JP2012190011A - Resist composition and manufacturing method of resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition which can manufacture a resist pattern with good CD uniformity and with reduced defects.SOLUTION: A resist composition contains (A1) resin having a structural unit represented by a formula (I), (A2) resin that has a structural unit represented by a formula (II) and is insoluble or poorly soluble in an aqueous alkali solution but becomes soluble in the aqueous alkali solution by the action of acid, (B) an acid generator, and (E) a solvent. In the formulas, Rrepresents a hydrocarbon group having a fluorine atom; and ring Trepresents a 3-34C sultone ring that may contain a substitution group.

Description

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

In Patent Document 1, a resin composed of a structural unit represented by the formula (u-A) and a structural unit represented by the formula (u-B), a structural unit represented by the formula (u-C), and a formula A resist composition containing a resin composed of a structural unit represented by (u-D) and a structural unit represented by formula (u-B), an acid generator, and a solvent is described.

JP 2010-197413 A

  In a resist pattern formed by a conventional resist composition, CD uniformity may not always be satisfied, or the number of defects generated may be extremely large.

［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。
Ｒ^２は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］

［式（ＩＩ）中、
環Ｔ^１は、置換基を有していてもよい炭素数３〜３４のスルトン環を表す。
Ｘ^１は、炭素数１〜６のアルカンジイル基を表す。
Ｘ^２は、酸素原子又は−Ｎ（Ｒ^ｃ）−（但し、Ｒ^ｃは水素原子又は炭素数１〜６のアルキル基である。）を表す。
Ｚ^１は、＊−Ｘ^３−ＣＯ−Ｏ−、＊−Ｘ^３−ＣＯ−Ｎ（Ｒ^ｃ）−、＊−Ｘ^３−Ｏ−ＣＯ−又は＊−Ｘ^３−Ｎ（Ｒ^ｃ）−ＣＯ−（但し、Ｒ^ｃは水素原子又は炭素数１〜６のアルキル基を表す。Ｘ^３は炭素数１〜６のアルカンジイル基を表す。＊はＸ^２との結合手を表す。）で表される基、若しくは単結合を表す。
Ｒ^３は、水素原子又はメチル基を表す。］
［２］式（Ｉ）において、Ｒ²が、炭素数１〜６のフッ化アルキル基である［１］記載のレジスト組成物。
［３］式（Ｉ）において、Ａ^１が、炭素数２〜４のアルカンジイル基である［１］又は［２］記載のレジスト組成物。
［４］式（ＩＩ）において、環Ｔ^１が、多環式のスルトン環である［１］〜［３］のいずれか記載のレジスト組成物。
［５］式（ＩＩ）において、環Ｔ^１が、式（Ｔ１）で表される環である［１］〜［４］のいずれか記載のレジスト組成物。

［式（Ｔ１）中、
Ｒ^４は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、オキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基あるいは炭素数２〜４のアシル基を表す。
ｍは、０〜１１である。
＊は、酸素原子との結合手を表す。］
［６］式（ＩＩ）において、−Ｘ^２−Ｚ^１−Ｘ^１−が、−Ｏ−ＣＨ_２−ＣＨ_２−、−Ｏ−ＣＨ_２−ＣＨ_２−Ｏ−ＣＯ−ＣＨ_２−又は−Ｏ−ＣＨ_２−ＣＨ_２−ＮＨ−ＣＯ−ＣＨ_２−である［１］〜［５］のいずれか記載のレジスト組成物。
［７］さらに溶剤を含有する上記［１］〜［６］のいずれか記載のレジスト組成物。 The present invention includes the following inventions.
[1] (A1) a resin having a structural unit represented by formula (I),
(A2) a resin having a structural unit represented by the formula (II), insoluble or hardly soluble in an alkaline aqueous solution, and soluble in an alkaline aqueous solution by the action of an acid;
(B) A resist composition containing an acid generator.

[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.
R ² represents a C 1-10 hydrocarbon group having a fluorine atom. ]

[In the formula (II),
Ring T ¹ represents a C3-C34 sultone ring which may have a substituent.
X ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
X ² represents an oxygen atom or —N (R ^c ) — (where R ^c is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
Z ^{1 is, * - X 3 -CO-O} -, * - X 3 -CO-N (R c) -, * - X 3 -O-CO- or ^{* -X 3 -N (R c)} -CO -(Wherein R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X ³ represents an alkanediyl group having 1 to 6 carbon atoms, * represents a bond to X ² ). Represents a group or a single bond.
R ³ represents a hydrogen atom or a methyl group. ]
[2] The resist composition according to [1], wherein in formula (I), R ² is a fluorinated alkyl group having 1 to 6 carbon atoms.
[3] The resist composition according to [1] or [2], wherein in formula (I), A ¹ is an alkanediyl group having 2 to 4 carbon atoms.
[4] The resist composition according to any one of [1] to [3], wherein in formula (II), ring T ¹ is a polycyclic sultone ring.
[5] The resist composition according to any one of [1] to [4], wherein in formula (II), ring T ¹ is a ring represented by formula (T1).

[In the formula (T1),
R ⁴ is a C 1-12 alkyl group optionally having a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, an oxy group, a cyano group, a C 1-12 alkoxy group, a C 6-12 12 represents an aryl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
m is 0-11.
* Represents a bond with an oxygen atom. ]
[6] In the formula (II), —X ² —Z ¹ —X ¹ — is —O—CH ₂ —CH ₂ —, —O—CH ₂ —CH ₂ —O—CO—CH ₂ — or —O. The resist composition according to any one of [1] to [5], which is —CH ₂ —CH ₂ —NH—CO—CH ₂ —.
[7] The resist composition according to any one of [1] to [6], further containing a solvent.

[8] (1) A step of applying the resist composition according to any one of [1] to [7] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including:

The present invention further includes the following inventions.
[9] The resist composition according to [1] or [2], wherein in formula (I), A ¹ is an ethylene group.

  According to the resist composition of the present invention, a resist pattern with good CD uniformity and few defects can be produced.

In this specification, "(meth) acrylic monomer" means at least one monomer having the structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " To do. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

<Resist composition>
The resist composition of the present invention comprises:
(A) resin (hereinafter sometimes referred to as “resin (A)”), and
(B) An acid generator (hereinafter may be referred to as “acid generator (B)”).
Here, the resin (A) includes the following resins.
(A1) a resin having a structural unit represented by formula (I),
(A2) A resin having a structural unit represented by the formula (II), insoluble or hardly soluble in an alkaline aqueous solution, and soluble in an alkaline aqueous solution by the action of an acid.
The resist composition of the present invention preferably further contains (E) a solvent (hereinafter sometimes referred to as “solvent (E)”).
The resist composition of the present invention preferably further contains a basic compound (C).

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

［式（Ｉ）中、
Ｒ¹は、水素原子又はメチル基を表す。
Ａ¹は、炭素数１〜６のアルカンジイル基を表す。
Ｒ²は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ <Resin (A1)>
The resin (A1) has a structural unit represented by the formula (I) (hereinafter sometimes referred to as “structural unit (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.
R ² represents a C 1-10 hydrocarbon group having a fluorine atom. ]

In the formula (I), as the alkanediyl group of A ¹ , methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 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.

The hydrocarbon group for R ² includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic type, and a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. .
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methyl group. Examples thereof include cycloalkyl groups such as cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, and norbornyl. Group, methylnorbornyl group and isobornyl group.

Examples of the hydrocarbon group having a fluorine atom for R ² include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Specifically, as the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2 , 2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoro (Ropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5- Decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2, 2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentyl Examples thereof include fluorinated alkyl groups such as a methyl group and a perfluorohexyl group.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

In formula (I), A ¹ is preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an ethylene group.
R ² is preferably a fluorinated alkyl group having 1 to 6 carbon atoms.
Examples of the structural unit (I) include the following.

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

［式（Ｉ’）中、Ｒ¹、Ａ¹及びＲ²は、上記と同じ意味を表す。］ The structural unit (I) is derived from a compound represented by the formula (I ′) (hereinafter sometimes referred to as “compound (I ′)”).

[In formula (I ′), R ¹ , A ¹ and R ² represent the same meaning as described above. ]

［式中、Ｒ¹、Ａ¹及びＲ²は、上記と同じ意味を表す。］
式（Ｉ’−１）で表される化合物と式（Ｉ’−２）で表される化合物とを、塩基性触媒の存在下で反応させることにより、化合物（Ｉ’）が得られる。この反応は、通常、溶媒の存在下で行われ、溶媒としては、テトラヒドロフランなどが用いられる。塩基性触媒としては、ピリジンなどを用いればよい。
式（Ｉ’−１）で表される化合物としては、市販品が挙げられる。市販品としては、ヒドロキシエチルメタクリレートなどが挙げられる。
式（Ｉ’−２）で表される化合物は、Ｒ^２の種類に応じて、対応するカルボン酸を無水物へと変換することで得ることができる。市販品としては、ヘプタフルオロ酪酸無水物などが挙げられる。 Compound (I ′) can be produced, for example, by the following reaction.

[Wherein R ¹ , A ¹ and R ² represent the same meaning as described above. ]
Compound (I ′) is obtained by reacting the compound represented by formula (I′-1) with the compound represented by formula (I′-2) in the presence of a basic catalyst. This reaction is usually performed in the presence of a solvent, and tetrahydrofuran or the like is used as the solvent. As the basic catalyst, pyridine or the like may be used.
A commercial item is mentioned as a compound represented by a formula (I'-1). Examples of commercially available products include hydroxyethyl methacrylate.
The compound represented by the formula (I′-2) can be obtained by converting the corresponding carboxylic acid into an anhydride depending on the type of R ² . Commercially available products include heptafluorobutyric anhydride.

The resin (A1) may have a structural unit different from the structural unit (I).
As the structural unit different from the structural unit (I), an acid labile structural unit (a1) described later, a structural unit derived from an acid stable monomer described later, a structural unit represented by the formula (IIIA), and used in this field And a structural unit derived from a known monomer, a structural unit represented by the formula (II) described later, and the like. A structural unit represented by the formula (IIIA) is preferable.

［式（ＩＩＩＡ）中、
Ｒ^１１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^１２は、−Ｏ−、^＊−ＣＯ−Ｏ−又は^＊−Ｏ−ＣＯ−（^＊は環Ｗ^１との結合手を表す）を表す。
Ｒ^１２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 (IIIA),
R ¹¹ represents a hydrogen atom or a methyl group.
Ring ^{W 2} represents a hydrocarbon ring having 6 to 10 carbon atoms.
A ¹² represents —O—, ^* —CO—O—, or ^* —O—CO— ( ^* represents a bond to ring W ¹ ).
R ¹² represents a C 1-6 alkyl group having a fluorine atom. ]

Examples of the hydrocarbon ring of ring W ² include an alicyclic hydrocarbon ring, and a saturated alicyclic hydrocarbon ring is preferable.
Examples of the saturated alicyclic hydrocarbon ring include the following rings.

As the ring W ² , for example, an adamantane ring or a cyclohexane ring is preferable, and an adamantane ring is more preferable.
The alkyl group having 1 to 6 carbon atoms and having a fluorine atom in R ^12, for example, fluorinated alkyl groups and the following groups mentioned above.

上記の構造単位において、Ｒ^１１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（ＩＩＩＡ）の具体例として挙げることができる。
中でも、式（ＩＩＩＡ−１）で表される構造単位又はＲ^１１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が特に好ましい。 As the structural unit represented by the formula (IIIA), for example, the structural unit represented by the following is preferable.

In the 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 (IIIA).
Among these, a structural unit represented by the formula (IIIA-1) or a structural unit in which a methyl group corresponding to R ¹¹ is replaced with a hydrogen atom is particularly preferable.

The content ratio of the structural unit (I) in the resin (A1) is preferably in the range of 5 to 100 mol%, more preferably in the range of 10 to 100 mol%, based on all the structural units of the resin (A1). The range of -100 mol% is more preferable, and the range of 80-100 mol% is especially preferable.
When the resin (A1) has the structural unit (IIIA), the content ratio of the structural unit (IIIA) in the resin (A1) is in the range of 1 to 95 mol% with respect to all the structural units of the resin (A1). The range of 2 to 80 mol% is more preferable, the range of 5 to 70 mol% is more preferable, the range of 5 to 50 mol% is particularly preferable, and the range of 5 to 30 mol% is particularly preferable.
Resin (A1) having structural units (I) and / or (IIIA) in such a content ratio is compound (I ′), structural unit (IIIA) relative to the total molar amount of all monomers used in the production of resin (A1). It can be produced by adjusting the molar amount of the monomer used for deriving.

Each structural unit (I) and / or (IIIA) constituting the resin (A1) is a single type or a combination of two or more types, and optionally, an acid labile structural unit (a1) described later, an acid stable It can be produced by a known polymerization method (for example, radical polymerization method) by combining a monomer and one or more structural units derived from monomers known in the art.
The weight average molecular weight of the resin (A1) is preferably 5,000 or more (more preferably 7,000 or more, more preferably 10,000 or more), 80,000 or less (more preferably 50,000 or less, further preferably Is 30,000 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 this analysis are explained in full detail in the Example of this application.

［式（ＩＩ）中、
環Ｔ^１は、置換基を有していてもよい炭素数３〜３４のスルトン環を表す。
Ｘ^１は、炭素数１〜６のアルカンジイル基を表す。
Ｘ^２は、酸素原子又は−Ｎ（Ｒ^ｃ）−（但し、Ｒ^ｃは水素原子又は炭素数１〜６のアルキル基である。）を表す。
Ｚ^１は、＊−Ｘ^３−ＣＯ−Ｏ−、＊−Ｘ^３−ＣＯ−Ｎ（Ｒ^ｃ）−、＊−Ｘ^３−Ｏ−ＣＯ−又は＊−Ｘ^３−Ｎ（Ｒ^ｃ）−ＣＯ−（但し、Ｒ^ｃは水素原子又は炭素数１〜６のアルキル基を表す。Ｘ^３は炭素数１〜６のアルカンジイル基を表す。＊はＸ^２との結合手を表す。）で表される基、若しくは単結合を表す。
Ｒ^３は、水素原子又はメチル基を表す。］ <Resin (A2)>
The resin (A2) has a structural unit represented by the formula (II) (hereinafter sometimes referred to as “structural unit (II)”), is insoluble or hardly soluble in an alkaline aqueous solution, and is alkaline aqueous solution by the action of an acid. Can be dissolved.

[In the formula (II),
Ring T ¹ represents a C3-C34 sultone ring which may have a substituent.
X ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
X ² represents an oxygen atom or —N (R ^c ) — (where R ^c is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
Z ^{1 is, * - X 3 -CO-O} -, * - X 3 -CO-N (R c) -, * - X 3 -O-CO- or ^{* -X 3 -N (R c)} -CO -(Wherein R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X ³ represents an alkanediyl group having 1 to 6 carbon atoms, * represents a bond to X ² ). Represents a group or a single bond.
R ³ represents a hydrogen atom or a methyl group. ]

Here, “can be dissolved in an alkaline aqueous solution by the action of an acid” means that the resin (A2) has an acid-labile group (hereinafter sometimes referred to as “acid-labile group”), It means insoluble or hardly soluble in an aqueous alkali solution before contact, but becomes soluble in an aqueous alkali solution after contact with an acid.
The resin (A2) further has a structural unit different from the structural unit (II), and this different structural unit has an acid labile group. That is, the resin (A2) includes a structural unit derived from a monomer having an acid labile group (hereinafter sometimes referred to as “acid labile group monomer (a1)”) in addition to the structural unit (II) (hereinafter referred to as “acid”). Labile group structural unit (a1) ”).
In addition, as long as the resin (A2) has the above-described properties, the resin (A2) is a structural unit derived from a monomer having no acid-labile group (hereinafter sometimes referred to as “acid-stable monomer”), a monomer known in the art And the structural unit represented by the structural unit (I) and the formula (IIIA) described above may be included.
The resin (A2) may be a different resin different from the resin (A1), or has a structural unit represented by the formula (I) and a structural unit represented by the formula (II), and an alkali. A resin that is insoluble or hardly soluble in an aqueous solution and can be dissolved in an alkaline aqueous solution by the action of an acid may be used.

スルトン環が有していてもよい置換基としては、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基あるいは炭素数２〜４のアシル基等が挙げられる。 The sultone ring in the ring T ¹ of the formula (II) refers to a ring containing —SO ₂ —O— as an atomic group constituting the ring.
Examples of the sultone ring group include a ring represented by any of the following formula (T ¹ -1), formula (T ¹ -2), formula (T ¹ -3), and formula (T ¹ -4). Can be mentioned. The sultone ring may be monocyclic but is preferably polycyclic. The polycyclic sultone ring refers to a condensed ring containing —SO ₂ —O— as an atomic group constituting the ring, and is represented by, for example, the formula (T ¹ -1) or the formula (T ¹ -2). A ring is mentioned. In addition, the sultone ring group may further include a hetero atom as an atomic group constituting the ring, in addition to —SO ₂ —O—, like the ring represented by the formula (T ¹ -2). Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Among them, an oxygen atom is preferable.

Examples of the substituent that the sultone ring may have include an alkyl group having 1 to 12 carbon atoms that may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, and 1 to 12 carbon atoms. Examples thereof include an alkoxy group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an acyl group having 2 to 4 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Examples of the alkyl group having a halogen atom include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group, A trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.
Examples of the alkyl group having a hydroxy group include a hydroxymethyl group and a 2-hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.
Aryl groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl. Group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl and the like.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.
Examples of the alkoxycarbonyl group include groups in which a carbonyl group is further bonded to an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.

In the formulas (T ¹ -1) to (T ¹ -4), the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.
The alkyl group having a halogen atom or a hydroxy group is preferably a hydroxymethyl group, a hydroxyethyl group, a trifluoromethyl group, or the like.
The alkoxycarbonyl group preferably has 6 or less carbon atoms, and more preferably a methoxycarbonyl group.
In addition, as a sultone ring, the sultone ring which does not have a substituent mentioned above from a viewpoint that manufacture of the compound which can derive | lead-out structural unit (II) is easy is preferable.

［式（Ｔ１’）中、
Ｘ¹¹、Ｘ¹²及びＸ¹³は、それぞれ独立に、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ^４は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、オキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基あるいは炭素数２〜４のアシル基を表す。
ｍ’は、０〜１０である。
＊は、酸素原子との結合手を表す。］ The ring T ¹ is preferably a ring represented by the following formula (T1 ′).

[In the formula (T1 ′),
X ¹¹ , X ¹² and X ¹³ each independently represent an oxygen atom, a sulfur atom or a methylene group.
R ⁴ is a C 1-12 alkyl group optionally having a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, an oxy group, a cyano group, a C 1-12 alkoxy group, a C 6-12 12 represents an aryl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
m ′ is 0-10.
* Represents a bond with an oxygen atom. ]

X ¹¹ , X ¹² and X ¹³ are each independently preferably an oxygen atom or a methylene group. When one of X ¹¹ , X ¹² and X ¹³ is an oxygen atom, the remaining two are methylene groups. Are preferred. In the case where one is an oxygen atom, X ¹¹ is preferably an oxygen atom.

［式（Ｔ１）中、
Ｒ^４は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、オキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシドジルオキシ基、炭素数２〜１２のアルコキシカルボニル基あるいは炭素数２〜４のアシル基を表す。
ｍは、０〜１１である。
＊は、酸素原子との結合手を表す。］
式（Ｔ１’）及び式（Ｔ１）では、ｍ及びｍ’は、好ましくは０又は１であり、より好ましくは０である。 Furthermore, as the ring ^{T 1,} a group represented by the formula (T1) is more preferable.

[In the formula (T1),
R ⁴ is a C 1-12 alkyl group optionally having a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, an oxy group, a cyano group, a C 1-12 alkoxy group, a C 6-12 It represents a 12 aryl group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
m is 0-11.
* Represents a bond with an oxygen atom. ]
In Formula (T1 ′) and Formula (T1), m and m ′ are preferably 0 or 1, and more preferably 0.

Examples of the formula (T1 ′) and the formula (T1) include the following groups.

Examples of alkanediyl groups include 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- Linear alkanediyl group such as 1,6-diyl group; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane- Examples include branched alkanediyl groups such as 1,4-diyl group and 2-methylbutane-1,4-diyl group.
The alkanediyl group of X ¹ is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a methylene group and an ethylene group, and further preferably a methylene group.
X ² is an oxygen atom.

The alkanediyl group for X ³ is preferably a linear alkanediyl group. Further, the alkanediyl group of X ³ preferably has 1 to 3 carbon atoms, and more preferably a methylene group or an ethylene group.
When Z ¹ is * —X ³ —CO—N (R ^c ) — or * —X ³ —N (R ^c ) —CO—, R ^c is preferably a hydrogen atom.

In particular, —X ² —Z ¹ —X ¹ — in the structural unit (II) is —O—CH ₂ —CH ₂ —, —O—CH ₂ —CH ₂ —O—CO—CH ₂ — or —O—. More preferred is CH ₂ —CH ₂ —NH—CO—CH ₂ —.

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

式（ａａ−１）〜式（ａａ−２４）のいずれかで表される構造単位（ＩＩ）の具体例において、Ｒ^３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（ＩＩ）の具体例として挙げることができる。

In the specific example of the structural unit (II) represented by any one of the formulas (aa-1) to (aa-24), the structural unit in which the methyl group corresponding to R ³ is replaced with a hydrogen atom is also a structural unit ( Specific examples of II) can be mentioned.

［式（ＩＩ’）中の符号はいずれも、前記と同義である。］ The structural unit (II) is derived from a compound represented by the following formula (II ′) (hereinafter referred to as “compound (II ′)”).

[All the symbols in formula (II ′) have the same meanings as described above. ]

式中、Ｘは、ハロゲン原子を表し、その他の符号は上記と同義である。
Ｘのハロゲン原子としては、塩素原子、臭素原子及びヨウ素原子が挙げられ、中でもヨウ素原子が好ましい。
化合物（ａａ１−ｂ）としては、上述の式（Ｔ^１−１）〜式（Ｔ^１−４）のいずれかで表される環において、これらの環を構成する水素原子の１つがヒドロキシ基に置換された化合物などが挙げられる。このように化合物（ａａ１−ｂ）を選択すれば、種々のスルトン環を有する化合物（ａａ１）を製造することができる。
化合物（ａａ１−ｂ）の代表例として、市場から容易に入手できるものを例示すると、以下に示すものが挙げられる。

Compound (II ′) can be produced by the following production method or a method analogous thereto.
Among the compounds (II ′), a compound (aa1) in which X ² is an oxygen atom, Z ¹ is a single bond, and X ¹ is an ethylene group includes a compound represented by the formula (aa1-a) and a formula (aa1-b) ) Can be obtained by reacting in a solvent in the presence of a catalyst. As the catalyst used here, potassium carbonate and potassium iodide are preferable, and as the solvent, acetonitrile is preferable.

In the formula, X represents a halogen atom, and other symbols are as defined above.
Examples of the halogen atom for X include a chlorine atom, a bromine atom and an iodine atom, and among them, an iodine atom is preferable.
As the compound (aa1-b), in the ring represented by any of the above formulas (T ¹ -1) to (T ¹ -4), one of hydrogen atoms constituting these rings is a hydroxy group Examples include substituted compounds. Thus, if compound (aa1-b) is selected, the compound (aa1) which has various sultone rings can be manufactured.
As typical examples of the compound (aa1-b), those readily available from the market are exemplified.

（式（ａａ１−ａ１）中の符号はいずれも、上記と同義である。）
式（ａａ１−ａ１）で表される化合物は、公知の方法により製造することができる。 Moreover, the compound (II ′) in which X ² is —NH— can be produced by replacing the compound (aa1-a) with a compound represented by the following formula (aa1-a1).

(All symbols in formula (aa1-a1) have the same meaning as above.)
The compound represented by the formula (aa1-a1) can be produced by a known method.

式（ａａ１−ｃ）で表される化合物としては、メタクリル酸クロリドなどが挙げられる。このメタクリル酸クロリドは市場から容易に入手できる。
式（ａａ１−ｄ）で表される化合物は、２-ハロエタノールであり、市場から容易に入手できる。このように市場から入手できるものの中でも、２-ヨードエタノールが好ましい。 Compound (aa1-a) can be produced by a known method.
For example, the method of making the compound represented by a formula (aa1-c) and the compound represented by a formula (aa1-d) react in a solvent in presence of a base catalyst is mentioned. The base catalyst used here is preferably pyridine, and the solvent is preferably tetrahydrofuran.

Examples of the compound represented by the formula (aa1-c) include methacrylic acid chloride. This methacrylic acid chloride is easily available from the market.
The compound represented by the formula (aa1-d) is 2-haloethanol and can be easily obtained from the market. Of those commercially available, 2-iodoethanol is preferred.

  In addition, the compound represented by a formula (aa1-a1) can also be manufactured if 2-haloethanol represented by a formula (aa1-d) is substituted by 2-haloethylamine. Moreover, when using 2-haloethylamine, you may protect the amino group contained in 2-haloethylamine with a suitable protective group as needed.

式中の符号はいずれも、前記と同義である。 In the case where X ² is an oxygen atom, Z ¹ is —CH ₂ —CH ₂ —O—CO—, and X ¹ is a methylene group, the compound (aa2) includes the compound represented by the formula (aa2-a) and the formula ( It can manufacture by making the compound represented by aa2-b) react in a solvent. As a solvent used here, acetonitrile is preferable.

All symbols in the formula are as defined above.

  Examples of the compound (aa2-a) that can be easily obtained from the market include 2-hydroxyethyl methacrylate.

Compound (aa2-b) can be produced, for example, by reacting a compound represented by formula (aa2-c) with a compound represented by formula (aa2-d) in a solvent. Tetrahydrofuran is preferred as the solvent used here.

式（ａａ２−ｅ）で表される化合物としては、例えば、以下で表される化合物などが挙げられる。この化合物は市場から容易に入手できる。

The compound represented by the formula (aa2-d) is obtained, for example, by reacting the compound represented by the formula (aa2-e) with the compound represented by the formula (aa2-f) in a solvent. Can do. As a solvent used here, chloroform is preferable.

As a compound represented by a formula (aa2-e), the compound represented by the following etc. is mentioned, for example. This compound is readily available from the market.

Examples of the compound (II ′) include the following compounds.

  The content of the structural unit (II) is preferably in the range of 2 to 40 mol%, more preferably in the range of 3 to 35 mol%, with respect to the total structural units (100 mol%) of the resin (A2). The range of 30 mol% is more preferable. Resin (A2) having structural unit (II) in such a content ratio is produced by adjusting the amount of compound (II ′) used relative to the total amount of all monomers used in the production of resin (A2). Can do.

<Acid unstable structural unit (a1)>
The “acid-labile group” means a group having a leaving group and leaving the leaving group upon 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^a3は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜２０の脂環式炭化水素基を表すか、Ｒ^a1及びＲ^a2は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。＊は結合手を表す。］

［式（２）中、Ｒ^ａ１’及びＲ^ａ２’は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合して炭素数２〜２０の２価の炭化水素基を形成し、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 Expression (1), R ^a1 ~R ^a3 each independently represent a cycloaliphatic hydrocarbon radical of the alkyl group or 3 to 20 carbon atoms having 1 to 8 carbon atoms, R ^a1 and R ^a2 are each Bonding 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-.

The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and dimethylcyclohexane. Examples thereof include a cycloalkyl group such as a hexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the following groups.

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

In Formula (1), the alicyclic hydrocarbon group of R ^{a1 to} R ^a3 preferably has 3 to 16 carbon atoms.
Examples of the acid labile group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, preferably 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- (Adamantan-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Examples of the hydrocarbon group include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group as described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the divalent hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include a group in which one hydrogen atom has been removed from the hydrocarbon group of R ² in formula (I).
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) from which the acid labile structural unit (a1) is derived preferably has a monomer having an acid labile group and a carbon-carbon double bond, more preferably an acid labile group. It is a (meth) acrylic monomer.

  Of the (meth) acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferred. If a resin obtained by polymerizing an acid labile monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used, the resolution of the resist pattern can be improved.

  As the structural unit (a1) derived from a (meth) acrylic monomer having an acid labile group and an alicyclic hydrocarbon group, the structural unit represented by the formula (a1-1) or the formula (a1- 2). These may be used alone or in combination of two or more. Hereinafter, these structural units may be referred to as a structural unit (a1-1) and a structural unit (a1-2), respectively.

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、それぞれ独立に、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊は−ＣＯ−との結合手を表す。
Ｒ^a4及びＲ^a5は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、それぞれ独立に、炭素数１〜８のアルキル基又は炭素数３〜１０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.
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 for 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 for R ^a6 and R ^a7 may be monocyclic or polycyclic, and examples thereof are the same as those described above.
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.

Examples of the monomer for deriving the structural unit represented by the formula (a1-1) include monomers described in JP 2010-204646 A. Monomers represented by the following formulas (a1-1-1) to (a1-1-8) are preferred, and monomers represented by the following formulas (a1-1-1) to (a1-1-4) are more preferred. .

Examples of the monomer for deriving the structural unit represented by the formula (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, 1- Examples include ethylcycloheptan-1-yl (meth) acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, 1-isopropylcyclopentan-1-yl (meth) acrylate, and the like. Monomers represented by the following formulas (a1-2-1) to (a1-2-6) are preferred, and monomers represented by the following formulas (a1-2-3) to (a1-2-4) are more preferred. A monomer represented by the following formula (a1-2-3) is more preferable.

  When the resin (A2) includes the structural unit represented by the formula (a1-1) and / or the structural unit represented by the formula (a1-2), the total content thereof is the total structure of the resin (A2). It is 10-95 mol% normally with respect to a unit, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

式（ａ１−５）中、
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。
Ｌ^１〜Ｌ^３は、酸素原子、硫黄原子又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−で表される基を表す。ここで、ｋ１は１〜７の整数を表し、＊はカルボニル基（−ＣＯ−）との結合手である。
Ｚ^１は、単結合又は炭素数１〜６のアルカンジイル基であり、該アルカンジイル基中に含まれるメチレン基は、オキシ基又はカルボニル基に置き換わっていてもよい。
ｓ１及びｓ１’は、それぞれ独立して、０〜４の整数を表す。 Examples of the monomer (a1) for deriving another structural unit (a1) include a monomer represented by the formula (a1-5) which is a (meth) acrylic monomer having an acid labile group (2) (hereinafter “ Monomer (a1-5) ”may be used. When the resin (A2) having a structural unit derived from the monomer (a1-5) is used for the resist composition of the present invention, the resulting resist pattern tends to have few defects.

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.
L ^{1 to} L ³ represent an oxygen atom, a sulfur atom, or a group represented by ^* —O— (CH ₂ ) _k1 —CO—O—. Here, k1 represents an integer of 1 to 7, and * is a bond with a carbonyl group (—CO—).
Z ¹ is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkanediyl group may be replaced with an oxy group or a carbonyl group.
s1 and s1 ′ each independently represents an integer of 0 to 4.

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 (A2) has a structural unit derived from the monomer (a1-5), the content ratio is in the range of 1 to 50 mol% with respect to all the structural units (100 mol%) of the resin (A2). Is preferable, the range of 3-45 mol% is more preferable, and the range of 5-40 mol% is further 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 and the adhesion to the substrate can be improved.

<Acid-stable monomer having a hydroxy group (a2)>
When the resist composition is used for KrF excimer laser exposure (248 nm), high energy beam exposure such as electron beam or EUV light, the acid-stable monomer (a2) having a hydroxy group is preferably a phenolic hydroxy which is a hydroxystyrene. An acid-stable monomer having a 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. Monomers represented by the following formulas (a2-1-1) to (a2-1-6) are preferred, and monomers represented by the following formulas (a2-1-1) to (a2-1-4) are more preferred. A monomer represented by the following formula (a2-1-1) or (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 thereof is usually 3 to 40 mol% with respect to all the structural units of the resin (A2). , Preferably it is 5-35 mol%, More preferably, it is 5-30 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^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^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。ｐ１が２以上のとき、複数のＲ^a21は同一又は相異なる。
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。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 to} 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 to} 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. When p1 is 2 or more, the plurality of R ^a21 are the same or different.
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 q1 is 2 or more, the plurality of R ^a22 are the same or different, and when r1 is 2 or more, the plurality of R ^a23 are the same or different.

In formula (a3-1) to formula (a3-3), L ^{a4 to} L ^a6 are preferably each independently —O— or ^* —O— (CH ₂ ) _k3 —CO—O—, More preferably, it is -O-. k3 is preferably an integer of 1 to 4, more preferably 1.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1 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. In the following formulas (a3-1-1) to (a3-1-4), (a3-2-1) to (a3-2-4), (a3-3-1) to (a3-3-4) Monomers represented by the following formulas (a3-1-1) to (a3-1-2) and (a3-2-3) to (a3-2-4) are more preferred, A monomer represented by formula (a3-1-1) or (a3-2-3) is more preferable.

  When the resin (A2) includes a structural unit derived from the acid-stable monomer (a3) having a lactone ring, the content is usually 5 to 70 mol% with respect to all the structural units of the resin (A2), Preferably it is 10-65 mol%, More preferably, it is 15-60 mol%.

When the resin (A2) is a copolymer of an acid labile monomer (a1) and an acid stable monomer, the structural unit (a1) derived from the acid labile monomer (a1) is 100 mol% of all structural units. On the other hand, it 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 acid labile structural unit (a1-1)) is preferably 15 mol% or more based on the acid labile structural unit (a1). When the ratio of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist is improved.

  The resin (A2) is preferably a copolymer of a monomer represented by the formula (II ′), an acid labile monomer (a1), and an acid stable monomer. In this copolymer, the monomer for deriving the acid labile structural unit (a1) is more preferably a monomer having an adamantyl group (a monomer deriving the structural unit (a1-1)) and a monomer having a cyclohexyl group ( A monomer deriving the structural unit (a1-2)) (more preferably a monomer deriving the structural unit (a1-1) having an adamantyl group). 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) in resin (A) are, for example, 0.01: 10 to 5:10, preferably 0.05: 10 to 3:10, more preferably 0.1: 10. It is contained at 2:10, particularly preferably 0.2: 10 to 1:10 (mass ratio).

<Resin other than resin (A1) and (A2)>
The resist composition of the present invention includes a resin other than the resins (A1) and (A2) described above, for example, the structural unit (a1) derived from the acid labile monomer (a1) and the structure derived from the acid stable monomer. In addition to the unit, a resin composed of a structural unit derived from a known monomer used in this field may be contained.
When the resist composition of this invention contains resin other than resin (A1) and (A2), these content rates are normal with respect to the total amount of resin (A) contained in the resist composition of this invention. It is 0.1-50 mass%, Preferably it is 0.5-30 mass%, More preferably, it is 1-20 mass%.

  In the resist composition of the present invention, the resin content is preferably 80% by mass or more in the solid content of the resist composition. In the present specification, the “solid content in the composition” means the total of resist composition components excluding the solvent (E) described later. The solid content in the composition and the 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). -Sulfonates), sulfones (e.g. disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). 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, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712. A compound capable of generating an acid by radiation described in No. 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、単結合又は２価の炭素数１〜１７の飽和炭化水素基を表し、前記２価の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１〜１８のアルキル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、前記アルキル基及び前記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 single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group is replaced by —O— or —CO—. May be.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the alkyl group and the above —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Can be mentioned.
In formula (B1), 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 include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and two or more of these groups. May be combined.
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, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, etc.) is added to the linear alkanediyl. Those having a side chain, for example, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group Branched alkanediyl groups such as 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 of L ^b1 is replaced by —O— or —CO— include formula (b1-1) to formula (b1-6). Incidentally, the formula (b1-1) ~ formula (b1-6) are described together the left and right in the equation (B1), the left ^{C (Q 1) (Q 2} ) - bound to, the right side Combines with -Y. The same applies to specific examples of the following formulas (b1-1) to (b1-6).

式（ｂ１−１）〜式（ｂ１−６）中、
Ｌ^b2は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b3は、単結合又は炭素数１〜１２の２価の飽和炭化水素基を表す。
Ｌ^b4は、炭素数１〜１３の２価の飽和炭化水素基を表す。但しＬ^b3及びＬ^b4の炭素数上限は１３である。
Ｌ^b5は、炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b6及びＬ^b7は、それぞれ独立に、炭素数１〜１５の２価の飽和炭化水素基を表す。但しＬ^b6及びＬ^b7の炭素数上限は１６である。
Ｌ^b8は、炭素数１〜１４の２価の飽和炭化水素基を表す。
Ｌ^b9及びＬ^b10は、それぞれ独立に、炭素数１〜１１の２価の飽和炭化水素基を表す。但しＬ^ｂ９及びＬ^ｂ１０の炭素数上限は１２である。
中でも、Ｌ^b1は、好ましくは式（ｂ１−１）〜式（ｂ１−４）のいずれか、より好ましくは式（ｂ１−１）又は式（ｂ１−２）、さらに好ましくは式（ｂ１−１）で表される２価の基であり、特に好ましくは、Ｌ^b2が単結合又は−ＣＨ_２−である式（ｂ１−１）で表される２価の基である。

In formula (b1-1) to formula (b1-6),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b6 and L ^b7 each independently represent a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b9 and L ^b10 each independently represent a divalent saturated hydrocarbon group having 1 to 11 carbon atoms. However, the upper limit of the carbon number of L ^b9 and L ^b10 is 12.
Among them, L ^b1 is preferably any one of formula (b1-1) to formula (b1-4), more preferably formula (b1-1) or formula (b1-2), and still more preferably formula (b1-1). And particularly preferably a divalent group represented by the formula (b1-1) in which L ^b2 is a single bond or —CH ₂ —.

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

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

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

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

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

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

As an alkyl group of Y, Preferably, a C1-C6 alkyl group is mentioned.
Examples of the substituent for the alkyl group and the alicyclic hydrocarbon group include a halogen atom, a hydroxy group, an oxo group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 carbon atoms. -16 alicyclic hydrocarbon group, C1-C12 alkoxy group, C6-C18 aromatic hydrocarbon group, C7-C21 aralkyl group, C2-C4 acyl group, glycidyl An oxy 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 carbon atoms) Represents an aromatic hydrocarbon group of -18. J2 represents an integer of 0-4).
The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, aralkyl group, and the like, which are substituents for Y, may further have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxy group, and an oxo group.

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.
Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl group, naphthylethyl group and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

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

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

Examples of Y include the following.

When Y is an alkyl group and L ^b1 is a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms, the methylene group of the divalent aliphatic hydrocarbon group bonded to Y is oxygen It is preferably replaced by an atom or a carbonyl group. In this case, the methylene group constituting the alkyl group of Y is not replaced with an oxygen atom or a carbonyl group.

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

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

  Examples of the cation contained in the acid generator (B) include organic onium cations such as organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations, and preferably organic sulfonium cations. Or it is an organic iodonium cation, More preferably, it is an aryl sulfonium cation.

Z ⁺ in formula (B1) is preferably represented by any of formula (b2-1) to formula (b2-4).

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represents a hydrocarbon group having 1 to 30 carbon atoms, and among these hydrocarbon groups, an alkyl group having 1 to 30 carbon atoms and an alicyclic carbonization having 3 to 18 carbon atoms. A hydrogen 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. The aromatic hydrocarbon group may have 2 to 4 acyl groups or glycidyloxy groups, and the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alicyclic group having 3 to 18 carbon atoms. You may have a hydrocarbon group or a C1-C12 alkoxy group.
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.
The alkyl group of R ^{b9 to} R ^b11 preferably has 1 to 12 carbon atoms, and the alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.
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. The aromatic hydrocarbon group is 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. May be substituted.
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 ^{b13 to} R ^b18 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents -S- or -O-.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 same or different, when p2 is 2 or more, the plurality of R ^b14 same or different, when s2 is 2 or more, the plurality of R ^b17 same Or, when t2 is 2 or more, a plurality of R ^b18 are the same or different, and when q2 is 2 or more, a plurality of R ^b15 are the same or different, and when r2 is 2 or more, R ^b16 is the same or different.

  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.

In the formulas (b2-1) to (b2-4), the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. Group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group.
The alicyclic hydrocarbon group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 2-alkyladamantan-2-yl group, or 1- (adamantan-1-yl). ) Alkane-1-yl group and isobornyl group.
The aromatic hydrocarbon group is preferably a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-cyclohexylphenyl group, a 4-methoxyphenyl group, or a biphenylyl group. And a naphthyl group.
Examples of the alkyl group (aralkyl group) whose substituent is an aromatic hydrocarbon group include a benzyl group.
Examples of the ring formed by R ^b9 and R ^b10 include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
^Examples of the ring formed by R ^b11 and R ^b12 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^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し、該アルキル基、アルコキシ基及び脂環式炭化水素基は、ハロゲン原子、ヒドロキシ基、炭素数１〜１２のアルコキシ基、炭素数６〜１８の芳香族炭化水素基、炭素数２〜４のアシル基又はグリシジルオキシ基で置換されていてもよい。
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^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 to} R ^b21 each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alicyclic ring having 3 to 18 carbon atoms. The alkyl group, alkoxy group and alicyclic hydrocarbon group are a halogen atom, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, carbon It may be substituted with an acyl group or a glycidyloxy group of 2-4.
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 to} 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. .

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

  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 (B1-17), more preferably an acid containing a triphenylsulfonium cation or a tolylsulfonium cation. Generator (B1-1), (B1-2), Formula (B1-3), (B1-6), Formula (B1-7), (B1-11), (B1-12), (B1-13) ) And (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) with respect to 100 parts by mass of the resin (A). Is 25 parts by mass or less).

<Solvent (E)>
The content rate of the solvent (E) contained in the resist composition of this invention is 90 mass% or more in a resist composition, for example, Preferably it is 92 mass% or more, More preferably, it is 94 mass% or more, for example, 99.9. It is not more than mass%, preferably not more than 99 mass%. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may be used by containing 1 type, and may contain 2 or more types.

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

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

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

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

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

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、Ｒ^c5、Ｒ^c6、Ｒ^c7及びＲ^c8は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c9は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜６のアルカノイル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^c9は同一又は相異なる。］
アルカノイル基としては、アセチル基、２−メチルアセチル基、２，２−ジメチルアセチル基、プロピオニル基、ブチリル基、イソブチリル基、ペンタノイル基、２，２−ジメチルプロピオニル基等が挙げられる。

[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. ]
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.

［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又はｐ３が２以上であるとき、それぞれ、複数のＲ^c14及び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, and when o3 or p3 is 2 or more, the plurality of R ^c14 and R ^c15 are the same or different, respectively.
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、ｒ３及びｓ３が２以上であるとき、それぞれ、複数のＲ^c18、Ｒ^c19及びＲ^c20は同一又は相異なる。
Ｌ^c2は、単結合又は炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

Wherein (C7) and formula ^{(C8), R c18, R} c19 and R ^c20 in each occurrence independently represent the same meaning as R ^c4.
q3, r3 and s3 each independently represent an integer of 0 to 3, when q3, r3 and s3 is 2 or more, each of a plurality of R ^c18, R ^c19 and R ^{c 20} is 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. ]

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

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

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

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

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

  Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater.

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

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. The exposure light source emits ultraviolet laser light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), electron beam or extreme ultraviolet light (EUV). ), And those that emit laser light from a solid-state laser light source (such as YAG or semiconductor laser) and emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region. it can.

The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection group reaction. 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 an alkali developer using a developing device.
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).
After development, it is preferable to rinse with ultrapure water to remove water remaining on the substrate and the pattern.

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

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified. The composition ratio of the resin (A) (copolymerization ratio of the structural unit derived from each monomer used for the production of the resin (A) to the resin (A)) is the amount of unreacted monomer in the reaction liquid after the polymerization is finished. It measured using the chromatography, and computed by calculating | requiring the monomer amount used for superposition | polymerization from the obtained result. The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows.
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

式（Ｋ−２）で表される化合物１０．００部、テトラヒドロフラン４０．００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（Ｋ−１）で表される化合物３３．０８部を、１時間かけて添加した後、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。攪拌後、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分間攪拌した後、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分間攪拌した後、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（Ｋ）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 1 [Synthesis of Compound Represented by Formula (K)]

10.00 parts of the compound represented by the formula (K-2), 40.00 parts of tetrahydrofuran and 7.29 parts of pyridine were charged into a reactor, stirred at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, 33.08 parts of the compound represented by the formula (K-1) was added to the obtained mixture over 1 hour, and then the temperature was further increased to reach 23 ° C. And 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. After stirring, the mixture was 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, and then allowed to stand and liquid-separated to recover the organic layer. To the collected organic layer, 90.38 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, then allowed to stand and liquid-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 (K).
MS (mass spectrometry): 326.0 (molecular ion peak)

式（Ｈ−２）で表される化合物８８．００部、メチルイソブチルケトン６１６．００部及びピリジン６０．９８部を、２３℃で３０分間攪拌混合し、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（Ｈ−１）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１４４６．２２部及び２％塩酸水溶液７０３．４１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３３７．６４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３６１．５６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４４３．９２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３６１．５６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（Ｈ）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 2 [Synthesis of Compound Represented by Formula (H)]

88.00 parts of the compound represented by the formula (H-2), 616.00 parts of methyl isobutyl ketone and 60.98 parts of pyridine were stirred and mixed at 23 ° C. for 30 minutes and cooled to 0 ° C. While maintaining the same temperature, 199.17 parts of the compound represented by formula (H-1) was added to the obtained mixture over 1 hour, and the temperature was further increased to about 10 ° C. For 1 hour. To the resultant reaction product, 1446.22 parts of n-heptane and 703.41 parts of 2% aqueous hydrochloric acid were added, and the mixture was stirred at 23 ° C. for 30 minutes. The organic layer recovered by standing and liquid separation was charged with 337.64 parts of 2% aqueous hydrochloric acid and stirred at 23 ° C. for 30 minutes. The organic layer was recovered by standing and liquid separation. To the recovered organic layer, 361.56 parts of ion-exchanged water was charged, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. The recovered organic layer was charged with 443.92 parts of 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. 361.56 parts of ion-exchanged water was added to the collected organic layer, stirred and left at 23 ° C. for 30 minutes, 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 (H).
MS (mass spectrometry): 276.0 (molecular ion peak)

式（Ｏ−２）で表される化合物３０．００部、メチルイソブチルケトン２１０．００部及びピリジン１８．００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（Ｏ−１）で表される化合物４８．５０部を、１時間かけて添加した後、更に、５℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物を、酢酸エチル６３０部、５％塩酸水溶液９９．６８部及びイオン交換水１２６部に添加し、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８６．５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。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１５７．５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。水洗後の有機層を濃縮し式（Ｏ）で表される化合物２７．６１部を得た。
ＭＳ（質量分析）：３５４．１（分子イオンピーク） Synthesis Example 3 [Synthesis of Compound Represented by Formula (O)]

30.00 parts of the compound represented by the formula (O-2), 210.00 parts of methyl isobutyl ketone and 18.00 parts of pyridine were stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, 48.50 parts of the compound represented by the formula (O-1) was added to the obtained mixture over 1 hour, and then the temperature was further increased to about 5 ° C. For 1 hour. The obtained reaction product was added to 630 parts of ethyl acetate, 99.68 parts of 5% aqueous hydrochloric acid solution and 126 parts of ion-exchanged water, and stirred at 23 ° C. for 30 minutes. The organic layer recovered by standing and separating was charged with 86.50 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, and allowed to stand and separate to wash the organic layer. Such washing operation was repeated twice. The recovered organic layer was charged with 157.50 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 to obtain 27.61 parts of a compound represented by the formula (O).
MS (mass spectrometry): 354.1 (molecular ion peak)

式（Ｐ−２）で表される化合物２７．３４部、メチルイソブチルケトン１９０．００部及びピリジン１８．００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（Ｐ−１）で表される化合物４８．５０部を、１時間かけて添加した後、更に、５℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物を、酢酸エチル５７０部、５％塩酸水溶液９９．６８部及びイオン交換水１２６部に添加し、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８６．５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。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１５０部を仕込み、２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。水洗後の有機層を濃縮し式（Ｐ）で表される化合物２３．８９部を得た。
ＭＳ（質量分析）：３４０．１（分子イオンピーク） Synthesis Example 4 [Synthesis of Compound Represented by Formula (P)]

27.34 parts of the compound represented by the formula (P-2), 190.00 parts of methyl isobutyl ketone and 18.00 parts of pyridine were stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, 48.50 parts of the compound represented by the formula (P-1) was added to the obtained mixture over 1 hour, and then the temperature was further increased to about 5 ° C. For 1 hour. The obtained reaction product was added to 570 parts of ethyl acetate, 99.68 parts of 5% aqueous hydrochloric acid solution and 126 parts of ion-exchanged water, and stirred at 23 ° C. for 30 minutes. The organic layer recovered by standing and separating was charged with 86.50 parts of a 10% aqueous potassium carbonate solution, stirred at 23 ° C. for 30 minutes, and allowed to stand and separate to wash the organic layer. Such washing operation was repeated twice. The recovered organic layer was charged with 150 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 to obtain 23.89 parts of a compound represented by the formula (P).
MS (mass spectrometry): 340.1 (molecular ion peak)

式（Ｌ−１）で表される化合物（商品名：ＮＳＴＡＢｕ 出光製）１４．００部及びクロロホルム１４０部を、反応器に込み、２３℃で３０分間攪拌した。その後、式（Ｌ−２）で表される化合物５２．４５部を滴下した。得られた混合物を２３℃で１時間攪拌し、さらに、式（Ｌ−２）で表される化合物５２．４５部を滴下した。さらに２３℃で２時間攪拌した。続いて、式（Ｌ−２）で表される化合物５２．４５部を滴下した。そのまま、２３℃で１時間攪拌し、得られた反応混合物を濃縮した。濃縮物に、クロロホルム２０部を添加・攪拌し、濃縮した。回収された濃縮物にｎ−ヘプタン３０部を添加し、３０分間攪拌し、ろ過することにより、式（Ｌ−３）で表される化合物１１．１９部を得た。 Synthesis Example 5 [Synthesis of Compound Represented by Formula (L)]

14.00 parts of a compound represented by the formula (L-1) (trade name: NSTABu Idemitsu) and 140 parts of chloroform were placed in a reactor and stirred at 23 ° C. for 30 minutes. Thereafter, 52.45 parts of the compound represented by the formula (L-2) was added dropwise. The obtained mixture was stirred at 23 ° C. for 1 hr, and 52.45 parts of the compound represented by the formula (L-2) was further added dropwise. The mixture was further stirred at 23 ° C. for 2 hours. Subsequently, 52.45 parts of the compound represented by the formula (L-2) was dropped. The resulting mixture was stirred at 23 ° C. for 1 hour, and the resulting reaction mixture was concentrated. To the concentrate, 20 parts of chloroform was added and stirred, and concentrated. 30 parts of n-heptane was added to the collected concentrate, stirred for 30 minutes, and filtered to obtain 11.19 parts of a compound represented by the formula (L-3).

式（Ｌ−３）で表される化合物１０．０３部及びアセトニトリル６０．１８部を、反応器に仕込み、２３℃で３０分間攪拌した。その後、式（Ｌ−４）で表される化合物６．９２部を加え、２３℃で１．５時間攪拌した。得られた反応混合物に、式（Ｌ−５）で表される化合物４．３３部及びアセトニトリル２．１７部を添加し、２３℃で８時間攪拌した。不溶物をろ過で除去し、得られたろ液に、５％シュウ酸水溶液７６．８６部及び酢酸エチル１８７．０４部を添加した。３０分間攪拌し、静置・分液した。回収された有機層に、イオン交換水９３．５２部を加え、２３℃で３０分間攪拌し、分液することにより有機層を水洗した。同様の水洗操作を５回繰り返した。回収された有機層を濃縮することにより、式（Ｌ）で表される化合物１０．４５部を得た。
ＭＳ（質量分析）：３６０．１（分子イオンピーク）

10.03 parts of a compound represented by the formula (L-3) and 60.18 parts of acetonitrile were charged into a reactor and stirred at 23 ° C. for 30 minutes. Thereafter, 6.92 parts of the compound represented by the formula (L-4) was added, and the mixture was stirred at 23 ° C. for 1.5 hours. To the obtained reaction mixture, 4.33 parts of the compound represented by the formula (L-5) and 2.17 parts of acetonitrile were added and stirred at 23 ° C. for 8 hours. Insoluble matter was removed by filtration, and 76.86 parts of a 5% aqueous oxalic acid solution and 187.004 parts of ethyl acetate were added to the obtained filtrate. The mixture was stirred for 30 minutes, allowed to stand and separated. To the collected organic layer, 93.52 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to wash the organic layer with water. The same water washing operation was repeated 5 times. The recovered organic layer was concentrated to obtain 10.45 parts of a compound represented by the formula (L).
MS (mass spectrometry): 360.1 (molecular ion peak)

式（Ｍ−３）で表される化合物１０．０３部及びアセトニトリル６０．１８部を、反応器に仕込んだ。２３℃で３０分間攪拌し、式（Ｍ−４）で表される化合物６．９２部を添加した。その後、２３℃で１．５時間攪拌した。得られた反応混合物に、式（Ｍ−５）で表される化合物４．３０部及びアセトニトリル２．１５部を添加し、２３℃で８時間攪拌した。不溶物をろ過で除去し、得られたろ液に、５％シュウ酸水溶液７６．８６部及び酢酸エチル１８７．０４部を添加した。３０分間攪拌し、静置・分液した。回収された有機層に、イオン交換水９３．５２部を加え、２３℃で３０分間攪拌し、分液することにより有機層を水洗した。同様の水洗操作を５回繰り返した。回収された有機層を濃縮することにより、式（Ｍ）で表される化合物１０．２２部を得た。
ＭＳ（質量分析）：３５９．１（分子イオンピーク） Synthesis Example 6 [Synthesis of Compound Represented by Formula (M)]

10.03 parts of the compound represented by the formula (M-3) and 60.18 parts of acetonitrile were charged into a reactor. The mixture was stirred at 23 ° C. for 30 minutes, and 6.92 parts of the compound represented by the formula (M-4) was added. Then, it stirred at 23 degreeC for 1.5 hours. To the obtained reaction mixture, 4.30 parts of a compound represented by the formula (M-5) and 2.15 parts of acetonitrile were added, and the mixture was stirred at 23 ° C. for 8 hours. Insoluble matter was removed by filtration, and 76.86 parts of a 5% aqueous oxalic acid solution and 187.004 parts of ethyl acetate were added to the obtained filtrate. The mixture was stirred for 30 minutes, allowed to stand and separated. To the collected organic layer, 93.52 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, and separated to wash the organic layer with water. The same water washing operation was repeated 5 times. The recovered organic layer was concentrated to obtain 10.22 parts of a compound represented by the formula (M).
MS (mass spectrometry): 359.1 (molecular ion peak)

テトラヒドロフラン３．６４部に、０℃で、リチウムアルミニウムハイドライド０．２６部を添加した後、式（Ｍ−３）で表される化合物１．７８部及びテトラヒドロフラン９．１０部の混合溶液を、２０分かけて添加した。２３℃まで昇温した後、更に２時間攪拌した。得られた反応マスを、６Ｎ塩酸２０部に滴下し、その後、ｔｅｒｔ−ブチルメチルエーテル３０部及びイオン交換水３０部を添加攪拌後、分液した。回収された有機層に、イオン交換水３０部を加え、攪拌した後、分液することにより有機層を水洗した。同様の水洗操作を５回繰り返した。回収された有機層を濃縮した後、回収された濃縮物に、酢酸エチル１０部を添加し３０分間攪拌後、ろ過することにより、式（Ｑ−１）で表される化合物０．８９部を得た。 Synthesis Example 7 [Synthesis of Compound Represented by Formula (Q)]

After adding 0.26 parts of lithium aluminum hydride to 3.64 parts of tetrahydrofuran at 0 ° C., a mixed solution of 1.78 parts of the compound represented by the formula (M-3) and 9.10 parts of tetrahydrofuran Added over minutes. After heating up to 23 degreeC, it stirred for further 2 hours. The obtained reaction mass was added dropwise to 20 parts of 6N hydrochloric acid, and then 30 parts of tert-butyl methyl ether and 30 parts of ion-exchanged water were added and stirred, followed by liquid separation. To the recovered organic layer, 30 parts of ion-exchanged water was added and stirred, followed by liquid separation to wash the organic layer with water. The same water washing operation was repeated 5 times. After concentrating the recovered organic layer, 10 parts of ethyl acetate was added to the recovered concentrate, stirred for 30 minutes, and then filtered to obtain 0.89 part of the compound represented by the formula (Q-1). Obtained.

式（Ｑ−１）で表される化合物０．７２部、Ｎ−メチルピロリジン０．９２部、メチルイソブチルケトン２０部を仕込み、攪拌下、式（Ｑ−２）で表される化合物０．６４部を添加し、６０℃で２４時間攪拌した。その後、反応マスにイオン交換水１０部及びメチルイソブチルケトン２０部を添加、攪拌後、分液水洗を行った。この水洗の操作を３回行った。回収された有機層を濃縮後、カラム（メルク シリカゲル６０−２００メッシュ、展開溶媒：酢酸エチル）分取することにより、式（Ｑ）で表される化合物０．３１部を得た。
ＭＳ（質量分析）：３０２．１（分子イオンピーク）

0.72 part of a compound represented by the formula (Q-1), 0.92 part of N-methylpyrrolidine and 20 parts of methyl isobutyl ketone were charged, and the compound 0.64 represented by the formula (Q-2) was stirred. Part was added and stirred at 60 ° C. for 24 hours. Thereafter, 10 parts of ion-exchanged water and 20 parts of methyl isobutyl ketone were added to the reaction mass, followed by stirring and liquid separation washing. This washing operation was performed three times. The collected organic layer was concentrated and fractionated by a column (Merck silica gel 60-200 mesh, developing solvent: ethyl acetate) to obtain 0.31 part of a compound represented by the formula (Q).
MS (mass spectrometry): 302.1 (molecular ion peak)

Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below. Hereinafter, these monomers are referred to as “monomer (A)” to “monomer (Q)”.

Synthesis Example 8 [Synthesis of Resin A1-1]
Monomer (H) was used as a monomer, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. To this solution, 0.7 mol% and 2.1 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), respectively, as initiators were added with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice to perform the reprecipitation operation twice. 8 × 10 ⁴ resin A1-1 (copolymer) was obtained with a yield of 77%. This resin A1-1 has the following structural units.

Synthesis Example 9 [Synthesis of Resin A1-2]
Monomer (K) and monomer (I) are used as monomers and mixed so that the molar ratio (monomer (H): monomer (I)) is 90:10. Dioxane was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 72 ° C. for about 5 hours. did. 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 1.3 × 10 ^{4 in} a yield of 70%. Got in. This resin A1-2 has the following structural units.

Synthesis Example 10 [Synthesis of Resin A1-3]
The monomer (L) was used as a monomer, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. To this solution, 0.7 mol% and 2.1 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), respectively, as initiators were added with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice, and the weight average molecular weight was 1.9. × 10 ⁴ resin A1-3 (copolymer) was obtained in 73% yield. This resin A1-3 has the following structural units.

Synthesis Example 11 [Synthesis of Resin A1-4]
Monomer (M) was used as a monomer, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. To this solution, 0.7 mol% and 2.1 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), respectively, as initiators were added with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of 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 1.8. × 10 ⁴ resin A1-4 (copolymer) was obtained in 76% yield. This resin A1-4 has the following structural units.

Synthesis Example 12 [Synthesis of Resin A2-1]
Monomer (A), monomer (E), monomer (B), monomer (C), monomer (L) are in a molar ratio [monomer (A): monomer (E): monomer (B): monomer (C): Monomer (L)] is mixed at a ratio of 32: 7: 8: 43: 10, and further, 1.5 mass times dioxane is mixed with this monomer mixture with respect to the total mass of all monomers. did. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. Polymerization was carried out by heating at 73 ° C. for about 5 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin is filtered and recovered, dissolved again in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered twice to perform reprecipitation. Purification gave a copolymer having a weight average molecular weight of 9.5 × 10 ³ in a yield of 81%. This copolymer has the following structural units respectively derived from the monomer (A), the monomer (E), the monomer (B), the monomer (C), and the monomer (L). Set to 1.

Synthesis Example 13 [Synthesis of Resin A2-2]
Monomer (D), monomer (E), monomer (B), monomer (C), monomer (L) are in a molar ratio [monomer (D): monomer (E): monomer (B): monomer (C): The monomer (L)] is mixed at a ratio of 35: 10: 6: 37: 12, and 1.5 mass times of dioxane is further mixed with this monomer mixture with respect to the total mass of all monomers. did. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. Polymerization was carried out by heating at 73 ° C. for about 5 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin is filtered and recovered, dissolved again in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered twice to perform reprecipitation. Purification was performed to obtain a copolymer having a weight average molecular weight of 8.0 × 10 ³ in a yield of 79%. This copolymer has the following structural units respectively derived from the monomer (D), the monomer (E), the monomer (B), the monomer (C), and the monomer (L). 2.

Synthesis Example 14 [Synthesis of Resin A2-3]
Monomer (A), monomer (E), monomer (B), monomer (F), monomer (C), monomer (L) are mixed in a molar ratio [monomer (A): monomer (E): monomer (B): Monomer (F): monomer (C): monomer (L)] is mixed in a ratio of 32: 7: 8: 10: 33: 10, and the total mass of all monomers is added to this monomer mixture. On the other hand, 1.5 mass times dioxane was mixed. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. Polymerization was carried out by heating at 73 ° C. for about 5 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin is filtered and recovered, dissolved again in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered twice to perform reprecipitation. Purification gave a copolymer having a weight average molecular weight of 7.9 × 10 ³ in a yield of 74%. This copolymer has the following structural units derived from the monomer (A), the monomer (E), the monomer (B), the monomer (F), the monomer (C), and the monomer (L), This is Resin A2-3.

Synthesis Example 15 [Synthesis of Resin A2-4]
Monomer (D), monomer (E), monomer (B), monomer (C), monomer (M) are in a molar ratio [monomer (D): monomer (E): monomer (B): monomer (C): Monomer (M)] is mixed at a ratio of 35: 10: 6: 37: 12, and 1.5 mass times of dioxane is further mixed with this monomer mixture with respect to the total mass of all monomers. did. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. Polymerization was carried out by heating at 73 ° C. for about 5 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin is filtered and recovered, dissolved again in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered twice to perform reprecipitation. Purification was performed to obtain a copolymer having a weight average molecular weight of 8.0 × 10 ³ in a yield of 79%. This copolymer has the following structural units derived from the monomer (D), the monomer (E), the monomer (B), the monomer (C), and the monomer (M), respectively. 4.

Synthesis Example 16 [Synthesis of Resin A2-5]
Monomer (D), monomer (E), monomer (B), monomer (C), monomer (Q) are in a molar ratio [monomer (D): monomer (E): monomer (B): monomer (C): Monomer (Q)] is mixed at a ratio of 35: 10: 6: 37: 12, and 1.5 mass times of dioxane is further mixed with this monomer mixture with respect to the total mass of all monomers. did. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. Polymerization was carried out by heating at 73 ° C. for about 5 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin is filtered and recovered, dissolved again in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered twice to perform reprecipitation. Purification gave a copolymer having a weight average molecular weight of 7.6 × 10 ³ in a yield of 62%. This copolymer has the following structural units derived from the monomer (D), the monomer (E), the monomer (B), the monomer (C) and the monomer (Q), respectively. 5

Synthesis Example 16 [Synthesis of Resin A2-6]
Monomer (D), monomer (N), monomer (B), monomer (C), monomer (L) are in a molar ratio [monomer (D): monomer (N): monomer (B): monomer (C): The monomer (L)] was mixed so as to be 35: 10: 6: 37: 12, 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, and heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The 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. 3 × 10 ³ resin A6 (copolymer) was obtained with a yield of 60%. This copolymer has the following structural units respectively derived from the monomer (D), the monomer (N), the monomer (B), the monomer (C), and the monomer (L). 6.

Synthesis Example 17 [Synthesis of Resin A2-7]
Monomer (D), monomer (N), monomer (B), monomer (F), monomer (C), monomer (Q) are mixed in a molar ratio [monomer (D): monomer (N): monomer (B): Monomer (F): Monomer (C): Monomer (Q)] is mixed to be 30: 14: 6: 10: 30: 10, and 1.5 mass times dioxane of the total monomer amount is added to the solution. did. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, and heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The 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 A9 (copolymer) was obtained with a yield of 64%. This copolymer has the following structural units derived from the monomer (D), the monomer (N), the monomer (B), the monomer (F), the monomer (C), and the monomer (Q), This is called Resin A2-7.

Synthesis Example 18 [Synthesis of Resin X1]
Monomer (G), monomer (C), and monomer (B) are used as the monomers and mixed so that the molar ratio (monomer (G): monomer (C): monomer (B)) is 35:45:20. 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 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. The molar ratio of each structural unit is structural unit (G): structural unit (C): structural unit (B) = 34.7: 45.4: 19.9.

Synthesis Example 19 [Synthesis of Resin X2]
As the monomer, the monomer (J) and the monomer (G) are used and mixed so that the molar ratio (monomer (J): monomer (G)) is 80:20. Dioxane 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. The molar ratio of each structural unit was structural unit (J): structural unit (G) = 80.2: 19.8.

<Preparation of resist composition>
Each of the components shown below was dissolved in a solvent in parts by mass shown in Table 1, and further filtered through a fluororesin filter having a pore size 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

<Resin>
Resin synthesized in the above synthesis example <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

<Immersion exposure evaluation of resist composition>
An organic antireflective coating composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to form an organic reflective film having a thickness of 78 nm on the wafer. A prevention film was formed. Next, the resist composition was applied (spin coated) on the organic antireflection film so that the film thickness after drying (pre-baking) was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature described in the “PB” column of Table 1 for 60 seconds to form a composition layer.
ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) on a silicon wafer on which the composition layer is formed, and a contact hole pattern (hole pitch 100 nm) Using a mask for forming a hole diameter of 70 nm), the exposure amount was changed stepwise to perform exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, the silicon wafer was heated (post-exposure baking process) on a hot plate at a temperature described in the “PEB” column of Table 1 for 60 seconds.
Next, this silicon wafer was subjected to paddle development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

  In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 55 nm was defined as the effective sensitivity.

<Evaluation of CD uniformity (CDU)>
In terms of effective sensitivity, the resist pattern formed using the mask was evaluated as follows. 24 hole diameters were measured for each hole, and the average value was taken as the average hole diameter of one hole. Within the same resist pattern, the same average hole diameter measurement was performed at 400 locations, and the standard deviation was determined using them as a population, and the CDU was determined at the following level.
When the standard deviation is less than 1.85 nm,
When the standard deviation is 1.85 nm or more and less than 2.00 nm, “◯”,
The case where the standard deviation was 2.00 nm or more was judged as “x”. Numerical values in parentheses indicate standard deviation (nm).

<Defect evaluation>
The resist composition was applied (spin coated) to a 12-inch silicon wafer (substrate) so that the film thickness after drying was 0.15 μm. After coating, the composition layer was formed on the wafer by pre-baking (PB) for 60 seconds on the direct hot plate at the temperature shown in the PB column of Table 1.
The wafer on which the composition layer was formed in this manner was subjected to water rinsing 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.

  According to the resist composition containing the resin of the present invention, a resist pattern having good CD uniformity and few defects can be produced.

Claims (8)

(A1) a resin having a structural unit represented by formula (I),
(A2) a resin having a structural unit represented by the formula (II), insoluble or hardly soluble in an alkaline aqueous solution, and soluble in an alkaline aqueous solution by the action of an acid;
(B) A resist composition containing an acid generator.

[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.
R ² represents a C 1-10 hydrocarbon group having a fluorine atom. ]

[In the formula (II),
Ring T ¹ represents a C3-C34 sultone ring which may have a substituent.
X ¹ represents an alkanediyl group having 1 to 6 carbon atoms.
X ² represents an oxygen atom or —N (R ^c ) — (where R ^c is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).
Z ^{1 is, * - X 3 -CO-O} -, * - X 3 -CO-N (R c) -, * - X 3 -O-CO- or ^{* -X 3 -N (R c)} -CO -(Wherein R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X ³ represents an alkanediyl group having 1 to 6 carbon atoms, * represents a bond to X ² ). Represents a group or a single bond.
R ³ represents a hydrogen atom or a methyl group. ] The resist composition according to claim 1, wherein R ² in formula (I) is a fluorinated alkyl group having 1 to 6 carbon atoms. In formula (I), A ¹ is claim 1 or 2 resist composition according alkanediyl group having 2 to 4 carbon atoms. The resist composition according to claim ¹ , wherein in formula (II), ring T ¹ is a polycyclic sultone ring. The resist composition according to claim ¹ , wherein in formula (II), ring T ¹ is a ring represented by formula (T1).

[In the formula (T1),
R ⁴ is a C 1-12 alkyl group optionally having a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, an oxy group, a cyano group, a C 1-12 alkoxy group, a C 6-12 12 represents an aryl group having 12 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
m is 0-11.
* Represents a bond with an oxygen atom. ] In the formula (II), —X ² —Z ¹ —X ¹ — represents —O—CH ₂ —CH ₂ —, —O—CH ₂ —CH ₂ —O—CO—CH ₂ — or —O—CH _2. The resist composition according to claim 1, which is —CH ₂ —NH—CO—CH ₂ —.   Furthermore, the resist composition in any one of Claims 1-6 containing a solvent. (1) The process of apply | coating the resist composition in any one of Claims 1-7 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: