JP2013257539A - Resist composition and method for manufacturing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition capable of manufacturing a resist pattern having high resolution.SOLUTION: A resist composition includes: a resin having a structural unit represented by a formula (I) and a structural unit containing an acid unstable group; and an acid generating agent containing an acid unstable group. [In the formula, Rrepresents a 1-6C alkyl group that may have a halogen atom, a hydrogen atom, or a halogen atom; Arepresents a single bond,-A-O-,-A-CO-O-,-A-CO-O-A-CO-O-, or-A-O-CO-A-O-; * represents a bond with -O-; and Aand Aeach represent independently 1-6C alkanediyl.]

Description

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

また、レジスト組成物から、フォトリソグラフィによりレジストパターンを形成する際、アルカリ現像液で現像するとポジ型レジストパターンが得られ、有機溶剤で現像するとネガ型レジストパターンが得られることが知られている（非特許文献１）。 Patent Document 1 describes a resist composition comprising a resin composed of a structural unit represented by the formula (u-A) and a structural unit represented by the formula (u-C), and triphenylsulfonium triflate. ing.

Further, it is known that when a resist pattern is formed from a resist composition by photolithography, a positive resist pattern is obtained when developed with an alkaline developer, and a negative resist pattern is obtained when developed with an organic solvent ( Non-patent document 1).

JP 2000-122294 A

Published by Techno Times Inc. Monthly Display '11 June p. 31

  An object of the present invention is to provide a resist composition capable of producing a resist pattern having an excellent resolution.

［式（Ｉ）中、
Ｒ¹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。
Ａ¹は、単結合、^＊−Ａ²−Ｏ−、^＊−Ａ²−ＣＯ−Ｏ−、^＊−Ａ²−ＣＯ−Ｏ−Ａ³−ＣＯ−Ｏ−又は^＊−Ａ²−Ｏ−ＣＯ−Ａ³−Ｏ−を表す。
＊は−Ｏ−との結合手を表す。
Ａ²及びＡ³は、それぞれ独立に、炭素数１〜６のアルカンジイル基を表す。］
［２］酸不安定基を有する酸発生剤が、式（ＩＩ−０）で表される酸発生剤である［１］記載のレジスト組成物。

［式（ＩＩ−０）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ⁰¹は、単結合又は置換基を有してもよい炭素数１〜２０の２価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
Ｒ⁴は、炭素数１〜１２の炭化水素基を表す。
環Ｗ¹は、置換基を有していてもよい炭素数３〜１８の炭化水素環を表す。
Ｚ⁺は、有機カチオンを表す。］
［３］さらに溶剤を含有する［１］又は［２］記載のレジスト組成物。
［４］（１）上記［１］〜［３］のいずれか一項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）組成物層を露光する工程、
（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 resist composition comprising a resin comprising a structural unit represented by formula (I) and a structural unit having an acid labile group, and an acid generator having an acid labile group.

[In the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —O—, ^* —A ² —CO—O—, ^* —A ² —CO—O—A ³ —CO—O—, or ^* —A ² —O—CO. -A ³ represents a -O-.
* Represents a bond with -O-.
A ² and A ³ each independently represents an alkanediyl group having 1 to 6 carbon atoms. ]
[2] The resist composition according to [1], wherein the acid generator having an acid labile group is an acid generator represented by the formula (II-0).

[In the formula (II-0),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ⁰¹ represents a C 1-20 divalent hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is —CO— or —O—. It may be replaced with.
R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms.
Ring W ¹ represents a hydrocarbon ring optionally having from 3 to 18 carbon atoms which may have a substituent.
Z ⁺ represents an organic cation. ]
[3] The resist composition according to [1] or [2], further containing a solvent.
[4] (1) A step of applying the resist composition according to any one of [1] to [3] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A method for producing a resist pattern, comprising a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

  According to the resist composition of the present invention, a high-resolution resist pattern can be produced.

The term "(meth) acrylic monomer" as used herein means at least one monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " . Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

<Resist composition>
The resist composition of the present invention comprises:
(A) a resin containing a structural unit represented by formula (I) and a structural unit having an acid labile group (hereinafter sometimes referred to as “resin (A)”), and (B) an acid having an acid labile group Contains a generator.
It is preferable that the resist composition of the present invention further contains a solvent (E).

<Resin (A)>
The resin (A) has a structural unit represented by the formula (I) and a structural unit having an acid labile group, and may further have a structural unit having no acid labile group.
In the present specification, the “acid labile group” is 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. Means.

［式（Ｉ）中、
Ｒ¹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。
Ａ¹は、単結合、^＊−Ａ²−Ｏ−、^＊−Ａ²−ＣＯ−Ｏ−、^＊−Ａ²−ＣＯ−Ｏ−Ａ³−ＣＯ−Ｏ−又は^＊−Ａ²−Ｏ−ＣＯ−Ａ³−Ｏ−を表す。
＊は−Ｏ−との結合手を表す。
Ａ²及びＡ³は、それぞれ独立に、炭素数１〜６のアルカンジイル基を表す。］ <Structural unit represented by formula (I)>
The resin (A) has a structural unit represented by the formula (I) (hereinafter sometimes referred to as “structural unit (I)”).

[In the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —O—, ^* —A ² —CO—O—, ^* —A ² —CO—O—A ³ —CO—O—, or ^* —A ² —O—CO. -A ³ represents a -O-.
* Represents a bond with -O-.
A ² and A ³ each independently represents an alkanediyl group having 1 to 6 carbon atoms. ]

Examples of the halogen atom for R ¹ in formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. , Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom for R ¹ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. Examples include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of the alkanediyl group of A ² and A ³ 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 and hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples include 4-diyl group and 2-methylbutane-1,4-diyl group.
A ¹ is preferably a single bond or ^* —A ² —CO—O—, more preferably a single bond, —CH ₂ —CO—O— or —C ₂ H ₄ —CO—O—. .

Specific examples of the structural unit (I) are shown below.

Regarding the structural units represented by formula (aa-1) to formula (aa-6), structural units in which the methyl group corresponding to R ¹ is replaced with a hydrogen atom are also exemplified as specific examples of structural unit (I). Can do.

［式（Ｉ’）中、Ｒ¹及びＡ¹は上記と同じ意味を表す。］ The structural unit (I) is derived from a compound represented by the formula (I ′) (hereinafter sometimes referred to as “compound (I ′)”).

[In formula (I ′), R ¹ and A ¹ represent the same meaning as described above. ]

［式中、Ｒ¹は上記と同じ意味を表す。］ The compound represented by the formula (I′-1), wherein A ¹ in the compound (I ′) is * —CH ₂ —CO—O— (* represents a bond to —CO—O—), The compound represented by formula (I′-1-a) can be obtained by reacting the compound represented by formula (I′-1-b) in a solvent. Here, methylene chloride, tetrahydrofuran, acetonitrile, and the like are preferably used as the solvent.

[Wherein R ¹ represents the same meaning as described above. ]

［式中、Ｒ¹は上記と同じ意味を表す。］
この反応においては、ジシクロヘキシルカルボジイミドなどの縮合触媒を用いることもできる。 The compound represented by the formula (I′-1-a) is obtained by reacting the compound represented by the formula (I′-1-c) with the compound represented by the formula (I′-1-d). Can be obtained. This reaction is preferably carried out in the presence of a solvent such as methylene chloride, tetrahydrofuran and acetonitrile.

[Wherein R ¹ represents the same meaning as described above. ]
In this reaction, a condensation catalyst such as dicyclohexylcarbodiimide can also be used.

式（Ｉ’−１−ｃ）で表される化合物として、目的の化合物（Ｉ’）に対応したＡ¹及びＲ¹を有する化合物を用いれば、目的の化合物（Ｉ’）を得ることができる。式（Ｉ’−１−ｃ）及び式（Ｉ’−１−ｄ）で表される化合物は、市場から容易に入手できる。 Examples of the compound represented by the formula (I′-1-c) include the following compounds.

If a compound having A ¹ and R ¹ corresponding to the target compound (I ′) is used as the compound represented by the formula (I′-1-c), the target compound (I ′) can be obtained. . The compounds represented by formula (I′-1-c) and formula (I′-1-d) are easily available from the market.

式（ａａ’−１）〜式（ａａ’−６）でそれぞれ表される化合物（Ｉ’）について、Ｒ¹に相当するメチル基が水素原子に置き換わった構造単位も、化合物（Ｉ’）の具体例として挙げることができる。 Examples of compound (I ′) include the following.

Regarding the compound (I ′) represented by each of the formulas (aa′-1) to (aa′-6), the structural unit in which the methyl group corresponding to R ¹ is replaced with a hydrogen atom is also represented by the compound (I ′). Specific examples can be given.

  The content of the structural unit (I) is preferably 1 to 80 mol%, more preferably 2 to 75 mol%, still more preferably 3 to 70 mol% with respect to all the structural units of the resin (A). %, Particularly preferably 5 to 65 mol%.

<Structural unit having acid labile group>
A structural unit having an acid labile group (hereinafter sometimes referred to as “acid labile structural unit”) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “acid labile monomer (a1)”). .
Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

［式（１）中、Ｒ^a1、Ｒ^a2及びＲ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数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は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。＊は結合手を表す。］

［式（２）中、Ｒ^a1'及びＲ^a2'は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a3'は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a2'及びＲ^a3'は互いに結合して炭素数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。］

[In the formula (1), R ^a1 , R ^a2 and 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 thereof. R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

[In Formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent hydrocarbon group. May be replaced by -O- or -S-. ]

アルキル基で置換された脂環式炭化水素基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基等が挙げられる。
式（１）においては、Ｒ^a1、Ｒ^a2及びＲ^a3で表される脂環式炭化水素基は、好ましくは炭素数３〜１６である。 ^Examples of the alkyl group represented by R ^a1 , R ^a2 and R ^a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group represented by R ^a1 , R ^a2 and R ^a3 may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group is an alkyl group. May be substituted. In this case, the carbon number of the alicyclic hydrocarbon group is 20 or less including the carbon number of the alkyl group.
Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond).

Examples of the alicyclic hydrocarbon group substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
In the formula (1), the alicyclic hydrocarbon group represented by R ^a1 , R ^a2 and R ^a3 preferably has 3 to 16 carbon atoms.

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 hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. In each formula, R ^a3 has the same meaning as described above, and * represents a bond to —O—.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and a carbon atom 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).

Examples of the hydrocarbon group represented by R ^{a1 ′} , R ^{a2 ′} and R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained 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 hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include a divalent aliphatic hydrocarbon group.

In Formula (2), it is preferable that at least one of R ^{a1 ′} and R ^{a2 ′} is a hydrogen atom.
Specific examples of the group represented by the formula (2) include the following groups. * Represents a bond.

  The acid labile 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 composition (A) having a structural unit derived from an acid labile 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. it can.

  As a structural unit derived from a (meth) acrylic monomer having a group represented by formula (1), preferably a structural unit represented by formula (a1-1) or a structure represented by formula (a1-2) Units are listed. These may be contained independently and 2 or more types may be contained. In this specification, the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) are represented by the structural unit (a1-1) and the structural unit (a1-2), respectively. The monomer that derives the structural unit (a1-1) and the monomer that derives the structural unit (a1-2) may be referred to as a monomer (a1-1) and a monomer (a1-2), respectively.

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜１８の脂環式炭化水素基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］

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

L ^a1 and L ^a2 are preferably —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, more preferably —O—. k1 is preferably an integer of 1 to 4, more preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
The alkyl group for R ^a6 and R ^a7 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group for R ^a6 and R ^a7 may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. . In this case, the carbon number of the alicyclic hydrocarbon group is 10 or less including the carbon number of the alkyl group. Specific examples include the same groups as those represented by R ^a1 , R ^a2 and R ^a3 in formula (1).
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 a monomer (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned. Among these, a monomer represented by any one of formula (a1-1-1) to formula (a1-1-8) is preferable, and any one of formula (a1-1-1) to formula (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, and 1-ethylcycloheptan-1-yl (meth). Examples include acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, and 1-isopropylcyclopentan-1-yl (meth) acrylate. Monomers represented by formula (a1-2-1) to formula (a1-2-12) are preferred, and are represented by formula (a1-2-3), formula (a1-2-4), formula (a1-2-9) Or a monomer represented by formula (a1-2-10) is more preferred, and a monomer represented by formula (a1-2-3) or formula (a1-2-9) is more preferred.

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

式（ａ１−５）中、
Ｒ³¹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］_k4−ＣＯ−Ｌ^a34−基を表す。ここで、ｋ４は１〜４の整数を表す。＊は、Ｌ^a31との結合手を表す。
Ｌ^a31、Ｌ^a32、Ｌ^a33及びＬ^a34は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。 As another acid labile monomer (a1), for example, a monomer represented by formula (a1-5) which is a (meth) acrylic monomer having an acid labile group (hereinafter referred to as “monomer (a1-5)”) May be used).

In formula (a1-5),
R ³¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or a * — [CH ₂ ] _k4 —CO—L ^a34 — group. Here, k4 represents an integer of 1 to 4. * Represents a bond with L ^a31 .
L ^a31 , L ^a32 , L ^a33 and L ^a34 each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3.

In formula (a1-5), R ³¹ is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ^a31 is preferably an oxygen atom.
One of L ^a32 and L ^a33 is preferably an oxygen atom and the other is a sulfur atom.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

Examples of the monomer (a1-5) include the following monomers.

  When the resin (A) has a structural unit derived from the monomer (a1-5), the content is preferably from 1 to 50 mol%, preferably from 3 to 45 mol, based on all structural units of the resin (A). % Is more preferable, and 5 to 40 mol% is more preferable.

<Structural unit without acid labile group>
The structural unit having no acid labile group (hereinafter sometimes referred to as “acid stable structural unit”) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “acid stable monomer”).
As an acid stable monomer, Preferably, the monomer which has a hydroxyl group or a lactone ring is mentioned. Acid stable monomer having a hydroxy group (hereinafter sometimes referred to as “acid stable monomer having a hydroxy group (a2)”) or acid stable monomer having a lactone ring (hereinafter referred to as “acid stable monomer having a lactone ring (a3)”) If a resin having a structural unit derived from (sometimes) is used, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Acid-stable monomer having a hydroxy group (a2)>
When the resist composition is used for high energy beam exposure such as KrF excimer laser exposure (248 nm), electron beam or EUV (ultra-ultraviolet light), the acid-stable monomer (a2) having a hydroxy group is preferably a hydroxystyrene. An acid stable monomer having a certain phenolic hydroxy group is used. When using short-wavelength ArF excimer laser exposure (193 nm) or the like, the acid-stable monomer (a2) having a hydroxy group is preferably an acid-stable monomer having a hydroxyadamantyl group represented by the formula (a2-1). use. The acid-stable monomer (a2) having a hydroxy group may be used alone or in combination of two or more.

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

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

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

As an acid stable monomer (a2-1) which has a hydroxyadamantyl group, the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A monomer represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferable, and represented by any one of formula (a2-1-1) to formula (a2-1-4). The monomer represented by Formula (a2-1-1) or Formula (a2-1-3) is more preferable.

  When the resin (A) includes a structural unit derived from the monomer represented by the formula (a2-1), the content is usually 1 to 45 mol% with respect to all the structural units of the resin (A). , Preferably it is 1-40 mol%, More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

<Acid-stable monomer having a lactone ring (a3)>
The lactone ring possessed by the acid stable monomer (a3) may be, for example, a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and a monocyclic lactone ring and other rings The condensed ring may be used. Among these lactone rings, a γ-butyrolactone ring or a condensed ring of γ-butyrolactone ring and another ring is preferable.

  The acid-stable monomer (a3) having a lactone ring is preferably represented by the formula (a3-1), the formula (a3-2) or the formula (a3-3). These 1 type may be used independently and may use 2 or more types together.

式（ａ３−１）、式（ａ３−２）及び式（ａ３−３）中、
Ｌ^a4、Ｌ^a5及びＬ^a6は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−を表す。
ｋ３は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a18、Ｒ^a19及びＲ^a20は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a21は、炭素数１〜４のアルキル基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a22及びＲ^a23は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４のアルキル基を表す。
ｑ１及びｒ１は、それぞれ独立に０〜３の整数を表す。ｐ１が２以上のとき、複数のＲ^a21は同一又は相異なり、ｑ１が２以上のとき、複数のＲ^a22は同一又は相異なり、ｒ１が２以上のとき、複数のＲ^a23は、同一又は相異なる。

In formula (a3-1), formula (a3-2) and formula (a3-3),
L ^a4 , L ^a5 and L ^a6 each independently represent —O— or ^* —O— (CH ₂ ) _k3 —CO—O—.
k3 represents an integer of 1 to 7. * Represents a bond with -CO-.
R ^a18 , R ^a19 and R ^a20 each independently represents a hydrogen atom or a methyl group.
R ^a21 represents an alkyl group having 1 to 4 carbon atoms.
p1 represents an integer of 0 to 5.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group, or an alkyl group having 1 to 4 carbon atoms.
q1 and r1 each independently represents an integer of 0 to 3. When p1 is 2 or more, a plurality of R ^a21 are the same or different, when q1 is 2 or more, a plurality of R ^a22 are the same or different, and when r1 is 2 or more, a plurality of R ^a23 are the same or different Different.

^Examples of the alkyl group for R ^a21 , R ^a22 and R ^a23 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a sec-butyl group.

In formula (a3-1), formula (a3-2) and formula (a3-3), L ^a4 , L ^a5 and L ^a6 are each independently —O— or ^* —O— (CH ₂ ) _k3 —. CO-O- is preferable, and -O- is more preferable. k3 is preferably an integer of 1 to 4, more preferably 1.
R ^a18 , R ^a19 , R ^a20 and 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 0 to 2, more preferably 0 or 1.

  Examples of the acid-stable monomer (a3) having a lactone ring include monomers described in JP 2010-204646 A. In the following formulas (a3-1-1) to (a3-1-4), (a3-2-1) to (a3-2-4), (a3-3-1) to (a3-3-4) Monomers represented by the following formulas (a3-1-1) to (a3-1-2) and (a3-2-3) to (a3-2-4) are more preferred, A monomer represented by formula (a3-1-1) or (a3-2-3) is more preferable.

  When the resin (A) includes a structural unit derived from the acid-stable monomer (a3) having a lactone ring, the content is usually 5 to 70 mol% with respect to all the structural units of the resin (A), Preferably it is 10-65 mol%, More preferably, it is 10-60 mol%.

When the resin (A) is a resin composed only of the structural unit (I) and the acid labile structural unit, these contents are respectively relative to the total structural unit of the resin (A),
Structural unit (I); 1 to 80 mol%
Acid-labile structural unit; 20-99 mol%
Is preferred,
Structural unit (I); 5-65 mol%
Acid labile structural unit; 35-95 mol%
Is more preferable.

When the resin (A) is a resin composed of the structural unit (I), the acid labile structural unit, and the acid stable structural unit, these content rates are respectively based on the total structural units of the resin (A),
Structural unit (I); 1 to 80 mol%
Acid-labile structural unit; 17-96 mol%
Acid stable structural unit; 3-82 mol%
Is preferred,
Structural unit (I); 2-75 mol%
Acid-labile structural unit; 20 to 93 mol%
Acid stable structural unit; 5-78 mol%
Is more preferred,
Structural unit (I); 5-65 mol%
Acid-labile structural unit; 30 to 90 mol%
Acid stable structural unit; 5 to 65 mol%
Is more preferable.

  Resin (A) is a structural unit derived from a monomer having an adamantyl group (particularly a structural unit represented by formula (a1-1)), preferably a total of structural units derived from an acid labile monomer (a1). It is preferable to contain 15 mol% or more with respect to the quantity. When the ratio of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

The resin (A) is preferably a resin comprising a structural unit (I), an acid labile structural unit, and an acid stable structural unit, that is, the compound (I ′), the acid labile monomer (a1), and an acid stable It is a copolymer with a monomer.
In this copolymer, the acid labile structural unit is preferably at least one of the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), more preferably. Is a structural unit (a1-1).
The acid stable structural unit is preferably at least one of a structural unit derived from the acid stable monomer (a2) and a structural unit derived from the acid stable monomer (a3). The acid stable monomer (a2) is preferably a monomer represented by the formula (a2-1). The acid stable monomer (a3) is preferably at least one of an acid stable monomer represented by the formula (a3-1) and an acid stable monomer represented by the formula (a3-2).

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do.
The weight average molecular weight of the resin (A) is preferably 2,500 or more (more preferably 3,000 or more, more preferably 4,000 or more), 50,000 or less (more preferably 30,000 or less, and further preferably 15,000 or less).

  The content of the resin (A) is preferably 80% by mass or more and 99% by mass or less in the solid content of the resist composition. In the present specification, the “solid content in the composition” means the total amount of components excluding the solvent (E) from the total amount of the resist composition. The solid content in the composition and the content of the resin (A) relative thereto can be measured, for example, by a known analysis means such as liquid chromatography or gas chromatography.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Examples of such a resin include a resin comprising a structural unit derived from an acid labile monomer (a1), a structural unit derived from an acid stable monomer, or a structural unit derived from a known monomer used in the field. Can be mentioned.
When the resist composition of this invention contains resin other than resin (A), these content rates are 0.1-50 mass% normally with respect to the total amount of resin, Preferably 0.5-30 It is mass%, More preferably, it is 1-20 mass%.

［式（ＩＩ−０）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ⁰¹は、単結合又は置換基を有してもよい炭素数１〜２０の２価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
Ｒ⁴は、炭素数１〜１２の炭化水素基を表す。
環Ｗ¹は、置換基を有していてもよい炭素数３〜１８の炭化水素環を表す。
Ｚ⁺は、有機カチオンを表す。］ <Acid generator (B)>
The acid generator (B) has an acid labile group. Here, as described above, the “acid labile group” is a group that forms a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid, for example, Examples include the group represented by the above formula (1) and the group represented by the formula (2). Examples of the acid generator (B) include the acid generators described in JP-A 2009-145408, JP-A 2009-229603, and JP-A 2010-111660, and Formula (II-0). And salts represented by the following (hereinafter sometimes referred to as “acid generator (II-0)”).

[In the formula (II-0),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ⁰¹ represents a C 1-20 divalent hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is —CO— or —O—. It may be replaced with.
R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms.
Ring W ¹ represents a hydrocarbon ring optionally having from 3 to 18 carbon atoms which may have a substituent.
Z ⁺ represents an organic cation. ]

In the formula (II-0), examples of the perfluoroalkyl group of Q ¹ and Q ² include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro group. Examples thereof include a tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group.
Q ¹ and Q ² are preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

［式（ＩＩ−０−Ｌ⁰¹）中、
Ｌ⁰²及びＬ⁰³は、それぞれ独立に、炭素数１〜８のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
環Ｗ⁰²は、炭素数３〜１２の飽和炭化水素環を表し、該飽和炭化水素環に含まれる−ＣＨ₂−は−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
ｖは、０〜２の整数を表す。
Ｒ⁵は、炭素数１〜６のアルキル基を表す。
ｗは、０〜２の整数を表す。ｗが２である場合、複数のＲ⁵は同じであっても異なっていてもよい。
ただし、Ｌ⁰²及びＬ⁰³のアルカンジイル基に含まれる炭素原子の数と、環Ｗ⁰²の飽和炭化水素環に含まれる炭素原子の数と、Ｒ⁵のアルキル基に含まれる炭素原子の総数との合計は、２０以下である。］ Examples of the divalent hydrocarbon group which may have a substituent in L ⁰¹ include an alkanediyl group or a divalent group represented by the formula (II-0-L ⁰¹ ).

[In the formula (II-0-L ⁰¹ )
L ⁰² and L ⁰³ each independently represent an alkanediyl group having 1 to 8 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—.
Ring W ⁰² represents a saturated hydrocarbon ring having 3 to 12 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon ring may be replaced by —CO— or —O—.
v represents an integer of 0 to 2.
R ⁵ represents an alkyl group having 1 to 6 carbon atoms.
w represents an integer of 0 to 2. When w is 2, the plurality of R ⁵ may be the same or different.
Provided that the number of carbon atoms contained in the alkanediyl group of L ⁰² and L ⁰³ , the number of carbon atoms contained in the saturated hydrocarbon ring of ring W ⁰² , and the total number of carbon atoms contained in the alkyl group of R ⁵ Is 20 or less. ]

Examples of the alkanediyl group of L ⁰¹ , L ⁰² and L ⁰³ 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- Linear alkanediyl groups such as 1,5-diyl group and hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples thereof include branched alkanediyl groups such as methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.
In particular, L ⁰² represents ^* —CO—O—L ⁰⁴ —, ^* —CO—O—L ⁰⁵ —O— or ^* —CO—O—L ⁰⁶ —CO—O— (L ⁰⁴ represents a single bond or carbon Represents an alkanediyl group having 1 to 6 carbon atoms, L ⁰⁵ represents an alkanediyl group having 1 to 5 carbon atoms, L ⁰⁶ represents an alkanediyl group having 1 to 4 carbon atoms, and * represents —C (Q ¹ ) (Represents a bond with (Q ² ) —).

L ⁰³ represents ^* —O—L ⁰⁷ — or ^* —CO—O—L ⁰⁸ — (L ⁰⁷ represents an alkanediyl group having 1 to 7 carbon atoms, and L ⁰⁸ represents an alkanediyl having 1 to 6 carbon atoms. Represents a group, and * represents a bond to the ring W ⁰² .

The saturated hydrocarbon ring of the ring W ⁰² refers to a ring composed of only carbon and hydrogen that does not contain an unsaturated bond. Examples of the saturated hydrocarbon ring of the ring W ⁰² include a cyclohexane ring and an adamantane ring, and an adamantane ring is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl grave, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. C1-C4 alkyl group is preferable, C1-C2 alkyl group is more preferable, and a methyl group is especially preferable.

［式（ＩＩ−０−Ａ）中、Ｗ⁰²、Ｒ⁵、ｖ及びｗは、上記と同じ意味を表す。
＊は、結合手を表す。］ Examples of the divalent group represented by the formula (II-0-A) include a divalent group represented by the following.

[In the formula (II-0-A), W ⁰² , R ⁵ , v and w represent the same meaning as described above.
* Represents a bond. ]

As described above, the hydrocarbon group of R ⁴ includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic type, and a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable. R ⁴ is particularly preferably an alkyl group having 1 to 6 carbon atoms.

As the hydrocarbon ring of the ring W ^1, a hydrocarbon ring having 3 to 12 carbon atoms is preferable. Of these, a saturated hydrocarbon ring is more preferable, and a cyclohexane ring and an adamantane ring are more preferable. As the group represented by the formula (II-A), the following groups are more preferable. * Represents a bond with -O-.

Examples of the substituent hydrocarbon ring having in the ring W ^1, in addition to R ^4, halogen atom or hydroxy group optionally substituted alkyl group having 1 to 6 carbon atoms, substituted with a halogen atom or a hydroxyl group Examples thereof include an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, and groups represented by formulas (II-1) to (II-4). Among them, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, an alkoxy group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, a hydroxy group, a formula (II-1) to a formula The group represented by (II-4) is preferable, and further, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, and formulas (II-1) to (II-4) The group represented is more preferred. * Represents a bond to ring W ¹ .
In particular, in the substituent of the hydrocarbon ring in the ring W ^1, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. preferable.

［式（ＩＩ−１）中、Ａ²は、炭素数１〜６のアルカンジイル基を表す。
Ｒ⁵は、炭素数１〜６のアルキル基を表す。］

［式（ＩＩ−２）中、Ｒ⁶、Ｒ⁷及びＲ⁸は、それぞれ独立に、炭素数１〜６のアルキル基を表す。］

［式（ＩＩ−３）中、Ｒ⁹、Ｒ¹⁰及びＲ¹¹は、それぞれ独立に、炭素数１〜６のアルキル基を表す。］

［式（ＩＩ−４）中、
Ｌ³は、炭素数１〜１０のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ₂−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
環Ｗ³は、炭素数３〜１８の飽和炭化水素環を表し、該飽和炭化水素環に含まれる−ＣＨ₂−は、−ＣＯ−又は−Ｏ−で置き換わっていてもよい。
Ｒ¹⁴は、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１〜６のアルコキシカルボニル基、ヒドロキシ基、炭素数１〜６のヒドロキシアルキル基又は炭素数１〜６のヒドロキシアルコキシ基を表す。
ｔは、０〜３の整数を表す。ｔが２又は３である場合、複数のＲ¹⁴は同一又は相異なる。］

[In Formula (II-1), A ² represents an alkanediyl group having 1 to 6 carbon atoms.
R ⁵ represents an alkyl group having 1 to 6 carbon atoms. ]

[In Formula (II-2), R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 6 carbon atoms. ]

[In Formula (II-3), R ⁹ , R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 6 carbon atoms. ]

[In the formula (II-4),
L ³ represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—.
Ring W ³ represents a saturated hydrocarbon ring having ^{3 to} 18 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon ring may be replaced by —CO— or —O—.
R ¹⁴ is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Represents a hydroxyalkoxy group.
t represents an integer of 0 to 3. When t is 2 or 3, the plurality of R ¹⁴ are the same or different. ]

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.
As the halogen atom-substituted alkyl group and the halogen atom-substituted alkoxy group, an alkyl group and an alkoxy group substituted with a fluorine atom are preferable.
Examples of the hydroxy group-substituted alkyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
Examples of the hydroxy group-substituted alkoxy group include a hydroxymethoxy group, a hydroxyethoxy group, a hydroxypropoxy group, and the like.
As a saturated hydrocarbon ring, the thing similar to the alicyclic hydrocarbon ring mentioned above is mentioned.
Examples of the alkoxycarbonyl group include groups in which a carbonyl group is bonded to an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group.

L ³ in the formula (II-4) represents ^* —O—L ⁷ —CO—O—, ^* —O—L ⁸ —CO—O—L ⁹ —O—, ^* —CO—O—L ¹⁰ —CO. -O-, ^* -O-CO-L ¹¹ -O- or ^* -OL ¹² -O- is preferred, ^* -O-L ⁷ -CO-O- or ^* -CO-OL ¹⁰ -CO-O-are more _{^{preferred, * -O-CH 2 -CO-}} O- or _{^{* -O-CH 2 -CO-O}} -C 2 H 4 -O- is particularly preferred. Here, L < ⁷ > -L < ¹² > represents a C1-C8 alkanediyl group each independently, and * represents the bond with ring W < ¹ >.
Examples of the saturated hydrocarbon ring of ring W ³ include the same as the above-described alicyclic hydrocarbon ring.

Examples of the group represented by the formula (II-1) include the following groups.

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

Examples of the group represented by the formula (II-3) include the following groups.

式（ＩＩ−４）で表される基のなかでも、式（ＩＩ−４−１）及び式（ＩＩ−４−２）で表される基が好ましい。 Examples of the group represented by the formula (II-4) include the following groups.

Of the groups represented by the formula (II-4), groups represented by the formula (II-4-1) and the formula (II-4-2) are preferable.

［式（ＩＩ）中、
Ｑ¹、Ｑ²、Ｒ⁴、環Ｗ¹及びＺ⁺は、式（ＩＩ−０）と同義である。
Ｌ¹は、単結合又は炭素数１〜１０のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ₂−は−ＣＯ−又は−Ｏ−で置き換わっていてもよい。］ Among these, L ⁰¹ is preferably a single bond or an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —CO— or —O—. . That is, the salt represented by the formula (II-0) is preferably a salt represented by the formula (II).

[In the formula (II),
^{Q 1, Q 2, R 4} , + ring W ¹ and Z are as defined for formula (II-0).
L ¹ represents a single bond or an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —CO— or —O—. ]

Examples of the alkanediyl group of L ¹ include the same alkanediyl groups as described above.

The group in which —CH ₂ — in the alkanediyl group of L ¹ is replaced by —O— or —CO— is, for example, a group represented by any one of formulas (b1-) to (b1-6) (b1- 1) to (b1-6) are described in accordance with the formula (II) on the left and right, and are bonded to C (Q ¹ ) (Q ² ) — on the left side, and two bonds represented by * Combine with -CO- on the right side of the hand. The same applies to specific examples of the following formulas (b1-1) to (b1-6).

［式中、Ｌ^b2〜Ｌ^b13は、それぞれ独立に、炭素数１〜８のアルカンジイル基を表す。］

[Wherein, L ^{b2 to} L ^b13 each independently represents an alkanediyl group having 1 to 8 carbon atoms. ]

Examples of the divalent group represented by the formula (b1-1) include the following.

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

Examples of the divalent group represented by the formula (b1-3) include the following.

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

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

Ｌ¹としては、なかでも、好ましくは式（ｂ１−１）〜式（ｂ１−４）のいずれか、より好ましくは式（ｂ１−１）又は式（ｂ１−２）、さらに好ましくは、単結合又は^＊−ＣＯ−Ｏ−Ｌ¹¹−（Ｌ¹¹は炭素数１〜６のアルカンジイル基を表し、＊は−ＣＱ¹Ｑ²−との結合手を表す）である。 Examples of the divalent group represented by the formula (b1-6) include the following.

L ¹ is preferably any one of formula (b1-1) to formula (b1-4), more preferably formula (b1-1) or formula (b1-2), and even more preferably a single bond. Or ^* —CO—O—L ¹¹ — (L ¹¹ represents an alkanediyl group having 1 to 6 carbon atoms, and * represents a bond to —CQ ¹ Q ² —).

［式（ＩＩ−４ａ）中、Ｑ¹、Ｑ²、Ｌ¹、Ｒ⁴、環Ｗ¹、Ｌ³、環Ｗ³、Ｒ¹⁴、ｔ及びＺ⁺は、上記と同じ意味を表す。］ Furthermore, as the salt (II), a salt represented by the following formula (II-4a) is preferable.

[In formula (II-4a), Q ¹ , Q ² , L ¹ , R ⁴ , ring W ¹ , L ³ , ring W ³ , R ¹⁴ , t and Z ⁺ represent the same meaning as described above. ]

Examples of the salt represented by the formula (II-0) include the following salts. In the following formula, Z ⁺ has the same meaning as described above.

Examples of the organic cation (Z ⁺ ) contained in the salt represented by the formula (II) include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation. And preferably an organic sulfonium cation or an organic iodonium cation, and more preferably any of the following formulas (b2-1), (b2-2), (b2-3) and (b2-4) It is an organic cation represented by

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represents a hydrocarbon group having 1 to 36 carbon atoms, and this hydrocarbon group is an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an alicyclic group having 3 to 36 carbon atoms. A hydrocarbon group and an aromatic hydrocarbon group having 6 to 36 carbon atoms are preferred. 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 have a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms. R ^b4 and R ^b5 may be combined to form a ring containing a sulfur atom.
R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represents an integer of 0 to 5, and when m2 is 2 or more, the plurality of R ^b7 may be the same or different. When n2 is 2 or more, the plurality of R ^b8 are It 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, or R ^b9 and R ^{b10 taken} together Forms a ring containing a sulfur atom to which. The methylene group contained in the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
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 ^b11 and R ^b12 together form a ring containing —CH—CO— to which they are attached. The methylene group contained in the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^b12 represents 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, and hydrogen contained in the alkyl group The 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 aliphatic hydrocarbon group having 1 to 12 carbon atoms or 1 carbon atom. It may be substituted with an -12 alkoxy group, an alicyclic hydrocarbon group having 3-18 carbon atoms, or an alkylcarbonyloxy group having 1-12 carbon atoms.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents an oxygen atom or a sulfur atom.
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 is When r2 is 2 or more, a plurality of R ^b16 may be the same or different. When s2 is 2 or more, a plurality of R ^b17 may be the same or different, and t2 is 2 or more. Sometimes, the plurality of R ^b18 may be the same or different.

特に、Ｒ^b9〜Ｒ^b11の脂環式炭化水素基は、好ましくは炭素数３〜１８、より好ましくは炭素数４〜１２である。 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. Is mentioned. In particular, the alkyl group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
Examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an alicyclic hydrocarbon group include a 1- (adamantan-1-yl) alkane-1-yl group.
Examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include an aralkyl group, and specifically include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group. Groups and the like.
The alicyclic hydrocarbon group 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. And cycloalkyl groups such as cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

In particular, the alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

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.
As an aromatic hydrocarbon group, phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-methoxyphenyl group And aryl groups such as p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenylyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
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 and the alicyclic hydrocarbon having 3 to 18 carbon atoms Groups are preferred.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group, that is, an aralkyl group, include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

As the alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, heptyloxy group Octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
As an aromatic hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 4-methoxyphenyl group etc. are mentioned, for example.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
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 aliphatic hydrocarbon group represented by R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms, and in particular, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert group. -A butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group and the like are preferable.
The alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and in particular, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl. Group, cyclodecyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group and isobornyl group are preferable.
The aromatic hydrocarbon group for R ^b12 includes a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-cyclohexylphenyl group, a 4-methoxyphenyl group, a biphenylyl group, and A naphthyl group and the like are preferable.
^Examples of the alkyl group in which a hydrogen atom of R ^b12 is substituted with an aromatic hydrocarbon group, that is, an aralkyl group, include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.
Examples of the ring formed together with the sulfur atom to which R ^b9 and R ^b10 are bonded include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and 1,4-oxathian-4-ium. A ring etc. are mentioned.
Examples of the ring formed with —CH—CO— in which R ^b11 and R ^b12 are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable, the cation represented by the formula (b2-1-1) is more preferable, and the cation (b2-1) is more preferable. Are triphenylsulfonium cations (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cations (in formula (b2-1-1), v2 = w2 = 0, x2 = 1 And R ^b21 is a methyl group.) Or a tolylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl. Group.)

式（ｂ２−１−１）中、
Ｒ^b19〜Ｒ^b21は、それぞれ独立に、ハロゲン原子（より好ましくはフッ素原子）ヒドロキシ基、炭素数１〜１８の脂肪族炭化水素基、炭素数１〜１２のアルコキシ基又は炭素数３〜１８の脂環式炭化水素基を表す。また、Ｒ^b19〜Ｒ^b21から選ばれる２つが一緒になって硫黄原子を含む環を形成してもよい。
ｖ２、ｗ２及びｘ２は、それぞれ独立に、０〜５の整数（好ましくは０又は１）を表す。
ｖ２が２以上のとき、複数のＲ^b19は同一又は相異なり、ｗ２が２以上のとき、複数のＲ^b20は同一又は相異なり、ｘ２が２以上のとき、複数のＲ^b21は同一又は相異なる。

In formula (b2-1-1),
R ^{b19 to} R ^b21 are each independently a halogen atom (more preferably a fluorine atom) hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 3 to 18 carbon atoms. Represents an alicyclic hydrocarbon group. It is also possible that two selected from R ^b19 to R ^b21 together form a ring containing a sulfur atom.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, the plurality of R ^b19 are the same or different, when w2 is 2 or more, the plurality of R ^b20 are the same or different, and when x2 is 2 or more, the plurality of R ^b21 are the same or different. .

Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a carbon number of 1 to 12 Of the alkoxy group.

  Specific examples of the cation include those described in JP2010-204646A.

For example, the following cations are mentioned as a cation (b2-1-1).

カチオン（ｂ２−３）としては、以下のカチオンが挙げられる。

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

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

  The salt represented by the formula (II-0) is a combination of a sulfonate anion and an organic cation. A sulfonate anion and an organic cation can be arbitrarily combined. Specific examples of the salt represented by the formula (II-0) are shown in Table 1. In Table 1, the salt represented by the formula (b1-s-1) is represented as “(b1-s-1)” according to the formula number, and the formula (b2-c-1) Is represented as “(b2-c-1)” or the like according to the formula number.

More preferable acid generator (II-0) includes the following.

（Ｒ⁴は、炭素数１〜１２の炭化水素基を表し、Ｒ^4’は、水素原子又は炭素数１〜１１の炭化水素基を表す。） When the acid generator (II) has a group represented by the formula (IIa) as an acid labile group, the group represented by the formula (IIa) contained in the acid generator is A group that decomposes to form a carboxy group is preferred.
It can be confirmed whether the group represented by the formula (IIa) of such an acid generator is decomposed by the action of an acid and converted into a carboxy group by the following method.
For example, an acid generator having a group represented by the formula (IIa) is dissolved in a solvent, and after adding an acid, the group represented by the formula (IIa) is converted into a carboxy group and a vinyl compound by heating. Is done.
As the solvent, dimethylformamide is preferable.
As the acid, hydrochloric acid is preferred.

(R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ^{4 ′} represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms.)

式（ＩＩ−１−ｂ）で表される化合物は、特開２００８−１３５５１号公報に記載された方法で合成することができる。 The salt represented by the formula (II-0) can be produced, for example, by the following methods (a) to (f) and a method analogous thereto. In addition, the code | symbol in the following formulas is synonymous with the above unless there is particular notice.
(A) Among the salts represented by the formula (II), the salt represented by the formula (II-1A) in which L ¹ is a single bond is a compound represented by the formula (II-1-a); It can manufacture by making the compound represented by a formula (II-1-b) react under a base catalyst.
Examples of the solvent include chloroform. Examples of the base catalyst include lithium amide.

The compound represented by the formula (II-1-b) can be synthesized by the method described in JP-A-2008-13551.

(B) Among the salts represented by the formula (II), the salt represented by the formula (II-2A) in which L ¹ is —CO—O—CH ₂ — can be produced by the following method.
First, the compound represented by the formula (II-1-a) and the compound represented by the formula (II-2-c) are reacted in the presence of a basic catalyst to thereby produce the formula (II-2-d). ) Can be obtained. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.
Next, the salt represented by the formula (II-1-b) and the compound represented by the formula (II-2-d) are reacted in the presence of a base catalyst to represent the formula (II-2). A salt can be obtained. Examples of the solvent include chloroform. Examples of the base catalyst include lithium amide.

［式中、Ｘ¹及びＸ²は、それぞれ独立に、ハロゲン原子を表す。］
ハロゲン原子としては、塩素原子が好ましい。

[Wherein, X ¹ and X ² each independently represent a halogen atom. ]
As the halogen atom, a chlorine atom is preferable.

(C) Among the salts represented by the formula (II), L ¹ is a single bond, the substituent of the ring W ¹ is the formula (II-4), and L ³ is ^* —O—L ⁷ —. Compound (II-3A) which is CO—O— (* is a bond to ring W ¹ ) can be produced by the following method.

First, a compound represented by formula (b1-c) is obtained by reacting a compound represented by formula (b1-a) with a compound represented by formula (b1-b) under a basic catalyst. be able to. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

Next, the compound represented by the formula (b1-e) is obtained by reacting the compound represented by the formula (b1-c) with the compound represented by the formula (b1-d) in the presence of a catalyst. it can. Examples of the solvent include dimethylformamide. Examples of the catalyst include potassium carbonate and potassium iodide.

Furthermore, the salt represented by the formula (II-3A) can be obtained by reacting the compound represented by the formula (b1-e) with the salt represented by the formula (b1-f) under a catalyst. it can. The reaction may be performed in a solvent. Examples of the solvent include monochlorobenzene. Examples of the catalyst include sulfuric acid.
The salt represented by the formula (b1-f) can be synthesized by the method described in JP-A-2008-127367.

(D) As a salt represented by Formula (II-0), the manufacturing method of the salt represented by Formula (II-0A) is shown below, for example.

［Ｘ¹及びＸ²は、それぞれ独立に、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、塩素原子が好ましい。］ A compound represented by the formula (b1-c) by reacting a compound represented by the formula (II-0A-a) and a compound represented by the formula (II-0A-b) under a basic catalyst. Can be obtained. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include pyridine.

[X ¹ and X ² each independently represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. ]

Next, by reacting the compound represented by the formula (II-0A-c) and the compound represented by the formula (II-0A-d) under a catalyst, the compound represented by the formula (II-0A-e) is represented. Can be obtained. Examples of the solvent include dimethylformamide. Examples of the catalyst include potassium carbonate and potassium iodide.

Furthermore, by reacting the salt represented by the formula (II-0A-f) with the compound represented by the formula (II-0A-g), the salt represented by the formula (II-0A-h) Can be obtained.
The salt represented by the formula (II-0A-f) can be synthesized, for example, by the method described in JP2008-13551A.

Subsequently, the compound represented by the formula (II-0A-e) and the salt represented by the formula (II-0A-h) are reacted in a solvent to represent the compound represented by the formula (II-0A). Can be obtained. Examples of the solvent include acetonitrile.

(E) For example, a method for producing a salt represented by the formula (II-0B) is shown below.

First, a compound represented by the formula (II-0A-c) and a compound represented by the formula (II-0B-d) are reacted with each other under a catalyst, thereby being represented by the formula (II-0B-e). Can be obtained. Examples of the solvent include dimethylformamide. Examples of the catalyst include potassium carbonate and potassium iodide.

Next, the salt represented by the formula (II-0B-h) is reacted with the compound represented by the formula (II-0B-g) to react with the salt represented by the formula (II-0B-h). Can be obtained.
The salt represented by the formula (II-0B-f) can be synthesized, for example, by the method described in JP-A-2008-13551.

Furthermore, the compound represented by the formula (II-0B-e) and the salt represented by the formula (II-0B-h) are reacted in a solvent to represent the formula (II-0B). A salt can be obtained. Examples of the solvent include acetonitrile.

(F) The manufacturing method of the salt represented by Formula (II-0C) is shown below.

First, by reacting a compound represented by the formula (II-0C-a) and a compound represented by the formula (II-0C-b) under a basic catalyst, the formula (II-0C-c) The compounds represented can be obtained. Examples of the solvent include tetrahydrofuran. Examples of the base catalyst include dimethylaminopyridine.

Next, a compound represented by the formula (II-0C-d) can be obtained by intramolecular reaction of the compound represented by the formula (II-0C-c) in the presence of a catalyst. Examples of the solvent include chloroform. Examples of the catalyst include m-chloroperbenzoic acid.

Further, the compound represented by the formula (II-0C-d) and the salt represented by the formula (II-0A-f) are reacted in the catalyst to form a salt represented by the formula (II-0C). Can be obtained. Examples of the solvent include chloroform. Examples of the catalyst include lithium amide.

The salt represented by the formula (II-0) may be used alone or in combination of two or more kinds when used as an acid generator.
In addition to the salt represented by the formula (II-0) described above, the resist composition of the present invention includes salts known as acid generators other than the salt represented by the formula (II-0) (for example, A salt composed of an organic cation contained in the salt (II-0) and a known anion (anion other than the sulfonate anion contained in the salt (II-0)), and a sulfonate anion contained in the salt (II-0) and A known cation (such as a salt comprising a cation other than the organic cation contained in the salt (II-0)) may be contained as an acid generator.

  As an acid generator used together with the salt represented by a formula (II-0), what is each represented by a formula (B1-1)-a formula (B1-20) is mentioned, for example. Among them, those containing an arylsulfonium cation are preferable, and the formula (B1-1), formula (B1-2), formula (B1-3, formula (B1-6), formula (B1-7), formula (B1-11) A salt represented by formula (B1-12), formula (B1-13), formula (B1-14), formula (B1-18), formula (B1-19) or formula (B1-20), preferable.

In the resist composition of the present invention, when only the acid generator (B) is contained as the acid generator, the content of the acid generator (B) is preferably 1 mass with respect to 100 parts by mass of the resin (A). Part or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass or less).
When an acid generator other than the acid generator (B) is used in combination, the total amount of the acid generator and the acid generator (B) is preferably 1 with respect to 100 parts by mass of the resin (A). It is at least part by mass (more preferably at least 3 parts by mass), preferably at most 40 parts by mass (more preferably at most 35 parts by mass). In this case, the ratio (mass) of the content of the acid generator (B): other acid generator is, for example, 5:95 to 95: 5, preferably 10:90 to 90:10, more preferably 15: 85-85: 15.

<Solvent (E)>
The content of the solvent (E) is, for example, 90% by mass or more in the resist composition, preferably 92% by mass or more, more preferably 94% by mass or more, for example 99.9% by mass or less, preferably 99% by mass or less. 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 And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may contain 1 type independently, and may contain 2 or more types.

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The resist composition of the present invention may contain a basic compound (C) that acts as a quencher.
The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines. The basic compound (C) is preferably a compound represented by the formula (C1) to a compound represented by the formula (C8), more preferably a compound represented by the formula (C1-1). It is done.

［式（Ｃ１）中、Ｒ^c1、Ｒ^c2及びＲ^c3は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数５〜１０の脂環式炭化水素基又は炭素数６〜１０の芳香族炭化水素基を表し、該アルキル基及び該脂環式炭化水素基に含まれる水素原子は、ヒドロキシ基、アミノ基又は炭素数１〜６のアルコ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、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５〜１０の脂環式炭化水素又は炭素数６〜１０の芳香族炭化水素基で置換されていてもよい。］

[In formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 represents an aromatic hydrocarbon group, and the hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be substituted with a hydroxy group, an amino group or an alkoxy group having 1 to 6 carbon atoms, The hydrogen atom contained in the aromatic hydrocarbon group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. It may be substituted with a group hydrocarbon group. ]

［式（Ｃ１−１）中、Ｒ^c2及びＲ^c3は、上記と同じ意味を表す。
Ｒ^c4は、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５〜１０の脂環式炭化水素又は炭素数６〜１０の芳香族炭化水素基を表す。
ｍ３は０〜３の整数を表し、ｍ３が２以上のとき、複数のＲ^c4は同一又は相異なる。］

[In Formula (C1-1), R ^c2 and R ^c3 represent the same meaning as described above.
R ^c4 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
m3 represents an integer of 0 to 3, and when m3 is 2 or more, the plurality of R ^c4 are the same or different. ]

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、Ｒ^c5、Ｒ^c6、Ｒ^c7及びＲ^c8は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c9は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜６のアルカノイル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^c9は同一又は相異なる。］

[In Formula (C2), Formula (C3) and Formula (C4), R ^c5 , R ^c6 , R ^c7 and R ^c8 each independently represent the same meaning as R ^c1 .
R ^c9 represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of R ^c9 are the same or different. ]

［式（Ｃ５）及び式（Ｃ６）中、Ｒ^c10、Ｒ^c11、Ｒ^c12、Ｒ^c13及びＲ^c16は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c14、Ｒ^c15及びＲ^c17は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｏ３及びｐ３は、それぞれ独立に０〜３の整数を表し、ｏ３が２以上であるとき、複数のＲ^c14は同一又は相異なり、ｐ３が２以上であるとき、複数のＲ^c15は、同一又は相異なる。
Ｌ^c1は、炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

[In Formula (C5) and Formula (C6), R ^c10 , R ^c11 , R ^c12 , R ^c13 and R ^c16 each independently represent the same meaning as R ^c1 .
R ^c14 , R ^c15 and R ^c17 each independently represent the same meaning as R ^c4 .
o3 and p3 each independently represents an integer of 0 to 3, and when o3 is 2 or more, the plurality of R ^c14 are the same or different, and when p3 is 2 or more, the plurality of R ^c15 are the same or Different.
L ^c1 represents an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

［式（Ｃ７）及び式（Ｃ８）中、Ｒ^c18、Ｒ^c19及びＲ^c20は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｑ３、ｒ３及びｓ３は、それぞれ独立に０〜３の整数を表し、ｑ３が２以上であるとき、複数のＲ^c18は同一又は相異なり、ｒ３が２以上であるとき、複数のＲ^c19は同一又は相異なり、及びｓ３が２以上であるとき、複数のＲ^c20は同一又は相異なる。
Ｌ^c2は、単結合又は炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

Wherein (C7) and formula ^{(C8), R c18, R} c19 and R ^c20 in each occurrence independently represent the same meaning as R ^c4.
q3, r3 and s3 each independently represent an integer of 0 to 3, and when q3 is 2 or more, the plurality of R ^c18 are the same or different, and when r3 is 2 or more, the plurality of R ^c19 are the same. Or when different and when s3 is 2 or more, the plurality of R ^c20 are the same or different.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

In the formulas (C1) to (C8), examples of the alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, the alkoxy group, and the alkanediyl group are the same as those described above.
Examples of the alkanoyl group include acetyl group, 2-methylacetyl group, 2,2-dimethylacetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and 2,2-dimethylpropionyl group.

  Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N- Dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tri Pentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyl Hexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonyl Amine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2- Examples include diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and preferably diisopropyl. Piruanirin. Particularly preferred include 2,6-diisopropylaniline.

Examples of the compound represented by the formula (C2) include piperazine.
Examples of the compound represented by the formula (C3) include morpholine.
Examples of the compound represented by the formula (C4) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound represented by the formula (C5) include 2,2′-methylenebisaniline.
Examples of the compound represented by the formula (C6) include imidazole and 4-methylimidazole.
Examples of the compound represented by the formula (C7) include pyridine and 4-methylpyridine.
Examples of the compound represented by the formula (C8) include 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′-dipiconylamine, bipyridine and the like.

  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.

  The content of the basic compound (C) in the solid content of the resist composition is preferably about 0.01 to 5% by mass, more preferably about 0.01 to 3% by mass, and particularly preferably 0.8. It is about 01 to 1% by mass.

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

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A), an acid generator having an acid labile group (for example, an acid generator (II-0), etc.), a solvent (E) used as necessary, and an acid generator. It can prepare by mixing an agent (B), a basic compound (C), and another component (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature range from the range of 10-40 degreeC according to the kind etc. of resin, the solubility with respect to solvent (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) The process of heating the composition layer after exposure, (5) The process of developing the composition layer after a heating is included.

  Application of the resist composition onto the substrate can be performed 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.

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 to form a composition layer from which the solvent has been removed. The temperature in this case is preferably about 50 to 200 ° C., for example. The 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. At this time, exposure is usually performed through a mask corresponding to a required pattern. 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.

The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection group reaction. As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.
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.

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

In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

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

<Application>
The resist composition of the present invention is a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly a liquid. It is suitable as a resist composition for 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 structure of the compound was confirmed by MASS (LC: Agilent 1100 type, MASS: Agilent LC / MSD type or LC / MSD TOF type).
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 HXL-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)

式（Ｋ−１）で表される化合物３３．４８部、ジシクロヘキシルカルボジイミド２３．９３部及び塩化メチレン４０部を、反応器に仕込み、混合した。得られた混合物を０℃程度まで冷却した後、式（Ｋ−２）で表される化合物１８．８３部を加え、０℃程度のまま、１時間攪拌した。２３℃まで昇温し、さらに３０分間攪拌した。不溶物をろ過して除去し、得られたろ液を濃縮して、式（Ｋ−３）で表される化合物４４．２８部を得た。 Synthesis Example 1 (Synthesis of monomer (M-K))

33.48 parts of the compound represented by the formula (K-1), 23.93 parts of dicyclohexylcarbodiimide and 40 parts of methylene chloride were charged into a reactor and mixed. After cooling the obtained mixture to about 0 ° C., 18.83 parts of the compound represented by the formula (K-2) was added, and the mixture was stirred for about 1 hour while maintaining about 0 ° C. The temperature was raised to 23 ° C., and the mixture was further stirred for 30 minutes. Insoluble matters were removed by filtration, and the obtained filtrate was concentrated to obtain 44.28 parts of a compound represented by the formula (K-3).

前記のようにして得られた式（Ｋ−３）で表される化合物１９．４２部、式（Ｋ−４）で表される化合物１８．２２部及びアセトニトリル２００部を、反応器に仕込み、混合した。得られた混合物を５０℃で３時間攪拌した。得られた混合物を濃縮し、クロロホルム３００部及びイオン交換水１５０部を加え、分液操作により、有機層を回収した。回収された有機層をイオン交換水１５０部で水洗し、有機層を濃縮した。濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：酢酸エチル）することにより、式（Ｍ−Ｋ）で表される化合物１２．８９部を得た。
ＭＳ（質量分析）：３０８．１（分子イオンピーク）

A reactor was charged with 19.42 parts of the compound represented by the formula (K-3) obtained as described above, 18.22 parts of the compound represented by the formula (K-4) and 200 parts of acetonitrile. Mixed. The resulting mixture was stirred at 50 ° C. for 3 hours. The obtained mixture was concentrated, 300 parts of chloroform and 150 parts of ion-exchanged water were added, and the organic layer was recovered by a liquid separation operation. The recovered organic layer was washed with 150 parts of ion exchange water, and the organic layer was concentrated. The concentrate is subjected to column fractionation (column fractionation conditions stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd. developing solvent: ethyl acetate) to obtain 12.89 parts of a compound represented by the formula (M-K). It was.
MS (mass spectrometry): 308.1 (molecular ion peak)

式（ＩＩ４９−ａ）で表される化合物（商品名：ＨＡＤＭ、出光製）２６．４４部、ジオキサン８０．００部を仕込み、２３℃で攪拌下、水酸化ナトリウム４．４０部をイオン交換水８０．００部に溶解した水溶液を３０分かけて滴下し、９０℃で３６時間攪拌した。反応マスを冷却し、イオン交換水４００．００部、酢酸エチル５００．０部及び塩化ナトリウム２００．０部を添加し、攪拌し、分液を行った。得られた有機層に３Ｎ塩酸４００．０部を添加し、攪拌し、分液を行った。得られた有機層にイオン交換水４００．００部を添加し、攪拌し、分液を行った。この水洗を３回行った。回収された有機層を濃縮し、以下の条件でカラム分取することにより、式（ＩＩ４９−ｂ）で表される化合物７．８９部を得た。
展開媒体；シリカゲル６０−２００メッシュ；メルク社製
展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１（容量比） Synthesis Example 2: Synthesis of salt represented by formula (II-49)

A compound represented by the formula (II49-a) (trade name: HADM, manufactured by Idemitsu) 26.44 parts and dioxane 80.00 parts were charged, and under stirring at 23 ° C., 4.40 parts of sodium hydroxide was ion-exchanged water An aqueous solution dissolved in 80.00 parts was dropped over 30 minutes and stirred at 90 ° C. for 36 hours. The reaction mass was cooled, 400.00 parts of ion-exchanged water, 500.0 parts of ethyl acetate and 200.0 parts of sodium chloride were added, stirred, and separated. To the obtained organic layer, 400.0 parts of 3N hydrochloric acid was added, stirred, and separated. To the obtained organic layer, 400.00 parts of ion exchanged water was added, stirred, and separated. This washing with water was performed three times. The recovered organic layer was concentrated and fractionated in a column under the following conditions to obtain 7.89 parts of a compound represented by the formula (II49-b).
Developing medium; silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 1/1 (volume ratio)

A compound represented by the formula (II49-c) (trade name: manufactured by CANL Kuraray) (4.61 parts) and N, N′-dimethylformamide (25.00 parts) were charged and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 1.66 parts of potassium carbonate and 0.84 part of potassium iodide were charged and stirred at 50 ° C. for 1 hour. The obtained mixture was cooled to 40 ° C., and a solution prepared by dissolving 3.93 parts of the compound represented by the formula (II49-b) in 25.00 parts of N, N′-dimethylformamide was added dropwise over 1 hour. And stirred at 75 ° C. for 5 hours. The obtained mixture was cooled to 23 ° C., 60.00 parts of chloroform and 60.00 parts of 1N hydrochloric acid were added, and the mixture was stirred and separated. The collected organic layer was repeatedly washed with 60.00 parts of ion-exchanged water until the aqueous layer became neutral. The recovered organic layer was concentrated and fractionated in a column under the following conditions to obtain 2.24 parts of a compound represented by the formula (II49-d).
Developing medium; silica gel 60-200 mesh; made by Merck developing solvent: ethyl acetate

  A salt represented by the formula (II49-e) was synthesized by the method described in Example 1 of JP-A-2008-127367. 1.75 parts of a salt represented by the formula (II49-e), 40.00 parts of monochlorobenzene and 1.87 parts of a compound represented by the formula (II49-d) were charged and stirred at 23 ° C. for 30 minutes. 0.16 parts and 10.00 parts of molecular sieve (trade name: Molecular sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. The obtained reaction product was concentrated, charged with 100 parts of chloroform and 50 parts of ion-exchanged water, and stirred and separated. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 parts of activated carbon, stirred at 23 ° C. for 30 minutes, and filtered. The filtrate was concentrated. The resulting concentrate was dissolved by adding 20 parts of acetonitrile, concentrated, added with 20 parts of ethyl acetate and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 0.44 parts of a salt represented by the formula (II-49) as an oily substance.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (−) Spectrum): M ⁻ 547.2

Synthesis Example 3: Synthesis of salt represented by formula (II-41)

250 parts of 1,3-adamantanediol and 2000 parts of tetrahydrofuran were charged, stirred at room temperature, 142 parts of pyridine were charged, and the temperature was raised to 40 ° C. Further, a mixed solution of 254 parts of chloroacetyl chloride and 500 parts of tetrahydrofuran was added dropwise over 80 minutes. Then, it stirred at 40 degreeC for 8 hours, and temperature was lowered | hung to 5 degreeC. 1000 parts of ion-exchanged water cooled to 5 ° C. was added and stirred, and the aqueous layer was recovered by liquid separation. 600 parts of ethyl acetate was added to the recovered aqueous layer, and the organic layer was recovered by liquid separation. To the collected organic layer, 600 parts of a 10% potassium carbonate aqueous solution at 5 ° C. was added, washed, and separated to recover the organic layer. Further, 600 parts of ion-exchanged water was added to the recovered organic layer and washed with water, followed by liquid separation to recover the organic layer. This washing operation was repeated 3 times. The collected organic layer was concentrated and fractionated in a column under the following conditions to obtain 75 parts of the compound represented by the formula (II41-a).
Developing medium; silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 1/1 (volume ratio)

式（ＩＩ４１−ｂ）で表される化合物（商品名：ＨＡＤＭ、出光製）２６．４４部、ジオキサン８０．００部を仕込み、２３℃で攪拌下、水酸化ナトリウム４．４０部をイオン交換水８０．００部に溶解した水溶液を３０分かけて滴下し、９０℃で３６時間攪拌した。反応マスを冷却し、イオン交換水４００．００部、酢酸エチル５００．０部及び塩化ナトリウム２００．０部を添加し、攪拌し、分液を行った。得られた有機層に３Ｎ塩酸４００．０部を添加し、攪拌し、分液を行った。得られた有機層にイオン交換水４００．００部を添加し、攪拌し、分液を行った。この水洗を３回行った。回収された有機層を濃縮し、以下の条件でカラム分取することにより、式（ＩＩ４１−ｃ）で表される化合物７．８９部を得た。
展開媒体；シリカゲル６０−２００メッシュ；メルク社製
展開溶媒：ｎ−ヘプタン／酢酸エチル＝１／１（容量比）

A compound represented by formula (II41-b) (trade name: HADM, manufactured by Idemitsu) 26.44 parts and dioxane 80.00 parts were charged, and stirred at 23 ° C., 4.40 parts of sodium hydroxide was ion-exchanged water. An aqueous solution dissolved in 80.00 parts was dropped over 30 minutes and stirred at 90 ° C. for 36 hours. The reaction mass was cooled, 400.00 parts of ion-exchanged water, 500.0 parts of ethyl acetate and 200.0 parts of sodium chloride were added, stirred, and separated. To the obtained organic layer, 400.0 parts of 3N hydrochloric acid was added, stirred, and separated. To the obtained organic layer, 400.00 parts of ion exchanged water was added, stirred, and separated. This washing with water was performed three times. The recovered organic layer was concentrated and fractionated in a column under the following conditions to obtain 7.89 parts of a compound represented by the formula (II41-c).
Developing medium; silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 1/1 (volume ratio)

4.88 parts of the compound represented by the formula (II41-a) and 25.00 parts of N, N′-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 1.66 parts of potassium carbonate and 0.84 part of potassium iodide were charged and stirred at 50 ° C. for 1 hour. The obtained mixture was cooled to 40 ° C., and a solution prepared by dissolving 3.93 parts of the compound represented by the formula (II41-c) in 25.00 parts of N, N′-dimethylformamide was added dropwise over 1 hour. And stirred at 75 ° C. for 5 hours. The obtained mixture was cooled to 23 ° C., 60.00 parts of chloroform and 60.00 parts of 1N hydrochloric acid were added, and the mixture was stirred and separated. The collected organic layer was repeatedly washed with 60.00 parts of ion-exchanged water until the aqueous layer became neutral. The collected organic layer was concentrated and fractionated in a column under the following conditions to obtain 2.54 parts of a compound represented by the formula (II41-d).
Developing medium; silica gel 60-200 mesh; made by Merck developing solvent: ethyl acetate

  A salt represented by the formula (II41-e) was synthesized by the method described in Example 1 of JP2008-127367A. 2.19 parts of a salt represented by the formula (II41-e), 50.00 parts of monochlorobenzene and 2.43 parts of a compound represented by the formula (II41-d) were charged and stirred at 23 ° C. for 30 minutes. 0.20 parts and 10.00 parts of molecular sieve (trade name: Molecular sieve 4A, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by reflux dehydration at 130 ° C. for 3 hours. The obtained reaction product was concentrated, charged with 100 parts of chloroform and 50 parts of ion-exchanged water, and stirred and separated. Water washing was performed 3 times. The obtained organic layer was charged with 1.00 parts of activated carbon, stirred at 23 ° C. for 30 minutes, and filtered. The filtrate was concentrated. The resulting concentrate was dissolved by adding 20 parts of acetonitrile, concentrated, added with 20 parts of ethyl acetate and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 0.62 part of a salt represented by the formula (II-41) as an oily substance.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (−) Spectrum): M ⁻ 561.2

式（ＩＩ１−ａ）で表される塩４．９８部及びアセトニトリル２５．００部を仕込み、２３℃で３０分間攪拌した。その後、式（ＩＩ１−ｂ）で表される化合物２．１７部を添加し、７０℃で２時間攪拌し、式（ＩＩ１−ｃ）で表される化合物を含む溶液を得た。得られた式（ＩＩ１−ｃ）で表される化合物を含む溶液に、５０℃で、式（ＩＩ１−ｄ）で表される化合物１．８６部、クロロホルム１４．９１部及びアセトニトリル２．７９部の混合溶液を１時間かけて滴下し、さらに、５０℃で１２時間攪拌した。得られた反応物を濃縮した。得られた濃縮物に、クロロホルム４０部及び２％シュウ酸水２０部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。得られた有機層に、イオン交換水２０部を加え、２３℃で３０分間攪拌した。その後、静置し、分液して有機層を得た。この水洗の操作をさらに５回行った。得られた有機層に活性炭０．８０部を仕込み、２３℃で３０分間攪拌し、ろ過した。ろ液を濃縮し、得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル５０部を加えて攪拌した。得られた上澄液を除去し、濃縮した。得られた濃縮物をアセトニトリルに溶解し、濃縮することにより、式（ＩＩ−１）で表される塩５．２４部を得た。 Synthesis Example 4: Synthesis of salt represented by formula (II-1)

4.98 parts of the salt represented by the formula (II1-a) and 25.00 parts of acetonitrile were charged and stirred at 23 ° C. for 30 minutes. Thereafter, 2.17 parts of the compound represented by the formula (II1-b) was added, and the mixture was stirred at 70 ° C. for 2 hours to obtain a solution containing the compound represented by the formula (II1-c). To the obtained solution containing the compound represented by the formula (II1-c), at 50 ° C., 1.86 parts of the compound represented by the formula (II1-d), 14.91 parts of chloroform and 2.79 parts of acetonitrile. Was added dropwise over 1 hour, and the mixture was further stirred at 50 ° C. for 12 hours. The resulting reaction was concentrated. To the obtained concentrate, 40 parts of chloroform and 20 parts of 2% oxalic acid water were added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes. Then, it left still and liquid-separated and obtained the organic layer. This washing operation was further performed 5 times. The obtained organic layer was charged with 0.80 part of activated carbon, stirred at 23 ° C. for 30 minutes, and filtered. The filtrate was concentrated, and 50 parts of tert-butyl methyl ether was added to the resulting concentrate and stirred. The resulting supernatant was removed and concentrated. The obtained concentrate was dissolved in acetonitrile and concentrated to obtain 5.24 parts of the salt represented by the formula (II-1).

MASS (ESI (+) Spectrum): M ⁺ 263.1
^{MASS (ESI (-) Spectrum)} : M - 337.1

Synthesis Example 5: Synthesis of salt represented by formula (II-9)

  A flask equipped with a thermometer and a stirrer was charged with 5.78 parts of sodium hydride and 15.00 parts of tetrahydrofuran, and stirred at 0 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 11.00 parts of a compound represented by the formula (II9-a) (5-hydroxy-2-adamantanone, manufactured by Tokyo Chemical Industry) and 40.00 parts of tetrahydrofuran was added at 0 ° C. for 2 hours. And added at 0 ° C. for 1 hour. To the obtained mixture, 8.50 parts of methoxymethyl chloride was further added at 0 ° C. over 40 minutes, and the mixture was stirred at 0 ° C. for 2 hours. To the obtained mixture, 55.00 parts of ion-exchanged water and 220.00 parts of ethyl acetate were added, and liquid separation was performed to recover the organic layer. To the recovered organic layer, 55.00 parts of ion exchange water was added, and liquid separation was performed to recover the organic layer. The recovered organic layer was concentrated to obtain 14.03 parts of a compound represented by the formula (II9-b).

To a flask equipped with a thermometer and a stirrer, 6.00 parts of tetrahydrofuran, 1.67 parts of lithium chloride and 0.41 parts of zinc chloride were added and stirred at room temperature for 30 minutes. To the obtained mixture, 40.76 ml of ethylmagnesium chloride was added at 23 ° C. over 1 hour, then cooled to 0 ° C., and 6.00 parts of the compound represented by the formula (II9-b) and tetrahydrofuran 12.00 were added. Part of the mixed solution was added over 1 hour, and the mixture was further stirred at 0 ° C. for 30 minutes. To the obtained mixture, 1.60 parts of acetic acid was added and stirred for 30 minutes. After concentrating the obtained mixture, 36.00 parts of ethyl acetate and 12.00 parts of a saturated aqueous ammonium chloride solution were added, and liquid separation was performed to recover the organic layer. To the recovered organic layer, 12.00 parts of ion-exchanged water was added, and liquid separation was performed to recover the organic layer. The washing operation was performed 3 times. To the collected organic layer, 1.00 part of magnesium sulfate was added, stirred and filtered. The collected filtrate layer was concentrated and fractionated in a column under the following conditions to obtain 5.00 parts of a compound represented by the formula (II9-c).
Developing medium; silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 1/1 (volume ratio)

  2. 5.00 parts of a compound represented by the formula (II9-d) obtained by the method described in JP-A-2008-13551, 30.00 parts of chloroform, a compound represented by the formula (II9-c) 12 parts, molecular sieve (trade name: Molecular sieve 5A, manufactured by Wako Pure Chemical Industries, Ltd.) 7.00 part and lithium amide 0.14 part were charged, heated to reflux at 80 ° C. for 120 hours, and then filtered. The obtained filtrate was charged with 0.28 part of oxalic acid and 7.50 parts of ion-exchanged water, and stirred and separated. Water washing was performed 6 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 6.88 parts of acetonitrile was added to the resulting concentrate to dissolve it, concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was concentrated to obtain 0.22 parts of a compound represented by the formula (II9-d). 0.22 part of the compound represented by the formula (II9-d) thus obtained was dissolved in 10 parts of chloroform, 5 parts of 1N hydrochloric acid was added, and the mixture was stirred at 23 ° C. for 30 minutes, followed by liquid separation. The obtained organic layer was concentrated to obtain 0.15 part of a salt represented by the formula (II-9).

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (−) Spectrum): M ⁻ 353.1

２−メチル−２−アダマンタノール２５．００部及びテトラヒドロフラン２００部を仕込み、室温で攪拌し、２−メチル−２−アダマンタノールの溶解確認後、ピリジン１４．２７部を仕込み、４０℃に昇温した。さらに、クロロアセチルクロリド２５．４７部及びテトラヒドロフラン５０部の混合溶液を１時間かけて滴下した。滴下後、４０℃で８時間攪拌し、５℃に温度を下げた。５℃に冷却したイオン交換水１００部を添加、攪拌し、分液により水層を回収した。回収された水層に酢酸エチル６５部を添加し、分液して有機層を回収した。回収された有機層に、５℃の１０％炭酸カリウム水溶液６５部を添加して洗浄し、分液して有機層を回収した後、回収された有機層にさらに、イオン交換水６５部を添加して水洗し、分液を行って有機層を回収した。この水洗操作を３回繰り返して行った。回収された有機層を濃縮し、得られた濃縮物にｎ−ヘプタン４０．００部を添加し、攪拌した後、ろ過後、乾燥して、式（ＩＩ−２１３−ａ）で表される化合物１７．６２部を得た。 Synthesis Example 6: Synthesis of salt represented by formula (II-213)

Charge 25.00 parts of 2-methyl-2-adamantanol and 200 parts of tetrahydrofuran, and stir at room temperature. After confirming dissolution of 2-methyl-2-adamantanol, charge 14.27 parts of pyridine and raise the temperature to 40 ° C. did. Further, a mixed solution of 25.47 parts of chloroacetyl chloride and 50 parts of tetrahydrofuran was added dropwise over 1 hour. After dropping, the mixture was stirred at 40 ° C. for 8 hours, and the temperature was lowered to 5 ° C. 100 parts of ion-exchanged water cooled to 5 ° C. was added and stirred, and the aqueous layer was recovered by liquid separation. 65 parts of ethyl acetate was added to the recovered aqueous layer, and the organic layer was recovered by liquid separation. To the recovered organic layer, 65 parts of a 10% potassium carbonate aqueous solution at 5 ° C. is added and washed, and after separating and recovering the organic layer, 65 parts of ion-exchanged water is further added to the recovered organic layer. The organic layer was recovered by washing with water and liquid separation. This washing operation was repeated 3 times. The recovered organic layer is concentrated, 40.00 parts of n-heptane is added to the obtained concentrate, and the mixture is stirred, filtered, dried, and the compound represented by the formula (II-213-a) 17.62 parts were obtained.

  15.00 parts of a compound represented by the formula (II-213-b) and 75 parts of N, N′-dimethylformamide were charged and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 6.40 parts of potassium carbonate and 1.92 parts of potassium iodide were charged and stirred at 50 ° C. for 1 hour. A solution prepared by dissolving 16.87 parts of the compound represented by the formula (II-213-a) in 33.74 parts of N, N′-dimethylformamide was added dropwise to the obtained mixture over 1 hour, and the mixture was stirred at 50 ° C. Stir for 5 hours. The obtained mixture was cooled to 23 ° C., 300 parts of ethyl acetate and 150 parts of ion-exchanged water were added, and the mixture was stirred and separated. The collected organic layer was repeatedly washed with 150 parts of ion-exchanged water until the aqueous layer became neutral. The recovered organic layer was concentrated, 150 parts of n-heptane was added to the resulting concentrate, and the mixture was stirred, filtered, dried, and the compound represented by formula (II-213-c) 22. 67 parts were obtained.

式（ＩＩ−２１３−ｃ）で表される化合物１５．００部及びアセトニトリル７５部を仕込み、２３℃で３０分間攪拌した後、５℃まで冷却した。得られた混合物に、水素化ホウ素ナトリウム０．７１部及びイオン交換水１０．６３部を仕込み、５℃で３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１００部を加えて攪拌し、分離した。回収された有機層をイオン交換水５０．００部で水層が中性になるまで水洗を繰り返した。回収された有機層を濃縮した後、以下の条件でカラム（シリカゲル６０−２００メッシュ；メルク社製 展開溶媒：酢酸エチル）分取することにより、式（ＩＩ−２１３−ｄ）で表される化合物１２．４３部を得た。

15.00 parts of a compound represented by the formula (II-213-c) and 75 parts of acetonitrile were charged, stirred at 23 ° C. for 30 minutes, and then cooled to 5 ° C. To the obtained mixture, 0.71 part of sodium borohydride and 10.63 parts of ion-exchanged water were added and stirred at 5 ° C. for 3 hours. To the obtained mixture, 50 parts of ion-exchanged water and 100 parts of ethyl acetate were added, stirred and separated. The recovered organic layer was repeatedly washed with 50.00 parts of ion-exchanged water until the aqueous layer became neutral. After the collected organic layer is concentrated, a compound represented by the formula (II-213-d) is obtained by separating a column (silica gel 60-200 mesh; developed solvent: ethyl acetate) under the following conditions. 12.43 parts were obtained.

A salt represented by the formula (II-213-e) was synthesized by the method described in JP 2008-127367 A.
First, 10.00 parts of a salt represented by the formula (II-213-e) and 60 parts of acetonitrile were charged, stirred at 40 ° C. for 30 minutes, and 4.44 parts of a compound represented by the formula (II-213-f) were added. The solution containing the compound represented by the formula (II-213-g) was obtained by charging and stirring at 50 ° C. for 1 hour.

  To the obtained solution containing the compound represented by the formula (II-213-g), 9.19 parts of the compound represented by the formula (II-213-d) was charged and stirred at 23 ° C. for 1 hour. To the obtained reaction mass, 100 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred and separated. Water washing was performed 5 times. The obtained organic layer was charged with 1.00 parts of activated carbon, stirred at 23 ° C. for 30 minutes, and filtered. After concentrating the filtrate, 50 parts of acetonitrile was added to dissolve the resulting concentrate, the mixture was concentrated, 50 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 50 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated, and the resulting concentrate was fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to obtain the formula (II-213). ) Was obtained.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (−) Spectrum): M ⁻ 559.2

Synthesis Example 7: Synthesis of salt represented by formula (II-183)

A compound represented by the formula (II-183-a) (trade name: NLA-tBu, manufactured by Kuraray Co., Ltd.) 25.43 parts, 100.00 parts of tetrahydrofuran and 1.14 parts of trifluoroacetic acid were charged, and the mixture was heated at 50 ° C. for 2 hours. Stir. Thereafter, 0.42 part of potassium iodide was added and stirred at 50 ° C. for 10 hours. After adding 30.00 parts of ion-exchanged water and 60.00 parts of ethyl acetate to the obtained mixture and stirring, liquid separation was performed to recover the organic layer. To the collected organic layer, 30.00 parts of ion-exchanged water was added and washed, followed by liquid separation to recover the organic layer. This liquid separation washing operation was repeated 3 times. The recovered organic layer was concentrated and then fractionated on a column under the following conditions to obtain 18.9 parts of a compound represented by the formula (II-183-b).
Developing medium; silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 10/1 (volume ratio)

  250 parts of 2-methyl-2-adamantanol and 2000 parts of tetrahydrofuran were charged and stirred at room temperature. After confirming dissolution of 2-methyl-2-adamantanol, 142.73 parts of pyridine were charged and the temperature was raised to 40 ° C. Further, a mixed solution of 254.74 parts of chloroacetyl chloride and 509 parts of tetrahydrofuran was added dropwise over 80 minutes. After dropping, the mixture was stirred at 40 ° C. for 8 hours, and the temperature was lowered to 5 ° C. 1052 parts of ion-exchanged water cooled to 5 ° C. was added and stirred, and the aqueous layer was recovered by liquid separation. To the recovered aqueous layer, 631 parts of ethyl acetate was added, and the mixture was separated to recover the organic layer. The recovered organic layer was washed by adding 631 parts of a 10% aqueous potassium carbonate solution at 5 ° C., and separated to recover the organic layer. Then, 631 parts of ion-exchanged water was further added to the recovered organic layer. The organic layer was recovered by washing with water and liquid separation. This washing operation was repeated 3 times. The recovered organic layer is concentrated, 500 parts of n-heptane is added to the resulting concentrate, and the mixture is stirred, filtered, dried, and 195 parts of a compound represented by the formula (II-183-c). Got.

  10.20 parts of a compound represented by the formula (II-183-b) and 102.05 parts of dimethylformamide were charged and stirred at room temperature to dissolve the compound represented by the formula (II-183-b). Thereafter, 3.56 parts of potassium carbonate and 0.89 parts of potassium iodide were added, and the temperature was raised to 50 ° C. After further stirring for 1 hour, the temperature was raised to 100 ° C. A mixed solution of 12.50 parts of the compound represented by the formula (II-183-c) and 37.50 parts of dimethylformamide was added to the obtained mixture over 60 minutes, and the mixture was stirred at 100 ° C. for 3 hours. After returning the obtained mixture to room temperature, 166.70 parts of ion-exchanged water and 333.40 parts of ethyl acetate were added, followed by stirring and liquid separation to recover the organic layer. To the collected organic layer, 83.35 parts of 5% aqueous potassium carbonate solution was added and washed, and liquid separation was performed to collect the organic layer. To the collected organic layer, 166.70 parts of ion-exchanged water was further added for washing, and liquid separation was performed to collect the organic layer. This washing operation was repeated 5 times. 1 part of magnesium sulfate was added to the recovered organic layer, and the mixture was stirred and then filtered to recover the organic layer. After the collected organic layer was concentrated, 55.5 parts of n-heptane was added and stirred at room temperature for 1 hour, and then the precipitate was filtered off, dried and dried according to formula (II-183-d). 16.80 parts of the compound represented were obtained.

  A salt represented by the formula (II-183-e) was synthesized by the method described in JP-A-2008-13551. 4.52 parts of salt represented by formula (II-183-e), 30.00 parts of chloroform, 4.44 parts of compound represented by formula (II-183-d), molecular sieve (trade name: molecular sieve) 5A, manufactured by Wako Pure Chemical Industries, Ltd.) 5.00 parts and 0.14 part of lithium amide were charged, heated to reflux at 80 ° C. for 5 hours, and filtered. The obtained filtrate was charged with 0.28 part of oxalic acid and 7.50 parts of ion-exchanged water, and stirred and separated. Water washing was performed 6 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 7.00 parts of acetonitrile was added to dissolve the resulting concentrate, and the mixture was concentrated, concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 0.89 part of a salt represented by the formula (II-183) as an oily substance.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (−) Spectrum): M ⁻ 561.1

Synthesis Example 8: Synthesis of salt represented by formula (II-167)

16.42 parts of a compound represented by the formula (II-167-a) (5-norbornene-2,3-dicarboxylic acid anhydride, manufactured by Wako Pure Chemical Industries, Ltd.) and 53.29 parts of tetrahydrofuran were charged and dissolved by stirring at 23 ° C. did. To the obtained mixture, 2.44 parts of dimethylaminopyridine was added at 23 ° C., followed by stirring at 50 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 16.63 parts of 2-methyl-2-adamantanol and 53.29 parts of tetrahydrofuran was further added dropwise over 1 hour, followed by stirring at 50 ° C. for 10 hours. To the obtained mixture, 30 parts of ion-exchanged water and 60 parts of ethyl acetate were added and washed, followed by liquid separation to recover the organic layer. 30 parts of ion-exchanged water was added to the collected organic layer for washing, and liquid separation was performed to collect the organic layer. This liquid separation washing operation was repeated 3 times. The collected organic layer was concentrated and then fractionated on a column under the following conditions to obtain 25.2 parts of a compound represented by the formula (II-167-b).
Developing medium: silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 20/1 (volume ratio)

After charging 16.50 parts of the compound represented by the formula (II-167-b) and 200.00 parts of chloroform and stirring at 23 ° C., the compound represented by the formula (II-167-b) was dissolved. 17.23 parts of m-chloroperbenzoic acid was added at 23 ° C., and the mixture was stirred at 23 ° C. for 6 hours. To the obtained mixture, 30 parts of ion-exchanged water and 60 parts of ethyl acetate were added and washed, followed by liquid separation to recover the organic layer. 30 parts of ion-exchanged water was added to the collected organic layer for washing, and liquid separation was performed to collect the organic layer. This liquid separation washing operation was repeated 3 times. After the collected organic layer was concentrated, 14.7 parts of a compound represented by the formula (II-167-c) was obtained by fractionating the column under the following conditions.
Developing medium: silica gel 60-200 mesh; manufactured by Merck developing solvent: n-heptane / ethyl acetate = 20/1 (volume ratio)

  A salt represented by the formula (II-167-d) was synthesized by the method described in JP-A-2008-13551. 4.52 parts of salt represented by formula (II-167-d), 30.00 parts of chloroform, 3.81 parts of compound represented by formula (II-167-c), molecular sieve (trade name: molecular sieve) 5A, manufactured by Wako Pure Chemical Industries, Ltd.) 5.00 parts and 0.14 part of lithium amide were charged, heated to reflux at 80 ° C. for 5 hours, and filtered. The obtained filtrate was charged with 0.28 part of oxalic acid and 7.50 parts of ion-exchanged water, and stirred and separated. Water washing was performed 6 times. The obtained organic layer was charged with 1.00 part of activated carbon, stirred at 23 ° C. for 30 minutes, and then filtered. After the filtrate was concentrated, 7.00 parts of acetonitrile was added to dissolve the resulting concentrate, and the mixture was concentrated, concentrated, 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 1.12 parts of a salt represented by the formula (II-167) as an oily substance.

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (−) Spectrum): M ⁻ 503.1

式（Ｂ１−５−ａ）で表される塩５０．４９部及びクロロホルム２５２．４４部を反応器に仕込み、２３℃で３０分間攪拌した後、式（Ｂ１−５−ｂ）で表される化合物１６．２７部を滴下し、２３℃で１時間攪拌することにより、式（Ｂ１−５−ｃ）で表される塩を含む溶液を得た。得られた式（Ｂ１−５−ｃ）で表される塩を含む溶液に、式（Ｂ１−５−ｄ）で表される塩４８．８０部及びイオン交換水８４．１５部を添加し、２３℃で１２時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、該クロロホルム層にイオン交換水８４．１５部を添加し、水洗した。この操作を５回繰り返した。得られたクロロホルム層に、活性炭３．８８部を添加攪拌し、ろ過した。回収されたろ液を濃縮し、得られた残渣に、アセトニトリル１２５．８７部を添加攪拌し、濃縮した。得られた残渣に、アセトニトリル２０．６２部及びｔｅｒｔ−ブチルメチルエーテル３０９．３０部を加えて２３℃で３０分間攪拌し、上澄み液を除去し、濃縮した。得られた残渣に、ｎ−ヘプタン２００部を添加、２３℃で３０分間攪拌し、ろ過することにより、式（Ｂ１−５）で表される塩６１．５４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ⁺ ３７５．２
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ^- ３３９．１ Synthesis Example 9: Synthesis of salt represented by formula (B1-5)

50.49 parts of the salt represented by the formula (B1-5-a) and 252.44 parts of chloroform are charged into a reactor, stirred at 23 ° C. for 30 minutes, and then represented by the formula (B1-5-b). 16.27 parts of the compound was added dropwise and stirred at 23 ° C. for 1 hour to obtain a solution containing a salt represented by the formula (B1-5-c). To the obtained solution containing the salt represented by the formula (B1-5-c), 48.80 parts of the salt represented by the formula (B1-5-d) and 84.15 parts of ion-exchanged water are added, The mixture was stirred at 23 ° C. for 12 hours. Since the resulting reaction solution was separated into two layers, the chloroform layer was separated and removed, and 84.15 parts of ion-exchanged water was further added to the chloroform layer and washed with water. This operation was repeated 5 times. To the obtained chloroform layer, 3.88 parts of activated carbon was added and stirred, followed by filtration. The collected filtrate was concentrated, and 125.87 parts of acetonitrile was added to the resulting residue, and the mixture was stirred and concentrated. To the obtained residue, 20.62 parts of acetonitrile and 309.30 parts of tert-butyl methyl ether were added and stirred at 23 ° C. for 30 minutes, and the supernatant was removed and concentrated. To the obtained residue, 200 parts of n-heptane was added, stirred at 23 ° C. for 30 minutes, and filtered to obtain 61.54 parts of the salt represented by the formula (B1-5).
MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (−) Spectrum): M ⁻ 339.1

以下、これらのモノマーを、その符号に応じて、「モノマー（Ｍ−Ａ）」〜「モノマー（Ｍ−Ｌ）」という。 Synthesis of Resin (A) Compounds (monomers) used in the synthesis of resin (A) are shown below.

Hereinafter, these monomers are referred to as “monomer (MA)” to “monomer (ML)” depending on the reference numerals.

[Synthesis of Resin A1]
As a monomer, a monomer (MG), a monomer (ME), a monomer (MB), a monomer (M-H), and a monomer (M-K) are used, and the molar ratio (monomer (MG) : Monomer (ME): Monomer (MB): Monomer (M-H): Monomer (M-K)) were mixed so that the ratio was 32: 7: 8: 43: 10. 1.5 mass times dioxane was added to make 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 dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.6. A × 10 ³ resin A1 (copolymer) was obtained in a yield of 80%. This resin A1 has the following structural units.

[Synthesis of Resin A2]
As a monomer, a monomer (MF), a monomer (M-I), a monomer (M-J), a monomer (MD) and a monomer (M-K) are used, and the molar ratio (monomer (MF)) : Monomer (M-I): monomer (M-J): monomer (MD): monomer (M-K)) were mixed so that 45: 14: 2.5: 22.5: 16, Dioxane of 1.5 mass times the total monomer amount was added to make 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 73 ° 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 dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 8.8. A × 10 ³ resin A2 (copolymer) was obtained with a yield of 71%. This resin A2 has the following structural units.

[Synthesis of Resin A3]
As a monomer, a monomer (M−F), a monomer (M−I), a monomer (M−J), a monomer (M−D), a monomer (M−H), and a monomer (M−K) are used, and a molar ratio thereof. (Monomer (MF): Monomer (M-I): Monomer (M-J): Monomer (MD): Monomer (M-H): Monomer (M-K))) 45: 14: 2. It mixed so that it might become 5: 17.5: 5: 16, and the dioxane 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 dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 8.3. A × 10 ³ resin A3 (copolymer) was obtained in a yield of 69%. This resin A3 has the following structural units.

[Synthesis of Resin A4]
As a monomer, a monomer (MF), a monomer (ML), a monomer (MJ), a monomer (MD), and a monomer (MK) are used, and the molar ratio [monomer (MF) : Monomer (ML): monomer (M-J): monomer (MD): monomer (M-K)] is mixed to be 45: 14: 2.5: 22.5: 16, A solution was prepared by adding propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by reprecipitation operation of filtering the resin twice. Resin A4 (copolymer) having a molecular weight of 8.2 × 10 ³ was obtained in a yield of 66%. This resin A4 has the following structural units.

[Synthesis of Resin A5]
As a monomer, a monomer (MG), a monomer (ML), a monomer (MB), a monomer (M-H), and a monomer (M-K) are used, and the molar ratio [monomer (MG) : Monomer (ML): monomer (MB): monomer (M-H): monomer (M-K)] to be 32: 7: 8: 43: 10 1.5 mass times propylene glycol monomethyl ether acetate 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 again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by reprecipitation operation of filtering the resin twice. Resin A5 (copolymer) having a molecular weight of 7.9 × 10 ³ was obtained in a yield of 82%. This resin A5 has the following structural units.

[Synthesis of Resin H1]
Monomer (MA) and monomer (MC) are used as monomers and mixed so that the molar ratio (monomer (MA): monomer (MC)) is 40:60. An amount of 1.5 mass times dioxane was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.4 mol% and 4.2 mol%, respectively, based on the total monomer amount, and these were added at 70 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and the reprecipitation operation of filtering the resin was performed twice, and the weight average molecular weight was 5.0. A × 10 ³ resin H1 (copolymer) was obtained in a yield of 92%. This resin H1 has the following structural units.

<Preparation of resist composition>
Each of the components shown below was dissolved in a solvent at parts by mass shown in Table 2, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

酸発生剤ＩＩ−３３ ５０ｍｇをジメチルスルホキサイド０．７９３５ｇに溶解し、２０％塩酸０．０２１６ｇを添加し、８０℃で１時間攪拌した。その後、酸発生剤ＩＩ−３３の分解物を確認したところ、カルボン酸が生成しており、以下の化合物であることを確認した。

<Resin>
A1 to A5, H1: Resin A1 to Resin A5, Resin H1
<Acid generator>
II-33: synthesized according to examples of JP-A-2008-69146

50 mg of acid generator II-33 was dissolved in 0.7935 g of dimethyl sulfoxide, 0.0216 g of 20% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 1 hour. Then, when the decomposition product of acid generator II-33 was confirmed, carboxylic acid was producing | generating and it confirmed that it was the following compounds.

酸発生剤ＩＩ−４９ ５０ｍｇをジメチルスルホキサイド０．７９４８ｇに溶解し、２０％塩酸０．０２１２ｇを添加し、８０℃で１時間攪拌した。その後、酸発生剤ＩＩ−４９の分解物を確認したところ、カルボン酸が生成し、以下の化合物であることを確認した。

II-49:

50 mg of acid generator II-49 was dissolved in 0.7948 g of dimethyl sulfoxide, 0.0212 g of 20% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 1 hour. Then, when the decomposition product of acid generator II-49 was confirmed, carboxylic acid produced | generated and it confirmed that it was the following compounds.

酸発生剤ＩＩ−４１ ５０ｍｇをジメチルスルホキサイド０．７９５８ｇに溶解し、２０％塩酸０．０２１６ｇを添加し、８０℃で１時間攪拌した。その後、酸発生剤ＩＩ−４１の分解物を確認したところ、カルボン酸が生成し、以下の化合物であることを確認した。

II-41:

50 mg of acid generator II-41 was dissolved in 0.7958 g of dimethyl sulfoxide, 0.0216 g of 20% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 1 hour. Then, when the decomposition product of acid generator II-41 was confirmed, carboxylic acid produced | generated and it confirmed that it was the following compounds.

酸発生剤ＩＩ−１ ５０ｍｇをジメチルスルホキサイド０．７９２１ｇに溶解し、２０％塩酸０．０２０８ｇを添加し、８０℃で１時間攪拌した。その後、酸発生剤ＩＩ−１の分解物を確認したところ、カルボン酸が生成し、以下の化合物であることを確認した。

II-1:

50 mg of acid generator II-1 was dissolved in 0.7921 g of dimethyl sulfoxide, 0.0208 g of 20% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 1 hour. Then, when the decomposition product of acid generator II-1 was confirmed, carboxylic acid produced | generated and it confirmed that it was the following compounds.

酸発生剤ＩＩ−９ ５０ｍｇをジメチルスルホキサイド０．７９４２ｇに溶解し、２０％塩酸０．０２２１ｇを添加し、８０℃で１時間攪拌したあと、酸発生剤ＩＩ−９の分解物を確認したところ、カルボン酸が生成し、以下の化合物であることを確認した。

II-9:

50 mg of acid generator II-9 was dissolved in 0.7942 g of dimethyl sulfoxide, 0.0221 g of 20% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 1 hour, and then a decomposition product of acid generator II-9 was confirmed. However, it was confirmed that carboxylic acid was produced and was the following compound.

酸発生剤ＩＩ−２１３ ５０ｍｇをジメチルスルホキサイド０．７９４６ｇに溶解し、２０％塩酸０．０２１９ｇを添加し、１００℃で１時間攪拌した後、酸発生剤ＩＩ−２１３の分解物を、¹Ｈ−ＮＭＲによって分析した。その結果、カルボキシ基及びビニルプロトン(分解物)に帰属するピークが確認された。 II-213:

The acid generator II-213 50 mg was dissolved in dimethyl sulfoxide 0.7946G, adding 20% hydrochloric acid 0.0219G, After stirring for 1 hour at 100 ° C., decomposed substance of the acid generator II-213, ¹ Analysis by H-NMR. As a result, peaks attributable to carboxy groups and vinyl protons (decomposed product) were confirmed.

酸発生剤ＩＩ−１８３ ５０ｍｇをジメチルスルホキサイド０．７９２１ｇに溶解し、２０％塩酸０．０２０４ｇを添加し、１００℃で１時間攪拌した後、酸発生剤ＩＩ−１８３の分解物を、¹Ｈ−ＮＭＲによって分析した。その結果、カルボキシ基及びビニルプロトン(分解物)に帰属するピークが確認された。 II-183:

The acid generator II-183 50 mg was dissolved in dimethyl sulfoxide 0.7921G, adding 20% hydrochloric acid 0.0204G, After stirring for 1 hour at 100 ° C., decomposed substance of the acid generator II-183, ¹ Analysis by H-NMR. As a result, peaks attributable to carboxy groups and vinyl protons (decomposed product) were confirmed.

酸発生剤ＩＩ−１６７ ５０ｍｇをジメチルスルホキサイド０．７９３３ｇに溶解し、２０％塩酸０．０２０８ｇを添加し、１００℃で１時間攪拌した後、酸発生剤ＩＩ−１６７の分解物を、¹Ｈ−ＮＭＲによって分析した。その結果、カルボキシ基及びビニルプロトン(分解物)に帰属するピークが確認された。 II-167:

The acid generator II-167 50 mg was dissolved in dimethyl sulfoxide 0.7933G, adding 20% hydrochloric acid 0.0208G, After stirring for 1 hour at 100 ° C., decomposed substance of the acid generator II-167, ¹ Analysis by H-NMR. As a result, peaks attributable to carboxy groups and vinyl protons (decomposed product) were confirmed.

Ｂ１−５：

Ｂ２：トリフェニルスルホニウム トリフレート（ＴＰＳ−１０５ ミドリ化学（株）製） B1-3: synthesized according to the example of JP 2010-152341 A

B1-5:

B2: Triphenylsulfonium triflate (manufactured by TPS-105 Midori Chemical Co., Ltd.)

<Basic compound: Quencher>
C1: 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

Examples 1 to 19 and Comparative Example 1
<Manufacture of negative resist pattern>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer, and baked under the conditions of 205 ° C. and 60 seconds, whereby an organic layer having a thickness of 78 nm was obtained. An antireflection film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After coating, the composition layer was formed on the silicon wafer by pre-baking on a direct hot plate at the temperature described in the column “PB” in Table 2 for 60 seconds. An ArF excimer laser stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized illumination) is applied to the silicon wafer on which the composition layer is formed at a 1: 1 line and Using a mask for forming a space pattern (pitch 70 nm to 100 nm), the exposure was changed in stages and exposed. 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 2. Next, the composition layer on the silicon wafer was subjected to dynamic dispense development at 23 ° C. for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer, thereby producing a negative resist pattern. .

<Resolution evaluation>
Observe the resist pattern with a scanning electron microscope,
What resolves 43nm ◎,
○, which resolves 45nm
The case where 45 nm was not resolved or resolved but the top was round, there was tailing, or pattern collapse was observed was marked as x.
The results are shown in Table 3. The number in parentheses indicates the resolution.

Examples 20 to 38 and Comparative Example 2
Except for changing the developer to 2-heptanone (manufactured by Kyowa Hakko Co., Ltd.), the same operation as above was performed to produce a negative resist pattern, and the same evaluation as in Example 1 was performed. The results are shown in Table 4.

  From the above results, it can be seen that a high-resolution negative resist pattern can be produced according to the resist composition of the present invention.

<Preparation of resist composition>
Each of the components shown below was dissolved in the following solvent in parts by mass shown in Table 5 and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

Examples 39 to 45 and Comparative Example 3
<Manufacture of resist pattern>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 78 nm. An organic antireflection film was formed. Subsequently, the resist composition was spin-coated on the organic antireflection film so that the film thickness after drying (pre-baking) was 85 nm.
The obtained silicon wafer was pre-baked (PB) for 60 seconds at a temperature described in the “PB” column of Table 5 on a direct hot plate to form a composition layer. On the wafer on which the resist composition film (composition layer) was thus formed, using an ArF excimer stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light] The line and space pattern was subjected to immersion exposure by changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking (PEB) was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 5, and further with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Paddle development was performed to obtain a resist pattern.

  In the obtained resist pattern, the exposure amount at which the line width and space width of the 50 nm line-and-space pattern were 1: 1 was defined as effective sensitivity.

<Resolution evaluation>
In effective sensitivity, the resist pattern is observed with a scanning electron microscope.
What resolves 43nm ◎,
○, which resolves 45nm
The case where 45 nm was not resolved or resolved but the top was round, there was tailing, or pattern collapse was observed was marked as x.
The results are shown in Table 6. The number in parentheses indicates the resolution.

  According to the resist composition of the present invention, a high-resolution resist pattern can be produced and used for fine processing of semiconductors.

Claims (4)

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

[In the formula (I),
R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
A ¹ is a single bond, ^* —A ² —O—, ^* —A ² —CO—O—, ^* —A ² —CO—O—A ³ —CO—O—, or ^* —A ² —O—CO. -A ³ represents a -O-.
* Represents a bond with -O-.
A ² and A ³ each independently represents an alkanediyl group having 1 to 6 carbon atoms. ] The resist composition according to claim 1, wherein the acid generator having an acid labile group is an acid generator represented by the formula (II-0).

[In the formula (II-0),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ⁰¹ represents a C 1-20 divalent hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is —CO— or —O—. It may be replaced with.
R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms.
Ring W ¹ represents a hydrocarbon ring optionally having from 3 to 18 carbon atoms which may have a substituent.
Z ⁺ represents an organic cation. ]   Furthermore, the resist composition of Claim 1 or 2 containing a solvent. (1) The process of apply | coating the resist composition as described in any one of Claims 1-3 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 method for producing a resist pattern, comprising a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.