JP6688147B2 - Salt, acid generator, resin, resist composition, and method for producing resist pattern - Google Patents

Description

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

Patent Document 1 describes a resist composition containing the following compound.

Further, Patent Document 1 describes a resist composition containing a resin containing a structural unit derived from the following compound.

JP, 2010-53121, A

  In the resist composition containing the above compound and the resist composition using the resin containing the structural unit derived from the above compound, CD uniformity (CDU) may not always be satisfied.

［式（Ｉ）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｒ^１及びＲ^２は、互いに独立に、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。
Ｘ^１は、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−又は＊−Ｏ−を表し、＊はＣ（Ｒ^１）（Ｒ^２）又はＣ（Ｑ^１）（Ｑ^２）との結合位を表す。
Ａ^１は、炭素数４〜１８の２価の脂環式炭化水素基を含む炭素数４〜２４の炭化水素基を表す。
Ａ^２は、炭素数２〜１２の２価の炭化水素基を表す。
Ｒ^３及びＲ^４は、互いに独立に、水素原子又は炭素数１〜６の１価の飽和炭化水素基を表す。
Ｒ^５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は、式（Ｉ−Ａ）で表される基を表す。］

［式（Ｉ−Ａ）中、
Ａ^３は、炭素数２〜３６の２価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−ＣＯ−で置き換わっていてもよく、該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に置換されてもよい。］
〔２〕Ｘ^１が、＊−ＣＯ−Ｏ−であり、＊はＣ（Ｒ^１）（Ｒ^２）又はＣ（Ｑ^１）（Ｑ^２）との結合位を表す〔１〕に記載の化合物。
〔３〕Ａ^１が、アダマンタンジイル基を含む炭化水素基である〔１〕又は〔２〕記載の塩。
〔４〕Ａ^２が、炭素数２〜６のアルカンジイル基である〔１〕〜〔３〕のいずれか記載の化合物。
〔５〕式（Ｉ−Ａ）で表される基が、式（Ｉ−Ｂ）で表される基である〔１〕〜〔４〕のいずれか記載の化合物。

［式（Ｉ−Ｂ）中、＊はＳＯ_２との結合手を表す。］
〔６〕〔１〕〜〔５〕のいずれか記載の化合物を含有する酸発生剤。
〔７〕〔１〕〜〔５〕のいずれか記載の化合物に由来する構造単位を含む樹脂。
〔８〕さらに、式（Ｉ）で表される化合物に由来する構造単位以外の、酸不安定基を有する構造単位を含む〔７〕記載の樹脂。
〔９〕酸不安定基を有する構造単位が、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選ばれる少なくとも１つである〔８〕記載の樹脂。

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^ａ１及びＬ^ａ２は、互いに独立に、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^ａ４及びＲ^ａ５は、互いに独立に、水素原子又はメチル基を表す。
Ｒ^ａ６及びＲ^ａ７は、互いに独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合せた基を表す。
ｍ１は、０〜１４の整数を表す。
ｎ１は、０〜１０の整数を表す。
ｎ１’は、０〜３の整数を表す。］
〔１０〕〔７〕〜〔９〕のいずれか記載の樹脂と、酸発生剤とを含むレジスト組成物。
〔１１〕酸発生剤が、〔６〕に記載の酸発生剤である〔１０〕記載のレジスト組成物。
〔１２〕式（Ｉ）で表される化合物に由来する構造単位に以外の酸不安定基を有する構造単位を含む樹脂と、〔６〕に記載の酸発生剤とを含むレジスト組成物。
〔１３〕酸発生剤が、式（Ｂ１）で表される塩である〔１０〕に記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ^１１及びＱ^１２は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］
〔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〔１０〕〜〔１３〕のいずれか記載のレジスト組成物。
〔１５〕（１）〔１０〕〜〔１４〕のいずれか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 compound represented by the formula (I).

[In the formula (I),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each 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 is, * - CO-O -, * - O-CO- , * -O- and represents, * is ^{C (R 1) (R 2} ) or ^{C (Q 1) (Q 2} ) and the coupling position Represents
A ¹ represents a hydrocarbon group having 4 to 24 carbon atoms, including a divalent alicyclic hydrocarbon group having 4 to 18 carbon atoms.
A ² represents a divalent hydrocarbon group having 2 to 12 carbon atoms.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A represents a group represented by formula (IA). ]

[In the formula (IA),
A ³ represents a divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S— or —CO—, The hydrogen atom contained in the hydrocarbon group may be replaced with a halogen atom or a hydroxy group. ]
[2] The compound according to [1], wherein X ¹ is * -CO-O-, and * represents a bonding position with C (R ¹ ) (R ² ) or C (Q ¹ ) (Q ² ). .
[3] The salt according to [1] or [2], wherein A ¹ is a hydrocarbon group containing an adamantanediyl group.
[4] The compound according to any one of [1] to [3], wherein A ² is an alkanediyl group having 2 to 6 carbon atoms.
[5] The compound according to any one of [1] to [4], wherein the group represented by the formula (IA) is a group represented by the formula (IB).

[In formula (IB), * represents a bond with SO ₂ . ]
[6] An acid generator containing the compound according to any one of [1] to [5].
[7] A resin containing a structural unit derived from the compound according to any one of [1] to [5].
[8] The resin according to [7], which further contains a structural unit having an acid labile group other than the structural unit derived from the compound represented by the formula (I).
[9] The structural unit having an acid labile group is at least one selected from the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) [8]. Resin.

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond with —CO—. Representing a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these.
m1 represents the integer of 0-14.
n1 represents the integer of 0-10.
n1 'represents the integer of 0-3. ]
[10] A resist composition containing the resin according to any one of [7] to [9] and an acid generator.
[11] The resist composition according to [10], wherein the acid generator is the acid generator according to [6].
[12] A resist composition comprising a resin containing a structural unit having an acid labile group other than the structural unit derived from the compound represented by the formula (I), and the acid generator according to [6].
[13] The resist composition according to [10], wherein the acid generator is a salt represented by the formula (B1).

[In the formula (B1),
Q ¹¹ and Q ¹² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon group is, -O - - -CH ₂ contained in the hydrogen radical, - SO ₂ - or -CO- may be replaced with.
Z ⁺ represents an organic cation. ]
[14] The resist composition according to any one of [10] to [13], further including 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 [10] to [14] onto a substrate,
(2) a step of drying the composition after coating to form a composition layer,
(3) exposing the composition layer
A method for producing a resist pattern, comprising the step of (4) heating the composition layer after exposure, and (5) developing the composition layer after heating.

  By using the resist composition using the compound of the present invention, a resist pattern can be produced with excellent CD uniformity (CDU).

In the present specification, unless otherwise specified, in the description of the structural formula of the compound, “aliphatic hydrocarbon group” means a linear or branched hydrocarbon group, and “alicyclic hydrocarbon group” means an aliphatic hydrocarbon group. It means a group in which a number of hydrogen atoms corresponding to the valence is removed from the ring of a cyclic hydrocarbon. The "aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bound to an aromatic ring. When stereoisomers are present, all stereoisomers are included.
In the present specification, "(meth) acrylic monomer" means at least one monomer having a _"CH 2 = _CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " structure of To do. Similarly, “(meth) acrylate” means “at least one of acrylate and methacrylate”. The expressions such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning. Further, in the groups described in the present specification, any of those having both a linear structure and a branched structure may be used.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described below from the total amount of the resist composition.

［式（Ｉ）中、Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｒ^１及びＲ^２は、互いに独立に、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。
Ｘ^１は、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−又は＊−Ｏ−を表し、＊はＣ（Ｒ^１）（Ｒ^２）又はＣ（Ｑ^１）（Ｑ^２）との結合位を表す。
Ａ^１は、炭素数４〜１８の２価の脂環式炭化水素基を含む炭素数４〜２４の炭化水素基を表す。
Ａ^２は、炭素数２〜１２の２価の炭化水素基を表す。
Ｒ^３及びＲ^４は、互いに独立に、水素原子又は炭素数１〜６の１価の飽和炭化水素基を表す。
Ｒ^５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は、式（Ｉ−Ａ）で表される基を表す。］

［式（Ｉ−Ａ）中、Ａ^３は、炭素数２〜３６の２価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−ＣＯ−で置き換わっていてもよく、該炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基に置換されてもよい。］ <Compound represented by Formula (I) (hereinafter sometimes referred to as Compound (I))>

[In the formula (I), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each 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 is, * - CO-O -, * - O-CO- , * -O- and represents, * is ^{C (R 1) (R 2} ) or ^{C (Q 1) (Q 2} ) and the coupling position Represents
A ¹ represents a hydrocarbon group having 4 to 24 carbon atoms, including a divalent alicyclic hydrocarbon group having 4 to 18 carbon atoms.
A ² represents a divalent hydrocarbon group having 2 to 12 carbon atoms.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A represents a group represented by formula (IA). ]

[In the formula (IA), A ³ represents a divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S— or —. It may be replaced by CO-, and the hydrogen atom contained in the hydrocarbon group may be replaced by a halogen atom or a hydroxy group. ]

The perfluoroalkyl group of Q ¹ , Q ² , R ¹ and R ² includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group and a perfluorotert-butyl group. , Perfluoropentyl group, perfluorohexyl group and the like.
Q ¹ and Q ² independently of each other are preferably a trifluoromethyl group or a fluorine atom, and more preferably a fluorine atom.
R ¹ and R ² are independently of each other, preferably a hydrogen atom or a fluorine atom.
z is preferably 0.

X ¹ is preferably * -CO-O- (* represents a bonding position with C (R ¹ ) (R ² ) or C (Q ¹ ) (Q ² )).

The hydrocarbon group containing a divalent alicyclic hydrocarbon group having 4 to 18 carbon atoms of A ^{1 is} a divalent alicyclic hydrocarbon group having 4 to 18 carbon atoms or a divalent alicyclic hydrocarbon group. Examples thereof include a divalent group formed by combining the group and an alkanediyl group having 1 to 6 carbon atoms. That is, the number of carbon atoms of the hydrocarbon group here is 4 to 24, and preferably 5 to 20.
Examples of the divalent alicyclic hydrocarbon group include a cyclopentanediyl group, a cyclohexanediyl group, an adamantanediyl group, a norbornanediyl group and the like, preferably a cyclohexanediyl group and an adamantanediyl group, more preferably adamantane. A diyl group is mentioned.
Examples of the alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group. In the chain alkanediyl group, and the linear alkanediyl group, an alkyl group (in particular, an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, tert-butyl group, etc.), ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3- Examples thereof include branched alkanediyl groups such as diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

Examples of the hydrocarbon group containing a divalent alicyclic hydrocarbon group having 4 to 18 carbon atoms represented by A ¹ include an adamantanediyl group or a divalent group formed by combining an adamantanediyl group and an alkanediyl group. A divalent group formed by combining an alkanediyl group or an adamantanediyl group and a methylene group is more preferable, and a divalent group formed by combining an adamantanediyl group and a methylene group is further preferable. .

The divalent hydrocarbon group having 2 to 12 carbon atoms of A ² is formed by an alkanediyl group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group or a combination thereof. A divalent group is mentioned.
Examples of the alkanediyl group include linear alkanes such as ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group. The diyl group and the linear alkanediyl group include an alkyl group (in particular, an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group). Group having a side chain), ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, Examples thereof include branched alkanediyl groups such as a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.

  Examples of the divalent alicyclic hydrocarbon group include a cyclopentanediyl group, a cyclohexanediyl group, an adamantanediyl group, a norbornanediyl group, and the like, preferably a cyclohexanediyl group and an adamantanediyl group, more preferably adamantane. The diyl group is raised.

  Examples of the divalent aromatic hydrocarbon group include phenylene group, naphthylene group, anthrylene group, p-methylphenylene group, p-tert-butylphenylene group, p-adamantylphenylene group, tolyl group, xylylene group, cumenylene group and mesitylene group. Group, biphenylene group, phenanthrylene group, 2,6-diethylphenylene group, 2-methyl-6-ethylphenylene group and the like.

