JP2014115627A - Resist composition and resist pattern production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition that enables production of a resist pattern with excellent line edge roughness (LER).SOLUTION: A resist composition contains a resin that includes a structural unit represented by formula (I) and a (meth) acrylic acid ester structure unit including a 1-20C perfluoroalkyl group and does not include an acid-labile group, a resin that includes a specific structural unit including a sultone ring and a structural unit including an acid-labile group, and an acid generator. In the formula (I), Ris a hydrogen atom or a methyl group, Ris a 3-18C alicyclic hydrocarbon group, and a hydrogen atom included in the alicyclic hydrocarbon group may be substituted with a 1-8C aliphatic hydrocarbon group or a hydroxy group, where a hydrogen atom bonding to a carbon atom at a bonding position to Lis not substituted with a 1-8C aliphatic hydrocarbon group.

Description

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

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

JP 2010-197413 A

  In some cases, a resist pattern formed by a conventional resist composition does not always satisfy the line edge roughness (LER) sufficiently.

［式（Ｉ）中、
Ｒ¹は、水素原子又はメチル基を表す。
Ｒ²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。但し、Ｌ¹との結合位置にある炭素原子に結合する水素原子は、炭素数１〜８の脂肪族炭化水素基で置換されない。
Ｌ¹は、単結合又は炭素数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いてもよい。］

［式（ａ４）中、
Ｒ³は、水素原子又はメチル基を表す。
Ｒ⁴は、炭素数１〜２０のフッ素原子を有する飽和炭化水素基を表す。］

［式（ＩＩ）中、
環Ｔ¹は、置換基を有していてもよい炭素数３〜３４のスルトン環を表す。
Ｚ¹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−１）で表される基を表す。

（式（ａ−１）中、
ｓは０又は１の整数を表す。
Ｘ¹⁰及びＸ¹¹は、それぞれ独立に、酸素原子、イミノ基、カルボニル基、カルボニルオキシ基、オキシカルボニル基、カルボニルイミノ基又はイミノカルボニル基を表す。
Ａ¹⁰、Ａ¹¹及びＡ¹²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２価の脂肪族炭化水素基を表す。ただし、Ａ¹⁰、Ａ¹¹及びＡ¹²の炭素数の合計は７以下である。）
Ｚ²は、単結合又はカルボニル基を表す。
Ｒ⁷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。］
［２］前記式（Ｉ）におけるＲ²が、無置換の炭素数３〜１８の脂環式炭化水素基である［１］記載のレジスト組成物。
［３］式（ａ４）で表される構造単位が、式（ａ４−０）で表される構造単位である［１］又は［２］記載のレジスト組成物。

［式（ａ４−０）中、
Ｒ⁵は、水素原子又はメチル基を表す。
Ｌ⁴は、炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ³は、炭素数１〜８のペルフルオロアルカンジイル基を表す。
Ｒ⁶は、水素原子又はフッ素原子を表す。］
［４］式（Ｉ）で表される構造単位及び式（ａ４）で表される構造単位を有し、かつ、酸不安定基を有さない樹脂中の式（Ｉ）で表される構造単位の含有率は、式（Ｉ）で表される構造単位及び式（ａ４）で表される構造単位を有し、かつ、酸不安定基を有さない樹脂の全構造単位に対して、２５〜７５モル％である［１］〜［３］のいずれかに記載のレジスト組成物。
［５］酸不安定基を有する構造単位が、式（ａ１−１）で表される構造単位及び式（ａ１−２）で表される構造単位からなる群から選ばれる少なくとも一種である［１］〜［４］のいずれか記載のレジスト組成物。

［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。］
［６］（１）［１］〜［５］のいずれか記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥させて組成物層を形成する工程、
（３）組成物層に露光する工程、
（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。 The present invention includes the following inventions.
[1] A resin containing a structural unit represented by formula (I) and a structural unit represented by formula (a4), and having no acid labile group,
A resist composition comprising a resin comprising a structural unit represented by formula (II) and a structural unit having an acid labile group, and an acid generator.

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the bonding position with L ¹ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ¹ represents a single bond or a C 1-18 divalent saturated hydrocarbon group, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

[In the formula (a4),
R ³ represents a hydrogen atom or a methyl group.
R ⁴ represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]

[In the formula (II),
Ring T ¹ represents a sultone ring having 3 to 34 carbon atoms which may have a substituent.
Z ¹ represents an optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-1).

(In the formula (a-1),
s represents an integer of 0 or 1.
X ¹⁰ and X ¹¹ each independently represent an oxygen atom, an imino group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a carbonylimino group or an iminocarbonyl group.
A ¹⁰ , A ¹¹ and A ¹² each independently represent a C 1-5 divalent aliphatic hydrocarbon group which may have a substituent. However, the total number of carbon atoms of A ¹⁰ , A ¹¹ and A ¹² is 7 or less. )
Z ² represents a single bond or a carbonyl group.
R ⁷ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. ]
[2] The resist composition according to [1], wherein R ² in the formula (I) is an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms.
[3] The resist composition according to [1] or [2], wherein the structural unit represented by the formula (a4) is a structural unit represented by the formula (a4-0).

[In the formula (a4-0),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁴ represents an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a C 1-8 perfluoroalkanediyl group.
R ⁶ represents a hydrogen atom or a fluorine atom. ]
[4] A structure represented by the formula (I) in a resin having the structural unit represented by the formula (I) and the structural unit represented by the formula (a4) and having no acid labile group. The content rate of the unit is based on the total structural unit of the resin having the structural unit represented by the formula (I) and the structural unit represented by the formula (a4) and having no acid labile group. The resist composition according to any one of [1] to [3], which is 25 to 75 mol%.
[5] The structural unit having an acid labile group is at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2) [1. ]-[4] The resist composition in any one of.

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

  According to the resist composition of the present invention, an excellent line edge roughness (LER) resist pattern can be produced. In addition, the number of defects in the obtained resist pattern can be reduced.

In the present specification, unless otherwise specified, in the description of the structural formula of a compound, “aliphatic hydrocarbon group” means a linear or branched hydrocarbon group, and “alicyclic hydrocarbon group” means A group obtained by removing a number of hydrogen atoms corresponding to the valence from the ring of an alicyclic hydrocarbon. The “aromatic hydrocarbon group” also includes a group in which a hydrocarbon group is bonded to an aromatic ring. When stereoisomers exist, all stereoisomers are included.
Further, "(meth) acrylic monomer" means at least one monomer having a structure of "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- ". Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

<Resist composition>
The resist composition of the present invention contains a resin (hereinafter sometimes referred to as “resin (A)”) and an acid generator (hereinafter sometimes referred to as “acid generator (B)”).
Here, the resin (A) is
Resin containing the structural unit represented by the formula (I) and the structural unit represented by the formula (a4) and having no acid labile group (hereinafter sometimes referred to as “resin (A1)”) As well as
A resin containing a structural unit represented by the formula (II) and a structural unit having an acid labile group (hereinafter sometimes referred to as “resin (A2)”) is contained.
It is preferable that the resist composition of the present invention further contains a solvent (E).
Further, a basic compound (C) may be contained.
In the present specification, the “acid labile group” is a group having a leaving group and forming a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group by contact with an acid. Means.

<Resin (A)>
The resin (A) contained in the resist composition of the present invention contains the resins (A1) and (A2) described above, and contains resins other than the resins (A1) and (A2) described later. Also good.

［式（Ｉ）中、
Ｒ¹は、水素原子又はメチル基を表す。
Ｒ²は、炭素数３〜１８の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は炭素数１〜８の脂肪族炭化水素基又はヒドロキシ基で置換されていてもよい。但し、Ｌ¹との結合位置にある炭素原子に結合する水素原子は、炭素数１〜８の脂肪族炭化水素基で置換されない。
Ｌ¹は、単結合又は炭素数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いてもよい。］ <Resin (A1)>
Resin (A1) includes a structural unit represented by formula (I) (hereinafter sometimes referred to as “structural unit (I)”) and a structural unit represented by formula (a4) (hereinafter referred to as “structural unit (a4)”). May be included). Further, the resin (A1) will be described later unless it has an acid labile group, that is, unless it contains a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a)”). A structural unit having no acid labile group may be contained.
<Structural unit (I)>
Resin (A1) contains structural unit (I).

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the bonding position with L ¹ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ¹ represents a single bond or a C 1-18 divalent saturated hydrocarbon group, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

The alicyclic hydrocarbon group for R ² may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include alkyl groups such as octyl group and 2-ethylhexyl group.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-hydroxyadamantyl group and a 3-methyladamantyl group.
R ² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ¹ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, preferably a divalent aliphatic saturated hydrocarbon group. .
Examples of the divalent aliphatic saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a 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、カルボニルオキシ基又はオキシカルボニル基を表す。
Ｌ^x1は、炭素数１〜１６の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x2は、単結合又は炭素数１〜１５の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x1及びＬ^x2の合計炭素数は、１６以下である。
式（Ｌ１−２）中、
Ｌ^x3は、炭素数１〜１７の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x4は、単結合又は炭素数１〜１６の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x1及びＬ^x2の合計炭素数は、１７以下である。
式（Ｌ１−３）中、
Ｌ^x5は、炭素数１〜１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^x6及びＬ^x7は、それぞれ独立に、単結合又は炭素数１〜１４の２価の脂肪族飽和炭化水素基を表す。
ただし、Ｌ^x5、Ｌ^x6及びＬ^x7の合計炭素数は、１５以下である。
式（Ｌ１−４）中、
Ｌ^x8及びＬ^x9は、単結合又は炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。
Ｗ^x1は、炭素数３〜１５の２価の脂環式飽和炭化水素基を表す。
ただし、Ｌ^x8、Ｌ^x9及びＷ^x1の合計炭素数は、１５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 groups represented by formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

In formula (L1-1),
X ^x1 represents a carbonyloxy group or an oxycarbonyl group.
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
However, the total carbon number of L ^x1 and L ^x2 is 16 or less.
In formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total carbon number of L ^x1 and L ^x2 is 17 or less.
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6 and L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9 and W ^x1 is 15 or less.

L ^x1 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group, more preferably a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond.
L ^x3 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.
W ^x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

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

As group represented by a formula (L1-2), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-3), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-4), the bivalent group shown below is mentioned, for example.

L ¹ is preferably a single bond or a group represented by the formula (L1-1).

Examples of the structural unit (I) include those listed below and those listed below for the structural unit (a2-1).

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

［式（Ｉ’）中、Ｒ¹、Ｒ²及びＬ¹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 and L ¹ represent the same meaning as described above. ]

Compound (I ′) may be a commercially available product or one produced by a known method. Here, the known method includes, for example, a method of condensing (meth) acrylic acid or a derivative thereof (for example, (meth) acrylic acid chloride etc.) and alcohol (HO-L ¹ -R ² ). . Commercially available products include adamantane-1-yl methacrylate and adamantane-1-yl acrylate.

［式（ａ４）中、
Ｒ³は、水素原子又はメチル基を表す。
Ｒ⁴は、炭素数１〜２０のフッ素原子を有する飽和炭化水素基を表す。］ <Structural unit (a4)>
Resin (A1) contains structural unit (a4).

[In the formula (a4),
R ³ represents a hydrogen atom or a methyl group.
R ⁴ represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]

Examples of the saturated hydrocarbon group having a fluorine atom for R ⁴ include 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 Propyl) 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; and alicyclic hydrocarbon groups having a fluorine atom such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

［式（ａ４−０）中、
Ｒ⁵は、水素原子又はメチル基を表す。
Ｌ⁴は、炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ³は、炭素数１〜８のペルフルオロアルカンジイル基を表す。
Ｒ⁶は、水素原子又はフッ素原子を表す。］ The structural unit (a4) is preferably a structural unit represented by the formula (a4-0).

[In the formula (a4-0),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁴ represents an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a C 1-8 perfluoroalkanediyl group.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

As the perfluoroalkanediyl group of L ³ , a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluorobutane-1,4 -Diyl group, perfluoropentane-1,5-diyl group, perfluorohexane-1,6-diyl group, perfluoroheptane-1,7-diyl group, perfluorooctane-1,8-diyl group and the like.

L ⁴ is preferably a methylene group or an ethylene group, and more preferably a methylene group.
L ³ is preferably a C 1-6 perfluoroalkanediyl group, more preferably a C 1-3 perfluoroalkanediyl group.

Examples of the structural unit (a4) include the following.

In the structural unit, a structural unit in which a methyl group corresponding to R ⁵ is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a4).

［式（ａ４’）中、Ｒ³及びＲ⁴は、上記と同じ意味を表す。］ The structural unit (a4) is derived from a compound represented by the formula (a4 ′) (hereinafter sometimes referred to as “compound (a4 ′)”).

[In formula (a4 ′), R ³ and R ⁴ represent the same meaning as described above. ]

Compound (a4 ′) may be a commercially available product or one produced by a known method. Here, the known method includes, for example, a method of condensing (meth) acrylic acid or a derivative thereof (for example, (meth) acrylic acid chloride etc.) and alcohol (HO-R ⁴ ). As a commercial item, the compound etc. which are represented by the following are mentioned.

The content of the structural unit (I) in the resin (A1) is preferably from 25 to 80 mol%, more preferably from 25 to 75 mol%, more preferably from 30 to 70 mol%, based on all the structural units of the resin (A1). Is more preferable, and 40 to 60 mol% is particularly preferable.
The content of the structural unit (a4) in the resin (A1) is preferably 20 to 75 mol%, more preferably 25 to 75 mol%, and more preferably 30 to 70 mol% with respect to all the structural units of the resin (A1). Is more preferable, and 40 to 60 mol% is particularly preferable.
The total content of the structural unit (I) and the structural unit (a4) is preferably 50 mol% or more, more preferably 70 mol% or more, and more preferably 90 mol% or more with respect to all the structural units of the resin (A1). It is particularly preferable that substantially only the structural unit (I) and the structural unit (a4) are present.
When the content of the structural unit (I) and the structural unit (a4) is within the above range, a resist pattern with excellent line edge roughness (LER) can be manufactured, and in particular, a resist pattern with few defects is manufactured. it can.

Each structural unit (I) and structural unit (a4) constituting the resin (A1) can be used alone or in combination of two or more. Resin (A1) can be manufactured by a well-known polymerization method (for example, radical polymerization method) combining only 1 type or 2 types or more of compound (I ') and compound (a4'), respectively. The content rate of each structural unit which resin (A1) has can be adjusted with the usage-amount of the compound used for superposition | polymerization.
The weight average molecular weight of the resin (A1) is preferably 5,000 or more (more preferably 7,000 or more, more preferably 10,000 or more), 80,000 or less (more preferably 50,000 or less, further preferably Is 30,000 or less). A weight average molecular weight is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography analysis, and the detailed analysis conditions of this analysis are explained in full detail in the Example of this application.

［式（ａ４−１）中、
Ｒ^f3は、水素原子又はメチル基を表す。
Ｌ^3’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いてもよい。
Ｒ^f4は、炭素数１〜２０のフッ素原子を有する飽和炭化水素基を表す。］

［式（ａ４−２）中、
Ｒ^f5は、水素原子又はメチル基を表す。
Ｌ^4’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いてもよい。
Ｒ^f6は、炭素数１〜２０のフッ素原子を有する炭化水素基を表す。］

［式（ａ４−３）中、
Ｒ^f7は、水素原子又はメチル基を表す。
Ｌ^5’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２価の飽和炭化水素基を表す。
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の飽和炭化水素基を表す。
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。］
ただし、Ｌ^5’、Ａ^f13及びＡ^f14の合計炭素数は２０である。 The resin (A1) may have a structural unit different from the structural unit (I) and the structural unit (a4).
The structural unit different from the structural unit (I) and the structural unit (a4) includes a structural unit represented by the formula (a4-1), a structural unit represented by the formula (a4-2), and a formula (a4-3). ), Structural units derived from known monomers used in the field, and the like. The structural unit represented by the formula (a4-1) may be referred to as “structural unit (a4-1)” or the like depending on the formula number.

[In the formula (a4-1),
R ^f3 represents a hydrogen atom or a methyl group.
L ^{3 ′} 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.
R ^f4 represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]

[In the formula (a4-2),
R ^f5 represents a hydrogen atom or a methyl group.
L ^{4 ′} 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.
R ^f6 represents a hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]

[In the formula (a4-3),
R ^f7 represents a hydrogen atom or a methyl group.
L ^{5 ′} represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents a C 1-18 divalent saturated hydrocarbon group which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 has a fluorine atom. ]
However, the total number of carbon atoms of L ^{5 ′} , A ^f13 and A ^f14 is 20.

Examples of the alkanediyl group of L ^{5 ′} include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Linear alkanediyl groups such as diyl group, hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane- Examples include branched alkanediyl groups such as 1,2-diyl group, 1-methylbutane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.

The divalent saturated hydrocarbon group for A ^f13 is, for example, an aliphatic saturated hydrocarbon group or an alicyclic saturated hydrocarbon group.
The saturated hydrocarbon group which may have a fluorine atom of 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 aliphatic saturated 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 group, Examples thereof include perfluoroalkanediyl groups such as perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be monocyclic or polycyclic. Examples of the monocyclic divalent alicyclic saturated hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

The saturated hydrocarbon group for A ^f14 is, for example, an aliphatic saturated hydrocarbon group or an alicyclic saturated hydrocarbon group.
Examples of the aliphatic saturated hydrocarbon group which may have a fluorine atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 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, heptyl group Perfluoroheptyl group, octyl group and perfluorooctyl group.
The alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated 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 polycyclic alicyclic saturated hydrocarbon group include an adamantyl group, a norbornyl group, a perfluoroadamantyl group, and the like.
Examples of the group in which an aliphatic saturated hydrocarbon group and an alicyclic saturated hydrocarbon group are combined include an adamantylmethyl group, a norbornylmethyl group, a perfluoroadamantylmethyl group, and the like.

In formula (a4-3), L ^{5 ′} is preferably an ethylene group.
A ^f13 is preferably an aliphatic saturated hydrocarbon group, and the aliphatic saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably has 2 to 3 carbon atoms.
The saturated 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.

Examples of the structural unit (a4-1) include the following.

In the above structural unit, a structural unit in which a methyl group corresponding to R ^f3 is replaced by a hydrogen atom can also be given as a specific example of the structural unit (a4-1).

Examples of the structural unit (a4-2) include the following.

In the above structural unit, a structural unit in which a methyl group corresponding to R ^f5 is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a4-2).

Examples of the structural unit (a4-3) include the following.

In the above structural unit, a structural unit in which a methyl group corresponding to R ^f7 is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a4-3).

［式（ａ４’−１）中、Ｒ^f3、Ｒ^f4及びＬ^3’は、上記と同じ意味を表す。］ The structural unit (a4-1) is derived from a compound represented by the formula (a4′-1) (hereinafter sometimes referred to as “compound (a4′-1)”).

[In formula (a4′-1), R ^f3 , R ^f4 and L ^{3 ′} represent the same meaning as described above. ]

［式中、Ｒ^f3、Ｒ^f4及びＬ^3’は、上記と同じ意味を表す。］
溶媒としては、テトラヒドロフラン等が挙げられる。また、塩基性触媒としては、ピリジン等が挙げられる。
式（ａ４’−１−１）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、市販品を利用することができる。また、例えば、（メタ）アクリル酸又はその誘導体（例えば、（メタ）アクリル酸クロリド等）と、ジオール（ＨＯ−Ｌ^3’−ＯＨ）とを縮合する公知の方法によって得られたものを利用することができる。
式（ａ４’−１−２）で表される化合物としては、Ｒ^f4の種類に応じて、対応するカルボン酸を無水物へと変換して用いることができる。市販品としては、ヘプタフルオロ酪酸無水物等がある。 Compound (a4′-1) is, for example, a compound represented by formula (a4′-1-1) and a compound represented by formula (a4′-1-2) in a solvent in a basic catalyst. It can manufacture by making it react in presence of.

[Wherein, R ^f3 , R ^f4 and L ^{3 ′} represent the same meaning as described above. ]
Examples of the solvent include tetrahydrofuran. Examples of the basic catalyst include pyridine.
Examples of the compound represented by the formula (a4′-1-1) include hydroxyethyl methacrylate, and commercially available products can be used. Further, for example, those obtained by a known method of condensing (meth) acrylic acid or a derivative thereof (for example, (meth) acrylic acid chloride etc.) and diol (HO-L ^{3 ′} -OH) are used. be able to.
As the compound represented by the formula (a4′-1-2), the corresponding carboxylic acid can be converted into an anhydride depending on the type of R ^f4 . Commercially available products include heptafluorobutyric anhydride.

［式（ａ４’−２）中、Ｒ^f5、Ｒ^f6及びＬ^4’は、上記と同じ意味を表す。］ The structural unit (a4-2) is derived from a compound represented by the formula (a4′-2) (hereinafter sometimes referred to as “compound (a4′-2)”).

[In formula (a4′-2), R ^f5 , R ^f6 and L ^{4 ′} represent the same meaning as described above. ]

Compound (a4′-2) is, for example, a compound represented by formula (a4′-2-1) and a compound represented by formula (a4′-2-2) in the presence of a catalyst. It can manufacture by making it react under. As the solvent, dimethylformamide or the like is used. As the catalyst, potassium carbonate, potassium iodide and the like are used.

［式中、Ｒ^f6及びＬ^4’は、上記と同じ意味を表す。］
式（ａ４’−２−３）で表される化合物は、Ｌ^4’の種類に応じて適当なものを用いることができる。
式（ａ４’−２−３）で表される化合物として、例えば、クロロアセチルクロリド等を用いることによりＬ^4’がメチレン基である場合の式（ａ４’−２−２）で表される化合物を製造することができる。このクロロアセチルクロリドは市場から容易に入手できる。
式（ａ４’−２−４）で表される化合物は、Ｒ^f6の種類に応じて適当なアルコールを用いることができる。
式（ａ４’−２−４）で表される化合物として、例えば、２，２，３，３，４，４，４−ヘプタフルオロ−１−ブタノール等を用いることによりＲ^f6がフッ素原子で置換された脂肪族炭化水素基である式（ａ４’−２−２）で表される化合物を製造することができる。この２，２，３，３，４，４，４−ヘプタフルオロ−１−ブタノールは市場から容易に入手できる。 A commercially available product can be used as the compound represented by the formula (a4′-2-1). Examples of such commercially available products include methacrylic acid.
The compound represented by the formula (a4′-2-2) is obtained by reacting, for example, a compound represented by the formula (a4′-2-3) with a compound represented by the formula (a4′-2-4). Can be manufactured. This reaction is carried out in a solvent in the presence of a base catalyst. The solvent used in this reaction is tetrahydrofuran or the like. As the base catalyst, pyridine or the like is used.

[Wherein, R ^f6 and L ^{4 ′} represent the same meaning as described above. ]
As the compound represented by the formula (a4′-2-3), an appropriate compound can be used depending on the type of L ^{4 ′} .
As the compound represented by the formula (a4′-2-3), for example, a compound represented by the formula (a4′-2-2) when L ^{4 ′} is a methylene group by using chloroacetyl chloride or the like. Can be manufactured. This chloroacetyl chloride is readily available from the market.
As the compound represented by the formula (a4′-2-4), an appropriate alcohol can be used depending on the type of R ^f6 .
By using, for example, 2,2,3,3,4,4,4-heptafluoro-1-butanol as the compound represented by the formula (a4′-2-4), R ^f6 is substituted with a fluorine atom. A compound represented by the formula (a4′-2-2), which is an aliphatic hydrocarbon group thus produced, can be produced. This 2,2,3,3,4,4,4-heptafluoro-1-butanol is readily available from the market.

［式（ａ４’−３）中、Ｒ^f7、Ｌ^5’、Ａ^f13、Ｘ^f12及びＡ^f14は、上記と同じ意味を表す。］ The structural unit (a4-3) is derived from a compound represented by the formula (a4′-3) (hereinafter sometimes referred to as “compound (a4′-3)”).

[In Formula (a4′-3), R ^f7 , L ^{5 ′} , A ^f13 , X ^f12 and A ^f14 represent the same meaning as described above. ]

［式中、Ｒ^f7、Ｌ^5’、Ａ^f13、Ｘ^f12及びＡ^f14は、上記と同じ意味を表す。］ The compound represented by the formula (a4′-3) reacts, for example, a compound represented by the formula (a4′-3-1) with a carboxylic acid represented by the formula (a4′-3-2). Can be obtained.
This reaction is usually performed in the presence of a solvent. As the solvent, tetrahydrofuran, toluene and the like are used. In the reaction, a known esterification catalyst (for example, an acid catalyst or a carbodiimide catalyst) may coexist.

[Wherein, R ^f7 , L ^{5 ′} , A ^f13 , X ^f12 and A ^f14 represent the same meaning as described above. ]

As the compound represented by the formula (a4′-3-1), a commercially available product may be used, or it may be produced by a known method. Examples of the known method include a method of condensing (meth) acrylic acid or a derivative thereof (for example, (meth) acrylic acid chloride or the like) and a diol (HO-L ^{5 ′} -OH). Examples of commercially available products include hydroxyethyl methacrylate.
The carboxylic acid represented by the formula (a4′-3-2) can be produced by a known method. For example, any one of the following compounds may be used.

<Resin (A2)>
The resin (A2) includes a structural unit represented by the formula (II) (hereinafter sometimes referred to as “structural unit (II)”) and a structural unit (a) having an acid labile group. Further, the resin (A2) may contain a structural unit having no acid labile group (however, different from the structural unit (II), hereinafter may be referred to as “structural unit (s)”).

［式（ＩＩ）中、
環Ｔ¹は、置換基を有していてもよい炭素数３〜３４のスルトン環を表す。
Ｚ¹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−１）で表される基を表す。

（式（ａ−１）中、
ｓは０又は１の整数を表す。
Ｘ¹⁰及びＸ¹¹は、それぞれ独立に、酸素原子、イミノ基、カルボニル基、カルボニルオキシ基、オキシカルボニル基、カルボニルイミノ基又はイミノカルボニル基を表す。
Ａ¹⁰、Ａ¹¹及びＡ¹²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２価の脂肪族炭化水素基を表す。ただし、Ａ¹⁰、Ａ¹¹及びＡ¹²の炭素数の合計は７以下である。）
Ｚ²は、単結合又はカルボニル基を表す。
Ｒ⁷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。］ <Structural unit (II)>
Resin (A2) contains structural unit (II).

[In the formula (II),
Ring T ¹ represents a sultone ring having 3 to 34 carbon atoms which may have a substituent.
Z ¹ represents an optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-1).

(In the formula (a-1),
s represents an integer of 0 or 1.
X ¹⁰ and X ¹¹ each independently represent an oxygen atom, an imino group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a carbonylimino group or an iminocarbonyl group.
A ¹⁰ , A ¹¹ and A ¹² each independently represent a C 1-5 divalent aliphatic hydrocarbon group which may have a substituent. However, the total number of carbon atoms of A ¹⁰ , A ¹¹ and A ¹² is 7 or less. )
Z ² represents a single bond or a carbonyl group.
R ⁷ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. ]

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

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

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

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

［式（Ｔ１’）中、
Ｘ^11aは、それぞれ独立に、酸素原子、硫黄原子又はメチレン基を表す。
Ｒ⁴¹は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基あるいは炭素数２〜４のアシル基を表す。
ｍａは、０〜９の整数を表す。ｍａが２以上のとき、複数のＲ⁴¹は同一又は相異なる。
＊は、酸素原子との結合手を表す。］ The ring T ¹ is preferably a ring represented by the following formula (T1 ′).

[In the formula (T1 ′),
X ^11a each independently represents an oxygen atom, a sulfur atom or a methylene group.
R ⁴¹ is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, or an aryl having 6 to 12 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
ma represents an integer of 0 to 9. When ma is 2 or more, the plurality of R ⁴¹ are the same or different.
* Represents a bond with an oxygen atom. ]

X ^11a is preferably an oxygen atom or a methylene group, more preferably X ¹¹ is an oxygen atom.
R ⁴¹ is preferably a C 1-12 alkyl group which may have a halogen atom or a hydroxy group.

［式（Ｔ１）中、
Ｒ⁸は、ハロゲン原子又はヒドロキシ基を有していてもよい炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシジルオキシ基、炭素数２〜１２のアルコキシカルボニル基あるいは炭素数２〜４のアシル基を表す。
ｍは、０〜９の整数を表す。ｍが２以上のとき、複数のＲ⁸は同一又は相異なる。
＊は、酸素原子との結合手を表す。］
式（Ｔ１’）におけるｍａ及び式（Ｔ１）におけるｍは、好ましくは０又は１であり、より好ましくは０である。 Further, the ring T ¹ is preferably a ring represented by the formula (T1).

[In the formula (T1),
R ⁸ is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, or an aryl having 6 to 12 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 4 carbon atoms.
m represents an integer of 0 to 9. When m is 2 or more, the plurality of R ⁸ are the same or different.
* Represents a bond with an oxygen atom. ]
Ma in the formula (T1 ′) and m in the formula (T1) are preferably 0 or 1, and more preferably 0.

Examples of the ring represented by the formula (T1 ′) and the ring represented by the formula (T1) include the following rings.

As the alkanediyl group for Z ¹ , 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; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group And branched alkanediyl groups such as pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group.
Examples of the substituent for the alkanediyl group of Z ¹ include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group include the same groups as described above.

The group represented by the formula (a-1) (hereinafter sometimes referred to as “group (a-1)”) is an oxygen atom, an imino group, a carbonyl group, a carbonyloxy group, as in X ¹⁰ and X ¹¹ . , An atom or an atomic group such as an oxycarbonyl group, a carbonylimino group or an iminocarbonyl group.
Examples of the divalent aliphatic hydrocarbon group of A ¹⁰ , A ¹¹ and A ¹² include alkanediyl groups. Examples of the alkanediyl group include the same ones as described above. Examples of the substituent in the divalent aliphatic hydrocarbon group include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.

Specific examples of the group (a-1) are shown below. In the following groups, two bonds represented by * respectively represent a bond with a sulfur atom on the left side and a bond with Z ² on the right side.

などが挙げられる。 As the group (a-1) having an oxygen atom,

Etc.

などが挙げられる。 As the group (a-1) having an imino group,

Etc.

などが挙げられる。 As the group (a-1) having a carbonyl group,

Etc.

などが挙げられる。 As the group (a-1) having a carbonyloxy group,

Etc.

などが挙げられる。 As the group (a-1) having an oxycarbonyl group,

Etc.

などが挙げられる。 As the group (a-1) having a carbonylimino group,

Etc.

などが挙げられる。 As the group (a-1) having an iminocarbonyl group,

Etc.

In the structural unit (II), Z ¹ is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, and further preferably a methylene group.
Z ² is preferably a carbonyl group.
R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group.

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

式（ａａ−１）〜式（ａａ−２４）のいずれかで表される構造単位（ＩＩ）の具体例において、Ｒ⁷に相当するメチル基が水素原子に置き換わった構造単位も、構造単位（ＩＩ）の具体例として挙げることができる。

In the specific example of the structural unit (II) represented by any one of the formulas (aa-1) to (aa-24), the structural unit in which the methyl group corresponding to R ⁷ is replaced with a hydrogen atom is also a structural unit ( Specific examples of II) can be mentioned.

［式（ＩＩ’）中の符号はいずれも、前記と同義である。］
化合物（ＩＩ’）は、例えば、特開２０１２−１５８７４２号公報記載の方法によって又はこの方法に準じて製造することができる。 The structural unit (II) is derived from a compound represented by the following formula (II ′) (hereinafter sometimes referred to as “compound (II ′)”).

[All the symbols in formula (II ′) have the same meanings as described above. ]
Compound (II ′) can be produced, for example, by the method described in JP2012-158742A or according to this method.

  The content of the structural unit (II) in the resin (A2) is preferably 1 to 80 mol%, more preferably 2 to 75 mol%, and still more preferably based on the total structural units of the resin (A2). Is 3 to 70 mol%, particularly preferably 5 to 65 mol%.

<Structural unit (a)>
Examples of the acid labile group contained in the structural unit (a) include a group represented by the formula (1) and a group represented by the formula (2).

［式（１）中、Ｒ^a1〜Ｒ^a3は、それぞれ独立に、炭素数１〜８のアルキル基、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^a1'及びＲ^a2'は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表し、Ｒ^a3'は、炭素数１〜２０の炭化水素基を表すか、Ｒ^a2'及びＲ^a3'は互いに結合して炭素数２〜２０の２価の炭化水素基を形成し、該炭化水素基及び該２価の炭化水素基に含まれるメチレン基は、酸素原子又は硫黄原子で置き換わっていてもよい。］

[In the formula (1), R ^{a1 to} 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 of these, or R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms. * Represents a bond. ]

[In Formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the methylene group contained in the hydrocarbon group and the divalent hydrocarbon group is It may be replaced with an oxygen atom or a sulfur atom. ]

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。アルキル基と脂環式炭化水素基とを組合わせた基は、好ましくは炭素数２０以下である。 ^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. A group in which an alkyl group and an alicyclic hydrocarbon group are combined preferably has 20 or less carbon atoms.

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

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).

Ｒ^a1'及びＲ^a2'のうち、少なくとも１つは水素原子であることが好ましい。 Examples of the hydrocarbon group for R ^{a1 ′ to} R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
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.
In the case where R ^{a2 ′} and R ^{a3 ′} are combined to form a divalent hydrocarbon group, the * —C (R ^{a1 ′} ) (R ^{a2 ′} ) (OR ^{a3 ′} ) group includes the following groups (in the formula: , * Represents a bond.). The divalent hydrocarbon group preferably has 3 to 12 carbon atoms.

At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

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

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

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

  As a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (1), a structural unit represented by the formula (a1-0) is preferably represented by the formula (a1-1). The structural unit represented by a structural unit or a formula (a1-2) is mentioned. These may be used alone or in combination of two or more. In this specification, the structural unit represented by formula (a1-0), the structural unit represented by formula (a1-1), and the structural unit represented by formula (a1-2) are each represented by structural unit (a1). -0), structural unit (a1-1) and structural unit (a1-2), a monomer for deriving structural unit (a1-0), a monomer for deriving structural unit (a1-1), and a structural unit (a1- The monomer that induces 2) may be referred to as monomer (a1-0), monomer (a1-1), and monomer (a1-2), respectively.

［式（ａ１−０）中、
Ｌ^a01は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k01−ＣＯ−Ｏ−を表し、ｋ０１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04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。］

[In the formula (a1-0),
L ^a01 represents an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 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. ]

［式（ａ１−１）及び式（ａ１−２）中、
Ｌ^a1及びＬ^a2は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k1−ＣＯ−Ｏ−を表し、ｋ１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a4及びＲ^a5は、水素原子又はメチル基を表す。
Ｒ^a6及びＲ^a7は、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 represent an oxygen atom or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a4 and R ^a5 represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 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 ^a01 is preferably an oxygen atom or k-O is an integer of 1 to 4 ^* —O— (CH ₂ ) _k01 —CO—O— or k01 is 1 ^* —O— (CH ₂ ) _k01 —CO -O-, more preferably an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03, and R ^a04 , 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 ^a02 , R ^a03 and R ^a04 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group ^{represented by} R ^a02 , R ^a03 and R ^a04 preferably has 8 or less carbon atoms, more preferably 6 or less.
The group combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less, combining the alkyl group and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

L ^a1 and L ^a2 are preferably an oxygen atom or ^* —O— (CH ₂ ) _k1 —CO—O— in which k1 is an integer of 1 to 4, more preferably an oxygen atom or k1 is 1. ^* —O— (CH ₂ ) _k1 —CO—O—.
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.
The group combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less, combining the alkyl group and the alicyclic hydrocarbon group. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.
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 the monomer (a1-0), for example, a monomer represented by any one of the formulas (a1-0-1) to (a1-0-12) is preferable, and the formula (a1-0-1) to the formula ( A monomer represented by any one of a1-0-10) is more preferable.

In the above structural unit, a structural unit in which a methyl group corresponding to R ^a01 is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a1-0).

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

  When the resin (A2) includes the structural unit (a1-0) and / or the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is the total structure of the resin (A2). It is 10-95 mol% normally with respect to a unit, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

式（ａ１−５）中、
Ｒ^a11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^a11は、単結合又は＊−［ＣＨ₂］_k1’−ＣＯ−Ｌ^a14−を表す。ここで、ｋ１’は１〜４の整数を表す。＊は、Ｌ^a11との結合手を表す。
Ｌ^a11、Ｌ^a12、Ｌ^a13及びＬ^a14は、それぞれ独立に、酸素原子又は硫黄原子を表す。
ｓ１は、１〜３の整数を表す。
ｓ１’は、０〜３の整数を表す。 Examples of the structural unit (a) also include a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”).

In formula (a1-5),
R ^a11 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom.
Z ^a11 represents a single bond or * — [CH ₂ ] _{k1 ′} —CO—L ^a14 —. Here, k1 ′ represents an integer of 1 to 4. * Represents a bond with L ^a11 .
L ^a11 , L ^a12 , L ^a13 and L ^a14 each independently represent an oxygen atom or a sulfur atom.
s1 represents an integer of 1 to 3.
s1 ′ represents an integer of 0 to 3.

In formula (a1-5), R ^a11 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ^a11 is preferably an oxygen atom.
One of L ^a12 and L ^a13 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 ^a11 is preferably a single bond or * —CH ₂ —CO—O—.

The monomer that derives the structural unit (a1-5) may be referred to as a monomer (a1-5). As a monomer (a1-5), the following monomers are mentioned, for example.

  The structural unit (a) having an acid labile group in the resin (A2) includes the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2), and the structural unit (a1-5). 1 type or more selected from the group consisting of) is preferable, and two or more types are more preferable, a combination of the structural unit (a1-1) and the structural unit (a1-2), the structural unit (a1-1) and the structural unit (a1- 5), a combination of structural unit (a1-1) and structural unit (a1-0), a combination of structural unit (a1-2) and structural unit (a1-0), a structural unit (a1-5) and a structure Combination of unit (a1-0), structural unit (a1-0), combination of structural unit (a1-1) and structural unit (a1-2), or structural unit (a1-0), structural unit (a1-1) ) And the structural unit (a1-5) Preferably the al, combination of the combination of the structural units (a1-1) and the structural unit (a1-2) or structural units (a1-1) and the structural units, (a1-5) is particularly preferred.

  When the resin (A2) has the structural unit (a1-5), the content is preferably from 1 to 50 mol%, more preferably from 3 to 45 mol%, based on all structural units of the resin (A2). 5 to 40 mol% is more preferable.

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”). The monomer (s) may be any monomer that does not have an acid labile group, and examples thereof include known monomers used in this field.
The structural unit (s) is preferably a structural unit (s) having a hydroxy group or a lactone ring. Structural unit (s) having a hydroxy group (hereinafter sometimes referred to as “structural unit (a2)”) and / or structural unit (s) containing a lactone ring (hereinafter sometimes referred to as “structural unit (a3)”) If a resin having s is used for preparing a resist composition, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When the resist composition of the present invention is applied to ArF excimer laser exposure (193 nm) or the like, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2). When applied to high energy beam exposure such as KrF excimer laser exposure (248 nm), electron beam or EUV (extreme ultraviolet light), the structural unit (a2) having a phenolic hydroxy group may be used as the structural unit (a2). preferable. Moreover, the structural unit (a2) may contain one kind alone, or two or more kinds may be used in combination.

式（ａ２−１）中、
Ｌ^a3は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−を表し、
ｋ２は、１〜７の整数を表す。＊はカルボニル基との結合手を表す。
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。 When the resin (A2) has a structural unit (a2), the structural unit (a2) is preferably a structural unit (a2) having an alcoholic hydroxy group.
As the structural unit (a2) having an alcoholic hydroxy group, a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”) is preferable.

In formula (a2-1),
L ^a3 represents an oxygen atom or ^* —O— (CH ₂ ) _k2 —CO—O—,
k2 represents an integer of 1 to 7. * Represents a bond with a carbonyl group.
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 an oxygen _{atom, -O- (CH 2) f1 -CO} -O- and is (wherein f1 is an integer from 1 to 4), more preferably It is an oxygen atom.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

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

  When resin (A2) contains structural unit (a2-1), the content rate is 1-45 mol% normally with respect to all the structural units of resin (A2), Preferably it is 1-40 mol%. More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

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

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

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

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

In the formula (a3-1) to the formula (a3-3), L ^{a4 to} L ^a6 are preferably each independently an oxygen atom or k—3 is an integer of 1 to 4 * —O— (CH ₂ ) A group represented by _{k 3} —CO—O—, more preferably an oxygen atom and * —O—CH ₂ —CO—O—, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are preferably a carboxy group, a cyano group, or a methyl group.
p1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

  As a monomer which introduce | transduces structural unit (a3), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example, Formula (a3-1-1)-Formula (a3-1-4), Formula (a3) 2-1) to the formula (a3-2-4) and the formula (a3-3-1) to the formula (a3-3-4) are preferable, and the monomer represented by the formula (a3-1-1) is preferable. The monomer represented by any one of formula (a3-1-2) and formula (a3-3-3) to formula (a3-2-4) is more preferable, and the formula (a3-1-1) or formula The monomer represented by (a3-2-3) is more preferable.

When the resin (A2) 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 (A2). More preferably, it is 15-60 mol%.
Moreover, the content rate of a structural unit (a3-1), a structural unit (a3-2), and a structural unit (a3-3) is 5-60 mol% with respect to all the structural units of resin (A2), respectively. Is preferable, 5-50 mol% is more preferable, and 10-50 mol% is further more preferable.

  The resin (A2) is a resin containing the structural unit (II) and the structural unit (a), and preferably a resin containing the structural unit (II), the structural unit (a), and the structural unit (s). More preferably, it is a resin comprising the structural unit (II), the structural unit (a), and the structural unit (s).

When the resin (A2) is a resin composed only of the structural unit (II) and the structural unit (a), these contents are respectively relative to the total structural units of the resin (A2).
Structural unit (II); 1-80 mol%
Structural unit (a); 20 to 99 mol% is preferred,
Structural unit (II); 2-75 mol%
Structural unit (a); 25 to 98 mol% is more preferred,
Structural unit (II); 5-65 mol%
The structural unit (a); 35 to 95 mol% is more preferable.

When the resin (A2) is a resin composed of the structural unit (II), the structural unit (a), and the structural unit (s), each of these contents is based on the total structural unit of the resin (A2),
Structural unit (II); 1-80 mol%
Structural unit (a); 17-96 mol%
Structural unit (s); 3-82 mol% is preferable,
Structural unit (II); 2-75 mol%
Structural unit (a); 20-93 mol%
Structural unit (s); 5-78 mol% is more preferable,
Structural unit (II); 5-65 mol%
Structural unit (a); 30 to 90 mol%
The structural unit (s); 5 to 65 mol% is more preferable.

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

  The resin (A2) 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 (a). 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 (A2) can be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using monomers that lead to these structural units. it can. The content rate of each structural unit which resin (A2) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (A2) is preferably 2,500 or more (more preferably 3,000 or more, more preferably 4,000 or more), 50,000 or less (more preferably 30,000 or less, further preferably 15,000 or less).

  In the resin (A), the resin (A1) and the resin (A2) are, for example, resin (A1): resin (A2) = 0.01: 10 to 5:10, preferably 0.05: 10 to 3:10. More preferably 0.1: 10 to 2:10, still more preferably 0.2: 10 to 1:10 (mass ratio).

<Resin other than resin (A1) and (A2)>
The resist composition of the present invention may contain a resin other than the above-described resins (A1) and (A2), for example, a resin consisting only of the structural unit (s).

  In the resist composition of the present invention, the content of the resin (A) is preferably 80% by mass or more and 99% by mass or less in the solid content of the resist composition. In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) 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)>
Although an acid generator is classified into a nonionic type and an ionic type, any may be used for the acid generator (B) of the resist composition of this invention. Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonates), sulfones (e.g. disulfone, ketosulfone, sulfonyldiazomethane) and the like. The ionic acid generator is typically an onium salt containing an onium cation (for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712 The compound which generate | occur | produces an acid by the radiation as described in etc. can be used. 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 an acid generator represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).

［式（Ｂ１）中、
Ｑ^b1及びＱ^b2は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。
Ｌ^b1は、単結合又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メチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ｙは、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メチレン基は、酸素原子、スルホニル基又はカルボニル基に置き換わっていてもよい。
Ｚｂ⁺は、有機カチオンを表す。］

[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a C1-C17 divalent saturated hydrocarbon group which may have a single bond or a substituent, and the methylene group contained in the saturated hydrocarbon group is an oxygen atom or a carbonyl group. It may be replaced.
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. The methylene group contained in the alicyclic hydrocarbon group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group.
Zb ⁺ represents an organic cation. ]

Examples of the perfluoroalkyl group for Q ^b1 and Q ^b2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, A perfluorohexyl group etc. are mentioned.
Q ^b1 and Q ^b2 are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom.

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

Examples of the group in which the methylene group contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by an oxygen atom or a carbonyl group are represented by any of formulas (b1-1) to (b1-7). Groups. The formula (b1-1) to the formula (b1-7) are described in accordance with the formula (B1) on the left and right sides, and C (Q ^b1 ) on the left side of two bonds represented by *, respectively. Bonded with (Q ^b2 )-and on the right side with -Y. The same applies to specific examples of the following formulas (b1-1) to (b1-7).

式（ｂ１−１）〜式（ｂ１−７）中、
Ｌ^b2は、単結合又は炭素数１〜１５の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b2'は、単結合又は炭素数１〜１５の２価の脂肪族飽和炭化水素基を表し、該脂肪族飽和炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。
Ｌ^b3は、単結合又は炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b4は、炭素数１〜１３の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b4'は、単結合又は炭素数１〜１３の２価の脂肪族飽和炭化水素基を表し、該脂肪族飽和炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。但しＬ^b3、Ｌ^b4及びＬ^b4'の合計炭素数の上限は１４である。
Ｌ^b5は、単結合又は炭素数１〜１４の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b6は、炭素数１〜１５の２価の脂肪族飽和炭化水素基を表し、該脂肪族飽和炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。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価の脂肪族飽和炭化水素基を表す。
Ｌ^b8は、炭素数１〜１６の２価の脂肪族飽和炭化水素基を表し、該脂肪族飽和炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。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価の脂肪族飽和炭化水素基を表す。
Ｌ^b10は、炭素数１〜１４の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b10'は、単結合又は炭素数１〜１３の２価の脂肪族飽和炭化水素基を表し、該脂肪族飽和炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。但しＬ^b9、Ｌ^b10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価の脂肪族飽和炭化水素基を表す。
Ｌ^b13は、炭素数１〜１２の２価の脂肪族飽和炭化水素基を表す。
Ｌ^b13'は、単結合又は炭素数１〜１１の２価の脂肪族飽和炭化水素基を表し、該脂肪族飽和炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。但しＬ^b11、Ｌ^b12、Ｌ^b13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価の脂肪族飽和炭化水素基を表す。
Ｌ^b16は、炭素数１〜１４の２価の脂肪族飽和炭化水素基を表し、該脂肪族飽和炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。但しＬ^b14、Ｌ^b15及びＬ^b16の合計炭素数の上限は１４である。

In formula (b1-1) to formula (b1-7),
L ^b2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^{b2 ′} represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, and the hydrogen atom contained in the aliphatic saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b4 represents a divalent aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^{b4 ′} represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and the hydrogen atom contained in the aliphatic saturated hydrocarbon group may be substituted with a fluorine atom. However, the upper limit of the total carbon number of L ^b3 , L ^b4 and L ^{b4 ′} is 14.
L ^b5 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^b6 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms, and the hydrogen atom contained in the aliphatic saturated hydrocarbon group may be substituted with a fluorine atom. 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 aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^b8 represents a C 1-16 divalent aliphatic saturated hydrocarbon group, and the hydrogen atom contained in the aliphatic saturated hydrocarbon group may be substituted with a fluorine atom. 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 aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b10 represents a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
L ^{b10 ′} represents a single bond or a C 1-13 divalent aliphatic saturated hydrocarbon group, and the hydrogen atom contained in the aliphatic saturated hydrocarbon group may be substituted with a fluorine atom. However, the upper limit of the total carbon number of L ^b9 , L ^b10 and L ^{b10 ′} is 14.
L ^b11 and L ^b12 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 11 carbon atoms.
L ^b13 represents a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^{b13 ′} represents a single bond or a C 1-11 divalent aliphatic saturated hydrocarbon group, and the hydrogen atom contained in the aliphatic saturated hydrocarbon group may be substituted with a fluorine atom. However, the upper limit of the total carbon number of L ^b11 , L ^b12 , L ^b13 and L ^{b13 ′} is 12.
L ^b14 and L ^b15 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms.
L ^b16 represents a C 1-14 divalent aliphatic saturated hydrocarbon group, and the hydrogen atom contained in the aliphatic saturated hydrocarbon group may be substituted with a fluorine atom. However, the upper limit of the total carbon number of L ^b14 , L ^b15 and L ^b16 is 14.

L ^b1 is preferably a group represented by any one of formulas (b1-1) to (b1-4), more preferably a group represented by formula (b1-1) or formula (b1-2). Can be mentioned.

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

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

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

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

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

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

Examples of the group represented by the formula (b1-7) 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, heptyl group, 2 -Alkyl groups, such as an ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, are mentioned, Preferably, a C1-C6 alkyl group is mentioned.
Examples of the alicyclic hydrocarbon group include groups represented by formulas (Y1) to (Y11).
Examples of the group in which the methylene group contained in the alicyclic hydrocarbon group of Y is replaced with an oxygen atom, a sulfonyl group, or a carbonyl group include groups represented by formulas (Y12) to (Y26).

  Especially, as an alicyclic hydrocarbon group of Y, Preferably it is group represented by either of Formula (Y1)-Formula (Y19), More preferably, Formula (Y11), Formula (Y14), Formula ( Y15) or a group represented by formula (Y19), more preferably a group represented by formula (Y11) or formula (Y14).

Examples of the substituent for the alkyl group in Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aromatic hydrocarbon having 6 to 18 carbon atoms. Group, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or — (CH ₂ ) _j2 —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, 3 to 3 carbon atoms, 16 represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, j2 represents an integer of 0 to 4).
Examples of the substituent for the alicyclic hydrocarbon group in 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 halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group, mesityl group. , Aryl groups such as biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.

Examples of Y include the following.

In addition, when Y is an alkyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, in the divalent saturated hydrocarbon group, The methylene group at the bonding position is preferably replaced with an oxygen atom or a carbonyl group. In this case, the methylene group contained in the alkyl group of Y is not replaced with an oxygen atom or a carbonyl group. The same applies when the 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 5 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent. The methylene group contained may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is more preferably an adamantyl group, a hydroxyadamantyl group or an oxoadamantyl group.

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

Examples of the organic cation (Zb ⁺ ) contained in the acid generator (B1) include organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an arylsulfonium cation is more preferable.

  Examples of preferable cations include cations represented by formulas (Z1) to (Z4).

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

P ⁴ and P ⁵ each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
P ⁶ and P ⁷ each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or P ⁶ and P ^{7 taken} together Forms a ring containing a sulfur atom to which.
P ⁸ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
P ⁹ represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group has 1 to 12 carbon atoms. It may be substituted with an alkoxy group or an alkylcarbonyloxy group.
P ⁸ and P ⁹ together form a ring containing —CH—CO— to which they are attached.

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

特に、Ｐ⁶〜Ｐ⁹の脂環式炭化水素基は、好ましくは炭素数３〜３６であり、より好ましくは炭素数３〜１８、さらに好ましくは炭素数４〜１２である。 Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Is mentioned. In particular, the P ^{6 to} P ⁹ aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms.
Examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an alicyclic hydrocarbon group include a 1- (adamantan-1-yl) alkane-1-yl group.
Examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include an aralkyl group, and specifically include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group. Groups and the like.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. And cycloalkyl groups such as cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

In particular, the P ^{6 to} P ⁹ alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 4 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a 2-alkyladamantan-2-yl group, and a methyl group. A norbornyl group, an isobornyl group, etc. are mentioned.
As an aromatic hydrocarbon group, phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, p-cyclohexylphenyl group, p-adamantylphenyl group And aryl groups such as tolyl group, xylyl group, cumenyl group, mesityl group, biphenylyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl, and the like.
When the aromatic hydrocarbon group includes an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, the aliphatic hydrocarbon group having 1 to 18 carbon atoms and the alicyclic hydrocarbon having 3 to 18 carbon atoms Groups are preferred.

As the alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, heptyloxy group Octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.
As an aromatic hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 4-methoxyphenyl group etc. are mentioned, for example.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

The ring formed by combining P ^a and P ^b may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings, and a sulfur atom As long as it contains one or more, one or more oxygen atoms may be further contained. Examples of the ring include a ring having 3 to 18 carbon atoms, and a ring having 4 to 18 carbon atoms is preferable. Moreover, the ring containing a sulfur atom includes a 3-membered ring to a 12-membered ring, and preferably a 3-membered ring to a 7-membered ring.
The ring formed by combining P ⁶ and P ⁷ may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings, As long as it contains one or more, it may further contain one or more oxygen atoms. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring.
The ring formed by combining P ⁸ and P ⁹ may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings, and —CH— As long as it contains CO-, it may further contain one or more sulfur atoms and / or one or more oxygen atoms, that is, an oxygen atom, a sulfur atom, or a carbonyl group. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring.

Examples of the ring containing a sulfur atom formed by P ⁶ and P ⁷ together include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4 -Ium ring etc. are mentioned.
Examples of the ring containing —CH—CO— formed by P ⁸ and P ⁹ together include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

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

式（Ｚ５）中、
Ｐ¹〜Ｐ³は、それぞれ独立に、ハロゲン原子、ヒドロキシ基、炭素数１〜１８の脂肪族炭化水素基、炭素数３〜１８の脂環式炭化水素基又は炭素数１〜１２のアルコキシ基を表すか、Ｐ¹〜Ｐ³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する。
ｚ１、ｚ２及びｚ３は、それぞれ独立に、０〜５の整数を表す。ｚ１、ｚ２及びｚ３のいずれかが２以上のとき、複数のＰ¹、Ｐ²、Ｐ³は、それぞれ、同一又は相異なる。

In formula (Z5),
P ^{1 to} P ³ are each independently a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Or two selected from P ^{1 to} P ³ together form a ring containing a sulfur atom.
z1, z2 and z3 each independently represents an integer of 0 to 5. When any of z1, z2 and z3 is 2 or more, the plurality of P ¹ , P ² and P ³ are the same or different from each other.

The ring formed by combining two selected from P ^{1 to} P ³ may be any of monocyclic, polycyclic, aromatic and non-aromatic rings. As long as it contains the above, it may contain one or more oxygen atoms.
The P ^{1 to} P ³ aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, and the alicyclic hydrocarbon group preferably has 4 to 18 carbon atoms.
Among these, P ^{1 to} P ³ each independently represent a halogen atom (more preferably a fluorine atom), a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, or P ¹ It is preferable that two selected from P ³ together form a ring containing an oxygen atom and a sulfur atom. Each z is independently preferably 0 or 1.

  Examples of the cation represented by the formulas (Z1) to (Z5) include organic cations described in JP2010-204646A.

The acid generator (B1) is a combination of the above-described sulfonate anion and organic cation. The above-mentioned sulfonate anion and cation can be arbitrarily combined.
As an acid generator (B1), what is represented by either of a formula (B1-1)-a formula (B1-22) is mentioned, for example. Among them, those containing an arylsulfonium cation are preferable. Formula (B1-1), Formula (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 (B1-20), Formula (B1-21), and Formula (B1-22) Or a salt represented by any of the above.

  Content of an acid generator (B) becomes like this. Preferably it is 1 mass part or more with respect to 100 mass parts of resin (A), More preferably, it is 3 mass parts or more. Moreover, Preferably it is 30 mass parts or less, More preferably, it is 25 mass parts 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 may contain individually by 1 type and may contain 2 or more types.

<Basic compound (C)>
The basic compound (C) is preferably a basic nitrogen-containing organic compound, and examples thereof include amines and ammonium salts. Examples of amines include aliphatic amines, aromatic amines, primary amines, secondary amines, and tertiary amines. The basic compound (C) is preferably a compound represented by any one of the formulas (C1) to (C8) and (C1-1), more preferably represented by the formula (C1-1). The compound which is made is mentioned.

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

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

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

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

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、Ｒ^c5、Ｒ^c6、Ｒ^c7及びＲ^c8は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c9は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜７のアシル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^c9は互いに同一又は相異なる。］

[In Formula (C2), Formula (C3) and Formula (C4), R ^c5 , R ^c6 , R ^c7 and R ^c8 each independently represent the same meaning as R ^c1 .
R ^c9 represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an acyl group having 2 to 7 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of R ^c9 are the same or different from each other. ]

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

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

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

Wherein (C7) and formula ^{(C8), R c18, R} c19 and R ^c20 in each occurrence independently represent the same meaning as R ^c4.
q3, r3 and s3 each independently represent an integer of 0 to 3, and when q3 is 2 or more, the plurality of R ^c18 are the same or different from each other, and when r3 is 2 or more, the plurality of R ^c19 are When the same or different from each other and s3 is 2 or more, the plurality of R ^c20 are the same or different from each other.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, a carbonyl group, —C (═NH) —, a sulfur atom, 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 acyl group include acetyl group, 2-methylacetyl group, 2,2-dimethylacetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, 2,2-dimethylpropionyl group, and benzoyl group.

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

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

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

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

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

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

  Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater. By adjusting the conditions of the coating apparatus, the film thickness of the composition after coating can be adjusted. Examples of the substrate include a silicon wafer. This substrate may be washed before applying the resist composition, or an antireflection film may be formed using a commercially available organic antireflection film composition.

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 types of laser light 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, extreme ultraviolet light (EUV), etc. it can. In this specification, irradiating these radiations may be collectively referred to as “exposure”. The exposure is usually performed through a mask corresponding to a desired resist pattern. When the exposure light source is an electron beam, a desired pattern may be directly drawn without using a photomask.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection reaction of the acid labile group of the resin (A). As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., 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 exposure, or a resist composition for EUV exposure, particularly for immersion exposure. It is suitable as a resist composition and is useful for fine processing of semiconductors.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
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（ＩＩ−１−１）で表される化合物２５．００部、トリエチルアミン５７．７９部、ジメチルアミノピリジン０．０３部及びアセトニトリル２５０部を反応器に仕込み、２３℃で３０分間攪拌し、２℃に冷却した。この混合物に、温度５℃以下に保った状態下で、式（ＩＩ−１−２）で表される化合物５１．００部を３０分かけて滴下した。得られた混合物を２℃で３０分間攪拌し、２３℃程度まで昇温し、同温度で１時間攪拌した。得られた反応混合物にイオン交換水２５部を添加攪拌し、濃縮した。濃縮物に、クロロホルム２５０部及びイオン交換水１２５部を添加・攪拌し、分液することにより有機層を水洗した。同様の水洗操作を３回繰り返した。回収された有機層を濃縮することにより、式（ＩＩ−１−３）で表される化合物３．５８部を得た。 Synthesis Example 1 [Synthesis of Compound Represented by Formula (II-1)]

25.00 parts of a compound represented by the formula (II-1-1), 57.79 parts of triethylamine, 0.03 part of dimethylaminopyridine and 250 parts of acetonitrile were charged into a reactor, and stirred at 23 ° C. for 30 minutes. Cooled to ° C. To this mixture, 51.00 parts of the compound represented by the formula (II-1-2) was added dropwise over 30 minutes while keeping the temperature at 5 ° C. or lower. The obtained mixture was stirred at 2 ° C. for 30 minutes, heated to about 23 ° C., and stirred at the same temperature for 1 hour. To the resulting reaction mixture, 25 parts of ion-exchanged water was added, stirred and concentrated. To the concentrate, 250 parts of chloroform and 125 parts of ion-exchanged water were added and stirred, followed by liquid separation to wash the organic layer with water. The same water washing operation was repeated three times. The collected organic layer was concentrated to obtain 3.58 parts of a compound represented by the formula (II-1-3).

式（ＩＩ−１−４）で表される化合物３．００部、式（ＩＩ−１−５）で表される化合物４．７３部、ジメチルアミノピリジン０．００３部及びテトラヒドロフラン３０部を、反応器に仕込み、２３℃で３０分間攪拌し、２℃に冷却した。この混合物に、温度５℃以下に保った状態下で、式（ＩＩ−１−３）で表される化合物２．７６部及びテトラヒドロフラン１３．７８部を３０分かけて滴下した。得られた混合物を２℃で１時間攪拌し、２３℃程度まで昇温し、同温度で２０時間攪拌した。得られた反応混合物にイオン交換水１５部を添加攪拌し、濃縮した。濃縮物に、酢酸エチル３０部を添加・攪拌し、分液することにより有機層を回収した。得られた有機層に、イオン交換水３０部を添加し、３０分間攪拌し、静置・分液した。回収された有機層に、１０％炭酸カリウム水溶液３０部を加え、２３℃で３０分間攪拌し、水層を分液・除去した。回収された有機層に、１Ｎ塩酸３０部を加え、２３℃で３０分間攪拌し、水層を分液・除去した。回収された有機層を濃縮することにより、式（ＩＩ−１）で表される化合物２．７８部を得た。
ＭＳ（質量分析）：３３２．０（分子イオンピーク）

A compound represented by the formula (II-1-4) is reacted with 3.00 parts, a compound represented by the formula (II-1-5) 4.73 parts, 0.003 parts dimethylaminopyridine and 30 parts tetrahydrofuran. The vessel was charged, stirred at 23 ° C. for 30 minutes, and cooled to 2 ° C. To this mixture, 2.76 parts of the compound represented by the formula (II-1-3) and 13.78 parts of tetrahydrofuran were added dropwise over 30 minutes while keeping the temperature at 5 ° C. or lower. The resulting mixture was stirred at 2 ° C. for 1 hour, heated to about 23 ° C., and stirred at the same temperature for 20 hours. To the resulting reaction mixture, 15 parts of ion-exchanged water was added, stirred and concentrated. To the concentrate, 30 parts of ethyl acetate was added and stirred, and the organic layer was recovered by liquid separation. To the obtained organic layer, 30 parts of ion-exchanged water was added, stirred for 30 minutes, and allowed to stand and separate. To the collected organic layer, 30 parts of a 10% aqueous potassium carbonate solution was added and stirred at 23 ° C. for 30 minutes, and the aqueous layer was separated and removed. To the collected organic layer, 30 parts of 1N hydrochloric acid was added and stirred at 23 ° C. for 30 minutes, and the aqueous layer was separated and removed. The recovered organic layer was concentrated to obtain 2.78 parts of a compound represented by the formula (II-1).
MS (mass spectrometry): 332.0 (molecular ion peak)

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、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部を添加攪拌し、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、上澄み液を除去し、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、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 2: 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, and 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 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 filtered to obtain 61.54 parts of the salt represented by the formula (B1-5).
MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (−) Spectrum): M ^- 339.1

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

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

Synthesis Example 3 [Synthesis of Resin A1-1]
As the monomer, monomer (I′-1) and monomer (a4′-0-1) were used, and the molar ratio (monomer (I′-1): monomer (a4′-0-1)) was 50:50. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 4 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / water mixed solvent to precipitate a resin, and this resin is filtered to obtain a resin A1-1 (copolymer) having a weight average molecular weight of 1.1 × 10 ^4. Obtained at 89%. This resin A1-1 has the following structural units.

Synthesis Example 4 [Synthesis of Resin A1-2]
As the monomer, monomer (I′-2) and monomer (a4′-0-1) were used, and the molar ratio (monomer (I′-2): monomer (a4′-0-1)) was 50:50. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 4 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin A1-2 (copolymer) having a weight average molecular weight of 1.2 × 10 ^{4 in} a yield. Obtained at 92%. This resin A1-2 has the following structural units.

Synthesis Example 5 [Synthesis of Resin A1-3]
As the monomer, monomer (I′-1) and monomer (a4′-0-1) were used, and the molar ratio (monomer (I′-1): monomer (a4′-0-1)) was 75:25. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 4 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / water mixed solvent to precipitate a resin, and this resin is filtered to obtain a resin A1-3 (copolymer) having a weight average molecular weight of 9.8 × 10 ^3. Obtained at 87%. This resin A1-3 has the following structural units.

Synthesis Example 6 [Synthesis of Resin A1-4]
As the monomer, monomer (I′-1) and monomer (a4′-0-1) were used, and the molar ratio (monomer (I′-1): monomer (a4′-0-1)) was 25:75. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 4 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture is poured into a large amount of a methanol / water mixed solvent to precipitate a resin, and this resin is filtered to obtain a resin A1-4 (copolymer) having a weight average molecular weight of 1.3 × 10 ^4. Obtained at 90%. This resin A1-4 has the following structural units.

Synthesis Example 7 [Synthesis of Resin A1-5]
As the monomer, monomer (I′-1) and monomer (a4′-0-12) were used, and the molar ratio [monomer (I′-1): monomer (a4′-0-12)] was 50:50. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 3 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added based on the total amount of monomers, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin A1-5 (copolymer) having a weight average molecular weight of 1.0 × 10 ^4. Obtained at 91%. This resin A1-5 has the following structural units.

Synthesis Example 8 [Synthesis of Resin A1-6]
As the monomer, monomer (I′-1) and monomer (a4′-0-16) were used, and the molar ratio [monomer (I′-1): monomer (a4′-0-16)] was 50:50. Then, methyl isobutyl ketone 1.2 mass times the total monomer amount was added to make a solution. To this solution, 4.5 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added with respect to the total monomer amount, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate a resin, and this resin was filtered to obtain a resin A1-6 (copolymer) having a weight average molecular weight of 1.2 × 10 ^4. Obtained at 98%. This resin A1-6 has the following structural units.

Synthesis Example 9 [Synthesis of Resin A2-1]
As the monomer, monomer (a1-1-3), monomer (a1-2-3), monomer (a2-1-3), monomer (a3-2-3) and monomer (II-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-3): monomer (a2-1-3): monomer (a3-2-3): monomer (II-1)] is 45:14: It mixed so that it might become 2.5: 22: 16.5, and the propylene glycol monomethyl ether acetate of 1.5 mass times of the total monomer amount was added, and it was set as the solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and the resin was filtered to obtain a resin A2-1 having a weight average molecular weight of 8.5 × 10 ³ . (Copolymer) was obtained with a yield of 62%. This resin A2-1 had the following structural units and was soluble in butyl acetate.

Synthesis Example 10 [Synthesis of Resin A2-2]
As monomers, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-3), monomer (a3-1-1) and monomer ( II-1) and its molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-2-3): monomer (a3 -1-1): monomer (II-1)] is mixed so as to be 45: 14: 2.5: 22: 6.5: 10, and propylene glycol monomethyl ether of 1.5 mass times the total monomer amount. Acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate a resin, and the resin was filtered to obtain a resin A2-2 having a weight average molecular weight of 8.5 × 10 ³ . (Copolymer) was obtained with a yield of 60%. This resin A2-2 had the following structural units and was soluble in butyl acetate.

Synthesis Example 11 [Synthesis of Resin A2-3]
The monomer (a1-1-2), the monomer (a1-2-3), the monomer (a2-1-1), the monomer (II-1) and the monomer (a3-1-1) are mixed in a molar ratio [monomer (a1 -1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (II-1): monomer (a3-1-1)] is 45: 14: 2.5: It mixed so that it might become a ratio of 10: 28.5, and also 1.5 mass times dioxane was mixed with this monomer mixture with respect to the total mass of all the monomers. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. It added so that it might become. This was polymerized by heating at 75 ° C. for about 5 hours. Thereafter, the polymerization reaction solution was poured into a large amount of a mixed solvent of methanol and water (mass ratio methanol: water = 4: 1) to precipitate the resin. This resin was filtered and collected. Again, the resin is dissolved in dioxane, poured into a large amount of methanol / water mixed solvent, the resin is precipitated, the precipitated resin is filtered and recovered twice, and purified by reprecipitation, weight average. Resin A2-3 (copolymer) having a molecular weight of 8.5 × 10 ³ was obtained in a yield of 61%. This resin A2-3 had the following structural units and was soluble in butyl acetate.

Synthesis Example 12 [Synthesis of Resin A2-4]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-3) and monomer (II-1) The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-2-3): monomer (II-1)] is 45:14: It mixed so that it might become 2.5: 22: 16.5, and the propylene glycol monomethyl ether acetate of 1.5 mass times of the total monomer amount was added, and it was set as the solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate the resin, and the resin was filtered to obtain a resin A2-4 having a weight average molecular weight of 8.0 × 10 ³ . (Copolymer) was obtained with a yield of 70%. This resin A2-4 has the following structural units and was soluble in butyl acetate.

Synthesis Example 13 [Synthesis of Resin A2-5]
As the monomer, monomer (a1-1-3), monomer (a1-5-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (II-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-5-1): monomer (a2-1-3): monomer (a3-2-3): monomer (II-1)] is 45:14: It mixed so that it might become 2.5: 22: 16.5, and the propylene glycol monomethyl ether acetate of 1.5 mass times of the total monomer amount was added, and it was set as the solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate a resin, and the resin is filtered to obtain a resin A2-5 having a weight average molecular weight of 7.9 × 10 ³ . (Copolymer) was obtained with a yield of 68%. This resin A2-5 has the following structural units and was soluble in butyl acetate.

Synthesis Example 14 [Synthesis of Resin A2-6]
As the monomer, monomer (a1-1-3), monomer (a1-0-9), monomer (a2-1-3), monomer (a3-2-3) and monomer (II-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-0-9): monomer (a2-1-3): monomer (a3-2-3): monomer (II-1)] is 45:14: It mixed so that it might become 2.5: 22: 16.5, and the propylene glycol monomethyl ether acetate of 1.5 mass times of the total monomer amount was added, and it was set as the solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate a resin, and the resin is filtered to obtain a resin A2-6 having a weight average molecular weight of 8.3 × 10 ³ . (Copolymer) was obtained with a yield of 69%. This resin A2-6 has the following structural units and was soluble in butyl acetate.

Synthesis Example 15 [Synthesis of Resin A2-7]
As the monomer, monomer (a1-0-10), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-3) and monomer (II-1) were used, and their moles The ratio [monomer (a1-0-10): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-2-3): monomer (II-1)] is 45:14: It mixed so that it might become 2.5: 22: 16.5, and the propylene glycol monomethyl ether acetate of 1.5 mass times of the total monomer amount was added, and it was set as the solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.6 mol% and 4.8 mol%, respectively, with respect to the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture is poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate a resin, and the resin is filtered to obtain a resin A2-7 having a weight average molecular weight of 7.6 × 10 ³ . (Copolymer) was obtained with a yield of 62%. This resin A2-7 had the following structural units and was soluble in butyl acetate.

Synthesis Example 16 [Synthesis of Resin A2-8]
As the monomer, monomer (a1-1-3), monomer (a1-0-1), monomer (a2-1-3), monomer (a3-2-3) and monomer (II-1) The ratio [monomer (a1-1-3): monomer (a1-0-1): monomer (a2-1-3): monomer (a3-2-3): monomer (II-1)] is 45:14: It mixed so that it might become 2.5: 22: 16.5, and the propylene glycol monomethyl ether acetate of 1.5 mass times of the total monomer amount was added, and it was set as the solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / ion-exchanged water = 4/1 mixing solution to precipitate a resin, and the resin was filtered to obtain a resin A2-8 having a weight average molecular weight of 8.1 × 10 ³ . (Copolymer) was obtained with a yield of 65%. This resin A2-8 has the following structural units and was soluble in butyl acetate.

Synthesis Example 17 [Synthesis of Resin X1]
As the monomer, monomer (a1-1-1), monomer (a3-1-1) and monomer (a2-1-1) were used, and the molar ratio (monomer (a1-1-1): monomer (a3-1) -1): The monomer (a2-1-1)) was mixed to be 35:45:20, and 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.0 mol% and 3.0 mol%, respectively, based on the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was dissolved again in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 7.0. A × 10 ³ resin X1 was obtained with a yield of 75%. This resin X1 has the following structural units.

Synthesis Example 18 [Synthesis of Resin X2]
As the monomer, monomer (a4-2-3) and monomer (a1-1-1) were used, and the molar ratio (monomer (a4-2-3): monomer (a1-1-1)) was 80:20. The mixture was mixed so that 1.5 mass times dioxane of the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.5 mol% and 1.5 mol%, respectively, based on the total monomer amount, and these were added at 70 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in dioxane, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and a weight average molecular weight of 2.8. A × 10 ⁴ resin X2 (copolymer) was obtained with a yield of 70%. This resin X2 has the following structural units.

Examples 1 to 14 and Comparative Example 1
<Preparation of resist composition>
As shown in Table 1, each component was mixed and dissolved, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

Ｂ３：特開２００５−２２１７２１号公報の実施例に従って合成した塩

<Resin>
A1-1 to A1-6: Resins A1-1 to A1-6
A2-1 to A2-8: Resins A2-1 to A2-8
X1, X2: Resins X1, X2
<Acid generator>
B1-5: a salt represented by the formula (B1-5) B2: a salt synthesized according to the example of WO2008 / 99869 and the example of JP2010-26478A

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

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

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

<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 the application, this silicon wafer was pre-baked on a direct hot plate at a temperature described in the “PB” column of Table 1 for 60 seconds to form a composition layer on the silicon wafer.
ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, Annular σ _out = 0.85 σ _in = 0.65 XY− pol. Illumination], using a mask for forming a trench pattern (pitch 120 nm / trench width 40 nm), the exposure amount was changed stepwise to perform exposure. 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 width of the trench pattern was 40 nm was defined as effective sensitivity.

<Line edge roughness evaluation (LER)>
About the obtained resist pattern, the fluctuation width of the unevenness | corrugation of a wall surface was observed and measured with the scanning electron microscope. This swing is
○ that is 3.5 nm or less,
What exceeded 3.5 nm was set as x. The results are shown in Table 2. A numerical value in parentheses indicates a swing width (nm).

<Defect evaluation>
ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized illumination] for forming a 1: 1 line and space pattern (pitch 80 nm) Using the mask, a negative resist pattern was manufactured by performing the same operation as above except that exposure was performed with an exposure amount at which the line width and space width of the obtained line and space pattern were 1: 1.
Thereafter, the number of defects (pieces) on the line pattern on the wafer was measured using a defect inspection apparatus [KLA-2360; manufactured by KLA Tencor]. The results are shown in Table 2.

  According to the resist composition of the present invention, a negative resist pattern having excellent line edge roughness can be produced, and the number of defects in the obtained resist pattern is small.

Claims (6)

A resin comprising a structural unit represented by formula (I) and a structural unit represented by formula (a4) and having no acid labile group,
A resist composition comprising a resin comprising a structural unit represented by formula (II) and a structural unit having an acid labile group, and an acid generator.

[In the formula (I),
R ¹ represents a hydrogen atom or a methyl group.
R ² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group or hydroxy group having 1 to 8 carbon atoms. May be. However, the hydrogen atom bonded to the carbon atom at the bonding position with L ¹ is not substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
L ¹ represents a single bond or a C 1-18 divalent saturated hydrocarbon group, and the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. ]

[In the formula (a4),
R ³ represents a hydrogen atom or a methyl group.
R ⁴ represents a saturated hydrocarbon group having a fluorine atom having 1 to 20 carbon atoms. ]

[In the formula (II),
Ring T ¹ represents a sultone ring having 3 to 34 carbon atoms which may have a substituent.
Z ¹ represents an optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-1).

(In the formula (a-1),
s represents an integer of 0 or 1.
X ¹⁰ and X ¹¹ each independently represent an oxygen atom, an imino group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a carbonylimino group or an iminocarbonyl group.
A ¹⁰ , A ¹¹ and A ¹² each independently represent a C 1-5 divalent aliphatic hydrocarbon group which may have a substituent. However, the total number of carbon atoms of A ¹⁰ , A ¹¹ and A ¹² is 7 or less. )
Z ² represents a single bond or a carbonyl group.
R ⁷ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. ] ^2. The resist composition according to claim 1, wherein R2 in the formula (I) is an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms. The resist composition according to claim 1 or 2, wherein the structural unit represented by the formula (a4) is a structural unit represented by the formula (a4-0).

[In the formula (a4-0),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁴ represents an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a C 1-8 perfluoroalkanediyl group.
R ⁶ represents a hydrogen atom or a fluorine atom. ]   Containing the structural unit represented by the formula (I) in the resin having the structural unit represented by the formula (I) and the structural unit represented by the formula (a4) and having no acid labile group The rate is 25 to 75 with respect to all structural units of the resin having the structural unit represented by formula (I) and the structural unit represented by formula (a4) and having no acid labile group. The resist composition according to claim 1, wherein the resist composition is mol%. The structural unit having an acid labile group is at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). 5. The resist composition according to any one of 4 above.

[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. ] (1) The process of apply | coating the resist composition in any one of Claims 1-5 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: