JP2018024852A - Resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin capable of producing a resist pattern having a good mask error factor (MEF), and a resist composition.SOLUTION: The resin contains a structural unit represented by formula (I) and a structural unit represented by formula (a3-4) [Ais a single bond or a C1-18 hydrocarbon; Aand Aare each a C1-18 hydrocarbon; Rto Rare each a C1-6 saturated hydrocarbon; Ris a C1-6 alkyl group, H, or a halogen atom; Lis a single bond or a -CO-O- group-containing group; Ris carboxy, cyano, or a C1-4 aliphatic hydrocarbon group; and w1 is an integer of 0-8].SELECTED DRAWING: None

Description

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

Patent Document 1 describes a resist composition containing a resin composed of the following structural units.

JP 2009-42748 A

  A resist pattern formed from a resist composition containing the above resin may not always satisfy the mask error factor (MEF).

［式（Ｉ）中、Ａ^１は、単結合又は炭素数１〜１８の２価の炭化水素基を表す。
Ａ^２及びＡ^３は、それぞれ独立に、炭素数１〜１８の２価の炭化水素基を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、炭素数１〜６の飽和炭化水素基を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は炭素数１〜６の飽和炭化水素基を表す。］

［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、単結合、^＊−Ｌ^ａ８−Ｏ−、^＊−Ｌ^ａ８−ＣＯ−Ｏ−、^＊−Ｌ^ａ８−ＣＯ−Ｏ−Ｌ^ａ９−ＣＯ−Ｏ−又は^＊−Ｌ^ａ８−Ｏ−ＣＯ−Ｌ^ａ９−Ｏ−を表す。
＊は−Ｏ−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。
Ｒ^ａ２５は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｗ１は、０〜８のいずれかの整数を表す。ｗ１が２以上のとき、複数のＲ^ａ２５は互いに同一であってもよく、異なってもよい。］
［２］Ａ^２及びＡ^３が、それぞれ独立して、メチレン基又はエチレン基である［１］に記載の樹脂。
［３］Ａ^１が、炭素数１〜８のアルカンジイル基である［１］又は［２］に記載の樹脂。
［４］さらに、酸不安定基を有する構造単位を含有する［１］〜［３］のいずれかに記載の樹脂。
［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］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］に記載のレジスト組成物。
［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］のいずれか記載のレジスト組成物。
［８］（１）［５］〜［７］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 formula (I) and a structural unit represented by formula (a3-4).

[In formula (I), ^{A 1} represents a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms.
A ² and A ³ each independently represent a divalent hydrocarbon group having 1 to 18 carbon atoms.
R ¹ and R ² each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. ]

[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 a single bond, ^* —L ^a8 —O—, ^* —L ^a8 —CO—O—, ^* —L ^a8 —CO—O—L ^a9 —CO—O— or ^* —L ^a8 —O—CO ^-La9- O- is represented.
* Represents a bond with -O-.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
R ^a25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
w1 represents an integer of 0 to 8. When w1 is 2 or more, the plurality of R ^a25 may be the same as or different from each other. ]
[2] The resin according to [1], wherein A ² and A ³ are each independently a methylene group or an ethylene group.
[3] The resin according to [1] or [2], wherein A ¹ is an alkanediyl group having 1 to 8 carbon atoms.
[4] The resin according to any one of [1] to [3], further comprising a structural unit having an acid labile group.
[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], further comprising a resin containing a structural unit having a fluorine atom.
[7] The resist composition according to any one of [5] or [6], further comprising a salt that generates an acid having a lower acidity than an acid generated from an acid generator.
[8] (1) A step of applying the resist composition according to any one of [5] to [7] 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,
A method for producing a resist pattern including:

  By using the resist composition using the resin of the present invention, a resist pattern can be produced with a good mask error factor (MEF).

In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. The notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning.
In addition, unless otherwise specified, “aliphatic hydrocarbon group” refers to linear and branched hydrocarbon groups, and “alicyclic hydrocarbon group” refers to cyclic hydrocarbon groups and / or cyclic hydrocarbon groups. This means a group to which a hydrogen group is bonded. The “aromatic hydrocarbon group” also includes a group in which a hydrocarbon group is bonded to 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 has a structural unit represented by formula (I) (hereinafter sometimes referred to as structural unit (I)) and a structural unit represented by formula (a3-4) (hereinafter referred to as “structural unit (a3)”. -4) ”))) (hereinafter also referred to as“ resin (A) ”).

［式（Ｉ）中、
Ａ^１は、単結合又は炭素数１〜１８の２価の炭化水素基を表す。
Ａ^２及びＡ^３は、それぞれ独立に、炭素数１〜１８の２価の炭化水素基を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、炭素数１〜６の飽和炭化水素基を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は炭素数１〜６の飽和炭化水素基を表す。］ <Structural unit (I)>

[In the formula (I),
A ¹ represents a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms.
A ² and A ³ each independently represent a divalent hydrocarbon group having 1 to 18 carbon atoms.
R ¹ and R ² each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. ]

Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by A ¹ , A ² and A ³ include an alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned, The thing which combined 2 or more types among these groups may be used.
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 Linear alkanediyl groups such as
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, hexane-2,5-diyl group, 2-methyl- Branched alkanediyl groups such as 5-methylhexane-2,5-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. Group;
Phenylene group, naphthylene group, anthrylene group, p-methylphenylene group, p-tert-butylphenylene group, p-adamantylphenylene group, tolyl group, xylylene group, cumenylene group, mesitylene group, biphenylene group, phenanthrylene group, 2,6 -Aromatic hydrocarbon groups such as diethylphenylene group and 2-methyl-6-ethylphenylene.

A ¹ is preferably a monocyclic divalent alicyclic saturated hydrocarbon group or an alkanediyl group having 1 to 8 carbon atoms, and is a cycloalkanediyl group or an alkanediyl group having 1 to 4 carbon atoms. More preferably, it is more preferably a cycloalkanediyl group.
A ² and A ³ are each independently preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and even more preferably a methylene group.

Examples of the saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include methyl group, ethyl group, propyl group, butyl group, isobutyl group, sec-butyl group, tert- Examples thereof include alkyl groups such as butyl group, pentyl group and hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; and groups formed by combining these.
R ¹ , R ² , R ³ and R ⁴ are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group.

Examples of the structural unit (I) include the structural units described below. The structural unit (I) is preferably a structural unit (I-1) to a structural unit (I-6).

［式（Ｉ０）中、Ａ^１、Ａ^２、Ａ^３、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ、上記と同じ意味を表す。］
化合物（Ｉ０）は、下記式で表される化合物等が挙げられる。

The structural unit (I) is derived from a compound represented by the formula (I0) (hereinafter sometimes referred to as the compound (I0)).

[In Formula (I0), A ¹ , A ² , A ³ , R ¹ , R ² , R ³ and R ⁴ each represent the same meaning as described above. ]
Examples of compound (I0) include compounds represented by the following formulae.

  The content of the structural unit (I) is usually from 0.1 to 50 mol%, preferably from 1 to 30 mol%, more preferably from 2 to 10 mol%, based on all monomers in the resin (A). More preferably, it is 2 to 6 mol%.

  Compound (I0) can be produced by reacting the compound represented by formula (Ia) in a solvent under a base catalyst.

[Wherein R ¹ , R ² , R ³ , R ⁴ , A ¹ , A ² and A ³ represent the same meaning as described above. ]

Examples of the base catalyst include sodium hydroxide.
Examples of the solvent include methanol.

  The compound represented by the formula (Ia) is produced by reacting the compound represented by the formula (Ib) with the compound represented by the formula (Ic) in a solvent. Can do.

  Examples of the solvent include dimethylformamide.

  The compound represented by the formula (Ib) includes the compound represented by the formula (Id), the compound represented by the formula (Ie1), and the compound represented by the formula (Ie2). Can be produced in the presence of a base catalyst in a solvent.

Examples of the base catalyst include pyridine and N-methylpyrrolidine.
Examples of the solvent include toluene, tetrahydrofuran and the like.
Examples of the compound represented by the formula (Id) include compounds represented by the following.

Examples of the compound represented by the formula (I-e1) and the formula (I-e2) include compounds represented by the following.

［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、単結合、^＊−Ｌ^ａ８−Ｏ−、^＊−Ｌ^ａ８−ＣＯ−Ｏ−、^＊−Ｌ^ａ８−ＣＯ−Ｏ−Ｌ^ａ９−ＣＯ−Ｏ−又は^＊−Ｌ^ａ８−Ｏ−ＣＯ−Ｌ^ａ９−Ｏ−を表す。
＊は−Ｏ−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。
Ｒ^ａ２５は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｗ１は、０〜８のいずれかの整数を表す。ｗ１が２以上のとき、複数のＲ^ａ２５は互いに同一であってもよく、異なってもよい。］ <Structural unit (a3-4)>

[In the formula (a3-4),
R ^a24 represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
L ^a7 is a single bond, ^* —L ^a8 —O—, ^* —L ^a8 —CO—O—, ^* —L ^a8 —CO—O—L ^a9 —CO—O— or ^* —L ^a8 —O—CO ^-La9- O- is represented.
* Represents a bond with -O-.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
R ^a25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
w1 represents an integer of 0 to 8. When w1 is 2 or more, the plurality of R ^a25 may be the same as or different from each other. ]

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by ^Ra25 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. .
Examples of the halogen atom represented by R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group represented by ^Ra24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Preferably, a C1-C4 alkyl group is mentioned, More preferably, a methyl group or an ethyl group is mentioned.
Examples of the alkyl group having a halogen atom represented by Ra ²⁴ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluorotert-butyl group, perfluoropentyl. Group, perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like.
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.

（式中、Ｒ^ａ２４、Ｌ^ａ７は、上記と同じ意味を表す。） ^Examples of the alkanediyl group represented by ^La8 and ^La9 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 and the like.
L ^a7 is preferably a single bond or ^* -L ^a8 —CO—O—, and more preferably a single bond, —CH ₂ —CO—O— or —C ₂ H ₄ —CO—O—.
In formula (a3-4), formula (a3-4) ′ is particularly preferred.

(Wherein R ^a24 and L ^a7 represent the same meaning as described above.)

Examples of the structural unit (a3-4) include the following structural units and structural units in which a methyl group corresponding to R ^a24 in the following structural units is replaced with a hydrogen atom.

The content of the structural unit (a3-4) is usually from 5 to 95 mol%, preferably from 10 to 95 mol%, more preferably from 15 to 90 mol%, based on all structural units of the resin (A). %.
Resin (A) may contain 2 or more types of structural units (a3-4).

Resin (A) may contain 2 or more types of structural units (I).
The resin (A) preferably further has a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). Here, the “acid labile group” means a group having a leaving group and forming a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid. .

［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。
＊は酸素原子又は硫黄原子との結合手を表す。］

［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メチレン基は、酸素原子又は硫黄原子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。
＊酸素原子又は硫黄原子とのは結合手を表す。］ <Structural unit (a1)>
The structural unit (a1) is derived from a monomer having no halogen atom and having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”).
In the resin (A), the acid labile group contained in the structural unit (a1) preferably includes a group represented by the following formula (1) and / or a group represented by the formula (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 with an oxygen atom or a sulfur atom. ]

[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 the hydrocarbon group and the divalent heterocyclic group The methylene group contained in may be replaced with an oxygen atom or a sulfur atom.
X represents an oxygen atom or a sulfur atom.
* 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、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基、シクロヘキシルメチル基、アダマンチルメチル基、ノルボルニルエチル基等が挙げられる。
ｎａは、好ましくは０である。 ^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 of 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 decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). Carbon number of the alicyclic hydrocarbon group of R ^{a1 to} R ^a3 is preferably 3 to 16.

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

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where 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 preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

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

Ｒ^a1'及びＲ^a2'のうち、少なくとも１つは水素原子であることが好ましい。 Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as 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.
^{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.

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.

  The structural unit derived from the (meth) acrylic monomer having a group represented by the formula (1) is preferably a structural unit represented by the formula (a1-0) (hereinafter referred to as the structural unit (a1-0)). The structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)) or the structural unit represented by the formula (a1-2) (hereinafter, And may be referred to as a structural unit (a1-2).). These may be used alone or in combination of two or more.

［式（ａ１−０）、式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a01は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k01−ＣＯ−Ｏ−を表し、ｋ０１は１〜７のいずれかの整数を表し、＊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。
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のいずれかの整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子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のいずれかの整数を表す。
ｎ１は、０〜１０のいずれかの整数を表す。
ｎ１’は、０〜３のいずれかの整数を表す。］

[In Formula (a1-0), Formula (a1-1) and Formula (a1-2),
L ^a01 represents an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, k01 represents any 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 ^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 —CO—. Represents a bond with
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 any integer of 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents any integer of 0 to 3. ]

L ^a01 is preferably an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, and more preferably an oxygen atom. k01 is preferably any integer of 1 to 4, more preferably 1.
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 for R ^a02 , R ^a03 and R ^a04 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group ^{represented by} R ^a02 , R ^a03 and R ^a04 preferably has 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 a group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
R ^a02 and R ^a03 are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

L ^a1 and L ^a2 are each independently preferably —O— or ^* —O— (CH ₂ ) _{k1 ′} —CO—O—, more preferably —O—. k1 ′ is an integer of 1 to 4, and is preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
^Examples of the alkyl group for R ^a6 and R ^a7 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, Examples include n-heptyl group, 2-ethylhexyl group, n-octyl group and the like.
The alicyclic hydrocarbon group for R ^a6 and R ^a7 may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Cycloalkyl groups such as cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include 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.
Examples of the group formed by combining the alkyl group of R ^a6 and R ^a7 and the alicyclic hydrocarbon group include an aralkyl group, and examples thereof include a benzyl group and a phenethyl group.
The carbon number of the alkyl group represented by R ^a6 and R ^a7 is preferably 6 or less, more preferably 1 to 3, and further preferably 2 or 3.
Carbon number of the alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably 3-8, more preferably 3-6.
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 formulas (a1-0-1) to (a1-0-12) is preferable, and formula (a1-0-1) to 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 structural unit (a1-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A structural unit represented by formula (a1-1-1) to formula (a1-1-8) is preferable.

The structural unit (a1-2) is preferably a structural unit represented by any one of the formulas (a1-2-1) to (a1-2-12), and more preferably the formula (a1-2). -3), a structural unit represented by formula (a1-2-4), formula (a1-2-9) or formula (a1-2-10), more preferably formula (a1-2-3) ), A formula (a1-2-5), a formula (a1-2-9) or a formula (a1-2-11), more preferably a formula (a1-2-5) or a formula It is a structural unit represented by (a1-2-11).

  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 the sum total of a unit, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

［式（ａ１−５）中、Ｒ^a8は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊−（ＣＨ₂）_h3−ＣＯ−Ｌ⁵⁴−を表し、ｈ３は１〜４のいずれかの整数を表し、＊は、Ｌ⁵¹との結合手を表す。
Ｌ⁵¹、Ｌ⁵²、Ｌ⁵³及びＬ⁵⁴は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３のいずれかの整数を表す。
ｓ１’は、０〜３のいずれかの整数を表す。 Examples of the structural unit having an acid labile group include a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”).

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

As a halogen atom, a fluorine atom and a chlorine atom are mentioned, Preferably a fluorine atom is mentioned. 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—.
As s1, 1 is preferable.
As s1 ', the integer in any one of 0-2 is preferable.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

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), it is preferable that the content rate is 1-50 mol% with respect to the sum total of all the structural units of resin (A), 3-45 It is more preferable that it is mol%, and it is further more preferable that it is 5-40 mol%.

Furthermore, examples of the structural unit (a1) include the following structural units.

  When the resin (A) includes any one of the structural unit (a1-3-1) to the structural unit (a1-3-7), the content is 10 to 10% with respect to all the structural units of the resin (A). 95 mol% is preferable, 15-90 mol% is more preferable, 20-85 mol% is further 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いてもよい炭素数１〜６のアルキル基を表す。
Ｒ^a33は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアルキルカルボニル基、炭素数２〜４のアルキルカルボニルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｌａは０〜４のいずれかの整数を表す。ｌａが２以上である場合、複数のＲ^a33は互いに同一であっても異なってもよい。
Ｒ^a34及びＲ^a35はそれぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a36は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a35及びＲ^a36は互いに結合してそれらが結合する−Ｃ−Ｏ−とともに炭素数２〜２０の２価の炭化水素基を形成し、該炭化水素基及び該２価の炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−又は−Ｓ−で置き換わってもよい。］ The structural unit having a group represented by the formula (2) in the structural unit (a1) may be referred to as a structural unit represented by the formula (a1-4) (hereinafter referred to as “structural unit (a1-4)”). .).

[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 alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl An oxy group or a methacryloyloxy group is represented.
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 Together with —C—O— to which they are bonded to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent hydrocarbon group is — O- or -S- may be substituted. ]

^Examples of the alkyl group in R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, 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 in R ^a32 and R ^a33 include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1 , 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, etc. Is 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 alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group, aromatic hydrocarbon group, and include groups formed by combining these, alkyl groups and alicyclic hydrocarbon groups Examples thereof include the same groups as the alkyl group and the alicyclic hydrocarbon group in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 .
The aromatic hydrocarbon group includes phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl. Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
Examples of the combined group include a group obtained by combining the above-described alkyl group and alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, and an aryl-cyclohexyl group such as a phenylcyclohexyl group. In particular, as R ^a36 , 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 Is mentioned.

In formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
As la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, 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. A group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. The aromatic hydrocarbon group for R ^a36 is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

As a structural unit (a1-4), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Preferably, hydrogen atom corresponding to ^{R a32} in equation (a1-4-1) represented respectively to Formula (a1-4-8) structural units and structural units (a1-4) is replaced by a methyl group structure And more preferably, structural units represented by formula (a1-4-1) to formula (a1-4-5), respectively.

  When the resin (A) includes the structural unit (a1-4), 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.

  The structural unit (a1) having an acid labile group in the resin (A) is at least selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2). 1 or more types are preferable, and at least 2 types or more are more preferable, the combination of a structural unit (a1-1) and a structural unit (a1-2), the combination of a structural unit (a1-1) and a structural unit (a1-0), a structure The combination of the unit (a1-2) and the structural unit (a1-0), the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2) are more preferable, and the structural unit (a1 The combination of -1) and the structural unit (a1-2) is particularly preferred.

  Resin (A) further contains a monomer having no halogen atom and no acid labile group (hereinafter sometimes referred to as “monomer (s)”) and / or other structural unit (t) described later. You may contain.

<Structural unit (s)>
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 the resin (A) has a structural unit (a2) having a phenolic hydroxy group, the content is preferably from 5 to 95 mol%, more preferably from 10 to 80 mol, based on all structural units of the resin (A). % Is more preferable, and 15 to 80 mol% is more preferable.

式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表す。
ｋ２は１〜７のいずれかの整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０のいずれかの整数を表す。 Examples of the structural unit (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 any 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 of 1 to 4) More preferably, it 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, more preferably a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

As a structural unit (a2-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A structural unit represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferred, and any one of formula (a2-1-1) to formula (a2-1-4) The structural unit represented is more preferable, and the structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is 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%.

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 (extreme ultraviolet light) is used as an exposure light source, the structural unit (a2) is The structural unit (a2) having a phenolic hydroxy group is preferred. When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) is preferably a structural unit (a2) having an alcoholic hydroxy group.
Resin (A) may contain 2 or more types of structural units (a2).

<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. Preferably, a bridged ring containing a γ-butyrolactone ring or a γ-butyrolactone ring structure is used.

  The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), or the formula (a3-3). 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のいずれかの整数を表す。
）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のいずれかの整数を表す。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のいずれかの整数を表す。
）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のいずれかの整数を表す。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のいずれかの整数を表す。
）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のいずれかの整数を表す。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。］

[In the formula (a3-1),
L ^a4 represents —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7).
) Represents a group represented by * 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 any 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 —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7).
) Represents a group represented by * 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 any 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 —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7).
) Represents a group represented by * 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 any integer of 0 to 3. When r1 is 2 or more, the plurality of R ^a23 are the same or different from each other. ]

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.

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 are preferably each independently, preferably —O— or k3 is an integer of 1 to 4 * —O—. A group represented by (CH ₂ ) _k3 —CO—O—, more preferably —O— and * —O—CH ₂ —CO—O—, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

  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), the formula (a3-1-1) to the formula (a3-1-4), the formula (a3-2-1) to the formula (a3-2-4), and the formula (a3-3) 1) to formula (a3-3-4) are preferred, and formula (a3-1-1), formula (a3-1-2), formula (a3-2-1) and formula (a3-2-3) to The structural unit represented by any one of formula (a3-2-4) is more preferable.

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%.
Each content rate of the structural unit represented by Formula (a3-1), Formula (a3-2), and Formula (a3-3) is usually 5 to 60 mol% with respect to all the structural units of the resin (A). Preferably, it is 5-50 mol%, More preferably, it is 10-50 mol%.

<Other structural units (t)>
The resin (A) may contain another structural unit (t) as a structural unit other than 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 having a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”) and a non-leaving hydrocarbon group. And a structural unit (hereinafter sometimes referred to as “structural unit (a5)”).

［式（ａ４−０）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^５は、単結合又は炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ^３は、炭素数１〜８のペルフルオロアルカンジイル基又は炭素数５〜１２のペルフルオロシクロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ <Structural unit (a4)>
The halogen atom in the structural unit (a4) is preferably a fluorine atom. 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 ⁵ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a C 1-8 perfluoroalkanediyl group or a C 5-12 perfluorocycloalkanediyl group.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

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

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

L ⁵ is preferably a single bond, a methylene group or an ethylene group, 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 following.

In the above structural unit, a structural unit in which a methyl group corresponding to R ⁵ is replaced with a hydrogen atom can also be given as a specific example of the structural unit (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−ＣＨ₂−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ａ^a41は、置換基を有していてもよい炭素数１〜６のアルカンジイル基又は式（ａ−ｇ１１）で表される基を表す。ただし、Ａ^ａ４１及びＲ^ａ４２のうち少なくとも１つは、置換基としてハロゲン原子（好ましくはフッ素原子）を有する。

〔式（ａ−ｇ１１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１〜５の２価の脂肪族炭化水素基を表す。
Ａ^a43は、置換基を有していてもよい炭素数１〜５の２価の脂肪族炭化水素基又は単結合を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。
ただし、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は６以下である。〕
ただし、Ａ^a41及びＲ^a42のうち少なくとも一方は、置換基としてハロゲン原子を有する基である。
＊及び＊＊は結合手を表し、＊が−Ｏ−ＣＯ−Ｒ^ａ４２との結合手を表す。］
ｓは０が好ましい。 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 an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g11). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In the formula (a-g11),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a ^C 1-5 divalent aliphatic hydrocarbon group which may have a substituent.
A ^a43 represents a ^C 1-5 divalent aliphatic hydrocarbon group which may have a substituent or a single bond.
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 6 or less. ]
However, at least one of A ^a41 and R ^a42 is a group having a halogen atom as a substituent.
* And ** represent a bond, and * represents a bond with —O—CO—R ^a42 . ]
s is preferably 0.

芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、アントリル基、ビフェニリル基、フェナントリル基及びフルオレニル基等が挙げられる。 ^Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl, pentadecyl, hexyldecyl And alkyl groups such as a heptadecyl group and an octadecyl group. Examples of the cyclic alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* Represents a bond.) And a polycyclic alicyclic hydrocarbon group.

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.

The hydrocarbon group for R ^a42 is preferably a chain or cyclic aliphatic hydrocarbon group or a group formed by combining these. These groups may have a carbon-carbon unsaturated bond, but chain and cyclic aliphatic saturated hydrocarbon groups and groups formed by combining them are more preferable.

［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。
＊はカルボニル基との結合手を表す。］ ^Examples of the substituent for R ^a42 include a halogen atom and 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),
X ^a43 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 with a carbonyl group. ]

^As the aliphatic hydrocarbon group for A ^a45, the same groups as those exemplified for R ^a42 can be mentioned.
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3). .

When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and still more preferably a carbon number. It is a 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 carbon number contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

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

1-6 are preferable and, as for carbon number of the aliphatic hydrocarbon group of ^Aa46 , 1-3 are more preferable.
4-15 are preferable, as for carbon number of the aliphatic hydrocarbon group of ^Aa47 , 5-12 are more preferable, and a cyclohexyl group or an adamantyl group is further more preferable.

Examples of the group represented by the formula (a-g2) include the following groups.

^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 A ^a41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

^Examples of the aliphatic hydrocarbon group represented by A ^a42 , A ^a43, and A ^{a44 in} the group represented by the formula (a-g1) (hereinafter sometimes referred to as “group (a-g1)”) include a methylene group and an ethylene group. Propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl Group, 2-methylpropane-1,2-diyl group and the like. Examples of these substituents include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.

^Examples of the group (a-g1) in which X ^a42 is an oxygen atom include the following groups. In the following examples, * and ** each represent a bond, and ** is a bond with —O—CO—R ^a42 .

Examples of the group (a-g1) in which X ^a42 is a carbonyl group include the following groups.

Examples of the group (a-g1) in which X ^a42 is a carbonyloxy group include the following groups.

Examples of the group (a-g1) in which X ^a42 is an oxycarbonyl group include the following groups.

［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), a structural unit represented by the formula (a4-2) is 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 either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group. And cycloalkyl groups such as dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and 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, 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.
Specifically, as the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, 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, 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- (perfluoro (Ropropyl) 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, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2, 2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentyl Examples thereof include fluorinated alkyl groups such as a methyl group and a perfluorohexyl group.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

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

Examples of the structural unit (a4-2) include the following structural units.

Examples of the structural unit (a4) include the following structural units.

  When the resin (A) has a structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, based on all structural units of the resin (A). More preferably, it is 10 mol%.

［式（ａ５−１）中、
Ｒ⁵¹は、水素原子又はメチル基を表す。
Ｒ⁵²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基で置換されていてもよい。但し、Ｌ⁵⁵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。
Ｌ⁵⁵は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、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-elimination hydrocarbon group that the structural unit (a5) has include a linear, branched, or cyclic hydrocarbon group, and preferably 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 may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. . However, the hydrogen atom bonded to the carbon atom at the coupling position with the L ⁵⁵ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ⁵⁵ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a methylene group contained in the saturated hydrocarbon group may be replaced by 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. , Alkyl groups such as octyl group and 2-ethylhexyl group.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ⁵⁵ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. .
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.

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

In 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 ^x1 and L ^x2 is 17 or less.
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6 and L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9 and W ^x1 is 15 or less.

L ^x1 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group, 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, more preferably a single bond.
L ^x3 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group.
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, 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, 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, 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.

^L55 is preferably a single bond, a methylene group, an ethylene group or a group represented by the formula (L1-1), more preferably a single bond or a group represented by the formula (L1-1). .

As the structural unit (a5-1), structural units shown below and structural units in which a methyl group corresponding to R ⁵¹ in the following structural units is replaced with a hydrogen atom can be mentioned.

  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%.

  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.

Each structural unit constituting the resin (A) may be used alone or in combination of two or more. When the resin (A) is produced using a monomer that derives these structural units, the compound ( I0) acts as a chain transfer agent. The usage-amount of compound (I0) is 0.1-50 mol% normally with respect to all the monomers of resin (A), Preferably it is 1-30 mol%, More preferably, it is 2-10 mol% is there. 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). In the present specification, the weight average molecular weight is a value obtained by gel permeation chromatography under the conditions described in Examples.

  As for the content rate of resin (A), 80 to 99 mass% is preferable with respect to solid content of a resist composition. The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Resist composition>
The resist composition of the present invention contains a resin (A) and an acid generator.
The resist composition preferably contains a quencher (hereinafter sometimes referred to as “quencher (C)”) and a solvent (hereinafter sometimes referred to as “solvent (E)”).

<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 containing a structural unit having a fluorine atom.

As the resin containing a structural unit having a fluorine atom, a resin containing the structural unit (a4) (however, the structural unit (I) is not included; hereinafter may be referred to as “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). .
The resin (X) preferably does not contain the structural unit (a1).
Examples of the structural unit that the resin (X) may further include a structural unit derived from the structural unit (a2), the structural unit (a3), and other known monomers.
The weight average molecular weight of the resin (X) is preferably 8,000 or more (more preferably 10,000 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 resin (X) is included, the content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). 40 parts by mass, particularly preferably 2 to 30 parts by mass.

  As for the total content rate of resin other than resin (A) and resin (A), 80 to 99 mass% is preferable with respect to solid content of a resist composition. The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator (B) may be either nonionic or ionic. 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. Two or more acid generators (B) may be used in combination.

［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、炭素数１〜２４の２価の飽和炭化水素基を表し、該２価の飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該２価の飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよい。
Ｙは、置換基を有していてもよいメチル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−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 a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — 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.

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.

［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。］

[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 the same 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 Formula (b1-10) and Formula (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 alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y11) and formulas (Y36) to (Y38).
When —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO—, the number may be one or two or more. . Examples of such a group include groups represented by formula (Y12) to formula (Y35).

Among them, the group represented by any one of the formulas (Y1) to (Y20), the formula (Y30), and the formula (Y31) is preferable, and the formula (Y11), the formula (Y15), and the formula (Y Y16), a group represented by formula (Y20), formula (Y30) or formula (Y31), and more preferably a group represented by formula (Y11), formula (Y15) or formula (Y30).
When Y constitutes a spiro ring such as formula (Y28) to formula (Y33), 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 fluorine atom is not substituted on the methylene group adjacent to the oxygen atom are preferred.

Examples of the substituent for the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, or-( CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic group having 6 to 18 carbon atoms). Represents a hydrocarbon group, and ja represents an integer of 0 to 4).
Examples of the substituent for the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, and an alicyclic group having 3 to 16 carbon atoms. A hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or — (CH ₂ ) _ja- O-CO-R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic carbon atom having 6 to 18 carbon atoms). Represents a hydrogen group, and ja represents an integer of 0 to 4).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, and the like.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group, mesityl group. , Aryl groups such as biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
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, heptyl group, 2 -Ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. are mentioned.
Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as 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 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 Y include the following.

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

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and the alicyclic carbonization The methylene group constituting the hydrogen group or adamantyl 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.

  The sulfonate anion in the salt represented by the formula (B1) is an anion represented by the formula (B1-A-1) to the formula (B1-A-55) [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 (B1-A-33), Formula (B1-A-36) to Formula (B1-A-40), Formula (B1-A-47) to Formula (B1-A-55) An anion 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 formed by, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. More preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q 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 Formula (B1) include anions represented by Formula (B1a-1) to Formula (B1a-34), respectively.

  Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) To (B1a-34) are 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、それぞれ独立に、炭素数１〜３０の脂肪族炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜３６の芳香族炭化水素基を表し、該脂肪族炭化水素基に含まれる水素原子は、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数３〜１２の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜１８の脂肪族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、ヒドロキシ基又は炭素数１〜１２のアルコキシ基で置換されていてもよい。
Ｒ^ｂ４とＲ^ｂ５とは、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、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
ｍ２及びｎ２は、それぞれ独立に０〜５のいずれかの整数を表す。
ｍ２が２以上のとき、複数のＲ^ｂ７は同一で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、それぞれ独立に、炭素数１〜３６の脂肪族炭化水素基又は炭素数３〜３６の脂環式炭化水素基を表す。
Ｒ^ｂ９とＲ^ｂ１０とは、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の脂肪族炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^ｂ１２は、炭素数１〜１２の脂肪族炭化水素基、炭素数３〜１８の脂環式炭化水素基又は炭素数６〜１８の芳香族炭化水素基を表し、該脂肪族炭化水素に含まれる水素原子は、炭素数６〜１８の芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜１２のアルコキシ基又は炭素数１〜１２のアルキルカルボニルオキシ基で置換されていてもよい。
Ｒ^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、それぞれ独立に、ヒドロキシ基、炭素数１〜１２の脂肪族炭化水素基又は炭素数１〜１２のアルコキシ基を表す。
Ｌ^ｂ３１は、−Ｓ−又は−Ｏ−を表す。
ｏ２、ｐ２、ｓ２、及びｔ２は、それぞれ独立に、０〜５のいずれかの整数を表す。
ｑ２及びｒ２は、それぞれ独立に、０〜４のいずれかの整数を表す。
ｕ２は、０又は１を表す。
ｏ２が２以上のとき、複数のＲ^ｂ１３は同一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 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may 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, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represents an integer of 0 to 5.
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 aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may 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 aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the aliphatic hydrocarbon. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is an alkoxy group having 1 to 12 carbon atoms or 1 to 1 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
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, an 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 represents 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. ]

Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Of the alkyl group. In particular, the aliphatic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo group. Examples thereof include cycloalkyl groups such as heptyl group, cyclooctyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

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

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

As aromatic hydrocarbon group, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantylphenyl group , Aryl groups such as a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
When the aromatic hydrocarbon group includes an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, the aliphatic hydrocarbon group having 1 to 18 carbon atoms or the alicyclic hydrocarbon group having 3 to 18 carbon atoms is preferable.
Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the aliphatic hydrocarbon 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). -1) or a combination with a cation (b2-3).

  Preferred examples of the acid generator (B1) include those represented by formulas (B1-1) to (B1-48), respectively. Among them, the formula (B1-1) to formula (B1) containing an arylsulfonium cation. -3), Formula (B1-5) to Formula (B1-7), Formula (B1-11) to Formula (B1-14), Formula (B1-20), Formula (B1-21) to Formula (B1- 26), formula (B1-29), and those represented by formula (B1-31) to formula (B1-48), respectively, are particularly preferable.

  In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less with respect to 100 parts by mass of the resin (A). (More preferably 25 parts by mass or less). The resist composition of the present invention may contain one kind of acid generator (B) alone, or may contain plural kinds.

<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 salts represented by the following formulas, and JP 2012-229206 A, JP 2012-6908 A, and JP 2012-72109 A. And salts described in JP2011-39502A and JP2011-191745A.

  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) The process of apply | coating the resist composition of this invention 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.

  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, the irradiation of 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.

  In the resist composition of the present invention, the resin (X) tends to have a high distribution on the surface in the composition layer, and elution of the acid generator or the like into the immersion exposure liquid during immersion exposure can be suppressed. . Further, the advancing contact angle and the receding contact angle caused by the resin (X) exhibit water repellency and enable high-speed scanning exposure without leaving water droplets.

<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)

  Moreover, the structure of the compound was confirmed by measuring molecular ion peaks using mass spectrometry (LC: Model 1100 manufactured by Agilent, MASS: LC / MSD manufactured by Agilent). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

式（Ｉ−１−ａ）で表される化合物２０部、トルエン１６０部及びピリジン２７．１部を混合し、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ−１−ｂ）で表される化合物６９部及びトルエン１００部の混合溶液を１時間かけて滴下し、さらに２３℃で１２時間攪拌した。得られた混合物に、イオン交換水１００部を混合し、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４回繰り返した。得られた有機層を濃縮した後、得られた濃縮残渣にｎ−ヘプタン１００部を加え、２３℃で３０分間攪拌し、ろ過することにより、式（Ｉ−１−ｃ）で表される化合物３５．９部を得た。 Synthesis Example 1: Synthesis of compound represented by formula (I-1)

20 parts of the compound represented by the formula (I-1-a), 160 parts of toluene and 27.1 parts of pyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 69 parts of the compound represented by the formula (I-1-b) and 100 parts of toluene was added dropwise over 1 hour, and the mixture was further stirred at 23 ° C. for 12 hours. The organic layer was washed with water by mixing 100 parts of ion-exchanged water with the resulting mixture, stirring at 23 ° C. for 30 minutes, allowing to stand and separating. Such water washing operation was repeated 4 times. After concentrating the obtained organic layer, 100 parts of n-heptane is added to the obtained concentrated residue, stirred at 23 ° C. for 30 minutes, and filtered to obtain a compound represented by the formula (I-1-c). 35.9 parts were obtained.

式（Ｉ−１−ｃ）で表される化合物１０部、式（Ｉ−１−ｄ）で表される化合物７．４部及びジメチルホルムアミド７０部を混合し、２３℃で２時間攪拌した。得られた混合物に、イオン交換水５０部及び酢酸エチル２００部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水５０部を混合し、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。得られた有機層を濃縮することにより、式（Ｉ−１−ｅ）で表される化合物９．７部を得た。

10 parts of the compound represented by the formula (I-1-c), 7.4 parts of the compound represented by the formula (I-1-d), and 70 parts of dimethylformamide were mixed and stirred at 23 ° C. for 2 hours. To the obtained mixture, 50 parts of ion-exchanged water and 200 parts of ethyl acetate were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 50 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand and liquid-separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer was concentrated to obtain 9.7 parts of a compound represented by the formula (I-1-e).

式（Ｉ−１−ｅ）で表される化合物３部、メタノール２４部及び１０％水酸化ナトリウム水溶液３部を混合し、２３℃で２時間攪拌した。得られた反応溶液に、酢酸０．４４部を混合し、２３℃で３０分間攪拌した後、濃縮した。得られた濃縮残渣に、酢酸エチル２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水１０部を混合し、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。得られた有機層を濃縮し、濃縮マスをカラムクロマトグラフィー（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＝３／１）を用いて分取することにより、式（Ｉ−１）で表される化合物１部を得た。
ＭＡＳＳ：２９４．１（分子イオンピーク）

3 parts of the compound represented by the formula (I-1-e), 24 parts of methanol, and 3 parts of 10% aqueous sodium hydroxide solution were mixed and stirred at 23 ° C. for 2 hours. To the obtained reaction solution, 0.44 part of acetic acid was mixed, stirred at 23 ° C. for 30 minutes, and concentrated. To the resulting concentrated residue, 20 parts of ethyl acetate and 10 parts of ion-exchanged water were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 10 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer is concentrated, and the concentrated mass is separated using column chromatography (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 3/1). Thereby obtaining 1 part of a compound represented by the formula (I-1).
MASS: 294.1 (Molecular ion peak)

式（Ｉ−１−ａ）で表される化合物１０部、テトラヒドロフラン部、ピリジン１１．９０部及びジメチルアミノピリジン１．６７部を混合し、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ−２−ｂ）で表される化合物２５．８部及びテトラヒドロフラン２５部の混合溶液を２時間かけて滴下し、さらに２３℃で１２時間攪拌した。得られた混合物に、酢酸エチル１００部及びイオン交換水１００部を混合し、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。得られた有機層に、イオン交換水１００部を混合し、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。得られた有機層を濃縮し、濃縮マスをカラムクロマトグラフィー（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＝３／１）を用いて分取することにより、式（Ｉ−２−ｃ）で表される化合物１５．８部を得た。 Synthesis Example 2: Synthesis of compound represented by formula (I-2)

10 parts of the compound represented by the formula (I-1-a), tetrahydrofuran part, 11.90 parts of pyridine and 1.67 parts of dimethylaminopyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 25.8 parts of the compound represented by the formula (I-2-b) and 25 parts of tetrahydrofuran was dropped over 2 hours, and the mixture was further stirred at 23 ° C. for 12 hours. To the obtained mixture, 100 parts of ethyl acetate and 100 parts of ion-exchanged water were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. To the obtained organic layer, 100 parts of ion-exchanged water was mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer is concentrated, and the concentrated mass is separated using column chromatography (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 3/1). Gave 15.8 parts of the compound represented by the formula (I-2-c).

式（Ｉ−２−ｃ）で表される化合物１０．７部、式（Ｉ−１−ｄ）で表される化合物７．４部及びジメチルホルムアミド７０部を混合し、２３℃で２時間攪拌した。得られた混合物に、イオン交換水５０部及び酢酸エチル２００部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水５０部を混合し、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。得られた有機層を濃縮することにより、式（Ｉ−２−ｅ）で表される化合物９．９部を得た。

10.7 parts of the compound represented by the formula (I-2-c), 7.4 parts of the compound represented by the formula (I-1-d) and 70 parts of dimethylformamide were mixed and stirred at 23 ° C. for 2 hours. did. To the obtained mixture, 50 parts of ion-exchanged water and 200 parts of ethyl acetate were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 50 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand and liquid-separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer was concentrated to obtain 9.9 parts of a compound represented by the formula (I-2-e).

式（Ｉ−２−ｅ）で表される化合物３．２部、メタノール２４部及び１０％水酸化ナトリウム水溶液３部を混合し、２３℃で２時間攪拌した。得られた反応溶液に、酢酸０．４部を混合し、２３℃で３０分間攪拌した後、濃縮した。得られた濃縮残渣に、酢酸エチル２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水１０部を混合し、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。得られた有機層を濃縮し、濃縮マスをカラムクロマトグラフィー（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＝３／１）を用いて分取することにより、式（Ｉ−２）で表される化合物０．９１部を得た。
ＭＡＳＳ：３２２．１（分子イオンピーク）

3.2 parts of the compound represented by the formula (I-2-e), 24 parts of methanol and 3 parts of 10% aqueous sodium hydroxide solution were mixed and stirred at 23 ° C. for 2 hours. To the resulting reaction solution, 0.4 part of acetic acid was mixed, stirred at 23 ° C. for 30 minutes, and concentrated. To the resulting concentrated residue, 20 parts of ethyl acetate and 10 parts of ion-exchanged water were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 10 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer is concentrated, and the concentrated mass is separated using column chromatography (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 3/1). As a result, 0.91 part of a compound represented by the formula (I-2) was obtained.
MASS: 322.1 (molecular ion peak)

式（Ｉ−３−ａ）で表される化合物２８部、トルエン１６０部及びピリジン２７．１部を混合し、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ−１−ｂ）で表される化合物６９部及びトルエン１００部の混合溶液を１時間かけて滴下し、さらに２３℃で１２時間攪拌した。得られた混合物に、イオン交換水１００部を混合し、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４回繰り返した。得られた有機層を濃縮した後、得られた濃縮残渣にｎ−ヘプタン１００部を加え、２３℃で３０分間攪拌し、ろ過することにより、式（Ｉ−３−ｃ）で表される化合物２２．４部を得た。 Synthesis Example 3: Synthesis of compound represented by formula (I-3)

28 parts of the compound represented by the formula (I-3-a), 160 parts of toluene and 27.1 parts of pyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 69 parts of the compound represented by the formula (I-1-b) and 100 parts of toluene was added dropwise over 1 hour, and the mixture was further stirred at 23 ° C. for 12 hours. The organic layer was washed with water by mixing 100 parts of ion-exchanged water with the resulting mixture, stirring at 23 ° C. for 30 minutes, allowing to stand and separating. Such water washing operation was repeated 4 times. After concentrating the obtained organic layer, 100 parts of n-heptane was added to the obtained concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and filtered to obtain a compound represented by the formula (I-3-c). 22.4 parts were obtained.

式（Ｉ−３−ｃ）で表される化合物１１．５部、式（Ｉ−１−ｄ）で表される化合物７．４部及びジメチルホルムアミド７０部を混合し、２３℃で２時間攪拌した。得られた混合物に、イオン交換水５０部及び酢酸エチル２００部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水５０部を混合し、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。得られた有機層を濃縮することにより、式（Ｉ−３−ｅ）で表される化合物８．９部を得た。

11.5 parts of the compound represented by the formula (I-3-c), 7.4 parts of the compound represented by the formula (I-1-d) and 70 parts of dimethylformamide were mixed and stirred at 23 ° C. for 2 hours. did. To the obtained mixture, 50 parts of ion-exchanged water and 200 parts of ethyl acetate were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 50 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand and liquid-separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer was concentrated to obtain 8.9 parts of a compound represented by the formula (I-3-e).

式（Ｉ−３−ｅ）で表される化合物３．５部、メタノール２４部及び１０％水酸化ナトリウム水溶液３部を混合し、２３℃で２時間攪拌した。得られた反応溶液に、酢酸０．４４部を混合し、２３℃で３０分間攪拌した後、濃縮した。得られた濃縮残渣に、酢酸エチル２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水１０部を混合し、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。得られた有機層を濃縮し、濃縮マスをカラムクロマトグラフィー（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＝３／１）を用いて分取することにより、式（Ｉ−３）で表される化合物１．２８部を得た。
ＭＡＳＳ：３５０．２（分子イオンピーク）

3.5 parts of the compound represented by the formula (I-3-e), 24 parts of methanol and 3 parts of 10% aqueous sodium hydroxide solution were mixed and stirred at 23 ° C. for 2 hours. To the obtained reaction solution, 0.44 part of acetic acid was mixed, stirred at 23 ° C. for 30 minutes, and concentrated. To the resulting concentrated residue, 20 parts of ethyl acetate and 10 parts of ion-exchanged water were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 10 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer is concentrated, and the concentrated mass is separated using column chromatography (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 3/1). Gave 1.28 parts of the compound represented by the formula (I-3).
MASS: 350.2 (molecular ion peak)

式（Ｉ−５−ａ）で表される化合物２７．４部、トルエン１６０部及びピリジン２７．１部を混合し、２３℃で３０分間攪拌した。得られた混合物に、式（Ｉ−１−ｂ）で表される化合物６９部及びトルエン１００部の混合溶液を１時間かけて滴下し、さらに２３℃で１２時間攪拌した。得られた混合物に、イオン交換水１００部を混合し、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４回繰り返した。得られた有機層を濃縮した後、得られた濃縮残渣にｎ−ヘプタン１００部を加え、２３℃で３０分間攪拌し、ろ過することにより、式（Ｉ−５−ｃ）で表される化合物２６．５部を得た。 Synthesis Example 4: Synthesis of compound represented by formula (I-5)

27.4 parts of the compound represented by the formula (I-5-a), 160 parts of toluene and 27.1 parts of pyridine were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 69 parts of the compound represented by the formula (I-1-b) and 100 parts of toluene was added dropwise over 1 hour, and the mixture was further stirred at 23 ° C. for 12 hours. The organic layer was washed with water by mixing 100 parts of ion-exchanged water with the resulting mixture, stirring at 23 ° C. for 30 minutes, allowing to stand and separating. Such water washing operation was repeated 4 times. After concentrating the obtained organic layer, 100 parts of n-heptane was added to the obtained concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes and filtered to obtain a compound represented by the formula (I-5-c). 26.5 parts were obtained.

式（Ｉ−５−ｃ）で表される化合物１１．４部、式（Ｉ−１−ｄ）で表される化合物７．４部及びジメチルホルムアミド７０部を混合し、２３℃で２時間攪拌した。得られた混合物に、イオン交換水５０部及び酢酸エチル２００部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水５０部を混合し、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。得られた有機層を濃縮することにより、式（Ｉ−５−ｅ）で表される化合物１０．２部を得た。

11.4 parts of the compound represented by the formula (I-5-c), 7.4 parts of the compound represented by the formula (I-1-d) and 70 parts of dimethylformamide were mixed and stirred at 23 ° C. for 2 hours. did. To the obtained mixture, 50 parts of ion-exchanged water and 200 parts of ethyl acetate were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 50 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand and liquid-separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer was concentrated to obtain 10.2 parts of a compound represented by the formula (I-5-e).

式（Ｉ−５−ｅ）で表される化合物３．４部、メタノール２４部及び１０％水酸化ナトリウム水溶液３部を混合し、２３℃で２時間攪拌した。得られた反応溶液に、酢酸０．４４部を混合し、２３℃で３０分間攪拌した後、濃縮した。得られた濃縮残渣に、酢酸エチル２０部及びイオン交換水１０部を混合し、２３℃で３０分間攪拌し、静置、分液することにより有機層を得た。得られた有機層に、イオン交換水１０部を混合し、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。得られた有機層を濃縮し、濃縮マスをカラムクロマトグラフィー（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＝３／１）を用いて分取することにより、式（Ｉ−５）で表される化合物１．２９部を得た。
ＭＡＳＳ：３４８．１（分子イオンピーク）

3.4 parts of the compound represented by the formula (I-5-e), 24 parts of methanol and 3 parts of 10% aqueous sodium hydroxide solution were mixed and stirred at 23 ° C. for 2 hours. To the obtained reaction solution, 0.44 part of acetic acid was mixed, stirred at 23 ° C. for 30 minutes, and concentrated. To the resulting concentrated residue, 20 parts of ethyl acetate and 10 parts of ion-exchanged water were mixed, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to obtain an organic layer. The organic layer thus obtained was mixed with 10 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such water washing operation was repeated three times. The obtained organic layer is concentrated, and the concentrated mass is separated using column chromatography (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm developing solvent: n-heptane / ethyl acetate = 3/1). Gave 1.29 parts of the compound represented by the formula (I-5).
MASS: 348.1 (molecular ion peak)

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

Example 1 [Synthesis of Resin A1]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-1), monomer (a3-4-2) and compound (I-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-1): monomer (a3-4-2): compound (I-1)] is 35:15: It mixed so that it might be set to 2.5: 47.5: 5, and the propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added, and it was set as the 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 added to a methanol / water mixed solvent, repulped, and then subjected to a refining operation of filtering twice to obtain a resin A1 having a weight average molecular weight of 9.0 × 10 ^{3 in} a yield of 63%. This resin A1 has the following structural units.

Example 2 [Synthesis of Resin A2]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-1), monomer (a3-4-2) and compound (I-2) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-1): monomer (a3-4-2): compound (I-2)] is 35:15: The same operation as in Example 1 was performed except that mixing was performed so that the ratio was 2.5: 47.5: 5, and a resin A2 having a weight average molecular weight of 8.7 × 10 ³ was obtained in a yield of 60%. This resin A2 has the following structural units.

Example 3 [Synthesis of Resin A3]
As the monomer, monomer (a1-1-3), monomer (a1-2-11), monomer (a2-1-1), monomer (a3-4-2) and compound (I-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-11): monomer (a2-1-1): monomer (a3-4-2): compound (I-1)] is 35:15: Except for mixing so as to be 2.5: 47.5: 5, the same procedure as in Example 1 was performed to obtain Resin A3 having a weight average molecular weight of 8.6 × 10 ^{3 in} a yield of 64%. This resin A3 has the following structural units.

Example 4 [Synthesis of Resin A4]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-11), the monomer (a2-1-1), the monomer (a3-4-2) and the compound (I-2) The ratio [monomer (a1-1-3): monomer (a1-2-11): monomer (a2-1-1): monomer (a3-4-2): compound (I-2)] is 35:15: Except for mixing so as to be 2.5: 47.5: 5, the same procedure as in Example 1 was performed to obtain Resin A4 having a weight average molecular weight of 8.9 × 10 ^{3 in} a yield of 60%. This resin A4 has the following structural units.

Example 5 [Synthesis of Resin A5]
As the monomer, monomer (a1-2-1), monomer (a1-2-7), monomer (a2-1-2), monomer (a3-4-2) and compound (I-2) were used, and their moles The ratio [monomer (a1-2-1): monomer (a1-2-7): monomer (a2-1-2): monomer (a3-4-2): compound (I-2)] is 31: 9: Except for mixing so as to be 22: 38: 3.5, the same procedure as in Example 1 was performed to obtain Resin A5 having a weight average molecular weight of 7.6 × 10 ^{3 in} a yield of 78%. This resin A5 has the following structural units.

Example 6 [Synthesis of Resin A6]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-1), monomer (a3-4-2) and compound (I-3) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-1): monomer (a3-4-2): compound (I-3)] is 35:15: Except for mixing so as to be 2.5: 47.5: 5, the same procedure as in Example 1 was performed to obtain Resin A6 having a weight average molecular weight of 8.5 × 10 ^{3 in} a yield of 63%. 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 (a2-1-1), monomer (a3-4-2) and compound (I-5) were used, The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-1): monomer (a3-4-2): compound (I-5)] is 35:15: Except for mixing so as to be 2.5: 47.5: 5, the same procedure as in Example 1 was performed to obtain Resin A7 having a weight average molecular weight of 8.1 × 10 ^{3 in} a yield of 60%. This resin A7 has the following structural units.

Example 8 [Synthesis of Resin A8]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (I-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (I-1)] is 35:15: Except for mixing so as to be 2.5: 47.5: 5, the same procedure as in Example 1 was performed to obtain Resin A8 having a weight average molecular weight of 8.6 × 10 ^{3 in} a yield of 68%. This resin A8 has the following structural units.

Example 9 [Synthesis of Resin A9]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (I-3) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (I-3)] is 35:15: Except for mixing so as to be 2.5: 47.5: 5, the same procedure as in Example 1 was performed to obtain Resin A9 having a weight average molecular weight of 8.1 × 10 ^{3 in} a yield of 60%. This resin A9 has the following structural units.

Example 10 [Synthesis of Resin A10]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (I-5) were used, The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (I-5)] is 35:15: Except for mixing so as to be 2.5: 47.5: 5, the same procedure as in Example 1 was performed to obtain Resin A10 having a weight average molecular weight of 7.9 × 10 ^{3 in} a yield of 57%. This resin A10 has the following structural units.

Synthesis Example 5 [Synthesis of Resin AX1]
As the monomer, the monomer (a1-2-1), the monomer (a1-2-7), the monomer (a2-1-2), the monomer (a3-x1) and the compound (I-2) were used, and the molar ratio [ Monomer (a1-2-1): Monomer (a1-2-7): Monomer (a2-1-2): Monomer (a3-x1): Compound (I-2)] is 31: 9: 22: 38: The mixture was mixed to 3.5, and 1.5 mass times propylene glycol monomethyl ether acetate of 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 added to a methanol / water mixed solvent, repulped, and then subjected to a purification operation of filtration twice to obtain a resin AX1 having a weight average molecular weight of 7.3 × 10 ^{3 in} a yield of 76%. This resin AX1 has the following structural units.

Synthesis Example 6 [Synthesis of Resin X1]
Monomer (a4-1-7) was used as a monomer, and 1.5 mass times of methyl isobutyl ketone as the total monomer amount was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the solution in an amount of 0.7 mol% and 2.1 mol%, respectively, with respect to 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 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 1.8 × 10 ^{4 in} a yield of 77%. This resin X1 has the following structural units.

Synthesis Example 7 [Synthesis of Resin X2]
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 1.2 mass times the total monomer amount was added to make 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 methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin X2 (copolymer) having a weight average molecular weight of 1.0 × 10 ^{4 in} a yield of 91%. Got in. 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.

<Resin>
A1 to A10, AX1, X1, X2: Resin A1 to Resin A10, Resin AX1, Resin X1, Resin X2
<Acid generator>
B1-21: a salt represented by the formula (B1-21) (synthesized according to Examples in JP 2012-224611 A)
B1-22: a salt represented by the formula (B1-22) (synthesized according to Examples in JP 2012-224611 A)

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

<Manufacture of resist pattern and its evaluation>
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 45 nm was defined as the effective sensitivity.

<Evaluation of mask error factor (MEF)>
In terms of effective sensitivity, a resist pattern was formed using masks having mask hole diameters (hole diameters of light transmitting portions of the mask) of 57 nm, 56 nm, 55 nm, 54 nm, and 53 nm (all hole pitches were 90 nm). The slope of the regression line when the mask hole diameter was plotted on the horizontal axis and the hole diameter of the resist pattern formed (transferred) on the substrate by exposure was plotted on the vertical axis was calculated as the MEF value.
When the MEF value is 5.0 or less, the MEF is evaluated as good.
A MEF value exceeding 5.0 was evaluated as x when the MEF was not good.
The results are shown in Table 2. Numerical values in parentheses indicate MEF values.

  Since the resist composition containing the resin of the present invention can produce a resist pattern with a good mask error factor (MEF), it is suitable for fine processing of semiconductors.

Claims (8)

A resin comprising a structural unit represented by formula (I) and a structural unit represented by formula (a3-4).

[In formula (I), ^{A 1} represents a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms.
A ² and A ³ each independently represent a divalent hydrocarbon group having 1 to 18 carbon atoms.
R ¹ and R ² each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ³ and R ⁴ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. ]

[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 a single bond, ^* —L ^a8 —O—, ^* —L ^a8 —CO—O—, ^* —L ^a8 —CO—O—L ^a9 —CO—O— or ^* —L ^a8 —O—CO ^-La9- O- is represented.
* Represents a bond with -O-.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
R ^a25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
w1 represents an integer of 0 to 8. When w1 is 2 or more, the plurality of R ^a25 may be the same as or different from each other. ] The resin according to claim 1, wherein A ² and A ³ are each independently a methylene group or an ethylene group. The resin according to claim 1 or 2, wherein A ¹ is an alkanediyl group having 1 to 8 carbon atoms.   Furthermore, the resin in any one of Claims 1-3 containing the structural unit which has an acid labile group.   A resist composition containing the resin according to claim 1 and an acid generator.   Furthermore, the resist composition of Claim 5 containing resin containing the structural unit which has a fluorine atom.   The resist composition according to claim 5 or 6, further comprising a salt that generates an acid having a weaker acidity than an acid generated from an acid generator. (1) A step of applying the resist composition according to any one of claims 5 to 7 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,
A method for producing a resist pattern including: