JP6039278B2 - Resist composition and method for producing resist pattern - Google Patents

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) and an acid generator is described.

JP 2010-197413 A

  A resist pattern formed by a conventional resist composition may not always have a satisfactory CD uniformity.

［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。
Ａ¹³は、ハロゲン原子を有していてもよい２価の炭素数１〜１８の脂肪族炭化水素基を表す。
Ｘ¹²は、＊−ＣＯ−Ｏ−又は＊−Ｏ−ＣＯ−を表し、＊は、Ａ¹³との結合手を表す。
Ａ¹⁴は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。］
［２］式（Ｉ）のＡ^１が、エチレン基である［１］記載のレジスト組成物。
［３］式（Ｉ）のＡ¹³が、炭素数１〜６のペルフルオロ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（Ｉ）のＸ¹²が、＊−ＣＯ−Ｏ−（＊は、Ａ¹³との結合手を表す。）である［１］〜［３］のいずれか記載のレジスト組成物。
［５］式（Ｉ）のＡ¹⁴が、シクロプロピルメチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基又はアダマンチル基である［１］〜［４］のいずれか記載のレジスト組成物。
［６］酸発生剤において、アルカリ現像液の作用により開裂する構造が、式（Ｂａ）で表される基又は式（Ｂｂ）で表される基である［１］〜［５］のいずれか記載のレジスト組成物。

［式（Ｂａ）中、Ｒ²³は、フッ素原子を有する炭素数１〜６のアルキル基を表す。］

［式（Ｂｂ）中、Ｒ²⁴は、フッ素原子を有する炭素数１〜６のアルキル基を表す。
Ｒ²⁵及びＲ²⁶は、それぞれ独立に、水素原子又はフッ素原子を表す。］
［７］酸発生剤が、式（ＩＩ−ａ）で表される酸発生剤又は式（ＩＩ−ｂ）で表される酸発生剤であるである［１］〜［６］のいずれか記載のレジスト組成物。

［式（ＩＩ−ａ）又は式（ＩＩ−ｂ）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。
Ｌ²¹は、単結合又は２価の炭素数１〜１７のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙは、炭素数３〜１８の２価の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｒ²³〜Ｒ²⁶は、上記と同じ意味を表す。］
［８］式（ＩＩ−ａ）及び式（ＩＩ−ｂ）のＺ^＋が、トリアリールスルホニウムカチオンである［７］記載のレジスト組成物。
［９］（１）上記［１］〜［８］のいずれか記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層を露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resin having a structural unit represented by the formula (I),
A resin that is insoluble or hardly soluble in an alkaline aqueous solution and that can be dissolved in an alkaline aqueous solution by the action of an acid (but not including the structural unit represented by formula (I)), and a structure that is cleaved by the action of an alkaline developer 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.
A ¹³ represents a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a halogen atom.
X ¹² represents * —CO—O— or * —O—CO—, and * represents a bond to A ¹³ .
A ¹⁴ represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. ]
[2] The resist composition according to [1], wherein A ^{1 in the} formula (I) is an ethylene group.
[3] The resist composition according to [1] or [2], wherein A ^{13 in the} formula (I) is a perfluoroalkanediyl group having 1 to 6 carbon atoms.
[4] The resist composition according to any one of [1] to [3], wherein X ^{12 in} formula (I) is * —CO—O— (* represents a bond to A ¹³ ).
A ¹⁴ [5] Formula (I) is, cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group or an adamantyl group [1] to resist composition according to any one of [4].
[6] In the acid generator, any one of [1] to [5], wherein the structure that is cleaved by the action of an alkali developer is a group represented by the formula (Ba) or a group represented by the formula (Bb): The resist composition as described.

[In Formula (Ba), R ²³ represents a C 1-6 alkyl group having a fluorine atom. ]

[In the formula (Bb), R ²⁴ represents a C 1-6 alkyl group having a fluorine atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a fluorine atom. ]
[7] Any one of [1] to [6], wherein the acid generator is an acid generator represented by the formula (II-a) or an acid generator represented by the formula (II-b). Resist composition.

[In formula (II-a) or formula (II-b),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ²¹ represents a single bond or a divalent alkanediyl group having 1 to 17 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—.
Y represents a C 3-18 divalent alicyclic hydrocarbon group, and —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced by —O— or —CO—. .
R ^{23 to} R ²⁶ represent the same meaning as described above. ]
[8] The resist composition according to [7], wherein Z ^{+ in} formula (II-a) and formula (II-b) is a triarylsulfonium cation.
[9] (1) A step of applying the resist composition according to any one of [1] to [8] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer,
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

  According to the resist composition of the present invention, a resist pattern can be produced with excellent CD uniformity. In addition, the number of defects in the obtained resist pattern can be reduced.

In the present specification, unless otherwise specified, in the description of the structural formula of the compound, the following examples of substituents are applied to any structural formula having the same substituent while appropriately selecting the number of carbon atoms. . Those which can be linear, branched or cyclic include any of them, and they may be mixed. When stereoisomers exist, all stereoisomers are included.
Further, "(meth) acrylic monomer" means at least one monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- ". Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

<Resist composition>
The resist composition of the present invention comprises:
Resin (hereinafter sometimes referred to as “resin (A)”) and an acid generator having a structure that is cleaved by the action of an alkali developer.
The resist composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as “solvent (E)”). Further, it preferably contains a basic compound (hereinafter sometimes referred to as “basic compound (C)”).

<Resin (A)>
The resin (A) contained in the resist composition of the present invention is
A resin having a structural unit represented by the formula (I) (hereinafter sometimes referred to as “resin (A1)”) and a resin that is insoluble or hardly soluble in an aqueous alkali solution and becomes soluble in an aqueous alkali solution by the action of an acid ( However, the structural unit represented by the formula (I) is not included) (hereinafter sometimes referred to as “resin (A2)”).
Moreover, resin other than resin (A1) and (A2) which is mentioned later may be contained.

［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。
Ａ¹³は、ハロゲン原子を有していてもよい炭素数１〜１８の２価の脂肪族炭化水素基を表す。
Ｘ¹²は、＊−ＣＯ−Ｏ−又は＊−Ｏ−ＣＯ−を表し、＊は、Ａ¹³との結合手を表す。
Ａ¹⁴は、ハロゲン原子を有していてもよい炭素数１〜１７の脂肪族炭化水素基を表す。］ <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.
A ¹³ represents a C divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a halogen atom.
X ¹² represents * —CO—O— or * —O—CO—, and * represents a bond to A ¹³ .
A ¹⁴ represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. ]

The alkanediyl group A ^1, methylene group, ethylene group, propane-1,3-diyl, propane-1,2-diyl group, butane-1,4-diyl, pentane-1,5-diyl , A straight-chain alkanediyl group such as hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 -Branched alkanediyl groups such as a diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group.

Examples of the halogen atom for A ¹³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is preferred.
The aliphatic hydrocarbon group for A ¹³ includes either a chain or a cyclic group, and a divalent aliphatic hydrocarbon group in which these are combined. The aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group, more preferably an alkanediyl group and a divalent cyclic aliphatic carbonization. It is a hydrogen group.
The aliphatic hydrocarbon group which may have a halogen atom for A ¹³ is preferably a saturated aliphatic hydrocarbon group which may have a fluorine atom.
Examples of the divalent chain aliphatic hydrocarbon group which may have a halogen atom (preferably a fluorine atom) include a methylene group, a difluoromethylene group, an ethylene group, a perfluoroethylene group, a propanediyl group, and a perfluoropropanediyl group. Group, butanediyl group, perfluorobutanediyl group, pentanediyl group, perfluoropentanediyl group, dichloromethylene group and dibromomethylene group.
The divalent cyclic aliphatic hydrocarbon group which may have a halogen atom (preferably a fluorine atom) may be monocyclic or polycyclic. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group, a perfluorocyclohexanediyl group, and a perchlorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

The aliphatic hydrocarbon group for A ¹⁴ includes either a chain or a cyclic group, and an aliphatic hydrocarbon group in which these are combined. The aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a halogen atom for A ¹⁴ is preferably a saturated aliphatic hydrocarbon group which may have a fluorine atom, more preferably an alkyl group or an alicyclic group. It is a hydrocarbon group.
Examples of the chain aliphatic hydrocarbon group which may have a halogen atom (preferably a fluorine atom) include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoro Ethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2 2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,4,4-nonafluoropentyl group and pentyl group, hexyl Group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group, trichloromethyl group and tribromomethyl group, etc. It is below.
The cyclic aliphatic hydrocarbon group which may have a halogen atom (preferably a fluorine atom) may be monocyclic or polycyclic. Examples of the monocyclic aliphatic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a perfluorocyclohexyl group, and a perchlorocyclohexyl group. Examples of the polycyclic aliphatic hydrocarbon group include an adamantyl group, a norbornyl group, a perfluoroadamantyl group, and the like.
Examples of the aliphatic hydrocarbon group in which a chain aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group are combined include a cyclopropylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a perfluoroadamantyl group. A methyl group etc. are mentioned.

In formula (I), A ¹ is preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an ethylene group.
The aliphatic hydrocarbon group for A ¹³ preferably has 1 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms.
The aliphatic hydrocarbon group for A ¹⁴ preferably has 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. Among them, A ¹⁴ is preferably an aliphatic hydrocarbon group having 3 to 12 carbon atoms including an alicyclic hydrocarbon group, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. It is a group.

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、Ａ¹³、Ｘ¹²及びＡ¹⁴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 , A ¹³ , X ¹² and A ¹⁴ represent the same meaning as described above. ]

式（Ｉｓ−１）で表される化合物は、市販品であってもよいし、公知の方法で製造したものでもよい。ここで、公知の方法とは、例えば、（メタ）アクリル酸又はその誘導体（例えば、（メタ）アクリル酸クロリドなど）と、適当なジオール（ＨＯ−Ａ^１−ＯＨ）とを縮合する方法が挙げられる。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（Ｉｓ−２）で表されるカルボン酸は、公知の方法により製造することができる。式（Ｉｓ−２）で表されるカルボン酸としては、例えば、以下の化合物が挙げられる。

The compound represented by the formula (I ′) can be produced, for example, by reacting the compound represented by the formula (Is-1) with the carboxylic acid represented by the formula (Is-2). .
This reaction is usually performed in the presence of a solvent. As the solvent, tetrahydrofuran, toluene and the like are used. In the reaction, a known esterification catalyst (for example, an acid catalyst, a carbodiimide catalyst, etc.) may coexist.

The compound represented by the formula (Is-1) may be a commercially available product or a product produced by a known method. Here, the known method includes, for example, a method of condensing (meth) acrylic acid or a derivative thereof (for example, (meth) acrylic acid chloride) with an appropriate diol (HO-A ¹ -OH). It is done. Examples of commercially available products include hydroxyethyl methacrylate.
The carboxylic acid represented by the formula (Is-2) can be produced by a known method. Examples of the carboxylic acid represented by the formula (Is-2) include the following compounds.

The resin (A1) may have a structural unit different from the structural unit (I).
The structural unit different from the structural unit (I) includes a structural unit derived from an acid labile monomer (a1) described later, a structural unit derived from an acid stable monomer described later, and a structure represented by the formula (III-1). A unit (hereinafter sometimes referred to as a structural unit (III-1)), a structural unit represented by the formula (III-2) (hereinafter sometimes referred to as a structural unit (III-2)), and used in the art Examples include a structural unit derived from a known monomer, a structural unit represented by the formula (II) described later, and the like. The structural unit (III-1) or the structural unit (III-2) is preferable.

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

［式（ＩＩＩ−２）中、
Ｒ³³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。
Ａ²³は、−Ｏ−、^＊−ＣＯ−Ｏ−又は^＊−Ｏ−ＣＯ−（^＊は環Ｗ^２との結合手を表す）を表す。
Ｒ³⁴は、フッ素原子を有する炭素数１〜６のアルキル基を表す。］

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

[In the formula (III-2),
R ³³ represents a hydrogen atom or a methyl group.
Ring ^{W 2} represents a hydrocarbon ring having 6 to 10 carbon atoms.
A ²³ represents —O—, ^* —CO—O—, or ^* —O—CO— ( ^* represents a bond to ring W ² ).
R ³⁴ represents a C 1-6 alkyl group having a fluorine atom. ]

As the alkanediyl group for A ¹¹ , a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group , A straight-chain alkanediyl group such as hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 -Branched alkanediyl groups such as a diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group.

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

フッ素原子を有する脂環式炭化水素基としては、ペルフルオロシクロヘキシル基、ペルフルオロアダマンチル基等のフッ化シクロアルキル基が挙げられる。 The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a saturated aliphatic hydrocarbon ring. Examples of the saturated aliphatic hydrocarbon ring include the following rings.

Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

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

Examples of the structural unit (III-1) include the following.

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 (III-1).

上記の構造単位において、Ｒ³³に相当するメチル基が水素原子に置き換わった構造単位も、構造単位（ＩＩＩ−２）の具体例として挙げることができる。 Examples of the structural unit (III-2) include the following.

In the above structural unit, a structural unit in which a methyl group corresponding to R ³³ is replaced by a hydrogen atom can also be given as a specific example of the structural unit (III-2).

The content of the structural unit (I) in the resin (A1) is preferably in the range of 5 to 100 mol% and more preferably in the range of 10 to 100 mol% with respect to all the structural units of the resin (A1).
When resin (A1) contains structural unit (III-1) and / or structural unit (III-2), these total content is 1-95 mol with respect to all the structural units of resin (A1). % Range is preferable, 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.
In addition, as for structural unit (III-1): structural unit (III-2), 0: 100-100: 0 (mass ratio) is mentioned, for example, 3: 97-97: 3 is preferable, and 50: 50- 95: 5 is more preferable.
Resin (A1) having such a content of structural unit (I) and, if necessary, structural unit (III-1) and / or structural unit (III-2) is the total monomer used in the production of resin (A1). The compound (I ′), the monomer for deriving the structural unit (III-1), and the molar amount of the monomer for deriving the structural unit (III-2) relative to the total molar amount of can be prepared.

Each structural unit constituting the resin (A1) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do.
The weight average molecular weight of the resin (A1) is preferably 5,000 or more (more preferably 7,000 or more, 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 an analysis are explained in full detail in the Example of this application.

<Resin (A2)>
The resin (A2) is insoluble or hardly soluble in the alkaline aqueous solution and can be dissolved in the alkaline aqueous solution by the action of an acid. Here, “can be dissolved in an alkaline aqueous solution by the action of an acid” means having an acid labile group and insoluble or hardly soluble in an alkaline aqueous solution before contact with the acid, but after contact with the acid. It means that it becomes soluble in an alkaline aqueous solution.
Therefore, the resin (A2) can be obtained by polymerizing one or more monomers having an acid labile group (hereinafter sometimes referred to as “acid labile monomer (a1)”).
Further, the resin (A2) is a monomer having the above-described properties and having no acid-labile group (hereinafter referred to as “acid-stable monomer”) unless it contains the structural unit represented by the formula (I). The derived structural unit, a monomer known in the art, the structural unit (III-1), and the structural unit (III-2) may be included.

<Acid labile monomer (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、該炭化水素基及び該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-.

Examples of the alkyl group represented by R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. In this case, the carbon number of the alicyclic hydrocarbon group is 20 or less including the carbon number of the alkyl group.
Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic saturated hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the following groups (* represents a bond).

式（１）においては、Ｒ^a1〜Ｒ^a3の脂環式炭化水素基は、好ましくは炭素数３〜１６であり、より好ましくは炭素数４〜１６である。
式（１）で表される酸に不安定な基としては、例えば、１，１−ジアルキルアルコキシカルボニル基（式（１）中、Ｒ^a1〜Ｒ^a3がアルキル基である基、好ましくはｔｅｒｔ−ブトキシカルボニル基）、２−アルキルアダマンタン−２−イルオキシカルボニル基（式（１）中、Ｒ^a1、Ｒ^a2及び炭素原子がアダマンチル基を形成し、Ｒ^a3がアルキル基である基）及び１−（アダマンタン−１−イル）−１−アルキルアルコキシカルボニル基（式（１）中、Ｒ^a1及びＲ^a2がアルキル基であり、Ｒ^a3がアダマンチル基である基）等が挙げられる。 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. * Represents a bond with -O-.

In Formula (1), the alicyclic hydrocarbon group of R ^{a1 to} R ^a3 preferably has 3 to 16 carbon atoms, and more preferably 4 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 for R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the divalent hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include a divalent aliphatic hydrocarbon group.
In formula (2), it is preferable that at least one of R ^{a1 ′} and R ^{a2 ′} is a hydrogen atom.
Specific examples of the group represented by the formula (2) include the following groups. * Represents a bond.

  The monomer (a1) having an acid labile group is preferably a monomer having an acid labile group and a carbon-carbon double bond, more preferably a (meth) acryl having an acid labile group. 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 the 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 (meth) acrylic monomer having an acid labile group and an alicyclic hydrocarbon group, a monomer represented by the formula (a1-1) (hereinafter sometimes referred to as a monomer (a1-1)) .) Or a monomer represented by formula (a1-2) (hereinafter may be referred to as monomer (a1-2)). These may be used alone or in combination of two or more.

［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。
ｎ２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.
n2 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. The alicyclic hydrocarbon group for R ^a6 and R ^a7 preferably has 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
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.
n2 is preferably 0 or 1.

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

Examples of the monomer (a1-2) include 1-ethyl-1-cyclopentan-1-yl (meth) acrylate, 1-ethyl-cyclohexane-1-yl (meth) acrylate, and 1-ethyl-1-cycloheptane. Examples include -1-yl (meth) acrylate, 1-methyl-1-cyclopentan-1-yl (meth) acrylate, and 1-isopropyl-1-cyclopentan-1-yl (meth) acrylate. A monomer represented by any one of formula (a1-2-1) to formula (a1-2-12) is preferred, and formula (a1-2-3) to formula (a1-2-4) or formula (a1- The monomer represented by any one of 2-9) to formula (a1-2-10) is more preferred, and the monomer represented by formula (a1-2-3) or formula (a1-2-9) is more preferred. .

  When the resin (A2) contains structural units derived from the monomer (a1-1) and / or the monomer (a1-2), the total content thereof is usually 10 with respect to all the structural units of the resin (A2). It is -95 mol%, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

式（ａ１−５）中、
Ｒ^３５は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^１は、単結合又は＊−［ＣＨ₂］_k４−ＣＯ−Ｌ^４−基を表す。ここで、ｋ４は１〜４の整数を表す。＊は、Ｌ^１との結合手を表す。
Ｌ^１、Ｌ^２、Ｌ^３及びＬ^４は、それぞれ独立に、−Ｏ−又は−Ｓ−を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。 Examples of the other acid labile monomer (a1) include a monomer represented by the formula (a1-5) which is a (meth) acrylic monomer having an acid labile group (2) (hereinafter referred to as “monomer (a1-5)”. ) ”May be used.

In formula (a1-5),
R ³⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ¹ represents a single bond or a * — [CH ₂ ] _k ⁴ —CO—L ⁴ — group. Here, k4 represents an integer of 1 to 4. * Represents a bond to ^{L 1.}
L ¹ , L ² , L ³ and L ⁴ each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3.

In the formula (a1-5), R ³⁵ 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 is preferably from 1 to 50 mol%, more preferably from 3 to 45 mol, based on all structural units of the resin (A2). % Is more preferable, and 5 to 40 mol% is more preferable.

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

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

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

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

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

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

  When the resin (A2) includes a structural unit derived from the monomer represented by the formula (a2-1), the content thereof is usually 1 to 45 mol% with respect to all the structural units of the resin (A2). , Preferably it is 1-40 mol%, More preferably, it is 1-35 mol%, More preferably, it is 2-30 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。
Ｒ^a22及びＲ^a23は、それぞれ独立に、カルボキシ基、シアノ基又は炭素数１〜４のアル
キル基を表す。
ｑ１及びｒ１は、それぞれ独立に０〜３の整数を表す。ｐ１、ｑ１又はｒ１が２以上の
とき、それぞれ、複数のＲ^a21、Ｒ^a22又は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.
R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group, or an alkyl group having 1 to 4 carbon atoms.
q1 and r1 each independently represents an integer of 0 to 3. When p1, q1 or r1 is 2 or more, a plurality of R ^a21 , R ^a22 or R ^a23 are the same or different, respectively.

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. Formula (a3-1-1) to Formula (a3-1-4), Formula (a3-2-1) to Formula (a3-2-4), and Formula (a3-3-1) to Formula (a3-3) -4) is preferred, and the monomers represented by formula (a3-1-1) to formula (a3-1-2) and formula (a3-2-3) to formula (a3-2-4) are preferred. The monomer represented by either is more preferable, and the monomer represented by the formula (a3-1-1) or the formula (a3-2-3) is more preferable.

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

When the resin (A2) is a copolymer of a monomer (a1) having an acid labile group and an acid stable monomer, the structural unit derived from the monomer (a1) having an acid labile group is: Preferably it is 10-80 mol% with respect to 100 mol% of all structural units, More preferably, it is 20-60 mol%.
Resin (A2) is a structural unit derived from a monomer having an adamantyl group (especially monomer (a1-1) having an acid labile group) with respect to monomer (a1) having an acid labile group. It is preferable to contain 15 mol% or more. When the ratio of the monomer having an adamantyl group is increased, the dry etching resistance of the resist is improved.

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

Each structural unit constituting the resin (A2) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. can do.
The weight average molecular weight of the resin (A2) is preferably 2,500 or more (more preferably 3,000 or more) and 30,000 or less (more preferably 10,000 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. 2:10, more 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 above-described resins (A1) and (A2), for example, a structural unit derived from the acid-labile monomer (a1) described above, a structural unit derived from an acid-stable monomer, A resin having at least one selected from structural units derived from known monomers used in the field may be contained.

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

<Acid generator>
The acid generator has a structure that is cleaved by the action of an alkali developer.
The structure that is desorbed by the action of an alkali developer refers to a structure that is cleaved by the action of an alkali developer in the development process for producing a resist pattern. In other words, it refers to a base dissociable group that decomposes by the action of an alkali and converts it to an alkali-soluble group.
When such an acid generator is brought into contact with an alkaline developer in the development step, this structure is cleaved to form a hydrophilic group (for example, a hydroxy group or a carboxy group).
As used herein, the term “cleavage” means that the bond is broken and divided into a plurality of molecules, and does not include a ring-opening reaction.

［式（Ｂａ）中、Ｒ²³は、フッ素原子を有する炭素数１〜６のアルキル基を表す。］

［式（Ｂｂ）中、Ｒ²⁴は、フッ素原子を有する炭素数１〜６のアルキル基を表す。
Ｒ²⁵及びＲ²⁶は、それぞれ独立に、水素原子又はフッ素原子を表す。］ The structure that is cleaved by the action of the alkali developer is preferably a group represented by the following formula (Ba) or a group represented by the formula (Bb).

[In Formula (Ba), R ²³ represents a C 1-6 alkyl group having a fluorine atom. ]

[In the formula (Bb), R ²⁴ represents a C 1-6 alkyl group having a fluorine atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a fluorine atom. ]

Examples of the alkyl group having a fluorine atom for R ²³ and R ²⁴ include a 1,1,1-trifluoroethyl group, a perfluoroethyl group, a 1,1,1,2,2-pentafluoropropyl group, a perfluoropropyl group, 1,1,1,2,2,3,3-peptafluorobutyl group, perfluorobutyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, perfluoropentyl group A perfluorohexyl group is preferred.

このような構造（塩基解離性基）を有する酸発生剤は、以下の方法で、開裂したことを確認できる。
例えば、塩基解離性基を有する酸発生剤を溶剤に溶解し、アルカリ溶液を添加し、加熱する。これによって、塩基解離性基を、アルカリ可溶性基（ヒドロキシ基又はカルボキシル基）に変換させることができる。アルカリ可溶性基の確認方法としては、生成した化合物の酸性度測定、ＮＭＲ測定及びＭＳ測定などが挙げられる。
溶剤としては、ジメチルホルムアミドが好ましい。
アルカリとしては、テトラメチルアンモニウムヒドロキシドが好ましい。 For example, the group represented by the formula (Ba) is cleaved by the action of an alkali to generate a hydroxy group. Further, the group represented by the formula (Bb) is cleaved by the action of an alkali to generate a carboxyl group.

It can be confirmed that the acid generator having such a structure (base dissociable group) is cleaved by the following method.
For example, an acid generator having a base dissociable group is dissolved in a solvent, an alkaline solution is added, and the mixture is heated. Thereby, the base dissociable group can be converted into an alkali-soluble group (hydroxy group or carboxyl group). Examples of the method for confirming the alkali-soluble group include acidity measurement, NMR measurement and MS measurement of the produced compound.
As the solvent, dimethylformamide is preferable.
As the alkali, tetramethylammonium hydroxide is preferable.

［式（ＩＩ−ａ）又は式（ＩＩ−ｂ）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。
Ｌ²¹は、単結合又は２価の炭素数１〜１７のアルカンジイル基を表し、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｙは、炭素数３〜１８の２価の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。
Ｒ²³〜Ｒ²⁶は、上記と同じ意味を表す。］
式（ＩＩ−ａ）及び式（ＩＩ−ｂ）において、正電荷を有するＺ^＋で示される有機カチオンを除去してなる負電荷を有するものを「スルホン酸アニオン」ということがある。 The acid generator includes an acid generator represented by the following formula (II-a) or formula (II-b), each containing a group represented by the formula (Ba) or a group represented by the formula (Bb). It is preferable that

[In formula (II-a) or formula (II-b),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ²¹ represents a single bond or a divalent alkanediyl group having 1 to 17 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—.
Y represents a C 3-18 divalent alicyclic hydrocarbon group, and —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced by —O— or —CO—. .
R ^{23 to} R ²⁶ represent the same meaning as described above. ]
In the formulas (II-a) and (II-b), those having a negative charge obtained by removing the organic cation represented by Z ⁺ having a positive charge may be referred to as “sulfonate anion”.

Examples of the perfluoroalkyl group of Q ¹ and Q ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. And perfluorohexyl group.
Q ¹ and Q ² are preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

As the alkanediyl group of L ²¹ , a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group , A straight-chain alkanediyl group such as hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 -Branched alkanediyl groups such as a diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group.

Examples of the group in which —CH ₂ — contained in the alkanediyl group of L ²¹ is replaced by —O— or —CO— are represented by any of the following formulas (b1-1) to (b1-7): Group. The formulas (b1-1) to (b1-7) are described in accordance with the formula (I) on the left and right, and among the two bonds indicated by *, the left bond is C (Q ¹ ) It is bonded to the carbon atom of (Q ² ). The same applies to specific examples of the following formulas (b1-1) to (b1-7).

式（ｂ１−１）〜式（ｂ１−７）中、
Ｌ^b2は、単結合又は炭素数１〜１５のアルカンジイル基を表す。
Ｌ^b3は、単結合又は炭素数１〜１２のアルカンジイル基を表す。
Ｌ^b4は、炭素数１〜１３のアルカンジイル基を表す。但しＬ^b3及びＬ^b4の合計炭素数の上限は１３である。
Ｌ^b5は、炭素数１〜１５のアルカンジイル基を表す。
Ｌ^b6は、単結合又は炭素数１〜１５のアルカンジイル基を表す。
Ｌ^b7は、炭素数１〜１５のアルカンジイル基を表す。但しＬ^b6及びＬ^b7の合計炭素数の上限は１６である。
Ｌ^b8は、炭素数１〜１４のアルカンジイル基を表す。
Ｌ^b9及びＬ^b10は、それぞれ独立に、炭素数１〜１１のアルカンジイル基を表す。但しＬ^b9及びＬ^b10の合計炭素数の上限は１２である。
Ｌ^b11は、単結合又は炭素数１〜１３のアルカンジイル基を表す。
Ｌ^b12は、炭素数１〜１４のアルカンジイル基を表す。但しＬ^b11及びＬ^b12の合計炭素数の上限は１４である。

In formula (b1-1) to formula (b1-7),
L ^b2 represents a single bond or an alkanediyl group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or an alkanediyl group having 1 to 12 carbon atoms.
L ^b4 represents an alkanediyl group having 1 to 13 carbon atoms. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents an alkanediyl group having 1 to 15 carbon atoms.
L ^b6 represents a single bond or an alkanediyl group having 1 to 15 carbon atoms.
L ^b7 represents an alkanediyl group having 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^b6 and L ^b7 is 16.
L ^b8 represents an alkanediyl group having 1 to 14 carbon atoms.
L ^b9 and L ^b10 each independently represent an alkanediyl group having 1 to 11 carbon atoms. However, the upper limit of the total carbon number of L ^b9 and L ^b10 is 12.
L ^b11 represents a single bond or an alkanediyl group having 1 to 13 carbon atoms.
L ^b12 represents an alkanediyl group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b11 and L ^b12 is 14.

Among them, L ²¹ is preferably a group represented by any one of formulas (b1-1) to (b1-4), more preferably represented by formula (b1-1) or formula (b1-3). More preferably a divalent group represented by formula (b1-1). In particular, a divalent group represented by the formula (b1-1) in which L ^b2 is a single bond or an alkanediyl group having 1 to 6 carbon atoms, that is, * —CO—O— (CH ₂ ) _u — (u is 0 Represents an integer of ˜6, and * is preferably a bond with —C (Q ¹ ) (Q ² ) —, and is represented by the formula (b1-1) which is a single bond or a methylene group. Are more preferable, that is, * —CO—O— and * —CO—O—CH ₂ —.

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

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

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

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

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

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

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

The divalent alicyclic hydrocarbon group for Y is preferably a group represented by the following.

Ｙとしては、多環の脂環式炭化水素基が好ましく、アダマンタン環を含む多環の脂環式炭化水素基がより好ましい。 Examples of the group in which —CH ₂ — contained in the divalent alicyclic hydrocarbon group is replaced by —O— or —CO— include groups represented by the following.

Y is preferably a polycyclic alicyclic hydrocarbon group, more preferably a polycyclic alicyclic hydrocarbon group containing an adamantane ring.

Examples of the salt represented by the formula (II-a) include the following salts.

Examples of the salt represented by the formula (II-b) include the following salts.

Examples of the organic cation represented by Z ⁺ include organic onium cations such as an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable.

More preferably, for example, Formula (Z1) to Formula (Z4) are included.

In formula (Z1) to formula (Z4),
Do P ^{a to} P ^c each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms? , P ^a and P ^b together form a ring containing a sulfur atom. The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.

P ⁴ and P ⁵ each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
P ⁶ and P ⁷ each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or P ⁶ and P ⁷ are bonded to each other. Bonded together with a sulfur atom to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring). —CH ₂ — contained in the ring may be replaced by —O—, —S—, or —CO—.
P ⁸ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
P ⁹ represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group has 1 to 12 carbon atoms. May be substituted with an alkoxy group or an alkylcarbonyloxy group.
P ⁸ and P ⁹ may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with —CH—CO— to which they are bonded. —CH ₂ — contained in the ring may be replaced by —O—, —S—, or —CO—.

P ¹⁰ to P ¹⁵ each independently represent a hydroxy group, an aliphatic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms.
E represents -S- or -O-.
i, j, p, r, x and y each independently represents an integer of 0 to 5;
q represents 0 or 1;
v and w each independently represent an integer of 0 to 4.
When i is 2 or more, the plurality of P ⁴ are the same or different from each other, when j is 2 or more, the plurality of P ⁵ are the same or different from each other, and when p is 2 or more, the plurality of P ¹⁰ Are the same or different from each other, and when r is 2 or more, the plurality of P ¹¹ are the same or different from each other, and when x is 2 or more, the plurality of P ¹⁴ are the same or different from each other and y is 2 or more. When a plurality of P ¹⁵ are the same or different from each other, v is 2 or more, a plurality of P ¹² are the same or different from each other, and when w is 2 or more, a plurality of P ¹³ are the same or different from each other. Different.

特に、Ｐ^６〜Ｐ^８の脂環式炭化水素基は、好ましくは炭素数３〜３６であり、より好ましくは炭素数３〜１８、さらに好ましくは炭素数４〜１２である。 Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Is mentioned. In particular, the P ^{6 to} P ⁸ aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms.
Examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an alicyclic hydrocarbon group include a 1- (adamantan-1-yl) alkane-1-yl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. And cycloalkyl groups such as cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic saturated hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.

In particular, the P ^{6 to} P ⁸ alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 4 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a 2-alkyladamantan-2-yl group, and An isobornyl group etc. are mentioned.
As an aromatic hydrocarbon group, phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-methoxyphenyl group And aryl groups such as p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
When the aromatic hydrocarbon group includes an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 36 carbon atoms and an alicyclic hydrocarbon group having 3 to 36 carbon atoms are preferable.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group, that is, an aralkyl group, include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

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

Examples of the ring and the P ^a and P ^b together form a monocyclic, polycyclic, aromatic or non-aromatic, it may be any of the rings of the saturated and unsaturated, sulfur atom 1 or more, it may further contain one or more sulfur atoms and / or one or more oxygen atoms. This ring preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

Examples of the ring formed together with the sulfur atom to which P ⁶ and P ⁷ are bonded include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring. Etc.
Examples of the ring formed with —CH—CO— to which P ⁸ and P ⁹ are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

Among the cations represented by the formulas (Z1) to (Z4), the formula (Z1) is preferable, the cation represented by the formula (Z5) is more preferable, and the triphenylsulfonium cation (in the formula (Z5), z is 0), in diphenyl tolyl sulfonium cation (formula (Z5), a z1 = z2 = 0, z3 = 1, P 3 is a methyl group.) or in tritolylsulfonium cation (formula (Z5), z1 = Z2 = z3 = 1, and P ¹ , P ² and P ³ are all methyl groups).

式（Ｚ５）中、
Ｐ^１〜Ｐ^３は、それぞれ独立に、ハロゲン原子、ヒドロキシ基、炭素数１〜３６の脂肪族炭化水素基、炭素数３〜３６の脂環式炭化水素基又は炭素数１〜１２のアルコキシ基を表すか、Ｐ^１〜Ｐ^３から選ばれる２つが一緒になってイオウ原子を含む環を形成している。
ｚ１、ｚ２及びｚ３は、それぞれ独立に、０〜５の整数を表す。ｚ１が２以上であるとき、複数のＰ^１は互いに同一又は相異なり、ｚ２が２以上であるとき、複数のＰ^２は互いに同一又は相異なり、ｚ３が２以上であるとき、複数のＰ^３は互いに同一又は相異なる。

In formula (Z5),
P ^{1 to} P ³ are each independently a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Or two selected from P ^{1 to} P ³ together form a ring containing a sulfur atom.
z1, z2 and z3 each independently represents an integer of 0 to 5. When z1 is 2 or more, a plurality of P ¹ are the same or different from each other, when z2 is 2 or more, the plurality of P ² same or different from each other, when z3 is 2 or more, a plurality of P ³ Are the same or different from each other.

The ring formed by combining two selected from P ^{1 to} P ³ may be any of monocyclic, polycyclic, aromatic and non-aromatic rings. As long as it contains the above, it may contain one or more sulfur atoms and / or one or more oxygen atoms.
The P ^{1 to} P ³ aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, and the alicyclic hydrocarbon group preferably has 4 to 36 carbon atoms.
Among them, each of P ^{1 to} P ³ independently represents 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, or P ¹ two selected from to P ³ it is preferable to form a ring containing an oxygen atom and a sulfur atom together. z1, z2, and z3 are each independently preferably 0 or 1.

Examples of the cation represented by the formula (Z5) include the following.

Examples of the cation represented by the formula (Z1) include the following cations.

式（Ｚ３）で表されるカチオンとしては、以下のカチオンが挙げられる。

Examples of the cation represented by the formula (Z2) include the following cations.

Examples of the cation represented by the formula (Z3) include the following cations.

  Moreover, the cation described in Unexamined-Japanese-Patent No. 2010-204646 may be sufficient as a cation.

  The acid generator is a combination of a sulfonate anion and an organic cation. These sulfonate anions and organic cations can be arbitrarily combined. The combinations of sulfonate anions and organic cations are shown in Table 1 below. In Table 1 below, the sulfonate anion represented by the formula (b1-s-1) is represented as “(b1-s-1)” according to the formula number, and the formula (b2-s-1) The organic cation represented by c-1) is represented as “(b2-c-1)” or the like according to the formula number.

More preferable acid generators include the following salts.

The acid generator can be produced by the following production method or a method analogous thereto.
For example, a salt represented by the formula (II-a) is obtained by reacting a compound represented by the formula (II-aa) and a compound represented by the formula (II-ab) under a basic catalyst. It can manufacture by making it react. Examples of the solvent include chloroform. Examples of the base catalyst include N-methylpyrrolidine.

Examples of the compound represented by the formula (II-aa) include compounds described in JP-A-2006-257078.
Examples of the compound represented by the formula (II-ab) include heptafluorobutyryl chloride.

  The acid generator represented by the formula (II-a) or the acid generator represented by the formula (II-b) may be used singly or in combination, or both may be used simultaneously.

<An acid generator other than an acid generator having a structure that is cleaved by the action of an alkali developer>
The resist composition may further contain, as an acid generator, a known acid generator other than an acid generator having a structure that is cleaved by the action of an alkali developer (hereinafter referred to as “other acid generator”). Good. Other acid generators may be ionic acid generators or nonionic generators, but ionic acid generators are preferred. An ionic acid generator is different from an acid generator having a structure in which both cations and anions constituting the ionic acid generator are cleaved by the action of an alkali developer, and an acid generator having a structure that is cleaved by the action of an alkali developer. Comprising a combination of the same cation as the organic cation constituting the cation and a known anion other than the sulfonate anion constituting the acid generator having a structure that is cleaved by the action of the alkali developer, cleaved by the action of the alkali developer Any one of a combination of the same anion as the sulfonate anion constituting the acid generator having a structure and a known cation other than the organic cation constituting the acid generator having a structure that is cleaved by the action of an alkali developer. May be.

Examples of other acid generators include those represented by formula (B1-1) to formula (B1-20). Among these, those containing a triphenylsulfonium cation, a tolylsulfonium cation or a tolylsulfonium cation are preferable, and are represented by the formula (B1-1), formula (B1-2), formula (B1-3), formula (B1-6), formula The salts represented by (B1-7), formula (B1-11), formula (B1-12), formula (B1-13) and formula (B1-14) are more preferred.

The content of the acid generator is preferably 1% by mass or more (more preferably 3% by mass or more), preferably 40% by mass or less (more preferably 35% by mass or less) with respect to the resin (A2).
Moreover, when it contains another acid generator, the total content of the acid generator having a structure that is cleaved by the action of an alkali developer and the other acid generator is preferably 1 with respect to the resin (A2). It is at least mass% (more preferably at least 3 mass%), preferably at most 40 mass% (more preferably at most 35 mass%).
When the resist composition contains an acid generator having a structure that is cleaved by the action of an alkali developer and other acid generators, the ratio (mass) of the content of the acid generator and the other acid generator is, for example, 5: 95-95: 5, preferably 10: 90-90: 10, more preferably 15: 85-85: 15.

<Solvent (E)>
When the solvent (E) is contained in the resist composition of the present invention, the content thereof is, for example, 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more in the resist composition, for example 99 0.9 mass% or less, preferably 99 mass% or less. The content of the solvent (E) can be measured by a known analysis means such as liquid chromatography or gas chromatography.

  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 individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

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

［式（Ｃ５）及び式（Ｃ６）中、Ｒ^c10、Ｒ^c11、Ｒ^c12、Ｒ^c13及びＲ^c16は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c14、Ｒ^c15及びＲ^c17は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｏ３及びｐ３は、それぞれ独立に０〜３の整数を表し、ｏ３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が２以上であるとき、複数のＲ^c18は同一又は相異なり、ｒ３が２以上であるとき、複数のＲ^c1９は同一又は相異なり、及びｓ３が２以上であるとき、複数のＲ^c20は同一又は相異なる。
Ｌ^c2は、単結合又は炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

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

In formula (C1) to formula (C8) and formula (C1-1), the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, alkanediyl group are the same as those described above. Is mentioned.
Examples of the alkanoyl group include acetyl group, 2-methylacetyl group, 2,2-dimethylacetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and 2,2-dimethylpropionyl group.

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

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

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

  When the resist composition of the present invention contains a basic compound (C), the content thereof is preferably about 0.01 to 5% by mass, more preferably 0, based on the solid content of the resist composition. About 0.01 to 3% by mass, particularly preferably about 0.01 to 1% by mass.

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

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A) containing a resin (A1) and a resin (A2), an acid generator, and optionally a solvent (E), a basic compound (C), and other components (F). Can be prepared by mixing. 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.

  Thus, after mixing each of resin (A), an acid generator, the solvent (E) used as needed, a basic compound (C), and a component (F) with preferable content, it is 0. A resist composition can be prepared by filtration using a filter of about 003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) A step of applying the resist composition of the present invention 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.

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

Drying is performed using, for example, a heating device such as a hot plate (so-called pre-baking) or using a decompression device. As a result, the solvent is removed by evaporation from the resist composition, and a composition layer is formed. As for the temperature in this case, about 50-200 degreeC is illustrated, for example. The pressure is exemplified by 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 laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser, etc.) Various types of laser beam can be used, such as those that convert the wavelength of the laser beam from) to radiate a harmonic laser beam in the far ultraviolet region or the vacuum ultraviolet region. The exposure machine may irradiate an electron beam or extreme ultraviolet light (EUV).

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 suitable as 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 machines. It is.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The structure of the compound was confirmed by MASS (LC: Agilent 1100 type, MASS: Agilent LC / MSD type or LC / MSD TOF type).
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

式（Ａ−２）で表される化合物９．６０部、テトラヒドロフラン３８．４０部及びピリジン５．９９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（Ａ−１）で表される化合物１４．００部を、１時間かけて添加し、さらに、１０℃程度まで温度を上げ、同温度で１時間攪拌した。得られた式（Ａ−３）で表される化合物を含む反応混合物に、式（Ａ−４）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）１４．５１部及び式（Ａ−５）で表される化合物８．２０部を添加し、２３℃で３時間攪拌した。得られた反応溶液に、酢酸エチル２７１．９５部及び５％塩酸水溶液１６．５７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、飽和炭酸水素ナトリウム水溶液６３．６４部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水６７．９９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て、得られた濃縮物に、酢酸エチル１０７．７１部を添加し完全に溶解するまで攪拌し、ｎ−ヘプタン６４６．２６部を滴下した。滴下終了後、２３℃で３０分間攪拌し、ろ過することにより、式（Ａ）で表される化合物１５．１１部を得た。
ＭＳ（質量分析）：４８６．２（分子イオンピーク） Synthesis Example 1: [Synthesis of Compound Represented by Formula (A)]

9.60 parts of the compound represented by the formula (A-2), 38.40 parts of tetrahydrofuran and 5.99 parts of pyridine were stirred and mixed at 23 ° C. for 30 minutes and cooled to 0 ° C. While maintaining the same temperature, 14.00 parts of the compound represented by the formula (A-1) is added to the obtained mixture over 1 hour, and the temperature is further increased to about 10 ° C. Stir for 1 hour. The reaction mixture containing the compound represented by the formula (A-3) thus obtained was added to the compound (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) 14 represented by the formula (A-4). .51 parts and 8.20 parts of the compound represented by formula (A-5) were added, and the mixture was stirred at 23 ° C. for 3 hours. To the obtained reaction solution, 271.95 parts of ethyl acetate and 16.57 parts of 5% aqueous hydrochloric acid were added, and the mixture was stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and separating, 63.64 parts of a saturated aqueous sodium hydrogen carbonate solution was added, 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 organic layer after washing was charged with 67.9 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 the resulting concentrate, 107.71 parts of ethyl acetate was added and stirred until completely dissolved, and 646.26 parts of n-heptane was added dropwise. After completion of dropping, the mixture was stirred at 23 ° C. for 30 minutes and filtered to obtain 15.11 parts of the compound represented by the formula (A).
MS (mass spectrometry): 486.2 (molecular ion peak)

式（Ｂ−２）で表される化合物６．３２部、テトラヒドロフラン３０．００部及びピリジン５．９９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（Ｂ−１）で表される化合物１４．００部を、１時間かけて添加し、さらに、１０℃程度まで温度を上げ、同温度で１時間攪拌した。得られた式（Ｂ−３）で表される化合物を含む反応混合物に、式（Ｂ−４）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）１４．５１部及び式（Ｂ−５）で表される化合物８．２０部を添加し、２３℃で３時間攪拌した。得られた反応溶液に、酢酸エチル２７０部及び５％塩酸水溶液１６．５７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、飽和炭酸水素ナトリウム水溶液６５部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水６５部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。水洗後の有機層を濃縮した。得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル）することにより、式（Ｂ）で表される化合物９．９０部を得た。
ＭＳ（質量分析）：４３４．１（分子イオンピーク） Synthesis Example 2: [Synthesis of Compound Represented by Formula (B)]

6.32 parts of the compound represented by the formula (B-2), 30.00 parts of tetrahydrofuran and 5.99 parts of pyridine were stirred and mixed at 23 ° C. for 30 minutes and cooled to 0 ° C. While maintaining the same temperature, 14.00 parts of the compound represented by the formula (B-1) was added to the obtained mixture over 1 hour, and the temperature was further increased to about 10 ° C. Stir for 1 hour. The reaction mixture containing the compound represented by the formula (B-3) thus obtained was added to the compound (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) 14 represented by the formula (B-4). .51 parts and 8.20 parts of the compound represented by formula (B-5) were added, and the mixture was stirred at 23 ° C. for 3 hours. To the obtained reaction solution, 270 parts of ethyl acetate and 16.57 parts of 5% aqueous hydrochloric acid were added, and the mixture was stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and separating, 65 parts of a saturated aqueous sodium hydrogen carbonate solution was added, 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 organic layer after washing was charged with 65 parts of ion exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated. The obtained concentrate is subjected to column fractionation (column fractionation conditions stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd., developing solvent: n-heptane / ethyl acetate), whereby compound 9 represented by formula (B) 90 parts were obtained.
MS (mass spectrometry): 434.1 (molecular ion peak)

式（Ｃ−２）で表される化合物７．０８部、テトラヒドロフラン３０．００部及びピリジン５．９９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（Ｃ−１）で表される化合物１４．００部を、１時間かけて添加し、さらに、１０℃程度まで温度を上げ、同温度で１時間攪拌した。得られた式（Ｃ−３）で表される化合物を含む反応混合物に、式（Ｃ−４）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）１４．５１部及び式（Ｃ−５）で表される化合物８．２０部を添加し、２３℃で３時間攪拌した。得られた反応溶液に、酢酸エチル２７０部及び５％塩酸水溶液１６．５７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、飽和炭酸水素ナトリウム水溶液６５部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水６５部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。このような水洗操作を５回繰り返した。水洗後の有機層を濃縮した。得られた濃縮物を、カラム分取（カラム分取条件 固定相：メルク社製シリカゲル６０−２００メッシュ 展開溶媒：ｎ−ヘプタン／酢酸エチル）することにより、式（Ｃ）で表される化合物１０．２４部を得た。
ＭＳ（質量分析）：４４６．１（分子イオンピーク） Synthesis Example 3: [Synthesis of Compound Represented by Formula (C)]

7.08 parts of the compound represented by the formula (C-2), 30.00 parts of tetrahydrofuran and 5.99 parts of pyridine were stirred and mixed at 23 ° C. for 30 minutes and cooled to 0 ° C. While maintaining the same temperature, 14.00 parts of the compound represented by the formula (C-1) was added to the obtained mixture over 1 hour, and the temperature was further increased to about 10 ° C. Stir for 1 hour. To the reaction mixture containing the compound represented by the formula (C-3) thus obtained, the compound represented by the formula (C-4) (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) 14 .51 parts and 8.20 parts of the compound represented by formula (C-5) were added, and the mixture was stirred at 23 ° C. for 3 hours. To the obtained reaction solution, 270 parts of ethyl acetate and 16.57 parts of 5% aqueous hydrochloric acid were added, and the mixture was stirred at 23 ° C. for 30 minutes. To the organic layer recovered by standing and separating, 65 parts of a saturated aqueous sodium hydrogen carbonate solution was added, 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 organic layer after washing was charged with 65 parts of ion exchanged water, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated. The obtained concentrate is subjected to column fractionation (column fractionation conditions stationary phase: silica gel 60-200 mesh manufactured by Merck & Co., Ltd. developing solvent: n-heptane / ethyl acetate), whereby compound 10 represented by formula (C) is obtained. .24 parts were obtained.
MS (mass spectrometry): 446.1 (molecular ion peak)

式（Ｅ−１）で表される化合物２５部及びテトラヒドロフラン２５部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に、式（Ｅ−２）で表される化合物１０．２部、ピリジン１１．２部及びテトラヒドロフラン３０部の混合溶液を、１時間かけて添加し、更に、２５℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物に、酢酸エチル２００部及びイオン交換水５０部を添加攪拌後、分液して有機層を回収した。回収された有機層を濃縮した後、得られた濃縮物に、ｎ−ヘプタン５００部を添加攪拌後、ろ過することにより、式（Ｅ−３）で表される化合物４０．１８部を得た。得られた式（Ｅ−３）で表される化合物３５．２１部、テトラヒドロフラン１６０部、式（Ｅ−５）で表される化合物２２．８部及びピリジン８．３部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に式（Ｅ−４）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）３３．６部及びクロロホルム１４０部を添加し、２３℃で１８時間攪拌した。得られた反応溶液に、ｎ−ヘプタン８５０部及び５％塩酸水溶液７７部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、１０％炭酸カリウム水溶液６１部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水２３０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することにより、式（Ｅ）で表される化合物３１．５部を得た。
ＭＳ（質量分析）：４２０．１（分子イオンピーク） Synthesis Example 4: [Synthesis of Compound Represented by Formula (E)]

25 parts of the compound represented by the formula (E-1) and 25 parts of tetrahydrofuran were charged, stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, a mixed solution of 10.2 parts of the compound represented by the formula (E-2), 11.2 parts of pyridine and 30 parts of tetrahydrofuran was added to the obtained mixture over 1 hour. Furthermore, the temperature was raised to about 25 ° C., and the mixture was stirred at the same temperature for 1 hour. To the obtained reaction product, 200 parts of ethyl acetate and 50 parts of ion-exchanged water were added and stirred, followed by liquid separation to recover the organic layer. After the collected organic layer was concentrated, 500 parts of n-heptane was added to the resulting concentrate and stirred, followed by filtration to obtain 40.18 parts of a compound represented by the formula (E-3). . The obtained compound (E-3) 35.21 parts, tetrahydrofuran (160 parts), compound (E-5) 22.8 parts and pyridine 8.3 parts were charged at 23 ° C. After stirring and mixing for 30 minutes, the mixture was cooled to 0 ° C. While maintaining the same temperature, 33.6 parts of the compound represented by the formula (E-4) (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) and 140 parts of chloroform were added to the obtained mixture. The mixture was added and stirred at 23 ° C. for 18 hours. To the obtained reaction solution, 850 parts of n-heptane and 77 parts of 5% aqueous hydrochloric acid solution were added, and stirred at 23 ° C. for 30 minutes. 61 parts of 10% aqueous potassium carbonate solution was added to the organic layer recovered by standing and liquid separation, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed by standing and liquid separation. Such washing operation was repeated twice. The organic layer after washing was charged with 230 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 31.5 parts of a compound represented by the formula (E).
MS (mass spectrometry): 420.1 (molecular ion peak)

式（Ｆ−１）で表される化合物２５部及びテトラヒドロフラン２５部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に、式（Ｆ−２）で表される化合物８．５部、ピリジン１１．２部及びテトラヒドロフラン２５部の混合溶液を、１時間かけて添加し、更に、２５℃程度まで温度を上げ、同温度で１時間攪拌した。得られた反応物に、酢酸エチル１９０部及びイオン交換水５０部を添加攪拌後、分液して有機層を回収した。回収された有機層を濃縮した後、得られた濃縮物に、ｎ−ヘプタン１５０部を添加攪拌後、上澄み液を除去した後、濃縮することにより、式（Ｆ−３）で表される化合物２８．７部を得た。得られた式（Ｆ−３）で表される化合物１９．８部、テトラヒドロフラン９０部、式（Ｆ−５）で表される化合物１０．３部及びピリジン５．０部を仕込み、２３℃で３０分間攪拌混合した後、０℃まで冷却した。同温度を保持したまま、得られた混合物に式（Ｆ−４）で表される化合物（１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド塩酸塩）１５．２部を添加し、２３℃で１８時間攪拌した。得られた反応溶液に、ｎ−ヘプタン４５０部及び５％塩酸水溶液４７部を加え、２３℃で３０分間攪拌した。静置、分液することにより回収された有機層に、１０％炭酸カリウム水溶液３７部を加え、２３℃で３０分間攪拌し、静置、分液することにより有機層を洗浄した。このような洗浄操作を２回繰り返した。洗浄後の有機層に、イオン交換水１２０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することにより、式（Ｆ）で表される化合物２０．１部を得た。
ＭＳ（質量分析）：４０６．１（分子イオンピーク） Synthesis Example 5 [Synthesis of Compound Represented by Formula (F)]

25 parts of the compound represented by the formula (F-1) and 25 parts of tetrahydrofuran were charged, stirred and mixed at 23 ° C. for 30 minutes, and then cooled to 0 ° C. While maintaining the same temperature, a mixed solution of 8.5 parts of the compound represented by the formula (F-2), 11.2 parts of pyridine, and 25 parts of tetrahydrofuran was added to the obtained mixture over 1 hour. Furthermore, the temperature was raised to about 25 ° C., and the mixture was stirred at the same temperature for 1 hour. To the obtained reaction product, 190 parts of ethyl acetate and 50 parts of ion-exchanged water were added and stirred, followed by liquid separation to recover the organic layer. After the collected organic layer is concentrated, 150 parts of n-heptane is added to the resulting concentrate, and after stirring, the supernatant is removed and then concentrated to give a compound represented by formula (F-3) 28.7 parts were obtained. 19.8 parts of the compound represented by formula (F-3), 90 parts of tetrahydrofuran, 10.3 parts of compound represented by formula (F-5) and 5.0 parts of pyridine were charged at 23 ° C. After stirring and mixing for 30 minutes, the mixture was cooled to 0 ° C. While maintaining the same temperature, 15.2 parts of the compound represented by the formula (F-4) (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) was added to the obtained mixture, and 23 Stir at 18 ° C. for 18 hours. To the obtained reaction solution, 450 parts of n-heptane and 47 parts of 5% hydrochloric acid aqueous solution were added and stirred at 23 ° C. for 30 minutes. 37 parts of 10% aqueous potassium carbonate solution was added to the organic layer recovered by standing and liquid separation, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed by standing and liquid separation. Such washing operation was repeated twice. To the organic layer after washing, 120 parts of ion-exchanged water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated to obtain 20.1 parts of a compound represented by the formula (F).
MS (mass spectrometry): 406.1 (molecular ion peak)

Synthesis Example 6: Synthesis of salt represented by formula (II-1)

A salt represented by the formula (II-1-a) was synthesized by the method described in Example 2 of JP-A-2006-257078. A salt represented by the formula (II-1-a) (3.00 parts), chloroform (30.00 parts) and N-methylpyrrolidine (0.85 part) were charged, and the mixture was stirred at 0 ° C. for 30 minutes. Thereafter, 1.74 parts of the compound represented by the formula (II-1-b) were charged therein, and the mixture was stirred at 0 ° C. for 3 hours. To the obtained reaction product, 150 parts of chloroform and 40 parts of a 5% oxalic acid aqueous solution were charged, stirred and separated. The recovered organic layer was charged with 50 parts of ion-exchanged water, and stirred and separated. This water washing was performed 5 times. The obtained organic layer was charged with 1.00 parts of activated carbon, stirred at 23 ° C. for 30 minutes, and filtered. The filtrate was concentrated, 10 parts of acetonitrile was added to dissolve the resulting concentrate, the mixture was concentrated, 20 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 2.19 parts of the salt represented by the formula (II-1).
MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 535.1

Synthesis Example 7: Synthesis of salt represented by formula (II-9)

  A salt represented by the formula (II-9-a) was synthesized by the method described in Example 2 of JP-A-2006-257078. A salt represented by the formula (II-9-a) (3.00 parts), chloroform (30.00 parts) and N-methylpyrrolidine (0.85 parts) were charged, and the mixture was stirred at 0 ° C. for 30 minutes. Thereafter, 1.57 parts of the compound represented by the formula (II-9-b) was added thereto, followed by stirring at 0 ° C. for 3 hours. To the obtained reaction product, 150 parts of chloroform and 40 parts of a 5% oxalic acid aqueous solution were charged, stirred and separated. The recovered organic layer was charged with 50 parts of ion-exchanged water, and stirred and separated. This water washing was performed 5 times. The obtained organic layer was charged with 1.00 parts of activated carbon, stirred at 23 ° C. for 30 minutes, and filtered. The filtrate was concentrated, 10 parts of acetonitrile was added to dissolve the resulting concentrate, the mixture was concentrated, 20 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 20 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to obtain 1.84 parts of the salt represented by the formula (II-9).

MS (ESI (+) Spectrum): M ⁺ 263.1
MS (ESI (-) Spectrum): M ^- 435.1

以下、これらの化合物をその式番号に応じて、「モノマー（ａ１−１−２）」などという。 Synthesis of Resin (A) The compounds used for the synthesis of resin (A) are shown below.

Hereinafter, these compounds are referred to as “monomer (a1-1-2)” or the like according to the formula number.

Synthesis Example 8: [Synthesis of Resin A1-1]
Monomer (a4-1-7) and monomer (A) are used as monomers and mixed so that the molar ratio (monomer (a4-1-7): monomer (A)) is 90:10. An amount of 1.5 mass times dioxane 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, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 1.7. × obtain a 10 ⁴ resin A1-1 in 82% yield. This resin A1-1 has the following structural units.

Synthesis Example 9: [Synthesis of Resin A1-2]
Monomer (B) 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 2.0. × obtain a 10 ⁴ resin A1-2 in 85% yield. This resin A1-2 has the following structural units.

Synthesis Example 10: [Synthesis of Resin A1-3]
Monomer (C) was used as the 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. A 10 ⁴ resin A1-3 was obtained with a yield of 83%. This resin A1-3 has the following structural units.

Synthesis Example 11: [Synthesis of Resin A1-4]
Monomer (E) was used as a monomer, and methyl isobutyl ketone 1.2 mass times the total monomer amount was added to prepare a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 60 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-4 having a weight average molecular weight of 2.6 × 10 ^{4 in} a yield of 89%. This resin A1-4 has the following structural units.

Synthesis Example 12: [Synthesis of Resin A1-5]
Monomer (F) was used as the monomer, and 1.2 mass times of methyl isobutyl ketone as the total monomer amount was added to prepare a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and these were heated at 60 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of n-heptane to precipitate a resin, and this resin was filtered to obtain a resin A1-5 having a weight average molecular weight of 3.9 × 10 ^{4 in} a yield of 90%. This resin A1-5 has the following structural units.

Synthesis Example 13: [Synthesis of Resin A2-1]
The monomer (a1-1-3), the monomer (a1-2-3), the monomer (a2-1-1), the monomer (a3-1-1) and the monomer (a3-2-3) are mixed in a molar ratio [ Monomer (a1-1-3): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3)] is 30:14 : 6: 20: 30 The mixture was further mixed, and 1.5 mass times of dioxane was further mixed with this monomer mixture with respect to the total mass of all monomers. 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. It added so that it might become. This was polymerized 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 was filtered and collected. It is again dissolved in dioxane, poured into a mixed solvent of a large amount of methanol and water to precipitate the resin, and the precipitated resin is filtered and collected twice to perform reprecipitation purification, and the weight average molecular weight is 8 the copolymer is .1 × 10 ³ was obtained in a yield of 65%. This copolymer is monomer (a1-1-3), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3). These have the following structural units derived from each, and are referred to as Resin A2-1.

Synthesis Example 14: [Synthesis of Resin A2-2]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1) and monomer (a3-2-3) are mixed in a molar ratio [ Monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3)] is 30:14 : 6: 20: 30 The mixture was further mixed, and 1.5 mass times of dioxane was further mixed with this monomer mixture with respect to the total mass of all monomers. 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. It added so that it might become. This was polymerized 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 was filtered and collected. Again, it is dissolved in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and collected twice to perform reprecipitation purification, and the weight average molecular weight is 7 A copolymer of .8 × 10 ³ was obtained with a yield of 68%. This copolymer is monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3). These have the following structural units derived from each, and are referred to as Resin A2-2.

Synthesis Example 15: [Synthesis of Resin A2-3]
Monomer (1-1-2), monomer (a2-1-1) and monomer (a3-1-1) are mixed in a molar ratio [monomer (1-1-2): monomer (a2-1-1): Monomer (a3-1-1)] was mixed so as to be 50:25:25, and 1.5 mass times dioxane was further mixed with respect to the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in proportions of 1 mol% and 3 mol%, respectively, with respect to the total number of moles of all monomers. Then, this was heated at 80 ° C. for about 8 hours to carry out polymerization. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin was filtered and collected. Again, the obtained resin is dissolved in dioxane, poured into a large amount of methanol / water mixed solvent to precipitate the resin, and the precipitated resin is filtered and recovered three times for reprecipitation purification. A copolymer having a weight average molecular weight of about 9.2 × 10 ³ was obtained in a yield of 60%. This copolymer has structural units derived from the following monomers derived from the monomer (1-1-2), the monomer (a2-1-1) and the monomer (a3-1-1), respectively. Yes, this is Resin A2-3.

Synthesis Example 16: [Synthesis of Resin A2-4]
The monomer (a1-1-3), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-2-3), and monomer (a3-1-1) are mixed in a molar ratio [ Monomer (a1-1-3): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-2-3): monomer (a3-1-1)] is 30:14 : 6: 20: 30 The mixture was mixed and 1.5 mass times dioxane of the total monomer amount was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was 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. × give 10 ³ of copolymer in 60% yield. This copolymer is monomer (a1-1-3), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) The following structural units derived from each of the above are referred to as Resin A2-4.

Synthesis Example 17: [Synthesis of Resin A2-5]
The monomer (a1-1-3), monomer (a1-5-1), monomer (a2-1-1), monomer (a3-2-3) and monomer (a3-1-1) are mixed in a molar ratio [ Monomer (a1-1-3): Monomer (a1-5-1): Monomer (a2-1-1): Monomer (a3-2-3): Monomer (a3-1-1)] is 30:14 : 6: 20: 30 The mixture was mixed and 1.5 mass times dioxane of the total monomer amount was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and 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 7.4. × give 10 ³ of copolymer in 62% yield. This copolymer is monomer (a1-1-3), monomer (a1-5-1), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) These have the following structural units derived from each, and are referred to as Resin A2-5.

Synthesis Example 18: [Synthesis of Resin X1]
As the monomer, monomer (a1-1-1), monomer (a3-1-1) and monomer (a2-1-1) were used, and the molar ratio (monomer (a1-1-1): monomer (a3-1) -1): The monomer (a2-1-1)) was mixed to be 35:45:20, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.0 mol% and 3.0 mol%, respectively, based on the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.0. A × 10 ³ resin X1 was obtained with a yield of 75%. This resin X1 has the following structural units.

Synthesis Example 19: [Synthesis of Resin X2]
Monomer (F) and monomer (a1-1-1) are used as monomers and mixed so that the molar ratio (monomer (F): monomer (a1-1-1)) is 80:20. An amount of 1.5 mass times dioxane was added to prepare a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.5 mol% and 1.5 mol%, respectively, based on the total monomer amount, and these were added at 70 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 2.8. A × 10 ⁴ resin X2 (copolymer) was obtained in a yield of 70%. This resin X2 has the following structural units.

<Preparation of resist composition>
Resins A1-1 to A1-5, A2-1 to A2-5, X1 to X2 obtained in Synthesis Examples 8 to 19;
Acid generator II-1 obtained in Synthesis Example 4
Acid generators B1 to B3 shown below;
Basic compound C1 shown below;
Each was dissolved in the solvent shown below in parts by mass shown in Table 2, and further filtered through a fluororesin filter having a pore diameter of 0.2 μm to prepare a resist composition.

酸発生剤ＩＩ−１の５０ｍｇをジメチルスルホキサイド０．７９２４部ｇに溶解し、２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液０．２５ｇを添加し、１時間攪拌したあと、酸発生剤ＩＩ−１の分解物を確認したところ、開裂して以下の化合物が生成されていることを確認した。

<Acid generator>
II-1: Salt represented by formula (II-1) synthesized in the above synthesis example

50 mg of the acid generator II-1 was dissolved in 0.7924 g of dimethyl sulfoxide, 0.25 g of an aqueous 2.38 mass% tetramethylammonium hydroxide solution was added, and the mixture was stirred for 1 hour, and then the acid generator II. When the decomposition product of -1 was confirmed, it was cleaved and it was confirmed that the following compounds were produced.

酸発生剤ＩＩ−９の５０ｍｇをジメチルスルホキサイシド０．７９２４ｇに溶解し、２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液０．２５ｇを添加し、２３℃で１時間攪拌したあと、酸発生剤ＩＩ−９の分解物を確認したところ、塩基解離性基が開裂して以下の化合物が生成されていることを確認した。

II-9: salt represented by formula (II-9) synthesized in the above synthesis example

50 mg of the acid generator II-9 was dissolved in 0.7924 g of dimethyl sulfoxide, and 0.25 g of an aqueous 2.38 mass% tetramethylammonium hydroxide solution was added and stirred at 23 ° C. for 1 hour, and then the acid generator. When the decomposition product of II-9 was confirmed, it was confirmed that the base dissociable group was cleaved and the following compound was produced.

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

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 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, on the organic antireflection film, the above resist composition was applied (spin coated) so that the film thickness after drying was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature described in the “PB” column of Table 2 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) / A mask for forming a hole diameter of 70 nm) was used for immersion exposure by changing the exposure stepwise. 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 for 60 seconds at the temperature described in the “PEB” column of Table 2. Next, this silicon wafer was subjected to paddle development for 60 seconds with a 2.38% tetramethylammonium hydroxide aqueous solution.

  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 hole diameter of a pattern formed with a mask having a hole diameter of 70 nm was measured 24 times per hole, and the average value was taken as the average hole diameter of one hole. A standard deviation is obtained using a population obtained by measuring 400 average hole diameters of a pattern formed with a mask having a hole diameter of 70 nm in the same wafer,
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”.

<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 at the temperature shown in the PB column of Table 2 on a direct hot plate.
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].
These results are shown in Table 3.

  According to the resist composition of the present invention, a resist pattern can be produced with CD uniformity (CDU), and the number of occurrences of defects in the obtained resist pattern is small.

Claims (9)

A resin having a structural unit represented by the formula (I),
A resin that is insoluble or hardly soluble in an alkaline aqueous solution and that can be dissolved in an alkaline aqueous solution by the action of an acid (but not including the structural unit represented by formula (I)), and a structure that is cleaved by the action of an alkaline developer 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.
A ¹³ represents a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms having a fluorine atom .
X ¹² represents * —CO—O— or * —O—CO—, and * represents a bond to A ¹³ .
A ¹⁴ represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. ] The resist composition according to claim 1, wherein A ^{1 in} formula (I) is an ethylene group. The resist composition according to claim 1, wherein A ^{13 in the} formula (I) is a C 1-6 perfluoroalkanediyl group. The resist composition according to claim 1, wherein X ^{12 in} formula (I) is * —CO—O— (* represents a bond to A ¹³ ). The resist composition according to claim 1, wherein A ^{14 in the} formula (I) is a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group. The resist composition according to claim 1, wherein in the acid generator, a structure that is cleaved by the action of an alkali developer is a group represented by the formula (Ba) or a group represented by the formula (Bb). object.

[In Formula (Ba), R ²³ represents a C 1-6 alkyl group having a fluorine atom. ]

[In the formula (Bb), R ²⁴ represents a C 1-6 alkyl group having a fluorine atom.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a fluorine atom. ] The resist composition according to claim 1, wherein the acid generator is an acid generator represented by formula (II-a) or an acid generator represented by formula (II-b).

[In formula (II-a) or formula (II-b),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ²¹ represents a single bond or a divalent alkanediyl group having 1 to 17 carbon atoms, and —CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—.
Y represents a C 3-18 divalent alicyclic hydrocarbon group, and —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced by —O— or —CO—. .
R ^{23 to} R ²⁶ represent the same meaning as described above. ] The resist composition according to claim 7, wherein Z ^{+ in} formula (II-a) and formula (II-b) is a triarylsulfonium cation. (1) The process of apply | coating the resist composition in any one of Claims 1-8 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: