28 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group is -O-, -S-, -CO- or-. It may be replaced with S (O) _2- .
* Represents the binding site with Ar ¹ or Ar ² .
ZR ⁺ represents an organic cation. )
Ar ¹ represents an aromatic hydrocarbon ring having 6 to 36 carbon atoms which may have a substituent.
Ar ² represents an aromatic hydrocarbon ring having 6 to 36 carbon atoms which may have a substituent. ]
[2] The salt according to [1], wherein Ar ¹ is benzene which may have a substituent or naphthalene which may have a substituent.
[3] The salt according to [1] or [2], wherein Ar ² is a benzene which may have a substituent.
[4] X ^r1 has a binding site with * -CO-O- or * -O-CO- (where * is C (R ^r1 ) (R ^r2 ) or C (Q ^r1 ) (Q ^r2 ). The salt according to any one of [1] to [3].
[5] L ^r1 is a single bond, an alkanediyl group (however, -CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-) or an alkanediyl group and a fat. A group composed of a combination with a cyclic saturated hydrocarbon group (provided that -CH _2- contained in an alkanediyl group in the combined group may be replaced with -O- or -CO-, and the alicyclic. -CH ₂ -contained in the saturated hydrocarbon group may be replaced with -O-, -S-, -CO- or -S (O) _2- ) [1] to [4]. The salt described in any of.
[6] An acid generator containing the salt according to any one of [1] to [5].
[7] A resist composition containing the acid generator according to [6] and a resin having an acid unstable group.
[8] The resist composition according to [7], which contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[9] (1) A step of applying the resist composition according to [7] or [8] onto a substrate,
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
(4) A method for producing a resist pattern, which comprises a step of heating the composition layer after exposure and (5) a step of developing the composition layer after heating.

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

In the present specification, the "(meth) acrylic monomer" is derived from a monomer having a structure of "CH ₂ = CH-CO-" and a monomer having a structure of "CH ₂ = C (CH ₃ ) -CO-". Means at least one species selected from the group of Similarly, "(meth) acrylate" and "(meth) acrylic acid" are "at least one selected from the group consisting of acrylate and methacrylate" and "at least one selected from the group consisting of acrylic acid and methacrylic acid, respectively". Means. When a structural unit having "CH ₂ = C (CH ₃ ) -CO-" or "CH ₂ = CH-CO-" is exemplified, a structural unit having both groups is similarly exemplified. It shall be. In addition, any of the groups described in the present specification that can have both a linear structure and a branched structure may be used. 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.

[Salt represented by formula (I)]
The present invention relates to a salt represented by the formula (I) (hereinafter, may be referred to as "salt (I)").
Of the salt (I), the side having a negative charge may be referred to as "anion (I)", and the side having a positive charge may be referred to as "cation (I)".
In the formula (I), the perfluoroalkyl groups of Q ^r1 , Q ^r2 , R ^r1 and R ^r2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group and a perfluorosec-butyl group. , Perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group and the like.
Q ^r1 and Q ^r2 are independently, preferably a trifluoromethyl group or a fluorine atom, and more preferably a fluorine atom.
R ^r1 and R ^r2 are independently, preferably hydrogen or fluorine atoms, respectively.
z ^r is preferably 0.

X ^r1 shall be * -CO-O- or * -O-CO- (* represents a bond with C (R ^r1 ) (R ^r2 ) or C (Q ^r1 ) (Q ^r2 )). Is preferable, and * -CO-O- (* represents a bond with C (R ^r1 ) (R ^r2 ) or C (Q ^r1 ) (Q ^r2 )) is more preferable.

Examples of the divalent saturated hydrocarbon group represented by L ^r1 include an alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and two or more of these groups. It may be a group that combines.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-Diyl group, Octane-1,8-Diyl group, Nonan-1,9-Diyl group, Decan-1,10-Diyl group, Undecan-1,11-Diyl group, Dodecan-1,12-Diyl group , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group. Alcandiyl group;
Etan-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Valuable alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. The group etc. can be mentioned.

L ^r1 is a single bond, an alkanediyl group (however, -CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-) or an alkanediyl group and an alicyclic saturation. A group composed of a combination with a hydrocarbon group (however, -CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-, and is contained in the alicyclic saturated hydrocarbon group. -CH _2- may be replaced with -O-, -S-, -CO- or -S (O) _2- ), preferably with a single bond, an alkanediyl group or an alkanediyl group. It is more preferable that the group is composed of a combination of an alicyclic saturated hydrocarbon group (however, -CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-). , Single bond, an alkanediyl group or a group consisting of a combination of an alkanediyl group and an adamantandiyl group (provided that -CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-. ) Is even more preferable, and L ^r1 is even more preferably a group containing an alicyclic hydrocarbon group.
Examples of the group consisting of a combination of an alkanediyl group and an alicyclic saturated hydrocarbon group include a * -alkandyl group-2 valent alicyclic saturated hydrocarbon group-alkanediyl group-and a * -2-valent alicyclic group. Saturated hydrocarbon groups-alkanediyl groups-(* represents a bond with ^Xr1 ) can be mentioned.
At least one of R ¹ and R ² represents a group represented by the formula (R-1), one of which is a group represented by the formula (R-1) and the other of which is a hydroxy group. preferable.

The aromatic hydrocarbon ring of Ar ¹ includes a monocyclic type, a condensed polycyclic type and a ring assembly, and examples thereof include aromatic hydrocarbon rings having 6 to 36 carbon atoms such as benzene, naphthalene, anthracene and biphenyl.
The aromatic hydrocarbon ring preferably has 6 to 24 carbon atoms, and more preferably 6 to 18 carbon atoms.

芳香族炭化水素基の置換基における組み合わせた基としては、ヒドロキシ基と炭素数１～１２のアルキル基とを組み合わせた基、炭素数１～１２のアルコキシ基と炭素数１～１２のアルコキシ基とを組み合わせた基、炭素数１～１２のアルキル基と炭素数６～１０の芳香族炭化水素基とを組み合わせた基等が挙げられる。
ヒドロキシ基と炭素数１～１２のアルキル基とを組み合わせた基としては、ヒドロキシメチル基、ヒドロキシエチル基等の炭素数１～１２のヒドロキシアルキル基等が挙げられる。
炭素数１～１２のアルコキシ基と炭素数１～１２のアルコキシ基とを組み合わせた基としては、エトキシエトキシ基等の炭素数２～２４のアルコキシアルコキシ基等が挙げられる。
炭素数１～１２のアルキル基と炭素数６～１０の芳香族炭化水素基とを組み合わせた基としては、ベンジル基等の炭素数７～２２のアラルキル基、トリル基、キシリル基等の炭素数１～１２のアルキル基を有する炭素数６～１０の芳香族炭化水素基が挙げられる。
炭素数３～１２の脂環式炭化水素基と炭素数６～１０の芳香族炭化水素基とを組み合わせた基としては、シクロヘキシルフェニル基等の炭素数３～１２の脂環式炭化水素基を有する炭素数６～１０の芳香族炭化水素基等が挙げられる。
Ａｒ^１及びＡｒ^２が置換基を有する場合、置換基は１つでもよいし、２以上でもよい。置換基が２以上の場合は、それらは同一でもよいし、異なっていてもよい。 The aromatic hydrocarbon ring of Ar ² includes a monocyclic type, a fused polycyclic type and a ring assembly, and examples thereof include aromatic hydrocarbon rings having 6 to 36 carbon atoms such as benzene, naphthalene, anthracene and biphenyl.
The aromatic hydrocarbon ring preferably has 6 to 24 carbon atoms, and more preferably 6 to 18 carbon atoms.
The substituents that Ar ¹ and Ar ² may have include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 2 to 13 carbon atoms. Examples thereof include an alkoxycarbonyl group, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or a group combining these groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and iodine.
Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. ..
The alkoxy group having 1 to 12 carbon atoms includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group and an undecyloxy group. Groups, dodecyloxy groups and the like can be mentioned.
The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms and the alkylcarbonyloxy group having 2 to 13 carbon atoms are groups in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Represents. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group and a butoxycarbonyl group, and examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
The alicyclic hydrocarbon group having 3 to 12 carbon atoms may be either a monocyclic or polycyclic group, and examples thereof include the groups shown below. ** is a bond with an aromatic hydrocarbon group.

The combined group in the substituent of the aromatic hydrocarbon group includes a group in which a hydroxy group and an alkyl group having 1 to 12 carbon atoms are combined, an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Examples thereof include a group in which the above is combined, a group in which an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined, and the like.
Examples of the group in which a hydroxy group and an alkyl group having 1 to 12 carbon atoms are combined include a hydroxyalkyl group having 1 to 12 carbon atoms such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the group in which an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms are combined include an alkoxyalkoxy group having 2 to 24 carbon atoms such as an ethoxyethoxy group.
As a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, the number of carbon atoms such as an aralkyl group having 7 to 22 carbon atoms such as a benzyl group, a trill group and a xylyl group Examples thereof include aromatic hydrocarbon groups having 6 to 10 carbon atoms having 1 to 12 alkyl groups.
As a group in which an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms are combined, an alicyclic hydrocarbon group having 3 to 12 carbon atoms such as a cyclohexylphenyl group is used. Examples thereof include aromatic hydrocarbon groups having 6 to 10 carbon atoms.
When Ar ¹ and Ar ² have substituents, the number of substituents may be one or two or more. If there are two or more substituents, they may be the same or different.

Ar ¹ is preferably benzene which may have a substituent or naphthalene which may have a substituent, and has a benzene or a hydroxy group or an alkyl group which may have a hydroxy group or an alkyl group. It is preferably naphthalene which may be used.
Ar ² is preferably benzene.

Examples of the anion (I) include the following anions. Among them, the anions represented by the formulas (Ia-1) to (Ia-12), the formula (Ia-17), the formula (Ia-18), and the formula (Ia-22) are preferable, and the formula (Ia-1) is preferable. ), Formula (Ia-2), Formula (Ia-5), Formula (Ia-6), Formula (Ia-9), Formula (Ia-10), Formula (Ia-17), Formula (Ia-18). , The anion represented by the formula (Ia-22) is more preferable.

Examples of the ZR ⁺ organic cation include an organic onium cation, an organic sulfonium cation, an organic iodinenium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Among these, organic sulfonium cations and organic iodonium cations are preferable, and aryl sulfonium cations are more preferable. Specifically, the cation represented by any of the formulas (b2-1) to (b2-4) (hereinafter, may be referred to as "cation (b2-1)" or the like depending on the formula number). Can be mentioned.

式（ｂ２－１）～式（ｂ２－４）において、
Ｒ^b4～Ｒ^b6は、それぞれ独立に、炭素数１～３０の鎖式炭化水素基、炭素数３～３６の脂環式炭化水素基又は炭素数６～３６の芳香族炭化水素基を表し、該鎖式炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１～１２のアルコキシ基、炭素数３～１２の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１～１８の脂肪族炭化水素基、炭素数２～４のアルキルカルボニル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１～１２のアルコキシ基で置換されていてもよい。
Ｒ^b4とＲ^b5とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b7及びＲ^b8は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０～５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^b7は同一でも異なってもよく、ｎ２が２以上のとき、複数のＲ^b8は同一でも異なってもよい。
Ｒ^b9及びＲ^b10は、それぞれ独立に、炭素数１～３６の鎖式炭化水素基又は炭素数３～３６の脂環式炭化水素基を表す。
Ｒ^b9とＲ^b10とは、互いに結合してそれらが結合する硫黄原子と一緒になって環を形成してもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b11は、水素原子、炭素数１～３６の鎖式炭化水素基、炭素数３～３６の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表す。
Ｒ^b12は、炭素数１～１２の鎖式炭化水素基、炭素数３～１８の脂環式炭化水素基又は炭素数６～１８の芳香族炭化水素基を表し、該鎖式炭化水素に含まれる水素原子は、炭素数６～１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１～１２のアルコキシ基又は炭素数１～１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^b11とＲ^b12とは、互いに結合してそれらが結合する－ＣＨ－ＣＯ－を含めて環を形成していてもよく、該環に含まれる－ＣＨ₂－は、－Ｏ－、－Ｓ－又は－ＣＯ－に置き換わってもよい。
Ｒ^b13～Ｒ^b18は、それぞれ独立に、ヒドロキシ基、炭素数１～１２の脂肪族炭化水素基又は炭素数１～１２のアルコキシ基を表す。
Ｌ^b31は、硫黄原子又は酸素原子を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０～５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０～４のいずれかの整数を表す。
ｕ２は０又は１を表す。
ｏ２が２以上のとき、複数のＲ^b13は同一又は相異なり、ｐ２が２以上のとき、複数のＲ^b14は同一又は相異なり、ｑ２が２以上のとき、複数のＲ^b15は同一又は相異なり、ｒ２が２以上のとき、複数のＲ^b16は同一又は相異なり、ｓ２が２以上のとき、複数のＲ^b17は同一又は相異なり、ｔ２が２以上のとき、複数のＲ^b18は同一又は相異なる。

In equations (b2-1) to (b2-4),
R ^b4 to R ^b6 independently represent a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atom contained in the chain hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. It may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be -O-, -S- or. It may be replaced with -CO-.
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.
R ^b9 and R ^b10 independently represent a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring may be -O-, -S- or. It may be replaced with -CO-.
R ^b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the chain hydrocarbon group. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or 1 to 12 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and -CH _2- contained in the ring is -O-, -S. -Or -CO- 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, multiple R ^b13s are the same or different, when p2 is 2 or more, multiple R ^b14s are the same or different, and when q2 is 2 or more, multiple R ^b15s are the same or different. , When r2 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. different.

特に、Ｒ^b9～Ｒ^b12の脂環式炭化水素基は、好ましくは炭素数３～１８、より好ましくは炭素数４～１２である。 The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
The chain hydrocarbon group includes an alkyl group of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group. Can be mentioned.
In particular, the chain hydrocarbon group of R ^b9 to R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either a monocyclic group or a polycyclic group, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclo. Cycloalkyl groups such as a heptyl group, a cyclooctyl group and a 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-methyladamantan-2-yl group and a 2-ethyladamantan-2-yl group. , 2-Isopropyl adamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which the hydrogen atom is substituted with an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenylyl group, a naphthyl group and a phenanthryl group.
The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and may have an aromatic hydrocarbon group having 1 to 18 carbon atoms (trill group). , Hydrocarbon group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and carbon number 3-18 Examples thereof include aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.).
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 chain hydrocarbon group in which the hydrogen atom is substituted with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group and a naphthylethyl group.

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

Rings formed by the bonds of R ^b4 and R ^b5 together with the sulfur atoms they bond to can be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. It may be a ring of. Examples of this ring include a ring having 3 to 18 carbon atoms, preferably a ring having 4 to 18 carbon atoms. Further, the ring containing a sulfur atom may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include the following rings.

The ring formed by R ^b9 and R ^b10 together may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. This ring may be a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-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 (b2-1) is preferable.
Examples of the cation (b2-1) include the following cations.

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

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

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

Examples of the salt (I) include the salts shown in Table 1. For example, in Table 1, the salt (I-1) is the salt shown below.

Among them, the salt (I) is salt (I-1) to salt (I-8), salt (I-11) to salt (I-13), salt (I-14), salt (I-17). -Salt (I-20), Salt (I-21) -Salt (I-28), Salt (I-31) -Salt (I-33), Salt (I-34), Salt (I-37)- Salt (I-40), Salt (I-41) -Salt (I-48), Salt (I-51) -Salt (I-53), Salt (I-54), Salt (I-57) -Salt (I-60), salt (I-61) -salt (I-68), salt (I-71) -salt (I-73), salt (I-74), salt (I-77) -salt ( I-80), salt (I-81) to salt (I-88), salt (I-91) to salt (I-93), salt (I-94), salt (I-97) to salt (I) -100), salt (I-101) to salt (I-108), salt (I-111) to salt (I-113), salt (I-114), salt (I-117) to salt (I-) 120), salt (I-121) to salt (I-128), salt (I-131) to salt (I-133), salt (I-134), salt (I-137) to salt (I-140) ), Salt (I-141) to salt (I-148), salt (I-151), salt (I-153), salt (I-154), salt (I-157) to salt (I-160). , Salt (I-169) to salt (I-176) are preferred.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
この反応における溶媒としては、クロロホルム、アセトニトリル等が挙げられる。
反応温度は通常５℃～８０℃であり、反応時間は通常０．５時間～２４時間である。
式（Ｉ－ｂ１）で表される塩及び式（Ｉ－ｂ２）で表される塩としては、例えば、以下で表される塩などが挙げられ、特開２００６－２５７０７８号公報、特開２００８－１２７３６７号公報、特開２０１２－１９３１７０号公報に記載された方法で製造することができる。

式（Ｉ－ａ）で表される化合物は、式（Ｉ－ｃ）で表される化合物と式（Ｉ－ｄ）で表される化合物とを、酸触媒の存在下、溶媒中で反応させることにより得ることができる。

（式中、全ての符号は、それぞれ前記と同じ意味を表す。） <Manufacturing method of salt (I)>
The salt (I) was obtained, for example, after reacting a salt represented by the formula (I-b1) and / or a salt represented by the formula (I-b2) with carbonyldiimidazole in a solvent. It can be obtained by reacting the reactant with the compound represented by the formula (Ia).

(In the formula, all the symbols have the same meanings as described above.)
Examples of the solvent in this reaction include chloroform, acetonitrile and the like.
The reaction temperature is usually 5 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.
Examples of the salt represented by the formula (I-b1) and the salt represented by the formula (I-b2) include salts represented by the following, and Japanese Patent Laid-Open No. 2006-257078, JP-A-2008. It can be produced by the method described in Japanese Patent Application Laid-Open No. 127367 and Japanese Patent Application Laid-Open No. 2012-193170.

In the compound represented by the formula (Ia), the compound represented by the formula (Ic) and the compound represented by the formula (Id) are reacted in a solvent in the presence of an acid catalyst. Can be obtained by

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

式（Ｉ－ｄ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場より容易に入手することができる。

Examples of the acid catalyst include p-toluenesulfonic acid.
Examples of the solvent include water and ethyl acetate.
The reaction temperature is usually 15 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.
Examples of the compound represented by the formula (Ic) include compounds represented by the following formula, which can be easily obtained from the market.

Examples of the compound represented by the formula (Id) include compounds represented by the following formula, which can be easily obtained from the market.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
この反応における溶媒としては、クロロホルム、アセトニトリル等が挙げられる。
反応温度は通常５℃～８０℃であり、反応時間は通常０．５時間～２４時間である。 Further, in the salt (I), the salt in which R ¹ is a hydroxy group (the monovalent salt represented by the formula (I1)) is, for example, a salt represented by the formula (I-b2) and a carbonyldiimidazole. Can be obtained by reacting with a compound represented by the formula (I1-a) and then treating with an acid.
In the salt (I), the salt in which ^R2 is a hydroxy group (monovalent salt represented by the formula (I2)) is, for example, a solvent of the salt represented by the formula (I-b1) and carbonyldiimidazole. It can be obtained by reacting the obtained reactant with the compound represented by the formula (I2-a) and treating with an acid.

(In the formula, all the symbols have the same meanings as described above.)
Examples of the solvent in this reaction include chloroform, acetonitrile and the like.
The reaction temperature is usually 5 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.

（式中、全ての符号は、それぞれ前記と同じ意味を表す。）
この反応における溶媒としては、クロロホルム、アセトニトリル、ｔｅｒｔ－ブチルメチルエーテル等が挙げられる。
酸触媒としては、カンファースルホン酸、ｐ－トルエンスルホン酸等が挙げられる。
反応温度は通常５℃～８０℃であり、反応時間は通常０．５時間～２４時間である。 The compound represented by the formula (I1-a) and the compound represented by the formula (I2-a) are a compound represented by the formula (Ia) and a compound represented by the formula (Ie). , Can be obtained by reacting in a solvent in the presence of an acid catalyst.

(In the formula, all the symbols have the same meanings as described above.)
Examples of the solvent in this reaction include chloroform, acetonitrile, tert-butylmethyl ether and the like.
Examples of the acid catalyst include camphorsulfonic acid and p-toluenesulfonic acid.
The reaction temperature is usually 5 ° C to 80 ° C, and the reaction time is usually 0.5 to 24 hours.

[Acid generator]
The acid generator of the present invention is an acid generator containing a salt (I). The salt (I) may be used alone or in combination of two or more.
In addition to the salt (I), the acid generator of the present invention may contain an acid generator known in the field of resist (hereinafter, may be referred to as "acid generator (B)"). The acid generator (B) may be used alone or in combination of two or more.

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

Examples of the acid generator (B) include JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, and Japanese Patent Publication No. 63-163452. Kaisho 62-153853, JP-A-63-146029, US Patent No. 3,779,778, US Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. A compound that generates an acid by the radiation described in the above can be used. Further, a compound produced by a known method may be used. The acid generator (B) may be used in combination of two or more.

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

[In formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. , The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH _2- may be replaced with —O—, —S (O) ₂ -or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group represented by Q ^b1 and Q ^b2 include groups similar to Q ^r1 and Q ^r2 of the salt (I).
It is preferable that Q ^b1 and Q ^b2 are independently fluorine atoms or trifluoromethyl groups, and it is more preferable that both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group in L ^b1 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a group formed by combining two or more kinds of groups.
Examples of these linear alkanediyl groups, branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups include groups similar to L ^r1 of the salt (I).

Examples of the group in which -CH _2- replaced by -O- or -CO- contained in the divalent saturated hydrocarbon group represented by L ^b1 are represented by the formulas (b1-1) to (b1-3). The group represented by any of the above is mentioned. In the groups represented by the formulas (b1-1) to (b1-3) and the groups represented by the formulas (b1-4) to (b1-11) which are specific examples thereof, * is-. Represents a bond with Y.

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

[In equation (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In equation (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of L ^b4 and L ^b5 is 22 or less.
In equation (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated hydrocarbon group may be substituted. -CH _2- contained in the hydrocarbon group may be replaced with -O- or -CO-.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. ]

In the groups represented by the formulas (b1-1) to (b1-3), when _-CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the carbon before the replacement is performed. Let the number be the number of carbon atoms of the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L ^b1 .

L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. -CH _2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

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

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

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

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

式（ｂ１－９）中、
Ｌ^b19は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b20は、単結合又は炭素数１～２３の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b19及びＬ^b20の合計炭素数は２３以下である。
式（ｂ１－１０）中、
Ｌ^b21は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b22は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^b23は、単結合又は炭素数１～２１の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b21、Ｌ^b22及びＬ^b23の合計炭素数は２１以下である。
式（ｂ１－１１）中、
Ｌ^b24は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子に置換されていてもよい。
Ｌ^b25は、炭素数１～２１の２価の飽和炭化水素基を表す。
Ｌ^b26は、単結合又は炭素数１～２０の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子、ヒドロキシ基又はアルキルカルボニルオキシ基に置換されていてもよい。該アルキルカルボニルオキシ基に含まれる－ＣＨ₂－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよく、該アルキルカルボニルオキシ基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。
ただし、Ｌ^b24、Ｌ^b25及びＬ^b26の合計炭素数は２１以下である。 Examples of the group represented by 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 is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. May be good. -CH _2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be 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 is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. May be good. -CH _2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be 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 is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. May be good. -CH _2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced with a hydroxy group.
However, the total carbon number of L ^b24 , L ^b25 and L ^b26 is 21 or less.

In addition, in the group represented by the formula (b1-11) from the group represented by the formula (b1-9), when the hydrogen atom contained in the saturated hydrocarbon group is replaced with the alkylcarbonyloxy group, it is replaced. The previous carbon number is taken as the carbon number of the saturated hydrocarbon group.

Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

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

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

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

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

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

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

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

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

Ｙで表される脂環式炭化水素基としては、式（Ｙ１）～式（Ｙ１１）、式（Ｙ３６）～式（Ｙ３８）で表される基が挙げられる。
Ｙで表される脂環式炭化水素基に含まれる－ＣＨ_２－が－Ｏ－、－Ｓ（Ｏ）_２－又は－ＣＯ－で置き換わる場合、その数は１つでもよいし、２以上でもよい。そのような基としては、式（Ｙ１２）～式（Ｙ３５）、式（Ｙ３９）～式（Ｙ４１）で表される基が挙げられる。 Examples of the group represented by the formula (b1-11) include the following.

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11) and the formulas (Y36) to (Y38).
When -CH _2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -S (O) _2- or -CO-, the number may be one or two or more. good. Examples of such a group include groups represented by the formulas (Y12) to the formula (Y35) and the formulas (Y39) to the formula (Y41).

Ｙとしては、好ましくは式（Ｙ１）～式（Ｙ２０）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）～式（Ｙ４１）のいずれかで表される基であり、より好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ１６）、式（Ｙ２０）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）又は式（Ｙ４０）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ３０）、式（Ｙ３９）又は式（Ｙ４０）で表される基である。
Ｙが式（Ｙ２８）～式（Ｙ３５）等のスピロ環である場合には、２つの酸素原子間のアルカンジイル基は、１以上のフッ素原子を有することが好ましい。また、ケタール構造に含まれるアルカンジイル基のうち、酸素原子に隣接するメチレン基には、フッ素原子が置換されていないのが好ましい。

Y is preferably a group represented by any one of the formulas (Y1) to (Y20), the formula (Y30), the formula (Y31), and the formula (Y39) to the formula (Y41), and more preferably the formula. (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y30), formula (Y31), formula (Y39) or formula (Y40), more preferably formula. (Y11), formula (Y15), formula (Y30), formula (Y39) or formula (Y40).
When Y is a spiro ring of the formula (Y28) to the formula (Y35) or the like, the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

As the substituent of the methyl group represented by Y, a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, and-( CH ₂ ) _ja -CO-O-R ^b1 group or-(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms and 3 to 16 carbon atoms. Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and -CH _2- contained in the alicyclic hydrocarbon group is -O-, -SO ₂ . -Or-CO- may be replaced, and the hydrogen atom contained in the alicyclic hydrocarbon group may be replaced with a hydroxy group or a fluorine atom. Ja is an integer of 0 to 4. Represented) and the like.
As the substituent of the alicyclic hydrocarbon group represented by Y, an alkyl group having 1 to 12 carbon atoms and an alicyclic group having 3 to 16 carbon atoms which may be substituted with a halogen atom, a hydroxy group or a hydroxy group may be used. Hydrocarbon groups, alkoxy groups with 1 to 12 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, aralkyl groups with 7 to 21 carbon atoms, alkylcarbonyl groups with 2 to 4 carbon atoms, glycidyloxy groups,-( CH ₂ ) _ja -CO-O-R ^b1 group or-(CH ₂ ) _ja -O-CO-R ^b1 group (in the formula, R ^b1 is an alkyl group having 1 to 16 carbon atoms and 3 to 16 carbon atoms. Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and -CH _2- contained in the alicyclic hydrocarbon group is -O-, -SO ₂ . -Or-CO- may be replaced, and the hydrogen atom contained in the alicyclic hydrocarbon group may be replaced with a hydroxy group or a fluorine atom. Ja is an integer of 0 to 4. Represented) and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like.
The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group and a dimethylcyclohexyl group.
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenylyl group, a naphthyl group and a phenanthryl group.
The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and may have an aromatic hydrocarbon group having 1 to 18 carbon atoms (trill group, xylyl group). Group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and fats with 3 to 18 carbon atoms Examples thereof include aromatic hydrocarbon groups having a cyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.).
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group and a nonyl group. Examples include a group, a decyl group, an undecyl group, a dodecyl group and the like.
Examples of the alkyl group substituted with the hydroxy group include hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the 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 aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group and the like.

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantane group which may have a substituent, and is said to be an alicyclic hydrocarbon. -CH _2- , which constitutes a hydrogen group or an adamantyl group, may be replaced with -CO-, -S (O) _2- or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the following.

Examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions represented by the formulas (B1-A-1) to (B1-A-55) [hereinafter, "anion (B1)" according to the formula number. -A-1) "and so on. ] Are preferable, and the formulas (B1-A-1) to (B1-A-4), formulas (B1-A-9), formulas (B1-A-10), and formulas (B1-A-24) to formulas (B1-A-24) to formulas are preferable. (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-55). Anions are more preferred.

ここで、Ｒ^ｉ２～Ｒ^ｉ７は、それぞれ独立に、例えば、炭素数１～４のアルキル基、好ましくはメチル基又はエチル基である。Ｒ^ｉ８は、例えば、炭素数１～１２の脂肪族炭化水素基、好ましくは炭素数１～４のアルキル基、炭素数５～１２の脂環式炭化水素基又はこれらを組合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基又はアダマンチル基である。Ｌ^Ａ４は、単結合又は炭素数１～４のアルカンジイル基である。
Ｑ^ｂ１及びＱ^ｂ２は、上記と同じ意味を表す。
式（Ｂ１）で表される塩におけるスルホン酸アニオンとしては、具体的には、特開２０１０－２０４６４６号公報に記載されたアニオンが挙げられる。

Here, R ⁱ² to R ⁱ⁷ are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is formed, for example, by an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. Group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. ^LA4 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ^b1 and Q ^b2 have the same meanings as described above.
Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions described in JP-A-2010-204646.

Examples of the sulfonic acid anion in the salt represented by the preferred formula (B1) include anions represented by the formulas (B1a-1) to (B1a-34).

Among them, the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-16), the formulas (B1a-18), the formulas (B1a-19), and the formulas (B1a-22). )-Anion represented by any of the formulas (B1a-34) is preferable.

Examples of the organic cation of Z ⁺ include the same as ZR ⁺ of the salt (I).

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

Examples of the acid generator (B) preferably include those represented by the formulas (B1-1) to (B1-48), and among them, those containing an arylsulfonium cation are preferable, and the acid generator (B1-1) contains an arylsulfonium cation. -Formula (B1-3), Formula (B1-5) -Formula (B1-7), Formula (B1-11) -Formula (B1-14), Formula (B1-20) -Formula (B1-26), Those represented by the formulas (B1-29) and the formulas (B1-31) to (B1-48) are particularly preferable.

When the acid generator of the present invention contains the acid generator (I) and the acid generator (B), the content ratio (mass ratio; acid generation) of the acid generator (I) and the acid generator (B). The agent (I): acid generator (B)) is usually 1:99 to 99: 1, preferably 2:98 to 98: 2, and more preferably 5:95 to 95: 5. , More preferably 10:90 to 90:10, and particularly preferably 15:85 to 85:15.

[Resist composition]
The resist composition of the present invention contains an acid generator containing a salt (I) and a resin having an acid unstable group (hereinafter, may be referred to as "resin (A)"). Here, the "acid-unstable group" has a leaving group, and the leaving group is removed by contact with an acid, and the constituent unit has a hydrophilic group (for example, a hydroxy group or a carboxy group). It means a group to be converted into a unit.
The resist composition of the present invention preferably contains a quencher (hereinafter, may be referred to as "citrate (C)") such as a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. , A solvent (hereinafter, may be referred to as "solvent (E)") is preferably contained.

<Resin (A)>
The resin (A) does not have a halogen atom and has a structural unit having an acid unstable group (hereinafter, may be referred to as “structural unit (a1)”). The resin (A) preferably 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 halogen atom and no acid-labile group (hereinafter, may be referred to as “structural unit (s)”), a structural unit (a1), and a structural unit. A structural unit other than the structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter, may be referred to as "structural unit (a4)"), a structural unit having a non-eliminating hydrocarbon group described later (hereinafter, "" (Sometimes referred to as structural unit (a5)) and other structural units derived from monomers known in the art. Here, an acid unstable group has a desorbing group and is in contact with an acid. Means a group that is eliminated by a group to form a hydrophilic group (for example, a hydroxy group or a carboxy group).

［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の非芳香族炭化水素環を形成する。
ｍａ及びｎａは、それぞれ独立して、０又は１を表し、ｍａ及びｎａの少なくとも一方は１を表す。
＊は結合手を表す。］

［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の複素環を形成し、該炭化水素基及び該複素環に含まれる－ＣＨ_２－は、－Ｏ－又は－Ｓ－で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
ｎａ’は、０又は１を表す。
＊は結合手を表す。］ <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 a group represented by the formula (1) (hereinafter, also referred to as a group (1)) and / or a group represented by the formula (2) (hereinafter, a group (2). ) Is also preferable.

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

[In the formula (2), Ra ^1'and Ra ^{2'independently} represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and Ra ^3'represents a hydrocarbon group having 1 to 20 carbon atoms. Represented, R ^a2'and R ^a3' are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and are contained in the hydrocarbon group and the heterocycle-CH ₂ . -May be replaced with -O- or -S-.
X represents an oxygen atom or a sulfur atom.
na'represents 0 or 1.
* 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、アダマンチルジメチル基、ノルボルニルエチル基等が挙げられる。
好ましくは、ｍａは０であり、ｎａは１である。
Ｒ^a1及びＲ^a2が互いに結合して非芳香族炭化水素環を形成する場合の－Ｃ（Ｒ^a1）（Ｒ^a2）（Ｒ^a3）としては、下記の基が挙げられる。非芳香族炭化水素環は、好ましくは炭素数３～１２である。＊は－Ｏ－との結合手を表す。

Examples of the alkyl group in R ^a1 , Ra ² and Ra ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
The alicyclic hydrocarbon group in R ^a1 , Ra ² and Ra ³ may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* indicates a bond). The alicyclic hydrocarbon group of R ^a1 to R ^a3 has preferably 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, an adamantyldimethyl group and a norbornyl group. Examples thereof include an ethyl group.
Preferably, ma is 0 and na is 1.
Examples of -C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R a ² are bonded to each other to form a non-aromatic hydrocarbon ring include the following groups. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

Ｒ^ａ１’及びＲ^ａ２’のうち、少なくとも１つは水素原子であることが好ましい。
ｎａ’は、好ましくは０である。 Examples of the hydrocarbon group in R ^a1' , R ^a2' and R ^a3' include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group combining these.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same groups as those mentioned in Ra ¹ , Ra ² and Ra ³ .
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a biphenylyl group and a naphthyl group.
Examples of the combined group include a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methyl). Phenyl group, p-tert-butylphenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon group Examples thereof include an aromatic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, and the like.
When R ^a2'and R ^a3' are bonded to each other to form a heterocycle together with the carbon atom and X to which they are bonded, -C (R ^a1' ) (R ^a3' )-X-R ^a2'is as follows. The basis of. * Represents a bond.

Of R ^a1'and R ^a2' , at least one is preferably a hydrogen atom.
na'is preferably 0.

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

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

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

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

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

[In the formula (a1-0), the formula (a1-1) and the formula (a1-2),
^La01 , ^La1 and ^La2 independently represent -O- or ^* -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents an integer of 1 to 7. -Represents a bond with CO-.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 independently 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.
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 any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]

R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
^La01 , La1 and ^La2 are preferably oxygen atoms or * -O- (CH ₂ ) _k01 -CO-O- (where ^k01 is preferably an integer of 1 to 4, more preferably. Is 1), more preferably an oxygen atom.
The alkyl groups, alicyclic hydrocarbon groups in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 and the groups in which these are combined are the same as the groups mentioned in R ^a1 to R ^a3 of the formula (1). The group is mentioned.
The number of carbon atoms of the alkyl group in R ^a02 , R ^a03 , and R ^a04 is preferably 1 to 6, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
The number of carbon atoms of the alkyl group in R ^a6 and R ^a7 is preferably 1 to 6, more preferably a methyl group, an ethyl group or an isopropyl group, and further preferably an ethyl group or an isopropyl group.
The alicyclic hydrocarbon groups of R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 have preferably 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of these alkyl groups and the alicyclic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
R ^a6 and R ^a7 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and further preferably an ethyl group or an isopropyl group.
m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1'is preferably 0 or 1.

The structural unit (a1-0) is, for example, a structural unit represented by any of the formulas (a1-0-1) to (a1-0-12) and R ^a01 in the structural unit (a1-0). Examples thereof include structural units in which the corresponding methyl group is replaced with a hydrogen atom, and structural units represented by any of the formulas (a1-0-1) to (a1-0-10) are preferable.

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

The structural unit (a1-2) corresponds to the structural unit represented by any of the equations (a1-2-1) to (a1-2-6) and R ^a5 in the structural unit (a1-2). Examples thereof include structural units in which a methyl group is replaced with a hydrogen atom, and formulas (a1-2-2), formulas (a1-2-5) and formulas (a1-2-6) are 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). With respect to the unit, it is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, still more preferably. It is 30 to 70 mol%.

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

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

Examples of the alkyl group in 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 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
Examples of the halogen atom in R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, and 1,1. 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, etc. Can be mentioned.
Examples of the alkoxy group 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 alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
Examples of the hydrocarbon group in R ^a34 , R ^a35 and R ^a36 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these, and an alkyl group and an alicyclic hydrocarbon group. Examples of the group include the same groups as the alkyl group and the alicyclic hydrocarbon group in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 .
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a biphenylyl group and a naphthyl group.
Examples of the combined group include a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methyl). Phenyl group, p-tert-butylphenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon group Examples thereof include an aromatic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, and the like. In particular, ^Ra36 includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining them. Can be mentioned.

In the formula (a1-4), a hydrogen atom is preferable as R ^a32 .
As R ^a33 , an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is further preferable.
As la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably an alkyl group or an alicyclic 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. It is a group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. The aromatic hydrocarbon group in R ^a36 is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.
-OC (R ^a34 ) (R ^a35 ) -OR ^a36 in the structural unit (a1-4) is contacted with an acid (for example, p-toluenesulfonic acid) and desorbed to form a hydroxy group.

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

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

式（ａ１－５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１～６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊－（ＣＨ₂）_h3－ＣＯ－Ｌ⁵⁴－を表し、ｈ３は１～４のいずれかの整数を表し、＊は、Ｌ⁵¹との結合手を表す。
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のいずれかの整数を表す。
ｓ１’は、０～３のいずれかの整数を表す。 Examples of the structural unit derived from the (meth) acrylic monomer having the group (2) include the structural unit represented by the formula (a1-5) (hereinafter, may be referred to as “structural unit (a1-5)”). Be done.

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

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Alkyl groups having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. The group is mentioned.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
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 structural unit (a1-5) include the structural unit derived from the monomer described in JP-A-2010-61117. Among them, the structural units represented by the formulas (a1-5-1) to (a1-5-4) are preferable, and they are represented by the formula (a1-5-1) or the formula (a1-5-2). Structural units are more preferred.

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

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

When the resin (A) contains structural units such as those of the above formulas (a1-3-1) to (a1-3-7), the content thereof is 10 with respect to all the structural units of the resin (A). It is preferably ~ 95 mol%, more preferably 15-90 mol%, still more preferably 20-85 mol%, even more preferably 20-70 mol%, and particularly preferably 20-60 mol%.

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

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

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

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

Examples of the halogen atom in R ^a50 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in ^Ra50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group and 1 , 1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3 , 3,4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluorohexyl The group is mentioned.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
Examples of the alkyl group in ^Ra51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group.
Examples of the alkoxy group in ^Ra51 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. 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 further preferable.
Examples of the alkylcarbonyl group in ^Ra51 include an acetyl group, a propionyl group, a butyryl group and the like.
Examples of the alkylcarbonyloxy group in ^Ra51 include an acetyloxy group, a propionyloxy group and a butyryloxy group.
R ^a51 is preferably a methyl group.

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

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

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

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

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

Examples of the structural unit (a2-A) include structural units derived from the monomers described in JP-A-2010-204634 and JP-A-2012-12577.
The structural unit (a2-A) includes a structural unit represented by the formulas (a2-2-1) to the formula (a2-2-6) and the formulas (a2-2-1) to the formula (a2-2-2). In the structural unit represented by 6), a structural unit in which the methyl group corresponding to ^Ra50 in the structural unit (a2-A) is replaced with a hydrogen atom can be mentioned. The structural unit (a2-A) is represented by a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), and a formula (a2-2-6). In the structural unit represented by the formula (a2-2-1), the structural unit represented by the formula (a2-2-3), or the structural unit represented by the formula (a2-2-6). , It is preferable that the methyl group corresponding to ^Ra50 in the structural unit (a2-A) is a structural unit in which a hydrogen atom is replaced.

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

式（ａ２－１）中、
Ｌ^a3は、－Ｏ－又は^＊－Ｏ－（ＣＨ₂）_k2－ＣＯ－Ｏ－を表し、
ｋ２は１～７のいずれかの整数を表す。＊は－ＣＯ－との結合手を表す。
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のいずれかの整数を表す。 Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include 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 of 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 any integer from 0 to 10.

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

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

When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on all the structural units of the resin (A). It is more preferably 1 to 35 mol%, further preferably 2 to 20 mol%, and even more preferably 2 to 10 mol%.

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

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

[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4),
L ^a4 , ^La 5 and ^{La 6} are independently represented by -O- or ^* -O- (CH ₂ ) _k3 -CO-O- (k3 represents an integer of 1 to 7). Represents a group.
L ^a7 is -O-, ^* -OL ^a8 -O-, ^{* -OL a8-CO-O-, * -OL a8 -} CO-O-L ^a9 -CO-O- or ^* -O-L ^a8 -O-CO-L ^a9 -O-represented.
L ^a8 and ^{La 9} each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom which may have a halogen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5.
q1 represents an integer of 0 to 3.
r1 represents any integer from 0 to 3.
w1 represents any integer from 0 to 8.
When p1, q1, r1 and / or w1 is 2 or more, the plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same or different from each other. ]

Examples of the aliphatic hydrocarbon group in R ^a21 , R ^a22 , R ^a23 and R a ²⁵ include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group. Be done.
Examples of the halogen atom in ^Ra24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group in ^Ra24 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like, and preferably have 1 to 4 carbon atoms. Alkyl group of, more preferably a methyl group or an ethyl group.
Alkyl groups having a halogen atom in ^Ra24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. Examples thereof include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

The alkanediyl group in ^La8 and ^La9 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples thereof include 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 k3 in -O- or * -O- (CH ₂ ) _k3 -CO-O-, respectively. Is an integer of 1 to 4, more preferably —O— and * —O— _CH2 -CO—O—, and even more preferably an oxygen atom.
R ^a18 to R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently, preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are independently, preferably an integer of 0 to 2, and more preferably 0 or 1.

（式中、Ｒ^ａ２４、Ｌ^ａ７は、上記と同じ意味を表す。） In the formula (a3-4), ^Ra24 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. Is.
^Ra25 is preferably a carboxy group, a cyano group or a methyl group.
L ^a7 is preferably -O- or ^* -OL ^a8 -CO-O-, and more preferably -O-, -O-CH ₂ -CO-O- or -O-C ₂ H _4- . It is CO-O-.
w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
In particular, the formula (a3-4) is preferably the formula (a3-4)'.

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

The structural unit (a3) is a structure derived from the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and the monomer described in JP-A-2012-41274. The unit is mentioned. The structural unit (a3) includes the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula (a3--2-2), and the formula (a3-3-3). 1), the structural unit represented by any of the equations (a3-3-2) and the equations (a3-4-1) to (a3-4-12), and in the structural unit, the equation (a3-1). )-The structural unit in which the methyl group corresponding to Ra 18, Ra ¹⁹ , Ra ²⁰ and Ra 24 in the formula ( ^a3-4 ) ^is replaced with a hydrogen atom is preferable.

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 content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is set with respect to all the structural units of the resin (A), respectively. 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is further preferable.

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

[In equation (a4),
R ⁴¹ represents a hydrogen atom or a methyl group.
R ⁴² represents a saturated hydrocarbon group having a fluorine atom having 1 to 24 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO. ]
Examples of the saturated hydrocarbon group represented by R ⁴² include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group combining these.

組み合わせた基としては、１以上のアルキル基又は１以上のアルカンジイル基と、１以上の脂環式炭化水素基とを組み合わせた基が挙げられ、－アルカンジイル基－脂環式炭化水素基、－脂環式炭化水素基－アルキル基、－アルカンジイル基－脂環式炭化水素基－アルキル基等が挙げられる。 Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. Can be mentioned. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups. Examples thereof include a polycyclic alicyclic hydrocarbon group such as (* indicates a bond).

Examples of the combined group include a group in which one or more alkyl groups or one or more alcandiyl groups and one or more alicyclic hydrocarbon groups are combined-alcandiyl group-alicyclic hydrocarbon group. -Ali ring type hydrocarbon group-alkyl group, -alkandyl group-ali ring type hydrocarbon group-alkyl group and the like can be mentioned.

［式（ａ４－０）中、
Ｒ^５４は、水素原子又はメチル基を表す。
Ｌ^４ａは、単結合又は炭素数１～４のアルカンジイル基を表す。
Ｌ^３ａは、炭素数１～８のペルフルオロアルカンジイル基又は炭素数３～１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ The structural unit (a4) is at least selected from the group consisting of the formula (a4-0), the formula (a4-1), the formula (a4-2), the formula (a4-3) and the formula (a4-4). A structural unit represented by one can be mentioned.

[In equation (a4-0),
R ⁵⁴ represents a hydrogen atom or a methyl group.
L ^4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

Examples of the alkanediyl group having 1 to 4 carbon atoms in L ^4a include a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and an ethane-1. , 1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like. Alkanediyl group is mentioned.

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

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

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

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

〔式（ａ－ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１～５の２価の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２価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。〕
＊は結合手であり、右側の＊が－Ｏ－ＣＯ－Ｒ^a42との結合手である。］

[In equation (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH _2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-. You may.
A ^a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the formula (ag1). However, at least one of ^Aa41 and ^Ra42 has a halogen atom (preferably a fluorine atom) as a substituent.

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

Examples of the saturated hydrocarbon group in R ^a42 include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

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

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

［式（ａ－ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＲ^a42との結合手を表す。）。
Ａ^a45は、ハロゲン原子を有していてもよい炭素数１～１７の脂肪族炭化水素基を表す。
＊は結合手を表す。］
ただし、Ｒ^a42－Ｘ^a43－Ａ^a45において、Ｒ^a42がハロゲン原子を有しない場合は、Ａ^a45は、少なくとも１つのハロゲン原子を有する炭素数１～１７の脂肪族炭化水素基を表す。 Examples of the substituent that R ^a42 may have include a halogen atom and a group represented by the formula (ag3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

[In the formula (ag3),
X ^a43 represents an oxygen atom, a carbonyl group, * -O-CO- or * -CO-O- (* represents a bond with R ^a42 ).
A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* Represents a bond. ]
However, in R ^a42- X ^a43 -A ^a45 , when R ^a42 does not have a halogen atom, A ^a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.

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

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

［式（ａ－ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数１～１７の２価の脂肪族炭化水素基を表す。
Ｘ^a44は、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＡ^a46との結合手を表す。）。
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。］ When R ^a42 is a saturated hydrocarbon having a group represented by the formula (ag3), R ^a42 is more preferably a group represented by the formula (ag2).

[In the formula (ag2),
A ^a46 represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents * -O-CO- or * -CO-O- (* represents a bond with A ^a46 ).
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, and further preferably A ^a47 having a cyclohexyl group or an adamantyl group.

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

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

The divalent aliphatic hydrocarbon groups of A ^a42 , A ^a43 and A ^a44 in the group represented by the formula (a-g1) include a linear or branched alkanediyl group and a monocyclic or polycyclic divalent group. Examples thereof include an alicyclic hydrocarbon group and a divalent aliphatic hydrocarbon group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, Examples thereof include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
Examples of the substituent of the divalent 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.

In the group represented by the formula (ag1), examples of the group in which X ^a42 is —O—, —CO—, —CO—O— or —O—CO— include the following groups. In the following examples, * and ** represent the bond, respectively, and ** is the bond with -O-CO-R ^a42 .

As the structural unit represented by the formula (a4-1), the methyl group corresponding to R ^a41 in the structural unit shown below and the structural unit represented by the formula (a4-1) in the following structural unit is a hydrogen atom. Examples include replaced structural units.

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

[In equation (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴⁴ represents an alkanediyl group having 1 to 6 carbon atoms, and -CH _2- contained in the alkanediyl group may be replaced with -O- or -CO-.
R ^f6 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms.
However, the upper limit of the total carbon number of L ⁴⁴ and R ^f6 is 21. ]

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

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

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

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

Examples of the alkanediyl group in L ⁵ include the same groups as those exemplified in the alkanediyl group in ^Aa41 .

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

Examples of the saturated hydrocarbon group of A ^f14 and the saturated hydrocarbon group which may have a fluorine atom include the same groups as those exemplified in R ^a42 . Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5-Nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group and the like fluoride Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group , Perfluoroadamantylmethyl group and the like are preferable.

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

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

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

[In equation (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents-(CH ₂ ) _j1 -,-(CH ₂ ) _j2 -O- (CH ₂ ) _{j3- or-} (CH ₂ ) _j4 -CO-O- (CH ₂ ) _j5- .
j1 to j5 each independently represent an integer of 1 to 6.
R ^f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom. ]

Examples of the saturated hydrocarbon group of R ^{f22 include the same saturated hydrocarbon group represented by R a42 .} R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic 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, an alkyl group having 1 to 6 carbon atoms having a fluorine atom is more preferable.

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

As the structural unit represented by the formula (a4-4), for example, in the following structural unit and the structural unit represented by the following formula, the methyl group corresponding to R ^f21 in the structural unit (a4-4) is hydrogen. A structural unit that has been replaced by an atom can be mentioned.

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で置換されていてもよい。
Ｌ⁵⁵は、単結合又は炭素数１～１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ_２－は、－Ｏ－又は－ＣＯ－に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group of the structural unit (a5) include a group having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).

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

The alicyclic hydrocarbon group in R ⁵² may be either a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and 2 -Alkyl groups such as ethylhexyl groups can be mentioned.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.
Examples of the divalent saturated hydrocarbon group in L ⁵⁵ include a divalent chain-type saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and a divalent chain-type saturated hydrocarbon group is preferable. ..
Examples of the divalent chain saturated hydrocarbon group include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanjiyl group and a pentandiyl group.
The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantandiyl group and a norbornanediyl group.

式（Ｌ１－１）中、
Ｘ^x1は、＊－Ｏ－ＣＯ－又は＊－ＣＯ－Ｏ－を表す（＊はＬ^ｘ１との結合手を表す。）。
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。
Ｌ^x1は、好ましくは、炭素数１～８の２価の脂肪族飽和炭化水素基、より好ましくは、メチレン基又はエチレン基である。
Ｌ^x2は、好ましくは、単結合又は炭素数１～８の２価の脂肪族飽和炭化水素基、より好ましくは、単結合である。
Ｌ^x3は、好ましくは、炭素数１～８の２価の脂肪族飽和炭化水素基である。
Ｌ^x4は、好ましくは、単結合又は炭素数１～８の２価の脂肪族飽和炭化水素基である。
Ｌ^x5は、好ましくは、炭素数１～８の２価の脂肪族飽和炭化水素基、より好ましくは、メチレン基又はエチレン基である。
Ｌ^x6は、好ましくは、単結合又は炭素数１～８の２価の脂肪族飽和炭化水素基、より好ましくは、メチレン基又はエチレン基である。
Ｌ^x7は、好ましくは、単結合又は炭素数１～８の２価の脂肪族飽和炭化水素基である。
Ｌ^x8は、好ましくは、単結合又は炭素数１～８の２価の脂肪族飽和炭化水素基、より好ましくは、単結合又はメチレン基である。
Ｌ^x9は、好ましくは、単結合又は炭素数１～８の２価の脂肪族飽和炭化水素基、より好ましくは、単結合又はメチレン基である。
Ｗ^x1は、好ましくは、炭素数３～１０の２価の脂環式飽和炭化水素基、より好ましくは、シクロヘキサンジイル基又はアダマンタンジイル基である。 Examples of the group in which _-CH2- contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ is replaced with -O- or -CO- are represented by the formulas (L1-1) to (L1-4). The groups represented are mentioned. In the following formula, * represents a bond with an oxygen atom.

In equation (L1-1),
X ^x1 represents * -O-CO- or * -CO-O- (* represents a bond with L ^x1 ).
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total number of carbon atoms of L ^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 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 ^{x 5} is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
W ^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 ⁵⁵ is preferably a single bond or a group represented by the formula (L1-1).

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

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%.

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

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

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

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

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

When -CH _2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-, for example, a divalent group represented by the formulas (X1) to (X53) is used. Can be mentioned. However, the number of carbon atoms before that -CH _2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following equation, * represents a bond with A ^x1 .

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

Examples of the organic cation represented by ZA ⁺ include cations similar to those of the ZR ⁺ organic cation of the salt (I).

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

[In the formula (II-2-A), R ^III3 , X ^III3 and ZA ⁺ have the same meanings as described above.
z represents an integer of 0 to 6.
R ^III2 and R ^III4 independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms, and when z is 2 or more, a plurality of R ^III2 and R ^III4 are identical to each other. It may or may not be different.
Q ^a and Q ^b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. ]

Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R ^III2 , R ^III4 , ^Qa and ^Qb include the same perfluoroalkyl group having 1 to 6 carbon atoms which is the substituent of A ^x1 described above. Be done.

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

[In the formula (II-2-A-1),
R ^III2 , R ^III3 , R ^III4 , Q ^a , Q ^b , z and ZA ⁺ have the same meanings as above.
R ^III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
^XI2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group may be replaced with -O-, -S- or -CO-. Often, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group. ]

Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ^III5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Examples thereof include a linear or branched alkyl group such as a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
Examples of the divalent saturated hydrocarbon group represented by ^{XI2 include those similar to the divalent saturated hydrocarbon group represented by X III3 .}

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

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

Examples of the structural unit represented by the formula (II-2-A') include the following structural units and the structural units described in International Publication No. 2012/050015. ZA ⁺ represents an organic cation.

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

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

Examples of the structural unit containing a cation in the formula (II-1-1) include structural units represented by the following.

Examples of the organic anion represented by A ⁻ include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, a carboxylic acid anion and the like. The organic anion represented by A ⁻ is preferably a sulfonic acid anion, and the sulfonic acid anion is more preferably an anion contained in the salt represented by the above-mentioned formula (B1).

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

Examples of the sulfonylmethide anion include the following.

Examples of the carboxylic acid anion include the following.

Examples of the structural unit represented by the formula (II-1-1) include structural units represented by the following.

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

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

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 a group consisting of a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group). At least one selected from, more preferably at least two.
The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by a structural unit (a2-1) or a structural unit (a2-A). The structural unit (a3) is preferably a group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4). It is at least one selected from.

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

<Resin other than resin (A)>
Examples of the resin other than the resin (A) include a resin containing a structural unit (a4) or a structural unit (a5) (hereinafter, may be referred to as a resin (X)) and the like.
As the resin (X), a resin containing the structural unit (a4) is particularly preferable.
In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total of all the structural units of the resin (X). , 45 mol% or more is more preferable.
Examples of the structural unit that the resin (X) may further include include a structural unit (a1), a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers. Above all, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5).
Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less), respectively. 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 of the present invention contains the resin (A2), the content thereof is usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) with respect to 100 parts by mass of the resin (A). be.
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). It is more preferably 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass.

The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. When a resin other than the resin (A) is contained, the total content of the resin (A) and the resin other than the resin (A) is 80% by mass or more and 99% by mass with respect to the solid content of the resist composition. It is preferably 90% by mass or more and 99% by mass or less, more preferably 90% by mass or less. The solid content of the resist composition and the content of the resin relative to the solid content can be measured by a known analytical means such as liquid chromatography or gas chromatography.

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

<Quencher (C)>
Examples of the quencher (C) include a basic nitrogen-containing organic compound and a salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B). The content of the quencher (C) is preferably about 0.01 to 5% by mass based on the solid content of the resist composition.
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.
Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, trypentylamine, trihexylamine, tri Heptylamine, Trioctylamine, Trinonylamine, Tridecylamine, Methyldibutylamine, Methyldipentylamine, Methyldihexylamine, Methyldicyclohexylamine, Methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, tri Isopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3 , 3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-di) Pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethen, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ) Etan, di (2-pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicorylamine, bipyridine and the like. Diisopropylaniline is preferable, and 2,6-diisopropylaniline is more preferable.
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 acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B) is usually a salt having an acid dissociation constant of -3 <pKa, preferably -1 <. It is a salt of pKa <7, more preferably a salt of 0 <pKa <5.
Examples of the salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B) include a salt represented by the following formula and a salt represented by the formula (D) described in JP-A-2015-147926. (Hereinafter, it may be referred to as "weak acid intramolecular salt (D)"), and JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502. Examples thereof include the salts described in JP-A-2011-191745. It is preferably a weak acid intramolecular salt (D).

レジスト組成物がクエンチャー（Ｃ）を含有する場合、クエンチャー（Ｃ）の含有率は、レジスト組成物の固形分中、通常、０．０１～５質量％であり、好ましくは０．０１～３質量％である。 Examples of the weak acid intramolecular salt (D) include the following salts.

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

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

<Preparation of resist composition>
The resist composition of the present invention comprises a salt (I), a resin (A) and an acid generator (B), and if necessary, a resin other than the resin (A) used, a solvent (E), and a citric acid ( It can be prepared by mixing 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. The substrate may be washed before the resist composition is applied, or an antireflection film or the like may be formed on the substrate.
By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure for drying under reduced pressure is preferably about ¹ to 1.0 × 105 Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. The exposure light source includes a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excima laser (wavelength 157 nm) that emits laser light in the ultraviolet region, and a solid-state laser light source (YAG or semiconductor laser). Etc.), and various ones such as those that radiate harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, those that irradiate electron beams, super-ultraviolet light (EUV), etc. are used. Can be done. In addition, in this specification, irradiation of these radiations may be generically referred to as "exposure". At the time of exposure, the exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, it may be exposed by direct drawing without using a mask.
The composition layer after exposure is heat-treated (so-called post-exposure bake) in order to promote the deprotection reaction at the acid unstable group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.
The heated composition layer is usually developed using a developer and a developer. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense method. The development temperature is preferably, for example, 5 to 60 ° C., and the development time is preferably, for example, 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any alkaline aqueous solution used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) can be mentioned. The alkaline developer may contain a surfactant.
After development, it is preferable to wash the resist pattern with ultrapure water and then remove the substrate and the water remaining on the pattern.
When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter, may be referred to as "organic developer") is used as the developer.
Examples of the organic solvent contained in the organic developer include a ketone solvent such as 2-hexanone and 2-heptanone; a glycol ether ester solvent such as propylene glycol monomethyl ether acetate; an ester solvent such as butyl acetate; and a glycol such as propylene glycol monomethyl ether. Examples include an ether solvent; an amide solvent such as N, N-dimethylacetamide; an aromatic hydrocarbon solvent such as anisole, and the like.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and further preferably substantially only the organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and substantially butyl acetate and / or 2 -It is more preferable that it is only heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a small amount of water.
At the time of development, the development may be stopped by substituting with a solvent of a type different from that of the organic developer.
It is preferable to wash the resist pattern after development with a rinsing solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

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

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part" 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. The analysis conditions for gel permeation chromatography are as follows.
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ℃
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh)
The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent 1100 type, MASS: Agilent LC / MSD type). In the following examples, the value of this molecular ion peak is indicated by "MASS". The structure of the isomer was confirmed by NMR (EX-270 type; manufactured by JEOL Ltd.).

式（Ｉ－１－ａ）で表される化合物２２．５７部及びイオン交換水３０部を混合し、２３℃で３０分間攪拌した後、６０℃に昇温した。得られた混合溶液に、式（Ｉ－１－ｂ）で表される化合物３０．５３部及びｐ－トルエンスルホン酸１．５６部を添加し、６０℃で１８時間攪拌した後、２３℃まで冷却した。得られた反応マスに、イオン交換水１００部を加えて２３℃で３０分間攪拌した後、ろ過した。回収されたろ物に、イオン交換水１００部を加えて２３℃で３０分間攪拌した後、ろ過した。この操作を５回行った。回収されたろ物を乾燥することにより、式（Ｉ－１―ｃ）で表される化合物２５．０４部を得た。
式（Ｉ－１―ｃ）で表される化合物
^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ）：δ（ｐｐｍ）
５．１２（ｓ，１Ｈ）、６．５８（ｍ，１Ｈ）、６．６６（ｍ，１Ｈ）、６．９２（ｍ，２Ｈ）、６．９６（ｍ，１Ｈ）、７．０９（ｍ，２Ｈ）、９．４０（ｂｒｓ，１Ｈ）、９．８８（ｂｒｓ，１Ｈ）

式（Ｉ－１－ｃ）で表される化合物１５．５５部及びアセトニトリル１００部を仕込み、２３℃で３０分間攪拌混合した後、０．２％カンファースルホン酸のクロロホルム溶液２．１３部を仕込み、２３℃で３０分間攪拌混合した。得られた混合物に、式（Ｉ－１－ｄ）で表される化合物６．５０部を２３℃で１時間かけて滴下した後、２３℃で１８時間攪拌混合した。得られた反応物に、トリエチルアミン０．０１４部を添加し、更に、クロロホルム１５０部及び２％炭酸水素ナトリウム水溶液５４部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、イオン交換水７０部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような水洗操作を３回繰り返した。得られた有機層を濃縮し、濃縮マスをカラム（シリカゲル６０Ｎ（球状、中性）１００－２１０μｍ；関東化学（株）製、展開溶媒：ｎ－ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ－１－ｅ）で表される化合物５．４２部及び式（Ｉ－７－ｅ）で表される化合物３．４４部をそれぞれ得た。
式（Ｉ－１－ｅ）で表される化合物
^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ）：δ（ｐｐｍ）
１．０９（ｔ，３Ｈ）、１．３８（ｄ，３Ｈ）、３．４７（ｑ，１Ｈ）、３．６７（ｑ，１Ｈ）、５．１２（ｓ，１Ｈ）、５．４０（ｑ，１Ｈ）、６．７６（ｍ，１Ｈ）、６．８１（ｍ，１Ｈ）、６．９２（ｍ，２Ｈ）、７．０９（ｍ，２Ｈ）、７．２５（ｍ，１Ｈ）、９．４０（ｂｒｓ，１Ｈ）
式（Ｉ－７－ｅ）で表される化合物
^１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ）：δ（ｐｐｍ）
１．０９（ｔ，３Ｈ）、１．４８（ｄ，３Ｈ）、３．４７（ｑ，１Ｈ）、３．６６（ｑ，１Ｈ）、５．１２（ｓ，１Ｈ）、５．４８（ｑ，１Ｈ）、６．５８（ｍ，１Ｈ）、６．６６（ｍ，１Ｈ）、６．９６（ｍ，３Ｈ）、７．３０（ｍ，２Ｈ）、９．８８（ｂｒｓ，１Ｈ）

式（Ｉ－１－ｆ）で表される塩４．３８部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物１．６２部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物を２３℃まで冷却した後、式（Ｉ－１－ｅ）で表される化合物３．１４部を添加し、さらに、２３℃で１８時間攪拌した。得られた反応物に、ｐ－トルエンスルホン酸２部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、さらに、５０℃で２時間攪拌した。得られた反応物に、クロロホルム６０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１）で表される塩５．６２部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３９９．０ Example 1: Synthesis of salt represented by the formula (I-1)

22.57 parts of the compound represented by the formula (I-1-a) and 30 parts of ion-exchanged water were mixed, stirred at 23 ° C. for 30 minutes, and then heated to 60 ° C. To the obtained mixed solution, 30.53 parts of the compound represented by the formula (I-1-b) and 1.56 parts of p-toluenesulfonic acid were added, and the mixture was stirred at 60 ° C. for 18 hours and then up to 23 ° C. Cooled. To the obtained reaction mass, 100 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and then filtered. To the recovered filtrate, 100 parts of ion-exchanged water was added, the mixture was stirred at 23 ° C. for 30 minutes, and then filtered. This operation was performed 5 times. The recovered filtrate was dried to obtain 25.04 parts of the compound represented by the formula (I-1-c).
Compound represented by formula (I-1-c)
^{1 1} H-NMR (DMSO-d): δ (ppm)
5.12 (s, 1H), 6.58 (m, 1H), 6.66 (m, 1H), 6.92 (m, 2H), 6.96 (m, 1H), 7.09 (m) , 2H), 9.40 (brs, 1H), 9.88 (brs, 1H)

15.55 parts of the compound represented by the formula (I-1-c) and 100 parts of acetonitrile were charged, and after stirring and mixing at 23 ° C. for 30 minutes, 2.13 parts of a chloroform solution of 0.2% camphorsulfonic acid was charged. , Stirred and mixed at 23 ° C. for 30 minutes. To the obtained mixture, 6.50 parts of the compound represented by the formula (I-1-d) was added dropwise at 23 ° C. over 1 hour, and then the mixture was stirred and mixed at 23 ° C. for 18 hours. To the obtained reaction product, 0.014 parts of triethylamine was added, 150 parts of chloroform and 54 parts of a 2% aqueous sodium hydrogen carbonate solution were further added, and the mixture was stirred at 23 ° C. for 30 minutes. 70 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed by standing and separating. Such a washing operation was repeated three times. The obtained organic layer is concentrated, and the concentrated mass is separated into a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 5.42 parts of the compound represented by the formula (I-1-e) and 3.44 parts of the compound represented by the formula (I-7-e) were obtained, respectively.
Compound represented by the formula (I-1-e)
^{1 1} H-NMR (DMSO-d): δ (ppm)
1.09 (t, 3H), 1.38 (d, 3H), 3.47 (q, 1H), 3.67 (q, 1H), 5.12 (s, 1H), 5.40 (q) , 1H), 6.76 (m, 1H), 6.81 (m, 1H), 6.92 (m, 2H), 7.09 (m, 2H), 7.25 (m, 1H), 9 .40 (brs, 1H)
Compound represented by the formula (I-7-e)
^{1 1} H-NMR (DMSO-d): δ (ppm)
1.09 (t, 3H), 1.48 (d, 3H), 3.47 (q, 1H), 3.66 (q, 1H), 5.12 (s, 1H), 5.48 (q) , 1H), 6.58 (m, 1H), 6.66 (m, 1H), 6.96 (m, 3H), 7.30 (m, 2H), 9.88 (brs, 1H)

4.38 parts of the salt represented by the formula (I-1-f) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.62 parts of the compound represented by the formula (I-1-g) was added, and the mixture was further stirred at 50 ° C. for 2 hours. After cooling the obtained reaction mixture to 23 ° C., 3.14 parts of the compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained reaction product, 2 parts of p-toluenesulfonic acid and 30 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, and then further stirred at 50 ° C. for 2 hours. 60 parts of chloroform was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, and then the supernatant is removed. By concentrating, 5.62 parts of the salt represented by the formula (I-1) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 399.0

式（Ｉ－１－ｆ）で表される塩４．３８部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物１．６２部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物を２３℃まで冷却した後、式（Ｉ－７－ｅ）で表される化合物３．１４部を添加し、さらに、２３℃で１８時間攪拌した。得られた反応物に、ｐ－トルエンスルホン酸２部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、さらに、５０℃で２時間攪拌した。得られた反応物に、クロロホルム６０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－７）で表される塩３．９２部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ３９９．０ Example 2: Synthesis of salt represented by the formula (I-7)

4.38 parts of the salt represented by the formula (I-1-f) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.62 parts of the compound represented by the formula (I-1-g) was added, and the mixture was further stirred at 50 ° C. for 2 hours. After cooling the obtained reaction mixture to 23 ° C., 3.14 parts of the compound represented by the formula (I-7-e) was added, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained reaction product, 2 parts of p-toluenesulfonic acid and 30 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, and then further stirred at 50 ° C. for 2 hours. 60 parts of chloroform was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, and then the supernatant is removed. By concentrating, 3.92 parts of the salt represented by the formula (I-7) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 399.0

式（Ｉ－１１－ｈ）で表される塩６．９７部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｅ）で表される化合物３．１４部を添加し、さらに、２３℃で１８時間攪拌した。得られた反応物に、ｐ－トルエンスルホン酸２部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、さらに、５０℃で２時間攪拌した。得られた反応物に、クロロホルム６０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１１）で表される塩４．２８部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ６０７．１ Example 3: Synthesis of salt represented by the formula (I-11)

6.97 parts of the salt represented by the formula (I-11-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 3.14 parts of the compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained reaction product, 2 parts of p-toluenesulfonic acid and 30 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, and then further stirred at 50 ° C. for 2 hours. 60 parts of chloroform was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, and then the supernatant is removed. By concentrating, 4.28 parts of the salt represented by the formula (I-11) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 607.1

式（Ｉ－１１－ｈ）で表される塩６．９７部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－７－ｅ）で表される化合物３．１４部を添加し、さらに、２３℃で１８時間攪拌した。得られた反応物に、ｐ－トルエンスルホン酸２部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、さらに、５０℃で２時間攪拌した。得られた反応物に、クロロホルム６０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１３）で表される塩４．２９部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ６０７．１ Example 4: Synthesis of salt represented by the formula (I-13)

6.97 parts of the salt represented by the formula (I-11-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. 3.14 parts of the compound represented by the formula (I-7-e) was added to the obtained mixed solution, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained reaction product, 2 parts of p-toluenesulfonic acid and 30 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, and then further stirred at 50 ° C. for 2 hours. 60 parts of chloroform was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, and then the supernatant is removed. By concentrating, 4.29 parts of the salt represented by the formula (I-13) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 607.1

式（Ｉ－１－ｆ）で表される塩８．７７部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物３．２４部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物を２３℃まで冷却した後、式（Ｉ－１－ｃ）で表される化合物２．４２部を添加し、さらに、５０℃で１８時間攪拌した。得られた反応物に、クロロホルム５０部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｉ－１７）で表される塩６．４４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：［Ｍ^２－＋Ｈ］^－ ５５６．９ Example 5: Synthesis of salt represented by the formula (I-17)

8.77 parts of the salt represented by the formula (I-1-f) and 50 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 3.24 parts of the compound represented by the formula (I-1-g) was added, and the mixture was further stirred at 50 ° C. for 2 hours. After cooling the obtained reaction mixture to 23 ° C., 2.42 parts of the compound represented by the formula (I-1-c) was added, and the mixture was further stirred at 50 ° C. for 18 hours. To the obtained reaction product, 50 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes and then filtered. 6.44 parts of the salt represented by (I-17) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): [M ^2- + H ^] -556.9

式（Ｉ－１１－ｈ）で表される塩６．９７部及びクロロホルム５０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｃ）で表される化合物１．２１部を添加し、さらに、５０℃で１８時間攪拌した。得られた反応物に、クロロホルム５０部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｉ－１９）で表される塩８．４４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：［Ｍ^２－＋Ｈ］^－ ９７３．２ Example 6: Synthesis of salt represented by the formula (I-19)

6.97 parts of the salt represented by the formula (I-11-h) and 50 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.21 part of the compound represented by the formula (I-1-c) was added, and the mixture was further stirred at 50 ° C. for 18 hours. To the obtained reaction product, 50 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes and then filtered. 8.44 parts of the salt represented by (I-19) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): [M ^2- + H ^] -973.2

式（Ｉ－１２－ｆ）で表される塩６．１６部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物１．６２部を添加し、さらに、５０℃で２時間攪拌することにより、式（Ｉ－１２－ｈ）で表される塩を含む混合物を得た。得られた式（Ｉ－１２－ｈ）で表される塩を含む混合物を２３℃まで冷却した後、式（Ｉ－１－ｅ）で表される化合物３．１４部を添加し、さらに、２３℃で１８時間攪拌することにより、式（Ｉ－１２－ｉ）で表される塩を含む混合物を得た。得られた式（Ｉ－１２－ｉ）で表される塩を含む混合物に、ｐ－トルエンスルホン酸２部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、さらに、５０℃で２時間攪拌した。得られた反応物に、クロロホルム６０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１２）で表される塩３．７９部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ５７７．１ Example 7: Synthesis of salt represented by the formula (I-12)

6.16 parts of the salt represented by the formula (I-12-f) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.62 parts of the compound represented by the formula (I-1-g) was added, and the mixture was further stirred at 50 ° C. for 2 hours to be represented by the formula (I-12-h). A mixture containing the salt to be added was obtained. After cooling the obtained mixture containing the salt represented by the formula (I-12-h) to 23 ° C., 3.14 parts of the compound represented by the formula (I-1-e) was added, and further. Stirring at 23 ° C. for 18 hours gave a mixture containing a salt represented by the formula (I-12-i). To the obtained mixture containing the salt represented by the formula (I-12-i), 2 parts of p-toluenesulfonic acid and 30 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes, and then further 50 ° C. Was stirred for 2 hours. 60 parts of chloroform was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, and then the supernatant is removed. By concentration, 3.79 parts of a salt represented by the formula (I-12) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 577.1

式（Ｉ－１２－ｆ）で表される塩６．１６部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物１．６２部を添加し、さらに、５０℃で２時間攪拌することにより、式（Ｉ－１２－ｈ）で表される化合物を含む混合物を得た。得られた式（Ｉ－１２－ｈ）で表される塩を含む混合物を２３℃まで冷却した後、式（Ｉ－７－ｅ）で表される化合物３．１４部を添加し、さらに、２３℃で１８時間攪拌することにより、式（Ｉ－１６９－ｉ）で表される塩を含む混合物を得た。得られた式（Ｉ－１６９－ｉ）で表される塩を含む混合物に、ｐ－トルエンスルホン酸２部及びイオン交換水３０部を加えて２３℃で３０分間攪拌した後、さらに、５０℃で２時間攪拌した。得られた反応物に、クロロホルム６０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル３０部を加えて、２３℃で３０分間攪拌した後、上澄み液を除去し、濃縮することにより、式（Ｉ－１６９）で表される塩３．２１部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ５７７．１ Example 8: Synthesis of salt represented by the formula (I-169)

6.16 parts of the salt represented by the formula (I-12-f) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. 1.62 parts of the compound represented by the formula (I-1-g) is added to the obtained mixed solution, and the mixture is further stirred at 50 ° C. for 2 hours to be represented by the formula (I-12-h). A mixture containing the compound to be used was obtained. After cooling the obtained mixture containing the salt represented by the formula (I-12-h) to 23 ° C., 3.14 parts of the compound represented by the formula (I-7-e) was added, and further. Stirring at 23 ° C. for 18 hours gave a mixture containing a salt represented by the formula (I-169-i). To the obtained mixture containing the salt represented by the formula (I-169-i), 2 parts of p-toluenesulfonic acid and 30 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes, and then further 50 ° C. Was stirred for 2 hours. 60 parts of chloroform was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 30 parts of tert-butylmethyl ether is added to the concentrated residue, and the mixture is stirred at 23 ° C. for 30 minutes, and then the supernatant is removed. By concentrating, 3.21 parts of a salt represented by the formula (I-169) was obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 577.1

式（Ｉ－１－ｆ）で表される塩９．９６部及びクロロホルム４０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物４．４０部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物を２３℃まで冷却した後、式（ＩＸ－３－ｄ）で表される化合物６．６９部を添加し、さらに、２３℃で１８時間攪拌した。得られた反応物に、クロロホルム５０部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル５０部を加えて、２３℃で３０分間攪拌した後、ろ過することにより、式（ＩＸ－３）で表される塩９．８４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ４５１．０ Synthesis example 1: Synthesis of salt represented by the formula (IX-3)

9.96 parts of the salt represented by the formula (I-1-f) and 40 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 4.40 parts of the compound represented by the formula (I-1-g) was added, and the mixture was further stirred at 50 ° C. for 2 hours. After cooling the obtained reaction mixture to 23 ° C., 6.69 parts of the compound represented by the formula (IX-3-d) was added, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained reaction product, 50 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 50 parts of tert-butylmethyl ether is added to the concentrated residue, the mixture is stirred at 23 ° C. for 30 minutes, and then filtered to obtain the formula (IX-3). ) Was obtained in an amount of 9.84 parts.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 451.0

式（Ｉ－１－ｆ）で表される塩９．９６部及びクロロホルム４０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物４．４０部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物を２３℃まで冷却した後、式（ＩＸ－５－ｄ）で表される化合物２．１４部を添加し、さらに、２３℃で１８時間攪拌した。得られた反応物に、クロロホルム５０部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。回収された有機層をろ過した後、ろ液を濃縮し、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル５０部を加えて、２３℃で３０分間攪拌した後、ろ過することにより、式（ＩＸ－５）で表される化合物８．０１部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：Ｍ^－ ２５１．０ Synthesis example 2: Synthesis of salt represented by the formula (IX-5)

9.96 parts of the salt represented by the formula (I-1-f) and 40 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 4.40 parts of the compound represented by the formula (I-1-g) was added, and the mixture was further stirred at 50 ° C. for 2 hours. After cooling the obtained reaction mixture to 23 ° C., 2.14 parts of the compound represented by the formula (IX-5-d) was added, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained reaction product, 50 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the filtrate is concentrated, 50 parts of tert-butylmethyl ether is added to the concentrated residue, the mixture is stirred at 23 ° C. for 30 minutes, and then filtered to obtain the formula (IX-5). ) Was obtained in an amount of 8.01 parts.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 251.0

式（Ｉ－１－ｆ）で表される塩７．９７部及びクロロホルム３０部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（Ｉ－１－ｇ）で表される化合物３．５２部を添加し、さらに、５０℃で２時間攪拌した。得られた反応混合物を２３℃まで冷却した後、式（ＩＸ－６－ｄ）で表される化合物０．９９部を添加し、さらに、２３℃で１８時間攪拌した。得られた混合物に、クロロホルム５０部及びイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層に、５％シュウ酸水溶液５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。得られた有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌した後、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、濃縮残渣に、ｔｅｒｔ－ブチルメチルエーテル５０部を加えて、２３℃で３０分間攪拌した後、ろ過することにより、式（ＩＸ－６）で表される塩５．９７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（－）Ｓｐｅｃｔｒｕｍ）：［Ｍ^２－＋Ｈ］^－ ４２４．９ Synthesis example 3: Synthesis of salt represented by the formula (IX-6)

7.97 parts of the salt represented by the formula (I-1-f) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 3.52 parts of the compound represented by the formula (I-1-g) was added, and the mixture was further stirred at 50 ° C. for 2 hours. After cooling the obtained reaction mixture to 23 ° C., 0.99 parts of the compound represented by the formula (IX-6-d) was added, and the mixture was further stirred at 23 ° C. for 18 hours. To the obtained mixture, 50 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 50 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, 50 parts of tert-butylmethyl ether is added to the concentrated residue, the mixture is stirred at 23 ° C. for 30 minutes, and then filtered to obtain a salt 5 represented by the formula (IX-6). Obtained .97 copies.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): [M ^2- + H ^] -424.9

Resin synthesis The compounds (monomers) used in the resin synthesis are shown below. Hereinafter, these monomers will be referred to as "monomer (a1-1-3)" or the like according to the formula number.

Synthesis Example 4 [Synthesis of resin A1]
As the monomer, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (II-2-A-1-1) are used, and the molar ratio [monomer] is used. (A1-4-2): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (II-2-A-1-1)] has a ratio of 35:24:38: 3. Further, the monomer mixture was mixed with methyl isobutyl ketone 1.5 times by mass with respect to the total mass of all the monomers. Azobisisobutyronitrile was added to the obtained mixture as an initiator so as to be 7 mol% based on the total number of moles of all the monomers, and this was heated at 83 ° C. for about 5 hours to carry out polymerization. .. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 6 hours and then separated. The obtained organic layer is poured into a large amount of n-heptane to precipitate a resin, and the resin is filtered and recovered to obtain a resin A1 (copolymer) having a weight ^average molecular weight of about 4.8 × 103 in a yield of 78. Obtained in%. This resin A1 has the following structural units.

Synthesis Example 5 [Synthesis of resin A2]
As the monomer, a monomer (a1-4-2), a monomer (a1-1-3) and a monomer (a1-2-6) are used, and the molar ratio thereof [monomer (a1-4-2): monomer (a1-1-1). -3): Monomer (a1-2-6)] is mixed in a ratio of 38:24:38, and the monomer mixture is further multiplied by 1.5 by mass with respect to the total mass of all the monomers. Methyl isobutyl ketone was mixed. Azobisisobutyronitrile was added to the obtained mixture as an initiator so as to be 7 mol% based on the total number of moles of all the monomers, and the mixture was heated at 85 ° C. for about 5 hours to carry out polymerization. .. Then, a p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 6 hours and then separated. The obtained organic layer is poured into a large amount of n-heptane to precipitate a resin, and the resin is filtered and recovered to obtain a resin A2 (copolymer) having a weight ^average molecular weight of about 4.6 × 103 in a yield of 74. Obtained in%. This resin A2 has the following structural units.

<Preparation of resist composition>
Each component shown in Table 2 and the following solvent were mixed, and the obtained mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

＜化合物（Ｉ）＞
Ｉ－１：式（Ｉ－１）で表される塩
Ｉ－７：式（Ｉ－７）で表される塩
Ｉ－１１：式（Ｉ－１１）で表される塩
Ｉ－１２：式（Ｉ－１２）で表される塩
Ｉ－１３：式（Ｉ－１３）で表される塩
Ｉ－１７：式（Ｉ－１７）で表される塩
Ｉ－１９：式（Ｉ－１９）で表される塩
Ｉ－１６９：式（Ｉ－１６９）で表される塩
ＩＸ－１：式（ＩＸ－１）で表される塩；特開２０１３－０６０４２４号公報記載の方法で合成

ＩＸ－２：式（ＩＸ－２）で表される塩；特開２００７－１９７４３２号公報記載の方法で合成

ＩＸ－３：式（ＩＸ－３）で表される塩
ＩＸ－４：式（ＩＸ－４）で表される塩；特開２００８－１３５５１号公報記載の方法で合成

ＩＸ－５：式（ＩＸ－５）で表される塩
ＩＸ－６：式（ＩＸ－６）で表される塩
＜クエンチャー（Ｃ）＞
Ｃ１－１：特開２０１１－３９５０２号公報記載の方法で合成

＜溶剤（Ｅ）＞
プロピレングリコールモノメチルエーテルアセテート ４００部
プロピレングリコールモノメチルエーテル １００部
γ－ブチロラクトン ５部 <Resin (A)>
A1, A2: Resin A1, Resin A2
<Acid generator (B)>
B1-25: Salt represented by the formula (B1-25); synthesized by the method described in JP-A-2011-126869

<Compound (I)>
I-1: Salt represented by the formula (I-1) I-7: Salt represented by the formula (I-7) I-111: Salt represented by the formula (I-11) I-12: Formula Salt represented by (I-12) I-13: Salt represented by formula (I-13) I-17: Salt represented by formula (I-17) I-19: Salt represented by formula (I-19) Salt represented by I-169: Salt represented by formula (I-169) IX-1: Salt represented by formula (IX-1); Synthesized by the method described in JP2013-060424

IX-2: Salt represented by the formula (IX-2); synthesized by the method described in JP-A-2007-197432.

IX-3: Salt represented by the formula (IX-3) IX-4: Salt represented by the formula (IX-4); Synthesized by the method described in JP-A-2008-13551.

IX-5: Salt represented by the formula (IX-5) IX-6: Salt represented by the formula (IX-6) <Quencher (C)>
C1-1: Synthesized by the method described in JP-A-2011-390502

<Solvent (E)>
Propylene Glycol Monomethyl Ether Acetate 400 Parts Propylene Glycol Monomethyl Ether 100 Parts γ-Butyrolactone 5 Parts

(Electron beam exposure evaluation of resist composition)
A 6 inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds. The resist composition was spin-coated on this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, on a direct hot plate, the composition layer was formed by prebaking at the temperature shown in the “PB” column of Table 2 for 60 seconds. A line-and-space pattern was directly drawn on the composition layer formed on the wafer by using an electron beam lithography machine [“HL-800D 50keV” manufactured by Hitachi, Ltd.] by changing the exposure amount stepwise. ..
After exposure, post-exposure baking was performed on a hot plate at the temperature shown in the “PEB” column of Table 2 for 60 seconds, and further paddle development was performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. , A resist pattern was obtained.
The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure amount at which the line width and the space width of the 60 nm line and space pattern were 1: 1 was defined as the effective sensitivity.

Line edge roughness evaluation (LER): The fluctuation width of the unevenness of the side wall surface of the resist pattern manufactured with effective sensitivity was measured with a scanning electron microscope, and the line edge roughness was determined. The results are shown in Table 3.

From the above results, it can be seen that the salt of the present invention and the resist composition containing this salt have good line edge roughness (LER).

The resist composition of the present invention has good line edge roughness and is useful for microfabrication of semiconductors.

Claims (9)

A salt represented by the formula (I).

[In formula (I),
R ¹ and R ² each independently represent a hydroxy group or a group represented by the formula (R-1). However, at least one of R ¹ and R ² represents a group represented by the formula (R-1).

(In formula (R-1),
Q ^r1 and Q ^r2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
R ^r1 and R ^r2 independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms.
z ^r represents an integer of 0 to 6, and when z ^r is 2 or more, a plurality of R ^r1 and R ^r2 may be the same as or different from each other.
X ^r1 represents -CO-O-, -O-CO-, -O-CO-O- or -O-.
L ^r1 represents a single bond or a divalent saturated hydrocarbon group having 1 to 28 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group is -O-, -S-, -CO- or-. It may be replaced with S (O) _2- .
* Represents the binding site with Ar ¹ or Ar ² .
ZR ⁺ represents an organic cation. )
Ar ¹ represents an aromatic hydrocarbon ring having 6 to 36 carbon atoms which may have a substituent.
Ar ² represents an aromatic hydrocarbon ring having 6 to 36 carbon atoms which may have a substituent. ] The salt according to claim 1, wherein Ar ¹ is benzene which may have a substituent or naphthalene which may have a substituent. The salt according to claim 1 or 2, wherein Ar ² is benzene which may have a substituent. X ^r1 is * -CO-O- or * -O-CO- (where * represents the binding site with C (R ^r1 ) (R ^r2 ) or C (Q ^r1 ) (Q ^r2 )). The salt according to any one of claims 1 to 3. L ^r1 is a single bond, an alkanediyl group (provided that -CH _2- contained in the alkanediyl group is replaced with -O- or -CO-) or an alkanediyl group and an alicyclic saturation. A group composed of a combination with a hydrocarbon group (provided that -CH _2- contained in an alkanediyl group in the combined group may be replaced with -O- or -CO-, and the alicyclic saturated carbonization. The —CH ₂ − contained in the hydrogen group may be replaced with —O—, —S—, —CO— or —S (O) ₂ −) according to any one of claims 1 to 4. Salt. An acid generator containing the salt according to any one of claims 1 to 5. A resist composition containing the acid generator according to claim 6 and a resin having an acid unstable group. The resist composition according to claim 7, which contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. (1) A step of applying the resist composition according to claim 7 or 8 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.