Examples of the divalent hydrocarbon group having 2 to 12 carbon atoms A ^2, preferably alkanediyl group having 2 to 6 carbon atoms, more preferably an alkanediyl group of 2 to 4 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 6 carbon atoms of R ³ and R ⁴ include a methyl group, an ethyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. A cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; and a group formed by combining these.
R ³ and R ⁴ are preferably each independently a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group for R ⁵ 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. Of these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
Examples of the halogen atom for R ⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group having a halogen atom of R ⁵ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro. Examples thereof include a hexyl group, a perchloromethyl group, a perbromomethyl group and a periodomethyl group.
R ⁵ is preferably a hydrogen atom or a methyl group.

The divalent hydrocarbon group having 2 to 36 carbon atoms of A ³ is formed by an alkanediyl group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group or a combination thereof. A divalent group is mentioned.
Examples of the alkanediyl group include linear alkanes such as ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group. The diyl group and the linear alkanediyl group include an alkyl group (in particular, an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group). Group having a side chain), ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, Examples thereof include branched alkanediyl groups such as a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.

  Examples of the divalent alicyclic hydrocarbon group include a cyclopentanediyl group, a cyclohexanediyl group, an adamantanediyl group, a norbornanediyl group, and the like, preferably a cyclohexanediyl group and an adamantanediyl group, more preferably adamantane. A diyl group is mentioned.

  Examples of the divalent aromatic hydrocarbon group include phenylene group, naphthylene group, anthrylene group, p-methylphenylene group, p-tert-butylphenylene group, p-adamantylphenylene group, tolyl group, xylylene group, cumenylene group and mesitylene group. Group, biphenylene group, phenanthrylene group, 2,6-diethylphenylene group, 2-methyl-6-ethylphenylene and the like.

Examples of the group represented by the formula (IA) include the following groups.

［式（Ｉ−Ｂ）中、＊はＳＯ_２との結合手を表す。］ The group represented by the formula (IA) is preferably a group represented by the formula (IB).

[In formula (IB), * represents a bond with SO ₂ . ]

Examples of the compound (I) include the following compounds.

  Among them, compound (I) is compound (I-1), compound (I-2), compound (I-3), compound (I-4), compound (I-5), compound (I-6). , Compound (I-7), compound (I-8), compound (I-9), compound (I-10), compound (I-11), compound (I-12), compound (I-13) and Compound (I-14), compound (I-15), compound (I-16)), compound (I-19) and compound (I-28) are preferable.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］ <Method for producing compound (I)>
The compound represented by the formula (I) is obtained by reacting the compound represented by the formula (Ia) with the compound represented by the formula (Ib) in a solvent in the presence of a catalyst. Can be manufactured by.

[In the formula, all symbols have the same meanings as described above. ]

Examples of the solvent include dimethylformamide, chloroform, acetonitrile and the like.
Examples of the catalyst include potassium carbonate, potassium iodide, pyridine, 2,6-lutidine and the like.
Examples of the compound represented by the formula (Ia) include compounds represented by the following formulas, 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。
Ｒ^４’は、Ｒ^４から、水素原子を除いた基を表す。］
溶媒としては、クロロホルム、テトラヒドロフランなどが挙げられる。
触媒としては、例えば、以下で表される塩などが挙げられる。

The compound represented by the formula (Ib) is obtained by reacting the compound represented by the formula (Ic) with the compound represented by the formula (Id) in the presence of a catalyst in a solvent. Can be obtained.

[In the formula, all symbols have the same meanings as described above.
R ^{4 ′} represents a group obtained by removing a hydrogen atom from R ⁴ . ]
Examples of the solvent include chloroform and tetrahydrofuran.
Examples of the catalyst include salts shown below.

A formula (I1-c) in which X ¹ is * -CO-O- (* represents a bonding position with C (R ¹ ) (R ² ) or C (Q ¹ ) (Q ² )). The compound represented by the formula (I1-e) can be obtained by reacting the compound represented by the formula (I1-e) with the compound represented by the formula (I1-f) in a solvent in the presence of a catalyst.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
溶媒としては、クロロホルム、テトラヒドロフランなどが挙げられる。
触媒としては、例えば、Ｔｉ（Ｏ−ｉ−Ｐｒ）_４で表される化合物などが挙げられる。
式（Ｉ１−ｅ）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 formula, all symbols have the same meanings as described above. ]
Examples of the solvent include chloroform and tetrahydrofuran.
Examples of the catalyst include compounds represented by Ti (O-i-Pr) ₄ .
Examples of the compound represented by the formula (I1-e) include compounds represented by the following formula, which can be easily obtained from the market.

Examples of the compound represented by the formula (I1-f) include compounds represented by the following formula, which can be easily obtained from the market.

  The compound represented by the formula (Id) is obtained by reacting the compound represented by the formula (Ig) with the compound represented by the formula (Ih) in the presence of a catalyst in a solvent. It can also be obtained.

［式中、全ての符号は、それぞれ前記と同じ意味を表す。］
溶媒としては、クロロホルム、テトラヒドロフランなどが挙げられる。
触媒としては、塩基触媒（例えば、トリエチルアミン）などが挙げられる。
式（Ｉ−ｇ）で表される化合物は、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。

式（Ｉ−ｈ）で表される化合物は、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 formula, all symbols have the same meanings as described above. ]
Examples of the solvent include chloroform and tetrahydrofuran.
Examples of the catalyst include a base catalyst (eg, triethylamine).
Examples of the compound represented by the formula (I-g) include compounds represented by the following formula, and they can be easily obtained from the market.

Examples of the compound represented by the formula (I-h) include compounds represented by the following formula, and they can be easily obtained from the market.

<Acid Generator Containing Compound Represented by Formula (I)>
The acid generator of the present invention is an acid generator containing the compound (I) as an active ingredient. In the acid generator, compound (I) may be used alone or in combination of two or more kinds.
The acid generator of the present invention may contain an acid generator known in the resist field (hereinafter sometimes referred to as “acid generator (B)”) as an active ingredient other than the compound (I). The acid generator (B) will be described later.
When the compound (I) and the acid generator (B) are contained as the acid generator, the ratio of the content of the compound (I) and the acid generator (B) (mass ratio; compound (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 further preferably 10:90 to 90:10. , And particularly preferably 15:85 to 85:15.

<Resin containing structural unit derived from compound represented by formula (I)>
The resin of the present invention is a resin containing a structural unit derived from compound (I) (hereinafter sometimes referred to as “resin (A)”). The resin (A) may be a homopolymer containing a structural unit derived from one type of compound (I) or a copolymer containing two or more types of structural units.
The content of the structural unit derived from the compound (I) is usually 0.1 to 20 mol% and preferably 0.5 to 10 mol% with respect to the total amount of the resin (A).

The resin (A) is a structural unit having an acid labile group other than the structural unit (I) in addition to the structural unit derived from the compound (I) (hereinafter sometimes referred to as the structural unit (I)). (Hereinafter sometimes referred to as “structural unit (a1)”). Here, the “acid-labile group” is a structural unit having a leaving group, the leaving group being released by contact with an acid, and the structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Means a group to be converted to.
The resin (A) preferably further contains a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”) and other structural units (hereinafter “structural unit (t)”) It may be said) etc.

<Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”).

［式（１）中、Ｒ^ａ１〜Ｒ^ａ３は、互いに独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組合せた基を表すか、Ｒ^ａ１及びＲ^ａ２は互いに結合してそれらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を形成する。
ｎａは、０又は１を表す。
＊は、結合手を表す。］ The acid labile group contained in the resin (A) is preferably the group (1) and / or the group (2).

[In the formula (1), R ^{a1 to} R ^a3 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group in which these are combined, or ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
na represents 0 or 1.
* Represents a bond. ]

［式（２）中、Ｒ^ａ１’及びＲ^ａ２’は、互いに独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合してそれらが結合する炭素原子及びＸとともに炭素数３〜２０の２価の複素環基を形成し、該炭化水素基及び該２価の複素環基に含まれる−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。
＊は、結合手を表す。］

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

^Examples of the alkyl group of R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group.
The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 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 (* represents a bond). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 is preferably an alicyclic hydrocarbon group having 3 to 16 carbon atoms.

Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a norbornylethyl group. Can be mentioned.
na is preferably 0.

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

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2- An alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantane- 1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group) and the like.

Ｒ^ａ１’及びＲ^ａ２’のうち、少なくとも１つは水素原子であることが好ましい。 Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as above.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl. Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl, and the like.
^{Examples of the} divalent heterocyclic group formed by R ^{a2 ′} and R ^{a3 ′} bonded to each other and the carbon atom to which they are bonded and X include the following groups. * Represents a bond.

At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

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

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

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

［式（ａ１−０）中、
Ｌ^ａ０１は、酸素原子又は＊−Ｏ−（ＣＨ_２）_ｋ０１−ＣＯ−Ｏ−を表し、ｋ０１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^ａ０１は、水素原子又はメチル基を表す。
Ｒ^ａ０２〜Ｒ^ａ０４は、互いに独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合せた基を表す。］

[In the formula (a1-0),
L ^a01 represents an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^{a02 to} R ^a04 each independently ^represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these. ]

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^ａ１及びＬ^ａ２は、互いに独立に、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ１−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^ａ４及びＲ^ａ５は、互いに独立に、水素原子又はメチル基を表す。
Ｒ^ａ６及びＲ^ａ７は、互いに独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合せることにより形成される基を表す。
ｍ１は、０〜１４の整数を表す。
ｎ１は、０〜１０の整数を表す。
ｎ１’は、０〜３の整数を表す。］

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

L ^a01 is preferably an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O— (provided that k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably. Is an oxygen atom.
Examples of the alkyl group of R ^{a02 to} R ^a04 , the alicyclic hydrocarbon group, and a group in which these are combined include the same groups as those described for R ^{a1 to} R ^a3 of the formula (1).
The alkyl group of R ^{a02 to} R ^a04 preferably has 6 or less carbon atoms.
The number of carbon atoms of the alicyclic hydrocarbon group of R ^{a02 to} R ^a04 is preferably 8 or less, more preferably 6 or less.
The group in which an alkyl group and an alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in which these alkyl groups and an alicyclic hydrocarbon group are combined. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, and a norbornylmethyl group. To be
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

L ^a1 and L ^a2 are preferably —O— or * —O— (CH ₂ ) _{k1 ′} —CO—O— (where k1 ′ is an integer of 1 to 4, preferably 1). ), And more preferably -O-.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and the group in which these are combined include the same groups as the groups described for R ^{a1 to} R ^a3 of the formula (1).
The carbon number of the alkyl group of R ^a6 and R ^a7 is preferably 6 or less.
The carbon number of the alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably 8 or less, more preferably 6 or less.
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.

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

In the above structural unit, a structural unit in which a methyl group corresponding to R ^a01 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a1-0).

  Examples of the monomer (a1-1) include the monomers described in JP2010-204646A. Among them, the monomer represented by any of the formulas (a1-1-1) to (a1-1-8) is preferable, and any of the formulas (a1-1-1) to (a1-1-4) is preferable. The monomer represented by is more preferable.

  Examples of the monomer (a1-2) include 1-methylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclopentan-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth). Acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, 1-ethylcycloheptan-1-yl (meth) acrylate, 1-ethylcyclooctane-1-yl (meth) acrylate, 1-isopropylcyclopentane-1 Examples include -yl (meth) acrylate, 1-isopropylcyclohexane-1-yl (meth) acrylate and the like. The monomer represented by any of the formulas (a1-2-1) to (a1-2-12) is preferable, and the formula (a1-2-3), the formula (a1-2-4), and the formula (a1- 2-9) and the monomer represented by Formula (a1-2-10) are more preferable, and the monomers represented by Formula (a1-2-3) and Formula (a1-2-9) are still more preferable.

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

［式（ａ１−３）中、
Ｒ^ａ９は、ヒドロキシ基を有していてもよい炭素数１〜３の脂肪族炭化水素基、カルボキシ基、シアノ基、水素原子又は−ＣＯＯＲ^ａ１３を表す。
Ｒ^ａ１３は、炭素数１〜８の脂肪族炭化水素基、炭素数３〜２０の脂環式炭化水素基、又はこれらを組合せることにより形成される基を表し、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよく、該脂肪族炭化水素基及び該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｒ^ａ１０〜Ｒ^ａ１２は、互いに独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組合せることにより形成される基を表すか、Ｒ^ａ１０及びＲ^ａ１１は互いに結合して、それらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を形成する。］ Further, the structural unit (a1) having the group (1) also includes a structural unit represented by the formula (a1-3). The structural unit represented by the formula (a1-3) may be referred to as a structural unit (a1-3). Further, the monomer that induces the structural unit (a1-3) may be referred to as a monomer (a1-3).

[In the formula (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxy group, a carboxy group, a cyano group, a hydrogen atom or —COOR ^a13 .
R ^a13 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these, and the aliphatic hydrocarbon group and The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group, and —CH ₂ — contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group is —O—. Alternatively, it may be replaced with -CO-.
R ^{a10 to} R ^a12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these, or R ^a10 and R ^a11 is bonded to each other to form, together with the carbon atom to which they are bonded, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. ]

Examples of the aliphatic hydrocarbon group which may have a hydroxy group for R ^a9 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a 2-hydroxyethyl group.
^Examples of —COOR ^a13 include groups in which a carbonyl group is bonded to an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group.
^Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^a13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and n. Examples include -hexyl group, n-heptyl group, 2-ethylhexyl group and n-octyl group.
^Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ^a13 include a cyclopentyl group, a cyclopropyl group, an adamantyl group, an adamantyl methyl group, a 1-adamantyl-1-methylethyl group, and 2-oxo-oxolane-3-. Examples thereof include an yl group and a 2-oxo-oxolan-4-yl group.
^Examples of the alkyl group of R ^{a10 to} R ^a12 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, an n-hexyl group, Examples thereof include n-heptyl group, 2-ethylhexyl group and n-octyl group.
The alicyclic hydrocarbon group of R ^{a10 to} R ^a12 may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. And cycloalkyl groups such as cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, and norbornyl. Group, a methylnorbornyl group, an isobornyl group, and the like.
As -C (R ^a10 ) (R ^a11 ) (R ^a12 ), when R ^a10 and R ^a11 are bonded to each other to form a divalent alicyclic hydrocarbon group together with the carbon atom to which they are bonded, The following groups are preferable.

  Specific examples of the monomer (a1-3) include 5-tert-butyl 5-norbornene-2-carboxylic acid, 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylic acid, and 5-norbornene-2-carboxylic acid. Acid 1-methylcyclohexyl, 5-norbornene-2-carboxylic acid 2-methyl-2-adamantyl, 5-norbornene-2-carboxylic acid 2-ethyl-2-adamantyl, 5-norbornene-2-carboxylic acid 1- (4 -Methylcyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1- (4-hydroxycyclohexyl) -1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1- (4-oxo Cyclohexyl) ethyl and 5-norbornene-2-carboxylic acid 1- (1-adamantyl) -1-methyl Chill, and the like.

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

  When the resin (A) contains the structural unit (a1-3), its content is preferably 10 to 95 mol% with respect to the total of all structural units of the resin (A), and preferably 15 to 90 mol%. %, And more preferably 20 to 85 mol%.

［式（ａ１−４）中、
Ｒ^ａ３２は、水素原子、ハロゲン原子、又は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^ａ３３は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｌａは０〜４の整数を表す。ｌａが２以上である場合、複数のＲ^ａ３３は互いに同一であっても異なってもよい。
Ｒ^ａ３４及びＲ^ａ３５は、互いに独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３６は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ３５及びＲ^ａ３６は互いに結合してそれらが結合するＣ−Ｏとともに炭素数３〜２０の２価の複素環基を形成し、該炭化水素基及び該２価の複素環基に含まれる−ＣＨ_２−は、−Ｏ−又は−Ｓ−で置き換わってもよい。］ As the structural unit (a1) having a group represented by the group (2), a structural unit represented by the formula (a1-4) (hereinafter, may be referred to as “structural unit (a1-4)”). Can be mentioned.

[In the formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
la represents an integer of 0 to 4. When la is 2 or more, a plurality of R ^a33 may be the same as or different from each other.
R ^a34 and ^{R a35} are independently of each other, 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 each And C—O to which they are bonded to form a divalent heterocyclic group having 3 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent heterocyclic group is —O. It may be replaced by -or -S-. ]

^Examples of the alkyl group of R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.
Examples of the halogen atom of R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, 1,1,2,2-tetrafluoro Ethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluoro Butyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n-perfluorohexyl group, etc. Can be mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
Examples of the hydrocarbon group R ^a34 and ^{R a35,} include the same groups as ^{R a1 'and R a2'} of formula (2).
R ^a36 is an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. Can be mentioned.

In formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and further preferably a methoxy group.
la is preferably 0 or 1, and more preferably 0.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
The hydrocarbon group for 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. And a C1-C18 alkyl group, a C3-C18 alicyclic aliphatic hydrocarbon group, or a C7-C18 aralkyl group. The alkyl group in R ^a36 and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group for R ^a36 has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.

  Examples of the monomer that leads to the structural unit (a1-4) include the monomers described in JP2010-204646A. Among them, the monomers represented by formula (a1-4-1) to formula (a1-4-8) are preferable, and formula (a1-4-1) to formula (a1-4-5) and formula (a1-). The monomers represented by 4-8) are more preferable.

  When the resin (A) has the structural unit (a1-4), the content thereof is preferably 10 to 95 mol% with respect to the total of all structural units of the resin (A), and is preferably 15 to 90. It is more preferably mol%, and further preferably 20 to 85 mol%.

［式（ａ１−５）中、
Ｒ^ａ８は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^ａ１は、単結合又は＊−（ＣＨ_２）_ｈ３−ＣＯ−Ｌ^５４−を表し、ｈ３は１〜４の整数を表し、＊は、Ｌ^５１との結合手を表す。
Ｌ^５１〜Ｌ^５４は、互いに独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。］ As the structural unit derived from the (meth) acrylic monomer having a group represented by the formula (2), a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)” There is also).

[In the formula (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or _{* - (CH 2) h3 -CO} -L 54 - represents, h3 represents an integer of 1 to 4, * ^represents a bond to ^{L 51.}
L ⁵¹ ~L ^54, independently of each other, represent -O- or -S-.
s1 represents an integer of 1 to 3.
s1 'represents the integer of 0-3. ]

Examples of the halogen atom include a fluorine atom and a chlorine atom, preferably a fluorine atom. Examples of the alkyl group 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 trifluoromethyl. Groups.
In formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
It is preferable that one of L ⁵² and L ⁵³ is -O- and the other is -S-.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

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

  When the resin (A) has the structural unit (a1-5), its content is preferably 1 to 50 mol% with respect to the total of all structural units of the resin (A), and 3 to 45. It is more preferably mol%, and further preferably 5 to 40 mol%.

As the structural unit (a1) having an acid labile group in the resin (A), the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2) and the structural unit (a1-5). ), One or more selected from the group consisting of), more preferably two or more, and a combination of structural unit (a1-1) and structural unit (a1-2), structural unit (a1-1) and structural unit (a1- 5) combination, structural unit (a1-1) and structural unit (a1-0) combination, structural unit (a1-2) and structural unit (a1-0) combination, structural unit (a1-5) and structure Combination of units (a1-0), structural unit (a1-0), combination of structural unit (a1-1) and structural unit (a1-2), structural unit (a1-0), structural unit (a1-1) And a structural unit (a1-5) are more preferable, and the structural unit (a1- ) And combinations of the structural units (a1-2), the combination is more preferable than the structural units (a1-1) and the structural unit (a1-5).
The structural unit (a1) preferably includes the structural unit (a1-1).

<Structural unit (s)>
The resin (A) of the present invention may further have a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”).
The structural unit (s) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”). As the monomer leading to the structural unit (s), a monomer having no acid labile group known in the resist field can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid labile group is preferable. A structural unit having a hydroxy group and having no acid labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a lactone ring and having no acid labile group When a resin having a unit (hereinafter sometimes referred to as “structural unit (a3)”) is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group contained in 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 KrF excimer laser (248 nm), electron beam or EUV (ultraviolet light) is used as an exposure light source, the structural unit (a2) is used. It is preferable to use the structural unit (a2) having a phenolic hydroxy group. When using an ArF excimer laser (193 nm) or the like, the structural unit (a2) is preferably the structural unit (a2) having an alcoholic hydroxy group, and more preferably the structural unit (a2-1). As the structural unit (a2), one type may be used alone, or two or more types may be used.

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

[In the formula (a2-0),
R ^a30 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents the integer of 0-4. When ma is an integer greater than or equal to 2, some R ^<a31 > may be mutually same or different. ]

^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom of R ^a30 include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1 , 1,2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3 , 3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl Group, an n-perfluorohexyl group and the like.
As R ^a30 , a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable, a hydrogen atom, a methyl group or an ethyl group is more preferable, and a hydrogen atom or a methyl group is further preferable.
^Examples of the alkoxy group of R ^a31 include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, a pentyloxy group and a hexyloxy group, and an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group. Is more preferable, and a methoxy group is still more preferable.
^Examples of the acyl group of R ^a31 include an acetyl group, a propionyl group and a butyryl group.
^Examples of the acyloxy group of R ^a31 include an acetyloxy group, a propionyloxy group and a butyryloxy group.
As ma, 0, 1 or 2 is preferable, 0 or 1 is more preferable, and 0 is further preferable.

Examples of the monomer that derives the structural unit (a2-0) include monomers described in JP 2010-204634 A.
Among them, the structural unit (a2-0) is represented by the formula (a2-0-1), the formula (a2-0-2), the formula (a2-0-3) and the formula (a2-0-4). Embedded image is preferred, and the structural unit represented by formula (a2-0-1) or formula (a2-0-2) is more preferred.

  The resin (A) containing the structural unit (a2-0) undergoes a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer that induces the structural unit (a2-0) is protected with a protective group, and then deprotected. It can be produced by processing. However, it is necessary to perform the deprotection treatment so that the acid labile group contained in the structural unit (a1) is not significantly impaired. An acetyl group etc. are mentioned as such a protective group.

  When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, its content is 5 to 95 mol% based on the total of all structural units of the resin (A). Is preferable, 10-80 mol% is more preferable, and 15-80 mol% is further preferable.

［式（ａ２−１）中、
Ｌ^ａ３は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ２−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^ａ１４は、水素原子又はメチル基を表す。
Ｒ^ａ１５及びＲ^ａ１６は、互いに独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。］ Examples of the structural unit (a2) having an alcoholic hydroxy group include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).

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

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

Examples of the monomer that derives the structural unit (a2-1) include the monomers described in JP2010-204646A. The monomer represented by any of the formulas (a2-1-1) to (a2-1-6) is preferable, and the monomer represented by any of the formulas (a2-1-1) to (a2-1-4) is represented. Is more preferable, and the monomer represented by formula (a2-1-1) or formula (a2-1-3) is further preferable.

  When the resin (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol, based on the total of all structural units of the resin (A). %, More preferably 1 to 35 mol%, further preferably 2 to 20 mol%.

<Structural unit (a3)>
The lactone ring contained in the structural unit (a3) may be a single ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. But it's okay. Preferably, a bridged ring containing a γ-butyrolactone ring, an adamantane lactone ring or a γ-butyrolactone ring structure is used.

［式（ａ３−１）中、
Ｌ^ａ４は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊は、カルボニル基との結合手を表す。
Ｒ^ａ１８は、水素原子又はメチル基を表す。
Ｒ^ａ２１は、炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５の整数を表す。ｐ１が２以上のとき、複数のＲ^ａ２１は互いに同一であっても異なってもよい。
式（ａ３−２）中、
Ｌ^ａ５は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊は、カルボニル基との結合手を表す。
Ｒ^ａ１９は、水素原子又はメチル基を表す。
Ｒ^ａ２２は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｑ１は、０〜３の整数を表す。ｑ１が２以上のとき、複数のＲ^ａ２２は互いに同一であっても異なってもよい。
式（ａ３−３）中、
Ｌ^ａ６は、−Ｏ−又は＊−Ｏ−（ＣＨ_２）_ｋ３−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊は、カルボニル基との結合手を表す。
Ｒ^ａ２０は、水素原子又はメチル基を表す。
Ｒ^ａ２３は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｒ１は、０〜３の整数を表す。ｒ１が２以上のとき、複数のＲ^ａ２３は互いに同一であっても異なってもよい。
式（ａ３−４）中、
Ｒ^ａ２４は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^ａ２５は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
Ｌ^ａ７は、単結合、^＊−Ｌ^ａ８−Ｏ−、^＊−Ｌ^ａ８−ＣＯ−Ｏ−、^＊−Ｌ^ａ８−ＣＯ−Ｏ−Ｌ^ａ９−ＣＯ−Ｏ−又は^＊−Ｌ^ａ８−Ｏ−ＣＯ−Ｌ^ａ９−Ｏ−を表す。
＊はカルボニル基との結合手を表す。
Ｌ^ａ８及びＬ^ａ９は、互いに独立に、炭素数１〜６のアルカンジイル基を表す。
ｗ１は、０〜８の整数を表す。ｗ１が２以上のとき、複数のＲ^ａ２５は互いに同一であってもよく、異なってもよい。］ 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). These may be contained alone or in combination of two or more.

[In the formula (a3-1),
L ^a4 represents -O- or _{* -O- (CH 2) k3 -CO} -O- (k3 represents. An integer of 1-7) is represented by the group. * Represents a bond with the carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents the integer of 0-5. When p1 is 2 or more, a plurality of R ^a21 may be the same or different.
In formula (a3-2),
L ^a5 represents a group represented by —O— or * —O— (CH ₂ ) _k3— CO—O— (k3 represents an integer of 1 to 7). * Represents a bond with the carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, a plurality of R ^a22 may be the same as or different from each other.
In formula (a3-3),
L ^a6 represents a group represented by —O— or * —O— (CH ₂ ) _k3— CO—O— (k3 represents an integer of 1 to 7). * Represents a bond with the carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, a plurality of R ^a23 may be the same as or different from each other.
In formula (a3-4),
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.
R ^a25 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
^La7 is a single bond, ^{* -La8-} O-, ^{* -La8-} CO-O-, ^{* -La8-} CO-O- ^La9- CO-O- or ^{* -La8-} O-CO. Represents ^-La9- O-.
* Represents a bond with the carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
w1 represents an integer of 0 to 8. When w1 is 2 or more, a plurality of R ^a25 may be the same as or different from each other. ]

Examples of the aliphatic hydrocarbon group such as R ^a21 include the following alkyl groups.
Examples of the halogen atom of R ^a24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
^Examples of the alkyl group for R ^a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. , Preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of R ^a24 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, a perfluoropentyl group. Hexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like can be mentioned.

^Examples of the alkanediyl group of L ^a8 and L ^a9 include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples thereof include 4-diyl group and 2-methylbutane-1,4-diyl group.

In formulas (a3-1) to (a3-3), L ^{a4 to} L ^a6 are independently of each other, preferably —O—, or k3 is an integer of 1 to 4 * —O— (CH ₂ ). a _k3 -CO-O-group represented by, more preferably -O- _{and, * - O-CH 2 -CO} -O- and, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 independently of each other are preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are, independently of each other, 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 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, and further preferably a hydrogen atom or a methyl group.
L ^a7 is preferably a single bond or * -L ^a8 -CO-O-, more preferably a single bond, -CH ₂ -CO-O- or -C ₂ H ₄ -CO-O-.
R ^a25 is preferably a carboxy group, a cyano group or a methyl group.
w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
Particularly, the formula (a3-4) is preferably the formula (a3-4) ′.

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

  Examples of the monomer that leads to the structural unit (a3) include 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. Can be mentioned. As the structural unit (a3), formula (a3-1-1) to formula (a3-1-6), formula (a3-2-1) to formula (a3-2-4), formula (a3-3-). 1) to the formula (a3-3-4) and the formula (a3-4-1) to the formula (a3-4-12), a structural unit represented by any one of the formula (a3-1-1), It is represented by any one of formula (a3-1-2) and formula (a3-2-3) to formula (a3-2-4) and formula (a3-4-1) to formula (a3-4-6). The structural unit represented by the formula (a3-1-1), the formula (a3-2-3) or the formula (a3-4-2) is further preferable.

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

When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol% with respect to the total of all structural units of the resin (A). And more preferably 10 to 60 mol%.
Further, the content rates of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) and the structural unit (a3-4) are, independently of each other, all the structural units of the resin (A). Is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and further preferably 10 to 50 mol%.

［式（ａ４−０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^５は、単結合又は炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ^３は、炭素数１〜８のペルフルオロアルカンジイル基又は炭素数３〜１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ <Structural unit (t)>
As the structural unit (t) which may be contained in the resin (A) of the present invention, a structural unit having a halogen atom in addition to the structural unit (a2) and the structural unit (a3) (hereinafter, referred to as “structural unit ( a)) ”) and a structural unit having a non-eliminating hydrocarbon group (hereinafter sometimes referred to as“ structural unit (a5) ”) and the like.
Examples of the structural unit (a4) include structural units represented by the formula (a4-0).

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

Examples of the aliphatic saturated hydrocarbon group for L ⁵ include alkanediyl groups having 1 to 4 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group. Such as a straight-chain alkanediyl group, a straight-chain alkanediyl group having a side chain of an alkyl group (especially, methyl group, ethyl group, etc.), ethane-1,1-diyl group, propane-1, Examples thereof include branched alkanediyl groups such as 2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.

Examples of the perfluoroalkanediyl group for L ³ include 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.
Examples of the perfluorocycloalkanediyl group for L ³ include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group and a perfluoroadamantanediyl group.

L ⁵ is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
L ³ is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

Examples of the structural unit (a4-0) include the structural units shown below.

［式（ａ４−１）中、
Ｒ^ａ４１は、水素原子又はメチル基を表す。
Ｒ^ａ４２は、置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、該炭化水素基に含まれる−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。］

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

[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—. Good.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1). ]

[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total carbon number of A ^a42 , A ^a43 , A ^a44 , X ^a41, and X ^a42 is 7 or less.
Of the two bonds represented by *, the * on the right side is a bond with -O-CO- ^Ra42 . ]

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

Examples of the chain type aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group. Group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Examples of the cyclic aliphatic hydrocarbon group include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and other cycloalkyl groups; decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* is a bond And a polycyclic alicyclic hydrocarbon group such as.

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

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

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents an aliphatic hydrocarbon group having at least one halogen atom and having 1 to 17 carbon atoms.
* Represents a bond. ]

^As the aliphatic hydrocarbon group for A ^a45, the same groups as those exemplified for R ^a42 can be mentioned.

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

［式（ａ−ｇ２）中、
Ａ^ａ４６は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
Ｘ^ａ４４は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^ａ４７は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^ａ４６、Ａ^ａ４７及びＸ^ａ４４の炭素数の合計は１８以下であり、Ａ^ａ４６及びＡ^ａ４７のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。
＊はカルボニル基との結合手を表す。］ The aliphatic hydrocarbon group having a group represented by formula (a-g3) is more preferably a group represented by formula (a-g2).

[In the formula (a-g2),
A ^a46 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents a carbonyloxy group or an oxycarbonyl group.
A ^a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total carbon number of A ^a46 , A ^a47, and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* Represents a bond with the carbonyl group. ]

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

A more preferable structure represented by * -A ^a46 -X ^a44 -A ^a47 is the following structure.

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

The aliphatic hydrocarbon group of A ^{a42 to} A ^a44 in the group (a-g1) may have a carbon-carbon unsaturated bond, but an aliphatic saturated hydrocarbon group is preferable. As the aliphatic saturated hydrocarbon group, an alkyl group (the alkyl group may be linear or branched) and an alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group are combined. And an aliphatic hydrocarbon group formed by the above. 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 aliphatic hydrocarbon group of A ^{a42 to} A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

^Examples of the group (a-g1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group include the following groups. In the following examples, * and ** each represent a bond, and ** is a bond with -O-CO-Ra ⁴² .

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

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

^Examples of the alkanediyl group of A ^f1 include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group. , A linear alkanediyl group such as hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 Examples thereof include branched alkanediyl groups such as -diyl group, 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain structure, a cyclic structure and a group formed by a combination thereof. The aliphatic hydrocarbon group is preferably an alkyl group or an alicyclic hydrocarbon group.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group and 2 And an ethylhexyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and cyclodecyl group. A cycloalkyl group is mentioned. As the polycyclic alicyclic hydrocarbon group, a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, a norbornyl group, Examples thereof include a methylnorbornyl group and an isobornyl group.

Examples of the hydrocarbon group having a fluorine atom of R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Examples of the alkyl group having a fluorine atom include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 1 , 1,2,2-Tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2- Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3 , 3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl 2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2 , 2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluoro Butyl) ethyl group, 1,1,2,2,3,3,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,5 Fluorinated alkyl groups such as a 6,6-dodecafluorohexyl group, a perfluoropentylmethyl group and a perfluorohexyl group can be mentioned.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

［式（ａ４−３）中、
Ｒ^ｆ１１は、水素原子又はメチル基を表す。
Ａ^ｆ１１は、炭素数１〜６のアルカンジイル基を表す。
Ａ^ｆ１３は、フッ素原子を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。
Ｘ^ｆ１２は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^ｆ１４は、フッ素原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^ｆ１３及びＡ^ｆ１４の少なくとも１つは、フッ素原子を有する脂肪族炭化水素基を表す。］ As A ^f1 in the formula (a4-2), an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.
R ^f1 is preferably a fluorinated alkyl group having 1 to 6 carbon atoms.

[In formula (a4-3),
R ^f11 represents a hydrogen atom or a methyl group.
A ^f11 represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 represents an aliphatic hydrocarbon group having a fluorine atom. ]

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

The aliphatic hydrocarbon group for A ^f13 includes a chain and cyclic aliphatic hydrocarbon group, and a divalent aliphatic hydrocarbon group formed by combining these. This aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f13 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. To be
Examples of the divalent chain aliphatic hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; difluoromethylene group, perfluoroethylene group. Group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoroalkanediyl group such as perfluoropentanediyl group.
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either a monocyclic group or a polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantanediyl group, a norbornanediyl group and a perfluoroadamantanediyl group.

The aliphatic hydrocarbon group for A ^f14 includes any of a chain structure and a cyclic structure, and an aliphatic hydrocarbon group formed by combining them. This aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f14 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Examples of the chain aliphatic hydrocarbon group which may have a fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1 , 2,2-Tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, Examples thereof include a heptyl group, a perfluoroheptyl group, an octyl group and a perfluorooctyl group.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl group and the like.

In the formula ^{(a4-3), A f11} is preferably an ethylene group.
The aliphatic hydrocarbon group of A ^f13 is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably an aliphatic hydrocarbon group having 2 to 3 carbon atoms.
As the aliphatic hydrocarbon group of A ^f14, an aliphatic hydrocarbon group having 3 to 12 carbon atoms is preferable, and an aliphatic hydrocarbon group having 3 to 10 carbon atoms is more preferable. Among them, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

  Examples of the structural unit represented by the formula (a4-2) include structural units represented by the formula (a4-1-1) to the formula (a4-1-22).

  Examples of the structural unit represented by the formula (a4-3) include structural units represented by the formulas (a4-1'-1) to (a4-1'-22).

［式（ａ４−４）中、
Ｒ^ｆ２１は、水素原子又はメチル基を表す。
Ａ^ｆ２１は、−（ＣＨ_２）_ｊ１−、−（ＣＨ_２）_ｊ２−Ｏ−（ＣＨ_２）_ｊ３−又は−（ＣＨ_２）_ｊ４−ＣＯ−Ｏ−（ＣＨ_２）_ｊ５−を表す。
ｊ１〜ｊ５は、互いに独立に、１〜６の整数を表す。
Ｒ^ｆ２２は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ The structural unit (a4) also includes a structural unit represented by the formula (a4-4).

[In the formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 _{is, - (CH 2) j1 -} , - (CH 2) j2 -O- (CH 2) j3 - or _{- (CH 2) j4 -CO-} O- (CH 2) j5 - represents a.
j1 to j5 each independently represent an integer of 1 to 6.
R ^f22 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

^Examples of the hydrocarbon group having a fluorine atom of R ^f22 include the same as the hydrocarbon group of R ^f2 in the formula (a4-2). R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, and a C 1-10 alkyl having a fluorine atom. A group is more preferable, and a C 1-6 alkyl group having a fluorine atom is further preferable.

In formula ^(A4-4), as the _{^{A f21, - (CH 2)}} j1 - , more preferably an ethylene group or a methylene group, more preferably a methylene group.

Examples of the structural unit represented by the formula (a4-4) include the following structural units.

  When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, and 2 to 15 mol% based on the total of all structural units of the resin (A). Is more preferable, and 3 to 10 mol% is further preferable.

［式（ａ５−１）中、
Ｒ^５１は、水素原子又はメチル基を表す。
Ｒ^５２は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。
ただし、Ｌ^５５との結合位置にある炭素原子に結合する水素原子は、炭素数１〜８の脂肪族炭化水素基で置換されない。
Ｌ^５５は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ Examples of the non-eliminating hydrocarbon group contained in the structural unit (a5) include linear, branched or cyclic hydrocarbon groups. Among them, the structural unit (a5) is preferably an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include structural units represented by the formula (a5-1).

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

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

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

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

[In the formula (L1-1),
X ^x1 represents a carbonyloxy group or an oxycarbonyl group.
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total carbon number of L ^x1 and L ^x2 is 16 or less.
In formula (L1-2),
L ^x3 represents a divalent saturated aliphatic hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total carbon number of L ^x3 and L ^x4 is 17 or less.
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^{x5 to} L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 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 saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
W ^x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a cyclohexanediyl group or an adamantanediyl group.

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

Examples of the group represented by the formula (L1-2) include the following divalent groups.

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

Ｌ^５５は、好ましくは単結合又は式（Ｌ１−１）で表される基である。 Examples of the group represented by the formula (L1-4) include the divalent groups 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 followings.

In formulas (a5-1-1) to (a5-1-18), a structural unit in which a methyl group corresponding to R ⁵¹ is replaced with a hydrogen atom may be mentioned as a specific example of the structural unit (a5-1). it can.

  When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, and preferably 2 to 20 mol% based on the total of all structural units of the resin (A). Is more preferable, and 3 to 15 mol% is further preferable.

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

The resin (A) is preferably a resin comprising a structural unit (I), a structural unit (a1) and a structural unit (s), that is, a compound (I), a monomer (a1) and a monomer (s). It is a polymer.
The structural unit (a1) is preferably at least one selected from the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), and more preferably the structural unit ( at least two kinds selected from a1-1) and structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1).
The structural unit (a3) is preferably selected from the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2) and the structural unit represented by the formula (a3-4). At least one.

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

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that induces these structural units. can do. The content of each structural unit contained in the resin (A) can be adjusted by the amount of the monomer used for polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, further preferably). 15,000 or less).
In the present specification, the weight average molecular weight is a value determined by gel permeation chromatography. Gel permeation chromatography can be measured under the analysis conditions described in the examples.

<Resist composition>
The resist composition of the present invention contains at least a resin and an acid generator. The resist composition of the present invention may include a structural unit derived from compound (I) or compound (I) in either the resin or the acid generator. The resist composition of the present invention comprises a resist composition having a resin containing a structural unit derived from compound (I) or a resin containing a structural unit derived from compound (I), and an acid generator containing compound (I). A resist composition containing is preferred.
The resist composition preferably contains a quencher (hereinafter sometimes referred to as “quencher (C)”) and preferably a solvent (hereinafter sometimes referred to as “solvent (E)”).

<resin>
The resin in the resist composition may be any resin containing at least a structural unit having an acid labile group. For example, a resin obtained by removing the structural unit derived from the compound (I) from the resin (A) (hereinafter sometimes referred to as “resin (AA)”), a resin containing the structural unit (a1) described above, a structural unit (a1) And a resin containing the structural unit (s) and / or the structural unit (t), the resin (A) described above, or a combination thereof. Among them, those containing the resin (A) are preferable as described above.

  When the resist composition contains the resin (A), the content thereof 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. The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Examples of such a resin include a resin (AA), a resin composed of only the structural unit (t), and a resin containing the structural unit (a4) (however, the structural unit (I) is not included. Hereinafter, “resin (X)”. “There are cases where it is called)” and the like. Examples of the structural unit that the resin (X) may further have include structural units (a1), structural units (a2), structural units (a3), and structural units derived from other known monomers.

For example, in the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, and more preferably 45 mol% or more, based on the total of all structural units of the resin (X). More preferably, it is more preferably 50 mol% or more.
The weight average molecular weight of the resin (X) is preferably 5,000 or more (more preferably 6,000 or more) and 80,000 or less (more preferably 60,000 or less).

When the resist composition contains a resin other than the resin (A), the total content of the resin (A) and the resin other than the resin (A) is 80% by mass or more and 99% or more based on the solid content of the resist composition. It is preferably not more than 90% by mass, more preferably not less than 90% by mass and not more than 99% by mass.
In particular, the content of the resin (X) is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 2 to 40 parts by mass with respect to 100 parts by mass of the resin (A). Parts, and particularly preferably 2 to 30 parts by mass.

<Acid generator>
The acid generator in the resist composition is an acid generator containing only the compound (I), an acid generator containing only the acid generator (B), an acid generator containing the compound (I) and the acid generator (B). Any of the agents may be used, but an acid generator containing the compound (I) and the acid generator (B) is preferable. In particular, when the resin described above does not contain a structural unit derived from the compound (I), an acid generator containing the compound (I) is more preferable.
When the compound (I) is used as an acid generator in the resist composition, the content of the compound (I) is the sum of the resin (for example, the resin (A) and the resin (AA) containing a structural unit having an acid labile group). The amount) is preferably 1 to 20% by mass, and more preferably 2 to 15% by mass.

<Acid generator (B)>
As the acid generator (B), either a nonionic or ionic acid generator may be used. Examples of the nonionic acid generator include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate) and sulfones. (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate 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 JP-A-63-163452. JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712. Compounds capable of generating an acid by the radiation described in etc. can be used. Moreover, you may use the compound manufactured by the well-known method.

［式（Ｂ１）中、
Ｑ^１１及びＱ^１２は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の１価の脂環式炭化水素基を表し、該１価の脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ^＋は、有機カチオンを表す。］ The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).

[In the formula (B1),
Q ¹¹ and Q ¹² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon group is, -O - - -CH ₂ contained in the hydrogen radical, - SO ₂ - or -CO- may be replaced with.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group of Q ¹¹ and Q ¹² 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 perfluoropentyl group. A hexyl group and the like can be mentioned.
Q ¹¹ and Q ¹² are preferably, independently of each other, a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and It may be a group formed by combining two or more of the 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, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group , Straight chain such as 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 An alkanediyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- A branched alkanediyl group such as a 1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 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 and the like. Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group and adamantane-2,6-diyl group Groups and the like.

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

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

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

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

The group represented by the formula (b1-1) or the formula (b1-3) is a group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO—. Is preferred.

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

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

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

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

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

  In formula (b1-10) and formula (b1-11), when the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with an acyloxy group, the number of carbon atoms in the acyloxy group, CO in the ester bond, and The number of carbon atoms in the divalent saturated hydrocarbon group, including the number of O atoms, is used.

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

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

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

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

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

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

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

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

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

Examples of the monovalent alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y11).
The group in which —CH ₂ — contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO— is represented by formula (Y12) to formula (Y38). And a group represented by.

  That is, in Y, two hydrogen atoms contained in the alicyclic hydrocarbon group are each substituted with an oxygen atom, and the two oxygen atoms are combined with an alkanediyl group having 1 to 8 carbon atoms to form a ketal ring. It may also have a structure in which oxygen atoms are bonded to different carbon atoms. However, in the case of forming a spiro ring represented by formula (Y28) to formula (Y33) or the like, it is preferable that the alkanediyl group between two oxygens 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.

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

Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, a monovalent n-alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. , glycidyloxy group, or _{- (CH 2) ja -O-} CO-R b1 group ^{(wherein, R b1} represents an alkyl group having 1 to 16 carbon atoms, a monovalent alicyclic hydrocarbon 3 to 16 carbon atoms Group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4) and the like.
As the substituent of the monovalent alicyclic hydrocarbon group represented by Y, a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 carbon atoms To 16 monovalent alicyclic hydrocarbon group, C1 to C12 alkoxy group, C6 to C18 monovalent aromatic hydrocarbon group, C7 to C21 aralkyl group, and C2 4 acyl group, glycidyloxy group, or _{- (CH 2) ja -O-} CO-R b1 group ^{(wherein, R b1} represents an alkyl group having 1 to 16 carbon atoms, monovalent cycloaliphatic of 3 to 16 carbon atoms It represents a cyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and ja represents an integer of 0 to 4) and the like.

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

Examples of Y include the following.

When Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon at the bonding position with Y -CH group ₂ - is preferably replaced by -O- or -CO-.

Y is preferably a monovalent 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. The methylene group constituting the group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the following.

  As the sulfonate anion in the salt represented by the formula (B1), an anion represented by the formula (B1-A-1) to the formula (B1-A-46) [hereinafter, "anion (B1 -A-1) "or the like. ] Are preferable, Formula (B1-A-1) -Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24) -Formula The anion represented by any one of (B1-A-33) and formula (B1-A-36) to formula (B1-A-40) is more preferable.

Here, R ^{i2 to} R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. Is more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹¹ and Q ¹² are the same as above.
Specific examples of the sulfonate anion in the salt represented by the formula (B1) include anions described in JP2010-204646A.

  Preferred examples of the sulfonate anion in the salt represented by the formula (B1) include anions represented by the formulas (B1a-1) to (B1a-22).

  Among them, formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19), formula (B1a-22). Anion represented by any of (1) to (4) is preferable.

Examples of the Z ⁺ organic cation include an organic onium cation, for example, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, an organic phosphonium cation, and the like, preferably an organic sulfonium cation or an organic iodonium cation. And more preferably an arylsulfonium cation.
Z ⁺ in the formula (B1) is preferably a cation represented by any of the formulas (b2-1) to (b2-4) [hereinafter, "cation (b2-1)" depending on the formula number, etc. There is a case. ].

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

[In the formulas (b2-1) to (b2-4),
R ^{b4 to} R ^b6 are, independently of each other, a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent one having 6 to 36 carbon atoms. Hydrogen atom contained in the monovalent aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or a monovalent alicyclic carbon group having 3 to 12 carbon atoms. It may be substituted with a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the monovalent alicyclic hydrocarbon group is a halogen atom or 1 to 18 carbon atoms. May be substituted with a monovalent aliphatic hydrocarbon group, an acyl group having 2 to 4 carbon atoms or a glycidyloxy group, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group may be a halogen atom or a hydroxy group. It may be substituted with a group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bound, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b7 and R ^b8 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 represent the integer of 0-5 mutually independently.
When m2 is 2 or more, a plurality of R ^b7 may be the same or different, and when n2 is 2 or more, a plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bound, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b11 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic carbon group having 6 to 18 carbon atoms. Represents a hydrogen group.
R ^b12 represents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the monovalent aliphatic hydrocarbon may be substituted with a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group. The hydrogen atom may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may be bonded together to form a ring containing —CH—CO—, and —CH ₂ — contained in the ring is —O—, —SO—. Alternatively, it may be replaced with -CO-.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents -S- or -O-.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5.
q2 and r2 represent the integer of 0-4 independently of each other.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13 may be the same or different, when p2 is 2 or more, a plurality of R ^b14 may be the same or different, and when q2 is 2 or more R ^b15 may be the same or different, when r2 is 2 or more, R ^b16 may be the same or different, and when s2 is 2 or more, R ^b17 is ^They may be the same or different, and when t2 is 2 or more, a plurality of R ^b18 may be the same or different. ]

Examples of the monovalent aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2 -The alkyl group of the ethylhexyl group is mentioned. Especially, the carbon number of the monovalent aliphatic hydrocarbon group of R ^{b9 to} R ^b12 is preferably 1 to 12.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic. As the monocyclic monovalent alicyclic hydrocarbon group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclo Examples thereof include cycloalkyl groups such as hexyl group, cycloheptyl group, cyclooctyl group and cyclodecyl group. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups.

In particular, the carbon number of the monovalent alicyclic hydrocarbon group of R ^{b9 to} R ^b12 is preferably 3 to 18, and more preferably 4 to 12.

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

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

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

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

The ring formed by R ^b9 and R ^b10 together with the sulfur atom to which they are bonded may be a monocyclic ring, polycyclic ring, aromatic ring, non-aromatic ring, saturated ring or unsaturated ring. Good. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include a thiolane-1-ium ring (tetrahydrothiophenium ring) and thian-1-ium. Ring, 1,4-oxathian-4-ium ring and the like.
The ring formed by R ^b11 and R ^{b12 taken} together may be any of a monocyclic ring, a polycyclic ring, an aromatic ring, a non-aromatic ring, a saturated ring and an unsaturated ring. Examples of this ring include a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring. To be

  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 acid generator (B1) is a combination of the above-mentioned sulfonate anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B1) is preferably an anion and a cation (b2) represented by any of the formula (B1a-1) to the formula (B1a-3) and the formula (B1a-7) to the formula (B1a-16). -1) or a combination with a cation (b2-3).

  The acid generator (B1) preferably includes those represented by formulas (B1-1) to (B1-32), among which formula (B1-1) and formula (B1) containing an arylsulfonium cation. -2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7), formula (B1-11), formula (B1-12), formula (B1- 13), formula (B1-14), formula (B1-13), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-24), formula (B1-25). ), The formula (B1-26), the formula (B1-29), the formula (B1-31) or the formula (B1-32).

The acid generator (B) may contain 2 or more types.
The content of the acid generator (B) is, for example, preferably 1 to 30 mass% and more preferably 3 to 25 mass% with respect to the resin (A).
In the resist composition, when the compound (I) and the acid generator (B) are used as the acid generator, the content of the compound (I) and the acid generator (B) is, for example, based on the resin (A). , Preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 30 parts by mass or less).
Note that these contents can be applied to a resin containing an acid labile group when the resin (A) is not contained in the resist composition.

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

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate. And the like; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; Solvent (E) may contain 1 type independently and may contain 2 or more types.

<Quencher (C)>
Examples of the quencher (C) include salts that generate an acid having a weaker acidity than the acid generated from a basic nitrogen-containing organic compound or an acid generator.
Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

  As the amine, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tri Heptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, Ludicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyl Didecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, piperazine, morpholine, piperidine and JP-A-11- No. 2575, a hindered amine compound having a piperidine skeleton, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl). ) Ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) Ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine, bipyridine and the like can be mentioned, preferably Is diisopropylaniline, particularly preferably 2,6-diisopropylaniline.

  Examples of ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide and 3- (trifluoromethyl) phenyltrimethyl. Examples thereof include ammonium hydroxide, tetra-n-butylammonium salicylate and choline.

As the salt that generates an acid having a weaker acidity than the acid generated from the acid generator, a salt represented by the following formula, a weak acid intramolecular salt represented by the formula (D), and JP 2012-229206A are disclosed. , JP2012-6908A, JP2012-72109A, JP2011-39502A and JP2011-191745A. A weak acid inner salt represented by formula (D) (hereinafter sometimes referred to as “weak acid inner salt (D)”) is preferable.
The acidity of a salt that generates an acid having a weaker acidity than the acid generated from the acid generator is represented by an acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the salt (I) and the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 <pKa, The salt is preferably -1 <pKa <7, more preferably 0 <pKa <5.

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

[In the formula (D), R ^D1 and R ^D2 are, independently of each other, a monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, and carbon. It represents an acyloxy group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group or a halogen atom.
m ′ and n ′ each independently represent an integer of 0 to 4, when m ′ is 2 or more, a plurality of R ^D1 may be the same or different, and when n ′ is 2 or more, A plurality of R ^D2 may be the same or different. ]

In the weak acid inner salt (D), the hydrocarbon groups of R ^D1 and R ^D2 include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group and The group etc. which are formed by combining these are mentioned.
Examples of the monovalent aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group and nonyl group.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and may be saturated or unsaturated. Examples thereof include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group and cyclododecyl group, norbornyl group, adamantyl group and the like.
Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group and a 4-ethylphenyl group. Propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group And aryl groups such as cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl.
The group formed by combining these includes an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, an aralkyl group (for example, a phenylmethyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenyl- group. 1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc.) and the like.

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

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

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

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

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

<Other ingredients>
The resist composition may contain a component other than the above-mentioned components (hereinafter sometimes referred to as “other component (F)”), if necessary. As the other component (F), additives known in the resist field, such as a sensitizer, a dissolution inhibitor, a surfactant, a stabilizer, and a dye can be used.

<Preparation of resist composition>
The resist composition can be prepared by mixing a resin and an acid generator, and if necessary, other resin, solvent (E), quencher (C) and 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 resin and the like, the solubility of the resin and the like in the solvent (E), and the like. 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 can be used.
After mixing the components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method of manufacturing 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 composition after coating to form a composition layer,
(3) 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.

  Application of the resist composition onto the substrate can be carried out by a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. The substrate may be washed before applying the resist composition, or an antireflection film or the like may be formed on the substrate.

The composition is dried to remove the solvent and form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called prebaking) or using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. In addition, the pressure for drying under reduced pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is usually exposed using an exposure device. The exposure machine may be an immersion exposure machine. As the exposure light source, one that emits a laser beam in the ultraviolet region such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm), a solid-state laser light source (YAG or semiconductor laser) Etc.) that emits harmonic laser light in the far-ultraviolet region or vacuum-ultraviolet region by wavelength conversion of laser light from, etc., electron beams, or those that emit ultra-ultraviolet light (EUV), etc. You can In the present specification, the irradiation of these radiations may be collectively referred to as “exposure”. At the time of exposure, the exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, it may be exposed by direct drawing without using a mask.

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

  The composition layer after heating is usually developed using a 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 5 to 60 ° C., and the development time is preferably 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be manufactured by selecting the type of developer as follows.

When a positive resist pattern is produced from the resist composition, an alkali developing solution is used as the developing solution. The alkaline developer may be any of various alkaline aqueous solutions used in this field. Examples thereof include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline). The alkaline developer may contain a surfactant.
After development, it is preferable to wash the resist pattern with ultrapure water, and then remove the water remaining on the substrate and the pattern.

When a negative resist pattern is produced from a resist composition, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer.
Examples of the organic solvent contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and substantially only the organic solvent. Is more preferable.
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. More preferably, it is only butyl acetate and / or 2-heptanone.
A surfactant may be contained in the organic developer. 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 different type from the organic developer.

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

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

A more specific description will be given with reference to examples. In the examples, “%” and “part” indicating the content or the amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Device: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guard column (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μL
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

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

式（Ｉ−１−ａ）で表される化合物５．００部、テトラヒドロフラン１０部及びトリエチルアミン４．７９部を添加し、その後、２３℃で３０分間攪拌し、０℃に冷却した。得られた混合物に、０℃で、式（Ｉ−１−ｂ）で表される化合物４．５０部を３０分かけて滴下し、さらに０℃で１時間攪拌した。得られた反応物に酢酸エチル１５０部、イオン交換水５０部及び飽和塩化アンモニウム水溶液５０部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１０／１）分取することにより、式（Ｉ−１―ｃ）で表される化合物３．３０部を得た。 Example 1: Synthesis of compound represented by formula (I-1)

5.00 parts of the compound represented by the formula (I-1-a), 10 parts of tetrahydrofuran and 4.79 parts of triethylamine were added, and then the mixture was stirred at 23 ° C. for 30 minutes and cooled to 0 ° C. 4.50 parts of the compound represented by the formula (I-1-b) was added dropwise to the obtained mixture at 0 ° C over 30 minutes, and the mixture was further stirred at 0 ° C for 1 hour. 150 parts of ethyl acetate, 50 parts of ion-exchanged water and 50 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated 5 times. The collected organic layer was concentrated, and the concentrated mass was collected by column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 10/1) to obtain the compound of formula (I 1.30 parts of the compound represented by 1-c) was obtained.

式（Ｉ−１−ｄ）で表される化合物５．７２部、式（Ｉ−１−ｅ）で表される化合物４．００部、式（Ｉ−１−ｆ）で表される化合物０．２６部及びクロロホルム６０部を添加し、２３℃で３０分間攪拌した。得られた混合溶液を、さらに、８０℃で１０時間脱水攪拌し、２３℃まで冷却した。得られた反応物に、クロロホルム２００部、イオン交換水１２５部及び飽和塩化ナトリウム水溶液４０部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。回収された有機層を濃縮することにより、式（Ｉ−１―ｇ）で表される化合物５．５４部を得た。

5.72 parts of the compound represented by the formula (I-1-d), 4.00 parts of the compound represented by the formula (I-1-e), compound 0 represented by the formula (I-1-f) .26 parts and 60 parts of chloroform were added, and the mixture was stirred at 23 ° C. for 30 minutes. The obtained mixed solution was further dehydrated and stirred at 80 ° C. for 10 hours and cooled to 23 ° C. Chloroform (200 parts), ion-exchanged water (125 parts) and saturated sodium chloride aqueous solution (40 parts) were added to the obtained reaction product, and the mixture was stirred at 23 ° C for 30 minutes, allowed to stand and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated 5 times. By concentrating the collected organic layer, 5.54 parts of the compound represented by the formula (I-1-g) was obtained.

式（Ｉ−１−ｇ）で表される化合物１．５９部、式（Ｉ−１−ｃ）で表される化合物１．２１部、式（Ｉ−１−ｈ）で表される化合物０．０１部及びテトラヒドロフラン２５部を添加し、２３℃で３０分間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル２００部、イオン交換水５０部及び飽和炭酸水素ナトリウム水溶液５部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮することにより、式（Ｉ−１―ｉ）で表される化合物１．４３部を得た。

1.59 parts of the compound represented by the formula (I-1-g), 1.21 parts of the compound represented by the formula (I-1-c), compound 0 represented by the formula (I-1-h) 0.01 part and 25 parts of tetrahydrofuran were added, and the mixture was stirred at 23 ° C. for 30 minutes and further at 23 ° C. for 18 hours. To the obtained reaction product, 200 parts of ethyl acetate, 50 parts of ion-exchanged water and 5 parts of a saturated sodium hydrogen carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. The collected organic layer was concentrated to obtain 1.43 parts of the compound represented by the formula (I-1-i).

式（Ｉ−１−ｊ）で表される化合物０．８９部、２，６−ルチジン０．４５部及びジメチルホルムアミド０．４部を添加し、２３℃で３０分間攪拌した。その後、式（Ｉ−１−ｉ）で表される化合物１．４８部を添加し、２３℃で１８時間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル３００部及び飽和塩化アンモニウム水溶液１００部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１）で表される化合物０．５１部を得た。
ＭＳ（質量分析）：７３３．２（分子イオンピーク）

0.89 parts of the compound represented by the formula (I-1-j), 0.45 part of 2,6-lutidine and 0.4 part of dimethylformamide were added, and the mixture was stirred at 23 ° C. for 30 minutes. Thereafter, 1.48 parts of the compound represented by the formula (I-1-i) was added, and the mixture was stirred at 23 ° C. for 18 hours and further at 23 ° C. for 18 hours. 300 parts of ethyl acetate and 100 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. The collected organic layer was concentrated, and the concentrated mass was collected by column (Kanto Chemical, silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the compound of formula (I 0.51 part of the compound represented by -1) was obtained.
MS (mass spectrometry): 733.2 (molecular ion peak)

式（Ｉ−２−ａ）で表される化合物３．７９部、テトラヒドロフラン１０部及びトリエチルアミン４．７９部を添加し、その後、２３℃で３０分間攪拌し、０℃に冷却した。得られた混合物に、０℃で、式（Ｉ−２−ｂ）で表される化合物４．５０部を３０分かけて滴下し、さらに０℃で１時間攪拌した。得られた反応物に酢酸エチル１００部、イオン交換水５０部及び飽和塩化アンモニウム水溶液５０部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝５／１）分取することにより、式（Ｉ−２―ｃ）で表される化合物３．１２部を得た。 Example 2: Synthesis of compound represented by formula (I-2)

3.79 parts of the compound represented by the formula (I-2-a), 10 parts of tetrahydrofuran and 4.79 parts of triethylamine were added, and then the mixture was stirred at 23 ° C for 30 minutes and cooled to 0 ° C. 4.50 parts of the compound represented by the formula (I-2-b) was added dropwise to the obtained mixture at 0 ° C over 30 minutes, and the mixture was further stirred at 0 ° C for 1 hour. 100 parts of ethyl acetate, 50 parts of ion-exchanged water and 50 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated 5 times. The recovered organic layer was concentrated, and the concentrated mass was collected by column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 5/1) to obtain the compound of formula (I -3.12 parts of the compound represented by 2-c) was obtained.

式（Ｉ−１−ｇ）で表される化合物１．５９部、式（Ｉ−２−ｃ）で表される化合物１．０３部、式（Ｉ−１−ｈ）で表される化合物０．０１部及びテトラヒドロフラン２５部を添加し、２３℃で３０分間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル２００部、イオン交換水５０部及び飽和炭酸水素ナトリウム水溶液５部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮することにより、式（Ｉ−２―ｉ）で表される化合物１．４６部を得た。

1.59 parts of the compound represented by the formula (I-1-g), 1.03 parts of the compound represented by the formula (I-2-c), compound 0 represented by the formula (I-1-h) 0.01 part and 25 parts of tetrahydrofuran were added, and the mixture was stirred at 23 ° C. for 30 minutes and further at 23 ° C. for 18 hours. To the obtained reaction product, 200 parts of ethyl acetate, 50 parts of ion-exchanged water and 5 parts of a saturated sodium hydrogen carbonate aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. By concentrating the collected organic layer, 1.46 parts of the compound represented by the formula (I-2-i) was obtained.

式（Ｉ−１−ｊ）で表される化合物０．８９部、２，６−ルチジン０．４５部及びジメチルホルムアミド０．４部を添加し、２３℃で３０分間攪拌した。その後、式（Ｉ−２−ｉ）で表される化合物１．４０部を添加し、２３℃で１８時間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル３００部及び飽和塩化アンモニウム水溶液１００部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２）で表される化合物０．５３部を得た。
ＭＳ（質量分析）：７０５．２（分子イオンピーク）

0.89 parts of the compound represented by the formula (I-1-j), 0.45 part of 2,6-lutidine and 0.4 part of dimethylformamide were added, and the mixture was stirred at 23 ° C. for 30 minutes. Thereafter, 1.40 parts of the compound represented by the formula (I-2-i) was added, and the mixture was stirred at 23 ° C. for 18 hours and further at 23 ° C. for 18 hours. 300 parts of ethyl acetate and 100 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. The collected organic layer was concentrated, and the concentrated mass was collected by column (Kanto Chemical, silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the compound of formula (I 0.53 parts of the compound represented by -2) was obtained.
MS (mass spectrometry): 705.2 (molecular ion peak)

式（Ｉ−１５−ｊ）で表される化合物０．６８部、２，６−ルチジン０．４５部及びジメチルホルムアミド０．４部を添加し、２３℃で３０分間攪拌した。その後、式（Ｉ−１−ｉ）で表される化合物１．４８部を添加し、２３℃で１８時間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル３００部及び飽和塩化アンモニウム水溶液１００部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１５）で表される化合物０．４９部を得た。
ＭＳ（質量分析）：６８３．２（分子イオンピーク） Example 3: Synthesis of compound represented by formula (I-15)

0.68 parts of the compound represented by the formula (I-15-j), 0.45 parts of 2,6-lutidine and 0.4 parts of dimethylformamide were added, and the mixture was stirred at 23 ° C for 30 minutes. Thereafter, 1.48 parts of the compound represented by the formula (I-1-i) was added, and the mixture was stirred at 23 ° C. for 18 hours and further at 23 ° C. for 18 hours. 300 parts of ethyl acetate and 100 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. The collected organic layer was concentrated, and the concentrated mass was collected by column (Kanto Chemical, silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the compound of formula (I Thus, 0.49 parts of the compound represented by -15) was obtained.
MS (mass spectrometry): 683.2 (molecular ion peak)

式（Ｉ−１６−ｊ）で表される化合物０．７４部、２，６−ルチジン０．４５部及びジメチルホルムアミド０．４部を添加し、２３℃で３０分間攪拌した。その後、式（Ｉ−１−ｉ）で表される化合物１．４８部を添加し、２３℃で１８時間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル３００部及び飽和塩化アンモニウム水溶液１００部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１６）で表される化合物０．６２部を得た。
ＭＳ（質量分析）：６９７．２（分子イオンピーク） Example 4: Synthesis of compound represented by formula (I-16)

0.74 parts of the compound represented by the formula (I-16-j), 0.45 parts of 2,6-lutidine and 0.4 parts of dimethylformamide were added, and the mixture was stirred at 23 ° C for 30 minutes. Thereafter, 1.48 parts of the compound represented by the formula (I-1-i) was added, and the mixture was stirred at 23 ° C. for 18 hours and further at 23 ° C. for 18 hours. 300 parts of ethyl acetate and 100 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. The collected organic layer was concentrated, and the concentrated mass was collected by column (Kanto Chemical, silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the compound of formula (I Thus, 0.62 parts of the compound represented by -16) was obtained.
MS (mass spectrometry): 697.2 (molecular ion peak)

式（Ｉ−１９−ｊ）で表される化合物０．４８部、２，６−ルチジン０．４５部及びジメチルホルムアミド０．４部を添加し、２３℃で３０分間攪拌した。その後、式（Ｉ−１−ｉ）で表される化合物１．４８部を添加し、２３℃で１８時間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル３００部及び飽和塩化アンモニウム水溶液１００部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝２／１）分取することにより、式（Ｉ−１９）で表される化合物０．３４部を得た。
ＭＳ（質量分析）：６３５．２（分子イオンピーク） Example 5: Synthesis of compound represented by formula (I-19)

0.48 part of the compound represented by the formula (I-19-j), 0.45 part of 2,6-lutidine and 0.4 part of dimethylformamide were added, and the mixture was stirred at 23 ° C. for 30 minutes. Thereafter, 1.48 parts of the compound represented by the formula (I-1-i) was added, and the mixture was stirred at 23 ° C. for 18 hours and further at 23 ° C. for 18 hours. 300 parts of ethyl acetate and 100 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. The recovered organic layer was concentrated, and the concentrated mass was collected by column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 2/1) to obtain the compound of formula (I 0.34 part of the compound represented by -19) was obtained.
MS (mass spectrometry): 635.2 (molecular ion peak)

式（Ｉ−２８−ｊ）で表される化合物０．８０部、２，６−ルチジン０．４５部及びジメチルホルムアミド０．４部を添加し、２３℃で３０分間攪拌した。その後、式（Ｉ−１−ｉ）で表される化合物１．４８部を添加し、２３℃で１８時間攪拌し、さらに、２３℃で１８時間攪拌した。得られた反応物に、酢酸エチル３００部及び飽和塩化アンモニウム水溶液１００部を加え、２３℃で３０分間攪拌し、静置、分液した。回収された有機層に、イオン交換水１００部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を２回繰り返した。回収された有機層を濃縮し、濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２８）で表される化合物０．４５部を得た。
ＭＳ（質量分析）：７１１．３（分子イオンピーク） Example 6: Synthesis of compound represented by formula (I-28)

0.80 part of the compound represented by the formula (I-28-j), 0.45 part of 2,6-lutidine and 0.4 part of dimethylformamide were added, and the mixture was stirred at 23 ° C for 30 minutes. Thereafter, 1.48 parts of the compound represented by the formula (I-1-i) was added, and the mixture was stirred at 23 ° C. for 18 hours and further at 23 ° C. for 18 hours. 300 parts of ethyl acetate and 100 parts of saturated ammonium chloride aqueous solution were added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 100 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and liquid-separated to wash the organic layer. This water washing operation was repeated twice. The collected organic layer was concentrated, and the concentrated mass was collected by column (Kanto Chemical, silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1) to obtain the compound of formula (I 0.45 part of the compound represented by -28) was obtained.
MS (mass spectrometry): 711.3 (molecular ion peak)

特開２００８−２０９９１７号公報に記載された方法によって得られた式（Ｂ１−２１−ｂ）で表される化合物３０．００部、式（Ｂ１−２１−ａ）で表される塩３５．５０部、クロロホルム１００部及びイオン交換水５０部を仕込み、２３℃で１５時間攪拌した。
得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、クロロホルム層にイオン交換水３０部を添加し、水洗した。この操作を５回繰り返した。
クロロホルム層を濃縮し、得られた残渣に、ｔｅｒｔ−ブチルメチルエーテル１００部を加えて２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１−２１−ｃ）で表される塩４８．５７部を得た。 Synthesis Example 1 [Synthesis of salt represented by formula (B1-21)]

30.00 parts of a compound represented by the formula (B1-21-b) obtained by the method described in JP 2008-209917 A, a salt represented by the formula (B1-21 -a) 35.50. Parts, 100 parts of chloroform and 50 parts of ion-exchanged water were charged and stirred at 23 ° C. for 15 hours.
Since the obtained reaction liquid was separated into two layers, the chloroform layer was separated and taken out, and further 30 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times.
The chloroform layer was concentrated, 100 parts of tert-butyl methyl ether was added to the obtained residue, the mixture was stirred at 23 ° C. for 30 minutes, and filtered to obtain a salt of the formula (B1-21-c) 48. 57 parts were obtained.

式（Ｂ１−２１−ｃ）で表される塩２０．００部、式（Ｂ１−２１−ｄ）で表される化合物２．８４部及びモノクロロベンゼン２５０部を仕込み、２３℃で３０分間攪拌した。
得られた混合液に、二安息香酸銅（ＩＩ）０．２１部を添加し、更に、１００℃で１時間攪拌した。得られた反応溶液を濃縮し、得られた残渣に、クロロホルム２００部及びイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮し、得られた残渣に、アセトニトリル５３．５１部に溶解し、濃縮した。その後、ｔｅｒｔ−ブチルメチルエーテル１１３．０５部を加えて攪拌し、ろ過することにより、式（Ｂ１−２１）で表される塩１０．４７部を得た。

20.00 parts of the salt represented by the formula (B1-21-c), 2.84 parts of the compound represented by the formula (B1-21-d) and 250 parts of monochlorobenzene were charged, and the mixture was stirred at 23 ° C. for 30 minutes. .
0.21 parts of copper (II) dibenzoate was added to the obtained mixed liquid, and the mixture was further stirred at 100 ° C. for 1 hour. The obtained reaction solution was concentrated, 200 parts of chloroform and 50 parts of ion-exchanged water were added to the obtained residue, and the mixture was stirred at 23 ° C. for 30 minutes, separated, and the organic layer was taken out. 50 parts of ion-exchanged water was added to the collected organic layer, the mixture was stirred at 23 ° C. for 30 minutes, and liquid-separated to take out the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the obtained residue was dissolved in 53.51 parts of acetonitrile and concentrated. Thereafter, 113.05 parts of tert-butyl methyl ether was added, stirred, and filtered to obtain 10.47 parts of the salt represented by the formula (B1-21).

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

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

11.26 parts of the salt represented by the formula (B1-22-a), 10.00 parts of the compound represented by the formula (B1-22-b), 50 parts of chloroform and 25 parts of deionized water were charged, and the temperature was 23 ° C. It was stirred for 15 hours. Since the obtained reaction liquid was separated into two layers, the chloroform layer was separated and taken out, and further 15 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated, 50 parts of tert-butyl methyl ether was added to the obtained residue, the mixture was stirred at 23 ° C. for 30 minutes, and filtered to obtain the salt represented by the formula (B1-22-c). Obtained 75 parts.

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

11.71 parts of the salt represented by the formula (B1-22-c), 1.70 parts of the compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged, and the mixture was heated at 23 ° C. for 30 minutes. It was stirred. 0.12 parts of copper (II) dibenzoate was added to the obtained mixed liquid, and the mixture was further stirred at 100 ° C. for 30 minutes. The obtained reaction solution was concentrated, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added to the obtained residue, the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was separated. 12.50 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C for 30 minutes.
Then, liquid separation was performed and the organic layer was taken out. This water washing operation was repeated 8 times. The obtained organic layer was concentrated, and 50 parts of tert-butyl methyl ether was added to the obtained residue and stirred.
Then, by filtration, 6.84 parts of a salt represented by the formula (B1-22) was obtained.

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

Synthesis of Resin (A) The compound (monomer) used for the synthesis of the resin (A) is shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-2)", "compound (I-1)" and the like according to their formula numbers.

Example 7 [Synthesis of Resin A1]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and compound (I-1) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3). ): Compound (I-1)] is mixed in a ratio of 30: 14: 6: 20: 25: 5, and further, 1.5 parts by weight of this monomer mixture are added to the total mass of all the monomers. A mass ratio of propylene glycol monomethyl ether acetate was mixed. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 73 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin A1 having a weight average molecular weight of 8.4 × 10 ³ with a yield of 75%. This resin A1 has the following structural units.

Example 8 [Synthesis of Resin A2]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and compound (I-2 ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3). ): Compound (I-2)] is mixed in a ratio of 30: 14: 6: 20: 25: 5, and the amount of the monomer mixture is 1.5. A mass ratio of propylene glycol monomethyl ether acetate was mixed. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin A2 having a weight average molecular weight of 8.6 × 10 ³ with a yield of 75%. This resin A2 has the following structural units.

Example 9 [Synthesis of Resin A3]
Monomer (a1-1-2), Monomer (a1-2-3), Monomer (a2-1-1), Monomer (a3-1-1), Monomer (a3-2-3) and Compound (I-15 ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3). ): Compound (I-15)] is mixed in a ratio of 30: 14: 6: 20: 25: 5, and the amount of the monomer mixture is 1.5. A mass ratio of propylene glycol monomethyl ether acetate was mixed. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin A3 having a weight average molecular weight of 7.9 × 10 ³ with a yield of 76%. This resin A3 has the following structural units.

Example 10 [Synthesis of Resin A4]
Monomer (a1-1-2), Monomer (a1-2-3), Monomer (a2-1-1), Monomer (a3-1-1), Monomer (a3-2-3) and Compound (I-16 ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3). ): Compound (I-16)] is mixed in a ratio of 30: 14: 6: 20: 25: 5, and the monomer mixture is mixed with 1.5 to the total mass of all the monomers. A mass ratio of propylene glycol monomethyl ether acetate was mixed. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin A4 having a weight average molecular weight of 8.2 × 10 ³ with a yield of 68%. This resin A4 has the following structural units.

Example 11 [Synthesis of Resin A5]
Monomer (a1-1-2), Monomer (a1-2-3), Monomer (a2-1-1), Monomer (a3-1-1), Monomer (a3-2-3) and Compound (I-19 ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3). ): Compound (I-19)] are mixed in a ratio of 30: 14: 6: 20: 25: 5, and the amount of the monomer mixture is 1.5. A mass ratio of propylene glycol monomethyl ether acetate was mixed. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain Resin A5 having a weight average molecular weight of 8.9 × 10 ³ with a yield of 63%. This resin A5 has the following structural units.

Example 12 [Synthesis of Resin A6]
Monomer (a1-1-2), Monomer (a1-2-3), Monomer (a2-1-1), Monomer (a3-1-1), Monomer (a3-2-3) and Compound (I-28) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3). ): Compound (I-28)] is mixed in a ratio of 30: 14: 6: 20: 25: 5, and the amount of the monomer mixture is 1.5. A mass ratio of propylene glycol monomethyl ether acetate was mixed. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin A6 having a weight average molecular weight of 8.3 × 10 ³ with a yield of 66%. This resin A6 has the following structural units.

Synthesis Example 3 [Synthesis of Resin AX1]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and compound (IX-1) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3). ): Compound (IX-1)] are mixed in a ratio of 30: 14: 6: 20: 25: 5, and the amount of the monomer mixture is 1.5. A mass ratio of propylene glycol monomethyl ether acetate was mixed. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 73 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin AX1 having a weight average molecular weight of 8.8 × 10 ³ with a yield of 72%. This resin AX1 has the following structural units.

Synthesis Example 4 [Synthesis of Resin AA1]
The monomer (a1-1-2), the monomer (a1-2-3), the monomer (a2-1-1), the monomer (a3-1-1) and the monomer (a3-2-3) are used in a molar ratio [ Monomer (a1-1-2): Monomer (a1-2-3): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (a3-2-3)] is 30:14. The mixture was mixed at a ratio of: 6: 20: 30, and to this monomer mixture, 1.5 mass times of propylene glycol monomethyl ether acetate was mixed with respect to the total mass of all the monomers. In the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were used as an initiator with respect to the total number of moles of all monomers, and 1.00 mol% and 3.00 mol%, respectively. Was added. This was polymerized by heating at 73 ° C. for about 5 hours.
The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin AA1 having a weight average molecular weight of 7.8 × 10 ³ with a yield of 76%. This resin AA1 has the following structural units.

Synthesis Example 5 [Synthesis of Resin X1]
The monomer (a4-1-7) was used as a monomer, and 1.2 mass times of the total amount of methyl isobutyl ketone was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in an amount of 0.7 mol% and 2.1 mol% with respect to the total amount of monomers, respectively, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin X1 having a weight average molecular weight of 1.7 × 10 ^{4 in} a yield of 76%. This resin X1 has the following structural units.

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

ＩＸ−２：式（ＩＸ−２）で表される化合物：特開２０１０−５３１２１号公報の実施例に従って合成

Ｂ１−２１：式（Ｂ１−２１）で表される塩
Ｂ１−２２：式（Ｂ１−２２）で表される塩
＜クエンチャー（Ｃ）＞
Ｄ１：（東京化成工業（株）製）

＜溶剤＞
プロピレングリコールモノメチルエーテルアセテート ２６５部
プロピレングリコールモノメチルエーテル ２０部
２−ヘプタノン ２０部
γ−ブチロラクトン ３．５部 <Resin (A)>
A1 to A6, AX1, AA1, X1: resin A1 to resin A6, resin AX1, resin AA1, resin X1
<Acid generator (B)>
I-1: Compound represented by formula (I-1) IX-1: Compound represented by formula (IX-1): Synthesized according to the example of JP 2010-53121 A

IX-2: Compound represented by Formula (IX-2): Synthesized according to the example of JP 2010-53121 A

B1-21: Salt represented by formula (B1-21) B1-22: Salt represented by formula (B1-22) <Quencher (C)>
D1: (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

<Production of resist pattern and its evaluation>
A silicon wafer is coated with a composition for organic antireflection film (ARC-29; manufactured by Nissan Kagaku Co., Ltd.) and baked at 205 ° C. for 60 seconds to give an organic reflection film having a film thickness of 78 nm on the wafer. The prevention film was formed. Next, the above resist composition was applied (spin-coated) on the organic antireflection film so that the film thickness after drying (prebaking) was 85 nm. After coating, the silicon wafer was prebaked on the direct hot plate at the temperature described in the "PB" column of Table 1 for 60 seconds to form a composition layer. A contact hole pattern (hole pitch 100 nm) was formed on a silicon wafer on which the composition layer was formed, using an ArF excimer stepper for immersion exposure (XT: 1900 Gi; ASML, NA = 1.35, 3/4 Annular XY polarized light). / Hole diameter 70 nm) was used, and the exposure amount was changed stepwise for exposure. Ultrapure water was used as the immersion medium.
After the exposure, the silicon wafer was heated (post-exposure bake treatment) on a hot plate at a temperature described in the “PEB” column of Table 1 for 60 seconds. Next, this silicon wafer was subjected to puddle development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

  In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 55 nm was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In terms of effective sensitivity, the hole diameter of the pattern formed by the mask was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The average hole diameter was measured for 400 holes formed on the same silicon wafer by the mask, and the standard deviation was determined using these as a population.
"○" when the standard deviation is less than 2.00 nm,
The case where the standard deviation was larger than 2.00 nm was judged as "x".
The results are shown in Table 2. Numerical values in parentheses indicate standard deviation (nm).

  The resist composition using the compound of the present invention is excellent in CD uniformity of the obtained resist pattern, and thus is suitable for fine processing of semiconductors and is extremely useful industrially.

Claims (15)

A compound represented by formula (I).

[In the formula (I),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each 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 is, * - CO-O -, * - O-CO- , * -O- and represents, * is ^{C (R 1) (R 2} ) or ^{C (Q 1) (Q 2} ) and the coupling position Represents
A ¹ represents a hydrocarbon group having 4 to 24 carbon atoms, including a divalent alicyclic hydrocarbon group having 4 to 18 carbon atoms.
A ² represents a divalent hydrocarbon group having 2 to 12 carbon atoms.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A represents a group represented by formula (IA). ]

[In the formula (IA),
A ³ represents a divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S— or —CO—, The hydrogen atom contained in the hydrocarbon group may be replaced with a halogen atom or a hydroxy group. ] The compound according to claim ¹ , wherein X ¹ is * -CO-O-, and * represents a bonding position with C (R ¹ ) (R ² ) or C (Q ¹ ) (Q ² ). The compound according to claim 1, wherein A ¹ is a hydrocarbon group containing an adamantanediyl group. A ² is A compound according to any one of claims 1 to 3 alkanediyl group having 2 to 6 carbon atoms. The compound according to any one of claims 1 to 4, wherein the group represented by formula (IA) is a group represented by formula (IB).

[In formula (IB), * represents a bond with SO ₂ . ]   An acid generator containing the compound according to claim 1.   A resin containing a structural unit derived from the compound according to claim 1.   The resin according to claim 7, further comprising a structural unit having an acid labile group other than the structural unit derived from the compound represented by the formula (I). The resin according to claim 8, wherein the structural unit having an acid labile group is at least one selected from the structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2).

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond with —CO—. Representing a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these.
m1 represents the integer of 0-14.
n1 represents the integer of 0-10.
n1 'represents the integer of 0-3. ]   A resist composition comprising the resin according to claim 7 and an acid generator.   The resist composition according to claim 10, wherein the acid generator is the acid generator according to claim 6.   A resist composition comprising a resin containing a structural unit having an acid labile group other than the structural unit derived from the compound represented by formula (I), and the acid generator according to claim 6. The resist composition according to claim 10, wherein the acid generator comprises a salt represented by the formula (B1).

[In the formula (B1),
Q ¹¹ and Q ¹² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the monovalent alicyclic hydrocarbon group is, -O - - -CH ₂ contained in the hydrogen radical, - SO ₂ - or -CO- may be replaced with.
Z ⁺ represents an organic cation. ]   The resist composition according to claim 10, 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 10 to 14 onto a substrate,
(2) a step of drying the composition after coating to form a composition layer,
(3) exposing the composition layer
(4) heating the composition layer after exposure, and (5) developing the composition layer after heating,
A method of manufacturing a resist pattern including: