JP2017088860A - Resist Composition and Resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin and a resist composition capable of producing a resist pattern with good CD uniformity.SOLUTION: The resin contains a structural unit represented by formula (I) and a structural unit having an acid-labile group, and the resist composition contains the resin. [X represents -O-, -S-, or -NR-; Rrepresents a hydrogen atom or an alkyl group; s and v each represent an integer of 1-4; Arepresents a single bond, a 1-6C alkanediyl group, or *-A-X-(A-X)-(A)-; * represents a bond with the group X; A, A, and Aeach represent an alkanediyl group; Xand Xeach represent -O-, -CO-O-, -O-CO-, or -O-CO-O-; and a and b each represent 0 or 1.]SELECTED DRAWING: None

Description

  The present invention relates to a resist composition and a resin.

特許文献２には、下記構造単位の組合せからなる樹脂が記載されている。

Patent Document 1 describes a resin comprising a combination of the following structural units.

Patent Document 2 describes a resin comprising a combination of the following structural units.

WO2009 / 078078 JP 2012-168497 A

  A resist pattern formed from a resist composition containing the above resin may not always satisfy CD uniformity (CDU).

［式（Ｉ）中、
Ｒ^１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。
Ｘは、−Ｏ−、−Ｓ−又は−ＮＲ^１１−を表す。
Ｒ^１１は水素原子又は炭素数１〜６のアルキル基を表す。
ｓ及びｖは、それぞれ独立に、１〜４の整数を表す。
Ｒ^２は、炭素数１〜６の脂肪族炭化水素基を表す。
ｕは、０〜３の整数を表し、ｕが２以上のとき、複数のＲ^２は互いに同一又は相異なる。
Ａ¹は、単結合、炭素数１〜６のアルカンジイル基又は＊−Ａ²−Ｘ¹−（Ａ³−Ｘ²）_a−（Ａ⁴）_b−を表す。＊は基Ｘとの結合手を表す。
Ａ²、Ａ³及びＡ⁴は、それぞれ独立に、炭素数１〜６のアルカンジイル基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−又は−Ｏ−ＣＯ−Ｏ−を表す。
ａは、０又は１を表す。
ｂは、０又は１を表す。］
〔２〕Ａ¹が、単結合である〔１〕記載の樹脂。
〔３〕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〔１〕又は〔２〕に記載の樹脂。

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組み合わせた基を表す。
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。］
〔４〕さらに、式（ａ３−４）で表される構造単位を含む〔１〕〜〔３〕のいずれかに記載の樹脂。

［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。
Ｌ^a7は、−Ｏ−、^＊−Ｏ−Ｌ^a8−Ｏ−、^＊−Ｏ−Ｌ^a8−ＣＯ−Ｏ−、^＊−Ｏ−Ｌ^a8−ＣＯ−Ｏ−Ｌ^a9−ＣＯ−Ｏ−又は^＊−Ｏ−Ｌ^a8−Ｏ−ＣＯ−Ｌ^a9−Ｏ−を表す。
＊はカルボニル基との結合手を表す。
Ｌ^a8及びＬ^a9は、互いに独立に、炭素数１〜６のアルカンジイル基を表す。］
〔５〕〔１〕〜〔４〕のいずれかに記載の樹脂及び酸発生剤を含有するレジスト組成物。
〔６〕酸発生剤が、式（Ｂ１）で表される塩である〔５〕記載のレジスト組成物。

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、置換基を有していてもよい炭素数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、水素原子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。］
〔７〕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〔５〕又は〔６〕記載のレジスト組成物。
〔８〕さらに、フッ素原子を有する構造単位を含む樹脂を含有する〔５〕〜〔７〕のいずれかに記載のレジスト組成物。
〔９〕（１）〔５〕〜〔８〕のいずれかに記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resin comprising a structural unit represented by the formula (I) and a structural unit having an acid labile group.

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
X represents —O—, —S—, or —NR ¹¹ —.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4.
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer of 0 to 3, and when u is 2 or more, the plurality of R ² are the same or different from each other.
A ¹ represents a single bond, alkanediyl group having 1 to 6 carbon atoms or ^{* -A 2 -X 1 - (A} 3 -X 2) a - (A 4) b - represents a. * Represents a bond with the group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² each independently represent —O—, —CO—O—, —O—CO— or —O—CO—O—.
a represents 0 or 1.
b represents 0 or 1. ]
[2] The resin according to [1], wherein A ¹ is a single bond.
[3] 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) [1] or The resin according to [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 to —CO—. Represents 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 obtained by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]
[4] The resin according to any one of [1] to [3], further comprising a structural unit represented by the formula (a3-4).

[In the 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.
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
* Represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]
[5] A resist composition comprising the resin according to any one of [1] to [4] and an acid generator.
[6] The resist composition according to [5], wherein the acid generator is a salt represented by the formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents an ^optionally substituted divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is —O— or -CO- may be substituted, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and —CH ₂ — contained in the monovalent alicyclic hydrocarbon group. May be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]
[7] The resist composition according to [5] or [6], further comprising a salt that generates an acid having a lower acidity than an acid generated from an acid generator.
[8] The resist composition according to any one of [5] to [7], further comprising a resin containing a structural unit having a fluorine atom.
[9] (1) A step of applying the resist composition according to any one of [5] to [8] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

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

In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. Notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning.
In addition, unless otherwise specified, groups such as “aliphatic hydrocarbon group” that can be linear, branched and / or ring include both. The “aromatic hydrocarbon group” also includes a hydrocarbon group containing an aromatic ring. When stereoisomers exist, all stereoisomers are included.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition.

<Resin>
The resin of the present invention is a resin containing a structural unit represented by the formula (I) (hereinafter sometimes referred to as “structural unit (I)”) and a structural unit having an acid labile group (hereinafter referred to as “resin (A)”. ) ”.

［式（Ｉ）中、
Ｒ^１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。
Ｘは、−Ｏ−、−Ｓ−又は−ＮＲ^１１−を表す。
Ｒ^１１は水素原子又は炭素数１〜６のアルキル基を表す。
ｓ及びｖは、それぞれ独立に、１〜４の整数を表す。
Ｒ^２は、炭素数１〜６の脂肪族炭化水素基を表す。
ｕは、０〜３の整数を表し、ｕが２以上のとき、複数のＲ^２は互いに同一又は相異なる。
Ａ¹は、単結合、炭素数１〜６のアルカンジイル基又は＊−Ａ²−Ｘ¹−（Ａ³−Ｘ²）_a−（Ａ⁴）_b−を表す。＊は基Ｘとの結合手を表す。
Ａ²、Ａ³及びＡ⁴は、それぞれ独立に、炭素数１〜６のアルカンジイル基を表す。
Ｘ¹及びＸ²は、それぞれ独立に、−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−又は−Ｏ−ＣＯ−Ｏ−を表す。
ａは、０又は１を表す。
ｂは、０又は１を表す。］ <Structural unit (I)>

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
X represents —O—, —S—, or —NR ¹¹ —.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4.
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer of 0 to 3, and when u is 2 or more, the plurality of R ² are the same or different from each other.
A ¹ represents a single bond, alkanediyl group having 1 to 6 carbon atoms or ^{* -A 2 -X 1 - (A} 3 -X 2) a - (A 4) b - represents a. * Represents a bond with the group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² each independently represent —O—, —CO—O—, —O—CO— or —O—CO—O—.
a represents 0 or 1.
b represents 0 or 1. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- An unsubstituted alkyl group having 1 to 6 carbon atoms such as a pentyl group and an n-hexyl group, and a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro-sec-butyl group, Examples thereof include haloalkyl groups having 1 to 6 carbon atoms such as a perfluoro-tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n- A hexyl group etc. are mentioned.
Either one of s and v is preferably 1.

Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl group. And alkyl groups such as an n-hexyl group.
R ² is preferably a methyl group or an ethyl group.
u is preferably 0 or 1.

A ^1, as the A ^2, A ³ and 6 alkanediyl group of A ^4, methylene group, ethylene group, propane-1,3-diyl, butane-1,4-diyl group, pentane - A linear alkanediyl group such as 1,5-diyl group and hexane-1,6-diyl group, a linear alkanediyl group, an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group) Group having a side chain such as ethane-1, propyl, isopropyl, butyl, sec-butyl, tert-butyl, etc., ethane-1,1-diyl, propane-1,2-diyl, butane- 1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group And branched alkanediyl groups such as It is done.

* —A ² —X ¹ — (A ³ —X ² ) _a — (A ⁴ ) _b — includes * —A ² —O—, * —A ² —CO—O—, * —A ² —O. —CO—O—, * —A ² —CO—O—A ⁴ —, * —A ² —O—CO—, * —A ² —CO—O—A ³ —CO—O—, * —A ² —CO—O—A ³ —CO—O—A ⁴ —, * —A ² —O—CO—A ³ —O—, * —A ² —O—A ³ —CO—O—, * —A ^{2 -CO-O-A 3 -O-} CO -, * - A 2 -O-CO-A 3 -O-CO- and the like. Among ^{them, * - A 2 -O -,} * - A 2 -CO-O- or * -A ² -O-CO-O- are preferable, * - A ² -CO-O- or * -A ² - O-CO-O- is more preferable. * Represents a bond with the group X.

A ¹ , A ² , A ³ and A ⁴ are preferably each independently an alkanediyl group having 1 to 6 carbon atoms.
A ¹ is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, and further preferably an alkanediyl group having 1 to 3 carbon atoms. .

The cyclic sulfoxide structure in the formula (I) is preferably a structure represented by any one of the formulas (S-1) to (S-9), and any of the formulas (S-1) to (S-3). The structure represented by the structure represented by is more preferable. * Represents a bond to ^{A 1.}

The structural unit (I) corresponds to R ¹ of the structural unit represented by the following formulas (I-1) to (I-28) and the structural unit represented by the following formulas (I-1) to (I-28). And a structural unit in which the methyl group to be substituted is a hydrogen atom or a trifluoromethyl group.

なかでも、式（Ｉ−１）〜式（Ｉ−３）で表される構造単位が好ましい。

Especially, the structural unit represented by Formula (I-1)-Formula (I-3) is preferable.

［式（Ｉ）中、Ａ^１、Ｒ^１、Ｒ^３、Ｘ、ｓ、ｖ及びｕは、上記と同じ意味を表す。］ The structural unit (I) is derived from a compound represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”).

[In the formula (I), A ¹ , R ¹ , R ³ , X, s, v and u have the same meaning as described above. ]

Compound (I) corresponds to R ¹ of compounds represented by formulas (I′-1) to (I′-28) and compounds represented by formulas (I′-1) to (I′-28). Examples include compounds in which a methyl group is replaced with a hydrogen atom or a trifluoromethyl group.

なかでも、式（Ｉ’−１）〜式（Ｉ’−３）で表される構造単位が好ましい。

Especially, the structural unit represented by Formula (I'-1)-Formula (I'-3) is preferable.

［式中、Ａ^１、Ｒ^１、Ｒ^３、Ｘ、ｓ、ｖ及びｕは、上記と同じ意味を表す。］
溶媒としては、酢酸及びアセトンなどが挙げられる。
酸化剤としては、過酸化水素などが挙げられる。 <Method for Producing Compound (I)>
Compound (I) can be obtained by oxidizing the compound represented by formula (I0-a) in a solvent.

[Wherein, A ¹ , R ¹ , R ³ , X, s, v, and u represent the same meaning as described above. ]
Examples of the solvent include acetic acid and acetone.
Examples of the oxidizing agent include hydrogen peroxide.

［式中、Ａ^１、Ｒ^１、Ｒ^３、ｓ、ｖ及びｕは、上記と同じ意味を表す。］
溶媒としては、ジメチルホルムアミド、クロロホルム、テトラヒドロフラン及びトルエンなどが挙げられる。
塩基触媒としては、炭酸カリウム、ヨウ化カリウム、ピリジン、ジメチルアミノピリジンなどが挙げられる。 In the compound (I0-a) in which X is —O—, the compound represented by the formula (Ia ′) and the compound represented by the formula (Ib) are mixed in a solvent in the presence of a base catalyst. Can be obtained by reaction.

[Wherein, A ¹ , R ¹ , R ³ , s, v, and u represent the same meaning as described above. ]
Examples of the solvent include dimethylformamide, chloroform, tetrahydrofuran and toluene.
Examples of the base catalyst include potassium carbonate, potassium iodide, pyridine, dimethylaminopyridine and the like.

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

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

The compound represented by the formula (I0-a) in which X is —S— represents the compound represented by the formula (Ia ″) instead of the compound represented by the formula (Ia ′). And can be obtained by carrying out the method described above.
Compound (I) wherein X is —NR ¹¹ — is prepared by using the compound represented by formula (Ia ′ ″) instead of the compound represented by formula (Ia ′) as described above. Can be obtained.

Examples of the compound represented by the formula (Ia ″) include compounds represented by the following formula.

Examples of the compound represented by the formula (Ia ′ ″) include compounds represented by the following formula.

Two or more structural units (I) contained in the resin (A) may be contained.
The content of the structural unit (I) contained in the resin (A) is usually 1 to 60 mol%, preferably 3 to 40 mol%, more preferably 4 with respect to all the structural units of the resin (A). It is -35 mol%, More preferably, it is 5-30 mol%, Most preferably, it is 5-25 mol%.

  In addition to the structural unit (I), the resin (A) of the present invention further has a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). An “acid-labile group” has a leaving group, and the leaving group is eliminated by contact with an acid, so that the structural unit is converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). Meaning a group.

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

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

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

[In 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. 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 —CH ₂ — contained in the ring group may be replaced by —O— or —S—.
X represents an oxygen atom or a sulfur atom.
* Represents a bond. ]

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

Examples of the group in which the alkyl group and the alicyclic hydrocarbon group are combined include, for example, an alkyl-cycloalkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and a methyladamantyl group, a cyclohexylmethyl group, Examples thereof include cycloalkyl-alkyl groups such as adamantylmethyl group and norbornylmethyl group, and alkyl-cycloalkyl-alkyl groups such as methylcyclohexylmethyl group.
na is preferably 0.

Examples of —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 include the following groups. The divalent alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, 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。 Groups formed by combining these include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, alkyl-cycloalkyl-alkyl groups, aralkyl groups (eg, phenylmethyl group, 1-phenylethyl group, 2-phenyl group). Ethyl group, 1-phenyl-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.), aryl-cycloalkyl groups (phenyladamantyl group, phenylcyclohexyl group, etc.) and the like.
^{Examples of the} divalent heterocyclic group formed together with the carbon atom and X to which R ^{a2 ′} and R ^{a3 ′} are bonded to each other and X include the following groups. * Represents a bond.

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

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^{a1 to} R ^a3 are alkyl groups in the formula (1), preferably a tert-butoxycarbonyl group), 2-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- ( And 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).

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, 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. If the resin (A) having a structural unit derived from the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

  In the resin (A), the content of the structural unit (a1) is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, based on all the structural units of the resin (A). Preferably it is 30-80 mol%.

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

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

[In 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 to a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and 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 combination thereof. ]

L ^a01 is preferably an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O— (where k01 is preferably an integer of 1 to 4, more preferably 1, and more preferably). Is an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03, and R ^a04 , the alicyclic hydrocarbon group, and a group obtained by combining these include the same groups as those described for R ^{a1 to} R ^a3 in formula (1).
The alkyl group of R ^a02 , R ^a03 and R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon group ^{represented by} R ^a02 , R ^a03 and R ^a04 is preferably an aliphatic hydrocarbon group having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
The group combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less, combining the alkyl group and the alicyclic hydrocarbon group. Examples of such groups 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. It is done.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.

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

[In 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 to —CO—. Represents 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 an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ]

R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

L ^a1 and L ^a2 are preferably —O— or * —O— (CH ₂ ) _{k1 ′} —CO—O— (where k1 ′ is an integer of 1 to 4, preferably 1). More preferably -O-.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and a group formed by combining these include the same groups as those ^exemplified for R ^{a1 to} R ^a3 of formula (1).
The alkyl group for R ^a6 and R ^a7 is preferably an alkyl group having 1 to 6 carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

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

As a monomer (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Among these, a monomer represented by any one of formula (a1-1-1) to formula (a1-1-8) is preferable, and any one of formula (a1-1-1) to formula (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include monomers represented by any of the formulas (a1-2-1) to (a1-2-12), and include the formula (a1-2-3) and the formula (a1). -2-4), a monomer represented by formula (a1-2-9) or formula (a1-2-10) is preferable, and a monomer represented by formula (a1-2-3) or formula (a1-2-9) More preferred is a monomer.

  When the resin (A) includes the structural unit (a1-0) and / or the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is the total structure of the resin (A). It is 10-95 mol% normally with respect to a unit, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

式（ａ１−３）中、
Ｒ^a9は、ヒドロキシ基を有していてもよい炭素数１〜３の脂肪族炭化水素基、カルボキシ基、シアノ基、水素原子又は−ＣＯＯＲ^a13を表す。
Ｒ^a13は、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表し、該アルキル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、該アルキル基及び該脂環式炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−−又は−ＣＯ−に置き換わっていてもよい。
Ｒ^a10、Ｒ^a11及びＲ^a12は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせることにより形成される基を表すか、Ｒ^a10及びＲ^a11は互いに結合して、それらが結合する炭素原子とともに炭素数３〜２０の２価の脂環式炭化水素基を形成する。 Furthermore, examples of the structural unit (a1) having the group (1) include 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). Moreover, the monomer which derives the structural unit (a1-3) may be referred to as a monomer (a1-3).

In 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 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, and the alkyl group and the alicyclic hydrocarbon group The hydrogen atom contained may be substituted with a hydroxy group, and —CH ₂ — contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with —O—— or —CO—. .
R ^a10 , R ^a11 and 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 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.

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

Examples of the aliphatic hydrocarbon group which may have a hydroxy group of R ^a9 include a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a hydroxymethyl group and a 2-hydroxyethyl group.
^Examples of the alkyl group having 1 to 8 carbon atoms of R ^{a10 to} R ^a12 and 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, and an n-pentyl group. Group, n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group and the like.
^Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ^a13 include a cyclopentyl group, a cyclopropyl group, an adamantyl group, an adamantylmethyl group, a 1-adamantyl-1-methylethyl group, and 2-oxo-oxolane-3- Yl group and 2-oxo-oxolan-4-yl group.
The alicyclic hydrocarbon group for 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 cyclopentyl. Cycloalkyl groups such as a group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, and norbornyl. Group, methylnorbornyl group, isobornyl group and the like.
-C (R ^a10 ) (R ^a11 ) (R ^a12 ) in the case where R ^a10 and R ^a11 are bonded to each other to form a divalent hydrocarbon group together with the carbon atom to which they are bonded, Groups are preferred.

  Specific examples of the monomer (a1-3) include 5-norbornene-2-carboxylic acid-tert-butyl, 5-norbornene-2-carboxylic acid 1-cyclohexyl-1-methylethyl, 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 1- (1-adamantyl) -1-methyl 5-norbornene-2-carboxylate Chill, and the like.

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

  When the resin (A) includes the structural unit (a1-3), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, based on all the structural units of the resin (A). 20-85 mol% is more preferable.

［式（ａ１−４）中、
Ｒ^a32は、水素原子、ハロゲン原子、又は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｌａは０〜４の整数を表す。ｌａが２以上である場合、複数のＲ^a33は互いに同一であっても異なってもよい。
Ｒ^a34及びＲ^a35はそれぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a36は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a35及びＲ^a36は互いに結合してこれが結合するＣ−Ｏとともに炭素数３〜２０の２価の複素環基を形成し、該炭化水素基及び該２価の複素環基に含まれる−ＣＨ₂−は、−Ｏ−又は−Ｓ−で置き換わってもよい。］ As the structural unit (a1) having a group represented by the group (2), a structural unit represented by the formula (a1-4) (hereinafter sometimes 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, the plurality of R ^a33 may be the same as or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are bonded to each other And C—O to which it is 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— or It may be replaced by -S-. ]

^Examples of the alkyl group for 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. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
Examples of the halogen atom for R ^a32 and R ^a33 include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,1. 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -A perfluorohexyl group etc. are 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. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
Examples of the hydrocarbon group R ^a34 and R ^a35, include the same groups as R ^{a1 'and} R ^a2' of formula (2).
^Ra36 includes an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. It is done.

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 or an ethoxy group, and further preferably a methoxy group.
la is preferably 0 or 1, more preferably 0.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, 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. It is a group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group in R ^a36 and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group in R ^a36 has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.

As a monomer which introduce | transduces structural unit (a1-4), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Especially, the monomer respectively represented by Formula (a1-4-1)-Formula (a1-4-8) is preferable, and Formula (a1-4-1)-Formula (a1-4-5) and Formula (a1-4) are preferable. The monomers represented by -8)) are more preferable.

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

式（ａ１−５）中、
Ｒ^a8は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊−（ＣＨ₂）_h3−ＣＯ−Ｌ⁵⁴−を表し、ｈ３は１〜４の整数を表し、＊は、Ｌ⁵¹との結合手を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。 As a structural unit derived from a (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)”) Is also included).

In formula (a1-5),
R ^a8 represents a C 1-6 alkyl group optionally having a halogen atom, a hydrogen atom, or a halogen atom.
Z ^a1 represents a single bond or * — (CH ₂ ) _h3 —CO—L ⁵⁴ —, h3 represents an integer of 1 to 4, and * represents a bond to L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. 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.
One of L ⁵² and L ⁵³ is preferably —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—. * Represents a bond to L ^51.

As a monomer which introduce | transduces structural unit (a1-5), the monomer described in Unexamined-Japanese-Patent No. 2010-61117 is mentioned, for example. Among these, 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 preferable. Is more preferable.

  When resin (A) has a structural unit (a1-5), the content rate is preferable 1-50 mol% with respect to all the structural units of resin (A), and 3-45 mol% is more preferable. 5 to 40 mol% is more preferable.

  The structural unit (a) having an acid labile group in the resin (A) includes the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2), and the structural unit (a1-5). ) Is preferably at least one selected from the group consisting of, and more preferably at least two, a combination of structural unit (a1-1) and structural unit (a1-2), structural unit (a1-1) and structural unit ( a1-5), a structural unit (a1-1) and a structural unit (a1-0), a structural unit (a1-2) and a structural unit (a1-0), and a structural unit (a1-5) And a combination of the structural unit (a1-0), a structural unit (a1-0), a combination of the structural unit (a1-1) and the structural unit (a1-2), a structural unit (a1-0), and a structural unit (a1- 1) and structural unit (a1-5) More preferably a combination, the combination of the structural units (a1-1) and the structural unit (a1-2), more preferably a combination of structural units (a1-1) and the structural unit (a1-5).

<Structural unit (s)>
The resin (A) further includes a structural unit having no acid labile group described below (hereinafter sometimes referred to as “structural unit (s)”), a structural unit having a halogen atom (hereinafter, “structural unit ( a4) ”)), a structural unit (a5) having a non-eliminating hydrocarbon group, and a structural unit derived from other known monomers. Especially, it is preferable that a structural unit (s) is included. The structural unit (s) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”). As the monomer (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 structure 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 If a resin having a unit (hereinafter sometimes referred to as “structural unit (a3)”) is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group 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 beam such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, the structural unit (a2) It is preferable to use the structural unit (a2) having a phenolic hydroxy group. When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2), and the structural unit (a2-1) is more preferable. As a structural unit (a2), 1 type may be included independently and 2 or more types may be included.

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

［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 an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ^a31 may be the same as or different from each other. ]

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an n-pentyl group, and an n-hexyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1,1. 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n -A perfluorohexyl group etc. are mentioned. R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the R ^a31 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

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 formula (a2-0-1), formula (a2-0-2), formula (a2-0-3), and formula (a2-0-4), respectively. What is represented is preferable, and what is represented by a formula (a2-0-1) or a formula (a2-0-2) is more preferable.

  The resin (A) containing the structural unit (a2-0) is subjected to a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer that derives the structural unit (a2-0) is protected with a protective group, and then deprotected. It can be manufactured by processing. However, when the deprotection treatment is performed, the acid labile group of the structural unit (a1) needs to be not significantly impaired. Examples of such protecting groups include acetyl groups.

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

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

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

Examples of the monomer that derives the structural unit (a2-1) include monomers described in JP 2010-204646 A. A monomer represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferable, and represented by any one of formula (a2-1-1) to formula (a2-1-4). The monomer represented by Formula (a2-1-1) or Formula (a2-1-3) is more preferable.

  When resin (A) contains a structural unit (a2-1), the content rate is 1-45 mol% normally with respect to all the structural units of resin (A), Preferably it is 1-40 mol%. More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. But you can. The lactone ring is preferably a bridged ring containing a γ-butyrolactone ring, an adamantane lactone ring or a γ-butyrolactone ring structure.

  The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These 1 type may be contained independently and 2 or more types may be contained.

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

[In the formula (a3-1),
L ^a4 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 a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5. When p1 is 2 or more, the plurality of R ^a21 are the same or different from each other.
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 a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, the plurality of R ^a22 are the same 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 a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, the plurality of R ^a23 are the same 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.
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
* Represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 and R ^a23 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. Can be mentioned.
Examples of the halogen atom for 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. , Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

^Examples of the alkanediyl group represented by L ^a8 and L ^a9 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 are each independently preferably —O— or k— is an integer of 1 to 4 * —O— (CH ₂ ) A group represented by _{k 3} —CO—O—, more preferably —O— and * —O—CH ₂ —CO—O—, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

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 still more preferably a hydrogen atom or a methyl group.
L ^a7 is preferably —O— or ^* —O—L ^a8 —CO—O—, and more preferably —O—, —O—CH ₂ —CO—O— or —O—C ₂ H. _4- CO-O-.

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

In the structural units represented by the following formulas (a3-4-1) to (a3-4-12), compounds in which the methyl group corresponding to R ^a24 is replaced with a hydrogen atom are also structural units (a3-4). ).

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Moreover, the content rate of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), and a structural unit (a3-4) is respectively with respect to all the structural units of resin (A1). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more preferable.

<Other structural units (t)>
The resin (A) may contain another structural unit (t) as a structural unit other than the structural unit (I), the structural unit (a1), and the structural unit (s). As the structural unit (t), in addition to the structural unit (a2) and the structural unit (a3), a structural unit which may have a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”) and non-depletion. And a structural unit (s) having a hydrocarbon separation group (hereinafter sometimes referred to as “structural unit (a5)”). The resin (A) may have a structural unit other than the above-described structural unit, and examples of such a structural unit include structural units well known in the art.

［式（ａ４−０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^４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。］ As the structural unit (a4), a structural unit represented by formula (a4-0) can be given.

[In the formula (a4-0),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁴ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a 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 ⁴ include a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group, and ethane-1,1- Branched alkanediyl such as diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group Groups.

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

L ⁴ is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
L ³ is preferably a C 1-6 perfluoroalkanediyl group, and more preferably a C ^1-3 C perfluoroalkanediyl group.

Examples of the structural unit (a4-0) include the structural units shown below. In the structural units represented by the following formulas (a1-0-1) to (a4-0-16), compounds in which the methyl group corresponding to R ⁵ is replaced by a hydrogen atom are also structural units (a4-0). ).

［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。
＊、＊＊は結合手であり、＊＊が−Ｏ−ＣＯ−Ｒ^ａ４２との結合手である。］ As the structural unit (a4), a structural unit represented by formula (a4-1) can be given.

[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—. Good.
A ^a41 represents a ^C1-C6 alkanediyl group which may have a substituent 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 a ^C 1-5 aliphatic hydrocarbon group which may have a substituent.
A ^a43 represents a C1-C5 aliphatic hydrocarbon group which may have a single bond or a substituent.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less.
* And ** are bonds, and ** is a bond with -O-CO-R ^a42 . ]

^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 the chain and cyclic aliphatic saturated hydrocarbon groups are preferable. The aliphatic saturated hydrocarbon group includes a straight chain or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic group formed by combining an alkyl group and an alicyclic hydrocarbon group. Group hydrocarbon group and the like.
Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl. Group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Cyclic aliphatic hydrocarbon groups 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 “represents a hand.”

  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 for R ^a42 include a halogen atom or a group represented by the formula (a-g3). As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom is mentioned.

[In the formula (a-g3),
^Xa43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents a C ^1-17 aliphatic hydrocarbon group having at least one halogen atom.
* Represents a bond. ]

^Examples of the aliphatic hydrocarbon group for A ^{a45 include} the same groups as those exemplified for R ^a42 .
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3). It is more preferable that
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 1-6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the number of carbons contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total number of carbon atoms in the group is preferably 15 or less, and more preferably 12 or less. When the group represented by the formula (a-g3) is used as a substituent, the number is preferably one.

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

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

^Examples of the structure represented by * -A ^a46 -X ^a44 -A ^a47 include the following structures.

^As the alkanediyl group of ^Aa41 , 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 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 include branched alkanediyl groups such as 2-methylbutane-1,4-diyl group.
^Examples of the substituent in the alkanediyl group of ^Aa41 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 still more preferably an ethylene group.

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

^Examples of the group (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—R ^a42 .

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

As the alkanediyl group of A ^f1 , a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group , A straight-chain 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 -Branched alkanediyl groups such as a diyl group, 1-methylbutane-1,4-diyl group, 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, a cyclic group, and a group formed by a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
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 -An ethylhexyl group is mentioned.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group. Can be mentioned. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, norbornyl group, A methyl norbornyl group and an isobornyl group are mentioned.

Examples of the hydrocarbon group having a fluorine atom for 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 a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2- Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3 , 3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl 2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2 , 2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluoro Butyl) ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5 Fluorinated alkyl groups such as 6,6-dodecafluorohexyl group, perfluoropentylmethyl group and 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.

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

［式（ａ４−３）中、
Ｒ^ｆ１１は、水素原子又はメチル基を表す。
Ａ^ｆ１１は、炭素数１〜６のアルカンジイル基を表す。
Ａ^ｆ１３は、フッ素原子を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。
Ｘ^ｆ１２は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^ｆ１４は、フッ素原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^ｆ１３及びＡ^ｆ１４の少なくとも１つは、フッ素原子を有する脂肪族炭化水素基を表す。］

[In the 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 a C 1-18 aliphatic hydrocarbon group 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 chain and cyclic aliphatic hydrocarbon groups, and divalent aliphatic hydrocarbon groups formed by combining them. The aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f13 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain 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 Groups, perfluoroalkanediyl groups such as perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a monocyclic or polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantanediyl group, a norbornanediyl group, a perfluoroadamantanediyl group, and the like.

Examples of the aliphatic hydrocarbon group for A ^f14 include chain and cyclic aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups formed by combining them. The aliphatic hydrocarbon group 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 a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 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, A heptyl group, a perfluoro heptyl group, an octyl group, a perfluorooctyl group, etc. are mentioned.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be 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, and a perfluoroadamantylmethyl group.

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

As the structural unit represented by the formula (a4-2), structural units represented by the formula (a4-1-1) to the formula (a4-1-22) can be given.

  Examples of the structural unit represented by formula (a4-3) include structural units represented by formula (a4-1′-1) to formula (a4-1′-22), respectively.

［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。］ Examples of the structural unit (a4) include 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 hydrocarbon groups as R ^f2 in 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. It is more preferably a group, more preferably a C 1-6 alkyl group having a fluorine atom.

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

Examples of the structural unit represented by the formula (a4-4) include the following structural units. In the structural unit represented by the following formula, a compound in which a methyl group corresponding to R ^f21 is replaced by a hydrogen atom can also be given as a specific example of the structural unit (a4-4).

  When resin (A) has a structural unit (a4), it is preferable that the content rate is 1-20 mol% with respect to the sum total of all the structural units of resin (A), and 2-15 mol% It is more preferable that it is 3 to 10 mol%.

［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。但し、Ｌ^５１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^５１は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。］ <Structural unit (a5)>
Examples of the non-leaving hydrocarbon group that the structural unit (a5) has include a linear, branched, or cyclic hydrocarbon group. Especially, it is preferable that a structural unit (a5) is an alicyclic hydrocarbon group.
As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.

[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 a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the coupling position with the L ⁵¹ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵¹ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

The alicyclic hydrocarbon group for R ⁵² may be 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.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include 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 octyl group and 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, more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ⁵¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. It is done.
Examples of the divalent aliphatic saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be 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.

  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 formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

［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^ｘ３Ｌ^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^ｘ６及びＬ^ｘ７の合計炭素数は、１５以下である。
式（Ｌ１−４）中、
Ｌ^ｘ８及びＬ^ｘ９は、単結合又は炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。
Ｗ^ｘ１は、炭素数３〜１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^ｘ８、Ｌ^ｘ９及びＷ^ｘ１の合計炭素数は、１５以下である。］

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

As group represented by a formula (L1-1), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-2), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-3), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-4), the bivalent group shown below is mentioned, for example.

L ⁵¹ is preferably a single bond or a group represented by the formula (L1-1).
Examples of the structural unit (a5-1) include the following.

Formula (a5-1-1) ~ formula ^(a5-1-18), structural units in which a methyl group is replaced by a hydrogen atom corresponding to ^{R 51} may also be mentioned as specific examples of the structural unit (a5-1) it can.

  When the resin (A) has the structural unit (a5), the content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, based on all structural units of the resin (A). More preferred is ˜15 mol%.

It is preferable that resin (A) does not contain the structural unit which has a fluorine atom. The structural unit having an acid labile group is preferably a structural unit having no fluorine atom. That is, the resin (A) is preferably a resin comprising the structural unit (I), the structural unit (a1), and the structural unit (s), that is, the compound (I), the monomer (a1), and the monomer (s). It is a copolymer.
The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group) and a structural unit. It is at least one of (a1-5), more preferably the structural unit (a1-1) or the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably at least one of structural units represented by a γ-butyrolactone ring, a bridged ring containing a γ-butyrolactone ring structure, or an adamantane lactone ring, and more preferably in the formula (a3-1). And at least one selected from the structural unit represented by formula (a3-2) and the structural unit represented by formula (a3-4), more preferably in formula (a3-4) The structural unit represented.

  The resin (A) may contain a structural unit derived from a monomer having an adamantyl group (particularly the structural unit (a1-1)) 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 derives these structural units. can do. The content rate of each structural unit which resin (A) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, further preferably 15,000 or less). The weight average molecular weight is a value determined by gel permeation chromatography.

<Resist composition>
The resist composition of the present invention contains a resin (A) and an acid generator (hereinafter sometimes referred to as “acid generator (B)”).
The resist composition contains a resin other than the resin (A), a quencher (hereinafter sometimes referred to as “quencher (C)”) and / or a solvent (hereinafter sometimes referred to as “solvent (E)”). It is preferable to do.

<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 composed only of the structural unit (s), a resin including the structural unit (a4) (hereinafter sometimes referred to as “resin (X)”), and the like.

<Resin (X)>
As the resin other than the resin (A), the resin (X) is preferable. In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, and still more preferably 50 mol% or more with respect to all the structural units of the resin (X). .
As the structural unit that the resin (X) may further have, structural units derived from the structural unit (a1), the structural unit (a2), the structural unit (a3), the structural unit (a5), and other known monomers. Examples of the unit include the structural unit (a5).
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). Preferably it is 1-40 mass parts, Most preferably, it is 2-30 mass parts.

  80 mass% or more and 99 mass% or less are preferable with respect to solid content of a resist composition, and, as for the total content rate of resin other than resin (A) and resin (A), 90 mass% or more and 99 mass% or less are more. preferable. 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.

<Acid generator (B)>
Although an acid generator is classified into a nonionic type and an ionic type, any may be used for the acid generator (B) of the resist composition of this invention. Nonionic acid generators 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. Typical examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712, etc. The compound which generate | occur | produces an acid by the radiation as described in 1 can be used. Moreover, you may use the compound manufactured by the well-known method. An acid generator (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

［式（Ｂ１）中、
Ｑ^１及びＱ^２は、互いに独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^ｂ１は、置換基を有していてもよい炭素数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、水素原子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 ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents an ^optionally substituted divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is —O— or -CO- may be substituted, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and —CH ₂ — contained in the monovalent alicyclic hydrocarbon group. May be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group of Q ¹ and Q ² 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 perfluoro group. A hexyl group etc. are mentioned.
Q ¹ and Q ² are preferably each independently a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.

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 these 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 , Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group Alkanediyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group 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, adamantane-2,6-diyl group, etc. 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 of L ^b1 is replaced by —O— or —CO— include any of formulas (b1-1) to (b1-3) The group represented by these is mentioned. 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, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In 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, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b4 and L ^b5 is 22 or less.
In 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, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. ]

In Formula (b1-1) to Formula (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 carbons before the replacement is represented by the carbon number of the saturated hydrocarbon group. It is 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.

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

［式（ｂ１−４）中、
Ｌ^ｂ８は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
式（ｂ１−５）中、
Ｌ^ｂ９は、炭素数１〜２０の２価の飽和炭化水素基を表す。
Ｌ^ｂ１０は、単結合又は炭素数１〜１９の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ９及びＬ^ｂ１０の合計炭素数は２０以下である。
式（ｂ１−６）中、
Ｌ^ｂ１１は、炭素数１〜２１の２価の飽和炭化水素基を表す。
Ｌ^ｂ１２は、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ１１及びＬ^ｂ１２の合計炭素数は２１以下である。
式（ｂ１−７）中、
Ｌ^ｂ１３は、炭素数１〜１９の２価の飽和炭化水素基を表す。
Ｌ^ｂ１４は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^ｂ１５は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ１３〜Ｌ^ｂ１５の合計炭素数は１９以下である。
式（ｂ１−８）中、
Ｌ^ｂ１６は、炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^ｂ１７は、炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^ｂ１８は、単結合又は炭素数１〜１７の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置換されていてもよい。
ただし、Ｌ^ｂ１６〜Ｌ^ｂ１８の合計炭素数は１９以下である。］ Examples of 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),
^Lb9 represents a C1-C20 bivalent saturated hydrocarbon group.
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 C1-C21 divalent saturated hydrocarbon group.
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 C1-C18 divalent saturated hydrocarbon group.
L ^b17 represents a C1- ^C18 divalent saturated hydrocarbon group.
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 C 1-8 divalent saturated hydrocarbon group.
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 ^C 1-6 divalent saturated hydrocarbon group.
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), respectively.

[In the formula (b1-9),
L ^b19 represents a single bond or a ^C1-C23 divalent saturated hydrocarbon group, 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. Also 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 substituted 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 ^C1-C21 divalent saturated hydrocarbon group, 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 substituted 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 substituted with a hydroxy group.
^However, the total number of carbon atoms of L b24 ^{~L b26} is 21 or less. ]

  In formulas (b1-9) to (b1-11), when a hydrogen atom contained in a 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 of the divalent saturated hydrocarbon group including the number of O is used.

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

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

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

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

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

Of 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.

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

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

Of 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).
When —CH ₂ — contained in the monovalent alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO—, the number may be one, or two or more There may be multiple. Examples of such a group include groups represented by formula (Y12) to formula (Y38).

  That is, Y represents a hydrogen atom contained in an alicyclic hydrocarbon group, each substituted with an oxygen atom, and the two oxygen atoms together with an alkanediyl group having 1 to 8 carbon atoms form a ketal ring. Alternatively, a structure in which an oxygen atom is bonded to each of different carbon atoms may be included. However, when a spiro ring such as formula (Y28) to formula (Y33) is formed, the alkanediyl group between two oxygens preferably has one or more fluorine atoms. Of the alkanediyl groups contained in the ketal structure, those in which the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom are preferred.

  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 (Y Y16), a formula (Y19), a formula (Y20), a group represented by formula (Y30) or a formula (Y31), and more preferably a group represented by formula (Y11), formula (Y15) or formula (Y30). Group to be used.

Examples of the substituent for the monovalent alicyclic hydrocarbon group represented by Y include 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. -16 monovalent alicyclic hydrocarbon group, C1-C12 alkoxy group, C6-C18 monovalent aromatic hydrocarbon group, C7-C21 aralkyl group, C2-C2 4 acyl group, glycidyloxy group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, monovalent fat having 3 to 16 carbon atoms) 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).

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and 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, mesityl group. Group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and 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.

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. ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula An anion represented by any one of (B1-A-33) and formulas (B1-A-36) to (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. More preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
L ⁴⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ¹ and Q ² are the same as described above.
Specific examples of the sulfonate anion in the salt represented by the formula (B1) include the anions described in JP 2010-204646 A.

Examples of the sulfonate anion in the salt represented by the preferable formula (B1) include anions represented by the formulas (B1a-1) to (B1a-22), respectively.

Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) Is preferable.
Examples of the organic cation of Z ⁺ include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation, and preferably organic sulfonium cation or organic iodonium cation. More preferably, an arylsulfonium cation is mentioned.
Z ⁺ in the formula (B1) is preferably a cation represented by any one of the formulas (b2-1) to (b2-4) [hereinafter referred to as “cation (b2-1)” or the like 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のアルキル基、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、該アルキル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のアルキル基、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のアルキル基又は炭素数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のアルキル基、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のアルキル基、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、該アルキル基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 Formula (b2-1)-Formula (b2-4),
R ^{b4 to} R ^b6 are each independently an alkyl group having 1 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms. And the hydrogen atom contained in the alkyl group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, or a monovalent group having 6 to 18 carbon atoms. The hydrogen atom contained in the monovalent alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl group having 2 to 4 carbon atoms. Alternatively, it may be substituted with a glycidyloxy group, and a hydrogen atom contained in the monovalent aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b7 and R ^b8 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 independently of each other.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 36 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 36 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an alkyl 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 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 has 1 to 12 carbon atoms. It may be substituted with an alkoxy group or an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may together form a ring containing —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring is —O—, —SO—. Alternatively, it may be replaced by -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 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more The plurality of R ^b15 may be the same or different. When r2 is 2 or more, the plurality of R ^b16 may be the same or different. When s2 is 2 or more, the plurality of R ^b17 is ^They may be the same or different, and when t2 is 2 or more, the plurality of R ^b18 may be the same or different. ]

中でも、Ｒ^ｂ９〜Ｒ^ｂ１２のアルキル基の炭素数は、好ましくは３〜１８であり、より好ましくは４〜１２である。 Examples of the alkyl 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-ethylhexyl group. It is done. Among them, the alkyl group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic monovalent alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclo And cycloalkyl groups such as a hexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic monovalent alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

Of ^these, the carbon number of the alkyl group of R ^{b9 to R b12} is preferably 3 to 18, more preferably from 4 to 12.

Examples of the monovalent alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, and an isobornyl group. Groups and the like. In the monovalent alicyclic hydrocarbon group substituted with a certain group having a hydrogen atom, the total number of carbon atoms of the monovalent alicyclic hydrocarbon group and the alkyl group is preferably 20 or less.
^Examples of the aliphatic hydrocarbon group of R ^b7, R ^b8 , and R ^{b13 to} R ^b18 include the same alkyl groups, alicyclic hydrocarbon groups, and groups obtained by combining them.

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 thereof include aryl groups such as 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 an alkyl group or a monovalent alicyclic hydrocarbon group, the alkyl group having 1 to 18 carbon atoms and the monovalent alicyclic carbon group having 3 to 18 carbon atoms A hydrogen group is preferred.
Examples of the monovalent aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

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

The ring that R ^b4 and R ^b5 may form together with the sulfur atom to which they are bonded is any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. There may be. As this ring, a C3-C18 ring is mentioned, Preferably a C4-C18 ring is mentioned. Moreover, as a ring containing a sulfur atom, 3-membered ring-12-membered ring are mentioned, Preferably 3-membered ring-7-membered ring are mentioned, Specifically, the following ring is mentioned.

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

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

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

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

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

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

  The acid generator (B1) is a combination of the above-described 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 one of formulas (B1a-1) to (B1a-3) and (B1a-7) to (B1a-16). And a combination with -1).

  Preferred examples of the acid generator (B1) include those represented by formulas (B1-1) to (B1-40), and preferably include formulas (B1-1) and formula (B) containing an arylsulfonium cation. B1-2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7), formula (B1-11), formula (B1-12), formula (B1) -13), formula (B1-14), formula (B1-17), formula (B1-20), formula (B1-21), formula (B1-23), formula (B1-24), formula (B1- 25), Formula (B1-26), Formula (B1-29), Formula (B1-31), Formula (B1-32), Formula (B1-33), Formula (B1-34), Formula (B1-35) ), Formula (B1-36), formula (B1-37), formula (B1-38), formula (B1-39) or formula (B1-40). It is.

The acid generator (B) may contain an acid generator other than the acid generator (B1).
In the resist composition of the present invention, the acid generator (B1) may contain one kind alone or plural kinds. Especially, it is preferable that the acid generator (B1) contains 2 or more types of acid generators. The content of the acid generator (B1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, based on the total amount of the acid generator (B). It is particularly preferable that only the agent (B1) is present.
The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 35 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).

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

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

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

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

  Specifically, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine , Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, Triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyl Cyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldinonylamine Decylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4 , 4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methyl Imidazole, 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 are preferable, diisopropylaniline is preferable, and 2,6-diisopropylaniline is particularly preferable.

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

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

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

[In the formula (D),
R ^D1 and R ^D2 are each independently 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, or an acyloxy group having 2 to 7 carbon atoms. Represents an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group, or a halogen atom.
m ′ and n ′ each independently represents an integer of 0 to 4, and when m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n ′ is 2 or more, the plurality of R ^D2 are Same or different. ]

The hydrocarbon group of R ^D1 and R ^D2 in the compound represented by the formula (D) is an alkyl group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a combination thereof. And the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and a nonyl group.
The monovalent alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be either 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 phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4- Propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group , Aryl groups such as cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.

  Examples of the group formed by combining these include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, an aralkyl group (for example, phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-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.), alkyl-aryl groups (for example, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropyl) Phenyl, 4-butylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexyl Nyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aryl-cycloalkyl group, cycloalkyl-aryl group (for example, p -An adamantylphenyl group).

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 a group in which an oxy group (—O—) is bonded to the acyl group.
Examples of the alkoxycarbonyl group include a group in which a carbonyl group (—CO—) is bonded to the above alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In the formula (D), R ^D1 and R ^D2 each independently represent 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, or 2 to 2 carbon atoms. Preferred are 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 each independently preferably an integer of 0 to 2, and more preferably 0. When m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n ′ is 2 or more, the plurality of R ^D2 are 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”. A commercially available compound can be used as the weak acid inner salt (D).

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

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

<Preparation of resist composition>
The resist composition of the present invention comprises the resin (A) and acid generator (B) of the present invention, and the resin (X), quencher (C), solvent (E) and other components used as necessary. It can be prepared by mixing (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (E), such as resin. An appropriate mixing 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 each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) A step of applying the resist composition of the present invention on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

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

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do. In this specification, irradiating these radiations may be collectively referred to as “exposure”. At the time of exposure, exposure is usually performed through a mask corresponding to a required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.

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

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

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

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents 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.
In the organic developer, the content of the organic solvent 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 still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing 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 the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

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

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or 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.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (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 molecular peaks 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９．００部、テトラヒドロフラン４５部、ピリジン８．２０部及びジメチルアミノピリジン０．５３部を添加し、式（Ｉ−１−ｂ）で表される化合物１３．３２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合物に、酢酸エチル２５０部を加え、５％塩酸９１部を仕込み、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、イオン交換水５０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−１−ｃ）で表される化合物９．４６部を得た。

式（Ｉ−１−ｃ）で表される化合物９．４３部及び酢酸４４．４０部を添加した後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）６．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後、濃縮残に、酢酸エチル１００部及びイオン交換水１００部を加え、２３℃で３０分間攪拌、静置、分液することにより有機層を回収した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：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６．４２部を得た。
ＭＳ（質量分析）：１８８．１（分子イオンピーク） Synthesis Example 1: Synthesis of compound represented by formula (I-1)

9.00 parts of the compound represented by the formula (I-1-a), 45 parts of tetrahydrofuran, 8.20 parts of pyridine and 0.53 part of dimethylaminopyridine were added, and the compound represented by the formula (I-1-b) was added. 13.32 parts of the above compound was added. Then, it stirred at 23 degreeC for 5 hours. To the obtained reaction mixture, 250 parts of ethyl acetate was added, 91 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and separating, 50 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such water washing operation was repeated three times. The collected organic layer was concentrated. The concentrated mass is separated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-1-c). 9.46 parts of compound were obtained.

After adding 9.43 parts of the compound represented by the formula (I-1-c) and 44.40 parts of acetic acid, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the obtained mixture, 6.00 parts of hydrogen peroxide (purity 31%) was added dropwise over 5 minutes, and the mixture was stirred at 23 ° C. for 3 hours. After concentrating the obtained reaction product, 100 parts of ethyl acetate and 100 parts of ion-exchanged water were added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The collected organic layer was concentrated. Compound 6 represented by the formula (I-1) is obtained by fractionating the concentrated mass in a column (Kanto Chemical Co., Inc. silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). .42 parts were obtained.
MS (mass spectrometry): 188.1 (molecular ion peak)

式（Ｉ−２−ａ）で表される化合物６．７５部、テトラヒドロフラン５０部、トリエチルアミン６．７２部及びジメチルアミノピリジン０．７０部を添加し、式（Ｉ−２−ｂ）で表される化合物９．２４部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合物に、酢酸エチル１００部を加え、５％塩酸５０部を仕込み、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、イオン交換水５０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２−ｃ）で表される化合物６．２４部を得た。

式（Ｉ−１−ｃ）で表される化合物５．１０部及び酢酸２２．２０部を添加した後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した。濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、静置、分液することにより有機層を回収した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：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３．６８部を得た。
ＭＳ（質量分析）：２０２．１（分子イオンピーク） Synthesis Example 2: Synthesis of compound represented by formula (I-2)

6.75 parts of the compound represented by formula (I-2-a), 50 parts of tetrahydrofuran, 6.72 parts of triethylamine and 0.70 part of dimethylaminopyridine were added, and represented by formula (I-2-b). 9.24 parts of the above compound was added. Then, it stirred at 23 degreeC for 5 hours. To the resulting reaction mixture, 100 parts of ethyl acetate was added, 50 parts of 5% hydrochloric acid was added, and the mixture was stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and separating, 50 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such water washing operation was repeated three times. The collected organic layer was concentrated. The concentrated mass is separated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-2-c). 6.24 parts of compound were obtained.

After adding 5.10 parts of the compound represented by the formula (I-1-c) and 22.20 parts of acetic acid, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the resulting mixture, 3.00 parts of hydrogen peroxide (purity 31%) was added dropwise over 5 minutes and stirred at 23 ° C. for 3 hours. The resulting reaction was concentrated. 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentrated residue, and the organic layer was recovered by stirring, allowing to stand, and separating at 30 ° C. for 30 minutes. The collected organic layer was concentrated. Compound 3 represented by the formula (I-2) is obtained by fractionating the concentrated mass in a column (Kanto Chemical Co., Inc. silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). .68 parts were obtained.
MS (mass spectrometry): 202.1 (molecular ion peak)

式（Ｉ−２５−ａ）で表される化合物５．９部、テトラヒドロフラン５０部、トリエチルアミン６．７部及びジメチルアミノピリジン０．７部を添加し、式（Ｉ−１−ｂ）で表される化合物９．２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合物に、酢酸エチル１００部を加え、さらに５％塩酸５０部を加え、２３℃で３０分間攪拌した。得られた混合物を静置、分液することにより回収された有機層に、イオン交換水５０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２５−ｃ）で表される化合物６．２２部を得た。

式（Ｉ−２５−ｃ）で表される化合物４．７部及び酢酸２２．２部を添加した後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後、濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、静置、分液することにより有機層を回収した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２５）で表される化合物３．１１部を得た。
ＭＳ（質量分析）：１８７．１（分子イオンピーク） Synthesis Example 3: Synthesis of compound represented by formula (I-25)

5.9 parts of a compound represented by the formula (I-25-a), 50 parts of tetrahydrofuran, 6.7 parts of triethylamine and 0.7 part of dimethylaminopyridine were added, and represented by the formula (I-1-b). 9.2 parts of the above compound was added. Then, it stirred at 23 degreeC for 5 hours. To the obtained reaction mixture, 100 parts of ethyl acetate was added, 50 parts of 5% hydrochloric acid was further added, and the mixture was stirred at 23 ° C. for 30 minutes. The organic layer recovered by standing and separating the obtained mixture was charged with 50 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand and separated, and the organic layer was washed with water. Such water washing operation was repeated three times. The collected organic layer was concentrated. The concentrated mass is fractionated by a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm, developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-25-c). 6.22 parts of compound were obtained.

After adding 4.7 parts of a compound represented by the formula (I-25-c) and 22.2 parts of acetic acid, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the resulting mixture, 3.00 parts of hydrogen peroxide (purity 31%) was added dropwise over 5 minutes and stirred at 23 ° C. for 3 hours. After concentrating the obtained reaction product, 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentration residue, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The collected organic layer was concentrated. Compound 3 represented by the formula (I-25) is obtained by fractionating the concentrated mass in a column (Kanto Chemical Co., Inc. silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). .11 parts were obtained.
MS (mass spectrometry): 187.1 (molecular ion peak)

式（Ｉ−２６−ａ）で表される化合物６．７部、テトラヒドロフラン５０部、トリエチルアミン６．７部及びジメチルアミノピリジン０．７部を添加し、式（Ｉ−１−ｂ）で表される化合物９．２部を添加した。その後、２３℃で５時間攪拌した。得られた反応混合物に、酢酸エチル１００部を加え、さらに５％塩酸５０部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、イオン交換水５０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２６―ｃ）で表される化合物５．９８部を得た。

式（Ｉ−２６−ｃ）で表される化合物５．１部及び酢酸２２．２部を添加した後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後、濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、静置、分液することにより有機層を回収した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−２６）で表される化合物３．２部を得た。
ＭＳ（質量分析）：２０１．１（分子イオンピーク） Synthesis Example 4: Synthesis of compound represented by formula (I-26)

6.7 parts of a compound represented by formula (I-26-a), 50 parts of tetrahydrofuran, 6.7 parts of triethylamine and 0.7 part of dimethylaminopyridine were added, and represented by formula (I-1-b). 9.2 parts of the above compound was added. Then, it stirred at 23 degreeC for 5 hours. To the obtained reaction mixture, 100 parts of ethyl acetate was added, 50 parts of 5% hydrochloric acid was further added, and the mixture was stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and separating, 50 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such water washing operation was repeated three times. The collected organic layer was concentrated. The concentrated mass is separated by a column (Kanto Kagaku Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1), and expressed by the formula (I-26-c). 5.98 parts of compound were obtained.

After adding 5.1 parts of a compound represented by the formula (I-26-c) and 22.2 parts of acetic acid, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the resulting mixture, 3.00 parts of hydrogen peroxide (purity 31%) was added dropwise over 5 minutes and stirred at 23 ° C. for 3 hours. After concentrating the obtained reaction product, 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentration residue, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The collected organic layer was concentrated. Compound 3 represented by the formula (I-26) is obtained by fractionating the concentrated mass into a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). .2 parts were obtained.
MS (mass spectrometry): 201.1 (molecular ion peak)

Synthesis Example 5: Synthesis of compound represented by formula (I-5)

式（Ｉ−５−ｃ）で表される化合物１９．３部、式（Ｉ−１−ａ）で表される化合物１０．４部及びアセトニトリル２００部を仕込み、２３℃で５時間攪拌した。得られた反応物を濃縮し、クロロホルム３００部及びイオン交換水１５０部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、イオン交換水１５０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を３回繰り返した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：酢酸エチル）分取することにより、式（Ｉ−５―ｄ）で表される化合物２２．２８部を得た。

式（Ｉ−５−ｄ）で表される化合物６．３部及び酢酸２２．２部を添加した後、２３℃で３０分間攪拌し、５℃まで冷却した。得られた混合物に、過酸化水素（純度３１％）３．００部を５分かけて滴下し、２３℃で３時間攪拌した。得られた反応物を濃縮した後、濃縮残に、酢酸エチル５０部及びイオン交換水５０部を加え、２３℃で３０分間攪拌、静置、分液することにより有機層を回収した。回収された有機層を濃縮した。濃縮マスをカラム（関東化学 シリカゲル６０Ｎ（球状、中性）１００−２１０μｍ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１）分取することにより、式（Ｉ−５）で表される化合物２．８９部を得た。
ＭＳ（質量分析）：２４６．１（分子イオンピーク） 33.5 parts of the compound represented by the formula (I-5-a), 23.9 parts of dicyclohexylcarbodiimide, and 40 parts of methylene chloride were charged and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 18.83 parts of the compound represented by the formula (I-5-b) was added at 0 ° C., and the mixture was stirred at 0 ° C. for 1 hour. The temperature was raised to 23 ° C., and the mixture was further stirred for 30 minutes, followed by filtration. The obtained filtrate was concentrated to obtain 42.2 parts of a compound represented by the formula (I-5-c).

19.3 parts of the compound represented by the formula (I-5-c), 10.4 parts of the compound represented by the formula (I-1-a) and 200 parts of acetonitrile were charged and stirred at 23 ° C. for 5 hours. The obtained reaction product was concentrated, 300 parts of chloroform and 150 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and separating, 150 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such water washing operation was repeated three times. The collected organic layer was concentrated. The concentrated mass was separated from a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: ethyl acetate) to obtain 22.28 parts of a compound represented by the formula (I-5-d). .

After adding 6.3 parts of the compound represented by the formula (I-5-d) and 22.2 parts of acetic acid, the mixture was stirred at 23 ° C. for 30 minutes and cooled to 5 ° C. To the resulting mixture, 3.00 parts of hydrogen peroxide (purity 31%) was added dropwise over 5 minutes and stirred at 23 ° C. for 3 hours. After concentrating the obtained reaction product, 50 parts of ethyl acetate and 50 parts of ion-exchanged water were added to the concentration residue, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. The collected organic layer was concentrated. Compound 2 represented by the formula (I-5) is obtained by fractionating the concentrated mass in a column (Kanto Chemical Co., Inc. silica gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 1/1). .89 parts were obtained.
MS (mass spectrometry): 246.1 (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、この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 6 [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-A-2008-209917, and a salt 35.50 represented by the formula (B1-21-a). Part, 100 parts of chloroform, and 50 parts of ion-exchanged water were 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 30 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated, 100 parts of tert-butyl methyl ether was added to the resulting residue, and the mixture was stirred at 23 ° C. for 30 minutes and filtered, whereby the salt represented by 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た。得られた残渣に、クロロホルム２００部及びイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層にイオン交換水５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この水洗操作を５回繰り返した。得られた有機層を濃縮した。得られた残渣を、アセトニトリル５３．５１部に溶解し、濃縮した。得られた濃縮物に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。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２３７．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ３３９．１

20.00 parts of a salt represented by the formula (B1-21-c), 2.84 parts of a compound represented by the formula (B1-21-d) and 250 parts of monochlorobenzene were charged and stirred at 23 ° C. for 30 minutes. . To the obtained mixed solution, 0.21 part of copper (II) dibenzoate was added, and the mixture was further stirred at 100 ° C. for 1 hour. The resulting reaction solution was concentrated. To the obtained residue, 200 parts of chloroform and 50 parts of ion-exchanged water were added, 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, and the mixture was stirred at 23 ° C. for 30 minutes and separated to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated. The obtained residue was dissolved in 53.51 parts of acetonitrile and concentrated. To the obtained concentrate, 113.05 parts of tert-butyl methyl ether was added and stirred, followed by filtration 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、この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 7 [Synthesis of salt represented by formula (B1-22)]

11.26 parts of a salt represented by the formula (B1-22-a), 10.00 parts of a compound represented by the formula (B1-22-b), 50 parts of chloroform and 25 parts of ion-exchanged water were charged 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 15 parts of ion exchange 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 resulting residue, and the mixture was stirred at 23 ° C. for 30 minutes and filtered to obtain the salt represented by the formula (B1-22-c) 11. 75 parts were obtained.

式（Ｂ１−２２−ｃ）で表される塩１１．７１部、式（Ｂ１−２２−ｄ）で表される化合物１．７０部及びモノクロロベンゼン４６．８４部を仕込み、２３℃で３０分間攪拌した。得られた混合液に、二安息香酸銅（ＩＩ）０．１２部を添加し、更に、１００℃で３０分間攪拌した。得られた反応溶液を濃縮した。得られた残渣に、クロロホルム５０部及びイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。回収された有機層にイオン交換水１２．５０部を加えて２３℃で３０分間攪拌し、分液して有機層を取り出した。この水洗操作を８回繰り返した。得られた有機層を濃縮した。得られた残渣に、ｔｅｒｔ−ブチルメチルエーテル５０部を加えて攪拌し、ろ過することにより、式（Ｂ１−２２）で表される塩６．８４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ２３７．１
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ３２３．０

11.71 parts of a salt represented by the formula (B1-22-c), 1.70 parts of a compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged, and the mixture was charged at 23 ° C. for 30 minutes. Stir. To the obtained mixed liquid, 0.12 part of copper (II) dibenzoate was added, and the mixture was further stirred at 100 ° C. for 30 minutes. The resulting reaction solution was concentrated. To the obtained residue, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. 12.50 parts of ion-exchanged water was added to the collected organic layer, stirred at 23 ° C. for 30 minutes, and separated to take out the organic layer. This washing operation was repeated 8 times. The obtained organic layer was concentrated. To the obtained residue, 50 parts of tert-butyl methyl ether was added, stirred, and filtered to obtain 6.84 parts of the salt represented by the formula (B1-22).
MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 323.0

以下、これらのモノマーを式番号に応じて「モノマー（ａ１−１−３）」等という。 Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below.

Hereinafter, these monomers are referred to as “monomer (a1-1-3)” or the like according to the formula number.

Example 1 [Synthesis of Resin A1]
As a monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-1), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-1): monomer (a2-1-1): monomer (a3-4-2)]] is 40: 9: The mixture was mixed so that the ratio was 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5 times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A1 having a weight average molecular weight of 8.2 × 10 ^{3 in} a yield of 62%. This resin A1 has the following structural units.

Example 2 [Synthesis of Resin A2]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-2), the monomer (a2-1-1) and the monomer (a3-4-2) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-2): monomer (a2-1-1): monomer (a3-4-2)]] is 40: 9: The mixture was mixed so that the ratio was 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5 times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A2 having a weight average molecular weight of 8.3 × 10 ^{3 in} a yield of 63%. This resin A2 has the following structural units.

Example 3 [Synthesis of Resin A3]
Monomer (a1-1-1) and monomer (I-2) are used as monomers and mixed so that the molar ratio [monomer (a1-1-1): monomer (I-2)] is 48:52. Then, 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to make a solution. To this solution, 0.6 mol% and 1.8 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, 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 the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A3 having a weight average molecular weight of 1.6 × 10 ^{4 in} a yield of 87%. This resin A3 has the following structural units.

Example 4 [Synthesis of Resin A4]
As the monomer, the monomer (a1-1-2), the monomer (a2-1-1), the monomer (a3-1-1) and the monomer (I-1) are used, and their molar ratio (monomer (a1-1-2) ): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (I-1)) is mixed so as to be 30: 20: 40: 10, and the total monomer amount is 1.5 mass. Doubled propylene glycol monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.8 mol% and 2.4 mol%, respectively, based on the total monomer amount, 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 the resin, and this resin was filtered. The obtained resin was poured again into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A4 (copolymer) having a weight average molecular weight of 1.0 × 10 ^{4 in} a yield of 72%. It was. This resin A4 has the following structural units.

Example 5 [Synthesis of Resin A5]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (I-5), monomer (a2-1-1) and monomer (a3-4-2) were used, The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-5): monomer (a2-1-1): monomer (a3-4-2)]] is 40: 9: The mixture was mixed so that the ratio was 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5 times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain Resin A5 having a weight average molecular weight of 7.9 × 10 ^{3 in} a yield of 58%. This resin A5 has the following structural units.

Example 6 [Synthesis of Resin A6]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-9), the monomer (I-25), the monomer (a2-1-1) and the monomer (a3-4-2) are used and their moles are used. The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-25): monomer (a2-1-1): monomer (a3-4-2)]] is 40: 9: The mixture was mixed so that the ratio was 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5 times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A6 having a weight average molecular weight of 8.8 × 10 ^{3 in} a yield of 60%. This resin A6 has the following structural units.

Example 7 [Synthesis of Resin A7]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (I-26), monomer (a2-1-1) and monomer (a3-4-2) were used, The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (I-26): monomer (a2-1-1): monomer (a3-4-2)]] is 40: 9: The mixture was mixed so that the ratio was 10: 2.5: 38.5, and propylene glycol monomethyl ether acetate 1.5 times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin A7 having a weight average molecular weight of 9.1 × 10 ^{3 in} a yield of 63%. This resin A7 has the following structural units.

Synthesis Example 8 [Synthesis of Resin AX1]
Monomer (a1-1-1) and monomer (IX-1) are used as monomers and mixed so that the molar ratio [monomer (a1-1-1): monomer (IX-1)] is 48:52. Then, 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to make a solution. To this solution, 0.6 mol% and 1.8 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, 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 the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain a resin AX1 having a weight average molecular weight of 1.7 × 10 ^{4 in} a yield of 87%. This resin AX1 has the following structural units.

Synthesis Example 9 [Synthesis of Resin AX2]
As the monomer, the monomer (a1-1-2), the monomer (a2-1-1), the monomer (a3-1-1) and the monomer (IX-2) were used, and the molar ratio (monomer (a1-1-2) ): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (IX-2)) is mixed so as to be 30: 20: 40: 10, and the total monomer amount is 1.5 mass. Doubled propylene glycol monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.8 mol% and 2.4 mol%, respectively, based on the total monomer amount, 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 the resin, and this resin was filtered. The obtained resin was again poured into a methanol / water mixed solvent and repulped, and this resin was filtered to obtain resin AX2 (copolymer) having a weight average molecular weight of 1.1 × 10 ^{4 in} a yield of 66%. It was. This resin AX2 has the following structural units.

Synthesis Example 10 [Synthesis of Resin X1]
As the monomer, monomer (a5-1-1) and monomer (a4-0-12) were used, and the molar ratio (monomer (a5-1-1): monomer (a4-0-12)) was 50:50. Then, methyl isobutyl ketone 0.6 mass times the total monomer amount was added to prepare a solution. To this solution, 3 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added based on the total amount of monomers, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin X1 having a weight average molecular weight of 1.5 × 10 ^{4 in} a yield of 88%. This resin X1 has the following structural units.

Synthesis Example 11 [Synthesis of Resin X2]
Monomer (a4-1-7) was used as a monomer, and methyl isobutyl ketone 1.2 times the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain Resin X2 having a weight average molecular weight of 7.8 × 10 ^{3 in} a yield of 86%. This resin X2 has the following structural units.

<Preparation of resist composition>
As shown in Table 1, the following components were mixed, and the resulting mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

＜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>
A1 to A7, X1, X2: Resin A1 to Resin A7, Resin X1, Resin X2
<Acid generator>
B1-21: salt represented by formula (B1-21) B1-22: salt represented by formula (B1-22) <Compound (D)>
D1: (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

<Evaluation of CD uniformity (CDU) (negative development)>
An organic antireflective coating composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to form an organic reflective film having a thickness of 78 nm on the wafer. A prevention film was formed. Next, on the organic antireflection film, the above resist composition was applied (spin coated) so that the film thickness after drying was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature described in the “PB” column of Table 1 for 60 seconds to form a composition layer. ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) on a silicon wafer on which the composition layer is formed, and a contact hole pattern (hole pitch 90 nm) Using a mask for forming a hole diameter of 55 nm), the exposure amount was changed stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

  In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 50 nm was defined as the effective sensitivity.

In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 55 nm was measured 24 times per hole, and the average value was taken as the average hole diameter of one hole. A standard deviation is obtained using a population obtained by measuring 400 average hole diameters of a pattern formed with a mask having a hole diameter of 70 nm in the same wafer,
If the standard deviation is 2.00 nm or less,
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).

<Evaluation of CD uniformity (CDU) (positive development)>
An organic antireflective coating composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to form an organic reflective film having a thickness of 78 nm on the wafer. A prevention film was formed. Next, the resist composition was applied (spin coated) on the organic antireflection film so that the film thickness after drying (pre-baking) was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature described in the “PB” column of Table 1 for 60 seconds to form a composition layer. ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) on a silicon wafer on which the composition layer is formed, and a contact hole pattern (hole pitch 100 nm) Using a mask for forming a hole diameter of 70 nm), the exposure amount was changed stepwise to perform exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, the silicon wafer was heated (post-exposure baking process) 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 paddle 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.

In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 70 nm was measured 24 times per hole, and the average value was taken as the average hole diameter of one hole. A standard deviation is obtained using a population obtained by measuring 400 average hole diameters of a pattern formed with a mask having a hole diameter of 70 nm in the same wafer,
When the standard deviation is 1.80 nm or less,
The case where the standard deviation was larger than 1.80 nm was judged as “x”.
The results are shown in Table 3. Numerical values in parentheses indicate standard deviation (nm).

  From the above results, it can be seen that according to the resin of the present invention and the resist composition using the resin, a resist pattern can be produced with good CD uniformity.

  Since the resin of the present invention and the resist composition using the resin are excellent in CD uniformity of the resulting resist pattern, they are suitable for fine processing of semiconductors.

Claims (9)

A resin comprising a structural unit represented by formula (I) and a structural unit having an acid labile group.

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
X represents —O—, —S—, or —NR ¹¹ —.
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
s and v each independently represent an integer of 1 to 4.
R ² represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
u represents an integer of 0 to 3, and when u is 2 or more, the plurality of R ² are the same or different from each other.
A ¹ represents a single bond, alkanediyl group having 1 to 6 carbon atoms or ^{* -A 2 -X 1 - (A} 3 -X 2) a - (A 4) b - represents a. * Represents a bond with the group X.
A ² , A ³ and A ⁴ each independently represent an alkanediyl group having 1 to 6 carbon atoms.
X ¹ and X ² each independently represent —O—, —CO—O—, —O—CO— or —O—CO—O—.
a represents 0 or 1.
b represents 0 or 1. ] The resin according to claim 1, wherein A ¹ is a single bond. 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). 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 to —CO—. Represents 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 obtained by combining these.
m1 represents the integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents an integer of 0 to 3. ] Furthermore, resin in any one of Claims 1-3 containing the structural unit represented by Formula (a3-4).

[In the 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.
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
* Represents a bond with a carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms. ]   A resist composition containing the resin according to claim 1 and an acid generator. The resist composition according to claim 5, wherein the acid generator is a salt represented by the formula (B1).

[In the formula (B1),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents an ^optionally substituted divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is —O— or -CO- may be substituted, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a hydrogen atom or a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and —CH ₂ — contained in the monovalent alicyclic hydrocarbon group. May be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]   The resist composition according to claim 5 or 6, further comprising a salt that generates an acid having a lower acidity than an acid generated from the acid generator.   Furthermore, the resist composition in any one of Claims 5-7 containing resin containing the structural unit which has a fluorine atom. (1) The process of apply | coating the resist composition in any one of Claims 5-8 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: