JP2014063150A - Resist composition and method of producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition that is superior in focus margin (DOF) when producing a resist pattern.SOLUTION: A resist composition contains a resin having a structural unit represented by formula (I), and an acid generator. In the formula (I), Rrepresents a 1-6C alkyl group that may include a halogen atom, a hydrogen atom or a halogen atom; and Rand Reach independently represent a 1-6C aliphatic hydrocarbon group, or together form a 5-20C ring with carbon atoms to which they bond.

Description

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

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

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

JP 2012-155314 A

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

  Conventional resist compositions may not always satisfy the focus margin (DOF) when producing a resist pattern.

［式（Ｉ）中、
Ｒ^１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。
Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜６の脂肪族炭化水素基を表すか、一緒になってそれらが結合する炭素原子とともに炭素数５〜２０の環を形成する。
Ｌ^１は、炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わってもよい。］
〔２〕 式（Ｉ）のＲ^２及びＲ^３が、一緒になってそれらが結合する炭素原子とともに炭素数５〜２０の環を形成する〔１〕記載のレジスト組成物。
〔３〕 （１）〔１〕又は〔２〕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）組成物層に露光する工程、
（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。
〔４〕式（Ｉ）で表される構造単位及び酸不安定基の構造単位を有する樹脂。 The present invention includes the following inventions.
[1] A resist composition containing a resin having a structural unit represented by formula (I) and an acid generator.

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or together form a ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded.
L ¹ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]
[2] The resist composition according to [1], wherein R ² and R ^{3 in} the formula (I) together form a ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded.
[3] (1) A step of applying the resist composition according to [1] or [2] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including:
[4] A resin having a structural unit represented by the formula (I) and a structural unit of an acid labile group.

  According to the resist composition of the present invention, a resist pattern can be produced with an excellent focus margin.

  In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. The notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning.

<Resist composition>
The resist composition of the present invention contains a resin having a structural unit represented by formula (I) (hereinafter sometimes referred to as “resin (A)”) and an acid generator (B).
It is preferable that the resist composition of the present invention further contains a solvent (E).
The resist composition of the present invention preferably further contains compound (II) and / or basic compound (C).

<Resin (A)>
The resin (A) includes a structural unit represented by the formula (I) (hereinafter sometimes referred to as “structural unit (I)”), and further has a structural unit other than the structural unit (I). Also good.
The structural unit other than the structural unit (I) includes a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”) and a structural unit having no acid labile group (hereinafter “structural unit ( s) ").
In the present specification, the acid labile group means a group having a leaving group, and the leaving group is eliminated by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). To do.

［式（Ｉ）中、
Ｒ^１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。
Ｒ^２及びＲ^３は、それぞれ独立に、炭素数１〜６の脂肪族炭化水素基を表すか、一緒になってそれらが結合する炭素原子とともに炭素数５〜２０の環を形成する。
Ｌ^１は、炭素数１〜１８の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わってもよい。］ <Structural unit (I)>
The structural unit (I) is represented by the formula (I).

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or together form a ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded.
L ¹ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

Examples of the halogen atom for R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group for R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. Preferably, it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom for R ¹ include 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. Perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

Examples of the aliphatic hydrocarbon group for R ² and R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and An alkyl group such as an n-hexyl group can be mentioned.
The ring formed by combining R ² and R ³ together with the carbon atom is preferably an alicyclic hydrocarbon ring having 5 to 10 carbon atoms, more preferably a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring. Or it is an adamantane ring, More preferably, it is a cyclohexane ring.
R ² and R ³ preferably form a ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded.

The divalent saturated hydrocarbon group of L ¹ is, for example, a divalent aliphatic saturated hydrocarbon group or a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. . Specific examples include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

式（Ｌ１−１）中、
Ｘ^x1は、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−又は−Ｏ−を表し、＊はＬ^x1との結合手を表す。
Ｌ^x1は、炭素数１〜１６の２価の飽和炭化水素基を表す。
Ｌ^x2は、炭素数１〜１６の２価の飽和炭化水素基を表す。
ただし、Ｌ^x1、Ｌ^x2及びＸ^x1の合計炭素数は、１８以下である。 Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include a group represented by the formula (L1-1). In the following formula, * represents a bond with -O-.

In formula (L1-1),
X ^x1 represents * —CO—O—, * —O—CO— or —O—, and * represents a bond to L ^x1 .
L ^x1 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total carbon number of L ^x1 , L ^x2 and X ^x1 is 18 or less.

X ^x1 is preferably * —CO—O— or * —O—CO—, more preferably * —O—CO—.
L ^x1 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, still more preferably a methylene group or an ethylene group.
L ^x2 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, still more preferably a methylene group or an ethylene group.

As group represented by a formula (L1-1), the bivalent group shown below is mentioned, for example.

L ¹ is preferably a group represented by the formula (L1-1). The group represented by the formula (L1-1) is preferably — (CH ₂ ) _n —O—CO—CH ₂ — (n represents an integer of 1 to 6), and more preferably. _{, - (CH 2) 2 -O} -CO-CH 2 - is.

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

Regarding the structural unit represented by any one of formulas (I-1) to (I-8), a structural unit in which a methyl group corresponding to R ¹ is replaced with a hydrogen atom is also a specific example of structural unit (I). Can be mentioned.

［式（Ｉ’）中、Ｒ^１、Ｒ^２、Ｒ^３及びＬ^１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 , R ² , R ³ and L ¹ represent the same meaning as described above. ]

Compound (I ′) can be synthesized, for example, by the method described in JP-A-2008-7421. In the following description, each symbol represents the same meaning as described above.
For example, in the formula (I), a method for producing a compound represented by the formula (IA) in which L ¹ is — (CH ₂ ) _n —O—CO—CH ₂ — is shown below.

式（ＩＡ−ｂ）で表される化合物としては、以下で表される化合物等が挙げられる。

First, the compound represented by the formula (IA-a) is reacted with the compound represented by the formula (IA-b) in the presence of a catalyst in a solvent, thereby being represented by the formula (IA-c). Can be obtained. Examples of the catalyst include pyridinium p-toluenesulfonate. Examples of the solvent include chloroform.

Examples of the compound represented by the formula (IA-b) include compounds represented by the following.

式（ＩＡ−ｄ）で表される化合物としては、ヒドロキシエチルメタクリレート等が挙げられる。 The compound represented by the formula (IA-c) and the compound represented by the formula (IA-d) are reacted in a solvent in the presence of a catalyst, thereby being represented by the formula (IA). A compound can be obtained. Examples of the catalyst include 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride. Examples of the solvent include chloroform.

Examples of the compound represented by the formula (IA-d) include hydroxyethyl methacrylate.

  The content of the structural unit (I) contained in the resin (A) is preferably 1 to 50 mol%, more preferably 3 to 40 mol%, still more preferably 5 with respect to the total structural units of the resin (A). -35 mol%.

［式（１）中、Ｒ^a1、Ｒ^a2及びＲ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜２０の脂環式炭化水素基又はこれらを組み合わせた基を表すか、Ｒ^a1及びＲ^a2は互いに結合して炭素数２〜２０の２価の炭化水素基を形成する。＊は結合手を表す。］

［式（２）中、Ｒ^１ａ’及びＲ^ａ２’は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^ａ３’は、炭素数１〜２０の炭化水素基を表すか、Ｒ^ａ２’及びＲ^ａ３’は互いに結合して炭素数２〜２０の２価の炭化水素基を形成し、該炭化水素基及び該２価の炭化水素基を構成する−ＣＨ_２−は、−Ｏ―又は―Ｓ−で置き換わってもよい。
Ｘは、酸素原子又は硫黄原子を表す。
＊は結合手を表す。］
式（２’）で表される基は、式（２）で表される基が好ましい。

［式（２）中、Ｒ^１ａ’、Ｒ^ａ２’及びＲ^ａ３’は上記と同じ意味を表す。］
<Structural unit (a1)>
The “acid-labile group” means a group that forms a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group upon contact with an acid as described above. Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2 ′).

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

[In Formula (2), R ^{1a ′} 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 — constituting the hydrocarbon group and the divalent hydrocarbon group. May be replaced by -O- or -S-.
X represents an oxygen atom or a sulfur atom.
* Represents a bond. ]
The group represented by the formula (2 ′) is preferably a group represented by the formula (2).

[In formula (2), R ^{1a ′} , R ^{a2 ′} and R ^{a3 ′} represent the same meaning as described above. ]

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

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

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. In each formula, R ^a3 has the same meaning as described above, and * represents a bond to —O—.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^{a1 to} R ^a3 are alkyl groups in the formula (1), preferably a tert-butoxycarbonyl group), 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- ( And adamantane-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the divalent hydrocarbon group formed by combining R ^{a2 ′} and R ^{a3 ′} include groups in which one hydrogen atom has been removed from the hydrocarbon groups of R ^{a1 ′ to} R ^{a3 ′} .
At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

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

  The monomer that leads to the structural unit (a1) (hereinafter sometimes referred to as “monomer (a1)”) preferably has a monomer having an acid labile group and an ethylenically unsaturated bond, and more preferably has an acid labile group. It is a (meth) acrylic monomer.

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

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

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

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

L ^a1 and L ^a2 are preferably —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, more preferably —O—. k1 is preferably an integer of 1 to 4, more preferably 1.
R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and the group obtained by combining these include the same groups as those described for R ^{a1 to} R ^a3 in formula (1).
The alkyl group for R ^a6 and R ^a7 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 preferably has 8 or less carbon atoms, more preferably 6 or less.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

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

Examples of the monomer (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, and 1-ethylcycloheptan-1-yl (meth). Acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, 1-methylcyclohexane-1-yl (meth) acrylate, 1-isopropylcyclopentan-1-yl (meth) acrylate, 1-isopropylcyclohexane-1- And yl (meth) acrylate. 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 (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol with respect to all the structural units of the resin (A). %, Preferably 15 to 90 mol%, more preferably 20 to 85 mol%.

［式（ａ１−５）中、
Ｒ³¹は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｚ^a1は、単結合又は＊−［ＣＨ₂］_k4−ＣＯ−Ｌ^a4−を表す。ここで、ｋ４は１〜４の整数を表す。＊は、Ｌ^a1との結合手を表す。
Ｌ^a1、Ｌ^a2、Ｌ^a3及びＬ^a4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。］ The structural unit derived from the (meth) acrylic monomer having a group represented by the formula (2 ′) is a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”). In some cases).

[In the formula (a1-5),
R ³¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or * — [CH ₂ ] _k4 —CO—L ^a4 —. Here, k4 represents an integer of 1 to 4. * Represents a bond with L ^a1 .
L ^a1 , L ^a2 , L ^a3 and L ^a4 each independently represent —O— or —S—.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3. ]

In formula (a1-5), R ³¹ is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ^a1 is preferably an oxygen atom.
One of L ^a2 and L ^a3 is preferably an oxygen atom and the other is a sulfur atom.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

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

  When the resin (A) has the structural unit (a1-5), the content is preferably from 1 to 95 mol%, more preferably from 3 to 90 mol%, based on all the structural units of the resin (A). 5 to 85 mol% is more preferable.

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

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

［式（ａ２−０）中、
Ｒ^a30は、水素原子、ハロゲン原子又はハロゲン原子を有してもよい炭素数１〜６のアルキル基を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、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２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上の整数である場合、複数のＲ^a31は互いに同一又は相異なる。］ Examples of the structural unit (a2) having a phenolic hydroxy group include a structural unit represented by the formula (a2-0) (hereinafter sometimes referred to as “structural unit (a2-0)”).

[In the formula (a2-0),
R ^a30 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents an integer of 0 to 4. When ma is an integer of 2 or more, the plurality of R ^a31 are the same or different from each other. ]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, for example.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, and hexyl group.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group having 2 to 4 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.

R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
The alkyl group for R ^a31 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
The alkoxy group of R ^a31 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

As a monomer which introduce | transduces structural unit (a2-0), the monomer described in Unexamined-Japanese-Patent No. 2010-204634 is mentioned, for example.
Among them, the structural unit (a2-0) is represented by formula (a2-0-1), formula (a2-0-2), formula (a2-0-3), and formula (a2-0-4), respectively. What is represented is preferable, and what is represented by a formula (a2-0-1) or a formula (a2-0-2) is more preferable.

  The resin (A) containing the structural unit (a2-0) is polymerized using a monomer in which the phenolic hydroxy group of the monomer that leads to the structural unit (a2-0) is protected with a protective group such as an acetyl group. It can be produced by carrying out a reaction and then deprotecting. However, when the deprotection treatment is performed, the acid labile group of the structural unit (a1) needs to be not significantly impaired.

  When the resin (A) has the structural unit (a2-0), the content is preferably from 5 to 95 mol%, more preferably from 10 to 80 mol%, based on all the structural units of the resin (A). 15-80 mol% is more preferable.

式（ａ２−１）中、
Ｌ^a3は、−Ｏ−又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表し、
ｋ２は１〜７の整数を表す。＊は−ＣＯ−との結合手を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。 Examples of the structural unit (a2) having an alcoholic hydroxy group include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).
As the structural unit (a2), the structural unit (a2-1) is more preferable.

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 a monomer which introduce | transduces structural unit (a2-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Especially, the monomer represented by either of formula (a2-1-1)-formula (a2-1-6) is preferable, and any of formula (a2-1-1)-formula (a2-1-4) The monomer represented by formula (a2-1-1) or the formula (a2-1-3) is more preferred.

  When the resin (A) contains the structural unit (a2), the content is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on all structural units of the resin (A). More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be, for example, a single ring such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, or a bridged ring including such a lactone ring structure. Good. Among these lactone rings, a bridged ring containing a γ-butyrolactone ring or a γ-butyrolactone ring structure is preferable.
As the structural unit (a3), one type may be used alone, or two or more types may be used in combination.

The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4) (hereinafter, depending on the formula number). Or “structural unit (a3-1)”). These 1 type may be used independently and may use 2 or more types together.

［式（ａ３−１）中、
Ｌ^a4は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ｋ４は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表し、ｐ１が２以上の場合、複数のＲ^a21は同じであってもよい。
式（ａ３−２）中、
Ｌ^a5は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ｋ４は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
ｑ１は、０〜３の整数を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表し、ｑ１が２以上の場合、複数のＲ^a22は同じであってもよい。
式（ａ３−３）中、
Ｌ^a6は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ｋ４は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
ｒ１は、０〜３の整数を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表し、ｒ１が２以上の場合、複数のＲ^a23は同じであってもよい。
式（ａ３−４）中、
Ｌ^a７は、酸素原子、＊−Ｏ−（ＣＨ₂）_k4−Ｏ−、＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−、＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ＣＨ₂）_k５−ＣＯ−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k4−Ｏ−ＣＯ−（ＣＨ₂）_k５−Ｏ−（ｋ４及びｋ５は、それぞれ独立に、１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a2４は、水素原子又はメチル基を表す。］

[In the formula (a3-1),
L ^a4 represents an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O— (k4 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
p1 represents an integer of 0 to 5.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when p1 is 2 or more, the plurality of R ^a21 may be the same.
In formula (a3-2),
L ^a5 represents an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O— (k4 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
q1 represents an integer of 0 to 3.
R ^a19 represents a hydrogen atom or a methyl group.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when q1 is 2 or more, a plurality of R ^a22 may be the same.
In formula (a3-3),
L ^a6 represents an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O— (k4 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
r1 represents an integer of 0 to 3.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when r1 is 2 or more, a plurality of R ^a23 may be the same.
In formula (a3-4),
L ^a7 is an oxygen atom, * —O— (CH ₂ ) _k4 —O—, * —O— (CH ₂ ) _k4 —CO—O—, * —O— (CH ₂ ) _k4 —CO—O— ( CH _{2) k5} -CO-O- or _{* -O- (CH 2) k4 -O} -CO- (CH 2) k5 -O- (k4 and k5 independently represents an integer of 1-7. ) Represents a group represented by * Represents a bond with a carbonyl group.
R ^a24 represents a hydrogen atom or a methyl group. ]

In formula (a3-1) to formula (a3-4), L ^{a4 to} L ^a7 are the same as those described for L ^a3 in formula (a2-1).
L ^{a4 to} L ^a7 are each independently an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O—, wherein k4 is an integer of 1 to 4, preferably an oxygen atom and * —O—CH ₂ —CO—O— is more preferable, and an oxygen atom is more preferable.
R ^{a18 to} R ^a21 and R ^a24 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are preferably integers of 0 to 2, more preferably 0 or 1. When p1 is 2, two R ^a21 may be the same as or different from each other. When q1 is 2, two R ^a22 may be the same as or different from each other, and r1 is 2. Two R ^a23 may be the same or different from each other.

Examples of the monomer for deriving the structural unit (a3-1) include the formula (a3-1-1), the formula (a3-1-2), the formula (a3-1-3), and the formula (a3-1-4). And monomers represented by any of the above.

Examples of the monomer that leads to the structural unit (a3-2) include, for example, the formula (a3-2-1), the formula (a3-2-2), the formula (a3-2-3), and the formula (a3-2-4). And monomers represented by any of the above.

Examples of the monomer that leads to the structural unit (a3-3) include, for example, the formula (a3-3-1), the formula (a3-3-2), the formula (a3-3-3), and the formula (a3-3-4). And monomers represented by any of the above.

Examples of the monomer that leads to the structural unit (a3-4) include the formula (a3-4-1), the formula (a3-4-2), the formula (a3-4-3), and the formula (a3-4-4). , A monomer represented by any one of formula (a3-4-5) and formula (a3-4-6).

In the above compound, a compound in which a methyl group corresponding to R ^a24 is replaced with a hydrogen atom can also be exemplified as a monomer for deriving the structural unit (a3-4).

  Among structural units (a3), formula (a3-1-1), formula (a3-1-2), formula (a3-2-3), formula (a3-2-4), formula (a3-4-) 1) or a structural unit derived from a monomer represented by the formula (a3-4-2) is more preferable, and the formula (a3-1-1), the formula (a3-2-3) or the formula (a3-4-2) The structural unit derived from a monomer represented by

  The structural unit (a3-1), the structural unit (a3-2), and the structural unit (a3-3) can be derived from the monomer (s) described in JP 2010-204646 A.

  The structural unit (a3-4) can be derived from the monomer (s) described in JP2012-41274A.

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Moreover, content of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), and a structural unit (a3-4) is respectively with respect to all the structural units of resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more preferable.

<Other structural units (s)>
Examples of the structural unit (s) include a structural unit having a halogen atom in addition to the structural unit (a2) and the structural unit (a3) (hereinafter sometimes referred to as “structural unit (a4)”).

式（ａ４−１）中、
Ｒ^a41は、水素原子又はメチル基を表す。
Ａ^a41は、置換基を有していてもよい炭素数１〜６のアルカンジイル基又は式（ａ−ｇ１）で表される基を表す。

（式（ａ−ｇ１）中、
ｓは０又は１を表す。
Ａ^a42及びＡ^a44は、それぞれ独立に、置換基を有していてもよい炭素数１〜５の脂肪族炭化水素基を表す。
Ａ^a43は、置換基を有していてもよい炭素数１〜５の脂肪族炭化水素基又は単結合を表す。
Ｘ^a41及びＸ^a42は、それぞれ独立に、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−又は−Ｏ−ＣＯ−を表す。）
Ｒ^a42は、置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
ただし、Ａ^a41及びＲ^a４２のうち少なくとも一方は、ハロゲン原子を有する基である。 As a structural unit (a4), the structural unit represented by a formula (a4-1) is mentioned, for example.

In formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1).

(In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent an ^optionally substituted aliphatic hydrocarbon group having 1 to 5 carbon atoms.
A ^a43 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent or a single bond.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—. )
R ^a42 represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
However, at least one of A ^a41 and R ^a42 is a group having a halogen atom.

芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、アントリル基、ビフェニリル基、フェナントリル基及びフルオレニル基等が挙げられる。 ^Examples of the hydrocarbon group for R ^a42 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined. The aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, but is preferably an aliphatic saturated hydrocarbon group. The aliphatic saturated hydrocarbon group may be either a chain or a cyclic group, and in particular, a linear or branched alkyl group, a monocyclic or polycyclic alicyclic hydrocarbon group, an alkyl group, and an alicyclic group. Examples thereof include an aliphatic hydrocarbon group combined with a hydrocarbon group.
Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, hexadecyl, pentadecyl, and hexyl. A decyl group, a heptadecyl group, an octadecyl group, etc. are mentioned.
Examples of the monocyclic aliphatic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond).

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthryl group, and a fluorenyl group.

^As the alkanediyl group of ^Aa41 , 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 substituent in the alkanediyl group of A ^a41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

Examples of the substituent of the alkanediyl group include a halogen atom.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom.

In the group represented by the formula (a-g1) of A ^a41 (hereinafter sometimes referred to as “group (a-g1)”), A ^a44 is ^bonded to —O—CO—R ^a42 .
As the aliphatic hydrocarbon group for A ^a42 , A ^a43 and A ^{a44 in} the group (a-g1), a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane- Examples include 1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
^Examples of the substituent in A ^a42 , A ^a43 and A ^a44 include a halogen atom, a hydroxy group, and an alkoxy group having 1 to 6 carbon atoms.

^Examples of the group (a-g1) in which X ^a42 is an oxygen atom include the following groups. In the following examples, among the two bonds represented by *, * on the right side is a bond with —O—CO—R ^a42 .

Examples of the group (a-g1) in which X ^a42 is a carbonyl group include the following groups.

Examples of the group (a-g1) in which X ^a42 is a carbonyloxy group include the following groups.

なかでも、Ａ^a42、Ａ^a43、Ａ^a44、Ｘ^a41及びＸ^a42の炭素数の合計は６以下であることが好ましい。 Examples of the group (a-g1) in which X ^a42 is an oxycarbonyl group include the following groups.

Among ^{them, A a42, A a43, A} a44, it is also preferred that the total number of carbon atoms of X ^a41 and X ^a42 is 6 or less.

［式（ａ−ｇ３）中、
Ｘ^a43は、酸素原子、カルボニル基、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^a45は、少なくとも１つのハロゲン原子を有する炭素数３〜１７の脂肪族炭化水素基を表す。］ ^Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups in which these are combined, and chain and cyclic aliphatic hydrocarbon groups, and A group in which these are combined is preferable and may have a carbon-carbon unsaturated bond, but a chain and cyclic aliphatic saturated hydrocarbon group and a group in which these are combined are more preferable. Specifically, the same group as R ^a41 is ^exemplified .
R ^a42 is preferably an aliphatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group having a halogen atom or a group represented by the formula (a-g3).

[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents a C ^3-17 aliphatic hydrocarbon group having at least one halogen atom. ]

When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and still more preferably a carbon number. It is a 1-6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.

When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the number of carbons contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total carbon number of the group is preferably 15 or less, more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

［式（ａ−ｇ２）中、
Ａ^a46は、ハロゲン原子を有していてもよい炭素数３〜１７の脂肪族炭化水素基を表す。
Ｘ^a44は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^a47は、ハロゲン原子を有していてもよい炭素数３〜１７の脂肪族炭化水素基を表す。
ただし、Ａ^a46、Ａ^a47及びＸ^a44の炭素数の合計は１８以下であり、Ａ^a46及びＡ^a47のうち、少なくとも一方は、少なくとも１つのハロゲン原子を有する。］ The aliphatic hydrocarbon having a group represented by the formula (a-g3) is more preferably a group represented by the formula (a-g2).

[In the formula (a-g2),
A ^a46 represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents a carbonyloxy group or an oxycarbonyl group.
A ^a47 represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47, and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom. ]

1-6 are preferable and, as for carbon number of the aliphatic hydrocarbon group of ^Aa46 , 1-3 are more preferable.
4-15 are preferable, as for carbon number of the aliphatic hydrocarbon group of A ^<a47> , 5-12 are more preferable, and A ^<a47> has a more preferable cyclohexyl group or an adamantyl group.

Among the combinations of A ^a46 and A ^a47, the more preferable, * - is represented by the partial structure represented by A ^a46 -X ^a44 -A ^a47 (* represents a bond to a carbonyl group), the following structure Is mentioned.

In formula (a4-1), at least one of A ^a41 and R ^a42 is a group having a halogen atom.

［式（ａ４−２）中、
Ｒ^ｆ1は、水素原子又はメチル基を表す。
Ａ^ｆ1は、炭素数１〜６のアルカンジイル基を表す。
Ｒ^ｆ2は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ As the structural unit (a4-1), a structural unit represented by the formula (a4-2) or the formula (a4-3) is preferable.

[In the formula (a4-2),
R ^f1 represents a hydrogen atom or a methyl group.
A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms.
R ^f2 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

As the alkanediyl group of A ^f1 , a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group Linear alkanediyl group such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group And branched alkanediyl groups such as 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

The hydrocarbon group for R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain group, a cyclic group, and a combination thereof. As the aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. .
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methyl group. Examples thereof include cycloalkyl groups such as cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, and norbornyl. Group, methylnorbornyl group and isobornyl group.

Examples of the hydrocarbon group having a fluorine atom for R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Specifically, as the alkyl group having a fluorine atom, a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2 , 2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoro (Ropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5- Decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2, 2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentyl Examples thereof include fluorinated alkyl groups such as a methyl group and a perfluorohexyl group.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

In formula (a4-2), an alkanediyl group having 2 to 4 carbon atoms is preferable, and as A ^f1 , an ethylene group is more preferable.
R ^f2 is preferably a fluorinated alkyl group having 1 to 6 carbon atoms.

［式（ａ４−３）中、
Ｒ^ｆ１１は、水素原子又はメチル基を表す。
Ａ^ｆ１１は、炭素数１〜６のアルカンジイル基を表す。
Ａ^ｆ１３は、フッ素原子を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表す。
Ｘ^ｆ１２は、カルボニルオキシ基又はオキシカルボニル基を表す。
Ａ^ｆ１４は、フッ素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。 ただし、Ａ^ｆ１３及びＡ^ｆ１４の少なくとも１つは、フッ素原子を有する脂肪族炭化水素基を表す。］

[In the formula (a4-3),
R ^f11 represents a hydrogen atom or a methyl group.
A ^f11 represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a C 1-18 aliphatic hydrocarbon group which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A ^f13 and A ^f14 represents an aliphatic hydrocarbon group having a fluorine atom. ]

^Examples of the alkanediyl group for A ^f11 include the same groups as the alkanediyl group for A ^f1 .

The aliphatic hydrocarbon group for A ^f13 includes either a chain or 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.
The aliphatic hydrocarbon group which may have a fluorine atom for A ^f13 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain aliphatic hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; difluoromethylene group, perfluoroethylene Groups, perfluoroalkanediyl groups such as perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantanediyl group, a norbornanediyl group, a perfluoroadamantanediyl group, and the like.

As the aliphatic hydrocarbon group for A ^f14 , either a linear or cyclic group and an aliphatic hydrocarbon group in which these are combined are included. 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 fluorine atom for A ^f14 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Examples of the chain aliphatic hydrocarbon group which may have a fluorine atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl 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, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group and pentyl group, hexyl group, perfluorohexyl group, A heptyl group, a perfluoro heptyl group, an octyl group, a perfluorooctyl group, etc. are mentioned.
Etc.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, and a perfluoroadamantylmethyl group.

In the formula ^(a4-3), examples of ^{A f11,} ethylene group is preferable.
The aliphatic hydrocarbon group for A ^f13 preferably has 1 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms.
The aliphatic hydrocarbon group for A ^f14 preferably has 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. Among them, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
Note that in at least one of A ^f13 and A ^f14 , the aliphatic hydrocarbon group preferably has a fluorine atom, and particularly preferably A ^f13 is a perfluoroaliphatic hydrocarbon group.

Examples of the monomer for deriving the structural unit represented by formula (a4-2) include monomers represented by formula (a4-1-1) to formula (a4-1-22), respectively.

Examples of the monomer for deriving the structural unit represented by formula (a4-3) include monomers represented by formula (a4-1′-1) to formula (a4-1′-22), respectively.

［式（ａ４−４）中、
Ｒ^f21は、水素原子又はメチル基を表す。
Ａ^f21は、−（ＣＨ_２）_ｊ１−、−（ＣＨ_２）_ｊ２−Ｏ−（ＣＨ_２）_ｊ３−又は−（ＣＨ_２）_ｊ４−ＣＯ−Ｏ−（ＣＨ_２）_ｊ５−を表す。
ｊ１〜ｊ５は、それぞれ独立に、１〜６の整数を表す。
Ｒ^f22は、フッ素原子を有する炭素数１〜１０の炭化水素基を表す。］ Examples of the structural unit (a4) include a structural unit represented by the formula (a4-4).

[In the formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents — (CH ₂ ) _j1 —, — (CH ₂ ) _j2 —O— (CH ₂ ) _j3 — or — (CH ₂ ) _j4 —CO—O— (CH ₂ ) _j5 —.
j1 to j5 each independently represents an integer of 1 to 6.
R ^f22 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

^Examples of the hydrocarbon group having a fluorine atom of R ^f22 include the same hydrocarbon groups as R ^f2 in formula (a4-2). R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, more preferably a C 1-10 alkyl group having a fluorine atom. Preferably, the C1-C6 alkyl group which has a fluorine atom is further more preferable.

In Formula (a4-4), as A ^f21 , — (CH ₂ ) _j1 — is preferable, an ethylene group or a methylene group is more preferable, and a methylene group is further preferable.

Examples of the monomer for deriving the structural unit represented by the formula (a4-4) include the following monomers.

  When resin (A) has structural unit (a4), 1-20 mol% is preferable with respect to all the structural units of resin (A), and, as for those total content, 2-15 mol% is more preferable 3 to 10 mol% is more preferable.

  The resin (A) may further have a structural unit other than the above-described structural unit, and examples of such a structural unit include structural units well known in the art.

  It is preferable that the resin (A) has a characteristic that it is decomposed by the action of an acid and the solubility in butyl acetate or 2-heptanone is reduced. Therefore, the resin (A) is preferably a resin containing the structural unit (I) and the structural unit (a1), and a resin comprising the structural unit (I), the structural unit (a1), and the structural unit (s), that is, a monomer ( A copolymer of I ′), monomer (a1) and monomer (s) is more preferred.

Resin (A) is composed of structural unit (I) (hereinafter “(I)”), structural unit (a1) (hereinafter “(a1)”), and structural unit (s) (hereinafter “(s)”). In the case of a resin, these constituent ratios are preferably
(I): 1 to 50 mol%
(A1): 20 to 60 mol%
(S): 30 to 70 mol%
And more preferably
(I): 3 to 40 mol%
(A1): 28 to 55 mol%
(S): 32-65 mol%
And more preferably
(I): 5-35 mol%
(A1): 28-50 mol%
(S): 37-65 mol%
It is.

When the resin (A) is a resin composed of the structural unit (I), the structural unit (a1), the structural unit (a2), and the structural unit (a3), these constituent ratios are preferably
(I): 1 to 50 mol%
(A1): 20 to 60 mol%
(A2): 1-35 mol%
(A3): 29 to 65 mol%
And more preferably
(I): 3 to 40 mol%
(A1): 28 to 55 mol%
(A2): 2 to 15 mol%
(A3): 30 to 65 mol%
And more preferably
(I): 5-35 mol%
(A1): 28-50 mol%
(A2): 2 to 6 mol%
(A3): 35-60 mol%
It is.

Resin (A) is composed of the structural unit (I), the structural unit (a1), the structural unit (a2) and / or the structural unit (a3), and the structural unit (a4) (hereinafter “(a4)”). These component ratios are preferably
(I): 1 to 50 mol%
(A1): 20 to 60 mol%
(A2) / (a3): 30 to 70 mol%
(A4): 1 to 20 mol%
And more preferably
(I): 3 to 40 mol%
(A1): 25-55 mol%
(A2) / (a3): 35 to 65 mol%
(A4): 2 to 15 mol%
And more preferably
(I): 5-35 mol%
(A1): 25 to 50 mol%
(A2) / (a3): 35 to 65 mol%
(A4): 3 to 10 mol%
It is.

The structural unit (a1) is preferably at least one of the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), more preferably the structural unit (a1- 1).
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably the structural unit (a2-1). The structural unit (a3) is preferably at least one of the structural unit (a3-1) and the structural unit (a3-2).

  The resin (A) may contain a structural unit derived from a monomer having an adamantyl group (particularly the structural unit (a1-1)) in an amount of 15 mol% or more based on the content of the structural unit (a1). preferable. When the content of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

Each structural unit constituting the resin (A) may be contained alone or in combination of two or more, and a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. Can be manufactured by.
The weight average molecular weight of the resin (A) is preferably 2,500 or more (more preferably 3,000 or more, more preferably 4,000 or more), 50,000 or less (more preferably 30,000 or less, and further preferably 15,000 or less). A weight average molecular weight is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography analysis. Detailed analysis conditions for this analysis are described in the Examples of the present application.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). An example of such a resin is a resin composed of only the structural unit (s).
Especially, as resin other than resin (A), resin (henceforth "resin (X)") which has structural unit (a4) is preferable. In the resin (X), the content ratio of the structural unit (a4) is preferably 80 mol% or more, more preferably 85 mol% or more, and still more preferably 90 mol% or more with respect to all the structural units of the resin (X). .
Examples of the structural unit that the resin (X) may further include include a structural unit derived from the structural unit (a3) and other known monomers in the structural unit (a2).
The weight average molecular weight of the resin (X) is preferably 8,000 or more (more preferably 10,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).

  When the resist composition of this invention contains resin (X), the content becomes like this. Preferably it is 1-60 mass parts with respect to 100 mass parts of resin (A), More preferably, it is 3-50 mass parts More preferably, it is 5-40 mass parts, Most preferably, it is 7-30 mass parts.

  The resin content in the resist composition of the present invention is preferably 80% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (D) described later from the total amount of the resist composition. The solid content of the resist composition and the resin content relative to the solid content can be measured, for example, by known analytical means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator is classified into a nonionic type and an ionic type, and any of the acid generators (B) of the resist composition of the present invention may be used. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonates), sulfones (e.g. disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712. A compound capable of generating an acid by radiation described in No. etc. can be used. Moreover, you may use the compound manufactured by the well-known method.

  The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1).

［式（Ｂ１）中、
Ｑ¹及びＱ²は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、置換基を有していてもよい炭素数１〜１７の２価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよく、該飽和炭化水素基に含まれる水素原子は、フッ素原子又はヒドロキシ基で置き換わっていてもよい。
Ｙは、置換基を有していてもよい炭素数１〜１８のアルキル基又は置換基を有していてもよい炭素数３〜１８の脂環式炭化水素基を表し、該アルキル基及び該脂環式炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＳＯ_２−又は−ＣＯ−に置き換わっていてもよい。
Ｚ⁺は、有機カチオンを表す。］

[In the formula (B1),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a C1-C17 divalent saturated hydrocarbon group which may have a substituent, and —CH ₂ — contained in the saturated hydrocarbon group is —O— or —CO—. The hydrogen atom contained in the saturated hydrocarbon group may be replaced with a fluorine atom or a hydroxy group.
Y represents an alkyl group having 1 to 18 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. —CH ₂ — contained in the alicyclic hydrocarbon group may be replaced by —O—, —SO ₂ — or —CO—.
Z ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Can be mentioned.
In formula (B1), Q ¹ and Q ² are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

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

式（ｂ１−１）〜式（ｂ１−８）中、
Ｌ^b2は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b3は、単結合又は炭素数１〜１２の２価の飽和炭化水素基を表す。
Ｌ^b4は、炭素数１〜１３の２価の飽和炭化水素基を表す。但しＬ^b3及びＬ^b4の合計炭素数の上限は１３である。
Ｌ^b５は、単結合又は炭素数１〜１４の２価の飽和炭化水素基を表す。
Ｌ^b６は、炭素数１〜１５の２価の飽和炭化水素基を表す。但しＬ^b5及びＬ^b6の合計炭素数の上限は１５である。
Ｌ^b７は、単結合又は炭素数１〜１５の２価の飽和炭化水素基を表す。
Ｌ^b８は、炭素数１〜１６の２価の飽和炭化水素基を表す。但しＬ^b７及びＬ^b８の合計炭素数の上限は１６である。
Ｌ^b9は、単結合又は炭素数１〜１３の２価の飽和炭化水素基を表す。
Ｌ^b10は、炭素数１〜１４の２価の飽和炭化水素基を表す。但しＬ^b9及びＬ^b10の合計炭素数の上限は１４である。
Ｌ^b11及びＬ^b12は、それぞれ独立に、単結合又は炭素数１〜１１の２価の飽和炭化水素基を表す。
Ｌ^b13は、炭素数１〜１２の２価の飽和炭化水素基を表す。但しＬ^b11、Ｌ^b12及びＬ^b13の合計炭素数の上限は１２である。
Ｌ^b14及びＬ^b15は、それぞれ独立に、単結合又は炭素数１〜１３の２価の飽和炭化水素基を表す。
Ｌ^b16は、炭素数１〜１４の２価の飽和炭化水素基を表す。但しＬ^b14、Ｌ^b15及びＬ^b16の合計炭素数の上限は１４である。
Ｌ^b17は、それぞれ独立に、単結合又は炭素数１〜１１の２価の飽和炭化水素基を表す。
Ｌ^b18及びＬ^b19は、炭素数１〜１２の２価の飽和炭化水素基を表す。但しＬ^b17、Ｌ^b18及びＬ^b19の合計炭素数の上限は１１である。
Ｌ^b1は、好ましくは式（ｂ１−１）〜式（ｂ１−４）及び式（ｂ１−８）のいずれかで表される基であり、さらに好ましくは式（ｂ１−１）、式（ｂ１−３）又は式（ｂ１−８）で表される基である。 Specific examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include any of the formulas (b1-1) to (b1-8) The group represented by these is mentioned. In addition, Formula (b1-1)-Formula (b1-8) have described the right and left according to Formula (B1), and among two bonds represented by *, C (Q ¹ ) Combined with (Q ² ) and combined with Y on the right side. The same applies to specific examples of formula (b1-1) to formula (b1-8) shown below.

In formula (b1-1) to formula (b1-8),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. However, the upper limit of the total carbon number of L ^b3 and L ^b4 is 13.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b6 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. However, the upper limit of the total carbon number of L ^b5 and L ^b6 is 15.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b8 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. However, the upper limit of the total carbon number of L ^b7 and L ^b8 is 16.
L ^b9 represents a single bond or a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b10 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b9 and L ^b10 is 14.
L ^b11 and L ^b12 each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b11 , L ^b12 and L ^b13 is 12.
L ^b14 and L ^b15 each independently represent a single bond or a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. However, the upper limit of the total carbon number of L ^b14 , L ^b15 and L ^b16 is 14.
L ^b17 each independently represents a single bond or a divalent saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b18 and L ^b19 represent a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. However, the upper limit of the total carbon number of L ^b17 , L ^b18 and L ^b19 is 11.
L ^b1 is preferably a group represented by any one of formula (b1-1) to formula (b1-4) and formula (b1-8), more preferably formula (b1-1) and formula (b1). -3) or a group represented by formula (b1-8).

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.

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

Examples of the substituent that the divalent saturated hydrocarbon group of L ^b1 may have include a halogen atom (preferably a fluorine atom), a hydroxy group, and the like. Examples of the group in which a hydrogen atom is substituted with a fluorine atom or a hydroxy group include the following divalent groups.

  Examples of the alkyl group for Y include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like, and preferably an alkyl group having 1 to 6 carbon atoms. .

Examples of the alicyclic hydrocarbon group for Y include groups represented by formulas (Y1) to (Y11). Examples of the group in which —CH ₂ — contained in the alicyclic hydrocarbon group is replaced by —O—, —SO ₂ — or —CO— are represented by formulas (Y12) to (Y26). Group to be used.

  The alicyclic hydrocarbon group of Y is preferably a group represented by any one of formulas (Y1) to (Y19), more preferably formula (Y11), formula (Y14), formula (Y15) or It is group represented by a formula (Y19), More preferably, it is group represented by a formula (Y11) or a formula (Y14).

Examples of the substituent for the alkyl group of Y include, for example, a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, or — (CH _{2) j2 -O-CO-R} b1 group (wherein, R ^b1 represents an alkyl group having 1 to 16 carbon atoms, an aromatic alicyclic hydrocarbon group or a C6-18 3 to 16 carbon atoms carbide Represents a hydrogen group, j2 represents an integer of 0 to 4, and the like.
Examples of the substituent for the alicyclic hydrocarbon group of Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and an aliphatic group having 3 to 16 carbon atoms. A cyclic hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or- (CH ₂ ) _{j 2} —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or an aromatic group having 6 to 18 carbon atoms) Represents a group hydrocarbon group, j2 represents an integer of 0 to 4, and the like.

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

Examples of Y include the following.

In addition, when Y is an alkyl group and L ^b1 is a linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated hydrocarbon group is at the bonding position with Y. CH ₂ — is preferably replaced by —O— or —CO—. In this case, —CH ₂ — contained in the alkyl group of Y is not replaced with —O— or —CO—. The same applies when a hydrogen atom contained in the alkyl group of Y and / or the divalent linear or branched saturated hydrocarbon group of L ^b1 is substituted with a substituent.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and is included in these groups. more -CH ₂ - may be replaced by -CO-. Y is particularly preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group.

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

Examples of the organic cation of Z ⁺ include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation, and preferably organic sulfonium cation or organic iodonium cation. More preferably an arylsulfonium cation.
Z ⁺ in formula (B1) is preferably a cation represented by any one of formula (b2-1) to formula (b2-4) [hereinafter referred to as “cation (b2-1)” or the like depending on the formula number, etc. There is a case. ].

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon The hydrogen atom contained in the 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, and the hydrogen atom contained in the aromatic hydrocarbon group The atom may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with the sulfur atom to which they are bonded.

R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.

R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) with the sulfur atom to which they are bonded. —CH ₂ — contained in the ring may be replaced by —O—, —SO— or —CO—.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the aliphatic hydrocarbon group includes The hydrogen atom contained may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) together with —CH—CO— to which they are bonded. —CH ₂ — contained in the ring may be replaced by —O—, —SO— or —CO—.

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

特に、Ｒ^b4〜Ｒ^b6の脂環式炭化水素基は、好ましくは炭素数３〜１８である。Ｒ^b9〜Ｒ^b11の脂環式炭化水素基は、好ましくは炭素数３〜１８、より好ましくは炭素数４〜１２である。 Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. And the like. In particular, the aliphatic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms.
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 includes the carbon number of the alkyl group, and is preferably 20 or less. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

In particular, the alicyclic hydrocarbon group of R ^{b4 to} R ^b6 preferably has 3 to 18 carbon atoms. The alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

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

Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantyl group. Examples thereof include a phenyl group, a biphenylyl group, a naphthyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. The aromatic hydrocarbon group also includes an aryl group in which an aromatic hydrocarbon group or an alicyclic hydrocarbon group is bonded to an aromatic ring. In this case, the number of carbon atoms is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. The number of carbons in the group can also be counted. The aromatic hydrocarbon group of R ^{b4 to} R ^b6 preferably has 6 to 224 carbon atoms.
Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
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.

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

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

Examples of the ring formed together with the sulfur atom to which R ^b9 and R ^b10 are bonded include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium. A ring etc. are mentioned.
Examples of the ring formed with —CH—CO— in which R ^b11 and R ^b12 are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

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

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

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

Among the cation (b2-1) to cation (b2-4), the cation (b2-1) is preferable, more preferably a cation represented by the formula (b2-1-1) (hereinafter referred to as “cation ( more preferably triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0), diphenyltolylsulfonium cation (formula In (b2-1-1), v2 = w2 = 0, x2 = 1, and R ^b21 is a methyl group.) Or a tolylsulfonium cation (in the formula (b2-1-1), v2 = w2 = x2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl groups.).

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

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

Among them, R ^b19 , R ^b20 and R ^b21 are preferably each independently a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is.

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

  The salt represented by the formula (B1) is a combination of the above-described sulfonate anion and the above-described organic cation. These can be arbitrarily combined, and preferably a combination of any one of anion (b1-1-1) to anion (b1-1-9) and a cation (b2-1-1), and an anion (b1-1) -3) to an anion (b1-1-5) and a combination of a cation (b2-3).

  As the acid generator (B1), those represented by the formulas (B1-1) to (B1-24) are more preferable, and the formula (B1-1) and the formula (B) containing a triarylsulfonium cation are preferable. B1-2), formula (B1-3), formula (B1-5), formula (B1-6), formula (B1-7), formula (B1-11), formula (B1-12), formula (B1) -13), formula (B1-14), formula (B1-13), formula (B1-23) and formula (B1-24), and formula (B1-20), formula (B1-21) or formula (B1) Those represented by −22) are particularly preferred.

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

<Solvent (E)>
The content of the solvent (E) is, for example, 90% by mass or more in the resist composition, preferably 92% by mass or more, more preferably 94% by mass or more, for example 99.9% by mass or less, preferably 99% by mass or less. It is. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

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

［式（ＩＩ）中、
Ｒ^Ｄ１及びＲ^Ｄ２は、それぞれ独立に、炭素数１〜１２の炭化水素基、炭素数１〜６のアルコキシ基、炭素数２〜７のアシル基、炭素数２〜７のアシルオキシ基、炭素数２〜７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０〜４の整数を表し、ｍ’が２以上の場合、複数のＲ^Ｄ１は同一又は相異なり、ｎが２以上の場合、複数のＲ^Ｄ２は同一又は相異なる。］ <Compound (II)>
Compound (II) is represented by Formula (II).

[In the formula (II),
R ^D1 and R ^D2 are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, or a carbon number Represents 2 to 7 alkoxycarbonyl groups, nitro groups or halogen atoms.
m ′ and n ′ each independently represents an integer of 0 to 4, and when m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n is 2 or more, the plurality of R ^D2 are the same. Or different. ]

In the compound (II), examples of the hydrocarbon group of R ^D1 and R ^D2 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof.
Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, and nonyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be either saturated or unsaturated. Examples thereof include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, and cyclododecyl group, norbornyl group, adamantyl group, and the like.
As aromatic hydrocarbon group, phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group , Aryl groups such as mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
These combinations include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, aralkyl groups (eg, phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1- Phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl Group) and the like.

Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the acyl group include an acetyl group, a propanoyl group, a benzoyl group, and a cyclohexanecarbonyl group.
Examples of the acyloxy group include a group in which an oxy group (—O—) is bonded to the acyl group.
Examples of the alkoxycarbonyl group include a group in which a carbonyl group (—CO—) is bonded to the above alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

R ^D1 and R ^D2 in formula (II) are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 2 to 4 carbon atoms. An acyl group, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom is preferable.
m ′ and n ′ are each independently preferably an integer of 0 to 2, and more preferably 0. When m is 2 or more, the plurality of R ^D1 are the same or different, and when n is 2 or more, the plurality of R ^D2 are the same or different.

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

  Compound (II) can be produced by the method described in “Tetrahedron Vol. 45, No. 19, p6281-6296”. Compound (II) may be a commercially available compound.

  0.01-12 mass parts is preferable with respect to 100 mass parts of resin (A), as for content of compound (II), 0.03-10 mass parts is more preferable, and 0.06-6 mass parts is further. preferable. The content ratio of compound (II) is preferably 0.01 to 10% by mass, more preferably 0.03 to 8% by mass, and still more preferably 0% with respect to the solid content of the resist composition. 0.05 to 5% by mass.

<Basic compound (C)>
The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Examples of 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。］ The compound represented by the formula (C1) is preferably a compound represented by the formula (C1-1).

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

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

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

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

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

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

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.

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

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

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

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

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

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

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do. In the present specification, the irradiation of these radiations may be collectively referred to as “exposure”. At the time of exposure, exposure is usually performed through a mask corresponding to a required pattern. When the exposure light source is an electron beam, it may be drawn directly without using a mask.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection reaction of the resin (A). The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., for example, and the development time is preferably 5 to 300 seconds, for example.

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

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

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

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

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

式（Ｉ１−ａ）で表される化合物４０部、式（Ｉ１−ｂ）で表される化合物１０７．５５部及びクロロホルム２００部を仕込み、２３℃で３０分間攪拌混合した後、式（Ｉ１−ｃ）で表される化合物２．２５部を添加した後、モレキュラーシーブ（３Ａ）１４部存在下、６０℃で１８時間還流攪拌した。２３℃まで冷却した後、得られた反応物に、１０％炭酸水素ナトリウム水溶液４０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、イオン交換水４０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後、濃縮残渣に、ｎ−ヘプタン２００部を仕込み、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｉ１−ｄ）で表される化合物３２．３８部を得た。

式（Ｉ１−ｄ）で表される化合物１５部、式（Ｉ１−ｅ）で表される化合物１０．９３部、クロロホルム７５部及びトリエチルアミン６．６５部を仕込み、２３℃で３０分間攪拌混合した後、０℃に冷却した。得られた混合物に、式（Ｉ１−ｆ）で表される化合物１７．４５部を添加した後、２３℃で１時間攪拌した。得られた反応物に、ｔｅｒｔ−ブチルメチルエーテル２８０部及び５％シュウ酸水溶液１３０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、イオン交換水１１０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液５０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、イオン交換水１１０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（Ｉ´−１）で表される化合物１１．３７部を得た。
ＭＳ（質量分析）：３２６．１（分子イオンピーク） Synthesis Example 1 [Synthesis of Compound Represented by Formula (I′-1)]

40 parts of the compound represented by the formula (I1-a), 107.55 parts of the compound represented by the formula (I1-b), and 200 parts of chloroform were charged and stirred and mixed at 23 ° C. for 30 minutes. After adding 2.25 parts of the compound represented by c), the mixture was stirred under reflux at 60 ° C. for 18 hours in the presence of 14 parts of molecular sieve (3A). After cooling to 23 ° C., 40 parts of a 10% aqueous sodium hydrogen carbonate solution was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes. The organic layer recovered by standing and separating was charged with 40 parts of ion-exchanged water and stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such washing operation was repeated 5 times. After concentration of the organic layer after washing with water, 200 parts of n-heptane was added to the concentrated residue, stirred at 23 ° C. for 30 minutes, and then filtered to obtain a compound 32.38 represented by the formula (I1-d). Got a part.

15 parts of the compound represented by the formula (I1-d), 10.93 parts of the compound represented by the formula (I1-e), 75 parts of chloroform and 6.65 parts of triethylamine were charged and mixed with stirring at 23 ° C. for 30 minutes. Thereafter, it was cooled to 0 ° C. After adding 17.45 parts of a compound represented by the formula (I1-f) to the obtained mixture, the mixture was stirred at 23 ° C. for 1 hour. To the obtained reaction product, 280 parts of tert-butyl methyl ether and 130 parts of 5% oxalic acid aqueous solution were added and stirred at 23 ° C. for 30 minutes. 110 parts of ion-exchanged water was added to the organic layer collected by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. To the collected organic layer, 50 parts of a 10% aqueous potassium carbonate solution was added and stirred at 23 ° C. for 30 minutes. 110 parts of ion-exchanged water was added to the organic layer collected by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated to obtain 11.37 parts of a compound represented by the formula (I′-1).
MS (mass spectrometry): 326.1 (molecular ion peak)

式（Ｉ２−ａ）で表される化合物４０部、式（Ｉ２−ｂ）で表される化合物９７．０４部及びクロロホルム２００部を仕込み、２３℃で３０分間攪拌混合した後、式（Ｉ２−ｃ）で表される化合物２．２５部を添加した後、モレキュラーシーブ（３Ａ）１４部存在下、６０℃で１８時間還流攪拌した。２３℃まで冷却した後、得られた反応物に、１０％炭酸水素ナトリウム水溶液４０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、イオン交換水４０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後、濃縮残渣に、ｎ−ヘプタン２００部を仕込み、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｉ２−ｄ）で表される化合物２８．４６部を得た。

式（Ｉ２−ｄ）で表される化合物１４部、式（Ｉ２−ｅ）で表される化合物１０．９３部、クロロホルム７５部及びトリエチルアミン６．６５部を仕込み、２３℃で３０分間攪拌混合した後、０℃に冷却した。得られた混合物に、式（Ｉ２−ｆ）で表される化合物１７．４５部を添加した後、２３℃で１時間攪拌した。得られた反応物に、ｔｅｒｔ−ブチルメチルエーテル２８０部及び５％シュウ酸水溶液１３０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、イオン交換水１００部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液５０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、イオン交換水１００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（Ｉ´−２）で表される化合物９．８５部を得た。
ＭＳ（質量分析）：３１２．１（分子イオンピーク） Synthesis Example 2 [Synthesis of Compound Represented by Formula (I′-2)]

40 parts of the compound represented by the formula (I2-a), 97.04 parts of the compound represented by the formula (I2-b), and 200 parts of chloroform were charged and stirred and mixed at 23 ° C. for 30 minutes. After adding 2.25 parts of the compound represented by c), the mixture was stirred under reflux at 60 ° C. for 18 hours in the presence of 14 parts of molecular sieve (3A). After cooling to 23 ° C., 40 parts of a 10% aqueous sodium hydrogen carbonate solution was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes. The organic layer recovered by standing and separating was charged with 40 parts of ion-exchanged water and stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such washing operation was repeated 5 times. After the organic layer after washing with water was concentrated, 200 parts of n-heptane was added to the concentrated residue, stirred at 23 ° C. for 30 minutes, and then filtered to obtain compound 28.46 represented by formula (I2-d). Got a part.

14 parts of the compound represented by the formula (I2-d), 10.93 parts of the compound represented by the formula (I2-e), 75 parts of chloroform and 6.65 parts of triethylamine were charged and mixed with stirring at 23 ° C. for 30 minutes. Thereafter, it was cooled to 0 ° C. After adding 17.45 parts of the compound represented by the formula (I2-f) to the obtained mixture, the mixture was stirred at 23 ° C. for 1 hour. To the obtained reaction product, 280 parts of tert-butyl methyl ether and 130 parts of 5% oxalic acid aqueous solution were added and stirred at 23 ° C. for 30 minutes. 100 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes. To the collected organic layer, 50 parts of a 10% aqueous potassium carbonate solution was added and stirred at 23 ° C. for 30 minutes. 100 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated to obtain 9.85 parts of a compound represented by the formula (I′-2).
MS (mass spectrometry): 312.1 (molecular ion peak)

式（Ｉ３−ａ）で表される化合物４部、式（Ｉ３−ｂ）で表される化合物１４．６３部及びクロロホルム２０部を仕込み、２３℃で３０分間攪拌混合した後、式（Ｉ３−ｃ）で表される化合物０．２３部を添加した後、モレキュラーシーブ（３Ａ）１．４部存在下、６０℃で２４時間還流攪拌した。２３℃まで冷却した後、得られた反応物に、１０％炭酸水素ナトリウム水溶液５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、イオン交換水１０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後、濃縮残渣に、ｎ−ヘプタン２０部及びｔｅｒｔ−ブチルメチルエーテル１０部を仕込み、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｉ３−ｄ）で表される化合物２．８８部を得た。

式（Ｉ３−ｄ）で表される化合物１．８６部、式（Ｉ３−ｅ）で表される化合物１．０９部、クロロホルム１０部及びトリエチルアミン０．６７部を仕込み、２３℃で３０分間攪拌混合した後、０℃に冷却した。得られた混合物に、式（Ｉ３−ｆ）で表される化合物１．７５部を添加した後、２３℃で１時間攪拌した。得られた反応物に、ｔｅｒｔ−ブチルメチルエーテル３０部及び５％シュウ酸水溶液１５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、イオン交換水１０部を仕込み２３℃で３０分間攪拌し、静置、分液することにより有機層を水洗した。回収された有機層に、１０％炭酸カリウム水溶液５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、イオン交換水１０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（Ｉ´−３）で表される化合物１．０３部を得た。
ＭＳ（質量分析）：３７８．２（分子イオンピーク） Synthesis Example 3 [Synthesis of Compound Represented by Formula (I′-3)]

After charging 4 parts of the compound represented by the formula (I3-a), 14.63 parts of the compound represented by the formula (I3-b) and 20 parts of chloroform, and stirring and mixing at 23 ° C. for 30 minutes, the compound of the formula (I3- After adding 0.23 parts of the compound represented by c), the mixture was refluxed and stirred at 60 ° C. for 24 hours in the presence of 1.4 parts of molecular sieve (3A). After cooling to 23 ° C., 5 parts of a 10% aqueous sodium hydrogen carbonate solution was added to the obtained reaction product, and the mixture was stirred at 23 ° C. for 30 minutes. 10 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated, and then the concentrated residue was charged with 20 parts of n-heptane and 10 parts of tert-butyl methyl ether, stirred at 23 ° C. for 30 minutes, and then filtered to obtain the formula (I3-d). 2.88 parts of a compound represented by the formula:

1.86 parts of a compound represented by the formula (I3-d), 1.09 parts of a compound represented by the formula (I3-e), 10 parts of chloroform and 0.67 part of triethylamine were charged and stirred at 23 ° C. for 30 minutes. After mixing, it was cooled to 0 ° C. To the obtained mixture, 1.75 parts of the compound represented by the formula (I3-f) was added, followed by stirring at 23 ° C. for 1 hour. To the obtained reaction product, 30 parts of tert-butyl methyl ether and 15 parts of 5% oxalic acid aqueous solution were added and stirred at 23 ° C. for 30 minutes. 10 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. To the collected organic layer, 5 parts of a 10% aqueous potassium carbonate solution was added and stirred at 23 ° C. for 30 minutes. 10 parts of ion-exchanged water was added to the organic layer recovered by standing and separating, and the mixture was stirred at 23 ° C. for 30 minutes, and the organic layer was washed with water by standing and separating. Such washing operation was repeated 5 times. The organic layer after washing with water was concentrated to obtain 1.03 parts of a compound represented by the formula (I′-3).
MS (mass spectrometry): 378.2 (molecular ion peak)

以下、これらのモノマーを式番号に応じて「モノマー（ａ１−１−２）」等という。 Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below.

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

Synthesis Example 4 [Synthesis of Resin A1]
As the monomer, monomer (a1-1-3), monomer (I′-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1) were used, and The molar ratio [monomer (a1-1-3): monomer (I′-1): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] is 45: 14: 2.5: 22: 16.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was stirred in methanol and filtered to obtain a resin A1 (copolymer) having a weight average molecular weight of 9.0 × 10 ^{3 in} a yield of 73%. This resin A1 has the following structural units.

Synthesis Example 5 [Synthesis of Resin A2]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) and monomer ( I′-1) and its molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-2-3): monomer ( a3-1-1): monomer (I′-1)] is mixed to 32: 7: 8: 13: 33: 7, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount is added. In addition, a solution was obtained. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice, and the weight average molecular weight was 8. 5 × 10 ³ resin A5 (copolymer) was obtained with a yield of 70%. This resin A2 has the following structural units.

Synthesis Example 6 [Synthesis of Resin A3]
As the monomer, monomer (a1-1-3), monomer (I′-12), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1) were used, The molar ratio [monomer (a1-1-3): monomer (I′-12): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] is 45: 14: 2.5: 22: 16.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was stirred in methanol and filtered to obtain a resin A3 (copolymer) having a weight average molecular weight of 9.4 × 10 ^{3 in} a yield of 71%. This resin A3 has the following structural units.

Synthesis Example 7 [Synthesis of Resin A4]
As the monomer, monomer (a1-1-3), monomer (I′-2), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1) were used, The molar ratio [monomer (a1-1-3): monomer (I′-2): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] is 45: 14: 2.5: 22: 16.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was stirred in methanol and filtered to obtain Resin A4 (copolymer) having a weight average molecular weight of 8.2 × 10 ^{3 in} a yield of 68%. This resin A4 has the following structural units.

Synthesis Example 8 [Synthesis of Resin A5]
As the monomer, monomer (a1-1-3), monomer (I′-3), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1) were used, and The molar ratio [monomer (a1-1-3): monomer (I′-3): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] is 45: 14: 2.5: 22: 16.5 was mixed, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained was stirred in methanol and filtered to obtain Resin A5 (copolymer) having a weight average molecular weight of 7.8 × 10 ^{3 in} a yield of 56%. This resin A5 has the following structural units.

Synthesis Example 9: [Synthesis of Resin H1]
As the monomer, monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-2-3), monomer (a3-1-1) and monomer ( IX) and its molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-2-3): monomer (a3-1) -1): monomer (IX)] was mixed to 32: 7: 8: 13: 33: 7, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators are added to the solution, respectively, with respect to the total monomer amount, and these are heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin thus obtained is again dissolved in dioxane, and a solution obtained by pouring the solution into a methanol / water mixed solvent is precipitated twice, and the resin is filtered twice to perform a reprecipitation operation twice. 7 × 10 ³ resin H1 (copolymer) was obtained in a yield of 72%. This resin H1 has the following structural units.

Synthesis Example 10 [Synthesis of Resin X1]
Monomer (a4-1-7) was used as a monomer, and 1.5 mass times dioxane of the total monomer amount was added to prepare a solution. Azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the solution in an amount of 0.7 mol% and 2.1 mol%, respectively, with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered.
The resin thus obtained was dissolved again in dioxane, and the solution obtained by pouring the solution into a methanol / water mixed solvent was precipitated twice, and the resin was filtered twice to perform the reprecipitation operation twice. 8 × 10 ⁴ resin X1 was obtained with a yield of 77%. This resin X1 has the following structural units.

式（Ｂ１−５−ａ）で表される塩５０．４９部及びクロロホルム２５２．４４部を反応器に仕込み、２３℃で３０分間攪拌した後、式（Ｂ１−５−ｂ）で表される化合物１６．２７部を滴下し、２３℃で１時間攪拌することにより、式（Ｂ１−５−ｃ）で表される塩を含む溶液を得た。得られた式（Ｂ１−５−ｃ）で表される塩を含む溶液に、式（Ｂ１−５−ｄ）で表される塩４８．８０部及びイオン交換水８４．１５部を添加し、２３℃で１２時間攪拌した。得られた反応液が２層に分離していたので、クロロホルム層を分液して取り出し、更に、該クロロホルム層にイオン交換水８４．１５部を添加し、水洗した。この操作を５回繰り返した。得られたクロロホルム層に、活性炭３．８８部を添加攪拌した後、ろ過した。回収されたろ液を濃縮し、得られた残渣に、アセトニトリル１２５．８７部を添加攪拌後、濃縮した。得られた残渣に、アセトニトリル２０．６２部及びｔｅｒｔ−ブチルメチルエーテル３０９．３０部を加えて２３℃で３０分間攪拌した後、上澄み液を除去した後、濃縮した。得られた残渣に、ｎ−ヘプタン２００部を添加、２３℃で３０分間攪拌した後、ろ過することにより、式（Ｂ１−５）で表される塩６１．５４部を得た。
ＭＡＳＳ（ＥＳＩ（＋）Ｓｐｅｃｔｒｕｍ）：Ｍ^＋ ３７５．２
ＭＡＳＳ（ＥＳＩ（−）Ｓｐｅｃｔｒｕｍ）：Ｍ⁻ ３３９．１ Synthesis Example 11 [Synthesis of salt represented by formula (B1-5)]

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

式（Ｂ１−２３−ａ）で表される化合物５．００部及びジメチルホルムアミド２５部を反応器に仕込み、２３℃で３０分間攪拌した後、トリエチルアミン３．８７部を滴下し、さらに、２３℃で３０分間攪拌した。得られた混合物に、式（Ｂ１−２３−ｂ）で表される化合物６．１４部をジメチルホルムアミド６．１４部に溶解した溶液を３０分かけて滴下し、さらに、２３℃で２時間攪拌した。得られた反応液に、イオン交換水２５部及び酢酸エチル１５０部を加え、２３℃で３０分間攪拌した後、分液し、有機層を回収した。回収された有機層に、イオン交換水７５部を仕込み２３℃で３０分間攪拌した後、分液し、有機層を回収した。この水洗の操作をさらに５回行った。得られた有機層を濃縮し、得られた濃縮物に、ｎ−ヘプタン９２．２０部を添加して攪拌した後、ろ過することにより、式（Ｂ１−２３−ｃ）で表される化合物２．６９部を得た。

Synthesis Example 12 [Synthesis of salt represented by formula (B1-23)]

5.00 parts of the compound represented by the formula (B1-23-a) and 25 parts of dimethylformamide were charged into a reactor and stirred at 23 ° C. for 30 minutes. Then, 3.87 parts of triethylamine was added dropwise, and further 23 ° C. For 30 minutes. A solution obtained by dissolving 6.14 parts of the compound represented by the formula (B1-23-b) in 6.14 parts of dimethylformamide was added dropwise to the obtained mixture over 30 minutes, and the mixture was further stirred at 23 ° C. for 2 hours. did. 25 parts of ion-exchanged water and 150 parts of ethyl acetate were added to the resulting reaction solution, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to recover the organic layer. The recovered organic layer was charged with 75 parts of ion-exchanged water and stirred at 23 ° C. for 30 minutes, followed by liquid separation to recover the organic layer. This washing operation was further performed 5 times. The obtained organic layer is concentrated, and 92.20 parts of n-heptane is added to the resulting concentrate, followed by stirring, followed by filtration to obtain a compound 2 represented by the formula (B1-23-c). .69 parts were obtained.

A salt represented by the formula (B1-23-d) was synthesized by the method described in JP 2008-127367 A.
2.99 parts of a salt represented by the formula (B1-23-d) and 15.00 parts of acetonitrile are charged into a reactor, stirred at 23 ° C. for 30 minutes, and then represented by the formula (B1-23-e). 1.30 parts of compound was charged and stirred at 70 ° C. for 2 hours. The obtained reaction product was cooled to 23 ° C. and then filtered to obtain a solution containing a compound represented by the formula (B1-23-f). A solution containing the compound represented by formula (B1-23-f) was charged with a solution prepared by dissolving 2.12 parts of the compound represented by formula (B1-23-c) in 6.36 parts of chloroform, For 23 hours. The obtained reaction product was concentrated, and 60 parts of chloroform and 30 parts of a 2% oxalic acid aqueous solution were added to the resulting concentrate, followed by stirring and liquid separation. This oxalic acid aqueous solution was washed twice. To the recovered organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred and separated. Water washing was performed 5 times. The obtained organic layer was concentrated, and the resulting concentrate was dissolved in 30 parts of acetonitrile and then concentrated. To the obtained concentrate, 50 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile, and concentrated to obtain 3.46 parts of the salt represented by the formula (B1-23).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 517.2

Examples 1-8 and Comparative Example 1
<Preparation of resist composition>
Each of the components shown below was dissolved in a solvent in parts by mass shown in Table 1, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

Ｂ１−５：式（Ｂ１−５）で表される塩

Ｂ１−２３：式（Ｂ１−２３）で表される塩

<Resin>
A1 to A5, H1, X1: Resin A1 to Resin A5, Resin H1, Resin X1
<Acid generator>
B1-3: synthesized according to the example of JP 2010-152341 A

B1-5: salt represented by formula (B1-5)

B1-23: salt represented by formula (B1-23)

<Compound (II)>
II1: (Tokyo Chemical Industry Co., Ltd.)

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

Examples 1-7 and Comparative Example 1
<Manufacture of negative resist pattern>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer, and baked under the conditions of 205 ° C. and 60 seconds, whereby an organic layer having a thickness of 78 nm was obtained. An antireflection film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After coating, the composition layer was formed on the silicon wafer by pre-baking on a direct hot plate for 60 seconds at the temperature described in the “PB” column of Table 1. An ArF excimer laser stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, Annular σ = 0.9 / 0.7 XY polarized light) on the composition layer formed on the silicon wafer, Using a mask for forming a line-and-space pattern (pitch 90 nm / line width 45 nm), exposure was carried out while changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium. After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

  In the obtained resist pattern, the exposure amount at which the line width of the trench pattern was 40 nm was defined as effective sensitivity.

<Focus margin evaluation (DOF)>
A negative resist pattern was manufactured in the same manner as described above except that the exposure was performed while changing the focus stepwise in terms of effective sensitivity. In the obtained resist pattern, the focus range in which the width of the trench pattern is 40 nm ± 5% (38 to 42 nm) was defined as DOF (nm). The results are shown in Table 2.

  From the above results, it can be seen that the resist composition of the present invention can produce a negative resist pattern with an excellent focus margin.

  The resist composition of the present invention is suitable for semiconductor microfabrication because the resulting resist pattern has an excellent focus margin, and is industrially useful.

Claims (4)

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

[In the formula (I),
R ¹ represents a C 1-6 alkyl group, a hydrogen atom or a halogen atom which may have a halogen atom.
R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or together form a ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded.
L ¹ represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ] The resist composition according to claim 1, wherein R ² and R ^{3 in} formula (I) together form a ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded. (1) The process of apply | coating the resist composition of Claim 1 or 2 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:   A resin having a structural unit represented by the formula (I) and a structural unit of an acid labile group.