JP2013231163A - Compound, resin, resist composition, and method for production of resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound useful as a material of the resin for a resist composition, capable of obtaining a pattern with less flaw marks and having good pattern.SOLUTION: There is provided a compound represented by formula (I) (wherein Ris hydrogen or methyl; Ais 1-6C alkanediyl; Ais 1-18C divalent saturated hydrocarbon having halogen; Xis *-CO-O- or *-O-CO-; * is a hand bonding to A; Ais a single bond or 1-6C alkanediyl; and Wis a heterocycle ring which may have a substituent).

Description

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

（式中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のフルオロアルキル基を表す。Ｗは多環式の脂肪族環式基を含む基である。） Patent Document 1 discloses a fluorine-containing polymer compound having a structural unit (f1) containing a basic acid dissociable group and a structural unit (f2-1) represented by the formula (f2-1), an alkali by the action of an acid. A resist composition containing a resin with increased solubility in an aqueous solution and an acid generator is described.

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. W is a group containing a polycyclic aliphatic cyclic group.)

JP 2010-197413 A

An object of the present invention is to provide a compound useful as a resin material for a resist composition that can obtain a pattern having a small number of defects and a good shape.

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ａ^１は、炭素数１〜６のアルカンジイル基を表す。
Ａ^２は、ハロゲン原子を有する炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｘ^１は、＊−ＣＯ−Ｏ−又は＊−Ｏ−ＣＯ−を表す。＊は、Ａ^２との結合手を表す。
Ａ^３は、単結合又は炭素数１〜６のアルカンジイル基を表す。
環Ｗ^１は、置換基を有してもよい複素環を表す。］
〔２〕環Ｗ^１が、環状エーテル構造を含む環である〔１〕記載の化合物。
〔３〕〔１〕又は〔２〕記載の化合物に由来する構造単位を有する樹脂。
〔４〕〔３〕記載の樹脂、酸の作用によりアルカリ水溶液への溶解性が増大する樹脂及び酸発生剤を含むレジスト組成物。
〔５〕（１）上記〔３〕または〔４〕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 compound represented by the formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
A ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
A ² represents a C 1-18 divalent saturated hydrocarbon group having a halogen atom.
X ¹ represents * —CO—O— or * —O—CO—. * Represents a bond to ^{A 2.}
A ³ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ring W ¹ represents a heterocyclic ring which may have a substituent. ]
[2] The compound according to [1], wherein the ring W ¹ is a ring containing a cyclic ether structure.
[3] A resin having a structural unit derived from the compound according to [1] or [2].
[4] A resist composition comprising the resin according to [3], a resin whose solubility in an alkaline aqueous solution is increased by the action of an acid, and an acid generator.
[5] (1) A step of applying the resist composition according to [3] or [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 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:

  ADVANTAGE OF THE INVENTION According to this invention, the resist composition which can form a resist pattern with few defects and a favorable shape can be obtained.

It is a figure which represents typically the cross-sectional shape in a line and space resist pattern.

  In this specification, unless otherwise specified, each substituent in the chemical formula applies the following examples of substituents while appropriately selecting the number of carbon atoms. In each group, when stereoisomers exist, all stereoisomers are included. In the following examples of substituents, the numerical value attached to “C” indicates the carbon number of each group.

The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
The aliphatic hydrocarbon group includes a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group (hereinafter sometimes referred to as “alicyclic hydrocarbon group”), and a group obtained by combining these. The chain aliphatic hydrocarbon group includes a linear aliphatic hydrocarbon group and a branched aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be an aliphatic unsaturated hydrocarbon group, but is preferably an aliphatic saturated hydrocarbon group.

Examples of the monovalent chain aliphatic hydrocarbon group include an alkyl group.
Examples of the alkyl group include a methyl group (C ₁ ), an ethyl group (C ₂ ), a propyl group (C ₃ ), a butyl group (C ₄ ), a pentyl group (C ₅ ), a hexyl group (C ₆ ), and heptyl. group _(C 7), octyl _(C 8), decyl (C _10), dodecyl (C _12), hexadecyl (C _14), pentadecyl (C _15), hexyl decyl group (C _16), heptadecyl Examples thereof include a group (C ₁₇ ) and an octadecyl group (C ₁₈ ).
Examples of the divalent chain aliphatic hydrocarbon group include an alkanediyl group obtained by removing one hydrogen atom from an alkyl group, and specific examples thereof include a methylene group, an 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-1,17-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 and 2-methylbutane-1,4-diyl group.

The cyclic aliphatic hydrocarbon group includes both monocyclic and polycyclic groups.
The monovalent monocyclic aliphatic hydrocarbon group is, for example, a group obtained by removing one hydrogen atom of a cycloalkane represented by the formulas (KA-1) to (KA-7).

The monovalent polycyclic aliphatic hydrocarbon group is, for example, a group obtained by removing one hydrogen atom of the aliphatic hydrocarbon represented by the formulas (KA-8) to (KA-23).

  Examples of the divalent cyclic aliphatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the alicyclic hydrocarbon of the formula (KA-1) to the formula (KA-23).

  As the substituent when the aliphatic hydrocarbon group has a substituent, for example, a halogen atom, a hydroxy group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aralkyl group, and an aryloxy group, unless otherwise specified. Etc.

Examples of the monovalent aromatic hydrocarbon group include a phenyl group (C ₆ ), a tolyl group (C ₇ ), a xylyl (C ₈ ), a cumenyl group (C ₉ ), a mesityl group (C ₉ ), and a naphthyl group (C ₁₀ ), Anthryl group (C ₁₄ ), biphenyl group (C ₁₂ ), phenanthryl group (C ₁₄ ) and aryl group such as fluorenyl group (C ₁₃ ).
Examples of the divalent aromatic hydrocarbon group include an arylene group obtained by removing one hydrogen atom from these aryl groups.

  Examples of the substituent in the case where the aromatic hydrocarbon group has a substituent include a halogen atom, an alkoxy group, an acyl group, an alkyl group, and an aryloxy group, unless otherwise specified.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of alkoxy groups include methoxy group (C ₁ ), ethoxy group (C ₂ ), propoxy group (C ₃ ), butoxy group (C ₄ ), pentyloxy group (C ₅ ), hexyloxy group (C ₆ ), heptyl Examples thereof include an oxy group (C ₇ ), an octyloxy group (C ₈ ), a decyloxy group (C ₁₀ ), and a dodecyloxy group (C ₁₂ ).
Examples of the acyl group include acetyl group (C ₂ ), propionyl group (C ₃ ), butyryl group (C ₄ ), valeryl group (C ₅ ), hexanoyl group (C ₆ ), heptanoyl group (C ₇ ), octanoyl group ( C _8), which alkyl group and a carbonyl group such as a decanoyl group (C ₁₀₎ and dodecanoyl groups (C ₁₂₎ is bonded, as well as those in which the aryl group and a carbonyl group such as benzoyl group (C ₇₎ is bonded Is mentioned.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group.
Examples of the aralkyl group include benzyl group (C ₇ ), phenethyl group (C ₈ ), phenylpropyl group (C ₉ ), naphthylmethyl group (C ₁₁ ), and naphthylethyl group (C ₁₂ ).
Aryloxy groups include phenyloxy group (C ₆ ), naphthyloxy group (C ₁₀ ), anthryloxy group (C ₁₄ ), biphenyloxy group (C ₁₂ ), phenanthryloxy group (C ₁₄ ) and full Examples include those in which an aryl group such as an oleenyloxy group (C ₁₃ ) and an oxygen atom are bonded.

Further, in the present specification, "(meth) acrylic monomer", at least one monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " means. 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.

［式（Ｉ）中、
Ｒ^１は、水素原子又はメチル基を表す。
Ａ^１は、炭素数１〜６のアルカンジイル基を表す。
Ａ^２は、ハロゲン原子を有する炭素数１〜１８の２価の飽和炭化水素基を表す。
Ｘ^１は、＊−ＣＯ−Ｏ−又は＊−Ｏ−ＣＯ−を表す。＊は、Ａ^２との結合手を表す。
Ａ^３は、単結合又は炭素数１〜６のアルカンジイル基を表す。
環Ｗ^１は、置換基を有してもよい複素環を表す。］ <Compound represented by formula (I)>
The compound of the present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”).

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
A ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
A ² represents a C 1-18 divalent saturated hydrocarbon group having a halogen atom.
X ¹ represents * —CO—O— or * —O—CO—. * Represents a bond to ^{A 2.}
A ³ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ring W ¹ represents a heterocyclic ring which may have a substituent. ]

Examples of the alkanediyl group represented by A ¹ and A ³ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane- 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.
A ¹ is preferably an ethylene group.
A ³ is preferably a methylene group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is preferred.
The saturated hydrocarbon group represented by A ² includes any of a chain type and a cyclic type, and a divalent saturated hydrocarbon group obtained by combining these. This saturated hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 2 to 3 carbon atoms.
The saturated hydrocarbon group having a halogen atom represented by A ² is preferably an aliphatic saturated hydrocarbon group having a fluorine atom.
Examples of the chain type divalent saturated hydrocarbon group having a halogen atom (preferably a fluorine atom) include a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a perfluorobutanediyl group, a perfluoropentanediyl group, a dichloromethylene group, and And a dibromomethylene group.
The cyclic divalent saturated hydrocarbon group having a halogen atom (preferably a fluorine atom) may be monocyclic or polycyclic. Examples of the monocyclic saturated hydrocarbon group include a perfluorocyclohexanediyl group and a perchlorocyclohexanediyl group. Examples of the polycyclic saturated hydrocarbon group include a perfluoroadamantanediyl group.

［式（ＩＡ）中、
ｓ１は、１〜４の整数を表す。ｔ１は、０〜２の整数を表す。但し、ｓ１＋ｔ１は、１〜４である。
Ｒ^２は、炭素数１〜１２の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−で置き換わっていてもよい。
ｕ１は、０〜９の整数を表し、ｕ１が２以上である場合、複数のＲ^２は同一又は相異なる。
＊ はＸ^１との結合手である。］ The heterocyclic ring represented by the ring W ¹ is preferably a ring having 2 to 6 carbon atoms, specifically, an alkylene group having 1 to 4 carbon atoms and at least one oxygen atom, nitrogen atom and / or A ring having a sulfur atom (preferably an oxygen atom). The atoms constituting the heterocyclic ring may have one or more substituents.
The heterocyclic ring represented by the ring W ¹ is preferably a ring containing a cyclic ether structure having 2 to 5 carbon atoms, more preferably an oxirane ring, an oxetane ring, a tetrahydrofuran ring or a tetrahydropyran ring, still more preferably. Is an oxirane ring or an oxetane ring.
Examples of the heterocyclic ring represented by the ring W ¹ include a ring represented by the formula (IA).

[In the formula (IA),
s1 represents an integer of 1 to 4. t1 represents the integer of 0-2. However, s1 + t1 is 1-4.
R ² represents a saturated hydrocarbon group having 1 to 12 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—.
u1 represents an integer of 0 to 9, when u1 is 2 or more, plural ^{R 2} are same or different.
* Represents a bond to ^{X 1.} ]

The substituent that the heterocyclic ring represented by the ring W ¹ has is an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, in which one or a plurality of methylene groups may be replaced with an oxygen atom. A hydrocarbon group is mentioned.
Examples of the aliphatic saturated hydrocarbon group include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group and hexyl group; cycloalkyl groups having 3 to 10 carbon atoms such as cyclohexyl group and adamantyl group. Group; etc. are mentioned.
As a ring represented by a formula (IA), the ring represented by the following is mentioned, for example. In the following formula, * represents a bond.

As compound (I), the following are mentioned, for example.

In the above compounds, compounds in which the methyl group corresponding to R ¹ is replaced with a hydrogen atom can also be mentioned as specific examples of the compound (I).

Among the compounds (I), the compound (IB) in which X ¹ is * —CO—O— (* represents a bond to A ² ) includes, for example, the compound (IB-a) and the compound (IB—). b) can be produced by reacting in a solvent in the presence of a condensing agent. Hereinafter, unless otherwise noted, the symbols are as defined above.

Tetrahydrofuran etc. are mentioned as a solvent used for this manufacturing method.
Examples of the condensing agent include 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
Examples of the compound (IB-a) include hydroxyethyl methacrylate and hydroxyethyl acrylate.

この製造方法に用いる溶媒としては、テトラヒドロフラン等が挙げられる。
化合物（ＩＢ−ｃ）としては、２，２，３，３，４，４−ヘキサフルオロペンタン二酸無水物及びテトラフルオロこはく酸無水物等が挙げられる。
化合物（ＩＢ−ｄ）としては、以下で表される化合物等が挙げられる。

化合物（ＩＢ−ｅ）として、ピリジン以外に、トリエチルアミン、ジイソプロピルエチルアミン、Ｎ―メチルモルホリン及びＮ―メチルピロリジン等を用いても同反応を行うことができる。 Compound (IB-b) can be produced by reacting compound (IB-c), compound (IB-d) and compound (IB-e) in a solvent.

Tetrahydrofuran etc. are mentioned as a solvent used for this manufacturing method.
Examples of the compound (IB-c) include 2,2,3,3,4,4-hexafluoropentanedioic anhydride and tetrafluorosuccinic anhydride.
Examples of the compound (IB-d) include compounds represented by the following.

In addition to pyridine, the same reaction can be carried out using triethylamine, diisopropylethylamine, N-methylmorpholine, N-methylpyrrolidine and the like as compound (IB-e).

<Resin having a structural unit derived from the compound represented by formula (I)>
The resin of the present invention is a resin having a structural unit derived from the compound represented by the formula (I) (hereinafter sometimes referred to as “resin (A1)”).
The resin (A1) has a structural unit derived from the compound represented by the formula (I) described above (hereinafter sometimes referred to as “structural unit (I)”).

The resin (A1) may have a structural unit different from the structural unit (I).
As the structural unit different from the structural unit (I), a structural unit derived from the acid labile monomer (a1) described later, a structural unit represented by the formula (III-1) (hereinafter “structural unit (III-1)”) A structural unit derived from an acid-stable monomer described later, such as a structural unit represented by the formula (III-2) (hereinafter sometimes referred to as “structural unit (III-2)”), And structural units derived from known monomers used in the above. The structural unit (III-1) or the structural unit (III-2) is preferable.

［式（ＩＩＩ−１）中、
Ｒ^１１は、水素原子又はメチル基を表す。
Ａ^１１は、炭素数１〜６のアルカンジイル基を表す。
Ｒ^１２は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］

[In the formula (III-1),
R ¹¹ represents a hydrogen atom or a methyl group.
A ¹¹ represents an alkanediyl group having 1 to 6 carbon atoms.
R ¹² represents a C 1-10 hydrocarbon group having a fluorine atom. ]

［式（ＩＩＩ−２）中、
Ｒ^２１は、水素原子又はメチル基を表す。
環Ｗ^２は、炭素数６〜１０の炭化水素環を表す。
Ａ^２２は、−Ｏ−、^＊−ＣＯ−Ｏ−又は^＊−Ｏ−ＣＯ−（^＊は環Ｗ^２との結合手を表す）を表す。
Ｒ^２２は、フッ素原子を有する炭素数１〜６のアルキル基を表す。］

[In the formula (III-2),
R ²¹ represents a hydrogen atom or a methyl group.
Ring ^{W 2} represents a hydrocarbon ring having 6 to 10 carbon atoms.
A ²² represents —O—, ^* —CO—O—, or ^* —O—CO— ( ^* represents a bond to ring W ² ).
R ²² represents a C 1-6 alkyl group having a fluorine atom. ]

The alkanediyl group represented by A ^11, include the same groups as A ¹ in formula (I).

Examples of the hydrocarbon group having a fluorine atom represented by R ¹² include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Examples of the alkyl group having a fluorine atom include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group including the following groups: Group, perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1 , 1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- ( -Fluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5 , 5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1 , 1,2,2,3,3,4,4,5,5-decafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl And fluorinated alkyl groups such as 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentylmethyl group and perfluorohexyl group.

  The alicyclic hydrocarbon group having a fluorine atom is preferably an alicyclic saturated hydrocarbon having a fluorine atom, and examples thereof include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

Examples of the hydrocarbon ring represented by ring W ² include an alicyclic hydrocarbon ring, and a saturated alicyclic hydrocarbon ring is preferable. Of these, an adamantane ring or a cyclohexane ring is preferable, and an adamantane ring is more preferable.

As structural unit (III-1), the following are mentioned, for example.

In the above structural unit, a structural unit in which a methyl group corresponding to R ¹¹ is replaced with a hydrogen atom can also be given as a specific example of the structural unit (III-1).

上記の構造単位において、Ｒ^２１に相当するメチル基が水素原子に置き換わった構造単位も、構造単位（ＩＩＩ−２）の具体例として挙げることができる。 Examples of the structural unit (III-2) include the structural units represented below.

In the above structural unit, a structural unit in which a methyl group corresponding to R ²¹ is replaced by a hydrogen atom can also be given as a specific example of the structural unit (III-2).

5-100 mol% is preferable with respect to all the structural units of resin (A1), and, as for content of structural unit (I) in resin (A1), 10-100 mol% is more preferable.
When resin (A1) contains structural unit (III-1) and / or structural unit (III-2), these total content is 1-95 mol with respect to all the structural units of resin (A1). % Is preferable, 2 to 80 mol% is more preferable, and 5 to 70 mol% is more preferable.
The content ratio (molar ratio) between the structural unit (III-1) and the structural unit (III-2) [content of the structural unit (III-1): content of the structural unit (III-2)] is Usually, it is 0: 100 to 100: 0, 3:97 to 97: 3 is preferable, and 50:50 to 95: 5 is more preferable.

The resin (A1) having each structural unit with such a content can be produced by using each monomer to be used in the above molar ratio with respect to the total amount of monomers used for producing the resin (A1). .
Each structural unit constituting the resin (A1) 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 (A1) is preferably 5,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). A weight average molecular weight is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography analysis, and the detailed analysis conditions of an analysis are explained in full detail in the Example of this application.

<Resist composition>
The resist composition of the present invention comprises:
(A) A resin (hereinafter sometimes referred to as “resin (A)”) and (B) an acid generator (hereinafter sometimes referred to as “acid generator (B)”).
Here, the resin (A) is
It may contain a resin (A1), and further (A2) a resin whose solubility in an alkaline aqueous solution is increased by the action of an acid (hereinafter sometimes referred to as “resin (A2)”).
The resist composition of the present invention may contain one or more resins (A1) and (A2).
The resin (A1) may have increased solubility in an alkaline aqueous solution due to the action of an acid, or may not increase solubility in an alkaline aqueous solution due to the action of an acid. In the present specification, the resin (A2) does not have the structural unit (I).
When the resin (A1) has increased solubility in an alkaline aqueous solution due to the action of an acid, the resist composition may be a composition containing only the resin (A1) as the resin (A). The resin (A) may be composed of a resin (A1) whose solubility in an alkaline aqueous solution is increased by the action of an acid and a resin (A1) whose solubility in an alkaline aqueous solution is not increased by the action of an acid. It may be made of a resin (A1) whose solubility in an alkaline aqueous solution is increased by the action of an acid.
The resist composition of the present invention preferably further contains (D) a solvent (hereinafter sometimes referred to as “solvent (D)”).

<Resin (A)>
The resin (A) contained in the resist composition of the present invention includes the resin (A1) described above, and further includes the resin (A2) and resins other than the resins (A1) and (A2) as described later. It may be.

<Resin (A2)>
Resin (A2) has increased solubility in an aqueous alkali solution due to the action of an acid. Here, “the solubility in an alkaline aqueous solution is increased by the action of an acid” means that the solubility in an alkaline aqueous solution is increased by contact with an acid. For example, it has an acid labile group (hereinafter sometimes referred to as “acid labile group”), and is insoluble or hardly soluble in an alkaline aqueous solution before contact with an acid, but after contact with an acid, an alkaline aqueous solution Resins that become soluble in
The resin (A2) can be obtained by polymerizing one or more of monomers (a1) having an acid labile group described below (hereinafter sometimes referred to as “acid labile monomer (a1)”). . The polymerization may be performed using a monomer other than the acid labile monomer (a1) as necessary.
The resin (A2) may have a structural unit derived from a monomer known in the art as long as it has the properties described above. Structural units derived from monomers known in the art include acid units such as the above-mentioned structural units (III-1) and (III-2) and structural units derived from the acid-stable monomer (a2) described below. Examples thereof include a structural unit derived from a monomer having no stabilizing group (hereinafter sometimes referred to as “acid-stable monomer”).

<Acid labile monomer (a1)>
The “acid labile group” means a group that has a leaving group, and the leaving group is removed by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

［式（１）中、Ｒ^a1、Ｒ^a２及びＲ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、又はアルキル基で置換されていてもよい炭素数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、前記炭化水素基及び前記２価の炭化水素基に含まれる−ＣＨ_２−は、−Ｏ―又は―Ｓ−で置き換わってもよい。］

[In the formula (1), R ^a1 , R ^a2 and R ^a3 are each independently an alkyl group having 1 to 8 carbon atoms or an alicyclic carbon atom having 3 to 20 carbon atoms which may be substituted with an alkyl group. R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

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

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

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

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms.

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 a carbon atom form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantane) -1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

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

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

  The acid labile monomer (a1) is preferably a monomer having an acid labile group and an ethylenic double bond, more preferably a (meth) acrylic monomer having an acid labile group.

  Among the (meth) acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. If a resin having a structural unit derived from an acid labile monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used for preparing a resist composition, the resolution of the resist pattern can be improved. .

  As a structural unit derived from a (meth) acrylic monomer having an acid labile group (1), a structural unit represented by the formula (a1-1) or a structural unit represented by the formula (a1-2) is preferable. Can be mentioned. 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、又はアルキル基で置換されていてもよい炭素数３〜１０の脂環式炭化水素基を表す。
ｍ１は０〜１４の整数を表す。
ｎ１は０〜１０の整数を表す。
ｎ１’は０〜３の整数を表す。］

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. Represents a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may be substituted with an alkyl group.
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 represented by R ^a6 and R ^a7 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 alkyl group for R ^a6 and R ^a7 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group represented by R ^a6 and R ^a7 may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an alkyl group. May be. In this case, the carbon number of the alicyclic hydrocarbon group is 18 or less including the carbon number of the alkyl group. Specific examples include the same groups as the alicyclic hydrocarbon groups represented by R ^{a1 to} R ^a3 in formula (1).
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

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

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

  When resin (A2) contains structural unit (a1-1) and / or structural unit (a1-2), these total content rates are 10-95 mol normally with respect to all the structural units of resin (A2). %, Preferably 15 to 90 mol%, more preferably 20 to 85 mol%.

式（ａ１−５）中、
Ｒ^３１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^１は、単結合又は＊−［ＣＨ₂］_k1−ＣＯ−Ｌ^４−基を表す。ここで、ｋ１は１〜４の整数を表す。＊は、Ｌ^１との結合手を表す。
Ｌ^１、Ｌ^２、Ｌ^３及びＬ^４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。 Examples of the other acid labile monomer (a1) include a monomer represented by the formula (a1-5) which is a (meth) acrylic monomer having an acid labile group (2) (hereinafter referred to as “monomer (a1-5)”. ) ”May be used.

In formula (a1-5),
R ³¹ represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ¹ represents a single bond or a * — [CH ₂ ] _k1 —CO—L ⁴ — group. Here, k1 represents an integer of 1 to 4. * Represents a bond to ^{L 1.}
L ¹ , L ² , L ³ and L ⁴ 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 ¹ is preferably an oxygen atom.
One of L ² and L ³ 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 ¹ is preferably a single bond or —CH ₂ —CO—O—.

As a monomer (a1-5), the following monomers are mentioned, for example.

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

<Acid stable monomer>
As an acid stable monomer, Preferably, the monomer which has a hydroxyl group or a lactone ring is mentioned. Acid stable monomer having a hydroxy group (hereinafter sometimes referred to as “acid stable monomer having a hydroxy group (a2)”) or acid stable monomer having a lactone ring (hereinafter referred to as “acid stable monomer having a lactone ring (a3)”) If a resin having a structural unit derived from (sometimes) is used, the resolution of the resist pattern and the adhesion to the substrate can be improved.

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

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

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

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

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

  When the resin (A2) includes a structural unit derived from the monomer represented by the formula (a2-1), the content is usually 3 to 45 mol% with respect to all the structural units of the resin (A2). , Preferably it is 3-40 mol%, More preferably, it is 3-35 mol%.

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

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

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

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

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

In Formula (a3-1) to Formula (a3-3), L ^a4 , L ^a5 and L ^a6 are each independently —O— or ^* —O— (CH ₂ ) _k3 —CO—O—. Is preferred, and -O- is more preferred. k3 is preferably an integer of 1 to 4, more preferably 1.
R ^a18 , R ^a19 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 to r1 are each independently preferably 0 to 2, more preferably 0 or 1.

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

  When the resin (A2) includes a structural unit derived from the acid-stable monomer (a3) having a lactone ring, the total content is usually 5 to 70 mol% with respect to all the structural units of the resin (A2). , Preferably it is 10-65 mol%, More preferably, it is 10-60 mol%.

When the resin (A2) is a copolymer of an acid labile monomer (a1) and an acid stable monomer, the structural unit derived from the acid labile monomer (a1) is based on the total structural unit of the resin (A2). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.
The content of the structural unit derived from the monomer having an adamantyl group (particularly the structural unit (a1-1)) is preferably 15 mol% or more based on the total of the structural units derived from the acid labile monomer (a1). is there. When the ratio of the structural unit derived from the monomer having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

  The resin (A2) is preferably a copolymer of an acid labile monomer (a1) and an acid stable monomer. In this copolymer, the acid labile monomer (a1) is more preferably at least one of the monomer (a1-1) having an adamantyl group and the monomer (a1-2) (preferably the monomer having a cyclohexyl group or a cyclopentyl group). One type, more preferably monomer (a1-1). The acid stable monomer is preferably an acid stable monomer (a2) having a hydroxy group and / or an acid stable monomer (a3) having a lactone ring. The acid-stable monomer (a2) having a hydroxy group is preferably an acid-stable monomer (a2-1) having a hydroxyadamantyl group, and the acid-stable monomer (a3) having a lactone ring is more preferably a γ-butyrolactone ring. The acid-stable monomer (a3-1) and the acid-stable monomer (a3-2) having a condensed ring of a γ-butyrolactone ring and a norbornane ring.

Each structural unit constituting the resin (A2) 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 (A2) 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, further preferably 15,000 or less).
Resin (A1) and resin (A2) content ratio (mass ratio) [resin (A1) content: resin (A2) content] is 0.01: 10 to 5:10, preferably 0.05. : 10 to 3:10, more preferably 0.1: 10 to 2.5: 10, and particularly preferably 0.2: 10 to 2:10.
In addition, the range of content ratio of resin (A1) and resin (A2) is a range in case resin (A2) does not contain structural unit (I).

<Resin other than resin (A1) and (A2)>
Examples of the resin other than the resins (A1) and (A2) include resins composed of structural units derived from known monomers used in this field, in addition to structural units derived from acid-stable monomers.
When resin (A) contains resin other than resin (A1) and (A2), these content rates are 0.1-50 mass% normally with respect to the total amount of resin (A), Preferably It is 0.5-30 mass%, More preferably, it is 1-20 mass%.

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

<Acid generator (B)>
The acid generator (B) is classified into a nonionic type and an ionic type, and any of them may be used in the resist composition of the present invention. 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). 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 sulfonate represented by the formula (B1).

［式（Ｂ１）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。
Ｌ^b1は、炭素数１〜２４の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙは、置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基、水素原子又はフッ素原子を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−で置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］

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

Examples of the perfluoroalkyl group represented by Q ¹ and Q ² include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluorotert-butyl group, perfluoropentyl. Group, perfluorohexyl group and the like.
Q ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group represented by L ^b1 include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, A combination of two or more of the 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;
An alkyl group (particularly an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group); For example, 1-methylbutane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4 A branched alkanediyl group such as a diyl group or 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

Examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group represented by L ^b1 is replaced by —O— or —CO— include any of formulas (b1-1) to (b1-7) The group represented by these is mentioned. In addition, in the formula (b1-1) to the formula (b1-7) and specific examples thereof, the left and right are described in accordance with the formula (B1), and each of the two bonds represented by * Bonded to C (Q ¹ ) (Q ² )-on the left side and to -Y on the right side.

式（ｂ１−１）〜式（ｂ１−７）中、
Ｌ^b2は、単結合又は炭素数１〜２２、好ましくは１〜１５の飽和炭化水素基を表す。
Ｌ^b3は、単結合又は炭素数１〜１９、好ましくは１〜１２の飽和炭化水素基を表す。
Ｌ^b4は、炭素数１〜２０、好ましくは１〜１３の飽和炭化水素基を表す。但しＬ^b3及びＬ^b4の合計炭素数の上限は２０、好ましくは１３である。
Ｌ^b５は、単結合又は炭素数１〜２１、好ましくは１〜１４の飽和炭化水素基を表す。
Ｌ^b６は、炭素数１〜２２、好ましくは１〜１５の飽和炭化水素基を表す。但しＬ^b5及びＬ^b6の合計炭素数の上限は２２、好ましくは１５である。
Ｌ^b７は、単結合又は炭素数１〜２２、好ましくは１５の飽和炭化水素基を表す。
Ｌ^b８は、炭素数１〜２３、好ましくは１〜１６の飽和炭化水素基を表す。但しＬ^b７及びＬ^b８の合計炭素数の上限は２３、好ましくは１〜１７である。
Ｌ^b9は、単結合又は炭素数１〜２０、好ましくは１〜１３の飽和炭化水素基を表す。
Ｌ^b10は、炭素数１〜２１、好ましくは１〜１４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、好ましくは１４である。
Ｌ^b11及びＬ^b12は、単結合又は炭素数１〜１８、好ましくは１〜１１の飽和炭化水素基を表す。
Ｌ^b13は、炭素数１〜１９、好ましくは１〜１２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、好ましくは１２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、好ましくは１〜１３の飽和炭化水素基を表す。
Ｌ^b16は、炭素数１〜２１、好ましくは１〜１４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、好ましくは１４である。
Ｌ^b2〜Ｌ^b16における飽和炭化水素基としては、アルカンジイル基が好ましく、Ｌ^b13における飽和炭化水素基としては、アルカンジイル基及び炭素数３〜１０の脂環式炭化水素基が好ましく、アルカンジイル基、シクロヘキシル基及びアダマンチル基がより好ましい。
中でも、Ｌ^b1は、好ましくは式（ｂ１−１）〜式（ｂ１−４）のいずれかで表される基であり、より好ましくは式（ｂ１−１）又は式（ｂ１−３）で表される基であり、さらに好ましくは式（ｂ１−１）で表される２価の基である。特にＬ^b1は、Ｌ^b2が単結合又は炭素数１〜６のアルカンジイル基である式（ｂ１−１）で表される基、即ち＊−ＣＯ−Ｏ−（ＣＨ_２）_ｕ−（ｕは０〜６の整数を表し、＊は、−Ｃ（Ｑ^１）（Ｑ^２）−との結合手を表す）であることが好ましく、Ｌ^b2が単結合又は−ＣＨ_２−である式（ｂ１−１）で表される基、即ち＊−ＣＯ−Ｏ−、＊−ＣＯ−Ｏ−ＣＨ_２−がより好ましい。

In formula (b1-1) to formula (b1-7),
L ^b2 represents a single bond or a saturated hydrocarbon group having 1 to 22 carbon atoms, preferably 1 to 15 carbon atoms.
L ^b3 represents a single bond or a saturated hydrocarbon group having 1 to 19 carbon atoms, preferably 1 to 12 carbon atoms.
L ^b4 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 20, preferably 13.
L ^b5 represents a single bond or a saturated hydrocarbon group having 1 to 21 carbon atoms, preferably 1 to 14 carbon atoms.
L ^b6 represents a saturated hydrocarbon group having 1 to 22 carbon atoms, preferably 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^b5 and L ^b6 is 22, preferably 15.
L ^b7 represents a single bond or a saturated hydrocarbon group having 1 to 22 carbon atoms, preferably 15 carbon atoms.
L ^b8 represents a saturated hydrocarbon group having 1 to 23 carbon atoms, preferably 1 to 16 carbon atoms. However, the upper limit of the total carbon number of L ^b7 and L ^b8 is 23, preferably 1-17.
L ^b9 represents a single bond or a saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms.
L ^b10 represents a saturated hydrocarbon group having 1 to 21 carbon atoms, preferably 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b9 and L ^b10 is 21, preferably 14.
L ^b11 and L ^{b12 each} represents a single bond or a saturated hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 11 carbon atoms.
L ^b13 represents a saturated hydrocarbon group having 1 to 19 carbon atoms, preferably 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b11 , L ^b12 and L ^b13 is 19, preferably 12.
L ^b14 and L ^b15 each independently represent a single bond or a saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms.
L ^b16 represents a saturated hydrocarbon group having 1 to 21 carbon atoms, preferably 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b14 , L ^b15 and L ^b16 is 21, preferably 14.
The saturated hydrocarbon group for L ^{b2 to} L ^b16 is preferably an alkanediyl group, and the saturated hydrocarbon group for L ^b13 is preferably an alkanediyl group or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, A group, a cyclohexyl group and an adamantyl group are more preferred.
Among them, L ^b1 is preferably a group represented by any one of formulas (b1-1) to (b1-4), and more preferably represented by formula (b1-1) or formula (b1-3). And more preferably a divalent group represented by the formula (b1-1). In particular, L ^b1 is a group represented by the formula (b1-1) in which L ^b2 is a single bond or an alkanediyl group having 1 to 6 carbon atoms, that is, * —CO—O— (CH ₂ ) _u — (u is It represents an integer of 0 to 6, and * is preferably a bond with —C (Q ¹ ) (Q ² ) —, and L ^b2 is a single bond or —CH ₂ —. -1), that is, * —CO—O— and * —CO—O—CH ₂ — are more preferable.

As group represented by a formula (b1-1), the following are mentioned, for example.

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

As group represented by a formula (b1-3), the following are mentioned, for example.

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

As group represented by a formula (b1-5), the following are mentioned, for example.

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

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

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by any of formulas (Y1) to (Y11).
Examples of the group in which —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO— include those represented by formulas (Y12) to (Y26). The group represented by either is mentioned.

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

Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 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). Represents an aromatic hydrocarbon group of 18. j2 represents an integer of 0 to 4).

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl; tolyl, xylyl, cumenyl, mesityl, biphenyl Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.

Examples of 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 sulfonate represented by the formula (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 sulfonate represented by the formula (B1) include anions described in JP-A No. 2010-204646.

Examples of the organic cation represented by Z ⁺ include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation, and preferably an organic sulfonium cation or an organic iodonium cation. And more preferably an arylsulfonium cation.
Z ⁺ is preferably a cation represented by any one of formulas (b2-1) to (b2-4).

In formula (b2-1) to formula (b2-4),
R ^b4 , R ^b5 and R ^b6 each independently represent a hydrocarbon group having 1 to 30 carbon atoms, and this hydrocarbon group is an alkyl group having 1 to 30 carbon atoms or an alicyclic group having 3 to 18 carbon atoms. A hydrocarbon group and an aromatic hydrocarbon group having 6 to 18 carbon atoms are preferred. The alkyl group may have a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon group includes a halogen atom and a carbon number. An alkyl group having 1 to 8 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group, the aromatic hydrocarbon group being a halogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, You may have a C3-C18 alicyclic hydrocarbon group or a C1-C12 alkoxy group. R ^b4 and R ^b5 may form a ring together with the sulfur atom to which they are bonded.
R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
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, and when n2 is 2 or more, the plurality of R ^b8 are the same or different. .
R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R ^b9 and R ^b10 are a sulfur atom to which they are bonded. Together with each other to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring). The methylene group contained in the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with —CH—CO— to which they are bonded. The methylene group contained in the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^b12 represents an alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group has It may be substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group having 1 to 12 carbon atoms.

^{R b13, R b14, R b15} , R b16, R b17 and R ^b18 each independently represent a hydroxy group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms.
L ^b11 represents an oxygen atom or a sulfur atom.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, multiple R ^b13 are the same or different, when p2 is 2 or more, multiple R ^b14 are the same or different, and when q2 is 2 or more, multiple R ^b15 are the same or different , When r2 is 2 or more, a plurality of R ^b16 are the same or different, when s2 is 2 or more, a plurality of R ^b17 are the same or different, and when t2 is 2 or more, a plurality of R ^b18 are the same or different Different.

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 having 1 to 8 carbon atoms. . In this case, the carbon number of the alicyclic hydrocarbon group is 20 or less including the carbon number of the alkyl group. Specific examples include the same groups as the alicyclic hydrocarbon groups represented by R ^a1 , R ^a2 and R ^a3 in the formula (1).

  Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

The alkyl group represented by R ^b9 , R ^b10 , R ^b11 and R ^b12 preferably has 1 to 12 carbon atoms, and in particular, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, A sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and the like are preferable.
The alicyclic hydrocarbon group represented by R ^b9 , R ^b10 and R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and in particular, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. A cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan-1-yl) alkane-1-yl group, an isobornyl group, and the like are preferable.
The aromatic hydrocarbon group represented by R ^b12 is a phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-methoxyphenyl group, Biphenylyl group, naphthyl group and the like are preferable.

The ring formed with the sulfur atom to which R ^b4 and R ^b5 are bonded may be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring, and a sulfur atom As long as it contains one or more, one or more sulfur atoms and / or one or more oxygen atoms may be further contained. 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 1,4-oxathian-4-ium. A ring etc. are mentioned.
Examples of the ring formed with —CH—CO— in which R ^b11 and R ^b12 are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

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

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

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

  Specific examples of the cation represented by the formula (b2-1-1) include cations described in JP 2010-204646 A.

    The acid generator (B1) is a combination of the above-described sulfonate anion and organic cation. The above-mentioned anion and cation can be arbitrarily combined, and preferably a combination of any one of anion (b1-1-1) to anion (b1-1-9) and cation (b2-1-1), and A combination of any one of anions (b1-1-3) to (b1-1-5) and a cation (b2-3) may be mentioned.

  The acid generator (B1) is preferably a salt represented by the formula (B1-1) to the formula (B1-20), more preferably a salt containing a triphenylsulfonium cation or a tolylsulfonium cation. More preferably, Formula (B1-1), Formula (B1-2), Formula (B1-3), Formula (B1-6), Formula (B1-7), Formula (B1-11), Examples thereof include a salt represented by the formula (B1-12), the formula (B1-13) or the formula (B1-14).

The content of the acid generator (B) is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 30 parts by mass or less (more preferably 25 parts by mass) with respect to 100 parts by mass of the resin (A). Part or less).
In the resist composition of the present invention, the acid generator (B) may contain a single acid generator or a plurality of acid generators.

<Basic compound (hereinafter sometimes referred to as “basic compound (C)”)>
The “basic compound” in the present specification means a compound having the property of capturing an acid, particularly a compound having the property of capturing an acid generated from an acid generator. It is said.

  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), more preferably a compound represented by the formula (C1-1).

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

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

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

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

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

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

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

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

[In Formula (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 represents an integer of 0 to 3, and when q3 is 2 or more, the plurality of R ^c18 are the same or different, and when r3 is 2 or more, the plurality of R ^c19 are the same. Or when different and when s3 is 2 or more, the plurality of R ^c20 are the same or different.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

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

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

Examples of the compound represented by the formula (C2) include piperazine.
Examples of the compound represented by the formula (C3) include morpholine.
Examples of the compound represented by the formula (C4) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound represented by the formula (C5) include 2,2′-methylenebisaniline.
Examples of the compound represented by the formula (C6) include imidazole and 4-methylimidazole.
Examples of the compound represented by the formula (C7) include pyridine and 4-methylpyridine.
Examples of the compound represented by the formula (C8) include 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1, 2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipiconylamine, bipyridine and the like.

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

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

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

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A), an acid generator (B), and a solvent (E), a basic compound (C) and other components (F) used as necessary. Can be prepared. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature range from the range of 10-40 degreeC according to the kind etc. of resin, the solubility with respect to solvent (E), such as resin. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

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

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

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking) or using a decompression device to form a composition layer from which the solvent has been removed. The temperature in this case is preferably about 50 to 200 ° C. The pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is exposed. The exposure is usually performed using an exposure machine, and an immersion exposure machine may be used. 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) And the like, and those that emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, those that irradiate an electron beam (EB) or EUV, and the like can be used.

The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection group reaction. As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.
The heated composition layer is usually developed using a developer using a developing device.
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 used here 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.
After development, it is preferable to rinse with ultrapure water to remove 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 is preferably an alcohol solvent or an ester solvent.
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 exposure, or a resist composition for EUV exposure, particularly for immersion exposure. It is suitable as a resist composition and is 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.
In the following examples, the structure of the compound was confirmed by mass spectrometry (LC is Agilent Model 1100, MASS is Agilent LC / MSD Model). The weight average molecular weight is a value determined by gel permeation chromatography under the following analysis 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）で表される化合物２５部及びテトラヒドロフラン２５部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に、式（Ｉ１−ｂ）で表される化合物１３．７３部、ピリジン１１．２２部及びテトラヒドロフラン４０部の混合溶液を、１時間かけて添加し、更に、２５℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物に、酢酸エチル２３２．３０部及びイオン交換水５８．０８部を添加攪拌後、分液して有機層を回収した。回収された有機層を濃縮した後、得られた濃縮物に、ｎ−ヘプタン３１０部を添加攪拌後、上澄み液を除去した後、濃縮することにより、式（Ｉ１−ｃ）で表される化合物４０．７４部を得た。得られた式（Ｉ１−ｃ）で表される化合物４０．７２部、テトラヒドロフラン１９２部、式（Ｉ１−ｅ）で表される化合物１５．２３部及びピリジン９．２６部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に式（Ｉ１−ｄ）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）２８．０６部を添加し、２３℃で２４時間攪拌した。得られた反応溶液に、ｎ−ヘプタン９０５部及び５％塩酸水溶液８５部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、１０％炭酸カリウム水溶液６７部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水２４０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。水洗後の有機層を濃縮した。得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝４／１ 重量比）することにより、式（Ｉ−１）で表される化合物５．７７部を得た。
ＭＳ（質量分析）：４５０．１（分子イオンピーク） Example 1: [Synthesis of Compound Represented by Formula (I-1)]

25 parts of the compound represented by the formula (I1-a) and 25 parts of tetrahydrofuran were charged, stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, a mixed solution of 13.73 parts of the compound represented by the formula (I1-b), 11.22 parts of pyridine and 40 parts of tetrahydrofuran was added to the obtained mixture over 1 hour. Furthermore, the temperature was raised to about 25 ° C., and the mixture was stirred at the same temperature for 1 hour. To the obtained reaction product, 232.30 parts of ethyl acetate and 58.08 parts of ion-exchanged water were added and stirred, followed by liquid separation to recover the organic layer. After the collected organic layer is concentrated, 310 parts of n-heptane is added to the resulting concentrate, and after stirring, the supernatant is removed and concentrated to obtain a compound represented by the formula (I1-c) 40.74 parts were obtained. 40.72 parts of the compound represented by the formula (I1-c), 192 parts of tetrahydrofuran, 15.23 parts of the compound represented by the formula (I1-e) and 9.26 parts of pyridine were charged at 23 ° C. After stirring and mixing for 30 minutes, the mixture was cooled to 0 ° C. While maintaining the same temperature, 28.06 parts of the compound represented by the formula (I1-d) (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) was added to the obtained mixture, and 23 Stir at 24 ° C. for 24 hours. To the obtained reaction solution, 905 parts of n-heptane and 85 parts of 5% hydrochloric acid aqueous solution were added and stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and liquid separation, 67 parts of 10% potassium carbonate aqueous solution was added and stirred at 23 ° C. for 30 minutes, and the organic layer was washed by standing and liquid separation. Such washing operation was repeated twice. The organic layer after washing was charged with 240 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated. The obtained concentrate was subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh, manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate = 4/1 weight ratio) to obtain the formula (I- 5.77 parts of the compound represented by 1) were obtained.
MS (mass spectrometry): 450.1 (molecular ion peak)

式（Ｉ１−ａ）で表される化合物２５部及びテトラヒドロフラン２５部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に、式（Ｉ２−ｂ）で表される化合物８．７６部、ピリジン１１．２２部及びテトラヒドロフラン４０部の混合溶液を、１時間かけて添加し、更に、２５℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物に、酢酸エチル２００部及びイオン交換水５０部を添加攪拌後、分液して有機層を回収した。回収された有機層を濃縮した後、得られた濃縮物に、ｎ−ヘプタン３００部を添加攪拌後、上澄み液を除去した後、濃縮することにより、式（Ｉ２−ｃ）で表される化合物３８．１１部を得た。得られた式（Ｉ２−ｃ）で表される化合物３６．６１部、テトラヒドロフラン１８０部、式（Ｉ１−ｅ）で表される化合物１５．２３部及びピリジン９．２６部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に式（Ｉ１−ｄ）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）２８．０６部を添加し、２３℃で２４時間攪拌した。得られた反応溶液に、ｎ−ヘプタン９００部及び５％塩酸水溶液８５部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、１０％炭酸カリウム水溶液６７部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水２００部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。水洗後の有機層を濃縮した。得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝４／１ 重量比）することにより、式（Ｉ−２）で表される化合物４．２８部を得た。
ＭＳ（質量分析）：４０８．１（分子イオンピーク） Example 2: Synthesis of compound represented by formula (I-2)

25 parts of the compound represented by the formula (I1-a) and 25 parts of tetrahydrofuran were charged, stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, a mixed solution of 8.76 parts of the compound represented by the formula (I2-b), 11.22 parts of pyridine and 40 parts of tetrahydrofuran was added to the obtained mixture over 1 hour. Furthermore, the temperature was raised to about 25 ° C., and the mixture was stirred at the same temperature for 1 hour. To the obtained reaction product, 200 parts of ethyl acetate and 50 parts of ion-exchanged water were added and stirred, followed by liquid separation to recover the organic layer. After the collected organic layer is concentrated, 300 parts of n-heptane is added to the resulting concentrate, and after stirring, the supernatant is removed and then concentrated to obtain a compound represented by the formula (I2-c) 38.11 parts were obtained. 36.61 parts of the compound represented by the formula (I2-c), 180 parts of tetrahydrofuran, 15.23 parts of the compound represented by the formula (I1-e) and 9.26 parts of pyridine were charged at 23 ° C. After stirring and mixing for 30 minutes, the mixture was cooled to 0 ° C. While maintaining the same temperature, 28.06 parts of the compound represented by the formula (I1-d) (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) was added to the obtained mixture, and 23 Stir at 24 ° C. for 24 hours. To the obtained reaction solution, 900 parts of n-heptane and 85 parts of 5% hydrochloric acid aqueous solution were added and stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and liquid separation, 67 parts of 10% potassium carbonate aqueous solution was added and stirred at 23 ° C. for 30 minutes, and the organic layer was washed by standing and liquid separation. Such washing operation was repeated twice. To the organic layer after washing, 200 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated. The obtained concentrate was subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh, manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate = 4/1 weight ratio) to obtain the formula (I- 2.28 parts of the compound represented by 2) were obtained.
MS (mass spectrometry): 408.1 (molecular ion peak)

式（Ｉ１１−ａ）で表される化合物１９．４部及びテトラヒドロフラン１９．４部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に、式（Ｉ１１−ｂ）で表される化合物１３．７３部、ピリジン１１．２２部及びテトラヒドロフラン４０部の混合溶液を、１時間かけて添加し、更に、２５℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物に、酢酸エチル２００部及びイオン交換水５０部を添加攪拌後、分液して有機層を回収した。回収された有機層を濃縮した後、得られた濃縮物に、ｎ−ヘプタン３００部を添加攪拌後、上澄み液を除去した後、濃縮することにより、式（Ｉ１１−ｃ）で表される化合物３６．２２部を得た。得られた式（Ｉ１１−ｃ）で表される化合物３５．８４部、テトラヒドロフラン１８０部、式（Ｉ１１−ｅ）で表される化合物１５．２３部及びピリジン９．２６部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に式（Ｉ１１−ｄ）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）２８．０６部を添加し、２３℃で２４時間攪拌した。得られた反応溶液に、ｎ−ヘプタン９００部及び５％塩酸水溶液８５部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、１０％炭酸カリウム水溶液６７部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水２００部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。水洗後の有機層を濃縮した。得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル＝４／１ 重量比）することにより、式（Ｉ−１１）で表される化合物４．９８部を得た。
ＭＳ（質量分析）：４００．１（分子イオンピーク） Example 3: Synthesis of compound represented by formula (I-11)

19.4 parts of the compound represented by the formula (I11-a) and 19.4 parts of tetrahydrofuran were charged, stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, a mixed solution of 13.73 parts of the compound represented by the formula (I11-b), 11.22 parts of pyridine and 40 parts of tetrahydrofuran was added to the obtained mixture over 1 hour. Furthermore, the temperature was raised to about 25 ° C., and the mixture was stirred at the same temperature for 1 hour. To the obtained reaction product, 200 parts of ethyl acetate and 50 parts of ion-exchanged water were added and stirred, followed by liquid separation to recover the organic layer. After the collected organic layer is concentrated, 300 parts of n-heptane is added to the resulting concentrate, and after stirring, the supernatant is removed and then concentrated to give a compound represented by the formula (I11-c) 36.22 parts were obtained. 35.84 parts of the compound represented by the formula (I11-c), 180 parts of tetrahydrofuran, 15.23 parts of the compound represented by the formula (I11-e) and 9.26 parts of pyridine were charged at 23 ° C. After stirring and mixing for 30 minutes, the mixture was cooled to 0 ° C. While maintaining the same temperature, 28.06 parts of the compound represented by the formula (I11-d) (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) was added to the obtained mixture, and 23 Stir at 24 ° C. for 24 hours. To the obtained reaction solution, 900 parts of n-heptane and 85 parts of 5% hydrochloric acid aqueous solution were added and stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and liquid separation, 67 parts of 10% potassium carbonate aqueous solution was added and stirred at 23 ° C. for 30 minutes, and the organic layer was washed by standing and liquid separation. Such washing operation was repeated twice. To the organic layer after washing, 200 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated. The obtained concentrate was subjected to column fractionation (column fractionation conditions, stationary phase: silica gel 60-200 mesh, manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate = 4/1 weight ratio) to obtain the formula (I- 11.98 parts of the compound represented by 11) were obtained.
MS (mass spectrometry): 400.1 (molecular ion peak)

式（ＩＩＩ―１−４ｍ−ｂ）で表される化合物８８部、メチルイソブチルケトン６１６部及びピリジン６０．９８部を、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に、式（ＩＩＩ―１−４ｍ−ａ）で表される化合物１９９．１７部を、１時間かけて添加した後、更に、１０℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物に、ｎ−へプタン１４５０部及び２％塩酸水溶液７００部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、２％塩酸水溶液３４０部を仕込み、２３℃で３０分間攪拌した。静置、分液することにより有機層を回収した。回収された有機層に、イオン交換水３６０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液４４５部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。このような洗浄操作を２回繰り返した。回収された有機層に、イオン交換水３６０部を仕込み、２３℃で３０分間攪拌、静置した後、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。回収された有機層を濃縮し式（ＩＩＩ―１−４ｍ）で表される化合物１６３．６５部を得た。
ＭＳ（質量分析）：２７６．０（分子イオンピーク） Synthesis Example 1: [Synthesis of Compound Represented by Formula (III-1-4m)]

88 parts of the compound represented by the formula (III-1-4m-b), 616 parts of methyl isobutyl ketone and 60.98 parts of pyridine were stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, 199.17 parts of the compound represented by the formula (III-1-4m-a) was added to the obtained mixture over 1 hour, and the temperature was further increased to about 10 ° C. And stirred at the same temperature for 1 hour. To the obtained reaction product, 1450 parts of n-heptane and 700 parts of 2% aqueous hydrochloric acid were added, and the mixture was stirred at 23 ° C. for 30 minutes. 340 parts of 2% aqueous hydrochloric acid solution was added to the organic layer recovered by standing and liquid separation, and stirred at 23 ° C. for 30 minutes. The organic layer was recovered by standing and liquid separation. To the collected organic layer, 360 parts of ion-exchanged water was charged, stirred at 23 ° C. for 30 minutes, allowed to stand and liquid-separated to wash the organic layer with water. The collected organic layer was charged with 445 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. Such washing operation was repeated twice. The recovered organic layer was charged with 360 parts of ion-exchanged water, stirred at 23 ° C. for 30 minutes and allowed to stand, and then separated to wash the organic layer with water. Such washing operation was repeated 5 times. The collected organic layer was concentrated to obtain 163.65 parts of a compound represented by the formula (III-1-4m).
MS (mass spectrometry): 276.0 (molecular ion peak)

式（ＩＩＩ―１−６ｍ−ｂ）で表される化合物１０．００部、テトラヒドロフラン４０部及びピリジン７．２９部を反応器に仕込み、２３℃で３０分間攪拌し、０℃まで冷却した。同温度を保持したまま、得られた混合物に、式（ＩＩＩ―１−６ｍ−ａ）で表される化合物３３．０８部を、１時間かけて添加し、更に、温度を上げ、２３℃に到達した時点で、同温度で３時間攪拌した。得られた反応物に、酢酸エチル３６１．５１部及び５％塩酸水溶液２０．１９部を加え、２３℃で３０分間攪拌した。攪拌、静置し、分液した。回収された有機層に、飽和炭酸水素ナトリウム水溶液８１．４２部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を回収した。回収された有機層に、イオン交換水９０．３８部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。この水洗操作を５回繰り返した。水洗後の有機層を濃縮し、式（ＩＩＩ―１−６ｍ）で表される化合物２３．４０部を得た。
ＭＳ（質量分析）：３２６．０（分子イオンピーク） Synthesis Example 2: [Synthesis of Compound Represented by Formula (III-1-6m)]

10.00 parts of the compound represented by the formula (III-1-6m-b), 40 parts of tetrahydrofuran and 7.29 parts of pyridine were charged into a reactor, stirred at 23 ° C. for 30 minutes, and cooled to 0 ° C. While maintaining the same temperature, 33.08 parts of the compound represented by the formula (III-1-6m-a) was added to the obtained mixture over 1 hour, and the temperature was further increased to 23 ° C. When it reached, it was stirred at the same temperature for 3 hours. To the obtained reaction product, 361.51 parts of ethyl acetate and 20.19 parts of 5% aqueous hydrochloric acid solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. The mixture was stirred, allowed to stand, and separated. To the recovered organic layer, 81.42 parts of a saturated aqueous sodium hydrogen carbonate solution was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to recover the organic layer. To the collected organic layer, 90.38 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 5 times. The organic layer after washing with water was concentrated to obtain 23.40 parts of a compound represented by the formula (III-1-6m).
MS (mass spectrometry): 326.0 (molecular ion peak)

以下、これらの化合物をその式番号に応じて、「モノマー（ａ１−１−１）」等という。 The compounds (monomers) used in the resin synthesis are shown below.

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

Example 4: [Synthesis of Resin A1-1]
Monomer (I-1) was used as a monomer, and 1.2 mass times of methyl isobutyl ketone as the total monomer amount was added to prepare a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 60 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-1 having a weight average molecular weight of 5.4 × 10 ^{4 in} a yield of 89%. This resin A1-1 has the following structural units.

Example 5: [Synthesis of Resin A1-2]
Monomer (III-1-4m) and monomer (I-1) are used as the monomers, and mixed so that the molar ratio [monomer (III-1-4m): monomer (I-1)] is 50:50. Then, 1.5 mass times methyl isobutyl ketone of the total monomer amount was added to make a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-2 (copolymer) having a weight average molecular weight of 2.7 × 10 ^{4 in} a yield of 78%. Got in. This resin A1-2 has the following structural units.

Example 6: [Synthesis of Resin A1-3]
Monomer (III-2-1m) and monomer (I-1) are used as monomers and mixed so that the molar ratio [monomer (III-2-1m): monomer (I-1)] is 10:90. Then, 1.5 mass times methyl isobutyl ketone of the total monomer amount was added to make a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total amount of monomers, and these were heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-3 (copolymer) having a weight average molecular weight of 3.8 × 10 ^{4 in} a yield of 86%. Got in. This resin A1-3 has the following structural units.

Example 7: [Synthesis of Resin A1-4]
Monomer (III-1-6m) and monomer (I-1) are used as monomers and mixed so that the molar ratio [monomer (III-1-6m): monomer (I-1)] is 50:50. Then, 1.5 mass times methyl isobutyl ketone of the total monomer amount was added to make a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-4 (copolymer) having a weight average molecular weight of 2.3 × 10 ^{4 in} a yield of 72%. Got in. This resin A1-4 has the following structural units.

Example 8: [Synthesis of Resin A1-5]
Monomer (I-2) was used as the monomer, and methyl isobutyl ketone 1.2 times the total monomer amount was added to prepare a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 60 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-5 having a weight average molecular weight of 4.7 × 10 ^{4 in} a yield of 83%. This resin A1-5 has the following structural units.

Example 9: [Synthesis of Resin A1-6]
Monomer (I-11) was used as the monomer, and 1.2 mass times of methyl isobutyl ketone as the total monomer amount was added to prepare a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 60 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-6 having a weight average molecular weight of 5.4 × 10 ^{4 in} a yield of 89%. This resin A1-6 has the following structural units.

Example 10: [Synthesis of Resin A1-7]
Monomer (III-1-4m) and monomer (I-11) are used as monomers and mixed so that the molar ratio [monomer (III-1-4m): monomer (I-11)] is 50:50. Then, 1.5 mass times methyl isobutyl ketone of the total monomer amount was added to make a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 75 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-7 (copolymer) having a weight average molecular weight of 2.9 × 10 ^{4 in} a yield of 80%. Got in. This resin A1-7 has the following structural units.

Synthesis Example 3 [Synthesis of Resin A2-1]
As the monomer, using monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1) and monomer (a3-2-3), The molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3)] It mixed so that it might be set to 30: 14: 6: 30: 20, and 1.5 mass times dioxane of the total monomer amount was added, and it was set as the solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are 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 resin thus obtained is again dissolved in dioxane, and a solution obtained by pouring the solution into a methanol / water mixed solvent is precipitated twice, and the resin is filtered twice to perform a reprecipitation operation twice. 2 × 10 ³ resin A2-1 (copolymer) was obtained with a yield of 78%. This resin A2-1 has the following structural units.

Synthesis Example 4 [Synthesis of Resin A2-2]
As the monomer, monomer (a1-1-2), monomer (a2-1-1) and monomer (a3-1-1) were used, and the molar ratio [monomer (a1-1-2): monomer (a2-1) -1): monomer (a3-1-1)] was mixed at 50:25:25, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, based on the total monomer amount, and these are heated at 80 ° C. for about 8 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 resin thus obtained was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 9. 2 × 10 ³ resin A2-2 (copolymer) was obtained with a yield of 60%. This resin A2-2 has the following structural units.

Synthesis Example 5 [Synthesis of Resin A2-3]
As the monomer, using monomer (a1-1-2), monomer (a1-2-9), monomer (a2-1-1), monomer (a3-1-1) and monomer (a3-2-3), The molar ratio [monomer (a1-1-2): monomer (a1-2-9): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3)] , 30: 14: 6: 30: 20, and 1.5 mass times dioxane of the total monomer amount was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 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 dioxane, and a solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated, and the resin was filtered twice. The weight-average molecular weight was 8.4. × 10 ³ of the resin A2-3 (copolymer) was obtained in 85% yield. This resin A2-3 has the following structural units.

Synthesis Example 6 [Synthesis of Resin A2-4]
As the monomer, using monomer (a1-1-2), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-1-1) and monomer (a3-2-3), The molar ratio [monomer (a1-1-2): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-1-1): monomer (a3-2-3)] , 35: 15: 3: 20: 27, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.8. × 10 ³ of the resin A2-4 (copolymer) was obtained in 81% yield. This resin A2-4 has the following structural units.

Synthesis Example 7 [Synthesis of Resin A2-5]
Using monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-1-1) and monomer (a3-2-3), the molar ratio [Monomer (a1-1-3): Monomer (a1-2-9): Monomer (a2-1-3): Monomer (a3-1-1): Monomer (a3-2-3)] is 35: The mixture was mixed at 15: 3: 20: 27, and 1.5 mass times dioxane 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 dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.9. × 10 ³ of the resin A2-5 (copolymer) was obtained in 73% yield. This resin A2-5 has the following structural units.

Synthesis Example 8 [Synthesis of Resin A2-6]
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 is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate a resin, and the resin is filtered to obtain a resin A2-6 having a weight average molecular weight of 7.8 × 10 ³ . (Copolymer) was obtained with a yield of 73%. This resin A2-6 has the following structural units.

Synthesis Example 9 [Synthesis of Resin X1]
As the monomer, monomer (a1-1-1), monomer (a3-1-1) and monomer (a2-1-1) were used, and the molar ratio [monomer (a1-1-1): monomer (a3-1) -1): monomer (a2-1-1)] was mixed at 35:45:20, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.0 mol% and 3.0 mol%, respectively, based on the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.0. A × 10 ³ resin X1 (copolymer) was obtained in a yield of 75%. This resin X1 has the following structural units.

Synthesis Example 10 [Synthesis of Resin X2]
As the monomer, monomer (f2-1) and monomer (a1-1-1) are used, and the molar ratio [monomer (f2-1): monomer (a1-1-1)] is 80:20. Then, 1.5 mass times dioxane of the total monomer amount was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.5 mol% and 1.5 mol%, respectively, based on the total monomer amount, and these were added at 70 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 2.8. A × 10 ⁴ resin X2 (copolymer) was obtained in a yield of 70%. This resin X2 has the following structural units.

<Preparation of resist composition>
Each component shown in Table 1 was dissolved in the following solvent in parts by mass shown in Table 1, and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to prepare a resist composition.

Ｂ２：ＷＯ２００８／９９８６９号の実施例及び、特開２０１０−２６４７８の実施例に従って合成

Ｂ３：特開２００５−２２１７２１の実施例に従って合成

In Table 1 and Table 3 below, each symbol represents the following compound.
<Resin>
Resins A1-1 to A1-3, A2-1 to A2-5, X1 to X2 synthesized in the synthesis examples described above
<Acid generator>
B1: Synthesis according to the example of JP 2010-152341 A

B2: synthesized according to examples of WO2008 / 99869 and JP2010-26478

B3: synthesized according to the example of JP-A-2005-221721

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

<Solvent>
Propylene glycol monomethyl ether acetate 265.0 parts Propylene glycol monomethyl ether 20.0 parts 2-heptanone 20.0 parts γ-butyrolactone 3.5 parts

<Defect evaluation>
The resist composition was applied to a 12-inch silicon wafer (substrate) with a spin coater so that the film thickness after drying (pre-baking) was 0.15 μm. After coating, the composition layer was formed on the wafer by pre-baking on a direct hot plate for 60 seconds at the temperature shown in the PB column of Table 1. The wafer on which the composition layer was thus formed was rinsed with water for 60 seconds using a developing machine [ACT-12; manufactured by Tokyo Electron Ltd.].
Thereafter, the number of defects on the wafer was measured using a defect inspection apparatus [KLA-2360; manufactured by KLA Tencor]. The results are shown in Table 2.

<Immersion exposure evaluation of resist composition>
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 silicon wafer coated with the resist composition was pre-baked on a direct hot plate for 60 seconds at the temperature described in the “PB” column of Table 1 to form a composition layer. An ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light] on a wafer on which the composition layer is formed in this manner, and a line and space pattern Using a mask for forming (pitch 90 nm / line 45 nm), 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 exposure, post-exposure baking is performed for 60 seconds on a hot plate at the temperature described in the “PEB” column of Table 1, and further paddle development is performed for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution. And a resist pattern was obtained.

  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.

<Shape evaluation>
A cross section of a 50 nm line pattern obtained with effective sensitivity was observed with a scanning electron microscope. A top shape close to a rectangle (drawing, FIG. 1 (a)) was marked with ◯, and a round top shape (drawing, FIG. 1 (b)) was marked with a cross. The results are shown in Table 2.

<Preparation of resist composition>
Each component shown in Table 3 was dissolved in the following solvent in the parts by mass shown in Table 3, and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to prepare a resist composition.

<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 “PB” column of Table 3 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 a silicon wafer on which the composition layer has been formed. Using a mask for forming a pitch of 90 nm / line of 45 nm, exposure was performed by 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 3. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured. In the obtained resist pattern, an exposure amount at which the line width and space width of the line and space pattern were 1: 1 was defined as effective sensitivity.

<Shape evaluation>
A cross section of a 45 nm line pattern obtained with effective sensitivity was observed with a scanning electron microscope. A top shape close to a rectangle (drawing, FIG. 1 (a)) was marked with ◯, and a round top shape (drawing, FIG. 1 (b)) was marked with a cross. The results are shown in Table 4.

<Defect evaluation>
ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized illumination] for forming a 1: 1 line and space pattern (pitch 80 nm) Using the mask, a negative resist pattern was manufactured by performing the same operation as above except that exposure was performed with an exposure amount at which the line width and space width of the obtained line and space pattern were 1: 1.
Thereafter, the number of defects (pieces) on the wafer was measured using a defect inspection apparatus [KLA-2360; manufactured by KLA Tencor]. The results are shown in Table 4.

  The resist composition of the present invention can produce a resist pattern that is excellent in shape and has a small number of defects.

(A) represents the resist pattern whose top shape is close to a rectangle.

(B) represents a resist pattern having a round top shape.

Claims (6)

A compound represented by formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
A ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
A ² represents a C 1-18 divalent saturated hydrocarbon group having a halogen atom.
X ¹ represents * —CO—O— or * —O—CO—. * Represents a bond to ^{A 2.}
A ³ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
Ring W ¹ represents a heterocyclic ring which may have a substituent. ] Ring W ^1, the compound according to claim 1, wherein the ring containing a cyclic ether structure.   A resin having a structural unit derived from the compound according to claim 1.   A resist composition comprising the resin according to claim 3 and an acid generator.   Furthermore, the resist composition of Claim 4 containing resin which the solubility to alkaline aqueous solution increases by the effect | action of an acid. (1) The process of apply | coating the resist composition of Claim 4 or 5 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:

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