JP2021187843A - Salt, acid generator, resist composition, and method for producing resist pattern - Google Patents

Abstract

To provide a salt capable of producing a resist pattern having good CD uniformity (CDU), an acid generator, and a resist composition containing the same.SOLUTION: The salt represented by formula (I), the acid generator, and the resist composition are provided. [In the formula, Q1 and Q2 each represent a fluorine atom or a perfluoroalkyl group; R1 and R2 each represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group; z represents an integer of 0-6; X1 represents *-CO-O-, *-O-CO- or the like; L1 represents a single bond or an optionally substituted hydrocarbon group; R3 represents a halogen atom; R4 represents a fluorinated alkyl group or an alkyl group, provided that -CH2- contained in these groups may be substituted with -O-, -CO- or the like; R5 represents an acid-labile group; m3 and m4 each represent an integer of 1-3 and m5 represents 1 or 2, provided that 3≤m3+m4+m5≤5; and Z+ represents an organic cation.]SELECTED DRAWING: None

Description

The present invention relates to a method for producing a salt, an acid generator, a resist composition and a resist pattern.

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

特許文献３には、下記式で表される塩を酸発生剤として含有するレジスト組成物が記載されている。

特許文献４には、下記式で表される塩を酸発生剤として含有するレジスト組成物が記載されている。

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

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

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

Patent Document 4 describes a resist composition containing a salt represented by the following formula as an acid generator.

Japanese Unexamined Patent Publication No. 2018-025789 Japanese Unexamined Patent Publication No. 2018-197226 Japanese Unexamined Patent Publication No. 2019-053287 Japanese Unexamined Patent Publication No. 2014-040387

An object of the present invention is to provide a salt capable of producing a resist pattern with better CD uniformity (CDU) than a resist pattern formed from the resist composition containing the above salt.

［式（Ｉ）中、
Ｑ^１及びＱ^２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^１及びＲ^２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^１及びＲ^２は互いに同一であっても異なってもよい。
Ｘ¹は、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−、＊−Ｏ−ＣＯ−Ｏ−又は＊−Ｏ−を表し、＊は、Ｃ（Ｒ^１）（Ｒ^２）又はＣ（Ｑ^１）（Ｑ^２）との結合部位を表す。
Ｌ¹は、単結合又は置換基を有してもよい炭素数１〜２８の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｒ^３は、ハロゲン原子を表す。
Ｒ^４は、炭素数１〜６のフッ化アルキル基又は炭素数１〜１２のアルキル基を表し、該フッ化アルキル基及び該アルキル基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｒ^５は、酸不安定基を表す。
ｍ３は、１〜３のいずれかの整数を表し、ｍ３が２以上のとき、複数のＲ^３は互いに同一であっても異なってもよい。
ｍ４は、１〜３のいずれかの整数を表し、ｍ４が２以上のとき、複数のＲ^４は互いに同一であっても異なってもよい。
ｍ５は、１又は２を表し、ｍ５が２のとき、２つのＲ^５は互いに同一であっても異なってもよい。
但し、３≦ｍ２＋ｍ４＋ｍ５≦５である。
Ｚ^＋は、有機カチオンを表す。］
［２］Ｒ^３がフッ素原子又はヨウ素原子である［１］に記載の塩。
［３］ｍ３が１又は２、ｍ５が１である［１］又は［２］に記載の塩。
［４］ｍ４が１、Ｒ^４が炭素数１〜６のアルコキシ基である［１］〜［３］のいずれかに記載の塩。
［５］ｍ３が１又は２であり、
少なくとも１つのＲ^３の結合位置が、ベンゼン環におけるＬ^１の結合位置に対してｍ位に結合している［１］〜［４］のいずれかに記載の塩。
［６］少なくとも１つのＯＲ^５の結合位置が、ベンゼン環におけるＬ^１の結合位置に対してｏ位又はｐ位に結合している［１］〜［５］のいずれかに記載の塩。
［７］Ｒ^５の酸不安定基が、式（Ｒ５−１）で表される基又は式（Ｒ５−２）で表される基である［１］〜［６］のいずれかに記載の塩。

［式（Ｒ５−１）中、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基、炭素数３〜２０の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^１４及びＲ^１５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の脂環式炭化水素基を形成する。
ｍは、０又は１を表す。
＊は結合部位を表す。］

［式（Ｒ５−２）中、Ｒ^１７及びＲ^１８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^１９は、炭素数１〜２０の炭化水素基を表すか、Ｒ^１８及びＲ^１９は互いに結合してそれらが結合する炭素原子及びＸ^ａとともに炭素数３〜２０の複素環基を形成し、該炭化水素基及び該複素環基に含まれる−ＣＨ_２−は、−Ｏ−又は−Ｓ−で置き換わってもよい。
Ｘ^ａは、酸素原子又は硫黄原子を表す。
ｎは、０又は１を表す。
＊は結合部位を表す。］
［８］Ｌ¹が、単結合、炭素数１〜６のアルカンジイル基又は炭素数１〜６のアルカンジイル基と炭素数３〜１８の脂環式飽和炭化水素基とを組み合わせてなる基（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く、該脂環式飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。）である［１］〜［７］のいずれかに記載の塩。
［９］Ｌ¹が、単結合、炭素数１〜６のアルカンジイル基又は^＊−Ｌ^４−ＣＯ−Ｏ−（但し、Ｌ^４は、置換基を有してもよい炭素数１〜２２の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。）である［１］〜［８］のいずれかに記載の塩。
［１０］［１］〜［９］のいずれかに記載の塩を含有する酸発生剤。
［１１］［１０］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。
［１２］酸不安定基を有する樹脂が、式（ａ１−１）で表される構造単位及び式（ａ１−２）で表される構造単位からなる群より選ばれる少なくとも１種を含む［１１］記載のレジスト組成物。

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は＊−Ｏ−（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^a4及びＲ^a5は、それぞれ独立に、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１〜６のアルキル基を表す。
Ｒ^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２〜８のアルケニル基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組合せた基を表す。
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。］
［１３］酸不安定基を有する樹脂が、さらに式（ａ２−Ａ）で表される構造単位を含む［１１］又は［１２］記載のレジスト組成物。

［式（ａ２−Ａ）中、
Ｒ^a50は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１〜６のアルキル基を表す。
Ｒ^a51は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜１２のアルコキシアルキル基、炭素数２〜１２のアルコキシアルコキシ基、炭素数２〜４のアルキルカルボニル基、炭素数２〜４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a50は、単結合又は^＊−Ｘ^a51−（Ａ^a52−Ｘ^a52）_nｂ−を表し、＊は−Ｒ^a50が結合する炭素原子との結合部位を表す。
Ａ^a52は、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。］
［１４］酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩をさらに含有する［１１］〜［１３］のいずれかに記載のレジスト組成物。
［１５］（１）［１１］〜［１４］のいずれかに記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程、を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A salt represented by the formula (I).

[In formula (I),
Q ¹ and ^{Q 2} each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
R ¹ and R ² independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms.
z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R ¹ and R ² may be the same or different from each other.
X ¹ represents * -CO-O-, * -O-CO-, * -O-CO-O- or * -O-, and * is C (R ¹ ) (R ² ) or C (Q). ¹⁾ represents the binding site to ^{(Q 2).}
L ¹ represents a hydrocarbon group having 1 to 28 carbon atoms which may have a single bond or a substituent, and −CH ₂ − contained in the hydrocarbon group is −O−, −S−, −SO. _It may be replaced with 2- or -CO-.
R ³ represents a halogen atom.
R ⁴ represents an alkyl group having 1 to 12 fluorinated alkyl group carbon atoms or 1 to 6 carbon atoms, -CH ₂ contained in the fluorinated alkyl group and the alkyl group - is -O- or -CO It may be replaced with-.
R ⁵ is an acid labile group.
m3 represents an integer of 1 to 3, when m3 is 2 or more, plural R ³ may be the same or different from each other.
m4 represents an integer of 1 to 3, when m4 is 2 or more, plural R ⁴ may be the same or different from each other.
m5 represents 1 or 2, when m5 is 2, the two R ⁵ may be the same or different from each other.
However, 3 ≦ m2 + m4 + m5 ≦ 5.
Z ⁺ represents an organic cation. ]
[2] The salt according to [1], wherein ^{R 3 is a fluorine atom or an iodine atom.}
[3] The salt according to [1] or [2], wherein m3 is 1 or 2, and m5 is 1.
Salt according to any one of [4] m4 is 1, ^{R 4} is an alkoxy group having 1 to 6 carbon atoms [1] to [3].
[5] m3 is 1 or 2,
The salt according to any one of [1] to [4], wherein the bond position of at least one R ^{3 is bonded to the m position with respect to the bond position of L 1 in the benzene ring.}
[6] at least one coupling position of the OR ⁵ is salt according to any one of bonded to o-position or p-position to the bonding position of L ¹ in the benzene ring [1] to [5].
[7] acid labile group ^{R 5} is a group represented by the formula (R5-1) or a group represented by the formula in (R5-2) [1] ~ according to any one of [6] salt.

Wherein ^{(R5-1), R 14, R} 15 and ^{R 16} are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, alicyclic having 3 to 20 carbon atoms Representing a hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, R ¹⁴ and R ¹⁵ are alibo rings having 3 to 20 carbon atoms together with carbon atoms bonded to each other and bonded to each other. Form a hydrocarbon group.
m represents 0 or 1.
* Represents the binding site. ]

[In the formula (R5-2), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁹ represents a hydrocarbon group having 1 to 20 carbon atoms. carded, R ¹⁸ and R ¹⁹ form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atoms and X ^a to which they are attached,, -CH ₂ contained in the hydrocarbon group and heterocyclic group -May be replaced by -O- or -S-.
^Xa represents an oxygen atom or a sulfur atom.
n represents 0 or 1.
* Represents the binding site. ]
[8] A group in which L ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms or an alkanediyl group having 1 to 6 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms in combination ( _{However, −CH 2} − contained in the alkanediyl group may be _{replaced with −O − or −CO −, and −CH 2} − contained in the alicyclic saturated hydrocarbon group is −O −,. -S -, - salt according to any or -CO- may be substituted with) a [1] ~ [7] - SO 2..
[9] L ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms or ^* -L ^4- CO-O- (where L ⁴ is a substituent having 1 to 22 carbon atoms. represents a hydrocarbon group, -CH ₂ contained in the hydrocarbon group - is, -O -, - S -, - SO 2 -. of or -CO- may be substituted with) a [1] - [ 8] The salt according to any one of.
[10] An acid generator containing the salt according to any one of [1] to [9].
[11] A resist composition containing the acid generator according to [10] and a resin having an acid unstable group.
[12] The resin having an acid unstable group contains at least one selected from the group consisting of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) [11]. ] The resist composition described.

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent -O- or * -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents -CO-. Represents a bond with.
R ^a4 and R ^a5 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a6 and R ^a7 are independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group or a group combining these groups.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ]
[13] The resist composition according to [11] or [12], wherein the resin having an acid unstable group further contains a structural unit represented by the formula (a2-A).

[In the 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 has 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, and a carbon number of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or ^* −X ^a51 − (A ^a52 −X ^a52 ) _nb −, and * represents a binding site with a carbon atom to which ^{−R a50 is bonded.}
A ^a52 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. ]
[14] The resist composition according to any one of [11] to [13], which further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[15] (1) A step of applying the resist composition according to any one of [11] to [14] onto a substrate.
(2) A step of drying the applied composition to form a composition layer,
(3) Step of exposing the composition layer,
A method for producing a resist pattern, which comprises (4) 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 containing the salt of the present invention, a resist pattern can be produced with good CD uniformity (CDU).

As used herein, unless otherwise noted, "(meth) acrylate" means "at least one selected from the group consisting of acrylates and methacrylates". Notations such as "(meth) acrylic acid" and "(meth) acryloyl" have the same meaning. 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. Is -O - - -CH ₂ contained in the hydrocarbon group or the like, - S -, - CO- or -SO ₂ - when replaced, it is assumed to apply similar examples in each group. The "combined group" means a group in which two or more kinds of exemplified groups are bonded, and the valence of these groups may be appropriately changed depending on the bonding form. "Derived" or "derived" means that the polymerizable C = C bond contained in the molecule becomes a -C-C- group by polymerization. If a steric isomer is present, it includes all steric isomers.
In the present specification, the "solid content of the resist composition" means the total amount of the components excluding the solvent (E) described later from the total amount of the resist composition.

［式（Ｉ）中、全ての符号は、それぞれ前記と同じ意味を表す。］ [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), all the symbols have the same meanings as described above. ]

In the formula (I), ^{the perfluoroalkyl groups of Q 1} , Q ² , R ¹ and R ² 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 ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.
R ¹ and R ² are independently, preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom.
z is preferably 0 or 1.
X ¹ is preferably * -CO-O-, * -O-CO-O- or * -O-CO-, and is preferably * -CO-O- or * -O-CO-O-. Is more preferable (* represents the binding site with ^{C (R 1} ) (R ² ) or C (Q ¹ ) (Q ^2)).

２価の芳香族炭化水素基としては、フェニレン基、ナフチレン基、アントリレン基、ビフェニレン基、フェナントリレン基等のアリーレン基等の芳香族炭化水素基が挙げられる。芳香族炭化水素基の炭素数は、好ましくは６〜１８であり、より好ましくは６〜１４であり、さらに好ましくは６〜１０である。
２価の鎖式炭化水素基、単環式又は多環式の２価の脂環式炭化水素基及び２価の芳香族炭化水素基のうち、２種以上を組み合わせた基としては、脂環式炭化水素基とアルカンジイル基とを組み合わせた基、芳香族炭化水素基とアルカンジイル基とを組み合わせた基及び脂環式炭化水素基と芳香族炭化水素基とを組み合わせた基が挙げられる。組み合わせにおいて、脂環式炭化水素基、芳香族炭化水素基、鎖式炭化水素基は、それぞれ２種以上を組み合わせてもよい。また、いずれの基がＸ^１に結合していてもよい。
脂環式炭化水素基とアルカンジイル基とを組み合わせた基としては、例えば、−２価の脂環式炭化水素基−アルカンジイル基−、−アルカンジイル基−２価の脂環式炭化水素基−アルカンジイル基−、−アルカンジイル基−２価の脂環式炭化水素基−等が挙げられる。
芳香族炭化水素基とアルカンジイル基とを組み合わせた基としては、例えば、−２価の芳香族炭化水素基−アルカンジイル基−、−アルカンジイル基−２価の芳香族炭化水素基−アルカンジイル基−、−アルカンジイル基−２価の芳香族炭化水素基−等が挙げられる。
脂環式炭化水素基と芳香族炭化水素基とを組み合わせた基としては、−芳香族炭化水素基−脂環式炭化水素基−、−脂環式炭化水素基−芳香族炭化水素基−、−脂環式炭化水素基−芳香族炭化水素基−脂環式炭化水素基−等が挙げられる。
Ｌ^１の炭素数１〜２８の２価の炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−Ｓ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｌ^１の炭素数１〜２８の炭化水素基に含まれる−ＣＨ_２−が−Ｏ−、−Ｓ−、−ＳＯ_２−又は−ＣＯ−に置き換わっている場合、置き換わる前の炭素数を該炭化水素基の炭素数とする。
Ｌ¹における炭化水素基に含まれる−ＣＨ₂−が、−Ｏ−、−Ｓ−、−ＳＯ_２−又は−ＣＯ−に置き換わった基としては、ヒドロキシ基（メチル基中に含まれる−ＣＨ₂−が、−Ｏ−に置き換わった基）、チオール基（メチル基中に含まれる−ＣＨ₂−が、−Ｓ−に置き換わった基）、カルボキシ基（エチル基中に含まれる−ＣＨ₂−ＣＨ₂−が、−Ｏ−ＣＯ−に置き換わった基）、アルコキシ基（アルキル基中に含まれる任意の位置の−ＣＨ₂−が、−Ｏ−に置き換わった基）、アルコキシカルボニル基（アルキル基中に含まれる任意の位置の−ＣＨ₂−ＣＨ₂−が、−Ｏ−ＣＯ−に置き換わった基）、アルキルカルボニル基（アルキル基中に含まれる任意の位置の−ＣＨ₂−が、−ＣＯ−に置き換わった基）、アルキルカルボニルオキシ基（アルキル基中に含まれる任意の位置の−ＣＨ₂−ＣＨ₂−が、−ＣＯ−Ｏ−に置き換わった基）、アルカンジイルオキシ基（アルカンジイル基中に含まれる任意の位置の−ＣＨ₂−が、−Ｏ−に置き換わった基）、アルカンジイルオキシカルボニル基（アルカンジイル基中に含まれる任意の位置の−ＣＨ₂−ＣＨ₂−が、−Ｏ−ＣＯ−に置き換わった基）、アルカンジイルカルボニル基（アルカンジイル基中に含まれる任意の位置の−ＣＨ₂−が、−ＣＯ−に置き換わった基）、アルカンジイルカルボニルオキシ基（アルカンジイル基中に含まれる任意の位置の−ＣＨ₂−ＣＨ₂−が、−ＣＯ−Ｏ−に置き換わった基）、アルキルチオ基（アルキル基中に含まれる任意の位置の−ＣＨ₂−が、−Ｓ−に置き換わった基）、アルキルスルホニル基（アルキル基中に含まれる任意の位置の−ＣＨ₂−が、−ＳＯ_２−に置き換わった基）、シクロアルコキシ基、シクロアルキルアルコキシ基、アルコキシカルボニルオキシ基、芳香族炭化水素基−カルボニルオキシ基、これらの基うち２種以上を組み合わせた基等が挙げられる。 Examples of the divalent hydrocarbon group in L ¹ include a divalent chain hydrocarbon group such as an alcandiyl group, a monocyclic or polycyclic (including spiro ring) divalent alicyclic hydrocarbon group, and the like. A divalent aromatic hydrocarbon group may be mentioned, and a group in which two or more of these groups are combined (for example, a divalent hydrocarbon group formed from an alicyclic hydrocarbon group and an alcandiyl group) may be used. ..
The alkanediyl group includes a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, and a 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 Linear group such as group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group. Alkanediyl group; and 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 and other branched alkanediyl groups. The group is mentioned. The number of carbon atoms of the alkanediyl group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, and even more preferably 1 to 4.
The monocyclic or polycyclic divalent alicyclic hydrocarbon group includes cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane. Monocyclic divalent alicyclic hydrocarbon group which is a cycloalkandyl group such as -1,5-diyl group; and norbornan-1,4-diyl group, norbornan-2,5-diyl group, adamantan- Examples thereof include polycyclic divalent divalent alicyclic hydrocarbon groups such as 1,5-diyl group and adamantan-2,6-diyl group. The alicyclic hydrocarbon group preferably has 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12.
Specifically, examples of the alicyclic hydrocarbon group include the groups represented below. The binding site can be any position.

Examples of the divalent aromatic hydrocarbon group include aromatic hydrocarbon groups such as an arylene group such as a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group and a phenanthrylene group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10.
Of the divalent chain hydrocarbon group, the monocyclic or polycyclic divalent alicyclic hydrocarbon group, and the divalent aromatic hydrocarbon group, the alicyclic group is a combination of two or more. Examples thereof include a group in which a formal hydrocarbon group and an alcandyl group are combined, a group in which an aromatic hydrocarbon group and an alcandyl group are combined, and a group in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined. In the combination, two or more kinds of alicyclic hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group may be combined. Further, any group may be bonded to X ^1.
Examples of the group in which the alicyclic hydrocarbon group and the alkandiyl group are combined include a -valent alicyclic hydrocarbon group-alcandiyl group-and a-alkandyl group-two-valent alicyclic hydrocarbon group. -Alcandiyl group-, -Alcandiyl group-2 valent alicyclic hydrocarbon group-etc.
Examples of the group in which the aromatic hydrocarbon group and the alcandiyl group are combined include a -valent aromatic hydrocarbon group-alkandyl group-, an alcandiyl group, and a -valent aromatic hydrocarbon group-alkandyl. Examples thereof include a group-, an arcandyl group, a -valent aromatic hydrocarbon group, and the like.
The groups that combine the alicyclic hydrocarbon group and the aromatic hydrocarbon group include: -aromatic hydrocarbon group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, -Ali ring hydrocarbon group-Aromatic hydrocarbon group-Ali ring hydrocarbon group-etc.
_{-CH 2-} contained in the divalent hydrocarbon group having ¹ to 28 carbon atoms of L 1 may be replaced with -O-, -S-, -SO _{2- or -CO-.}
When _{-CH 2-} contained in the hydrocarbon group having ¹ to 28 carbon atoms of L1 is replaced with -O-, -S-, -SO _2- or -CO-, the number of carbon atoms before the replacement is replaced with the hydrocarbon. The carbon number of the hydrogen group.
Is, -O - - -CH ₂ contained in the hydrocarbon group in ^{L 1, - S -, -} SO 2 - or Examples of the group replaced by -CO-, hydroxy group (-CH ₂ contained in the methyl group -Is a group in which -O- is replaced), a thiol group (a group in which -CH ₂ − contained in the methyl group is replaced with -S-), and a carboxy group (a group in which -CH ₂ -CH is contained in the ethyl group). ₂ − is a group in which −O—CO− is replaced), an alkoxy group (a group in which −CH ₂ − at an arbitrary position contained in an alkyl group is replaced with −O−), an alkoxycarbonyl group (in an alkyl group). _{-CH 2} -CH _{2- at} any position contained in is replaced with -O-CO-), alkylcarbonyl group (-CH _2-at any position contained in the alkyl group is -CO- (Group replaced with), alkylcarbonyloxy group (group in which −CH ₂ −CH ₂ − at any position contained in the alkyl group is replaced with −CO−O−), alkanediyloxy group (in alkanediyl group) _{-CH 2-at} any position contained in is replaced with -O-), alkanediyloxycarbonyl group (-CH ₂ -CH _2-at any position contained in the alkanediyl group is -O- -CO-replaced group), alkanediylcarbonyl group (-CH ₂ − at any position contained in the alkanediyl group is replaced with -CO-), alkanediylcarbonyloxy group (alkanediyl group) _{-CH 2} -CH _{2- at} any position contained in is replaced with -CO-O-), alkylthio group (-CH _2-at any position contained in the alkyl group is replaced with -S- Substituted group), alkylsulfonyl group (a group in which −CH ₂ − at _{any position contained in the alkyl group is replaced with −SO 2} −), cycloalkoxy group, cycloalkylalkoxy group, alkoxycarbonyloxy group, aromatic Examples thereof include group hydrocarbon groups-carbonyloxy groups, and groups in which two or more of these groups are combined.

Examples of the alkoxy group include an alkoxy group having 1 to 17 carbon atoms, and examples thereof include 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 and a nonyloxy group. Groups, decyloxy groups, undecyloxy groups and the like can be mentioned.
The alkoxycarbonyl group, an alkylcarbonyl group and an alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group.
Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 17 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include an alkylcarbonyl group having 2 to 18 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a butyryl group. Examples of the alkylcarbonyloxy group include an alkylcarbonyloxy group having 2 to 17 carbon atoms, and examples thereof include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
Examples of the alkanediyloxy group include an alkanediyloxy group having 1 to 17 carbon atoms, and examples thereof include a methyleneoxy group, an ethyleneoxy group, a propandiyloxy group, a butanediyloxy group, and a pentaneyloxy group.
Examples of the alkanediyloxycarbonyl group include an alkanediyloxycarbonyl group having 2 to 17 carbon atoms, and examples thereof include a methyleneoxycarbonyl group, an ethyleneoxycarbonyl group, a propandiyloxycarbonyl group, and a butanediyloxycarbonyl group. .. Examples of the alkanediylcarbonyl group include an alkanediylcarbonyl group having 2 to 18 carbon atoms, and examples thereof include a methylenecarbonyl group, an ethylenecarbonyl group, a propandiylcarbonyl group, a butanjiylcarbonyl group, and a pentaneylcarbonyl group. Examples of the alkanediylcarbonyloxy group include an alkanediylcarbonyloxy group having 2 to 17 carbon atoms, and examples thereof include a methylenecarbonyloxy group, an ethylenecarbonyloxy group, a propandiylcarbonyloxy group, and a butanediylcarbonyloxy group. ..
Examples of the alkylthio group include an alkylthio group having 1 to 17 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, and a propylthio group.
Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4.
Examples of the cycloalkoxy group include a cycloalkoxy group having 3 to 17 carbon atoms, and examples thereof include a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include a cycloalkylalkoxy group having 4 to 17 carbon atoms, and examples thereof include a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include an alkoxycarbonyloxy group having 2 to 16 carbon atoms, and examples thereof include a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyloxy group include an aromatic hydrocarbon group-carbonyloxy group having 7 to 17 carbon atoms, and examples thereof include a benzoyloxy group.
Further, -CH ₂ contained in the alicyclic hydrocarbon group - is, -O -, - CO- or -SO ₂ - as a substituted radicals, the group, and the like below. The binding site can be any position. Of the groups listed below, the position of -O- may be replaced by -S-.

The ^{substituent that L 1} may have includes a hydroxy group, a carboxy 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 an alkoxy group having 2 to 13 carbon atoms. Examples thereof include a carbonyl group, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group combining these groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a nonyl 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 substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a halogen atom, more preferably an alkyl group or a halogen atom having 1 to 4 carbon atoms, and a methyl group or a fluorine atom. Is even more preferable.

L ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms (however, −CH ₂ − contained in the alkanediyl group may be replaced with −O− or −CO−), and the number of carbon atoms. A group consisting of a combination of an alkanediyl group of 1 to 6 and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH ₂ − contained in the alkanediyl group becomes -O- or -CO-. _{It may be replaced, and -CH 2-} contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -SO _2- or -CO-) or 1 carbon number. A group consisting of a combination of an alkanediyl group of ~ 6 and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that −CH ₂ − contained in the alkanediyl group is −O. It may be replaced with − or −CO−), and is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms, an alkanediyl group having 1 to 4 carbon atoms and an alicyclic having 3 to 18 carbon atoms. A group composed of a combination with a type hydrocarbon group (however, −CH ₂ − contained in the alkanediyl group may be replaced with −O − or −CO −, and is contained in the alicyclic hydrocarbon group. −CH ₂ − may be replaced with −O−− or −CO−) or a group consisting of a combination of an alkanediyl group having 1 to 4 carbon atoms and a phenylene group which may have a substituent (may be substituted with −O−− or −CO−). _{However, it is more preferable that −CH 2} − contained in the hydrocarbon group is replaced with −O − or −CO−). In addition, the combination of the arcandyl group and the alicyclic hydrocarbon group or the aromatic hydrocarbon group here is * -alcandiyl group-an alicyclic hydrocarbon group or an aromatic hydrocarbon group-, * -alicyclic. Examples thereof include a formal hydrocarbon group or an aromatic hydrocarbon group-alcandiyl group-, * -an alicyclic hydrocarbon group-an alicyclic hydrocarbon group-an alcandyl group-and the like. * Represents a bond with ^{X 1.}
For example, L ¹ represents ^* -L ^4- CO-O- (wherein L ⁴ represents a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent and is contained in the hydrocarbon group-. CH ₂ - is, -O -, - S -, - SO 2 -. of or -CO- may be substituted with) may also be mentioned. In this case, L ⁴ is an alcandiyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, −CH ₂ − contained in the alicyclic hydrocarbon group is −O. -, _{-S-, -SO 2-} or -CO- may be replaced), an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and an alkane having 1 to 4 carbon atoms. A group consisting of a combination of a diyl group and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that −CH ₂₋ contained in the alkandiyl group may be replaced with −O− or −CO−. _{, -CH 2-} contained in the alicyclic hydrocarbon group may be replaced with -O-, -S-, -SO _2- or -CO-) or alkandyl having 1 to 4 carbon atoms. A group consisting of a combination of a group and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that −CH ₂₋ contained in the alkandiyl group is −O− or −CO−. (May be replaced with)), and the alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that −CH ₂ − contained in the alicyclic hydrocarbon group is −O− or −. It may be replaced with CO-), a phenylene group which may have a substituent, a group consisting of an alcandiyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. _{(However, −CH 2} − contained in the alkandiyl group may be replaced with −O − or −CO _{−, and −CH 2} − contained in the alicyclic hydrocarbon group is −O − or. It may be replaced with −CO−) or a group consisting of a combination of an alkylandyl group having 1 to 4 carbon atoms and a phenylene group which may have a substituent (provided that −CH is contained in the alkylandyl group. ₂ − may be replaced with −O− or −CO−).

Examples of the halogen atom represented by R ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R ³ is preferably a fluorine atom or an iodine atom.
The m3 is preferably 1 or 2.
Examples of the alkyl group having 1 to 12 carbon atoms R ^4, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, tert- butyl group, a pentyl group, a hexyl group, an octyl group, and nonyl group Alkyl groups can be mentioned. The number of carbon atoms of the alkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4.
When _{−CH 2} − contained in the alkyl group in ^{R 4} is replaced with −O − or −CO −, the carbon number before the replacement is taken as the total carbon number of the alkyl group.
Group, replacing a -O- - -CH ₂ contained in the alkyl group in R ⁴ - is, as a group replaced by -O- or -CO-, -CH ₂ hydroxy groups (contained in the methyl group ), A carboxy group (a group in which −CH ₂ −CH ₂ − contained in an ethyl group is replaced with −O—CO−), an alkoxy group (a group in which −CH ₂ − at an arbitrary position contained in an alkyl group is replaced), -O-replaced group), alkoxycarbonyl group (group in which -CH ₂ -CH _{2- at} any position contained in the alkyl group is replaced with -O-CO-), alkylcarbonyl group (in the alkyl group) _{-CH 2-at} any position contained in is replaced with -CO-), alkylcarbonyloxy group (-CH ₂ -CH _2-at any position contained in the alkyl group is -CO-O Groups replaced with −), groups in which two or more of these groups are combined, and the like can be mentioned.
The fluorinated alkyl group having 1 to 6 carbon atoms R ^4, trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoro Ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluoropentyl group , 2,2,3,3,4,5,5,5-Nonafluoropentyl group, perfluorohexyl group and other fluorinated alkyl groups. The alkyl fluoride group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.
R ⁴ -CH ₂ contained in the fluorinated alkyl group in - is, -O- or Examples of the group replaced by -CO-, -CH ₂ arbitrary position included in the fluoride alkoxy groups (fluorinated alkyl group -Is a group replaced by -O-), an alkoxycarbonyl group fluoride (a group in which -CH ₂ -CH _{2- at} any position contained in the alkyl fluoride group is replaced by -O-CO-), Alkoxyfluorinated carbonyl group (a group in which −CH ₂ − at any position contained in an alkyl fluoride group is replaced with −CO −), an alkylfluorinated carbonyloxy group (any contained in an alkyl fluoride group). A group in which −CH ₂ −CH ₂ − at the position is replaced with −CO−O−), a group in which two or more of these groups are combined, and the like can be mentioned.
Examples of the alkoxy group include an alkoxy group having 1 to 11 carbon atoms, and examples thereof 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 and a nonyloxy group. Examples thereof include a decyloxy group and an undecyloxy group.
Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 11 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group.
Examples of the alkylcarbonyl group include an alkylcarbonyl group having 2 to 12 carbon atoms, and examples thereof include an acetyl group, a propionyl group and a butyryl group.
Examples of the alkylcarbonyloxy group include an alkylcarbonyloxy group having 2 to 11 carbon atoms, and examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.
Examples of the fluorinated alkoxy group, the fluorinated alkoxycarbonyl group, the fluorinated alkylcarbonyl group and the fluorinated alkylcarbonyloxy group include a fluorinated alkoxy group having 1 to 5 carbon atoms, a fluorinated alkoxycarbonyl group having 2 to 5 carbon atoms, and carbon. Examples thereof include a fluorinated alkylcarbonyl group having a number of 2 to 6 and a fluorinated alkylcarbonyloxy group having 2 to 5 carbon atoms. For example, one or more hydrogen atoms of the groups exemplified above may be replaced with a fluorine atom.
R ⁴ is, -CH ₂ contained in the fluorinated alkyl group or an alkyl group (the fluorinated alkyl group and the alkyl group having 1 to 8 carbon atoms having 1 to 4 carbon atoms - is, -O- or -CO- in It may be replaced), more preferably an alkoxy group having 1 to 6 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms.
For m4, 1 or 2 is preferable, and 1 is more preferable.

［式（Ｒ５−１）中、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基、炭素数３〜２０の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^１４及びＲ^１５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の脂環式炭化水素基を形成する。
ｍは、０又は１を表す。
＊は結合部位を表す。］

［式（Ｒ５−２）中、Ｒ^１７及びＲ^１８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^１９は、炭素数１〜２０の炭化水素基を表すか、Ｒ^１８及びＲ^１９は互いに結合してそれらが結合する炭素原子及びＸ^ａとともに炭素数３〜２０の複素環基を形成し、該炭化水素基及び該複素環基に含まれる−ＣＨ_２−は、−Ｏ−又は−Ｓ−で置き換わってもよい。
Ｘ^ａは、酸素原子又は硫黄原子を表す。
ｎは、０又は１を表す。
＊は結合部位を表す。］ The acid unstable group of R ⁵ means a group which forms a hydroxy group by desorbing the acid unstable group when it comes into contact with an acid.
Examples of the acid unstable group include a group represented by the formula (R5-1) (hereinafter, sometimes referred to as “acid unstable group (R5-1)”) and a group represented by the formula (R5-2). Group (hereinafter, in some cases, referred to as “acid unstable group (R5-2)”) may be mentioned.

Wherein ^{(R5-1), R 14, R} 15 and ^{R 16} are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, alicyclic having 3 to 20 carbon atoms Representing a hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, R ¹⁴ and R ¹⁵ are alibo rings having 3 to 20 carbon atoms together with carbon atoms bonded to each other and bonded to each other. Form a hydrocarbon group.
m represents 0 or 1.
* Represents the binding site. ]

[In the formula (R5-2), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁹ represents a hydrocarbon group having 1 to 20 carbon atoms. carded, R ¹⁸ and R ¹⁹ form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atoms and X ^a to which they are attached,, -CH ₂ contained in the hydrocarbon group and heterocyclic group -May be replaced by -O- or -S-.
^Xa represents an oxygen atom or a sulfur atom.
n represents 0 or 1.
* Represents the binding site. ]

Ｒ^１４、Ｒ^１５及びＲ^１６の芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニル基、フェナントリル基等のアリール基が挙げられる。Ｒ^aa1、Ｒ^aa2及びＲ^aa3の芳香族炭化水素基の炭素数は、好ましくは６〜１４であり、より好ましくは６〜１０である。 Alkyl groups represented by R ¹⁴ , R ¹⁵ and R ¹⁶ include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. And so on. The alkyl groups of R ¹⁴ , R ¹⁵ and R ¹⁶ have preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
The alkenyl groups of R ¹⁴ , R ¹⁵ and R ¹⁶ include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group and isooctynyl group. Nonenyl group is mentioned.
The ^{alicyclic hydrocarbon group represented by R 14} , R ¹⁵ and R ¹⁶ 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 ¹⁴ , R ¹⁵ and R ^{16 has preferably 3 to 16 carbon atoms.}

Examples of the aromatic hydrocarbon group of R ¹⁴ , R ¹⁵ and R ¹⁶ include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group. ^{The aromatic hydrocarbon groups of Raa1} , ^Raa2 and ^Raa3 have preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.

Examples of the group in which the alkyl group and the alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, a norbornylethyl group and the like. Can be mentioned.
Examples of the group in which the alkyl group and the aromatic hydrocarbon group are combined include a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, and a 2,6-diethylphenyl group. Examples include a group, a 2-methyl-6-ethylphenyl group and the like.
Examples of the group in which the alicyclic hydrocarbon group and the aromatic hydrocarbon group are combined include a p-cyclohexylphenyl group and a p-adamantylphenyl group.
m is preferably 1.

^{Examples of -C (R 14} ) (R ¹⁵ ) (R ¹⁶ ) in the case where R ¹⁴ and R ¹⁵ are bonded to each other to form an alicyclic hydrocarbon group together with the carbon atom to which they are bonded include the following groups. Be done. The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms, and more preferably 3 to 12 carbon atoms. * Represents a bond with -O-.

Ｒ^１７及びＲ^１８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。
ｎは、好ましくは０である。 Examples of the hydrocarbon group of R ¹⁷ , R ¹⁸ and R ¹⁹ include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group formed by combining these.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
The combined group includes a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (alkylcycloalkyl group or cycloalkylalkyl group, etc.), an aralkyl group (benzyl group, etc.), and aromatic carbonization having an alkyl group. Hydrogen group (p-methylphenyl group, p-tert-butylphenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), fat Examples thereof include an aromatic hydrocarbon group having a cyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group (phenylcyclohexyl group, etc.) and the like.
When R ¹⁸ and R ¹⁹ are bonded to each other to form a heterocycle together with the carbon atom to which they are bonded and X ¹ , the following groups are used as ^{-C (R 17} ) (R ¹⁸ ) -X ^a- R ^19. Can be mentioned. * Represents a bond.

Of R ¹⁷ and R ¹⁸ , at least one is preferably a hydrogen atom.
n is preferably 0.

Specific examples of the acid unstable group (R5-1) include the following groups. * Represents a bond.

Specific examples of the acid unstable group (R5-2) include the following groups. * Represents a bond.

m5 is preferably 1.

Bonding position of -OR ⁵ is, o-position to the bonding position of L ¹ in the benzene ring, m-position may be either p-position, o-position or p-position is preferred.
The bond position of R ³ may be any of the о-position, the m-position, and the p-position with respect to the bond position ^{of L 1 on the benzene ring, but the о-position and the m-position are preferable, and the m-position is more preferable.} If m3 is 2, the two R ^3, relative to the bonding position of L ¹ in the benzene ring, and more preferably both are position m.
The bond position of R ⁴ may be any of the о-position, the m-position, and the p-position with respect to the bond position ^{of L 1 on the benzene ring, but the m-position is preferable.}

Examples of the anion (I) include anions represented by the following formulas (Ia-1) to (Ia-46).

Examples of the Z ⁺ organic cation include an organic onium cation, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation and the like. 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、炭素数１〜１８の脂肪族炭化水素基、炭素数１〜１２のフッ化アルキル基又は炭素数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、ハロゲン原子、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、該鎖式炭化水素基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、ハロゲン原子、ヒドロキシ基、炭素数１〜１２のフッ化アルキル基、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。
ｕ２が０のとき、ｏ２、ｐ２、ｑ２及びｒ２のうちいずれか１つは１以上であり、Ｒ^b13〜Ｒ^b1６のうち少なくとも１つはハロゲン原子であることが好ましく、ｕ２が１のとき、ｏ２、ｐ２、ｓ２、ｔ２、ｑ２及びｒ２のうちいずれか１つは１以上であり、Ｒ^b13〜Ｒ^b18のうち少なくとも１つはハロゲン原子であることが好ましい。

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. It may be substituted, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The aromatic hydrocarbon group may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms, or carbon. It may be substituted with the number 1 to 12 alkoxy groups.
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 halogen atom, 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. The contained 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 carbon atom. 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 halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 12 carbon atoms, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. ..
L ^b31 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5.
q2 and r2 each independently represent an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13s are the same or different, when p2 is 2 or more, a plurality of R ^b14s are the same or different, and when q2 is 2 or more, a plurality of R ^b15s are the same or different. when r2 is 2 or more, plural R ^b16 same or different, when s2 is 2 or more, plural R ^b17 same or different, when t2 is 2 or more, plural R ^b18 same or different different.
When u2 is 0, any one of o2, p2, q2 and r2 is preferably 1 or more, and ^{at least one of R b13 to} R ^b16 is preferably a halogen atom, and when u2 is 1, it is preferable. It is preferable that any one of o2, p2, s2, t2, q2 and r2 is 1 or more, and ^{at least one of R b13 to} R ^b18 is a halogen atom.

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 groups of R b9 to} R ^b12 preferably have 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.

The alicyclic hydrocarbon group in which the hydrogen atom is substituted with an aliphatic hydrocarbon group includes 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.
The fluoride alkyl group represents an alkyl group having 1 to 12 carbon atoms having a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and perfluorobutyl. The alkyl fluoride group preferably has 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.

Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a biphenyl group, a naphthyl group and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and the aromatic hydrocarbon group having a chain hydrocarbon group (trill group, xylyl group, cumenyl group, mesityl). Aromatic hydrocarbon group having an alicyclic hydrocarbon group (group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) p-cyclohexylphenyl group, p-adamantylphenyl group, etc.) and the like.
When the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are used. Is preferable.
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. * Represents the binding site.

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.

The salt (I) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the salt (I), the formulas (Ia-2) to (Ia-4), the formulas (Ia-12) to (Ia-15), and the formulas (Ia-17) to (Ia-24) are preferable. ), Formula (Ia-33) to formula (Ia-36), formula (Ia-39), formula (Ia-40), formula (Ia-43) to formula (Ia-46). Examples include combinations of anions with cations (b2-1), cations (b2-2), cations (b2-3) or cations (b2-4).

なかでも、塩（Ｉ）は、塩（Ｉ−１）〜塩（Ｉ−４）、塩（Ｉ−９）、塩（Ｉ−１０）、塩（Ｉ−１３）〜塩（Ｉ−２３）、塩（Ｉ−３３）〜塩（Ｉ−３６）、塩（Ｉ−４１）、塩（Ｉ−４２）、塩（Ｉ−４５）〜塩（Ｉ−５５）、塩（Ｉ−６５）〜塩（Ｉ−６８）、塩（Ｉ−７３）、塩（Ｉ−７４）、塩（Ｉ−７７）〜塩（Ｉ−８７）、塩（Ｉ−９７）〜塩（Ｉ−１００）、塩（Ｉ−１０５）、塩（Ｉ−１０６）、塩（Ｉ−１０９）〜塩（Ｉ−１１９）、塩（Ｉ−１２９）〜塩（Ｉ−１３２）、塩（Ｉ−１３７）、塩（Ｉ−１３８）、塩（Ｉ−１４１）〜塩（Ｉ−１５１）、塩（Ｉ−１６１）〜塩（Ｉ−１６４）、塩（Ｉ−１６９）、塩（Ｉ−１７０）、塩（Ｉ−１７３）〜塩（Ｉ−１８３）、塩（Ｉ−１９３）〜塩（Ｉ−１９６）、塩（Ｉ−２０１）、塩（Ｉ−２０２）、塩（Ｉ−２０５）〜塩（Ｉ−２１５）、塩（Ｉ−２２５）〜塩（Ｉ−２２８）、塩（Ｉ−２３１）、塩（Ｉ−２３２）、塩（Ｉ−２３５）〜塩（Ｉ−２３８）、塩（Ｉ−２３９）〜塩（Ｉ−２４２）、塩（Ｉ−２４５）、塩（Ｉ−２４６）、塩（Ｉ−２４９）〜塩（Ｉ−２５２）、塩（Ｉ−２５３）〜塩（Ｉ−２５６）、塩（Ｉ−２５９）、塩（Ｉ−２６０）、塩（Ｉ−２６３）〜塩（Ｉ−２６６）、塩（Ｉ−２６７）〜塩（Ｉ−２７０）、塩（Ｉ−２７３）、塩（Ｉ−２７４）、塩（Ｉ−２７７）〜塩（Ｉ−２８０）、塩（Ｉ−２８１）〜塩（Ｉ−２８４）、塩（Ｉ−２８７）、塩（Ｉ−２８８）、塩（Ｉ−２９１）〜塩（Ｉ−２９４）、塩（Ｉ−２９５）〜塩（Ｉ−２９８）、塩（Ｉ−３０１）、塩（Ｉ−３０２）、塩（Ｉ−３０５）〜塩（Ｉ−３０８）、塩（Ｉ−３０９）〜塩（Ｉ−３１２）、塩（Ｉ−３１５）、塩（Ｉ−３１６）、塩（Ｉ−３１９）〜塩（Ｉ−３２２）が好ましい。 Examples of the salt (I) include the salts shown in Table 1. In the table below, each reference numeral represents a reference numeral assigned to the above-mentioned structure representing an anion or cation. For example, the salt (I-1) means a salt composed of an anion represented by the formula (Ia-1) and a cation represented by the formula (b2-c-1), and represents the salt shown below.

Among them, the salt (I) is salt (I-1) to salt (I-4), salt (I-9), salt (I-10), salt (I-13) to salt (I-23). , Salt (I-33) to salt (I-36), salt (I-41), salt (I-42), salt (I-45) to salt (I-55), salt (I-65) to Salt (I-68), salt (I-73), salt (I-74), salt (I-77) to salt (I-87), salt (I-97) to salt (I-100), salt (I-105), salt (I-106), salt (I-109) to salt (I-119), salt (I-129) to salt (I-132), salt (I-137), salt ( I-138), salt (I-141) to salt (I-151), salt (I-161) to salt (I-164), salt (I-169), salt (I-170), salt (I) -173) -salt (I-183), salt (I-193) -salt (I-196), salt (I-201), salt (I-202), salt (I-205) -salt (I-) 215), salt (I-225) to salt (I-228), salt (I-231), salt (I-232), salt (I-235) to salt (I-238), salt (I-239) ) ~ Salt (I-242), Salt (I-245), Salt (I-246), Salt (I-249) ~ Salt (I-252), Salt (I-253) ~ Salt (I-256) , Salt (I-259), Salt (I-260), Salt (I-263) -Salt (I-266), Salt (I-267) -Salt (I-270), Salt (I-273), Salt (I-274), salt (I-277) to salt (I-280), salt (I-281) to salt (I-284), salt (I-287), salt (I-288), salt (I-291) -salt (I-294), salt (I-295) -salt (I-298), salt (I-301), salt (I-302), salt (I-305) -salt ( I-308), salt (I-309) to salt (I-312), salt (I-315), salt (I-316), salt (I-319) to salt (I-322) are preferable.

（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。 <Manufacturing method of salt (I)>
In the salt (I), the salt in which X ¹ is * -CO-O- (the salt represented by the formula (I1)) is, for example, a salt represented by the formula (I1-a) and a carbonyldiimidazole. Can be produced by reacting in a solvent and then further reacting with a compound represented by the formula (I1-b).

(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（Ｉ１−ｂ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場より容易に入手することができ、また、公知の製法により、容易に製造することができる。

Examples of the salt represented by the formula (I1-a) include salts represented below, and can be produced by the method described in JP-A-2008-127365.

Examples of the compound represented by the formula (I1-b) include compounds represented by the following formula, which can be easily obtained from the market and can be easily produced by a known manufacturing method. ..

（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（Ｉ２−ａ）で表される塩は、例えば、以下で表される塩などが挙げられ、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。

In the salt (I), the salt in which X ¹ is * -O-CO-O- (salt represented by the formula (I2)) is, for example, a salt represented by the formula (I2-a) and a carbonyldiimidazole. It can be produced by reacting imidazole in a solvent and then further reacting with a compound represented by the formula (I1-b).
Further, the salt represented by the formula (I2) is prepared by, for example, reacting the compound represented by the formula (I1-b) with carbonyldiimidazole in a solvent, and then further formulating the formula (I2-a). It can also be produced by reacting with the represented salt.

(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 (I2-a) include salts represented by the following, and can be produced by the method described in JP-A-2012-193170.

（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（Ｉ３−ｂ）で表される化合物としては、下記式で表される化合物等が挙げられ、市場より容易に入手することができる。

In the salt (I), the salt in which X ¹ is * -O-CO- (salt represented by the formula (I3)) is, for example, a compound represented by the formula (I3-b) in a solvent. , And carbonyldiimidazole, and then further react with the salt represented by the formula (I2-a).

(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 compound represented by the formula (I3-b) 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。）
この反応における塩基としては、水酸化カリウム等が挙げられる。
この反応における溶媒としては、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。 In the salt (I), the salt in which X ¹ is −O− (salt represented by the formula (I4)) is represented by the salt represented by the formula (I2-a) and the salt represented by the formula (I1-b). It can be obtained by reacting with the compound to be carried out in a solvent in the presence of a base.

(In the formula, all the symbols have the same meanings as described above.)
Examples of the base in this reaction include potassium hydroxide and the like.
Examples of the solvent in this reaction include 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.

In the salt (I), L ¹ is a group composed of a combination of an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH contained in the alkanediyl group). ₂ - may be replaced by -O- or -CO-, -CH ₂ contained in the alicyclic hydrocarbon group - is -O -, - S -, - SO ₂ - or -CO- The salt represented by the formula (I1-a) or the salt represented by the formula (I2-a) in synthesizing the salts represented by the formulas (I1) to (I4) is the salt. It can be produced by replacing the salt represented by with the salt represented by the following.

[Acid generator]
The acid generator of the present invention is an acid generator containing a salt (I). It may contain one kind of salt (I), or may contain two or more kinds of salt (I).
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.

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３〜２４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−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ１^＋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)”, but the salt (I). ) Is excluded.).

[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 24 carbon atoms which may have a substituent, and is contained in the alicyclic hydrocarbon group. CH ₂ - is, -O -, - SO ₂ - or -CO- may be replaced with.
Z1 ⁺ represents an organic cation. ]

The perfluoroalkyl groups in Q ^b1 and Q ^b2 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluoro. A hexyl group and the like can be mentioned.
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.
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, Decane-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.

_{Examples of the group in which −CH 2} − contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced with −O− or −CO− are the formulas (b1-1) to (b1-3). The group represented by any of the above is mentioned. In addition, in the group represented by the formulas (b1-1) to (b1-3) and the specific examples thereof, the formulas (b1-4) to (b1-11), * and ** refer to the binding site. Represents, * represents the binding site with -Y.

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

[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.}
* And ** represent the binding site, and * represents the binding site with Y. ]

In the groups represented by the formulas (b1-1) to (b1-3), when -CH _2- 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-.

［式（ｂ１−４）中、
Ｌ^b8は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
式（ｂ１−５）中、
Ｌ^b9は、炭素数１〜２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｌ^b10は、単結合又は炭素数１〜１９の２価の飽和炭化水素基を表し、該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し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｌ^b15は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該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し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｌ^b17は、炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^b18は、単結合又は炭素数１〜１７の２価の飽和炭化水素基を表し、該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。
］
Ｌ^b8は、好ましくは炭素数１〜４の２価の飽和炭化水素基である。
Ｌ^b9は、好ましくは炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b10は、好ましくは単結合又は炭素数１〜１９の２価の飽和炭化水素基であり、より好ましくは単結合又は炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b11は、好ましくは炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b12は、好ましくは単結合又は炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b13は、好ましくは炭素数１〜１２の２価の飽和炭化水素基である。
Ｌ^b14は、好ましくは単結合又は炭素数１〜６の２価の飽和炭化水素基である。
Ｌ^b15は、好ましくは単結合又は炭素数１〜１８の２価の飽和炭化水素基であり、より好ましくは単結合又は炭素数１〜８の２価の飽和炭化水素基である。
Ｌ^b16は、好ましくは炭素数１〜１２の２価の飽和炭化水素基である。
Ｌ^b17は、好ましくは炭素数１〜６の２価の飽和炭化水素基である。
Ｌ^b18は、好ましくは単結合又は炭素数１〜１７の２価の飽和炭化水素基であり、より好ましくは単結合又は炭素数１〜４の２価の飽和炭化水素基である。 The _{group in which -CH 2-} contained in the divalent saturated hydrocarbon group represented by ^{L b1} is replaced with -O- or -CO- is represented by the formula (b1-1) or the formula (b1-3). Is preferred.
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, and —CH ₂ − contained in the divalent saturated hydrocarbon group may be replaced with −O− or −CO−.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and 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, and −CH ₂ − contained in the divalent saturated hydrocarbon group is replaced with −O− or −CO−. May be good.
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, and —CH ₂ − contained in the divalent saturated hydrocarbon group may be replaced with −O− or −CO−.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and 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. _{The −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 substituted 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. _{The −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 substituted 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. _{The −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 substituted with a hydroxy group.
However, L ^b24, the total number of carbon atoms of 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 substituted 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.

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

Ｙで表される脂環式炭化水素基としては、好ましくは式（Ｙ１）〜式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）〜式（Ｙ４３）のいずれかで表される基であり、より好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ１６）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）で表される基であり、さらに好ましくは式（Ｙ１１）、式（Ｙ１５）、式（Ｙ２０）、式（Ｙ２６）、式（Ｙ２７）、式（Ｙ３０）、式（Ｙ３１）、式（Ｙ３９）、式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）で表される基である。
Ｙで表される脂環式炭化水素基が式（Ｙ２８）〜式（Ｙ３５）、式（Ｙ３９）〜式（Ｙ４０）、式（Ｙ４２）又は式（Ｙ４３）等の酸素原子を有する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。 Examples of the alicyclic hydrocarbon group represented by Y include groups represented by the formulas (Y1) to (Y11) and the formulas (Y36) to (Y38).
Is -O - - -CH ₂ contained in the alicyclic hydrocarbon group represented by Y, - SO ₂ - if or -CO- replaced by, to the number may be one, or two or more. Examples of such a group include groups represented by the formulas (Y12) to (Y35) and the formulas (Y39) to (Y43). * Represents the binding site with ^{L b1.}

The alicyclic hydrocarbon group represented by Y is preferably the formula (Y1) to the formula (Y20), the formula (Y26), the formula (Y27), the formula (Y30), the formula (Y31), and the formula (Y39). It is a group represented by any of the formulas (Y43), and more preferably the formulas (Y11), the formulas (Y15), the formulas (Y16), the formulas (Y20), the formulas (Y26), the formulas (Y27), and the formulas. (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), more preferably formula (Y11), formula (Y15), formula. (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43). ..
The alicyclic hydrocarbon group represented by Y is a spiro ring having an oxygen atom of the formula (Y28) to the formula (Y35), the formula (Y39) to the formula (Y40), the formula (Y42) or the formula (Y43). In some cases, the alkylandyl 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 having 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 the alkyl group and −CH ₂ − contained in the alicyclic hydrocarbon group are −O−. , -SO _2- or -CO- may be replaced, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group is replaced with a hydroxy group or a fluorine atom. Also, ja represents an integer of any of 0 to 4) and the like.
As the substituent of the alicyclic hydrocarbon group represented by Y, an alkyl group having 1 to 16 carbon atoms which may be substituted with a halogen atom, a hydroxy group or a hydroxy group (-CH _{2 contained in the alkyl group).} -May be replaced with -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and 7 to 21 carbon atoms. Aralkyl group, glycidyloxy group,-(CH ₂ ) _ja- CO-O-R ^b1 group or-(CH ₂ ) _ja- O-CO-R ^b1 group (in the formula, R ^{b1 has 1 to} 16 carbon atoms. Represents an alkyl group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and is included in the alkyl group and the alicyclic hydrocarbon group. -CH _2- may be replaced with -O-, -SO _2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced with the hydrogen atom. It may be replaced with a hydroxy group or a fluorine atom. Ja represents an integer of 0 to 4) 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 methylcyclohexyl group, a dimethylcyclohexyl 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. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl 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-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and carbon Aromatic hydrocarbon groups having alicyclic hydrocarbon groups of number 3 to 18 (p-adamantylphenyl group, p-cyclohexylphenyl group, etc.) are preferable. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10.
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. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4.
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 aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
_{Examples of the group in which -CH 2-} contained in the alkyl group is replaced with -O-, -SO _2- or -CO- are an alkoxy group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group or Examples include a group that combines these.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group. The alkoxy group has preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like. The alkoxycarbonyl group has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group and the like. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The alkylcarbonyloxy group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
Examples of the combined group include a group combining an alkoxy group and an alkyl group, a group combining an alkoxy group and an alkoxy group, a group combining an alkoxy group and an alkylcarbonyl group, and an alkoxy group and an alkylcarbonyloxy group. Examples include a group that combines the above.
Examples of the group in which the alkoxy group and the alkyl group are combined include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group and an ethoxymethyl group. The alkoxyalkyl group has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
Examples of the group in which the alkoxy group and the alkoxy group are combined include an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group. The alkoxyalkoxy group has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms.
Examples of the group in which the alkoxy group and the alkylcarbonyl group are combined include an alkoxyalkylcarbonyl group such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group and an ethoxypropionyl group. The alkoxyalkylcarbonyl group preferably has 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5.
Examples of the group in which the alkoxy group and the alkylcarbonyloxy group are combined include an alkoxyalkylcarbonyloxy group such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group and an ethoxypropionyloxy group. The alkoxyalkylcarbonyloxy group preferably has 3 to 13 carbon atoms, more preferably 3 to 7 carbon atoms, and even more preferably 3 to 5 carbon atoms.
_{The groups in which -CH 2-} contained in the alicyclic hydrocarbon group is replaced with -O-, -SO _2- or -CO- are the groups of the formulas (Y12) to (Y35) and the formulas (Y39) to. Examples thereof include a group represented by (Y43).

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group, more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent. _{-CH 2-} constituting the alicyclic hydrocarbon group or adamantyl group may be replaced with -CO-, -SO _{2- or -CO-.} Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the formula (Y42) and the formulas (Y100) to (Y114).

Examples of the anion in the salt represented by the formula (B1) include anions represented by the formulas (B1-A-1) to (B1-A-59) [hereinafter, "anion (B1-A)" according to the formula number. -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-59). Anions are more preferred.

ここでＲ^ｉ２〜Ｒ^ｉ７は、互いに独立に、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の鎖式炭化水素基、好ましくは炭素数１〜４のアルキル基、炭素数５〜１２の脂環式炭化水素基又はこれらを組合せることにより形成される基、より好ましくはメチル基、エチル基、シクロヘキシル基又はアダマンチル基である。Ｌ^Ａ４１は、単結合又は炭素数１〜４のアルカンジイル基である。Ｑ^ｂ１及びＱ^ｂ２は、上記と同じ意味を表す。
式（Ｂ１）で表される塩におけるアニオンとしては、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, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, independently of each other. R ⁱ⁸ is formed, for example, by a chain 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. ^LA41 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 anion in the salt represented by the formula (B1) include the anion described in JP-A-2010-204646.

Preferred examples of the anion in the salt represented by the formula (B1) include anions represented by the formulas (B1a-1) to (B1a-38).

Among them, the formulas (B1a-1) to (B1a-3), the formulas (B1a-7) to the formulas (B1a-16), the formulas (B1a-18), the formulas (B1a-19), and the formulas (B1a-22). )-Anion represented by any of the formulas (B1a-38) is preferable.

Examples ^{of the organic cation of Z1 +} include an organic onium cation, an organic sulfonium cation, an organic iodine cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation and the like. Among these, organic sulfonium cations and organic iodonium cations are preferable, and aryl sulfonium cations are more preferable. Examples of the aryl sulfonium cation include the same as the Z ⁺ cation in the formula (I).

The acid generator (B) is a combination of the above-mentioned 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), the combination of the anion represented by any of the formulas (B1a-22) to (B1a-38) and the cation (b2-1), the cation (b2-3) or the cation (b2-4) Can be mentioned.

Examples of the acid generator (B) preferably include those represented by the formulas (B1-1) to (B1-56), 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 (B1-56) are particularly preferable.

When the salt (I) and the acid generator (B) are contained as the acid generator, the ratio of the contents of the salt (I) and the acid biogenic agent (B) (mass ratio; salt (I): acid generator ( B)) is usually 1:99 to 99: 1, preferably 2:98 to 98: 2, more preferably 5:95 to 95: 5, and even more preferably 10:90 to 90. : 10, and particularly preferably 15:85 to 85:15.
In the resist composition of the present invention, the total content of the acid generator is preferably 1 part by mass or more and 45 parts by mass or less, and more preferably 1 part by mass or more with respect to 100 parts by mass of the resin (A) described later. It is 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less.

[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) 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). The structural unit other than the structural unit (a1) includes a structural unit having no acid unstable group (hereinafter, may be referred to as “structural unit (s)”), a structural unit (a1), and a structural unit other than the structural unit (s). Structural unit (for example, a structural unit having a halogen atom described later (hereinafter, may be referred to as “structural unit (a4)”), and a structural unit having a non-desorbed hydrocarbon group described later (hereinafter referred to as “structural unit (a5)”). In some cases) and other structural units derived from monomers known in the art.

［式（１）中、Ｒ^ａ１、Ｒ^ａ２及びＲ^ａ３は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基、炭素数３〜２０の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の非芳香族炭化水素環を形成する。
ｍａ及びｎａは、それぞれ独立して、０又は１を表し、ｍａ及びｎａの少なくとも一方は１を表す。
＊は結合部位を表す。］

［式（２）中、Ｒ^ａ１’及びＲ^ａ２’は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３〜２０の複素環を形成し、該炭化水素基及び該複素環に含まれる−ＣＨ_２−は、−Ｏ−又は−Ｓ−で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
ｎａ’は、０又は１を表す。
＊は結合部位を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid 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), Ra ¹ , Ra ² and Ra ³ are independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alicyclic hydrocarbon having 3 to 20 carbon atoms. Represents a group, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these, or R ^a1 and R ^a2 are non-aromatic hydrocarbons having 3 to 20 carbon atoms together with carbon atoms to which they are bonded to each other. Form a hydrocarbon ring.
ma and na independently represent 0 or 1, and at least one of ma and na represents 1.
* Represents the binding site. ]

[In the formula (2), R ^a1'and R ^a2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^a3' represents a hydrocarbon group having 1 to 20 carbon atoms. Represented, R ^a2'and R ^a3' are bonded to each other to form a 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 by -O- or -S-.
X represents an oxygen atom or a sulfur atom.
na'represents 0 or 1.
* Represents the binding site. ]

Ｒ^ａ１、Ｒ^ａ２及びＲ^ａ３における芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニル基、フェナントリル基等のアリール基が挙げられる。
組み合わせた基としては、上述したアルキル基と脂環式炭化水素基とを組み合わせた基（例えばシ、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のアルキルシクロアルキル基又はクロアルキルアルキル基）、ベンジル基等のアラルキル基、アルキル基を有する芳香族炭化水素基（ｐ−メチルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、２，６−ジエチルフェニル基、２−メチル−６−エチルフェニル基等）、脂環式炭化水素基を有する芳香族炭化水素基（ｐ−シクロヘキシルフェニル基、ｐ−アダマンチルフェニル基等）、フェニルシクロヘキシル基等のアリール−シクロアルキル基等が挙げられる。 好ましくは、ｍａは０であり、ｎａは１である。
Ｒ^a1及びＲ^a2が互いに結合して非芳香族炭化水素環を形成する場合の−Ｃ（Ｒ^a1）（Ｒ^a2）（Ｒ^a3）としては、下記の環が挙げられる。非芳香族炭化水素環は、好ましくは炭素数３〜１２である。＊は−Ｏ−との結合部位を表す。

^Examples of 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 alkenyl groups in R ^a1 , R ^a2 and R ^a3 include ethenyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, tert-butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups and isooctenyl groups. Nonenyl group is mentioned.
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 binding site) and the like. The alicyclic hydrocarbon group of R ^a1 , R ^a2 and R ^a3 has preferably 3 to 16 carbon atoms.

Examples of the aromatic hydrocarbon group in R ^a1 , Ra ² and Ra ³ include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
Examples of the combined group include a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group (for example, si, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, etc. Alkylcycloalkyl group or cloalkylalkyl group such as adamantyldimethyl group and norbornylethyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butyl) Aromatic hydrocarbon group having phenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and alicyclic hydrocarbon group (p. -Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. may be mentioned. 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 rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * Represents the binding site with -O-.

Ｒ^ａ１’及びＲ^ａ２’のうち、少なくとも１つは水素原子であることが好ましい。
ｎａ’は、好ましくは０である。 Examples of 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 formed by 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 aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-), trill group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned.
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 ^a2' )-X-R ^a3'is as follows. Ring of. * Represents a binding site.

Of R ^{a1 'and R a2',} it is preferable that at least one is a hydrogen atom.
na'is preferably 0.

Examples of the group (1) include the following groups.
In formula (1), R ^a1 , R ^a2 and 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 the binding site.

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

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−との結合部位を表す。
Ｒ^a01、Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１〜６のアルキル基を表す。
Ｒ^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、炭素数６〜１８の芳香族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２〜８のアルケニル基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１８の芳香族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。］ As the structural unit derived from the (meth) acrylic monomer having the group (1), the structural unit represented by the formula (a1-0) (hereinafter, may be referred to as the structural unit (a1-0)), the formula (. The structural unit represented by a1-1) (hereinafter, may be referred to as a structural unit (a1-1)) or the structural unit represented by the formula (a1-2) (hereinafter, referred to as a structural unit (a1-2)). In some cases). Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). 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),
L ^{a01, L a1} and ^{L a2} each independently, -O- or _{* -O- (CH 2) k1 -CO} -O- the stands, k1 represents an integer of 1-7, and * Represents a binding site with −CO−.
R ^a01 , R ^a4 and R ^a5 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a02 , R ^a03 and R ^a04 independently contain an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or these. Represents a combined group.
R ^a6 and R ^a7 independently have an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group 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 a hydrogen atom or a methyl group, and more preferably a methyl group.
L ^{a01, L a1} and ^{L a2} are preferably oxygen atom or _{* -O- (CH 2) k01 -CO} -O- and is (however, k01 is preferably either 1 to 4 integer, more preferably Is 1), more preferably an oxygen atom.
The alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^{a7 and the group in which these are combined include R a1 of} the group (1). ^Examples are similar to the groups mentioned in R a2 and R ^a3.
The alkyl group in R ^a02 , R ^a03 , and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
The alkyl group in R ^a6 and R ^a7 preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl group, an ethyl group, an isopropyl group or t- butyl group, more preferably an ethyl group, an isopropyl group Or it is a t-butyl group.
Alkenyl group for R ^a6 and R ^a7 is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably ethenyl, propenyl group, isopropenyl group or butenyl 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 ^{number of carbon atoms of the aromatic hydrocarbon groups of R a02} , R ^a03 , R ^a04 , R ^a6 and R ^a7 is preferably 6 to 12, and more preferably 6 to 10.
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.
The group in which an alkyl group and an aromatic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination with these alkyl groups and an aromatic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl 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 independently, preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group. , Ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group or naphthyl group, more preferably ethyl group, isopropyl group, t-butyl group, ethenyl group or phenyl 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 one of the formulas (a1-0-1) to (a1-0-18) 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, a halogen atom, a haloalkyl group (an alkyl group having a halogen atom) or another alkyl group, and the formulas (a1-0-1) to (a1-0-) are mentioned. 10), the structural unit represented by any of the formulas (a1-0-13) and the formula (a1-0-14) is 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 (a1-1-7) 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 formulas (a1-2-1) to (a1-2-14) and R ^{a5 in the structural unit (a1-2).} Structural units in which the methyl group is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group include formulas (a1-2-2), formulas (a1-2-5), formulas (a1-2-6). ) And the structural unit represented by any of the formulas (a1-2-10) to (a1-2-14) are preferable.

When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 80 mol%, preferably 5 to 75 mol%, based on all the structural units of the resin (A). Yes, more preferably 10-70 mol%.
When the resin (A) contains a structural unit (a1-1) and / or a structural unit (a1-2), the total content of these is usually 10 to 90 mol with respect to the total structural unit of the resin (A). %, Preferably 15-85 mol%, more preferably 20-80 mol%, still more preferably 20-75 mol%, still more preferably 20-70 mol%.

［式（ａ１−４）中、
Ｒ^a32は、水素原子、ハロゲン原子、又は、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜１２のアルコキシアルキル基、炭素数２〜１２のアルコキシアルコキシ基、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^a30は、単結合又は^＊−Ｘ^a31−（Ａ^a32−Ｘ^a32）_nc−を表し、＊は−Ｒ^a32が結合する炭素原子との結合部位を表す。
Ａ^a32は、炭素数１〜６のアルカンジイル基を表す。
Ｘ^a31及びＸ^a32は、それぞれ独立に、−Ｏ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
ｎｃは、０又は１を表す。
ｌａは０〜４のいずれかの整数を表す。ｌａが２以上のいずれかの整数である場合、複数のＲ^a33は互いに同一でも異なっていてもよい。
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 has 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, and a carbon number of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a30 represents a single bond or ^* −X ^a31 − (A ^a32 −X ^a32 ) _nc −, and * represents a binding site with a carbon atom to which ^{−R a32 is bonded.}
A ^a32 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a31 and X ^a32 independently represent -O-, -CO-O- or -O-CO-, respectively.
nc represents 0 or 1.
la represents any integer from 0 to 4. When la is any integer of 2 or more, the plurality of Ra ^33s may be the same or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, 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 the −CH ₂ − contained in the divalent hydrocarbon group are − It may be replaced by O- or -S-. ]

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 in Ra32} include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, and a 2,2,2-trifluoroethyl group. 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2 3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluoro Hexyl group is mentioned.
R ^a32 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 R a33 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 R a33 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.
^Examples of the alkoxyalkyl group in R a33 include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.
^Examples of the alkoxyalkoxy group in R a33 include methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, and tert-butoxymethoxy group. Can be mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethyl group or an ethoxyethyl group.
Examples of the alkylcarbonyl group in R ^a33 include an acetyl group, a propionyl group, a butyryl group and the like. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.
Examples of the alkylcarbonyloxy group in R ^a33 include an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.
R ^a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, and is preferably a fluorine atom, an iodine atom, a hydroxy group or a methyl. A group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group is more preferable, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group is further preferable.

* -X ^a31- (A ^a32- X ^a32 ) _nc- includes * -O-, * -CO-O-, * -O-CO-, * -CO-O-A ^{a32-CO-O-, * -O-CO-A a32 -O} -, * - O-A a32 -CO-O -, * - CO-O-A a32 -O-CO -, * - O-CO-A a32 -O-CO -, Can be mentioned. Of these, * ^{-CO-O-, * -CO-O-A a32-} CO-O- or * -O-A ^a32- 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 ^a32 is preferably a methylene group or an ethylene group.

A ^a30 is preferably single bond, * -CO-O- or * -CO-O-A ^a32- 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.

芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニル基、フェナントリル基等のアリール基が挙げられる。
組み合わせた基としては、上述したアルキル基と脂環式炭化水素基とを組み合わせた基（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のアルキルシクロアルキル基又はシクロアルキルアルキル基）、ベンジル基等のアラルキル基、アルキル基を有する芳香族炭化水素基（ｐ−メチルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、２，６−ジエチルフェニル基、２−メチル−６−エチルフェニル基等）、脂環式炭化水素基を有する芳香族炭化水素基（ｐ−シクロヘキシルフェニル基、ｐ−アダマンチルフェニル基等）、フェニルシクロヘキシル基等のアリール−シクロアルキル基等が挙げられる。特に、Ｒ^a36としては、炭素数１〜１８のアルキル基、炭素数３〜１８の脂環式炭化水素基、炭素数６〜１８の芳香族炭化水素基又はこれらを組み合わせることにより形成される基が挙げられる。 The la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group, aromatic hydrocarbon groups, and groups formed by combining these.
Examples of the alkyl 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 and the like.
The alicyclic hydrocarbon group may be either a monocyclic or polycyclic group. 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 binding site) and the like.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyl) Alkylcycloalkyl group such as dimethyl group, norbornylethyl group or cycloalkylalkyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having alkyl group (p-methylphenyl group, p-tert-butylphenyl) Aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-), trill group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) Cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned. 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.

R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 3 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} ) -O-R a36 in the structural unit (a1-4) is desorbed by contact with an acid (e.g. p- toluenesulfonic acid) to form a hydroxy group.
^{-OC (R a34) (R a35} ) -O-R a36 is preferably bonded to the o- or p- position of the benzene ring, and more preferably binds to the p- position.

Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, hydrogen atom corresponding to ^{R a32} in equation (a1-4-1) represented respectively to Formula (a1-4-18) structural units and structural units (a1-4) is a halogen atom, a haloalkyl group Alternatively, a structural unit replaced with an alkyl group can be mentioned, and more preferably, formulas (a1-4-1) to (a1-4-5), formulas (a1-4-10), and formulas (a1-4-13) are used. ) And the structural unit represented by the formula (a1-4-14), respectively.

When the resin (A) contains the structural units (a1-4), the content thereof is preferably 3 to 80 mol%, preferably 5 to 75, based on the total of all the structural units of the resin (A). It is more preferably mol%, further preferably 7 to 70 mol%, even more preferably 7 to 65 mol%, and particularly preferably 10 to 60 mol%.

式（ａ１−５）中、
Ｒ^a8は、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊−（ＣＨ₂）_h3−ＣＯ−Ｌ⁵⁴−を表し、ｈ３は１〜４のいずれかの整数を表し、＊は、Ｌ⁵¹との結合部位を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３のいずれかの整数を表す。
ｓ１’は、０〜３のいずれかの整数を表す。 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 binding site with ^{L 51.}
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ independently represent -O- or -S-, respectively.
s1 represents any 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 trifluoro group. Examples include methyl groups.
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 , one is preferably −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 (a1-5-2) 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). , 5-40 mol% is even more preferred, and 5-30 mol% is even more preferred.

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

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

樹脂（Ａ）が上記、（ａ１−６−１）〜（ａ１−６−３）のような構造単位を含む場合、その含有率は、樹脂（Ａ）の全構造単位に対して、１０〜６０モル％が好ましく、１５〜５５モル％がより好ましく、２０〜５０モル％がさらに好ましく、２０〜４５モル％がさらにより好ましく、２０〜４０モル％が特に好ましい。 Moreover, the following structural unit is also mentioned as a structural unit (a1).

When the resin (A) contains the structural units such as (a1-6-1) to (a1-6-3) described above, the content thereof is 10 to 10 with respect to all the structural units of the resin (A). 60 mol% is preferable, 15 to 55 mol% is more preferable, 20 to 50 mol% is further preferable, 20 to 45 mol% is even more preferable, and 20 to 40 mol% is particularly preferable.

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid unstable group (hereinafter, may be referred to as “monomer (s)”). As the monomer for deriving the structural unit (s), a monomer having no acid unstable group known in the resist field can be used.
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. , The structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. 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いてもよい炭素数１〜６のアルキル基を表す。
Ｒ^a51は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜１２のアルコキシアルキル基、炭素数２〜１２のアルコキシアルコキシ基、炭素数２〜４のアルキルカルボニル基、炭素数２〜４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Ａ^a50は、単結合又は＊−Ｘ^a51−（Ａ^a52−Ｘ^a52）_nb−を表し、＊は−Ｒ^a50が結合する炭素原子との結合部位を表す。
Ａ^a52は、それぞれ独立に、炭素数１〜６のアルカンジイル基を表す。
Ｘ^a51及びＸ^a52は、それぞれ独立に、−Ｏ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
ｎｂは、０又は１を表す。
ｍｂは０〜４のいずれかの整数を表す。ｍｂが２以上のいずれかの整数である場合、複数のＲ^a51は互いに同一でも異なっていてもよい。］ 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 the 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 has 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, and a carbon number of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or ^{* -X a51 - (A a52 -X} a52) nb - represents, * represents a binding site to the carbon atom to which -R ^a50 binds.
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 or different from each other. ]

^Examples of the halogen atom in R ^a50 and R a51 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, and a 2,2,2-trifluoroethyl group. 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2 3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluoro Hexyl group is mentioned.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, 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. 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 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. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.
^Examples of the alkoxyalkyl group in Ra51 include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group.
^Examples of the alkoxyalkoxy group in Ra51 include methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, and tert-butoxymethoxy group. Can be mentioned. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group.
^Examples of the alkylcarbonyl group in Ra51 include an acetyl group, a propionyl group, a butyryl group and the like. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group.
^Examples of the alkylcarbonyloxy group in Ra51 include an acetyloxy group, a propionyloxy group and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group.
R ^a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxyalkoxy group having 2 to 8 carbon atoms, and is preferably a fluorine atom, an iodine atom, a hydroxy group or a methyl. A group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxymethoxy group is more preferable, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group is further preferable.

^{* -X a51 - (A a52 -X} a52) nb - The, * - 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.

The structural unit (a2-A) includes a structural unit represented by the formulas (a2-2-1) to (a2-2-16) and the formulas (a2-2-1) to (a2-2-2). In the structural unit represented by 16), a structural unit in ^{which the methyl group corresponding to Ra50} in the structural unit (a2-A) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group 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). Structural unit, structural unit represented by the formula (a2-2-8), structural unit represented by the formulas (a2-2-12) to (a2-2-14), and the formula (a2-2-1). ), The structural unit represented by the formula (a2-2-3), the structural unit represented by the formula (a2-2-6), and the structural unit represented by the formula (a2-2-8). Structural unit, in the structural unit represented by the formulas (a2-2-12) to (a2-2-14), the structure in which the methyl group corresponding to ^{Ra50 in the structural unit (a2-A) is replaced with a hydrogen atom.} It is preferably a unit, a structural unit represented by the formula (a2-2-3), a structural unit represented by the formula (a2-2-8), and formulas (a2-2-12) to (a2-). The structural unit represented by 2-14) and the structural unit represented by the formula (a2-2-3) or the structural unit represented by the formula (a2-2-8), the formulas (a2-2-12) to In the structural unit represented by the formula (a2-2-14), ^{it is more preferable that the methyl group corresponding to Ra50} in the structural unit (a2-A) is replaced with a hydrogen atom, and it is more preferable that the structural unit is a structural unit represented by the formula (a2-A2-A). In the structural unit represented by 2-8) and the structural unit represented by the formula (a2-2-8), ^{the methyl group corresponding to Ra50} in the structural unit (a2-A) is replaced with a hydrogen atom. Is more preferable.

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%, based on the total 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−との結合部位を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０のいずれかの整数を表す。 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 any integer from 1 to 7. * Represents the binding site 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.

Formula (a2-1), L ^a3 is preferably, -O -, - O- (CH 2) f1 -CO-O- and is (wherein 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 1 to 20 mol%, and even more preferably 1 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部位を表す。
Ｒ^ａ１８、Ｒ^ａ１９及びＲ^ａ２０は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^ａ２４は、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｘ^ａ３は、−ＣＨ_２−又は酸素原子を表す。
Ｒ^ａ２１は炭素数１〜４の脂肪族炭化水素基を表す。
Ｒ^ａ２２、Ｒ^ａ２３及びＲ^ａ２５は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５のいずれかの整数を表す。
ｑ１は、０〜３のいずれかの整数を表す。
ｒ１は、０〜３のいずれかの整数を表す。
ｗ１は、０〜８のいずれかの整数を表す。
ｐ１、ｑ１、ｒ１及び／又はｗ１が２以上のとき、複数のＲ^ａ２１、Ｒ^ａ２２、Ｒ^ａ２３及び／又はＲ^ａ２５は互いに同一でも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 -, * - O-} L a8 -O -, * - O-L a8 -CO-O -, * - O-L a8 -CO-O-L a9 -CO-O- or * Represents −O−L ^a8 −O−CO−L ^a9 −O−.
L ^a8 and ^{La 9} each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents the binding site with the carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
R ^a24 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
X ^a3 is, -CH ₂ - represents an or an oxygen atom.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer from 0 to 5.
q1 represents any integer from 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, a 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 , Ra ²² , Ra ²³ and Ra ²⁵ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and 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 groups in La8} and ^La9 include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group and pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples thereof include a 4-diyl group and a 2-methylbutane-1,4-diyl group.

In the formula (a3-1) ~ formula ^(a3-3), L a4 ^{~L a6} are each independently preferably -O- _{or, * - O- (CH 2)} k3 -CO-O- in, k3 Is an integer of any of 1 to 4, more preferably —O− and * −O−CH ₂ −CO−O−, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently, preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are independently, preferably 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), R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, more 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 ^{* -O-L} a8 -CO-O-, more preferably an _{-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, 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.)

樹脂（Ａ）が構造単位（ａ３）を含む場合、その合計含有率は、樹脂（Ａ）の全構造単位に対して、通常５〜７０モル％であり、好ましくは１０〜６５モル％であり、より好ましくは１０〜６０モル％である。
また、構造単位（ａ３−１）、構造単位（ａ３−２）、構造単位（ａ３−３）又は構造単位（ａ３−４）の含有率は、それぞれ、樹脂（Ａ）の全構造単位に対して、５〜６０モル％が好ましく、５〜５０モル％がより好ましく、１０〜５０モル％がさらに好ましい。 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 formulas (a3-3-2) and the formulas (a3-4-1) to the formulas (a3-4-12), and in the structural unit, the formula (a3-1). ) ^R a18 in ~ formula ^{(a3-4), R a19, R} a20 and structural units in which a methyl group is replaced by a hydrogen atom corresponding to ^{R a24} are preferred.

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. Therefore, 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のハロゲン原子を有する飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。］
Ｒ⁴²で表される飽和炭化水素基は、鎖式飽和炭化水素基及び単環又は多環の脂環式飽和炭化水素基、並びに、これらを組み合わせることにより形成される基等が挙げられる。 <Structural unit (a4)>
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 halogen 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-type saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated 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以上の脂環式飽和炭化水素基とを組み合わせることにより形成される基が挙げられ、−アルカンジイル基−脂環式飽和炭化水素基、−脂環式飽和炭化水素基−アルキル基、−アルカンジイル基−脂環式飽和炭化水素基−アルキル基等が挙げられる。 The chain saturated hydrocarbon group 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 an octadecyl group. Can be mentioned.
Examples of the monocyclic or polycyclic alicyclic saturated 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. Examples thereof include a polycyclic alicyclic saturated hydrocarbon group such as a group (* represents a binding site).

Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups and one or more alicyclic saturated hydrocarbon groups, and examples thereof include-alkanediyl groups. -Alicyclic saturated hydrocarbon group, -Alicyclic saturated hydrocarbon group-Alkyl group, -Alkanediyl group-Alicyclic saturated hydrocarbon group-Alkyl group and the like can be mentioned.

［式（ａ４−０）中、
Ｒ⁵⁴は、水素原子又はメチル基を表す。
Ｌ^4ａは、単結合又は炭素数１〜４のアルカンジイル基を表す。
Ｌ^3ａは、炭素数１〜８のペルフルオロアルカンジイル基又は炭素数３〜１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ⁶⁴は、水素原子又はフッ素原子を表す。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4). ..

[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 ⁶⁴ represents a hydrogen atom or a fluorine atom. ]

^Examples of the alkanediyl group 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. Examples include branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group. Be done.

The perfluoroalkanediyl group in L ^3a includes a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a perfluoropropane-2,2. -Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2 -Diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like can be mentioned.
^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 R 54} 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価の飽和炭化水素基を表す。
Ａ^a43は、単結合又は置換基を有していてもよい炭素数１〜５の２価の飽和炭化水素基を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は７以下である。〕
＊は結合部位であり、右側の＊が−Ｏ−ＣＯ−Ｒ^a42との結合部位である。］

[In 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 (a-g1). However, ^{at least one of Aa41} and ^Ra42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In the formula (a-g1),
s represents 0 or 1.
A a ⁴² and A a ⁴⁴ each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a divalent saturated 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 the binding site, and * on the right is the binding site with -O-CO-R ^a42 . ]

^Examples of the saturated hydrocarbon group in R a42 include a chain hydrocarbon group, a monocyclic or polycyclic saturated 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以上の脂環式飽和炭化水素基とを組み合わせることにより形成される基が挙げられ、−アルカンジイル基−脂環式飽和炭化水素基、−脂環式飽和炭化水素基−アルキル基、−アルカンジイル基−脂環式飽和炭化水素基−アルキル基等が挙げられる。 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 saturated 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. Examples thereof include a polycyclic alicyclic hydrocarbon group such as a group (* represents a binding site).

Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups and one or more alicyclic saturated hydrocarbon groups, and examples thereof include-alkanediyl groups. -Alicyclic saturated hydrocarbon group, -Alicyclic saturated hydrocarbon group-Alkyl group, -Alkanediyl group-Alicyclic saturated hydrocarbon group-Alkyl group and the like can be mentioned.

［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。
Ａ^a45は、ハロゲン原子を有していてもよい炭素数１〜１７の飽和炭化水素基を表す。
＊はＲ^a42との結合部位を表す。］
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の飽和炭化水素基を表す。 ^{Examples of the substituent contained in} R a42 include at least one selected from the group consisting of 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 (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, * -O-CO- or * -CO-O-.
A ^a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* Represents the binding site with ^{R a42.} ]
However, in R ^a42- X ^a43- A ^a45 , when R ^a42 does not have a halogen atom, A ^a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms having at least one halogen atom.

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。 Saturated hydrocarbon groups in A ^a45 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl. Alkyl groups such as groups;
Monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; and decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* represents a binding site). ) Etc., a polycyclic alicyclic hydrocarbon group can be mentioned.

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

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

[In the formula (a-g2),
A ^a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents **-O-CO- or **-CO-O- (** represents the binding site with ^{A a46).}
A ^a47 represents a saturated 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 the binding site with the carbonyl group. ]

The saturated hydrocarbon group of A ^a46 preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
The saturated 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 (a-g2) is the following structure (* is a binding site with a carbonyl group).

The ^{alkanediyl group in A a41} includes a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-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 saturated hydrocarbon group represented by A a42} , A ^a43 and A ^{a44 in} the group represented by the formula (a-g1) includes a linear or branched alkandyl group and a monocyclic divalent alicyclic group. Examples thereof include a saturated hydrocarbon group and a divalent saturated hydrocarbon group formed by combining an alcandiyl group and a divalent alicyclic saturated 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 saturated hydrocarbon group represented by A a42, A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

In the group represented by the formula (a-g1), ^{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 binding site, respectively, and ** is the binding site 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。］ Examples of the structural unit represented by the formula (a4-1) include a structural unit represented by the formula (a4-2) and a structural unit represented by the formula (a4-3).

[In the formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ⁴⁴ represents an alkanediyl group having 1 to 6 carbon atoms, and −CH ₂ − contained in the alkanediyl group may be replaced with −O− or −CO−.
R ^f6 represents a saturated hydrocarbon group having 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 42.}
As the ^{alkanediyl group 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との結合部位を表す。）。
Ａ^f14は、フッ素原子を有していてもよい炭素数１〜１７の飽和炭化水素基を表す。
但し、Ａ^f13及びＡ^f14の少なくとも１つは、フッ素原子を有し、Ｌ⁵、Ａ^f13及びＡ^f14の合計炭素数の上限は２０である。］

[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 the binding site 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 of A a41.

The ^{divalent saturated hydrocarbon group which may have a fluorine atom in A f13} preferably has a divalent chain saturated hydrocarbon group which may have a fluorine atom and a fluorine atom. It is also a good divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkandyl group.
Examples of the divalent chain saturated 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 and a perfluoroethylene group. Examples thereof include a perfluoroalkanediyl group such as a perfluoropropanediyl group, a perfluorobutanediyl group and a perfluoropentanediyl group.
The divalent alicyclic saturated 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 divalent chain-type saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms. A divalent chain saturated hydrocarbon group having 2 to 3 carbon atoms is more preferable.
The saturated hydrocarbon group of A ^f14 is preferably a group containing a chain-type saturated hydrocarbon group having 3 to 12 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and is preferably a chain-type saturated hydrocarbon group having 3 to 10 carbon atoms. Groups containing hydrocarbon groups and alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms are more preferable. Among them, A ^f14 is preferably a group containing an alicyclic saturated 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 saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and an alkyl group having 1 to 10 carbon atoms having a fluorine atom is preferable. More preferably, an alkyl group having 1 to 6 carbon atoms having a fluorine atom is further 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 preferable.

［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との結合部位を表す。）。
Ｌ^x1は、炭素数１〜１６の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x2は、単結合又は炭素数１〜１５の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x1及びＬ^x2の合計炭素数は、１６以下である。
式（Ｌ１−２）中、
Ｌ^x3は、炭素数１〜１７の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x4は、単結合又は炭素数１〜１６の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x3及びＬ^x4の合計炭素数は、１７以下である。
式（Ｌ１−３）中、
Ｌ^x5は、炭素数１〜１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x6及びＬ^x7は、それぞれ独立に、単結合又は炭素数１〜１４の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x5、Ｌ^x6及びＬ^x7の合計炭素数は、１５以下である。
式（Ｌ１−４）中、
Ｌ^x8及びＬ^x9は、単結合又は炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。
Ｗ^x1は、炭素数３〜１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^x8、Ｌ^x9及びＷ^x1の合計炭素数は、１５以下である。 _{Examples of the group in which -CH 2-} 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, * and ** represent the binding sites, respectively, and * represents the binding site with the oxygen atom.

In formula (L1-1),
X ^x1 represents * -O-CO- or * -CO-O- (* represents the binding site with ^{L x1).}
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total number of carbon atoms of ^{L x 1} and L ^{x 2 is 16 or less.}
In formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total 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 equation (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 ^{x 1} is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a cyclohexanediyl group or an adamantandiyl 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).

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.

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。

When the resin (A) has the 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). ~ 15 mol% is more preferred.

<Structural unit (a6)>
Structural unit (a6) is, -SO ₂ - is a structural unit having a group, -SO ₂ - preferably has a group in the side chain.
-SO 2 _- structural unit having a group, -SO 2 _- may have a straight chain structure having a group, -SO 2 _- may have a branched structure having a group, -SO 2 _- may have a cyclic structure having the group (monocyclic and polycyclic structures). A structural unit having a cyclic structure having _{a −SO 2} − group is preferable, and a structural unit having a cyclic structure (sultone ring) containing _{−SO 2 −O− is more preferable.}

The sultone ring of the following formula ^(T 1 -1), formula ^(T 1 -2), include the rings represented by the formula ^(T 1 -3) and formula ^(T 1 -4). The binding site can be any position. The sultone ring may be a monocyclic type, but is preferably a polycyclic type. The polycyclic sultone ring, means a bridged ring containing _-SO 2 -O- as atomic group forming a ring, represented by formula ^(T 1 -1) and formula ^(T 1 -2) Ring is mentioned. Sultone ring, as the ring represented by the formula (T 1 ^-2), as an atomic group forming a ring, other than -SO 2 _-O-, may contain a further hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom or a nitrogen atom, and an oxygen atom is preferable.

The sulton ring may have a substituent, and as the substituent, an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxy group, a cyano group, or a hydroxy group may have a halogen atom or a hydroxy group. Examples thereof include an alkoxy group having ~ 12; an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms and an alkylcarbonyl group having 2 to 4 carbon atoms. Be done.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and a decyl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Is.
Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Examples thereof include a trichloromethyl group, a tribromomethyl group and a triiodomethyl group, preferably a trifluoromethyl group.
Examples of the alkyl group having a hydroxy group include a hydroxyalkyl group of a hydroxymethyl group and a 2-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 aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a trill group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group and a phenanthryl group. Groups include 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
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 alkoxycarbonyl group include a group in which an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or less carbon atoms, and more preferably a methoxycarbonyl group. Can be mentioned.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group.

［式（Ｔ１’）中、
Ｘ^１１は、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^４１は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基又は炭素数２〜４のアルキルカルボニル基を表す。
ｍａは、０〜９のいずれかの整数を表す。ｍａが２以上のとき、複数のＲ^４１は同一であっても異なってもよい。
結合部位は任意の位置である。］
Ｘ^１１は、好ましくは酸素原子又はメチレン基であり、より好ましくはメチレン基である。
Ｒ^４１としては、スルトン環の置換基と同様のものが挙げられ、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基が好ましい。 A sultone ring having no substituent is preferable from the viewpoint that the monomer for deriving the structural unit (a6) can be easily produced.
As the sultone ring, a ring represented by the following formula (T1') is preferable.

[In the formula (T1'),
X ¹¹ represents an oxygen atom, a sulfur atom or a methylene group.
R ⁴¹ is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, and an aryl having 6 to 12 carbon atoms. It represents a group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms.
ma represents an integer of 0 to 9. When ma is 2 or more, the plurality of R ^41s may be the same or different.
The binding site is at any position. ]
X ¹¹ is preferably an oxygen atom or a methylene group, and more preferably a methylene group.
Examples of R ⁴¹ include the same as the substituent of the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferable.

［式（Ｔ１）中、
Ｒ^８は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基あるいは炭素数２〜４のアルキルカルボニル基を表す。
ｍは、０〜９のいずれかの整数を表す。ｍが２以上のとき、複数のＲ^８は同一であっても異なってもよい。
結合部位は任意の位置である。］ As the sultone ring, the ring represented by the formula (T1) is more preferable.

[In formula (T1),
R ⁸ is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, and an aryl having 6 to 12 carbon atoms. It represents a group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms.
m represents any integer from 0 to 9. When m is 2 or more, the plurality of R ^8s may be the same or different.
The binding site is at any position. ]

Examples of R ⁸ are the same as those of ^{R 41.}
The ma in the formula (T1') and m in the formula (T1) are preferably 0 or 1, and more preferably 0.

Examples of the ring represented by the formula (T1') and the ring represented by the formula (T1) include the following rings. The binding site is at any position.

The structural unit having a sultone ring preferably has the following groups. * In the following groups represents a binding site.

-SO 2 _- structural unit having a group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group and the like.
Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth) acrylic monomer.

［式（Ｉｘ）中、Ｒ^ｘ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。
Ａ^ｘｘは、酸素原子、−Ｎ（Ｒ^ｃ）−又は硫黄原子を表す。
Ａ^ｘ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−、−ＣＯ−又は−Ｎ（Ｒ^ｄ）−に置き換わっていてもよい。
Ｘ^１１は、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^４１は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基又は炭素数２〜４のアルキルカルボニル基を表す。
ｍａは、０〜９のいずれかの整数を表す。ｍａが２以上のとき、複数のＲ^４１は同一であっても異なってもよい。
Ｒ^ｃ及びＲ^ｄは、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。］ The structural unit (a6) is preferably a structural unit represented by the formula (Ix).

[In the formula (Ix), R ^x represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom.
A ^xx represents an oxygen atom, -N (R ^c )-or a sulfur atom.
A ^x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and −CH ₂ − contained in the saturated hydrocarbon group is changed to −O−, −CO− or −N (R ^d ) −. It may be replaced.
X ¹¹ represents an oxygen atom, a sulfur atom or a methylene group.
R ⁴¹ is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, and an aryl having 6 to 12 carbon atoms. It represents a group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms.
ma represents an integer of 0 to 9. When ma is 2 or more, the plurality of R ^41s may be the same or different.
R ^c and R ^d represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms independently of each other. ]

^{Examples of the halogen atom of Rx} include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
^{Examples of the alkyl group of Rx} include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
^{Examples of the alkyl group having a halogen atom of Rx} include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. , Perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like.
^Rx 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.

Examples of the divalent saturated hydrocarbon group of A ^x, a linear alkanediyl group, branched alkanediyl group, a divalent alicyclic saturated hydrocarbon group having a monocyclic or polycyclic and the like, these A combination of two or more of the groups may be used.
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, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4- Branched alkanediyl groups such as diyl groups;
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.

Examples of R ⁴¹ , X ¹¹ and ma are the same as those in the equation (T1').
Examples of the sultone ring include the above-mentioned ones, and among them, the above-mentioned ones in which the bond position is specified are preferable.

Examples of the structural unit (a6) include the following structural units.

Among them, the structural units represented by the formula (a6-1), the formula (a6-2), the formula (a6-6), the formula (a6-7), the formula (a6-8) and the formula (a6-12). Is preferable, and structural units represented by the formulas (a6-1), formulas (a6-2), formulas (a6-7) and (a6-8) are more preferable.
When the resin (A) has the structural unit (a6), the content thereof is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and 3) with respect to all the structural units of the resin (A). ~ 30 mol% is more preferable.

<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. Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and the structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or sulfonio in the side chain. It is preferably a structural unit having a group and an organic anion.

［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.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3, the 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 which 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 may be a combination of these.
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;
Divalent monocycle such as cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group. Alicyclic saturated hydrocarbon group;
A divalent polycyclic alicyclic saturated hydrocarbon group such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group. And so on.

_{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 each of −CH 2} − contained in the saturated hydrocarbon group is replaced by −O−, −S− or −CO− is 17 or less. In the following formula, * and ** represent a binding site, and * represents a binding site 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 divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
X ⁶ represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
X ⁷ represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms.
X ⁸ represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

Examples ^{of the organic cation represented by ZA +} include an organic onium cation, an organic sulfonium cation, an organic iodine 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, it may be referred to as a cation represented by any of the above-mentioned formulas (b2-1) to (b2-4) (hereinafter, "cation (b2-1)" depending on the formula number. ).

［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は互いに同一でも、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 formula (II-2-A),
R ^III3 , X ^III3 and ZA ⁺ have the same meanings as above.
z represents any integer from 0 to 6.
R ^III2 and R ^III4 independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms, and when z is 2 or more, a plurality of R ^III2 and R ^III4 are the same or different from each other. May be.
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 , Q ^a and Q ^b include the same perfluoroalkyl group having 1 to 6 carbon atoms represented by ^{Q b1 described later.} ..

［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.
X ^I2 represents a divalent saturated hydrocarbon group of 1 to 11 carbon atoms, -CH ₂ contained in the saturated hydrocarbon group - is -O -, - it is replaced in 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 X ^I2, are the same as those of 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ｎＡ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-1), the structural unit represented by the formula (II-2-A-2) is preferable.

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

As the structural unit represented by the formula (II-2-A'), for example, the following structural unit, the ^{group corresponding to the methyl group of R III3} is a hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen atom. Examples thereof include structural units replaced with alkyl groups having 1 to 6 carbon atoms (for example, trifluoromethyl groups, etc.) and structural units described in International Publication No. 2012/050015. ZA ⁺ represents an organic cation.

［式（ＩＩ−１−１）中、
Ａ^ＩＩ１は、単結合又は２価の連結基を表す。
Ｒ^ＩＩ１は、炭素数６〜１８の２価の芳香族炭化水素基を表す。
Ｒ^ＩＩ２及びＲ^ＩＩ３は、それぞれ独立して、炭素数１〜１８の炭化水素基を表し、Ｒ^ＩＩ２及びＲ^ＩＩ３は互いに結合してそれらが結合する硫黄原子とともに環を形成していてもよい。
Ｒ^ＩＩ４は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよい炭素数１〜６のアルキル基を表す。
Ａ⁻は、有機アニオンを表す。］
Ｒ^ＩＩ１で表される炭素数６〜１８の２価の芳香族炭化水素基としては、フェニレン基及びナフチレン基等が挙げられる。
Ｒ^ＩＩ２及びＲ^ＩＩ３で表される炭化水素基としては、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。
アルキル基及び脂環式炭化水素基は、上記と同様のものが挙げられる。
芳香族炭化水素基としては、フェニル基、ナフチル基、アントリル基、ビフェニル基、フェナントリル基等のアリール基が挙げられる。
組み合わせた基としては、上述したアルキル基と脂環式炭化水素基とを組み合わせた基、ベンジル基等のアラルキル基、アルキル基を有する芳香族炭化水素基（ｐ−メチルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、トリル基、キシリル基、クメニル基、メシチル基、２，６−ジエチルフェニル基、２−メチル−６−エチルフェニル基等）、脂環式炭化水素基を有する芳香族炭化水素基（ｐ−シクロヘキシルフェニル基、ｐ−アダマンチルフェニル基等）、フェニルシクロヘキシル基等のアリール−シクロアルキル基等が挙げられる。
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 alkyl group and the alicyclic hydrocarbon group include the same as above.
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and a phenanthryl group.
Examples of the combined group include a group combining the above-mentioned alkyl group and an alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-). Aromatic hydrocarbon group having an alicyclic hydrocarbon group (butylphenyl group, trill group, xsilyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) (P-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. can be mentioned.
Examples of the halogen atom represented by R ^II4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 is 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 divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by ^{X III3 can be mentioned.}

As the structural unit containing a cation in the formula (II-1-1), the structural unit represented by the following, the ^{group corresponding to the methyl group of R II4} is a hydrogen atom, a halogen atom (for example, a fluorine atom) or Examples thereof include a structural unit in which an alkyl group having 1 to 6 carbon atoms (for example, a trifluoromethyl group or the like) which may have a halogen atom is replaced.

Examples of the organic anion represented by A ⁻ include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylic acid anion. The ^{organic anion represented by A −} is preferably a sulfonic acid anion, and examples of the sulfonic acid anion include the same as the anion represented by the above 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, and even more preferably at least two selected from the group consisting of structural units (a1-1) and structural units (a1-2).
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 the formula (a2-1) or a structural unit represented by the formula (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)>
The resist composition of the present invention may contain a resin other than the 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 (a2), a structural unit (a3), and a structural unit derived from other known monomers. Among them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), and more preferably a resin composed of only the structural unit (a4).
Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer for inducing these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by adjusting the amount of the monomer used for the polymerization.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that of the resin (A).
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, and further, with respect to 100 parts by mass of the resin (A). It is preferably 1 to 40 parts by mass, more 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. 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). When the resist composition contains the quencher (C), the content of the quencher (C) is preferably about 0.01 to 15% by mass based on the solid content of the resist composition, and 0. It is more preferably about 01 to 10% by mass, further preferably about 0.1 to 5% by mass, and even more preferably about 0.1 to 3% by mass.
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 the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, and the like. 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. As a salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B), preferably a salt that generates a carboxylic acid having a weaker acidity than the acid generated from the acid generator (B) (carboxylic). A salt having an acid anion), more preferably a weak acid intramolecular salt (D).

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

<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 quencher ( 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 at the time of vacuum drying is preferably about 1~1.0 × 10 ⁵ Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. 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 radiating the laser light from, electron beam, and those that irradiate super-ultraviolet light (EUV) 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 exposed composition layer is heat treated (so-called post-exposure bake) 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 developing device using a developing solution. 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 ° C
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".

式（Ｉ−１−ａ）で表される塩４．３８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−ｂ）で表される化合物１．７８部を添加し、さらに、５０℃で２時間攪拌した。得られた混合溶液に、式（Ｉ−１−ｃ）で表される化合物２．６６部を添加し、さらに、５０℃で３時間攪拌した後、２３℃まで冷却した。得られた混合物に、５％シュウ酸水溶液１５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１５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―ｄ）で表される塩４．０２部を得た。

式（Ｉ−１−ｄ）で表される塩１．２６部、式（Ｉ−１−ｆ）で表される化合物０．０５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−ｅ）で表される化合物０．２０部を添加し、２３℃で２時間攪拌した。得られた反応混合物に、クロロホルム１０部及び１０％炭酸カリウム水溶液１０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１０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４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０．８３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ４９４．９ Example 1: Synthesis of salt represented by the formula (I-1)

4.38 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.78 parts of the compound represented by the formula (I-1-b) was added, and the mixture was further stirred at 50 ° C. for 2 hours. To the obtained mixed solution, 2.66 parts of the compound represented by the formula (I-1-c) was added, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to 23 ° C. To the obtained mixture, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 15 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-1-). 4.02 parts of salt represented by d) was obtained.

1.26 parts of the salt represented by the formula (I-1-d), 0.05 part of the compound 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, 0.20 part of the compound represented by the formula (I-1-e) was added, and the mixture was stirred at 23 ° C. for 2 hours. To the obtained reaction mixture, 10 parts of chloroform and 10 parts of a 10% aqueous potassium carbonate solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 4 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-1). 0.83 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 494.9

式（Ｉ−３−ａ）で表される化合物５．３６部、式（Ｉ−１−ｆ）で表される化合物０．４６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−ｅ）で表される化合物２．００部を添加し、２３℃で２時間攪拌した。得られた反応混合物に、クロロホルム２０部及び１０％炭酸カリウム水溶液２０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。この水洗操作を４回繰り返した。得られた有機層を濃縮し、濃縮混合物をカラム（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＝５／１）分取することにより、式（Ｉ−３−ｄ）で表される化合物６．８９部を得た。

式（Ｉ−３−ｄ）で表される化合物６．８０部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合溶液に、水素化ホウ素ナトリウム０．３５部及びイオン交換水５．３０部の混合溶液を添加し、２３℃で１８時間攪拌した。得られた反応混合物を濃縮した後、濃縮残に、ｔｅｒｔ−ブチルメチルエーテル８０部及びイオン交換水４０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９０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、濃縮混合物をカラム（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＝２／１）分取することにより、式（Ｉ−３−ｅ）で表される化合物６．４３部を得た。

式（Ｉ−１−ａ）で表される塩４．３８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−ｂ）で表される化合物１．７８部を添加し、さらに、５０℃で２時間攪拌した。得られた混合溶液に、式（Ｉ−３−ｅ）で表される化合物３．６６部を添加し、さらに、５０℃で３時間攪拌した後、２３℃まで冷却した。得られた混合物に、５％シュウ酸水溶液１５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１５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−３）で表される塩４．４７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ５２３．０ Example 2: Synthesis of salt represented by the formula (I-3)

5.36 parts of the compound represented by the formula (I-3-a), 0.46 parts of the compound 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, 2.00 parts of the compound represented by the formula (I-1-e) was added, and the mixture was stirred at 23 ° C. for 2 hours. To the obtained reaction mixture, 20 parts of chloroform and 20 parts of a 10% potassium carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 60 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 4 times. The obtained organic layer is concentrated, and the concentrated mixture is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 6.89 parts of the compound represented by the formula (I-3-d) was obtained.

6.80 parts of the compound represented by the formula (I-3-d) and 30 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. A mixed solution of 0.35 parts of sodium borohydride and 5.30 parts of ion-exchanged water was added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 18 hours. After concentrating the obtained reaction mixture, 80 parts of tert-butyl methyl ether and 40 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 90 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, and the concentrated mixture is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2/1). As a result, 6.43 parts of the compound represented by the formula (I-3-e) was obtained.

4.38 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.78 parts of the compound represented by the formula (I-1-b) was added, and the mixture was further stirred at 50 ° C. for 2 hours. To the obtained mixed solution, 3.66 parts of the compound represented by the formula (I-3-e) was added, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to 23 ° C. To the obtained mixture, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 15 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-3). 4.47 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 523.0

式（Ｉ−１−ａ）で表される塩４．３８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−ｂ）で表される化合物１．７８部を添加し、さらに、５０℃で２時間攪拌した。得られた混合溶液に、式（Ｉ−２２５−ｃ）で表される化合物２．６６部を添加し、さらに、５０℃で３時間攪拌した後、２３℃まで冷却した。得られた混合物に、５％シュウ酸水溶液１５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１５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−２２５―ｄ）で表される塩３．２８部を得た。

式（Ｉ−２２５−ｄ）で表される塩１．２６部、式（Ｉ−１−ｆ）で表される化合物０．０５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−ｅ）で表される化合物０．２０部を添加し、２３℃で２時間攪拌した。得られた反応混合物に、クロロホルム１０部及び１０％炭酸カリウム水溶液１０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１０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４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−２２５）で表される塩０．６６部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ４９４．９ Example 3: Synthesis of salt represented by the formula (I-225)

4.38 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.78 parts of the compound represented by the formula (I-1-b) was added, and the mixture was further stirred at 50 ° C. for 2 hours. To the obtained mixed solution, 2.66 parts of the compound represented by the formula (I-225-c) was added, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to 23 ° C. To the obtained mixture, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 15 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-225-). 3.28 parts of salt represented by d) was obtained.

1.26 parts of the salt represented by the formula (I-225-d), 0.05 part of the compound 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, 0.20 part of the compound represented by the formula (I-1-e) was added, and the mixture was stirred at 23 ° C. for 2 hours. To the obtained reaction mixture, 10 parts of chloroform and 10 parts of a 10% aqueous potassium carbonate solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 4 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-225). 0.66 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 494.9

式（Ｉ−２２７−ａ）で表される化合物５．３６部、式（Ｉ−１−ｆ）で表される化合物０．４６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−ｅ）で表される化合物２．００部を添加し、２３℃で２時間攪拌した。得られた反応混合物に、クロロホルム２０部及び１０％炭酸カリウム水溶液２０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。この水洗操作を４回繰り返した。得られた有機層を濃縮し、濃縮混合物をカラム（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＝５／１）分取することにより、式（Ｉ−２２７−ｄ）で表される化合物６．９５部を得た。

式（Ｉ−２２７−ｄ）で表される化合物６．８０部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合溶液に、水素化ホウ素ナトリウム０．３５部及びイオン交換水５．３０部の混合溶液を添加し、２３℃で１８時間攪拌した。得られた反応混合物を濃縮した後、濃縮残に、ｔｅｒｔ−ブチルメチルエーテル８０部及びイオン交換水４０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９０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、濃縮混合物をカラム（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＝２／１）分取することにより、式（Ｉ−２２７−ｅ）で表される化合物５．３８部を得た。

式（Ｉ−１−ａ）で表される塩４．３８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−ｂ）で表される化合物１．７８部を添加し、さらに、５０℃で２時間攪拌した。得られた混合溶液に、式（Ｉ−２２７−ｅ）で表される化合物３．６６部を添加し、さらに、５０℃で３時間攪拌した後、２３℃まで冷却した。得られた混合物に、５％シュウ酸水溶液１５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１５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−２２７）で表される塩３．１２部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ５２３．０ Example 4: Synthesis of salt represented by the formula (I-227)

5.36 parts of the compound represented by the formula (I-227-a), 0.46 parts of the compound 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, 2.00 parts of the compound represented by the formula (I-1-e) was added, and the mixture was stirred at 23 ° C. for 2 hours. To the obtained reaction mixture, 20 parts of chloroform and 20 parts of a 10% potassium carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 60 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 4 times. The obtained organic layer is concentrated, and the concentrated mixture is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 6.95 parts of the compound represented by the formula (I-227-d) was obtained.

6.80 parts of the compound represented by the formula (I-227-d) and 30 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. A mixed solution of 0.35 parts of sodium borohydride and 5.30 parts of ion-exchanged water was added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 18 hours. After concentrating the obtained reaction mixture, 80 parts of tert-butyl methyl ether and 40 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 90 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, and the concentrated mixture is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2/1). As a result, 5.38 parts of the compound represented by the formula (I-227-e) was obtained.

4.38 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.78 parts of the compound represented by the formula (I-1-b) was added, and the mixture was further stirred at 50 ° C. for 2 hours. To the obtained mixed solution, 3.66 parts of the compound represented by the formula (I-227-e) was added, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to 23 ° C. To the obtained mixture, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 15 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-227). 3.12 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 523.0

式（Ｉ−２３６−ａ）で表される化合物７．６７部、式（Ｉ−１−ｆ）で表される化合物０．４６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−ｅ）で表される化合物２．００部を添加し、２３℃で２時間攪拌した。得られた反応混合物に、クロロホルム２０部及び１０％炭酸カリウム水溶液２０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。この水洗操作を４回繰り返した。得られた有機層を濃縮し、濃縮混合物をカラム（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＝５／１）分取することにより、式（Ｉ−２３６−ｄ）で表される化合物７．１１部を得た。

式（Ｉ−２３６−ｄ）で表される化合物６．４１部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合溶液に、水素化ホウ素ナトリウム０．２５部及びイオン交換水３．７５部の混合溶液を添加し、２３℃で１８時間攪拌した。得られた反応混合物を濃縮した後、濃縮残に、ｔｅｒｔ−ブチルメチルエーテル８０部及びイオン交換水４０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９０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、濃縮混合物をカラム（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＝２／１）分取することにより、式（Ｉ−２３６−ｅ）で表される化合物４．９７部を得た。

式（Ｉ−１−ａ）で表される塩４．３８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−ｂ）で表される化合物１．７８部を添加し、さらに、５０℃で２時間攪拌した。得られた混合溶液に、式（Ｉ−２３６−ｅ）で表される化合物４．９２部を添加し、さらに、５０℃で３時間攪拌した後、２３℃まで冷却した。得られた混合物に、５％シュウ酸水溶液１５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１５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−２３６）で表される塩５．９２部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ６４８．９ Example 5: Synthesis of salt represented by the formula (I-236)

7.67 parts of the compound represented by the formula (I-236-a), 0.46 parts of the compound 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, 2.00 parts of the compound represented by the formula (I-1-e) was added, and the mixture was stirred at 23 ° C. for 2 hours. To the obtained reaction mixture, 20 parts of chloroform and 20 parts of a 10% potassium carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 60 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 4 times. The obtained organic layer is concentrated, and the concentrated mixture is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 5/1). As a result, 7.11 parts of the compound represented by the formula (I-236-d) was obtained.

6.41 parts of the compound represented by the formula (I-236-d) and 30 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. A mixed solution of 0.25 parts of sodium borohydride and 3.75 parts of ion-exchanged water was added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 18 hours. After concentrating the obtained reaction mixture, 80 parts of tert-butyl methyl ether and 40 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 90 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, and the concentrated mixture is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2/1). As a result, 4.97 parts of the compound represented by the formula (I-236-e) was obtained.

4.38 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.78 parts of the compound represented by the formula (I-1-b) was added, and the mixture was further stirred at 50 ° C. for 2 hours. To the obtained mixed solution, 4.92 parts of the compound represented by the formula (I-236-e) was added, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to 23 ° C. To the obtained mixture, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 15 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-236). 5.92 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 648.9

式（Ｉ−２３８−ａ）で表される化合物７．５１部、ピリジン３．１３部、ジメチルアミノピリジン０．４４部及びテトラヒドロフラン４０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、式（Ｉ−２３８−ｂ）で表される化合物４．７０部を添加し、５℃で３０分間攪拌した後、さらに、２３℃で２時間撹拌した。得られた混合物に、クロロホルム６０部及び１０％炭酸カリウム水溶液１５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１５部を添加し、２３℃で３０分間攪拌した後、分液して有機層を取り出した。この洗浄操作を３回繰り返した。得られた有機層に、イオン交換水１５部を添加し、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３回繰り返した。得られた有機層を濃縮し、濃縮混合物をカラム（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）を用いて分取することにより、式（Ｉ−２３８−ｄ）で表される化合物８．１２部を得た。

式（Ｉ−２３８−ｄ）で表される化合物６．７８部及びアセトニトリル３０部を混合し、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合溶液に、水素化ホウ素ナトリウム０．２５部及びイオン交換水３．７５部の混合溶液を添加し、２３℃で１８時間攪拌した。得られた反応混合物を濃縮した後、濃縮残に、ｔｅｒｔ−ブチルメチルエーテル８０部及びイオン交換水４０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９０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、濃縮混合物をカラム（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＝２／１）分取することにより、式（Ｉ−２３８−ｅ）で表される化合物５．２７部を得た。

式（Ｉ−１−ａ）で表される塩４．３８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−ｂ）で表される化合物１．７８部を添加し、さらに、５０℃で２時間攪拌した。得られた混合溶液に、式（Ｉ−２３８−ｅ）で表される化合物５．２０部を添加し、さらに、５０℃で３時間攪拌した後、２３℃まで冷却した。得られた混合物に、５％シュウ酸水溶液１５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１５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−２３８）で表される塩５．８８部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ６７６．９ Example 6: Synthesis of salt represented by the formula (I-238)

7.51 parts of the compound represented by the formula (I-238-a), 3.13 parts of pyridine, 0.44 parts of dimethylaminopyridine and 40 parts of tetrahydrofuran were mixed, stirred at 23 ° C. for 30 minutes, and then 5 ° C. Cooled down to. To the obtained mixture, 4.70 parts of the compound represented by the formula (I-238-b) was added, and the mixture was stirred at 5 ° C. for 30 minutes and then at 23 ° C. for 2 hours. To the obtained mixture, 60 parts of chloroform and 15 parts of a 10% potassium carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. Fifteen 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. This cleaning operation was repeated 3 times. To the obtained organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. This washing operation was repeated 3 times. The obtained organic layer is concentrated, and the concentrated mixture is prepared using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 8.12 parts of the compound represented by the formula (I-238-d) was obtained.

6.78 parts of the compound represented by the formula (I-238-d) and 30 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. A mixed solution of 0.25 parts of sodium borohydride and 3.75 parts of ion-exchanged water was added to the obtained mixed solution, and the mixture was stirred at 23 ° C. for 18 hours. After concentrating the obtained reaction mixture, 80 parts of tert-butyl methyl ether and 40 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. 90 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, and the concentrated mixture is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2/1). As a result, 5.27 parts of the compound represented by the formula (I-238-e) was obtained.

4.38 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.78 parts of the compound represented by the formula (I-1-b) was added, and the mixture was further stirred at 50 ° C. for 2 hours. To the obtained mixed solution, 5.20 parts of the compound represented by the formula (I-238-e) was added, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to 23 ° C. To the obtained mixture, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 15 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (I-238). 5.88 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 676.9

式（Ｂ１−Ｘ５−ｄ）で表される化合物１．１１部、式（Ｉ−１−ｆ）で表される化合物０．０５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−ｅ）で表される化合物０．２０部を添加し、２３℃で２時間攪拌した。得られた反応混合物に、クロロホルム１０部及び１０％炭酸カリウム水溶液１０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１０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４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（Ｂ１−Ｘ５）で表される塩０．７７部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ４１１．０ Synthesis example 1: Synthesis of salt represented by the formula (B1-X5)

1.11 parts of the compound represented by the formula (B1-X5-d), 0.05 part of the compound 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, 0.20 part of the compound represented by the formula (I-1-e) was added, and the mixture was stirred at 23 ° C. for 2 hours. To the obtained reaction mixture, 10 parts of chloroform and 10 parts of a 10% aqueous potassium carbonate solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 4 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (B1-X5). 0.77 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 411.0

式（Ｉ−１−ａ）で表される塩４．３８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−ｂ）で表される化合物１．７８部を添加し、さらに、５０℃で２時間攪拌した。得られた混合溶液に、式（Ｂ１−Ｘ６−ｃ）で表される化合物２．３６部を添加し、さらに、５０℃で３時間攪拌した後、２３℃まで冷却した。得られた混合物に、５％シュウ酸水溶液１５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１５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（Ｂ１−Ｘ６―ｄ）で表される塩２．４４部を得た。

式（Ｂ１−Ｘ６−ｄ）で表される塩１．２０部、式（Ｉ−１−ｆ）で表される化合物０．０５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−ｅ）で表される化合物０．２０部を添加し、２３℃で２時間攪拌した。得られた反応混合物に、クロロホルム１０部及び１０％炭酸カリウム水溶液１０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１０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４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（Ｂ１−Ｘ６）で表される塩０．９３部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２６３．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ４６４．９ Synthesis example 2: Synthesis of salt represented by the formula (B1-X6)

4.38 parts of the salt represented by the formula (I-1-a) and 30 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 1.78 parts of the compound represented by the formula (I-1-b) was added, and the mixture was further stirred at 50 ° C. for 2 hours. To the obtained mixed solution, 2.36 parts of the compound represented by the formula (B1-X6-c) was added, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to 23 ° C. To the obtained mixture, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 15 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (B1-X6-). 2.44 parts of salt represented by d) was obtained.

1.20 parts of the salt represented by the formula (B1-X6-d), 0.05 part of the compound 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, 0.20 part of the compound represented by the formula (I-1-e) was added, and the mixture was stirred at 23 ° C. for 2 hours. To the obtained reaction mixture, 10 parts of chloroform and 10 parts of a 10% aqueous potassium carbonate solution were added, and the mixture was stirred at 23 ° C. for 30 minutes and then separated to remove the organic layer. After adding 10 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, the liquid was separated and the organic layer was taken out. This washing operation was repeated 4 times. The obtained organic layer was concentrated, 30 parts of tert-butylmethyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, and then the supernatant was removed and concentrated to obtain the formula (B1-X6). 0.93 parts of salt represented by is obtained.
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 464.9

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

Synthesis Example 3 [Synthesis of resin A1]
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 this was heated at 85 ° C. for about 5 hours to carry out polymerization. rice field. 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 resulting organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and recovered, yield 78 resin A1 (copolymer) is the weight average molecular weight of about 5.3 × 10 ³ Obtained in%. This resin A1 has the following structural units.

Synthesis Example 4 [Synthesis of resin A2]
As the monomer, a monomer (a1-4-2) and a monomer (a1-2-6) are used, and the molar ratio [monomer (a1-4-2): monomer (a1-2-6)] is 38:62. In addition, methyl isobutyl ketone was mixed with this monomer mixture in an amount of 1.5 times by mass based on 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 85 ° C. for about 5 hours to carry out polymerization. rice field. 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 resulting organic layer, to precipitate a resin poured into a large amount of n- heptane by filtration and recovered, the resin weight average molecular weight of about 5.4 × 10 ³ A2 (copolymer) to yield 89 Obtained in%. This resin A2 has the following structural units.

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

Ｂ１−Ｘ５：式（Ｂ１−Ｘ５）で表される塩
Ｂ１−Ｘ６：式（Ｂ１−Ｘ６）で表される塩
＜クエンチャー（Ｃ）＞
Ｃ１：特開２０１１−３９５０２号公報記載の方法で合成

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート 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>
A1, A2: Resin A1, Resin A2
<Salt (I)>
I-1: Salt represented by the formula (I-1) I-3: Salt represented by the formula (I-3) I-225: Salt represented by the formula (I-225) I-227: Formula represented by the formula (I-225) Salt represented by (I-227) I-236: Salt represented by formula (I-236) I-238: Salt represented by formula (I-238) <Acid generator (IX)>
B1-X1
B1-X2
B1-X3
B1-X4

B1-X5: Salt represented by the formula (B1-X5) B1-X6: Salt represented by the formula (B1-X6) <Quencher (C)>
C1: Synthesized by the method described in JP-A-2011-390502.

<Solvent>
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, a composition layer was formed by prebaking at the temperature shown in the “PB” column of Table 2 for 60 seconds. An electron beam lithography machine [“ELS-F125 125keV” manufactured by Elionix Inc.] was used on the composition layer formed on the wafer, and the exposure amount was changed stepwise to obtain a contact hole pattern (hole pitch 40 nm / hole). (Diameter 17 nm) was directly drawn.
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.

In the resist pattern obtained after development, the exposure amount at which the formed hole diameter was 17 nm was defined as the effective sensitivity.

比較組成物１〜４、参考組成物１、２と比較して、組成物１〜７での標準偏差が小さく、ＣＤ均一性（ＣＤＵ）評価が良好であった。 <CD uniformity (CDU) evaluation>
In the effective sensitivity, the hole diameter of the pattern formed with the hole diameter of 17 nm was measured 24 times for one hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was obtained by measuring the average hole diameter of a pattern formed with a hole diameter of 17 nm at 400 points in the same wafer as a population.
The results are shown in Table 3. The numbers in the table indicate the standard deviation (nm).

Compared with Comparative Compositions 1 to 4 and Reference Compositions 1 and 2, the standard deviations of the compositions 1 to 7 were small, and the CD uniformity (CDU) evaluation was good.

The resist composition containing the salt of the present invention is suitable for microfabrication of semiconductors and is extremely useful industrially because a resist pattern having good CD uniformity (CDU) can be obtained.

Claims (15)

A salt represented by the formula (I).

[In formula (I),
Q ¹ and ^{Q 2} each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
R ¹ and R ² independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms.
z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R ¹ and R ² may be the same or different from each other.
X ¹ represents * -CO-O-, * -O-CO-, * -O-CO-O- or * -O-, and * is C (R ¹ ) (R ² ) or C (Q). ¹⁾ represents the binding site to ^{(Q 2).}
L ¹ represents a hydrocarbon group having 1 to 28 carbon atoms which may have a single bond or a substituent, and −CH ₂ − contained in the hydrocarbon group is −O−, −S−, −SO. _It may be replaced with 2- or -CO-.
R ³ represents a halogen atom.
R ⁴ represents an alkyl group having 1 to 12 fluorinated alkyl group carbon atoms or 1 to 6 carbon atoms, -CH ₂ contained in the fluorinated alkyl group and the alkyl group - is -O- or -CO It may be replaced with-.
R ⁵ is an acid labile group.
m3 represents an integer of 1 to 3, when m3 is 2 or more, plural R ³ may be the same or different from each other.
m4 represents an integer of 1 to 3, when m4 is 2 or more, plural R ⁴ may be the same or different from each other.
m5 represents 1 or 2, when m5 is 2, the two R ⁵ may be the same or different from each other.
However, 3 ≦ m2 + m4 + m5 ≦ 5.
Z ⁺ represents an organic cation. ] The salt according to claim 1, wherein R ³ is a fluorine atom or an iodine atom. The salt according to claim 1 or 2, wherein m3 is 1 or 2 m5 is 1. m4 is 1, a salt according to any one of claims 1 to 3 ^{R 4} is an alkoxy group having 1 to 6 carbon atoms. m3 is 1 or 2
The salt according to any one of claims 1 to 4, wherein the bond position of at least one R ^{3 is bonded to the m position with respect to the bond position of L 1 in the benzene ring.} Binding position of at least one OR ⁵ is A salt according to any one of the o-position or attached to the p-position, according to claim 1 to 5 with respect to the binding position of L ¹ in the benzene ring. Acid labile group R ⁵ is, salts according to claim 1 is a group represented by the formula radical or formula represented by (R5-1) (R5-2).

Wherein ^{(R5-1), R 14, R} 15 and ^{R 16} are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, alicyclic having 3 to 20 carbon atoms Representing a hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, R ¹⁴ and R ¹⁵ are alibo rings having 3 to 20 carbon atoms together with carbon atoms bonded to each other and bonded to each other. Form a hydrocarbon group.
m represents 0 or 1.
* Represents the binding site. ]

[In the formula (R5-2), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁹ represents a hydrocarbon group having 1 to 20 carbon atoms. carded, R ¹⁸ and R ¹⁹ form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atoms and X ^a to which they are attached,, -CH ₂ contained in the hydrocarbon group and heterocyclic group -May be replaced by -O- or -S-.
^Xa represents an oxygen atom or a sulfur atom.
n represents 0 or 1.
* Represents the binding site. ] L ¹ is a group composed of a single bond, an alkanediyl group having 1 to 6 carbon atoms or an alkanediyl group having 1 to 6 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 18 carbon atoms (provided that the group is the same. _{-CH 2-} contained in the alkanediyl group may be replaced with -O- or -CO-, and -CH _2- contained in the alicyclic saturated hydrocarbon group is -O-, -S-. , -SO ₂ -or -CO-.) The salt according to any one of claims 1 to 7. L ¹ is a single bond, an alkanediyl group having 1 to 6 carbon atoms or ^* -L ^4- CO-O- (where L ⁴ is a hydrocarbon group having 1 to 22 carbon atoms which may have a substituent. the stands, -CH ₂ contained in the hydrocarbon group - is, -O -, - S -, - SO 2 -. of or -CO- may be replaced by) any one of claims 1 to 8 is The salt described in. An acid generator containing the salt according to any one of claims 1 to 9. A resist composition containing the acid generator according to claim 10 and a resin having an acid unstable group. The 11th aspect of the present invention, wherein the resin having an acid unstable group contains at least one selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2). Resist composition.

[In the formula (a1-1) and the formula (a1-2),
L ^a1 and L ^a2 independently represent -O- or * -O- (CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents -CO-. Represents a bond with.
R ^a4 and R ^a5 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a hydrogen atom, a halogen atom or a halogen atom.
R ^a6 and R ^a7 are independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. Represents a hydrocarbon group or a group combining these groups.
m1 represents any integer from 0 to 14.
n1 represents any integer from 0 to 10.
n1'represents an integer of 0 to 3. ] The resist composition according to claim 11 or 12, wherein the resin having an acid unstable group further contains a structural unit represented by the formula (a2-A).

[In the 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 has 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 alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, and a carbon number of carbon atoms. It represents an alkylcarbonyl group of 2 to 4, an alkylcarbonyloxy group of 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group.
A ^a50 represents a single bond or ^* −X ^a51 − (A ^a52 −X ^a52 ) _nb −, and * represents a binding site with a carbon atom to which ^{−R a50 is bonded.}
A ^a52 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. ] The resist composition according to any one of claims 11 to 13, further comprising 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 any one of claims 11 to 14 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 step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for manufacturing a resist pattern including.