JP2014029507A - Resist composition and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition from which a resist pattern with high resolution can be produced.SOLUTION: The resist composition comprises a resin including a structural unit having an acid-labile group, an acid generator expressed by formula (I), and an acid generator having an acid-labile group. In the formula, Xrepresents an alkanediyl group optionally having a substituent, in which a methylene group constituting the alkanediyl group may be replaced by an oxygen atom or a carbonyl group; Rrepresents a hydrocarbon group optionally having a substituent, in which a methylene group constituting the hydrocarbon group may be replaced by an oxygen atom or a carbonyl group; and Zrepresents an organic cation.

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 containing a resin, a salt represented by the formula (B1-X), and 2,6-diisopropylaniline.

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 2007-161707 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、
Ｘ²は、炭素数１〜６のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、ヒドロキシ基又は−ＯＲ⁵で置換されていてもよく、該アルカンジイル基を構成するメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｒ⁴及びＲ⁵は、それぞれ独立に、炭素数１〜２４の炭化水素基を表し、該炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよく、該炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］
〔２〕式（Ｉ）で表される酸発生剤が式（ＩＡ）で表される酸発生剤である〔１〕記載のレジスト組成物。

［式（ＩＡ）中、Ｘ²及びＺ⁺は、上記と同じ意味を表す。
Ｒ⁶は、炭素数１〜１７の炭化水素基を表し、該炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよく、該炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｒ⁷は、炭素数１〜６のアルキル基を表す。
Ｒ⁸は、炭素数１〜６のフッ素化アルキル基を表す。
ただし、Ｒ⁶、Ｒ⁷及びＲ⁸の合計炭素数は、２０以下である。］
〔３〕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メチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｒ^II4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。
ＺII⁺は、有機カチオンを表す。］
〔４〕さらに溶剤を含有する〔１〕〜〔３〕のいずれか１項記載のレジスト組成物。
〔５〕（１）上記〔１〕〜〔４〕のいずれか１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 containing a structural unit having an acid labile group, an acid generator represented by formula (I), and an acid generator having an acid labile group.

[In the formula (I),
X ² represents an alkanediyl group having 1 to 6 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a hydroxy group or —OR ⁵ , and a methylene group constituting the alkanediyl group May be replaced by an oxygen atom or a carbonyl group.
R ⁴ and R ⁵ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, and the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The methylene group contained in the group may be replaced with an oxygen atom or a carbonyl group.
Z ⁺ represents an organic cation. ]
[2] The resist composition according to [1], wherein the acid generator represented by the formula (I) is an acid generator represented by the formula (IA).

[In formula (IA), X ² and Z ⁺ represent the same meaning as described above.
R ⁶ represents a hydrocarbon group having 1 to 17 carbon atoms, the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the methylene group constituting the hydrocarbon group is May be replaced by an oxygen atom or a carbonyl group.
R ⁷ represents an alkyl group having 1 to 6 carbon atoms.
R ⁸ represents a fluorinated alkyl group having 1 to 6 carbon atoms.
However, the total carbon number of R ⁶ , R ⁷ and R ⁸ is 20 or less. ]
[3] 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 C1-C20 divalent hydrocarbon group which may have a single bond or a substituent, and the methylene group contained in the hydrocarbon group is replaced with an oxygen atom or a carbonyl group. Also good.
R ^II4 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.
ZII ⁺ represents an organic cation. ]
[4] The resist composition according to any one of [1] to [3], further containing a solvent.
[5] (1) A step of applying the resist composition according to any one of [1] to [4] 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 resist pattern having excellent resolution can be produced.

In the present specification, "(meth) acrylic monomer" means at least one monomer having a "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " structure of To do. Similarly, “(meth) acrylate” 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 resin comprising a structural unit having an acid labile group (hereinafter sometimes referred to as “resin (A)”),
An acid generator represented by formula (I) (hereinafter sometimes referred to as “acid generator (I)”) and an acid generator having an acid labile group (hereinafter referred to as “acid generator (II)”) ).
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.
It is preferable that the resist composition of the present invention further contains a solvent (E).
The resist composition of the present invention preferably further contains a basic compound (C).

<Resin (A)>
The resin (A) includes a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a)”). Furthermore, a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”) may be included.

［式（１）中、Ｒ^a1、Ｒ^a2及びＲ^a3は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜２０の脂環式炭化水素基を表すか、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価の炭化水素基を構成する１以上の−ＣＨ₂−は、−Ｏ―又は―Ｓ−で置き換わってもよい。 <Structural unit (a)>
As described above, the structural unit (a) is a structural unit having an acid labile group.
Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

Wherein (1), R ^a1, R ^a2 and R ^a3 each independently represent a cycloaliphatic hydrocarbon radical of the alkyl group or 3 to 20 carbon atoms having 1 to 8 carbon atoms, R ^a1 and R ^a2 combine with 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. Or R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group and one or more − constituting the divalent hydrocarbon group CH ₂ — may be replaced by —O— or —S—.

アルキル基と脂環式炭化水素基とを組合わせた基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基等が挙げられる。 ^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. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). The alicyclic hydrocarbon group represented by R ^a1 , R ^a2 and R ^a3 preferably has 3 to 16 carbon atoms.

Examples of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.

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 (a group in which R ^a1 , R ^a2 and R ^a3 are alkyl groups in the formula (1), preferably tert-butoxycarbonyl). Group), 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantan-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 R ^{a2 'and} R ^a3' is formed by bonding with, for example, R ^{a1 ',} R ^a2' is one obtained by removing groups a hydrogen atom from a hydrocarbon group and R ^{a3 '} Can be mentioned.
At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

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

  The monomer for deriving the structural unit (a) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, and more preferably a (meth) acrylic monomer having an acid labile group.

  Among the (meth) acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. If a resin having a structural unit (a) 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.

  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 used alone or in combination of two or more. 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、炭素数３〜１８の脂環式炭化水素基又はこれらを組合わせた基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］

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

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.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and the group obtained by combining these include the same groups as the groups represented by R ^a1 , R ^a2, and R ^a3 in formula (1). .
The alkyl group for R ^a6 and R ^a7 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 preferably has 8 or less carbon atoms, more preferably 6 or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

As 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). Acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, 1-isopropylcyclopentan-1-yl (meth) acrylate, 1-isopropylcyclohexane-1- And yl (meth) acrylate. Monomers represented by the formula (a1-2-1) to the formula (a1-2-12) are preferred, and the formula (a1-2-3) to the formula (a1-2-4) or the formula (a1-2-9) The monomer represented by formula (a1-2-10) is more preferable, and the monomer represented by formula (a1-2-3) or formula (a1-2-9) is more preferable.

  When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol with respect to all the structural units of the resin (A). %, Preferably 15 to 90 mol%, more preferably 20 to 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^a54−を表す。ここで、ｋ４は１〜４の整数を表す。＊は、Ｌ^a51との結合手を表す。
Ｌ^a51、Ｌ^a52、Ｌ^a53及びＬ^a54は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。］ As a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (2), a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”) There are).

[In the 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 * — [CH ₂ ] _k4 —CO—L ^a54 —. Here, k4 represents an integer of 1 to 4. * Represents a bond with L ^a51 .
L ^a51 , L ^a52 , L ^a53 and L ^a54 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 ^a51 is preferably an oxygen atom.
One of L ^a52 and L ^a53 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 that leads to the structural unit (a1-5) include the following monomers.

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

<Structural unit (s)>
The monomer for deriving the “structural unit (s)” which is a structural unit having no acid labile group is not particularly limited as long as it is a monomer having no acid labile group, and a known monomer in the resist field can be used. .
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid labile group is preferable. A structure having a hydroxy group and having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or a lactone ring and having no acid labile group If a resin having a unit (hereinafter sometimes referred to as “structural unit (a3)”) is used for the resist composition, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When the resist composition is applied to KrF excimer laser exposure (248 nm), high energy beam exposure such as electron beam or EUV (extreme ultraviolet light), the structural unit (a2) having a phenolic hydroxy group as the structural unit (a2) ) Is preferably used. When applied to ArF excimer laser exposure (193 nm) or the like, the structural unit (a2) is preferably a structural unit (a2) having an alcoholic hydroxy group, and more preferably a structural unit (a2-1). As the structural unit (a2), one type may be contained alone, or two or more types may be used in combination.

［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 structural unit (a2) having an alcoholic hydroxy group include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).

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

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

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

  When resin (A) contains structural unit (a2-1), the content rate is 3 to 45 mol% normally with respect to all the structural units of resin (A), Preferably it is 1 to 40 mol%. More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

<Structural unit (a3)>
The lactone ring contained in the structural unit (a3) may be, for example, a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and a bridged ring including these monocyclic lactone ring structures. But you can. Among these lactone rings, a γ-butyrolactone ring or a bridged ring containing a γ-butyrolactone ring structure is preferable.

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

［式（ａ３−１）中、
Ｌ^a4は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表す。
ｐ１は０〜５の整数を表す。ｐ１が２以上のとき、複数のＲ^a21は互いに同一又は相異なる。
式（ａ３−２）中、
Ｌ^a5は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｑ１は、０〜３の整数を表す。ｑ１が２以上のとき、複数のＲ^a22は互いに同一又は相異なる。
式（ａ３−３）中、
Ｌ^a6は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k3−ＣＯ−Ｏ−（ｋ３は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表す。
ｒ１は、０〜３の整数を表す。ｒ１が２以上のとき、複数のＲ^a23は互いに同一又は相異なる。］

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

In Formula (a3-1), Formula (a3-2), and Formula (a3-3), L ^a4 , L ^a5, and L ^a6 are each independently preferably an oxygen atom or an integer of k3 of 1 to 4. A group represented by * —O— (CH ₂ ) _k3 —CO—O—, more preferably an oxygen atom and * —O—CH ₂ —CO—O—, still more preferably an oxygen atom.
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 an integer of 0 to 2, more preferably 0 or 1.

  Examples of the monomer that leads to the structural unit (a3) include monomers described in JP 2010-204646 A. Formula (a3-1-1) to Formula (a3-1-4), Formula (a3-2-1) to Formula (a3-2-4), and Formula (a3-3-1) to Formula (a3-3) -4) is preferred, and the monomers represented by formula (a3-1-1) to formula (a3-1-2) and formula (a3-2-3) to formula (a3-2-4) are preferred. The monomer represented by either is more preferable, and the monomer represented by the formula (a3-1-1) or the formula (a3-2-3) is more preferable.

  When the resin (A) includes the structural unit (a3), the content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.

The content of the structural unit (a) in the resin (A) is preferably in the range of 1 to 100 mol%, more preferably in the range of 10 to 95 mol%, with respect to all the structural units of the resin (A). The range of 90 mol% is more preferable, and the range of 20 to 85 mol% is particularly preferable.
Resin (A) which has structural unit (a) with such a content rate can be manufactured by adjusting the use molar amount of the monomer with respect to the total molar amount of all the monomers used at the time of resin (A) manufacture.

In the case where the resin (A) is a resin composed of the structural unit (a) and the structural unit (s), these content rates are respectively based on the total structural units of the resin (A),
Structural unit (a); 10-95 mol%
Structural unit (s); 5 to 90 mol% is preferable,
Structural unit (a); 15-90 mol%
Structural unit (s); 10 to 85 mol% is more preferable,
Structural unit (a); 20 to 85 mol%
Structural unit (s); 15 to 80 mol% is more preferable.

  The resin (A) preferably contains 15 mol% or more of structural units derived from the monomer having an adamantyl group (particularly the structural unit (a1-1)) with respect to the total structural units (a). When the content of the structural unit having an adamantyl group is large, the dry etching resistance of the resist pattern is improved.

The resin (A) is preferably a resin composed of the structural unit (a) and the structural unit (s).
The structural unit (a) 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 the structural unit (a1- 1).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably the structural unit (a2-1). The structural unit (a3) is preferably at least one of the structural unit (a3-1) and the structural unit (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).

<Resin other than resin (A)>
The resist composition of the present invention includes a resin other than the above-described resin (A), for example, a resin having at least one selected from structural units (s) and structural units derived from known monomers used in the field. Etc. may be contained.
When the resist composition of this invention contains resin other than resin (A), the content rate is 0.1-50 mass% normally with respect to the total amount of resin contained in the resist composition of this invention. , Preferably it is 0.5-30 mass%, More preferably, it is 1-20 mass%.

  In the resist composition of the present invention, the total resin content is preferably 80% by mass or more and 99.9% by weight or less in the solid content of the resist composition. In the present specification, the “solid content in the composition” means the total of resist composition components excluding the solvent (E) described later. The solid content in the composition and the resin content relative thereto can be measured, for example, by a known analytical means such as liquid chromatography or gas chromatography.

［式（Ｉ）中、
Ｘ²は、炭素数１〜６のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、ヒドロキシ基又は−ＯＲ⁵で置換されていてもよく、該アルカンジイル基を構成する１以上のメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｒ⁴及びＲ⁵は、それぞれ独立に、炭素数１〜２４の炭化水素基を表し、該炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよく、該炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］ <Acid generator (I)>
The acid generator (I) is represented by the formula (I).

[In the formula (I),
X ² represents an alkanediyl group having 1 to 6 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a hydroxy group or —OR ⁵ , and one or more constituting the alkanediyl group The methylene group may be replaced with an oxygen atom or a carbonyl group.
R ⁴ and R ⁵ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, and the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The methylene group contained in the group may be replaced with an oxygen atom or a carbonyl group.
Z ⁺ represents an organic cation. ]

Examples of the alkanediyl group of X ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. Hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,3-diyl group, 2-methylpropane -1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like.
Of these, a methylene group is preferable.

Examples of the group in which one or more methylene groups constituting the alkanediyl group are replaced with an oxygen atom or a carbonyl group include the following divalent groups. * Represents a bond with CF ₂ .

Examples of the group in which the hydrogen atom contained in the alkanediyl group is substituted with a hydroxy group or —OR ^{5 and} at least one methylene group constituting the alkanediyl group is replaced with an oxygen atom include the following groups. . * Represents a bond with CF ₂ .

The hydrocarbon group for R ⁴ and R ⁵ may be either saturated or unsaturated, for example, a linear or branched alkyl group or alkenyl group, a monocyclic or polycyclic alicyclic hydrocarbon group , Aromatic hydrocarbon groups and the like, and a combination of two or more of these groups may be used.
Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Examples of the branched alkyl group include an isopropyl group, a sec-butyl group, and a tert-butyl group.
Examples of the linear or branched alkenyl group include a vinyl group and an α-methylvinyl group.
Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the polycyclic alicyclic hydrocarbon group include a norbornyl group and an adamantyl group.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, 2,6-diethylphenyl group, 2- And methyl-6-ethylphenyl.

［式（ＩＡ）中、Ｘ²及びＺ⁺は、上記と同じ意味を表す。
Ｒ⁶は、炭素数１〜１７の炭化水素基を表し、該炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置換されていてもよく、該炭化水素基を構成する１以上のメチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｒ⁷は、炭素数１〜６のアルキル基を表す。
Ｒ⁸は、炭素数１〜６のフッ素化アルキル基を表す。
ただし、Ｒ⁶、Ｒ⁷及びＲ⁸の合計炭素数は、２０以下である。］ The acid generator (I) is preferably an acid generator represented by the formula (IA).

[In formula (IA), X ² and Z ⁺ represent the same meaning as described above.
R ⁶ represents a hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and one or more constituting the hydrocarbon group The methylene group may be replaced with an oxygen atom or a carbonyl group.
R ⁷ represents an alkyl group having 1 to 6 carbon atoms.
R ⁸ represents a fluorinated alkyl group having 1 to 6 carbon atoms.
However, the total carbon number of R ⁶ , R ⁷ and R ⁸ is 20 or less. ]

Ｒ⁷のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。
Ｒ⁸のフッ素化アルキル基としては、トリフルオロメチル基、パーフルオロエチル基、１，１，２，２−テトラフルオロエチル基、パーフルオロブチル基、１，１，２，２，３，３，４，４−オクタフルオロブチル基等が挙げられ、好ましくはトリフルオロメチル基である。 Examples of the hydrocarbon group for R ⁶ include the same groups as those for R ⁴ , and an alicyclic hydrocarbon group is preferable.
Examples of the group in which one or more methylene groups constituting the hydrocarbon group are replaced with an oxygen atom or a carbonyl group include the following. * Represents a bond.

Examples of the alkyl group for R ⁷ include a methyl group, an ethyl group, a propyl group, and a butyl group.
As the fluorinated alkyl group for R ⁸ , a trifluoromethyl group, a perfluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a perfluorobutyl group, 1,1,2,2,3,3, Examples include 4,4-octafluorobutyl group, and a trifluoromethyl group is preferable.

Examples of the acid generator (I) include the following salts.

Examples of Z ⁺ include organic onium cations such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, an arylsulfonium cation is more preferable, and a cation represented by any one of the formulas (b2-1) to (b2-4) [hereinafter, depending on the formula number Sometimes referred to as “cation (b2-1)”. ] Is more preferable.

In formula (b2-1) to formula (b2-4),
Each of R ^{b4 to} R ^b6 independently 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; , R ^b4 and R ^b5 together form a ring containing a sulfur atom. The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic saturated 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 is substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, the plurality of R ^b7 are the same or different from each other, and when n2 is 2 or more, the plurality of R ^b8 are the same or different from each other.
R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or R ^b9 and R ^b10 are combined together. Together with the sulfur atom to which they are attached, forms a 3- to 12-membered ring (preferably a 3- to 7-membered ring). One or more —CH ₂ — constituting the ring may be replaced by —O—, —SO— or —CO—.
R ^b11 represents a hydrogen atom, 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.
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. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group has 1 to 12 carbon atoms. Or an alkoxycarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) together with —CH—CO— to which they are bonded. One or more —CH ₂ — constituting the ring may be replaced by —O—, —SO— or —CO—.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b24 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 are the same or different from each other. When p2 is 2 or more, the plurality of R ^b14 are the same or different from each other. When q2 is 2 or more, the plurality of R ^b15 are the same. Alternatively, when r2 is 2 or more, a plurality of R ^b16 are the same or different from each other, when s2 is 2 or more, a plurality of R ^b17 are the same or different from each other, and when t2 is 2 or more, a plurality of R ^{b16 b18} are the same or different from each other.

R ^b4 and R ^b5 may together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with the sulfur atom to which they are bonded.

特に、Ｒ^b9〜Ｒ^b11の脂環式炭化水素基は、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- An ethylhexyl group is mentioned. In particular, the aliphatic hydrocarbon group represented by 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.
The alicyclic hydrocarbon group 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 20 or less including the carbon number of the alkyl group. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

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

  Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, and an isobornyl group. Can be mentioned.

Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-adamantyl group. Substituted or unsubstituted phenyl groups such as phenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group; biphenylyl group, naphthyl group, phenanthryl 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 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.
In addition, when an alkyl group or an alicyclic hydrocarbon group is contained in an aromatic hydrocarbon group, a C1-C12 alkyl group and a C3-C18 alicyclic hydrocarbon group are preferable.

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

The ring containing a sulfur atom which may be formed by combining R ^b4 and R ^b5 is any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. As long as it contains one or more sulfur atoms, it may further contain one or more oxygen atoms. As the ring, a ring having 3 to 18 carbon atoms is preferable, and a ring having 4 to 18 carbon atoms is more preferable.

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 a 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.

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

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

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

  The acid generator (I) is a combination of the above anions and the above cations. These can be arbitrarily combined, and among them, the salt represented by the following is preferable.

［式中、Ｘ²、Ｒ⁴及びＺ⁺は、上記と同じ意味を表す。］ The acid generator (I) can be obtained, for example, by reacting a salt represented by the formula (I-0-1) with a compound represented by the formula (I-0-2) in a solvent. . Examples of the solvent include chloroform.

[Wherein, X ² , R ⁴ and Z ⁺ represent the same meaning as described above. ]

Examples of the salt represented by the formula (I-0-1) include salts represented by the following.

［式中、Ｒ⁴は、上記と同じ意味を表す。］
式（Ｉ−０−３）で表される化合物としては、例えば、以下で表される化合物等が挙げられる。

The compound represented by the formula (I-0-2) is obtained by reacting a salt represented by the formula (I-0-3) with a compound represented by the formula (I-0-4) in a solvent. Can be obtained.
Examples of the solvent include chloroform.

[Wherein R ⁴ represents the same meaning as described above. ]
Examples of the compound represented by the formula (I-0-3) include compounds represented by the following.

［式中、Ｘ²、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＺ⁺は、上記と同じ意味を表す。］ The salt represented by the formula (IA) can be obtained, for example, by reacting the salt represented by the formula (IA-1) with the compound represented by the formula (IA-2) in a solvent. Examples of the solvent include chloroform.

[Wherein, X ² , R ⁶ , R ⁷ , R ⁸ and Z ⁺ represent the same meaning as described above. ]

［式中、Ｘ²、Ｒ⁷、Ｒ⁸及びＺ⁺は、上記と同じ意味を表す。］
式（ＩＡ−３）で表される塩は、例えば、以下で表される塩等が挙げられる。

式（ＩＡ−４）で表される化合物としては、トリフルオロピルビン酸エチル等が挙げられる。 The salt represented by the formula (IA-1) is obtained by reacting the salt represented by the formula (IA-3) and the compound represented by the formula (IA-4) in a solvent in the presence of an acid catalyst. Can be manufactured. Examples of the solvent include dimethylformamide. Examples of the acid catalyst include p-toluenesulfonic acid.

[Wherein, X ² , R ⁷ , R ⁸ and Z ⁺ represent the same meaning as described above. ]
Examples of the salt represented by the formula (IA-3) include salts represented by the following.

Examples of the compound represented by the formula (IA-4) include ethyl trifluoropyruvate.

［式中、Ｒ⁶は、上記と同じ意味を表す。］
式（ＩＡ−５）で表される化合物としては、例えば、以下で表される化合物等が挙げられる。

The compound represented by the formula (IA-2) can be obtained by reacting the salt represented by the formula (IA-5) and the compound represented by the formula (IA-6) in a solvent. .
Examples of the solvent include chloroform.

[Wherein R ⁶ represents the same meaning as described above. ]
Examples of the compound represented by the formula (IA-5) include compounds represented by the following.

  The acid generator (I) may be used alone or in combination of two or more.

［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メチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｒ^II4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。
ＺII⁺は、有機カチオンを表す。］ <Acid generator (II)>
The acid generator (II) 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 (II) include the acid generators and formula (II-0) described in JP2009-145408A, JP2009-229603A, and JP2010-111660A. 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 C1-C20 divalent hydrocarbon group which may have a single bond or a substituent, and the methylene group contained in the hydrocarbon group is replaced with an oxygen atom or a carbonyl group. Also good.
R ^II4 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.
ZII ⁺ 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メチレン基は、酸素原子又はカルボニル基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メチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
ｖは、０〜２の整数を表す。
Ｒ^II5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Ｒ^II5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、Ｒ^II5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 the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
Ring W ⁰² represents a saturated hydrocarbon ring having 3 to 12 carbon atoms, and the methylene group contained in the saturated hydrocarbon ring may be replaced with an oxygen atom or a carbonyl group.
v represents an integer of 0 to 2.
R ^II5 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 ^II5 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 ^II5 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 ^II5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl tomb, 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、Ｒ^II5、ｖ及びｗは、上記と同じ意味を表す。
＊は、結合手を表す。］ The ring W ⁰² to which L ⁰² and L ⁰³ are bonded is represented by the following formula (II-0-A). In formula (II-0-A), the right and left sides are also described in formula (II-0-L ⁰¹ ). Of the two bonds represented by *, the left bond is L ^02. The right bond is bonded to ^L03 .

[In the formula (II-0-A), W ⁰² , R ^II5 , v and w represent the same meaning as described above.
* Represents a bond. ]

Examples of the divalent group represented by the formula (II-0-A) include a divalent group represented by the following.

As described above, the hydrocarbon group of R ^II4 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 ^II4 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-.

As a substituent which the hydrocarbon ring in the ring W ¹ has, in addition to R ^II4 , it may be substituted with a C 1-6 alkyl group, a halogen atom or a hydroxy group which may be substituted with a halogen atom or a hydroxy 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。
Ｒ^II5は、炭素数１〜６のアルキル基を表す。］

［式（ＩＩ−２）中、Ｒ^II6、Ｒ^II7及びＲ^II8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、Ｒ^II9、Ｒ^II10及びＲ^II11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メチレン基は、酸素原子又はカルボニル基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メチレン基は、酸素原子又はカルボニル基で置き換わっていてもよい。
Ｒ^II14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Ｒ^II14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 ^II5 represents an alkyl group having 1 to 6 carbon atoms. ]

Wherein ^{(II-2), R II6} , R II7 and R ^II8 each independently represents an alkyl group having 1 to 6 carbon atoms. ]

[In Formula (II-3), R ^II9 , R ^II10 and R ^II11 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 the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group.
Ring W ³ represents a saturated hydrocarbon ring having ^{3 to} 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon ring may be replaced with an oxygen atom or a carbonyl group.
R ^II14 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 ^II14 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、Ｒ^II4、環Ｗ¹及びＺII⁺は、式（ＩＩ−０）のそれらと同じ意味を表す。
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メチレン基は、酸素原子又はカルボニル基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 the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group. 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 ^II4 , ring W ¹ and ZII ⁺ represent the same meaning as those in formula (II-0).
L ¹ represents a single bond or an alkanediyl group having 1 to 10 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxygen atom or a carbonyl group. ]

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

Examples of the group in which the methylene group in the alkanediyl group of L ¹ is replaced by an oxygen atom or a carbonyl group include those represented by formula (b1-1) to formula (b1-6): (B1-6) describes the left and right in accordance with the formula (II), is bonded to C (Q ¹ ) (Q ² ) − on the left side, and of the two bonds represented by *, Combine with -CO- on the right. 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−Ｃ（Ｑ¹）（Ｑ²）−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 —C (Q ¹ ) (Q ² ) —).

［式（ＩＩ−４ａ）中、Ｑ¹、Ｑ²、Ｌ¹、Ｒ^II4、環Ｗ¹、Ｌ³、環Ｗ³、Ｒ^II14、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 ^II4 , Ring W ¹ , L ³ , Ring W ³ , R ^II14 , 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, ZII ⁺ has the same meaning as described above.

Examples of the organic cation (ZII ⁺ ) contained in the acid generator (II) include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation. Is an organic sulfonium cation or an organic iodonium cation, and more preferably, the above-described formula (b2-1), formula (b2-2), formula (b2-3), formula (b2-4) and (b2-1). -1) is an organic cation represented by any one of the above.

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 1-1 to Table 1-6. In the table, 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) The organic cation represented is represented as “(b2-c-1)” or the like according to the formula number.

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

（Ｒ^II4は、炭素数１〜１２の炭化水素基を表し、Ｒ^II4’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 ^II4 represents a hydrocarbon group having 1 to 12 carbon atoms, and R ^{II4 ′} 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-2A). A salt can be obtained. Examples of the solvent include chloroform. Examples of the base catalyst include lithium amide.

［式中、Ｘ^II1及びＸ^II2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 ^II1 and X ^II2 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.

［Ｘ^II1及びＸ^II2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 ^II1 and X ^II2 each independently represent 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, thereby being 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.
<Acid generator other than acid generator (I) and acid labile group (II)>
The resist composition of the present invention may contain an acid generator other than the acid generator (I) and the acid generator (II) described above (hereinafter sometimes referred to as “acid generator (B)”). .
The acid generator (B) may be either nonionic or ionic. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonate), sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712 The compound which generate | occur | produces an acid by the radiation as described in etc. can be used.

  The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “salt (B1)”).

［式（Ｂ１）中、
Ｑ^b1及びＱ^b2は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、炭素数１〜２４の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基に置き換わっていてもよく、該飽和炭化水素基を構成するメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｙは、水素原子、フッ素原子、置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基を構成するメチレン基は、酸素原子、スルホニル基又はカルボニル基に置き換わっていてもよい。
Ｚ１⁺は、有機カチオンを表す。］

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group, and methylene constituting the saturated hydrocarbon group The group may be replaced by an oxygen atom or a carbonyl group.
Y represents a hydrogen atom, a fluorine atom, or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the methylene group constituting the alicyclic hydrocarbon group is an oxygen atom, A sulfonyl group or a carbonyl group may be substituted.
Z1 ⁺ represents an organic cation. ]

^Examples of the perfluoroalkyl group for Q ^b1 and Q ^b2 include the same groups as those for Q ¹ and Q ² in formula (II-0).
Q ^b1 and Q ^b2 are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

Examples of the saturated hydrocarbon group for L ^b1 include an aliphatic saturated hydrocarbon group such as a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic alicyclic saturated hydrocarbon group, A combination of two or more of these groups may be used.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, Linear alkanediyl groups such as 17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group;
Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4- Branched alkanediyl groups such as diyl groups;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

Examples of the group in which one or more methylene groups constituting the saturated hydrocarbon group of L ^b1 are replaced by an oxygen atom or a carbonyl group include those represented by any of formulas (b1′-1) to (b1′-7). Group to be used. In addition, Formula (b1'-1)-Formula (b1'-7) has described the right and left according to Formula (B1), and it is C on the left side among the two bonds represented by *, respectively. It binds to (Q ^b1 ) (Q ^b2 ) — and on the right side to —Y. The same applies to specific examples of the following formulas (b1′-1) to (b1′-7).

式（ｂ１’−１）〜式（ｂ１’−７）中、
Ｌ^b2'は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表す。
Ｌ^b3'は、単結合又は炭素数１〜１９の２価の飽和炭化水素基を表す。
Ｌ^b4'は、炭素数１〜２０の２価の飽和炭化水素基を表す。但しＬ^b3'及びＬ^b4'の合計炭素数上限は２０である。
Ｌ^b5'は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表す。
Ｌ^b6'は、炭素数１〜２２の２価の飽和炭化水素基を表す。但しＬ^b5'及びＬ^b6'の合計炭素数上限は２２である。
Ｌ^b7'は、単結合又は炭素数１〜２２の２価の飽和炭化水素基を表す。
Ｌ^b8'は、炭素数１〜２３の２価の飽和炭化水素基を表す。但しＬ^b7'及びＬ^b8'の合計炭素数上限は２３である。
Ｌ^b9'は、単結合又は炭素数１〜１９の２価の飽和炭化水素基を表す。
Ｌ^b10'は、炭素数１〜２１の２価の飽和炭化水素基を表す。但しＬ^b9'及びＬ^b10'の合計炭素数の上限は２１である。
Ｌ^b11'及びＬ^b12'は、単結合又は炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｌ^b13'は、炭素数１〜１９の２価の飽和炭化水素基を表す。但しＬ^b11'、Ｌ^b12'及びＬ^b13'の合計炭素数の上限は１９である。
Ｌ^b14'及びＬ^b15'は、それぞれ独立に、単結合又は炭素数１〜２０の２価の飽和炭化水素基を表す。
Ｌ^b16'は、炭素数１〜２１の２価の飽和炭化水素基を表す。但しＬ^b14'、Ｌ^b15'及びＬ^b16'の合計炭素数の上限は２１である。

In formula (b1′-1) to formula (b1′-7),
L ^{b2 ′} represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms.
L ^{b3 ′} represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^{b4 ′} represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. However, the upper limit of the total carbon number of L ^{b3 ′} and L ^{b4 ′} is 20.
L ^{b5 ′} represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms.
L ^{b6 ′} represents a divalent saturated hydrocarbon group having 1 to 22 carbon atoms. However, the upper limit of the total carbon number of L ^{b5 ′} and L ^{b6 ′} is 22.
L ^{b7 ′} represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms.
L ^{b8 ′} represents a divalent saturated hydrocarbon group having 1 to 23 carbon atoms. However, the upper limit of the total carbon number of L ^{b7 ′} and L ^{b8 ′} is 23.
L ^{b9 ′} represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^{b10 ′} represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. However, the upper limit of the total carbon number of L ^{b9 ′} and L ^{b10 ′} is 21.
L ^{b11 ′} and L ^{b12 ′} represent a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^{b13 ′} represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. However, the upper limit of the total carbon number of L ^{b11 ′} , L ^{b12 ′} and L ^{b13 ′} is 19.
L ^{b14 ′} and L ^{b15 ′} each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms.
L ^{b16 ′} represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. However, the upper limit of the total carbon number of L ^{b14 ′} , L ^{b15 ′} and L ^{b16 ′} is 21.

Among them, L ^b1 is preferably any one of the formulas (b1′-1) to (b1′-4), more preferably the formula (b1′-1) or the formula (b1′-2), and more preferably the formula A divalent group represented by (b1′-1), particularly preferably a divalent group represented by the formula (b1′-1) in which L ^b2 is a single bond or —CH ₂ —. .

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.

Examples of the divalent group represented by the formula (b1′-6) include the following.

Examples of the divalent group represented by the formula (b1′-7) include the following.

Specific examples when the hydrogen atom contained in the saturated hydrocarbon group of L ^b1 is substituted with a fluorine atom or a hydroxy group include the following.

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y26).

  Especially, it is preferably a group represented by any one of formulas (Y1) to (Y19), more preferably represented by formula (Y11), formula (Y14), formula (Y15) or formula (Y19). And more preferably a group represented by formula (Y11) or formula (Y14).

Examples of the substituent for the alicyclic hydrocarbon group in Y include a halogen atom, a hydroxy group, an oxo group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 to 3 carbon atoms. 16 alicyclic hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, aralkyl groups having 7 to 21 carbon atoms, acyl groups having 2 to 4 carbon atoms, glycidyloxy Group or — (CH ₂ ) _j2 —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or 6 to 6 carbon atoms). 18 represents an aromatic hydrocarbon group, and j2 represents an integer of 0 to 4.

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

Examples of Y include the following.

  Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably a substituent (for example, an oxo group, a hydroxy group, etc.). A good adamantyl group, more preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group.

The sulfonate anion in the salt (B1) is preferably an anion represented by the formula (b1-1-1) to the formula (b1-1-9). In the following formulas, the definitions of the symbols have the same meaning as described above, and R ^b2 and R ^b3 each independently represent an alkyl group having 1 to 4 carbon atoms (preferably a methyl group).
Specific examples of the sulfonate anion in the salt (B1) include anions described in JP 2010-204646 A.

Examples of the organic cation (Z1 ⁺ ) contained in the salt (B1) include an organic onium cation such as an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. It is an organic sulfonium cation or an organic iodonium cation, more preferably an arylsulfonium cation, and still more preferably the same as the cation represented by any one of the formulas (b2-1) to (b2-4) described above. Is.

  Examples of the salt (B1) include salts represented by formulas (B1-1) to (B1-20), respectively. Among them, those containing an arylsulfonium cation are preferable. Formula (B1-1), Formula (B1-2), Formula (B1-3), Formula (B1-6), Formula (B1-7), Formula (B1-11) ), Formula (B1-12), Formula (B1-13), Formula (B1-14), Formula (B1-18), Formula (B1-19), or Formula (B1-20). More preferred are salts.

  The acid generator (B) may be used alone or in combination of two or more.

  When the resist composition contains only the acid generator (I) as the acid generator, the content of the acid generator (I) is preferably 1 part by mass or more with respect to 100 parts by mass of the resin (A) ( More preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass or less).

  When the resist composition contains the acid generator (I) and the acid generator (II), the total content of the acid generator (I) and the acid generator (II) is 100 masses of the resin (A). The amount is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 35 parts by mass or less). In this case, the content ratio (mass ratio) of the acid generator (I) and the acid generator (II) is, for example, 5:95 to 95: 5, preferably 10:90 to 90:10, and more preferably 15 : 85-85: 15.

When the resist composition contains an acid generator (I), an acid generator (II), and an acid generator (B), the acid generator (I), the acid generator (II), and the acid generator (B ) With respect to 100 parts by mass of the resin (A), preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 35 parts by mass or less). It is.
The ratio (mass ratio) between the total content of the acid generator (I) and the acid generator (II) and the content of the acid generator (B) is, for example, 5:95 to 95: 5, preferably 10: 90-90: 10, More preferably, it is 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 may contain individually by 1 type and may contain 2 or more types.

<Basic compound (C)>
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 any one of the formulas (C1) to (C8) and (C1-1), more preferably represented by the formula (C1-1). The compound which is made is mentioned.

［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は互いに同一又は相異なる。］

[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 from each other. ]

［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は互いに同一又は相異なる。］

[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 from each other. ]

［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は互いに同一又は相異なり、ｐ３が２以上であるとき、複数のＲ^c15は互いに同一又は相異なる。
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 represent an integer of 0 to 3, and when o3 is 2 or more, the plurality of R ^c14 are the same or different from each other, and when p3 is 2 or more, the plurality of R ^c15 are the same as each other 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は互いに同一又は相異なり、ｒ３が２以上であるとき、複数のＲ^c19は互いに同一又は相異なり、ｓ３が２以上であるとき、複数のＲ^c20は互いに同一又は相異なる。
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 from each other, and when r3 is 2 or more, the plurality of R ^c19 are When the same or different from each other and s3 is 2 or more, the plurality of R ^c20 are the same or different from each other.
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 formula (C1) to formula (C8) and formula (C1-1), the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, alkanediyl group are the same as those described above. Is mentioned.
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) is preferably about 0.01 to 5% by mass, more preferably about 0.01 to 3% by mass, and particularly preferably in the solid content of the resist composition. It is about 0.01-1 mass%.

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

<Preparation of resist composition>
The resist composition comprises a resin (A), an acid generator (I) and an acid generator (II), and a solvent (E), an acid generator (B), a basic compound (C) and a basic compound (C) used as necessary. It can prepare by mixing another component (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select the suitable temperature range from the range of 10-40 degreeC according to the solubility with respect to the solvent (E), such as a kind, etc. of 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.

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

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. 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 types of laser light such as those that convert the wavelength of laser light from the laser to emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, those that irradiate an electron beam or extreme ultraviolet light (EUV), etc. it can.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection group reaction of the resin (A). 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（Ｉ１−ａ）で表される塩を、特開２００８−７４０９号公報に記載された方法で合成した。式（Ｉ１−ａ）で表される塩１０．００部、ジメチルホルミアミド５０．００部、式（Ｉ１−ｂ）で表される化合物４．１８部及びｐ−トルエンスルホン酸０．７０部を仕込み、１００℃で２時間攪拌した。得られた反応液に、クロロホルム２００部及びイオン交換水５０部を仕込み、３０分間攪拌し、分液した。この水洗操作を３回繰り返した。回収された有機層を濃縮し、濃縮物をカラム（メルク シリカゲル６０−２００メッシュ 展開溶媒：クロロホルム／メタノール＝５／１）分取することにより、式（Ｉ１−ｃ）で表される塩２．４３部を得た。 Synthesis Example 1 [Synthesis of salt represented by formula (I-1)]

The salt represented by the formula (I1-a) was synthesized by the method described in JP-A-2008-7409. 10.00 parts of salt represented by formula (I1-a), 50.00 parts of dimethylformamide, 4.18 parts of compound represented by formula (I1-b) and 0.70 parts of p-toluenesulfonic acid And stirred at 100 ° C. for 2 hours. To the obtained reaction solution, 200 parts of chloroform and 50 parts of ion-exchanged water were added, stirred for 30 minutes, and separated. This washing operation was repeated three times. The collected organic layer is concentrated, and the concentrate is fractionated in a column (Merck silica gel 60-200 mesh developing solvent: chloroform / methanol = 5/1) to give a salt represented by the formula (I1-c) 2. 43 parts were obtained.

式（Ｉ１−ｄ）で表される化合物０．６３部及びクロロホルム１０部を仕込み、２３℃で３０分間攪拌し、式（Ｉ１−ｅ）で表される化合物０．５５部を仕込み、６０℃で１時間攪拌した。得られた反応物を２３℃まで冷却し、ろ過することにより、式（Ｉ１−ｆ）で表される化合物を含む溶液を得た。式（Ｉ１−ｆ）で表される化合物を含む溶液に、式（Ｉ１−ｃ）で表される塩２．１０部を仕込み、６０℃で６時間攪拌した。得られた反応物に、クロロホルム５０部及びイオン交換水２０部を仕込み、攪拌、分液を行った。水洗を５回行った。得られた有機層を濃縮し、得られた濃縮物をアセトニトリル２０部に溶解し、濃縮した。得られた濃縮物に、ｔｅｒｔ−ブチルメチルエーテル３０部を加えて攪拌し、上澄液を除去した。得られた残渣をアセトニトリルに溶解し、濃縮することにより、式（Ｉ−１）で表される塩１．６９部を得た。

0.63 part of a compound represented by the formula (I1-d) and 10 parts of chloroform were charged, stirred at 23 ° C. for 30 minutes, 0.55 part of a compound represented by the formula (I1-e) was charged, and 60 ° C. For 1 hour. The obtained reaction product was cooled to 23 ° C. and filtered to obtain a solution containing a compound represented by the formula (I1-f). A solution containing the compound represented by the formula (I1-f) was charged with 2.10 parts of the salt represented by the formula (I1-c) and stirred at 60 ° C. for 6 hours. To the obtained reaction product, 50 parts of chloroform and 20 parts of ion-exchanged water were charged, stirred and separated. Water washing was performed 5 times. The obtained organic layer was concentrated, and the resulting concentrate was dissolved in 20 parts of acetonitrile and concentrated. To the obtained concentrate, 30 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.69 parts of the salt represented by the formula (I-1).

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 573.1

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: manufactured by Merck, Inc. 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, Inc. 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: manufactured by Merck, Inc. Developing solvent: ethyl acetate

  A salt represented by the formula (II41-e) was synthesized by the method described in Example 1 of JP-A-2008-127367. 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, Inc. Developing solvent: n-heptane / ethyl acetate = 1/1 (volume ratio)

  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, and a compound 3.12 represented by the formula (II9-c). Part, molecular sieve (trade name: Molecular sieve 5A, manufactured by Wako Pure Chemical Industries, Ltd.) 7.00 part and lithium amide 0.14 part were heated 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, Inc. 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部を添加攪拌した後、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部を添加攪拌後、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分間攪拌した後、上澄み液を除去した後、濃縮した。得られた残渣に、ｎ−ヘプタン２００部を添加、２３℃で３０分間攪拌した後、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, 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 then 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 then filtered to obtain 61.54 parts of a 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式番号に応じて、「モノマー（ａ１−１−３）」等という。 Synthesis of Resin (A) Compounds (monomers) used in the synthesis of resin (A) are shown below.

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

Synthesis Example 10 [Synthesis of Resin A1]
As the monomer, using monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1), The molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] It mixed so that it might become 45: 14: 2.5: 22: 16.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added, and it was set as the solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and the resin was filtered to obtain a resin A1 having a weight average molecular weight of 7.8 × 10 ³ (co-polymer). Polymer) with a yield of 73%. This resin A1 has the following structural units and was soluble in butyl acetate.

Synthesis Example 11 [Synthesis of Resin A2]
As the monomer, using monomer (a1-1-3), monomer (a1-2-3), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1), The molar ratio [monomer (a1-1-3): monomer (a1-2-3): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] It mixed so that it might become 45: 14: 2.5: 22: 16.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added, and it was set as the solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and this resin was filtered to obtain a resin A2 having a weight average molecular weight of 7.8 × 10 ³ (co-polymer). Polymer) with a yield of 70%. This resin A2 had the following structural units and was soluble in butyl acetate.

Synthesis Example 12 [Synthesis of Resin A3]
The monomer (a1-1-2), monomer (a2-1-1) and monomer (a3-1-1) are mixed in a molar ratio [monomer (a1-1-2): monomer (2-1-1): Monomer (a3-1-1)] was mixed so as to be 50:25:25, and 1.5 mass times dioxane was further mixed with respect to the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in proportions of 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers. did. This was polymerized by heating at 80 ° C. for about 8 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin was filtered and collected. Again, the resin is dissolved in dioxane, poured into a mixed solvent of a large amount of methanol and water, the resin is precipitated, and the precipitated resin is filtered and recovered three times for reprecipitation purification, and the weight average Resin A3 (copolymer) having a molecular weight of about 9.2 × 10 ³ was obtained in a yield of 60%. This resin A3 had the following structural units and was soluble in butyl acetate.

Synthesis Example 13 [Synthesis of Resin A4]
As the monomer, using monomer (a1-1-3), monomer (a1-5-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1), The molar ratio [monomer (a1-1-3): monomer (a1-5-1): monomer (a2-1-3): monomer (a3-2-3)): monomer (a3-1-1)] However, it mixed so that it might become 45: 14: 2.5: 22: 16.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added, and it was set as the solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° 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 resin obtained was dissolved again in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and the weight-average molecular weight was 7. 6 × 10 ³ resin A4 was obtained with a yield of 68%. This resin A4 has the following structural units.

Synthesis Example 14 [Synthesis of Resin A5]
As the monomer, using monomer (a1-1-2), monomer (a1-5-1), monomer (a2-1-1), monomer (a3-2-3) and monomer (a3-1-1), The molar ratio [monomer (a1-1-2): monomer (a1-5-1): monomer (a2-1-1): monomer (a3-2-3)): monomer (a3-1-1)] Was mixed to be 30: 14: 6: 20: 30, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was 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 85%. This resin A5 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.

ＩＩ４９：式（ＩＩ−４９）で表される塩

酸発生剤ＩＩ−４９の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。

<Resin>
Resins A1 to A5 synthesized in the synthesis example described above,
<Acid generator>
I1: Salt represented by formula (I-1) I2: Central Glass Co., Ltd.

II49: salt represented by formula (II-49)

50 mg of the 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の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。

II41: salt represented by formula (II-41)

50 mg of the 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：

Ｂ１−Ｘ：特開２００７−１６１７０７号公報の実施例に従って合成

B1-3: synthesized according to the example of JP 2010-152341 A

B1-5:

B1-X: synthesized according to the example of JP-A No. 2007-161707

<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 13 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 composition layer formed on the silicon wafer at a 1: 1 line. Using a mask for forming an and-space pattern (pitch: 70 nm to 100 nm), exposure was performed while changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium. After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 2. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

<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 14 to 26 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 according to the resist composition of the present invention, a high-resolution resist pattern can be produced.

<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 27 to 33 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.

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

  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 (5)

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

[In the formula (I),
X ² represents an alkanediyl group having 1 to 6 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a hydroxy group or —OR ⁵ , and a methylene group constituting the alkanediyl group May be replaced by an oxygen atom or a carbonyl group.
R ⁴ and R ⁵ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, and the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The methylene group contained in the group may be replaced with an oxygen atom or a carbonyl group.
Z ⁺ represents an organic cation. ] 2. The resist composition according to claim 1, wherein the acid generator represented by the formula (I) is an acid generator represented by the formula (IA).

[In formula (IA), X ² and Z ⁺ represent the same meaning as described above.
R ⁶ represents a hydrocarbon group having 1 to 17 carbon atoms, the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the methylene group constituting the hydrocarbon group is May be replaced by an oxygen atom or a carbonyl group.
R ⁷ represents an alkyl group having 1 to 6 carbon atoms.
R ⁸ represents a fluorinated alkyl group having 1 to 6 carbon atoms.
However, the total carbon number of R ⁶ , R ⁷ and R ⁸ is 20 or less. ] 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 C1-C20 divalent hydrocarbon group which may have a single bond or a substituent, and the methylene group contained in the hydrocarbon group is replaced with an oxygen atom or a carbonyl group. Also good.
R ^II4 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.
ZII ⁺ represents an organic cation. ]   Furthermore, the resist composition as described in any one of Claims 1-3 containing a solvent. (1) The process of apply | coating the resist composition as described in any one of Claims 1-4 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: